a.College of Physics, Donghua University, Shanghai 201620, China
b.State Key Laboratory of Advanced Fiber Materials, Donghua University, Shanghai 201620, China
c.Textile Key Laboratory for Advanced Plasma Technology and Application, China National Textile & Apparel Council, Shanghai 201620, China
d.Magnetic Confinement Fusion Research Center, Ministry of Education of the People’s Republic of China, Shanghai 201620, China
chengran.du@dhu.edu.cn (C.R.D.)
jingzh@dhu.edu.cn (J.Z.)
收稿:2025-10-17,
录用:2026-01-12,
网络首发:2026-03-10,
纸质出版:2026-04-05
Scan QR Code
Cui, J.; Shao, L.; Wang, H. Z.; Du, C. R.; Zhang, J. Investigation of durable wettability of polyethylene separators via continuous atmospheric pressure plasma treatment with Ar/O2/tetramethylcyclotetrasiloxane. Chinese J. Polym. Sci. 2026, 44, 1126–1141 DOI: 10.1007/s10118-026-3569-x.
Jie Cui, Li Shao, Hao-Zhe Wang, et al. Investigation of Durable Wettability of Polyethylene Separators
Cui, J.; Shao, L.; Wang, H. Z.; Du, C. R.; Zhang, J. Investigation of durable wettability of polyethylene separators via continuous atmospheric pressure plasma treatment with Ar/O2/tetramethylcyclotetrasiloxane. Chinese J. Polym. Sci. 2026, 44, 1126–1141 DOI: 10.1007/s10118-026-3569-x. DOI:
Jie Cui, Li Shao, Hao-Zhe Wang, et al. Investigation of Durable Wettability of Polyethylene Separators
Continuous Ar/O
2
/TMCTS atmospheric-pressure plasma treatment enables durable wettability of polyethylene separators. After 30 s treatment
the electrolyte diffusion area increases by 17.5-fold and remains over 14-fold after 90 days. En
hanced wettability leads to higher ionic conductivity and reduced charge-transfer resistance.
The rapid decay of the surface wettability of plasma-treated polymers remains a critical limita
tion for their practical application in advanced materials. This study introduces a continuous atmospheric pressure plasma (APP) technique for fabricating polyethylene (PE) separators with durable wettability
and elucidates the underlying mechanism. A systematic comparison of APP treatments with non-deposition and deposition gases
including Ar
Ar/O
2
Ar/tetramethylcyclotetrasiloxane (TMCTS)
and Ar/O
2
/TMCTS
revealed the key impact factors in achieving durable wettability. Owing to the synergistic interactions of SiO
x
C
y
H
z
nanoparticulate deposition
physical etching
and oxidative functionalization
the PE separator treated by Ar/O
2
/TMCTS exhibited a 17.5-fold electrolyte wetting area compared to the original one. The improved surface energy and roughness of the SiO
x
C
y
H
z
nanoparticle coating enhanced its electrochemical performance. The ionic conductivity increased by 1.9 times
while the charge transfer resistance decreased by 73.7%. Remarkably
owing to further oxidation of the SiO
x
C
y
H
z
nanoparticle coating and the increase in its silica-like structure
the wetting area of the Ar/O
2
/TMCTS-treated separator was still over 14-fold larger than that of the original separator after aging for 90 days. This study demonstrates an eco-friendly and scalable approach for fabricating high-performance battery separators and provides mechanistic insights into durable wettability by APP.
Lu, Z.; Sui, F.; Miao, Y. E.; Liu, G.; Li, C.; Dong, W.; Cui, J.; Liu, T.; Wu, J.; Yang, C. Polyimide separators for rechargeable batteries. J. Energy Chem. 2021 , 58 , 170−197..
Lagadec, M. F.; Zahn, R.; Wood, V. Characterization and performance evaluation of lithium-ion battery separators. Nat. Energy 2018 , 4 , 16−25..
Zhao, L.; Li, Y.; Yu, M.; Peng, Y.; Ran, F. Electrolyte-wettability issues and challenges of electrode materials in electrochemical energy storage, energy conversion, and beyond. Adv. Sci . 2023 , 10 , 2300283..
Ma, C.; Nikiforov, A.; Hegemann, D.; De Geyter, N.; Morent, R.; Ostrikov, K. Plasma-controlled surface wettability: recent advances and future applications. Int. Mater. Rev. 2022 , 68 , 82−119..
Dai, X. K.; Yu, F. S.; Wen, J. W.; Wang, C. X.; Ma, X. L.; Yang, W.; Huang, G. Y.; Ye, H. M. Robust and high-wettability pristine poly(ether ether ketone) nanofiber separator for heat-resistant and safe lithium-ion battery. Chinese J. Polym. Sci. 2023 , 41 , 1937−1946..
Likitaporn, C.; Prathumrat, P.; Senthilkumar, N.; Tanalue, N.; Wongsalam, T.; Okhawilai, M. Engineering the separators for high electrolyte uptakes in Li-ion batteries. J. Energy Storage 2024 , 101 , 113861..
Leng, X.; Yang, M.; Li, C.; Arifeen, W. U.; Ko, T. J. High-performance separator for lithium-ion battery based on dual-hybridizing of materials and processes. Chem. Eng. J . 2022 , 433 , 133773..
Salim, N. E.; Nor, N. A. M.; Jaafar, J.; Ismail, A. F.; Qtaishat, M. R.; Matsuura, T.; Othman, M. H. D.; Rahman, M. A.; Aziz, F.; Yusof, N. Effects of hydrophilic surface macromolecule modifier loading on PES/O-g-C 3 N 4 hybrid photocatalytic membrane for phenol removal. Appl. Surf. Sci. 2019 , 465 , 180−191..
Gu, J. P.; Zhang, K. Y.; Li, X. T.; Dong, J.; Zhang, Q. H.; Zhao, X. Construction of safety and non-flammable polyimide separator containing carboxyl groups for advanced fast charing lithium-ion batteries. Chinese J. Polym. Sci. 2022 , 40 , 345−354..
Sun, S.; Wang, J.; Cui, X.; Chen, X.; Wang, Y.; Liu, J.; Zhu, L.; Yan, W. Plasma-strengthened ionic conducting network enabling highly safety separator toward a ll-climate lithium metal batteries. Appl. Surf. Sci . 2024 , 644 , 158796..
Gong, J.; Shi, S.; Cheng, S.; Yang, K.; Zheng, P.; Xu, Y.; Chai, J.; Zheng, Y.; Liu, Z.; Xie, M. High-performance and safe lithium-ion battery with precise ultrathin Al 2 O 3 -coated polyethylene separator. Appl. Surf. Sci . 2024 , 659 , 159918..
Antipova, V.; Omelyanchik, A.; Sobolev, K.; Pshenichnikov, S.; Vorontsov, S.; Korepanova, E.; Schitz, D.; Peddis, D.; Panina, L.; Levada, K.; Rodionova, V. Enhancing wettability and adhesive properties of PVDF-based substrates through non-thermal helium plasma surface modification. Polymer 2024 , 290 , 126567..
Correia, D. M.; Nunes-Pereira, J.; Alikin, D.; Kholkin, A. L.; Carabineiro, S. A. C.; Rebouta, L.; Rodrigues, M. S.; Vaz, F.; Costa, C. M.; Lanceros-Méndez, S. Surface wettability modification of poly(vinylidene fluoride) and copolymer films and membranes by plasma treatment. Polymer 2019 , 169 , 138−147..
Narimisa, M.; Onyshchenko, Y.; Morent, R.; De Geyter, N. Improvement of PET surface modification using an atmospheric pressure plasma jet with different shielding gases. Polymer 2021 , 215 , 123421..
Tian, C. X.; Zhang, T.; Song, Y. Q.; Ming, H.; Liu, P. Q.; Jiang, M. J.; Luo, F.; Li, J. H.; Tan, H.; Fu, Q. Elaborating polyurethane pillowy soft mat on polypropylene monofilament surface with stepwise surface treatments. Chinese J. Polym. Sci. 2022 , 40 , 1389−1401..
Domonkos, M.; Tichá, P.; Trejbal, J.; Demo, P. Applications of cold atmospheric pressure plasma technology in medicine, agriculture and food industry. Appl. Sci. 2021 , 11 , 4809..
Zhang, D.; Ding, Y.; Sun, W.; Qian, W.; Liu, W.; Yang, Q. Utilization of plasma-induced graft polymerization to modify anion-exchanging membranes for enhanced selective separation of organic/inorganic salts. Polymer 2025 , 335 , 128805..
Jin, S. Y.; Manuel, J.; Zhao, X.; Park, W. H.; Ahn, J. H. Surface-modified polyethylene separator via oxygen plasma treatment for lithium ion battery. J. Ind. Eng. Chem. 2017 , 45 , 15−21..
Tseng, Y. C.; Li, H. L.; Huang, C. Atmospheric-pressure plasma activation and surface characterization on polyethylene membrane separator. Jpn. J. Appl. Phys . 2016 , 56 , 01AF03..
Borcia, C.; Punga, I. L.; Borcia, G. Surface properties and hydrophobic recovery of polymers treated by atmospheric-pressure plasma. Appl. Surf. Sci. 2014 , 317 , 103−110..
Mortazavi, M.; Nosonovsky, M. J. A. S. S. A model for diffusion-driven hydrophobic recovery in plasma treated polymers. Appl. Surf. Sci. 2012 , 258 , 6876−6883..
Han, M.; Kim, D. W.; Kim, Y. C. Charged polymer-coated separators by atmospheric plasma-induced grafting for lithium-ion batteries. ACS Appl. Mater. Interfaces 2016 , 8 , 26073−26081..
[Xu, P.; Wu, X.; Yan, P.; He, Z.; Wu, S.; Wu, J.; Liao, B.; Wu, J. Application of plasma technology for lithium battery separator modification. Eur. Phys. J. Spec. Top . 2025 , DOI: 10.1140/epjs/s11734-025-01976-3..
Qin, S.; Wang, M.; Wang, C.; Jin, Y.; Yuan, N.; Wu, Z.; Zhang, J. Binder-free nanoparticulate coating of a polyethylene separator via a reactive atmospheric pressure plasma for lithium-ion batteries with improved performances. Adv. Mater. Interfaces 2018 , 5 , 1800579..
Jeon, H.; Jin, S. Y.; Park, W. H.; Lee, H.; Kim, H. T.; Ryou, M. H.; Lee, Y. M. Plasma-assisted water-based Al 2 O 3 ceramic coating for polyethylene-based microporous separators for lithium metal secondary batteries. Electrochim. Acta 2016 , 212 , 649−656..
Mostofi Sarkari, N.; Darvish, F.; Mohseni, M.; Ebrahimi, M.; Khani, M.; Eslami, E.; Shokri, B.; Alizadeh, M.; Dee, C. F. Surface characterization of an organosilane-grafted moisture-crosslinked polyethylene compound treated by air atmospheric pressure non-equilibrium gliding arc plasma. Appl. Surf. Sci. 2019 , 490 , 436−450..
Durán, I. R.; Profili, J.; Stafford, L.; Laroche, G. Unveiling the origin of the anti-fogging performance of plasma-coated glass: role of the structure and the chemistry of siloxane precursors. Prog. Org. Coat . 2020 , 141 , 105401..
Annamalai, M.; Gopinadhan, K.; Han, S. A.; Saha, S.; Park, H. J.; Cho, E. B.; Kumar, B.; Patra, A.; Kim, S.-W.; Venkatesan, T. Surface energy and wettability of van der Waals structures. Nanoscale 2016 , 8 , 5764−5770..
Wang, Q.; Miao, Q.; Wang, X.; Wang, T.; Xu, Q. Role of surface physicochemical properties of pipe materials on bio-clogging in leachate collection systems from a thermodynamic perspective. Sci. Total Environ . 2022 , 851 , 158263..
Kaelble, D. H. Dispersion-polar surface tension properties of organic solids. J. Adhes. 2008 , 2 , 66−81..
Wang, C.; Ruan, Y.; Xiong, X. Anti-swelling gel polymer electrolyte membrane for high-performance lithium-ion battery. J. Membr. Sci . 2025 , 716 , 123530..
Mao, X.; Shi, L.; Zhang, H.; Wang, Z.; Zhu, J.; Qiu, Z.; Zhao, Y.; Zhang, M.; Yuan, S. Polyethylene separator activated by hybrid coating improving Li + ion transference number and ionic conductivity for Li-metal battery. J. Power Sources 2017 , 342 , 816−824..
Wu, L. Y.; Chung, F. Y.; Huang, C. Synthesis and application of nano-organosilicon coating through cyclonic plasma deposition on a polymeric separator for lithium-ion batteries. J. Coat. Technol. Res. 2022 , 19 , 1159−1170..
Gangwar, R. K.; Hamdan, A.; Stafford, L. Nanoparticle synthesis by high-density plasma sustained in liquid organosilicon precursors. J. Appl. Phys . 2017 , 122 , 243301..
Wang, H.; Liu, Y.; Xue, S.; Xie, P.; He, J.; Koval, O.; Chen, Z.; Wang, R. Silicon oxide anticorrosion coating deposition on alloy steel surface by low temperature plasma. Surf. Coat. Technol . 2024 , 477 , 130338..
Owad, T. T. A.; Siddig, E. A. A.; Salih, R. E. M.; Zhang, Y.; Wang, C.; Xu, Y.; Zhang, J. Durable and recoverable hydrophilicity of polyethylene terephthalate fabric prepared with plasma selective etching. Surf. Interfaces 2022 , 32 , 102081..
[Gudmundsson, J. T.; Kouznetsov, I. G.; Patel, K. K.; Lieberman, M. A. Electronegativity of low-pressure high-density oxygen discharges. J. Phys. D: Appl. Phys . 2001 , 34 , 1100..
He, T.; Qian, Z.; Wang, Q.; Zhang, Y.; Wang, H.; Zhang, J.; Xu, Y. One step coating anti-reflective SiO 2 film for silicon solar cells applications by atmospheric pressure plasma jet. Mater. Lett . 2023 , 350 , 134915..
Wang, Z.; Zhu, H.; Yang, L.; Wang, X.; Liu, Z.; Chen, Q. Plasma Modified Polypropylene Membranes as the Lithium-Ion Battery Separators. Plasma Sci. Technol. 2016 , 18 , 424−429..
E. Abusrafa, A.; Habib, S.; Krupa, I.; Ouederni, M.; Popelka, A. Modification of Polyethylene by RF Plasma in Different/Mixture Gases. Coatings 2019 , 9 , 145..
Pai, C. S.; Miner, J. F.; Foo, P. D. Electron cyclotron resonance microwave discharge for oxide deposition using tetramethylcyclotetrasiloxane. J. Appl. Phys. 1993 , 73 , 3531−3538..
Nagasawa, H.; Yamamoto, Y.; Tsuda, N.; Kanezashi, M.; Yoshioka, T.; Tsuru, T. Atmospheric-pressure plasma-enhanced chemical vapor deposition of microporous silica membranes for gas separation. J. Membr. Sci. 2017 , 524 , 644−651..
Jung, Y. C.; Kim, S. K.; Kim, M. S.; Lee, J. H.; Han, M. S.; Kim, D. H.; Shin, W. C.; Ue, M.; Kim, D. W. Ceramic separators based on Li+-conducting inorganic electrolyte for high-performance lithium-ion b atteries with enhanced safety. J. Power Sources 2015 , 293 , 675−683..
Zhai, W.; Yu, H.; Chen, H.; Li, L.; Li, D.; Zhang, Y.; He, T. Stable fouling resistance of polyethylene (PE) separator membrane via oxygen plasma plus zwitterion grafting. Sep. Purif. Technol . 2022 , 293 , 121091..
Zhang, J.; Wavhal, D. S.; Fisher, E. R. Mechanisms of SiO2 film deposition from tetramethylcyclotetrasiloxane, dimethyldimethoxysilane, and trimethylsilane plasmas. J. Vac. Sci. Technol., A 2004 , 22 , 201−213..
Spyrides, S. M. M.; Alencastro, F. S.; Guimaraes, E. F.; Bastian, F. L.; Simao, R. A. Mechanism of oxygen and argon low pressure plasma etching on polyethylene (UHMWPE). Surf. Coat. Technol . 2019 , 378 , 124990..
Qi, Y.; Xiao, Z. G.; Mantei, T. D. Comparison of silicon dioxide layers grown from three polymethylsiloxane precursors in a high-density oxygen plasma. J. Vac. Sci. Technol., A 2003 , 21 , 1064−1068..
Grill, A.; Neumayer, D. A. J. Structure of low dielectric constant to extreme low dielectric constant SiCOH films: Fourier transform infrared spectroscopy characterization. J. Appl. Phys. 2003 , 94 , 6697−6707..
Babiker, D. M. D.; Usha, Z. R.; Wan, C.; Zhao, Y.; Deng, W.; Yang, H.; Tan, Y.; Chen, X.; Li, L. A polyolefin-based hybrid separator for durable and advanced lithium-/sodium-metal batteries. J. Energy Storage 2023 , 73 , 108888..
Liu, Y.; Tao, Y.; Lv, X.; Zhang, Y.; Di, M. Study on the surface properties of wood/polyethylene composites treated under plasma. Appl. Surf. Sci. 2010 , 257 , 1112−1118..
Wang, R.; Xia, Z.; Kong, X.; Liang, L.; Ostrikov, K. Etching and annealing treatment to improve the plasma-deposited SiOx film adhesion force. Surf. Coat. Technol . 2021 , 427 , 127840..
[Vandencasteele, N.; Reniers, F. Plasma-modified polymer surfaces: characterization using XPS. J. Electron. Spectrosc. Relat. Phenom . 2010, 178-179 , 394-408..
Egghe, T.; Ghobeira, R.; Morent, R.; Hoogenboom, R.; De Geyter, N. Comparative study of the aging behavior of plasma activated hexamethyldisiloxane-based plasma polymers and silicone elastomer thin films. Prog. Org. Coat . 2022 , 172 , 107091..
Aliakbarshirazi, S.; Ghobeira, R.; Egghe, T.; De Geyter, N.; Declercq, H.; Morent, R. New plasma-assisted polymerization/activation route leading to a high density primary amine silanization of PCL/PLGA nanofibers for biomedical applications. Appl. Surf. Sci . 2023 , 640 , 158380..
Profili, J.; Asadollahi, S.; Vinchon, P.; Dorris, A.; Beck, S.; Sarkassian, A.; Stafford, L. Recent progress on organosilicon coatings deposited on bleached unrefined Kraft paper by non-thermal plasma process at atmospheric pressure. Prog. Org. Coat . 2020 , 147 , 105865..
Mozetič, M. Aging of plasma-activated polyethylene and hydrophobic recovery of polyethylene polymers. Polymers 2023 , 15 , 4668..
Jokinen, V.; Suvanto, P.; Franssila, S. Oxygen and nitrogen plasma hydrophilization and hydrophobic recovery of polymers. Biomicrofluidics 2012 , 6 , 016501..
Wang, S.; Wang, Y.; Gao, M.; Huang, Y. Aging Effect of Plasma-Treated Carbon Fiber Surface: From an Engineering Point. Coatings 2024 , 14 , 80..
Davoodabadi, A.; Jin, C.; Wood Iii, D. L.; Singler, T. J.; Li, J. On electrolyte wetting through lithium-ion battery separators. Extreme Mech. Lett . 2020 , 40 , 100960..
Man, C.; Jiang, P.; Wong, K. W.; Zhao, Y.; Tang, C.; Fan, M.; Lau, W.; Mei, J.; Li, S.; Liu, H.; Hui, D. Enhanced wetting properties of a polypropylene separator for a lithium-ion battery by hyperthermal hydrogen induced cross-linking of poly(ethylene oxide). J. Mater. Chem. A 2014 , 2 , 11980−11986..
Xie, Y.; Zou, H.; Xiang, H.; Xia, R.; Liang, D.; Shi, P.; Dai, S.; Wang, H. Enhancement on the wettability of lithium battery separator toward nonaqueous electrolytes. J. Membr. Sci. 2016 , 503 , 25−30..
Owens, D. K.; Wendt, R. C. Estimation of the surface free energy of polymers. J. Appl. Polym. Sci. 1969 , 13 , 1741−1747..
Zhu, Y .; Yu, C.; Li, Y.; Zhu, Q; Zhou, L.; Cao, C.; Yu, T.; Du, F. Research on the changes in wettability of rice (Oryza sativa.) leaf surfaces atdifferent development stages using the OWRK method. Pest. Manage. Sci. 2013 , 70 , 462−469..
Encinas, N.; Pantoja, M.; Abenojar, J.; Martínez, M. A. Control of wettability of polymers by surface roughness modification. J. Adhes. Sci. Technol. 2010 , 24 , 1869−1883..
Zheng, Y.; Lin, G.; Mo, C.; He, L.; Tong, L.; Liu, X. Effect of thermal processing conditions on the structure and properties of porous PENK/PVDF composite films and its application as lithium-ions separators. Polymer 2024 , 297 , 126821..
Jeong, T.-Y.; Lee, Y. D.; Ban, Y.; Lee, J.; Lee, H.; Kwon, Y. K. Polyimide composite separator containing surface-modified hollow mesoporous silica nanospheres for lithium-ion battery application. Polymer 2021 , 212 , 123288..
Seo, B.; Wang, Y. Experimental Measurement of Molecular Diffusion and Evaporation Rate of Battery Organic Electrolytes in Ambient Air. J. Electrochem. Soc . 2021 , 168 , 060505..
Jeon, H.; Yeon, D.; Lee, T.; Park, J.; Ryou, M.-H.; Lee, Y. M. A water-based Al2O3 ceramic coating for polyethylene-based microporous separators for lithium-ion batteries. J. Power Sources 2016 , 315 , 161−168..
Liu, H.; Xu, J.; Guo, B.; He, X. Effect of Al 2 O 3 /SiO 2 composite ceramic layers on performance of polypropylene separator for lithium-ion batteries. Ceram. Int. 2014 , 40 , 14105−14110..
Cassie, A.; Baxter, S. Wettability of porous surfaces. Trans. Faraday Soc. 1944 , 40 , 546−551..
Zhou, Y. G.; Fan, L.; Li, H. Q.; Cui, Y. J.; Yu, S. F.; Wei, Z. Z.; Zhao, Y. Fibrous separator with surface modification and micro-nano fibers lamination enabling fast ion transport for lithium-ion batteries. Chinese J. Polym. Sci. 2022 , 41 , 222−232..
[Ma, C.; Wang, L.; Nikiforov, A.; Onyshchenko, Y.; Cools, P.; Ostrikov, K.; De Geyter, N.; Morent, R. Atmospheric-pressure plasma assisted engineering of polymer surfaces: From high hydrophobicity to superhydrophilicity. Appl. Surf. Sci . 2021, 535 , 147032..
Wenzel, R. N. Resistance of solid surfaces to wetting by water. Ind. Eng. Chem. Res. 1936 , 28 , 988−994..
Moradkhani, G.; Profili, J.; Robert, M.; Laroche, G.; Elkoun, S.; Mighri, F. Surface modification of flax fibers with TMCTS-based PECVD for improved thermo-mechanical properties of PLA/Flax fiber composites. Polymers 2024 , 16 , 360..
Park, M. K.; Song, W. S.; Kim, M. H.; Hong, S. J. Surface analysis of TMCTS-based SiOC(H) low- k dielectrics in post-etch strip of acl hardmask. Materials 2021 , 14 , 1144..
Wang, J.; Wang, M.; Ren, N.; Dong, J.; Li, Y.; Chen, C. High-areal-capacity thick cathode with vertically-aligned micro-channels for advanced lithium ion batteries. Energy Storage Mater. 2021 , 39 , 287−293..
[Joseph, J.; Murdock, A. T.; Seo, D. H.; Han, Z. J.; O'Mullane, A. P.; Ostrikov, K. Plasma enabled synthesis and processing of materials for lithium-ion batteries. Adv. Mater. Technol . 2018 , 3 , 1800070..
Nitou, M. V. M.; Tang, M.; Niu, Y.; Pang, Y.; Wan, Z.; Mawuli, S. E.; Leoba, J. A.; Xiaodong, F.; Lv, W. Separator with active coating for fast and stable Li-ion batteries. J. Power Sources 2024 , 602 , 234406..
Zhang, T.; Wang, X.; Liang, J.; Chen, Q.; Huang, J. Environmentally friendly separators based on cellulose diacetate-based crosslinked networks for lithium-ion batteries. Polymer 2024 , 290 , 126564..
Yang, N.; Liang, Y.; Jia, S. Enhanced thermal stability and electrochemical performance of polyacrylonitrile/cellulose acetate-electrospun fiber membrane by boehmite nanoparticles: application to high-performance lithium-ion batteries. Macromol. Mater. Eng . 2021 , 306 , 2100300..
0
浏览量
182
Downloads
0
CSCD
关联资源
相关文章
相关作者
相关机构
京公网安备11010802046900号