Advanced Applications of Atomic Force Microscopy in Energy Electrochemistry: from Electrocatalysis to Batteries

Abstract

Atomic force microscopy (AFM) has become an essential tool for probing electrode surfaces, nanoscale reactions, and material properties in electrochemical research. By exploiting tip–sample interactions, AFM enables ultrahigh-resolution imaging of surface topography and enables the in situ monitoring of structural and morphological evolution during electrochemical processes. This review strategically explores two pivotal domains—energy-related electrocatalysis and batteries—to elucidate the microscopic mechanisms behind phenomena, such as lithium deposition/stripping, solid–electrolyte interphase formation, and key reactions, including carbon dioxide electroreduction and hydrogen evolution reduction. Within these contexts, AFM-based force spectroscopy (e.g., force–displacement curves) provides insights into the mechanical properties of electrodes and interfacial layers, offering critical data for material design and optimization. Furthermore, electrical modes, including Kelvin probe force microscopy and conductive AFM, enable the nanoscale characterization of local conductivity and surface potential. Complementing these, piezoresponse force microscopy probes electromechanical coupling and ferroelectric domain dynamics, revealing how local polarization and strain govern ion transport and catalytic activity. Together, these techniques advance electrochemical studies from macroscopic averaging toward in situ, spatially resolved, and heterogeneous mechanistic analysis. The fundamental insights gained from this review deepen our understanding of electrochemical processes and offer a promising avenue for advancing related fields, such as supercapacitors, fuel cells, and photoelectrochemical systems. This review systematically examines various AFM operating modes to highlight recent advances in the nanoscale characterization of electrode materials for diverse energy-related electrocatalysis and battery systems. Furthermore, it critically discusses current limitations, emerging challenges, and future perspectives.

Keywords

Atomic force microscopy / Electrocatalysis / Battery

References

[1] Wang YQ, Fu J, Feng Y, et al.. Alkali metal cations induce structural evolution on Au(111) during cathodic polarization. J Am Chem Soc, 2024, 146(40): 27713-27724.

[2] Binnig G, Quate CF, Gerber C. Atomic force microscope. Phys Rev Lett, 1986, 56(9): 930-933.

[3] Toca-Herrera JL. Atomic force microscopy meets biophysics, bioengineering, chemistry, and materials science. Chemsuschem, 2019, 12(3): 603-611.

[4] Chen JB, Xu K. Applications of atomic force microscopy in materials, semiconductors, polymers, and medicine: a mini-review. Instrum Sci Technol, 2020, 48(15): 667-681.

[5] Chinese Society of Electrochemistry. The top ten scientific questions in electrochemistry. J Electrochem, 2024, 30(1): 2024121

[6] Ye C, Tu SB, Zhang SJ, et al.. Harnessing interfacial solvation structure for next-generation secondary batteries. Nat Energy, 2025, 11(2): 167-175.

[7] Grosse P, Gao D, Scholten F, et al.. Dynamic changes in the structure, chemical state and catalytic selectivity of Cu nanocubes during CO₂ electroreduction: size and support effects. Angew Chem Int Ed Engl, 2018, 57(21): 6192-6197.

[8] Yao YX, Wan J, Liang NY, et al.. Nucleation and growth mode of solid electrolyte interphase in Li-ion batteries. J Am Chem Soc, 2023, 145(14): 8001-8006.

[9] Chen M, Gong L, Zhitomirsky I, et al.. Unraveling the dynamic transformation of azobenzene-driven redox electrolytes for Zn-ion hybrid capacitors. Energy Environ Sci, 2025, 18(9): 4460-4469.

[10] Ma Q, Young J, Basuray S, et al.. Elucidating facet dependent electronic and electrochemical properties of Cu₂O nanocrystals using AFM/SCEM and DFT. NanoToday, 2022, 45. ArticleID: 101538

[11] Tang HC, Ding JT, Feng ZM, et al.. Ultrastable Ni-Fe-P-based heterostructures for seawater electrolysis. Adv Funct Mater, 2025, 36(27. ArticleID: e28467

[12] Shen C, Huang YB, Yang JR, et al.. Unraveling the mechanism of ion and electron migration in composite solid-state electrolyte using conductive atomic force microscopy. Energy Stor Mater, 2021, 39: 271-277

[13] Wang YN, Liu Y, Zhang XQ, et al.. In situ polymerized polysiloxane enables cohesive solid-electrolyte interphase for practical lithium-metal batteries. Adv Mater, 2025, 38. ArticleID: e19565

[14] Tao J, Chen Y, Bhardwaj A, Wen L, Li J, Kolosov OV, Lin Y, Hong Z, Huang Z, Mathur S. Combating Li metal deposits in all-solid-state battery via the piezoelectric and ferroelectric effects. Proc National Academy Sci, 2022, 119(41. ArticleID: e2211059119

[15] Shin H, Park J, Han S, et al.. Component-/structure-dependent elasticity of solid electrolyte interphase layer in Li-ion batteries: experimental and computational studies. J Power Sources, 2015, 277: 169-179.

[16] Melitz W, Shen J, Kummel AC, et al.. Kelvin probe force microscopy and its application. Surf Sci Rep, 2011, 66(1): 1-27.

[17] Peter F. Piezoresponse force microscopy and surface effects of perovskite ferroelectric nanostructures, 2006. Jülich, Forschungszentrum Jülich GmbH: 1-107

[18] Kontomaris SV, Malamou A, Stylianou A. The Hertzian theory in AFM nanoindentation experiments regarding biological samples: overcoming limitations in data processing. Micron, 2022, 155. ArticleID: 103228

[19] Derjaguin BV, Muller VM, Toporov YP. Effect of contact deformations on the adhesion of particles. J Colloid Interface Sci, 1975, 53(2): 314-326.

[20] Zahmatkeshsaredorahi A, Millan-Solsona R, Jakob DS, et al.. Kelvin probe force microscopy under ambient conditions. Nat Rev Methods Primers, 2025, 5(1): 53.

[21] Giannazzo F, Schilirò E, Greco G, et al.. Conductive atomic force microscopy of semiconducting transition metal dichalcogenides and heterostructures. Nanomaterials, 2020, 10(4): 803.

[22] Wang Q, Wei HH, Liu P, et al.. Recent advances in copper-based catalysts for electrocatalytic CO₂ reduction toward multi-carbon products. Nano Res Energy, 2024, 3(3. ArticleID: e9120112

[23] Nitopi S, Bertheussen E, Scott SB, et al.. Progress and perspectives of electrochemical CO₂ reduction on copper in aqueous electrolyte. Chem Rev, 2019, 119(12): 7610-7672.

[24] Chi LP, Niu ZZ, Zhang YC, Zhang XL, Liao J, Wu ZZ, Yu PC, Fan MH, Tang KB, Gao MR. Efficient and stable acidic CO₂ electrolysis to formic acid by a reservoir structure design. Proc National Academy Sci, 2023, 120(51. ArticleID: e2312876120

[25] Wang ZX, Kuchkaev A, Yakhvarov D, et al.. Monodispersed Cu-TCPP/Cu₂O hybrid microspheres: a superior cascade electrocatalyst toward CO₂ reduction to C₂ products. J Electrochem, 2023, 30(1–12): 2303271

[26] Wu ZZ, Yang PP, Gao MR. Dynamic evolution of copper-based catalysts during CO₂ electroreduction. Nano Mater Sci, 2024, 6: 100167

[27] Liu SK, Li YH, Wang D, et al.. Alkali cation-induced cathodic corrosion in Cu electrocatalysts. Nat Commun, 2024, 15(1): 5080.

[28] Han ZS, Han DL, Chen Z, et al.. Steering surface reconstruction of copper with electrolyte additives for CO₂ electroreduction. Nat Commun, 2022, 13(1. ArticleID: 3158

[29] Gao JC, Han ZS, Wang XY, et al.. Self-limited reconstruction realized via copper-ligand interaction for stabilizing high-selective CO₂ electromethanation. ACS Catal, 2023, 13(23): 15457-15466.

[30] Yue YY, Wu ZT, Ye ZL, et al.. Identifying Cu reconstruction mechanism in CO₂ and CO electroreduction via Cu⁺ detection and in situ atomic force microscopy. Sci China Mater, 2025, 68(7): 2381-2387.

[31] Wei J, Zhang Z, Gee W, et al.. Role of surface hydroxyls in atomic-scale copper restructuring during CO electroreduction. J Am Chem Soc, 2025, 147(49): 45178-45188.

[32] Simon GH, Kley CS, Roldan Cuenya BR. Potential-dependent morphology of copper catalysts during CO₂ electroreduction revealed by in situ atomic force microscopy. Angew Chem Int Ed Engl, 2021, 60(5): 2561-2568.

[33] Zhao Y, Gao S, Chen XY, et al.. In situ identification of dynamic active sites in the electrocatalytic nitrate reduction reaction. J Am Chem Soc, 2025, 147(35): 31722-31730.

[34] Gao XR, Xing Z, Wang MY, et al.. Comprehensive insights into solid-state electrolytes and electrode-electrolyte interfaces in all-solid-state sodium-ion batteries. Energy Stor Mater, 2023, 60: 102821

[35] Deng YC, You ZC, Lin GZ, et al.. Strategies for obtaining high-performance Li-ion solid-state electrolytes for solid-state batteries. J Electrochem, 2025, 31(10. ArticleID: 2516002

[36] Shen CL, Yan MY, Liao XB, et al.. Nanotrench superfilling facilitates embedded lithium anode for high-areal-capacity solid-state batteries. ACS Nano, 2024, 18(6): 5068-5078.

[37] Du A, Zhang J, Xu P, et al.. Regulating lithium metal nucleation and growth for dendrite suppression: from liquid-electrolyte to solid-state batteries. J Electrochem, 2025, 31(11. ArticleID: 2516001

[38] Shen ZZ, Zhang XS, Liu RZ, et al.. Tracing lithophilic sites: in situ nanovisualization of their migration and degradation in all-solid-state lithium batteries. J Am Chem Soc, 2026, 148(1): 1790-1800.

[39] Zhang XS, Wan J, Shen ZZ, et al.. In situ analysis of interfacial morphological and chemical evolution in all-solid-state lithium-metal batteries. Angew Chem Int Ed Engl, 2024, 63(38. ArticleID: e202409435

[40] Guo JL, Li NN, Zheng P. SnO₂ particles embedded into carbon coated mesoporous SiO_x rod as high volumetric capacity anode for lithium-ion batteries. J Electrochem, 2025, 31(2. ArticleID: 2410171

[41] Liu L, Xiang YX, Wang JH. From cell to atomic level: understanding the degradation in 99% coulombic efficiency and 450 Wh/kg anode-free pouch cells. J Am Chem Soc, 2025, 147(45): 41342-41354.

[42] Zhai Y, Zhong ZT, Kuang NN, et al.. Both resilience and adhesivity define solid electrolyte interphases for a high performance anode. J Am Chem Soc, 2024, 146(22): 15209-15218.

[43] Liu X, Zhu Q, Jiang A, Yue J, Yu D, Wang S, Dong S, Zhao J, Wang W, Lyu S, Wang J. Realizing a wide-temperature aluminum-foil-anode-based lithium-ion battery. Adv Funct Mater, 2026, 36(15. ArticleID: e21637

[44] Zhang G, Zhang T, Zhang Z, et al.. High-energy and fast-charging lithium metal batteries enabled by tuning Li⁺-solvation via electron-withdrawing and lithiophobicity functionality. Nat Commun, 2025, 16(1): 4722.

[45] Fang MM, Dong XB, Qi A, et al.. A tertiary amine-based electrolyte with methylation-mediated steric and electronic synergy for high-performance lithium metal batteries. Angew Chem Int Ed Engl, 2025, 64(43. ArticleID: e202511222

[46] Liu YR, Zhang M, Yu YH, et al.. Local electric fields coupled with Cl⁻ fixation strategy for improving seawater oxygen reduction reaction performance. J Electrochem, 2025, 31(9): 2504132.

[47] Xu Y, Li SD, Cao JW, et al.. Constructing a built-in electric field across an NiMo/NiMoP heterointerface for efficient and durable seawater electrolysis in anion exchange membrane electrolyzers. Energy Environ Sci, 2025, 18(10): 4811-4820.

[48] Wang WB, Bai F, Chu KB, et al.. Proton flux engineering via built-in electric fields in N-doped CuO@Co₃O₄@Ni(OH)₂ heterostructure for rechargeable Zn-NO₃⁻ /5-hydroxymethylfurfural multielectron transfer systems. Angew Chem Int Ed Engl, 2025, 64(44. ArticleID: e202514438

[49] Liu JQ, Sun XR, Lin K, et al.. Optimizing schottky rectifying effect in PtCu/WO_x heterojunctions to accelerate oxygen reduction kinetics. Nano Res, 2025, 19(3): 94908088.

[50] Ji K, Wang SY, Yao SY, et al.. Built-in electric field in Ru/CoP bifunctional electrocatalyst enhances hydrazine-assisted water splitting. Adv Mater, 2025, 37(29): 2503182.

[51] He M, Xu JB, Wang HT, et al.. Constructing a built-in electric field via polymer modification to boost D₂O reorientation and electron transfer for deuteroacetic acid electrosynthesis. J Am Chem Soc, 2025, 147(50): 46573-46581.

[52] Dong LW, Yan HJ, Liu QX, et al.. Quantification of charge transport and mass deprivation in solid electrolyte interphase for kinetically-stable low-temperature lithium-ion batteries. Angew Chem Int Ed Engl, 2024, 63(43): e202411029

[53] Wang XL, Li Y, Liu J, et al.. A robust dual-layered solid electrolyte interphase enabled by cation specific adsorption-induced built-in electrostatic field for long-cycling solid-state lithium metal batteries. Angew Chem Int Ed Engl, 2025, 64(10. ArticleID: e202421101

[54] Wen JM, Qiu B, Guan YB, et al.. Defect-driven ionic trap construction and interface modulation for rapid Li⁺ kinetics in composite solid electrolytes. Adv Mater, 2025, 38(10. ArticleID: e19541

[55] Munz M, Poon J, Frandsen W, et al.. Nanoscale electron transfer variations at electrocatalyst–electrolyte interfaces resolved by in situ conductive atomic force microscopy. J Am Chem Soc, 2023, 145(9): 5242-5251.

[56] Zhang LX, Xu DH, Chen H, et al.. Single-crystalline LiMg alloy anode for deep cycling all solid state lithium metal batteries. Adv Funct Mater, 2025, 35(9): 2416013.

[57] Yang C, Liang ZX, Zhang MY, et al.. High-voltage solid-state lithium batteries: a review of electrolyte design, interface engineering, and future perspectives. J Electrochem, 2025, 31(10): 2515003.

[58] Zhu RJ, Li ZC, Zhang W. All-solid-state sodium-ion batteries: a leading contender in the next-generation battery race. J Electrochem, 2025, 30(12): 2415002

[59] Shaukat H, Ali A, Bibi S, et al.. Piezoelectric materials: advanced applications in electro-chemical processes. Energy Rep, 2023, 9: 4306-4324.

[60] Gao HY, Zhou YM, Wang K, et al.. An in situ polymerized solid-state electrolyte for uniform lithium deposition via the piezoelectric effects. Adv Energy Mater, 2025, 15(28): 2501379.

[61] Ni Q, Ding Y, Wang CZ, et al.. Piezoelectric interlayer enabling a rechargeable quasisolid-state sodium battery at 0 °C. Adv Mater, 2024, 36(14): 2309298.

[62] Pan Z, Brett DJL, He G, et al.. Progress and perspectives of organosulfur for lithium-sulfur batteries. Adv Energy Mater, 2022, 12(8. ArticleID: 2103483

[63] Xie KY, You Y, Yuan K, et al.. Ferroelectric-enhanced polysulfide trapping for lithium-sulfur battery improvement. Adv Mater, 2017, 29(6): 1604724.

[64] Jiang J, Ontaneda J, Pal S, et al.. Enhanced polysulfide trapping in Li-S batteries by dipole alignment in ferroelectric BaTiO₃. Energy Environ Sci, 2024, 17(17): 6291-6301.

[65] Toki GFI, Hossain MK, Rehman WU, et al.. Recent progress and challenges in silicon-based anode materials for lithium-ion batteries. Ind Chem Mater, 2024, 2(2): 226-269.

[66] Ma KH, Sun CY, He YT, et al.. Piezoelectricity-driven structural stabilization and electrochemical enhancement in silicon anodes: a novel force-electric coupling framework. J Energy Chem, 2025, 109: 65-75.

[67] Zhang ZY, Said S, Smith K, et al.. Characterizing batteries by in situ electrochemical atomic force microscopy: a critical review. Adv Energy Mater, 2021, 11(38): 2101518.

[68] Zeng ZC, Huang SC, Wu DY, et al.. Electrochemical tip-enhanced Raman spectroscopy. J Am Chem Soc, 2015, 137(37): 11928-11931.

[69] Nanda J, Yang G, Hou T, et al.. Unraveling the nanoscale heterogeneity of solid electrolyte interphase using tip-enhanced Raman spectroscopy. Joule, 2019, 3(8): 2001-2019.

[70] Dazzi A, Prater CB. AFM-IR: technology and applications in nanoscale infrared spectroscopy and chemical imaging. Chem Rev, 2017, 117(7): 5146-5173.

[71] Watkins TS, Sarbapalli D, Counihan MJ, et al.. A combined SECM and electrochemical AFM approach to probe interfacial processes affecting molecular reactivity at redox flow battery electrodes. J Mater Chem A, 2020, 8(31): 15734-15745.

[72] Nonnenmacher M, O’Boyle M, Wickramasinghe HK. Surface investigations with a Kelvin probe force microscope. Ultramicrosc, 1992, 42–44: 268-273.

[73] Brouillard M, Bercu N, Zschieschang U, et al.. Experimental determination of the lateral resolution of surface electric potential measurements by Kelvin probe force microscopy using biased electrodes separated by a nanoscale gap and application to thin-film transistors. Nanoscale Adv, 2022, 4(8): 2018-2028.

[74] Vazirisereshk MR, Sumaiya SA, Chen R, et al.. Time-dependent electrical contact resistance at the nanoscale. Tribol Lett, 2021, 69(2): 1-9.

[75] Piquemal F, Kaja K, Chrétien P, et al.. A multi-resistance wide-range calibration sample for conductive probe atomic force microscopy measurements. Beilstein J Nanotechnol, 2023, 14(1): 1141-1148.

[76] Killgore JP, Robins L, Collins L. Electrostatically-blind quantitative piezoresponse force microscopy free of distributed-force artifacts. Nanoscale Adv, 2022, 4(8): 2036-2045.

[77] Gruverman A, Alexe M, Meier D. Piezoresponse force microscopy and nanoferroic phenomena. Nat Commun, 2019, 10(1): 1-9.

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