Statistical approach to design Zn particle size, shape, and crystallinity for alkaline batteries

Abstract

In modern alkaline batteries, the zinc anode is the performance-limiting and lifetime-limiting electrode, making the choice of zinc powder critical. Due to the various material fabrication processes that are used to manufacture industrial zinc powder, there exists a wide array of possible zinc particle shapes, sizes, and crystallinities. These industrial zinc powders are typically conceived, produced, and tested through trial-and-error processes using historical “rules of thumb.” However, a data-driven approach could more effectively elucidate the optimum combination of zinc particle properties. In this paper, the effect of Zn particle size, shape, and crystallinity on the achievable capacity and corrosion current is investigated. The Zn types are tested in both powder and slurry form. Following the data collection, a factorial-based statistical analysis is performed to determine the most statistically significant variables affecting capacity and corrosion. This information is then used to down-select to a subset of particles that are tested in cylindrical cells with an AA-equivalent geometry. The reported technique can be used to develop actionable principles for battery manufacturers to create cells that are more stable, longer lasting, and have higher energy densities.

Key words： zinc; anode; battery; optimization; capacity; corrosion

Acknowledgment

This work was supported by Duracell.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11708-024-0904-1.

Competing Interests

Financial conflicts of interest may exist for MZ and MH as Duracell employees, as well as WEM through consulting activities.

References

1 Dong W , Shi J L , Wang T S . . 3D zinc on carbon fiber composite framework anode for aqueous Zn-MnO₂ batteries. RSC Advances, 2018, 8(34): 19157–19163

2 Chen X , Zhou Z , Karahan H E . . Recent advances in materials and design of electrochemically rechargeable zinc–air batteries. Small, 2018, 14(44): 1801929

3 Prentice G , Chang Y , Shan X . A model for the passivation of the zinc electrode in alkaline electrolyte. Journal of the Electrochemical Society, 1991, 138(4): 890–894

4 Parker J F , Ko J S , Rolison D R . . Translating materials-level performance into device-relevant metrics for zinc-based batteries. Joule, 2018, 2(12): 2519–2527

5 Desai D , Wei X , Steingart D A . . Electrodeposition of preferentially oriented zinc for flow-assisted alkaline batteries. Journal of Power Sources, 2014, 256: 145–152

6 Chao D , Zhu C R , Song M . . A high-rate and stable quasi-solid-state zinc-ion battery with novel 2D layered zinc orthovanadate array. Advanced Materials, 2018, 30(32): 1803181

7 Mao Z , White R E . Mathematical modeling of a primary zinc/air battery. Journal of the Electrochemical Society, 1992, 139(4): 1105–1113

8 Cachet C , Saidani B , Wiart R . The behavior of zinc electrode in alkaline electrolytes: II. A kinetic analysis of anodic dissolution. Journal of the Electrochemical Society, 1992, 139(3): 644–654

9 Faegh E , Ng B , Hayman D . . Design of highly reversible zinc anodes for aqueous batteries using preferentially oriented electrolytic zinc. Batteries & Supercaps, 2020, 3(11): 1220–1232

10 Huang S , Wu W , Su Y . . Insight into the corrosion behaviour and degradation mechanism of pure zinc in simulated body fluid. Corrosion Science, 2021, 178: 109071

11 Levy A V , Chik P . The effects of erodent composition and shape on the erosion of steel. Wear, 1983, 89(2): 151–162

12 Sun K E K , Hoang T K A , Doan T N L . . Suppression of dendrite formation and corrosion on zinc anode of secondary aqueous batteries. ACS Applied Materials & Interfaces, 2017, 9(11): 9681–9687

13 He P , Huang J . Detrimental effects of surface imperfections and unpolished edges on the cycling stability of a zinc foil anode. ACS Energy Letters, 2021, 6(5): 1990–1995

14 Ariosa D , Elhordoy F , Dalchiele E A . . Texture vs morphology in ZnO nano-rods: On the X-ray diffraction characterization of electrochemically grown samples. Journal of Applied Physics, 2011, 110(12): 124901

15 Michlik T , Rosin A , Gerdes T . . Improved discharge capacity of zinc particles by applying bismuth-doped silica coating for zinc-based batteries. Batteries, 2019, 5(1): 32

16 He P , Huang J . Chemical passivation stabilizes Zn anode. Advanced Materials, 2022, 34(18): 2109872

17 Faegh E , Omasta T , Hull M . . Understanding the synamics of primary Zn−MnO₂ alkaline battery gassing with operando visualization and pressure cells. Journal of the Electrochemical Society, 2018, 165(11): A2528–A2535

18 Faegh E , Shrestha S , Zhao X . . In-depth structural understanding of zinc oxide addition to alkaline electrolytes to protect aluminum against corrosion and gassing. Journal of Applied Electrochemistry, 2019, 49(9): 895–907

19 Faegh E , Ng B , Lenhart B . . Partial deployment of Al in Zn–MnO₂ alkaline battery anodes to improve the capacity and reversibility. Journal of Power Sources, 2021, 506: 230167

20 Huot J Y , Malservisi M . High-rate capability of zinc anodes in alkaline primary cells. Journal of Power Sources, 2001, 96(1): 133–139

21 Glaeser W , Künzel-Keune S , Merkel P . The influence of discharge time on post-partial discharge gassing of zinc powder. Journal of Power Sources, 1999, 80(1–2): 72–77

22 Zhang X G . Fibrous zinc anodes for high power batteries. Journal of Power Sources, 2006, 163(1): 591–597

23 Zhang Q , Luan J , Fu L . . The three-dimensional dendrite-free zinc anode on a copper mesh with a zinc-oriented polyacrylamide electrolyte additive. Angewandte Chemie, 2019, 131(44): 15988–15994

24 Li H , Zhang W , Elezzabi A Y . Transparent zinc-mesh electrodes for solar-charging electrochromic windows. Advanced Materials, 2020, 32(43): 2003574

25 Chamoun M , Hertzberg B J , Gupta T . . Hyper-dendritic nanoporous zinc foam anodes. NPG Asia Materials, 2015, 7(4): e178

26 Ko J S , Geltmacher A B , Hopkins B J . . Robust 3D Zn sponges enable high-power, energy-dense alkaline batteries. ACS Applied Energy Materials, 2019, 2(1): 212–216

27 Dillip G R , Nagajyothi P C , Ramaraghavulu R . . Synthesis of crystalline zinc hydroxystannate and its thermally driven amorphization and recrystallization into zinc orthostannate and their phase-dependent cytotoxicity evaluation. Materials Chemistry and Physics, 2020, 248: 122946

28 Zhou J , Xie M , Wu F . . Encapsulation of metallic Zn in a hybrid MXene/graphene aerogel as a stable Zn anode for foldable Zn-ion batteries. Advanced Materials, 2022, 34(1): 2106897

29 Yang H , Yang Z , Wen X . . The in-situ growth of zinc-aluminum layered double hydroxides on graphene and its application as anode active materials for Zn–Ni secondary battery. Electrochimica Acta, 2017, 252: 507–515

30 Ruan P . . Achieving highly proton-resistant Zn–Pb anode through low hydrogen affinity and strong bonding for long-life electrolytic Zn//MnO₂ battery. Advanced Materials, 2023, 35(31): e2300577

31 Yi R , Shi X , Tang Y . . Carboxymethyl chitosan-modified zinc anode for high-performance zinc–iodine battery with narrow operating voltage. Small Structures, 2023, 4: 2300020

32 Chen X , Shi X , Ruan P . . Construction of an artificial interfacial layer with porous structure toward stable zinc-metal anodes. Small Science, 2023, 3(6): 2300007

33 Bayazitoglu Y , Brotzen F R , Zhang Y . Metal vapor condensation in a converging nozzle. Nanostructured Materials, 1996, 7(7): 789–803

34 Yang C C , Lin S J . Improvement of high-rate capability of alkaline Zn–MnO₂ battery. Journal of Power Sources, 2002, 112(1): 174–183

35 Marinković Z V , Mančić L , Marić R . . Preparation of nanostructured Zn–Cr–O spinel powders by ultrasonic spray pyrolysis. Journal of the European Ceramic Society, 2001, 21(10–11): 2051–2055

36 Lesz S , Tański T , Hrapkowicz B . . Characterisation of Mg–Zn–Ca–Y powders manufactured by mechanical milling. Journal of Achievements in Materials and Manufacturing Engineering, 2020, 103(2): 49–59

37 Inoguchi M , Suzuki K , Kageyama K . . Monodispersed and well-crystallized zinc oxide nanoparticles fabricated by microemulsion method. Journal of the American Ceramic Society, 2008, 91(12): 3850–3855

38 Rusu M , Sofian N , Rusu D . Mechanical and thermal properties of zinc powder filled high density polyethylene composites. Polymer Testing, 2001, 20(4): 409–417

39 Beji Z , Sun M , Smiri L S . . Polyol synthesis of non-stoichiometric Mn–Zn ferrite nanocrystals: Structural/microstructural characterization and catalytic application. RSC Advances, 2015, 5(80): 65010–65022

40 WangC C. Method for making irregular shaped single crystal particles and the use thereof in anodes for electrochemical cells. US patent 4487651, 1984

41 Lenhart B , Zuraw M , Mustain W . A scaleable method for enhancing the crystallinity of Zn powder to reduce corrosion and boost achievable capacity. Journal of the Electrochemical Society, 2023, 170(7): 070501

42 Bockelmann M , Becker M , Reining L . . Passivation of zinc anodes in alkaline electrolyte: Part I. Determination of the starting point of passive film formation. Journal of the Electrochemical Society, 2018, 165(13): A3048–A3055

43 Ye L , Lai Z , Liu J . . Effect of Ag particle size on electrical conductivity of isotropically conductive adhesives. IEEE Transactions on Electronics Packaging Manufacturing, 1999, 22(4): 299–302

44 Bockelmann M , Reining L , Kunz U . . Electrochemical characterization and mathematical modeling of zinc passivation in alkaline solutions: A review. Electrochimica Acta, 2017, 237: 276–298