Strontium‐Enriched Barite for Enhanced PbSO 4 Nucleation in Lead‐Acid Batteries

Campbell, Colin T.; Karakoti, Ajay S.; Lee, Shannon J.; Lapson, Carinna; Reed, David; Legg, Benjamin A.; Murugesan, Vijayakumar

doi:10.1002/smll.202409902

Strontium‐Enriched Barite for Enhanced PbSO ₄ Nucleation in Lead‐Acid Batteries

Journal Article · Mon Mar 03 00:00:00 EST 2025 · Small

DOI:https://doi.org/10.1002/smll.202409902· OSTI ID:2549506

^[1]; ^[1]; ^[1]; Lapson, Carinna ^[2]; Reed, David ^[1]; ^[1]; ^[1]

Pacific Northwest National Laboratory Richland WA 99354 USA
Department of Chemistry and Biochemistry, University of Oregon Eugene OR 97403 USA

Abstract

Barite (BaSO ₄ ) crystals are an important additive in lead acid batteries due to their ability to promote the controlled nucleation and growth of anglesite (PbSO ₄ ) during battery cycling. This is due to BaSO ₄ ’s isostructural match with PbSO ₄ , which facilitates epitaxial nucleation. However, BaSO ₄ ’s efficacy as a nucleation promoter is limited by lattice mismatches between the two phases of 1–5%. Here, strontium‐enriched barite, (Ba,Sr)SO ₄ , is synthesized to produce a nucleating promoter that displays an improved lattice match with PbSO ₄ . Nucleation of PbSO ₄ from Pb‐rich sulfuric acid solutions on strontium‐free and strontium‐enriched barite (up to 17 mol% Sr) is investigated using in‐situ atomic force microscopy and optical microscopy. At low strontium concentrations, PbSO ₄ forms by the Stranski–Krastanov growth pathway (monolayer + island formation), with most nucleation occurring on edges and surface defects. At higher concentrations, the layer‐by‐layer growth mechanism known as Frank van‐der‐Merwe growth is observed, which allows for facile growth of continuous PbSO ₄ films across the BaSO ₄ surface. These films are successfully re‐dissolved on exposure to Pb‐free sulfuric acid. The results show that strontium incorporation fundamentally alters the mechanism of PbSO ₄ nucleation on BaSO ₄ , and thus provides a potential avenue for creating improved nucleation promoters in lead‐acid batteries.

View Journal Article

Sponsoring Organization:: USDOE

OSTI ID:: 2549506

Journal Information:: Small, Journal Name: Small Journal Issue: 13 Vol. 21; ISSN 1613-6810

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (60)

A Most General and Facile Recipe for the Calculation of Heteroepitaxial Strain Grundmann, Marius physica status solidi (b), Vol. 257, Issue 12 https://doi.org/10.1002/pssb.202000323	journal	August 2020
Elastic constants of barytes and celestite Rao, T. Seshagri Proceedings of the Indian Academy of Sciences - Section A, Vol. 33, Issue 5 https://doi.org/10.1007/BF03173258	journal	May 1951
Direct calculation of thermodynamic properties of the barite/celestite solid solution from molecular principles Becker, U.; Fernández-González, A.; Prieto, M. Physics and Chemistry of Minerals, Vol. 27, Issue 4 https://doi.org/10.1007/s002690050258	journal	March 2000
Synthesis of barite, celestite and barium-strontium sulfate solid solution crystals Brower, Elise Geochimica et Cosmochimica Acta, Vol. 37, Issue 1 https://doi.org/10.1016/0016-7037(73)90253-6	journal	January 1973
The solubility of (Ba,Sr)SO4 precipitates: Thermodynamic equilibrium and reaction path analysis Felmy, Andrew R.; Rai, Dhanpat; Moore, Dean A. Geochimica et Cosmochimica Acta, Vol. 57, Issue 18 https://doi.org/10.1016/0016-7037(93)90487-H	journal	September 1993
Epitaxial strain and epitaxial bending Marcus, P. M. Surface Science, Vol. 366, Issue 1 https://doi.org/10.1016/0039-6028(96)00596-1	journal	October 1996
The physical origin of the two-dimensional towards three-dimensional coherent epitaxial Stranski-Krastanov transition Müller, P.; Kern, R. Applied Surface Science, Vol. 102 https://doi.org/10.1016/0169-4332(96)00009-8	journal	August 1996
Failure modes of valve-regulated lead/acid batteries Nakamura, K.; Shiomi, M.; Takahashi, K. Journal of Power Sources, Vol. 59, Issue 1-2 https://doi.org/10.1016/0378-7753(95)02317-8	journal	March 1996
Phosphoric acid as an electrolyte additive for lead/acid batteries in electric-vehicle applications Meissner, E. Journal of Power Sources, Vol. 67, Issue 1-2 https://doi.org/10.1016/S0378-7753(97)02506-8	journal	July 1997
Selection of pre-blended expanders for optimum lead/acid battery performance Boden, D. P. Journal of Power Sources, Vol. 73, Issue 1 https://doi.org/10.1016/S0378-7753(98)00026-3	journal	May 1998
Barite scale formation and dissolution at high ionic strength studied with atomic force microscopy Risthaus, Peter; Bosbach, Dirk; Becker, Udo Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 191, Issue 3 https://doi.org/10.1016/S0927-7757(00)00843-8	journal	November 2001
Thermodynamics of the solid solution - Aqueous solution system (Ba,Sr,Ra)SO4 + H2O: II. Radium retention in barite-type minerals at elevated temperatures Vinograd, V. L.; Kulik, D. A.; Brandt, F. Applied Geochemistry, Vol. 93 https://doi.org/10.1016/j.apgeochem.2017.10.019	journal	June 2018
Thermodynamics of the solid solution - Aqueous solution system (Ba,Sr,Ra)SO4 + H2O: I. The effect of strontium content on radium uptake by barite Vinograd, V. L.; Kulik, D. A.; Brandt, F. Applied Geochemistry, Vol. 89 https://doi.org/10.1016/j.apgeochem.2017.11.009	journal	February 2018
Synthesis of Nafion-reduced graphene oxide/polyaniline as novel positive electrode additives for high performance lead-acid batteries Zhang, Yong; Zhou, Cheng-Gang; Yan, Xin-hua Electrochimica Acta, Vol. 466 https://doi.org/10.1016/j.electacta.2023.143045	journal	October 2023
Lead batteries for utility energy storage: A review May, Geoffrey J.; Davidson, Alistair; Monahov, Boris Journal of Energy Storage, Vol. 15 https://doi.org/10.1016/j.est.2017.11.008	journal	February 2018
Improving particle size of BaSO4 with a unique glycerol base method and its impact on the negative active material of the lead-acid battery Hosseini, Shadi; Farhadi, Khalil; Banisaeid, Sepideh Journal of Energy Storage, Vol. 21 https://doi.org/10.1016/j.est.2018.11.003	journal	February 2019
Discrete carbon nanotubes promote resistance to corrosion in lead-acid batteries by altering the grid-active material interface Meyers, Jeremy P.; de Guzman, Rhet Caballes; Swogger, Steven W. Journal of Energy Storage, Vol. 32 https://doi.org/10.1016/j.est.2020.101983	journal	December 2020
Construction of conductive oxide layer on the surface of lead alloy grid for the long life of lead acid batteries Yang, Yi; He, Yapeng; Huang, Hui Journal of Energy Storage, Vol. 52 https://doi.org/10.1016/j.est.2022.104877	journal	August 2022
The saturation state of the world’s ocean with respect to (Ba,Sr)SO4 solid solutions Monnin, Christophe; Cividini, Damien Geochimica et Cosmochimica Acta, Vol. 70, Issue 13 https://doi.org/10.1016/j.gca.2006.04.002	journal	July 2006
Thermodynamic properties of the (Ba,Pb)SO4 solid solution under ambient conditions: Implications for the behavior of Pb and Ra in the environment Fernández-González, Angeles; Carneiro, Joana; Katsikopoulos, Dionisis Geochimica et Cosmochimica Acta, Vol. 105 https://doi.org/10.1016/j.gca.2012.11.042	journal	March 2013
Crystallization of zoned (Ba,Pb)SO4 single crystals from aqueous solutions in silica gel Fernández González, A.; Pedreira, V. B.; Prieto, M. Journal of Crystal Growth, Vol. 310, Issue 21 https://doi.org/10.1016/j.jcrysgro.2008.07.078	journal	October 2008
Anglesite (PbSO4) epitactic overgrowths and substrate-induced twinning on anhydrite (CaSO4) cleavage surfaces Morales, Juan; Astilleros, José Manuel; Fernández-Díaz, Lurdes Journal of Crystal Growth, Vol. 380 https://doi.org/10.1016/j.jcrysgro.2013.06.010	journal	October 2013
High rate partial-state-of-charge operation of VRLA batteries Moseley, Patrick T. Journal of Power Sources, Vol. 127, Issue 1-2 https://doi.org/10.1016/j.jpowsour.2003.09.005	journal	March 2004
Aging mechanisms and service life of lead–acid batteries Ruetschi, Paul Journal of Power Sources, Vol. 127, Issue 1-2 https://doi.org/10.1016/j.jpowsour.2003.09.052	journal	March 2004
Sulfation in lead–acid batteries Catherino, Henry A.; Feres, Fred F.; Trinidad, Francisco Journal of Power Sources, Vol. 129, Issue 1 https://doi.org/10.1016/j.jpowsour.2003.11.003	journal	April 2004
Effect of barium sulfate and strontium sulfate on charging and discharging of the negative electrode in a lead–acid battery Vermesan, H.; Hirai, N.; Shiota, M. Journal of Power Sources, Vol. 133, Issue 1 https://doi.org/10.1016/j.jpowsour.2003.11.071	journal	May 2004
Development of additives in negative active-material to suppress sulfation during high-rate partial-state-of-charge operation of lead–acid batteries Sawai, Ken; Funato, Takayuki; Watanabe, Masashi Journal of Power Sources, Vol. 158, Issue 2 https://doi.org/10.1016/j.jpowsour.2006.01.096	journal	August 2006
Influence of expander components on the processes at the negative plates of lead-acid cells on high-rate partial-state-of-charge cycling. Part I: Effect of lignosulfonates and BaSO4 on the processes of charge and discharge of negative plates Pavlov, D.; Nikolov, P.; Rogachev, T. Journal of Power Sources, Vol. 195, Issue 14 https://doi.org/10.1016/j.jpowsour.2009.11.060	journal	July 2010
Enhancing the performance of lead–acid batteries with carbon – In pursuit of an understanding Moseley, Patrick T.; Rand, David A. J.; Peters, Ken Journal of Power Sources, Vol. 295 https://doi.org/10.1016/j.jpowsour.2015.07.009	journal	November 2015
Sedimentation study on modified lead dioxide particles – For screening of potentially effective additives for lead-acid batteries Szabó, Zs; Broda, B.; Marosfői, B. Journal of Power Sources, Vol. 513 https://doi.org/10.1016/j.jpowsour.2021.230547	journal	November 2021
Advances and challenges in improvement of the electrochemical performance for lead-acid batteries: A comprehensive review Zhang, Yong; Zhou, Cheng-gang; Yang, Jing Journal of Power Sources, Vol. 520 https://doi.org/10.1016/j.jpowsour.2021.230800	journal	February 2022
High-pressure Raman study on the series Chen, Yen-Hua; Huang, Eugene; Yu, Shu-Cheng Solid State Communications, Vol. 149, Issue 45-46 https://doi.org/10.1016/j.ssc.2009.08.023	journal	December 2009
Nanoscale observations of the epitaxial growth of hashemite on barite (001) Shtukenberg, Alexander G.; Astilleros, José M.; Putnis, Andrew Surface Science, Vol. 590, Issue 2-3 https://doi.org/10.1016/j.susc.2005.06.013	journal	October 2005
Nanoscale anglesite growth on the celestite (001) face Pina, Carlos M.; Rico-García, Aida Surface Science, Vol. 603, Issue 17 https://doi.org/10.1016/j.susc.2009.07.007	journal	September 2009
Stranski–Krastanov mechanism of growth and the effect of misfit sign on quantum dots nucleation Prieto, J. E.; Markov, I. Surface Science, Vol. 664 https://doi.org/10.1016/j.susc.2017.05.018	journal	October 2017
Synergistic Enhancement of Lead and Selenate Uptake at the Barite (001)–Water Interface Yang, Peng; Rampal, Nikhil; Weber, Juliane Environmental Science & Technology, Vol. 56, Issue 23 https://doi.org/10.1021/acs.est.2c04413	journal	November 2022
Simultaneous Adsorption and Incorporation of Sr ²⁺ at the Barite (001)–Water Interface Bracco, Jacquelyn N.; Lee, Sang Soo; Stubbs, Joanne E. The Journal of Physical Chemistry C, Vol. 123, Issue 2 https://doi.org/10.1021/acs.jpcc.8b08848	journal	December 2018
Acidic Polysaccharides as Green Alternatives for Barite Scale Dissolution Sosa, Ricardo D.; Geng, Xi; Agarwal, Ankur ACS Applied Materials & Interfaces, Vol. 12, Issue 49 https://doi.org/10.1021/acsami.0c16653	journal	November 2020
Understanding and Controlling the Nucleation and Growth of Zn Electrodeposits for Aqueous Zinc-Ion Batteries Liu, Huitian; Zhang, Yamin; Wang, Chao ACS Applied Materials & Interfaces, Vol. 13, Issue 28 https://doi.org/10.1021/acsami.1c06131	journal	July 2021
Uptake of Pb and the Formation of Mixed (Ba,Pb)SO₄ Monolayers on Barite During Cyclic Exposure to Lead-Containing Sulfuric Acid Legg, Benjamin A.; Lee, Sang Soo; Garcia, Juan C. ACS Applied Materials & Interfaces, Vol. 15, Issue 8 https://doi.org/10.1021/acsami.2c18399	journal	February 2023
Growth Kinetics and Morphology of Barite Crystals Derived from Face-Specific Growth Rates Godinho, Jose R. A.; Stack, Andrew G. Crystal Growth & Design, Vol. 15, Issue 5 https://doi.org/10.1021/cg501507p	journal	March 2015
Nucleation Catalysis. Turnbull, David; Vonnegut, Bernard Industrial & Engineering Chemistry, Vol. 44, Issue 6 https://doi.org/10.1021/ie50510a031	journal	June 1952
Computing Lippmann Diagrams from Direct Calculation of Mixing Properties of Solid Solutions: Application to the Barite-Celestite System Prieto, M.; Fernández-González, A.; Becker, U. Aquatic Geochemistry, Vol. 6, Issue 2, p. 133-146 https://doi.org/10.1023/A:1009642619137	journal	June 2000
Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth Yan, Kai; Lu, Zhenda; Lee, Hyun-Wook Nature Energy, Vol. 1, Issue 3, Article No. 16010 https://doi.org/10.1038/nenergy.2016.10	journal	February 2016
The effect of barium sulfate-doped lead oxide as a positive active material on the performance of lead acid batteries Yuan, Xiqing; Hu, Jingping; Xu, Jingyi RSC Advances, Vol. 6, Issue 32 https://doi.org/10.1039/C6RA01873D	journal	January 2016
Combining theories and experiments to understand the sodium nucleation behavior towards safe sodium metal batteries Wang, Huan; Matios, Edward; Luo, Jianmin Chemical Society Reviews, Vol. 49, Issue 12 https://doi.org/10.1039/D0CS00033G	journal	January 2020
Heterogeneous Nucleation of Alkali Halide Crystals from Solution Upreti, M. C.; Walton, A. G. The Journal of Chemical Physics, Vol. 44, Issue 5 https://doi.org/10.1063/1.1726964	journal	March 1966
Temperature Dependence of Mineral Solubility in Water. Part 3. Alkaline and Alkaline Earth Sulfates Krumgalz, B. S. Journal of Physical and Chemical Reference Data, Vol. 47, Issue 2 https://doi.org/10.1063/1.5031951	journal	May 2018
The solubility of some sparingly soluble lead salts: An evaluation of the solubility in water and aqueous electrolyte solution Clever, H. Lawrence; Johnston, Francis J. Journal of Physical and Chemical Reference Data, Vol. 9, Issue 3 https://doi.org/10.1063/1.555628	journal	July 1980
Organic–mineral interfacial chemistry drives heterogeneous nucleation of Sr-rich (Ba _x , Sr _{1− x} )SO ₄ from undersaturated solution Deng, Ning; Stack, Andrew G.; Weber, Juliane Proceedings of the National Academy of Sciences, Vol. 116, Issue 27 https://doi.org/10.1073/pnas.1821065116	journal	May 2019
Nucleation and growth of thin films Venables, J. A.; Spiller, G. D. T.; Hanbucken, M. Reports on Progress in Physics, Vol. 47, Issue 4 https://doi.org/10.1088/0034-4885/47/4/002	journal	April 1984
Vegard’s law Denton, A. R.; Ashcroft, N. W. Physical Review A, Vol. 43, Issue 6 https://doi.org/10.1103/PhysRevA.43.3161	journal	March 1991
Coherent Stranski-Krastanov growth in 1+1 dimensions with anharmonic interactions: An equilibrium study Korutcheva, Elka; Turiel, Antonio M.; Markov, Ivan Physical Review B, Vol. 61, Issue 24 https://doi.org/10.1103/PhysRevB.61.16890	journal	June 2000
High-pressure transition to the post-barite phase in BaCrO 4 hashemite Santamaría-Pérez, D.; Kumar, Ravhi S.; Dos santos-García, A. J. Physical Review B, Vol. 86, Issue 9 https://doi.org/10.1103/PhysRevB.86.094116	journal	September 2012
Equilibrium Shapes and Properties of Epitaxially Strained Islands Spencer, B. J.; Tersoff, J. Physical Review Letters, Vol. 79, Issue 24 https://doi.org/10.1103/PhysRevLett.79.4858	journal	December 1997
Past, present, and future of lead–acid batteries Lopes, Pietro P.; Stamenkovic, Vojislav R. Science, Vol. 369, Issue 6506 https://doi.org/10.1126/science.abd3352	journal	August 2020
Lead–Carbon Electrode with Inhibitor of Sulfation for Lead-Acid Batteries Operating in the HRPSoC Duty Pavlov, D.; Nikolov, P. Journal of The Electrochemical Society, Vol. 159, Issue 8 https://doi.org/10.1149/2.035208jes	journal	January 2012
Intermobility of barium, strontium, and lead in chloride and sulfate leach solutions Rollog, Mark; Cook, Nigel J.; Guagliardo, Paul Geochemical Transactions, Vol. 20, Issue 1 https://doi.org/10.1186/s12932-019-0064-0	journal	September 2019
Solid-solution aqueous-solution equilibria; thermodynamic theory and representation Glynn, P. D.; Reardon, E. J. American Journal of Science, Vol. 290, Issue 2 https://doi.org/10.2475/ajs.290.2.164	journal	February 1990
Gwyddion: an open-source software for SPM data analysis Nečas, David; Klapetek, Petr Open Physics, Vol. 10, Issue 1 https://doi.org/10.2478/s11534-011-0096-2	journal	January 2012

Similar Records

Uptake of Pb and the Formation of Mixed (Ba,Pb)SO₄ Monolayers on Barite During Cyclic Exposure to Lead-Containing Sulfuric Acid

Journal Article · Wed Feb 15 19:00:00 EST 2023 · ACS Applied Materials and Interfaces · OSTI ID:1964117

Structural trends for celestite (SrSO[subscript 4]), anglesite (PbSO[subscript 4]), and barite (BaSO[subscript 4]): Confirmation of expected variations within the SO[subscript 4] groups

Journal Article · Thu May 10 00:00:00 EDT 2012 · Am. Mineral. · OSTI ID:1038604

Strontium‐Enriched Barite for Enhanced PbSO 4 Nucleation in Lead‐Acid Batteries

Citation Formats

References (60)

Similar Records

Related Subjects

Strontium‐Enriched Barite for Enhanced PbSO ₄ Nucleation in Lead‐Acid Batteries