Decoupling ion/electron transport through laser-engineered vertical microchannels for high-loading solid-state lithium metal batteries

Abstract

Realizing the full potential of solid-state lithium metal batteries requires high-loading cathodes; however, their practical implementation is fundamentally hindered by sluggish mass transport and severe polarization arising from highly tortuous ion-diffusion pathways. Herein, we report a scalable three-dimensional (3D) composite architecture that decouples ion and electron transport through laser-engineered vertical microchannels. By uniformly infiltrating a solid polymer electrolyte into these directional channels within a thick LiNi_0.8Co_0.1Mn_0.1O₂ cathode, the tortuous diffusion bottlenecks inherent to conventional electrodes are effectively alleviated. Spatiotemporal multiphysics simulations, together with operando impedance analysis, reveal that this 3D architecture markedly reduces mass-transfer resistance and mitigates localized concentration polarization. As a result, the integrated cathode delivers highly reversible redox chemistry, enabling stable cycling over a high-voltage window of up to 4.5 V and excellent rate capability up to 5.0 C. To further demonstrate its practical relevance, a prototype single-layer solid-state pouch cell based on this architecture achieves a stable capacity of 95 mAh with high Coulombic efficiency. This laser-patterning strategy offers a broadly applicable route to overcoming fundamental mass-transport limitations in thick solid-state cathodes, thereby accelerating the development of high-energy-density solid-state batteries.

Keywords

Solid-state lithium metal batteries / high-loading cathodes / mass transfer / high-voltage / laser-machining strategy

References

[1] Zhao Y,Gao Y,Huang Q.Stable Li metal anode by a polyvinyl alcohol protection layer via modifying solid-electrolyte interphase layer.Nano Energy2019;64:103893

[2] Li Z,Fu J.Nonflammable quasi-solid electrolyte for energy-dense and long-cycling lithium metal batteries with high-voltage Ni-rich layered cathodes.Energy Storage Mater2022;47:542-50

[3] Pan K,Qian W.A flexible ceramic/polymer hybrid solid electrolyte for solid-state lithium metal batteries.Adv Mater2020;32:2000399

[4] Yang J,Sun Z.Prolonging the cycling lifetime of lithium metal batteries with a monolithic and inorganic-rich solid electrolyte interphase.Energy Environ Sci2023;16:3837-46

[5] Jabbari V,Rasul MG,Mashayek F.In situ formation of stable solid electrolyte interphase with high ionic conductivity for long lifespan all-solid-state lithium metal batteries.Energy Storage Mater2023;57:1-13

[6] Liu L,Liu M.An ultrathin solid electrolyte for high-energy lithium metal batteries.Adv Funct Mater2024;34:2403154

[7] Huang H,Liu Z.Functional inorganic additives in composite solid-state electrolytes for flexible lithium metal batteries.Adv Powder Mater2024;3:100141

[8] Liang W,Dai L.Strong dipole moments and increased charge transfer in polymer-based solid electrolyte enable wide-temperature solid-state lithium metal batteries.Angew Chem Int Ed2025;64:e202513604

[9] Chen Z,Liu Q.Janus quasi-solid electrolyte membranes with asymmetric porous structure for high-performance lithium-metal batteries.Nano Micro Lett2024;16:114 PMCID:PMC10866846

[10] Kang Z,Zheng S.Exploring the failure mechanisms of quasi/all solid-state Li-ion batteries with Si-based electrodes.Energy Mater2026;6:600024

[11] Wu H,Wang C,Xu W.Recent progress in understanding solid electrolyte interphase on lithium metal anodes.Adv Energy Mater2020;11:2003092

[12] Su Y,Gao A.Rational design of a topological polymeric solid electrolyte for high-performance all-solid-state alkali metal batteries.Nat Commun2022;13:4181 PMCID:PMC9296621

[13] Wu F,Zhao Z.Double-network composite solid electrolyte with stable interface for dendrite-free Li metal anode.Energy Storage Mater2021;38:447-53

[14] Ye G,He M.All-solid-state lithium metal batteries with microdomain-regulated polycationic solid electrolytes.Adv Mater2025;37:2417829

[15] Liu Y,Yue X.A transformative molecular muscle solid electrolyte.J Am Chem Soc2025;148:1570-80

[16] Zhang Z.From liquid to solid-state lithium metal batteries: fundamental issues and recent developments.Nano Micro Lett2023;16:24 PMCID:PMC10661211

[17] Guo C,Tao R.Inorganic filler enhanced formation of stable inorganic-rich solid electrolyte interphase for high performance lithium metal batteries.Adv Funct Mater2023;33:2301111

[18] Jagger B.Solid electrolyte interphases in lithium metal batteries.Joule2023;7:2228-44

[19] Nie L,Wu X.A large-scale fabrication of flexible, ultrathin, and robust solid electrolyte for solid-state lithium-sulfur batteries.Adv Mater2024;36:2400115

[20] Sun Y,Xu S,Guo S.Molecular engineering toward robust solid electrolyte interphase for lithium metal batteries.Adv Mater2023;36:2311687

[21] Chen M,Ding Z.Upgrading electrode/electrolyte interphases via polyamide-based quasi-solid electrolyte for long-life nickel-rich lithium metal batteries.ACS Energy Lett2021:1280-9

[22] Shan T,Xiao D.Molecularly woven artificial solid electrolyte interphase.Angew Chem Int Ed2025;137:e202505056

[23] Wang Y,Li Z,Li Y.In-situ generation of fluorinated polycarbonate copolymer solid electrolytes for high-voltage Li-metal batteries.Energy Storage Mater2022;45:474-83

[24] Liu S,Piao N.An inorganic-rich solid electrolyte interphase for advanced lithium-metal batteries in carbonate electrolytes.Angew Chem Int Ed2020;60:3661-71

[25] Luo P,Song J.Understanding and mitigating acidic species in all-fluorinated electrolytes for a stable 572 Wh/kg lithium metal battery (LMB).Energy Storage Mater2025;78:104234

[26] Yu W,Liu Z.Physical-chemical dual networks enabled mechanically robust solid electrolytes for stress-strain regulation.Energy Storage Mater2026;85:104882

[27] Yang N,Su H.A chemically bonded ultraconformal layer between the elastic solid electrolyte and lithium anode for high-performance lithium metal batteries.Angew Chem Int Ed2023;62:e202304339

[28] Yang L,Feng Y.Breaking voltage limitations: triethyl phosphate-engineered PVDF-based electrolytes with dual-interphase stabilization for 4.7 V-class quasi-solid-state lithium metal batteries.J Am Chem Soc2025;147:25940-9

[29] Zhang S,Wang D.A stretchable and safe polymer electrolyte with a protecting-layer strategy for solid-state lithium metal batteries.Adv Sci2021;8:2003241 PMCID:PMC8336491

[30] Boaretto N,Cobos M.Quasi-solid polymer electrolytes with binary and ternary salt mixtures for high-voltage lithium metal batteries.Energy Mater2025;5:500040

[31] Xu D,Jin J.In situ generated fireproof gel polymer electrolyte with Li_6.4Ga_0.2La₃Zr₂O₁₂ as initiator and ion-conductive filler.Adv Energy Mater2019;9:1900611

[32] Yang Y,Wan J.An interdigitated Li-solid polymer electrolyte framework for interfacial stable all-solid-state batteries.Adv Energy Mater2022;12:2201160

[33] Ni S,Li C.A 3D framework with Li₃N-Li₂S solid electrolyte interphase and fast ion transfer channels for a stabilized lithium-metal anode.Adv Mater2022;35:2209028

[34] Lu P,Wu D.Rate-limiting mechanism of all-solid-state battery unravelled by low-temperature test-analysis flow.Energy Storage Mater2024;67:103316

[35] Shin SS,Choi S.Quantitative determination of lithium depletion during rapid cycling in sulfide-based all-solid-state batteries.Chem Commun2021;57:3453-6