Cited by 1,699Advanced Battery Materials and TechnologiesAdvancements in Battery MaterialsBattery Modeling and Management

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Fluoroethylene Carbonate Additives to Render Uniform Li Deposits in Lithium Metal Batteries

Zhang, Xue‐Qiang, Cheng, Xin‐Bing, Chen, Xiang, Yan, Chong, Zhang, Qiang·2017·Advanced Functional Materials

DOI 10.1002/adfm.201605989

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Abstract

Lithium (Li) metal has been considered as an important substitute for the graphite anode to further boost the energy density of Li‐ion batteries. However, Li dendrite growth during Li plating/stripping causes safety concern and poor lifespan of Li metal batteries (LMB). Herein, fluoroethylene carbonate (FEC) additives are used to form a LiF‐rich solid electrolyte interphase (SEI). The FEC‐induced SEI layer is compact and stable, and thus beneficial to obtain a uniform morphology of Li deposits. This uniform and dendrite‐free morphology renders a significantly improved Coulombic efficiency of 98% within 100 cycles in a Li | Cu half‐cell. When the FEC‐protected Li metal anode matches a high‐loading LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NMC) cathode (12 mg cm −2 ), a high initial capacity of 154 mAh g −1 (1.9 mAh cm −2 ) at 180.0 mA g −1 is obtained. This LMB with conversion‐type Li metal anode and intercalation‐type NMC cathode affords an emerging energy storage system to probe the energy chemistry of Li metal protection and demonstrates the material engineering of batteries with very high energy density.

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“Several additives have also been proposed to improve SEI quality, such as vinylene carbonate [16], ﬂuoroethylene carbonate [17], and ethylene sulﬁdes [18,19], that produce a very stable layer in carbonate-based electrolytes.”
Background
Uniformizing the lithium deposition by gradient lithiophilicity and conductivity for stable lithium-metal batteries.
Yu, Z., Yang, Q., Xue, W.-J., Shen, J.-Q., Zhang, J., Zhu, S.-M., Li, S., & Li, Y. (2023) · Nanoscale · doi:10.1039/d2nr06210k · Cited by 8
Roles of Trimethyl Borate in Constructing an Interphase on Li Anode: Angel or Demon?
Ding, J., Wen, Y.-C., Lan, X., & Hu, R.-Z. (2023) · ACS Applied Materials and Interfaces · doi:10.1021/acsami.2c19417 · Cited by 8
Long-Life Lithium-Metal Batteries with Dendrite-Free Anodes Enabled by Zn(Tfsi)2 Additive
Jia, Z.-Q., Lyu, H., Wang, W.-R., Qi, X.-Q., & Guo, S. (2022) · Social Science Research Network · doi:10.2139/ssrn.4233189 · Cited by 8
Stable Dendrite-Free High-Voltage Lithium Metal Batteries Enabled by Localized High Concentration Fluoroethylene Carbonate Based Electrolytes
Xue, H., He, W., Li, J., Zhang, D., Wang, X.-F., Zhou, S., & Yang, W. (2022) · ACS Applied Energy Materials · doi:10.1021/acsaem.2c02194 · Cited by 8
A Diluted Electrolyte for Long-Life Sulfurized Polyacrylonitrile-Based Anode-Free Li-S Batteries
Ma, T., Ren, X.-Y., Hu, L., Teng, W., Wang, X., Wu, G., Liu, J., Nan, D., Li, B.-H., & Yu, X. (2022) · Polymers · doi:10.3390/polym14163312 · Cited by 8
“used fluoroethylene carbonate (FEC) as electrolyte additive to form LiF in SEI [41].”
MethodInfluential
Imidazolium-Based Ionic Liquid as a Solid Electrolyte Interphase-Forming Additive for Lithium Metal Anodes
Wang, W., Ma, W., Yang, Q.-L., Lin, Z., Tang, J., Wang, M., He, Y., Fan, C., & Sun, K.-N. (2022) · Industrial & Engineering Chemistry Research · doi:10.1021/acs.iecr.2c00958 · Cited by 8
The interfacial engineering of metal electrodes for high-specific-energy and long-lifespan batteries
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Tailoring the Lithium Solid Electrolyte Interphase for Highly Concentrated Electrolytes with Direct Exposure to Halogenated Solvents
Thornburg, E. S., Haasch, R., & Gewirth, A. (2022) · ACS Applied Energy Materials · doi:10.1021/acsaem.1c03336.s001 · Cited by 8
Porous polyimide separator promotes uniform lithium plating for lithium‐free cells
Pai, J., Ku, H.-Y., Lin, C.-C., Chiang, C.-W., Hardwick, L., & Hu, C.-C. (2021) · Electrochemical Science Advances · doi:10.1002/elsa.202100091 · Cited by 8
Electrochemical properties of PVP-derived carbon nanospheres with various porosity and heteroatom contents in anode voltage range over full-cell operation
Kim, Y.-O., Yang, H.-S., Yoon, J., Jo, M. J., Youk, J. H., Lee, B.-S., & Yu, W.-R. (2021) · Journal of Industrial & Engineering Chemistry · doi:10.1016/j.jiec.2021.09.012 · Cited by 8
Stabilizing Ceramic-Based Electrolyte Interfaces with Self-Viscous Modification Strategy for Solid-State Lithium Batteries
Chen, L., Huang, S., Ma, D., Xiong, Y., Qiu, J.-Y., Cao, G.-P., & Zhang, H. (2021) · Energy & Fuels · doi:10.1021/acs.energyfuels.1c01202 · Cited by 8
Macromolecular-level polymer brush layer enabling geometric customization of lithium deposits
Zhang, M., Wang, H., Peng, B., Ma, D., Bai, M., Tang, X.-Y., Li, S.-W., Zhao, W.-Y., Liu, S.-Y., Wang, Z.-Q., et al. (2021) · doi:10.1016/j.xcrp.2021.100324 · Cited by 8
Highly efficient lithium utilization in lithium metal full-cell by simulated missile guidance and confinement systems
Zhou, J.-Q., Lu, H., Zhou, X., Ji, H., Sun, Y., Qian, T., & Yan, C.-L. (2020) · Science China Materials · doi:10.1007/s40843-020-1498-8 · Cited by 8
Self-citation
An ultra-stable lithium plating process enabled by the nanoscale interphase of a macromolecular additive
Jia, M.-M., Guo, Y., Bian, H., Zhang, Q., Zhang, L., & Zhang, S.-J. (2020) · doi:10.1039/d0ta08492a · Cited by 8
Self-citation
Garnet–PVDF composite film modified lithium manganese oxide cathode and sulfurized carbon anode from polyacrylonitrile for lithium-ion batteries
Berhe, G. B., Su, W.-N., Abrha, L. H., Bezabh, H., Hagos, T. M., Hagos, T. T., Huang, C.-J., Sahalie, N. A., Jote, B. A., Thirumalraj, B., et al. (2020) · Journal of Materials Chemistry A · doi:10.1039/d0ta05392a · Cited by 8
In Situ Polymerization of 1,3-Dioxane in Solid-State Lithium Batteries: A Mini-Review of Recent Developments
Wu, M.-J., Li, X., Mei, X.-C., Zhang, Y.-M., Zhang, J.-X., Zheng, C.-Y., Xue, J.-P., & Zhou, L. (2025) · Energy & Fuels · doi:10.1021/acs.energyfuels.5c01954 · Cited by 7
Interfacial Impacts of Diluent-Mediated Anion Conformational Changes in Locally Concentrated Ionic Liquid Electrolytes
Lim, M.-K., Chang, H., Kim, G., Seo, J., Kim, B., Choe, S., Lee, H.-C., Moon, J., & Lee, H. (2025) · Energy Storage Materials · doi:10.1016/j.ensm.2025.104288 · Cited by 7
Stabilizing the Solid/Liquid Interface in Quasi-Solid Electrolytes via Anion-Derived Interphase Formation in Concentrated Solutions
Kondo, J., Otani, K., Miyamoto, S., Hikosaka, H., Kondo, Y., Katayama, Y., & Yamada, Y. (2025) · ACS Applied Energy Materials · doi:10.1021/acsaem.4c03307 · Cited by 8
Tailoring the electronic conductivity of coating layer on the composite separator for Li metal anode
Xiang, T.-Q., Hu, Z., Huo, H., Zhou, J.-J., & Li, L. (2025) · Electrochimica Acta · doi:10.1016/j.electacta.2024.145394 · Cited by 7
Regulating interfacial reactions via quasi-solid polymer electrolyte to enable high-voltage lithium metal batteries
Fu, J., Zhou, X., Li, Z.-Y., Chen, J., & Guo, X. (2024) · Chemical Engineering Journal · doi:10.1016/j.cej.2024.156720 · Cited by 7
In Situ Electrochemical Polymerization of Cathode Electrolyte Interphase Enabling High-Performance Lithium Metal Batteries.
Sun, S., Yu, J., Ma, X.-Y., Fang, P.-D., Yang, M.-C., Yang, J., Wu, M., Hu, Y., & Yan, F. (2024) · Small · doi:10.1002/smll.202403145 · Cited by 7
Au-embedded mesoporous molecular sieve enables robust organic/inorganic hybrid solid electrolyte interphase for high-performance lithium metal batteries
Liu, Y., Zhang, Q., Dang, C.-C., Dong, J., Kong, L., Li, M., Zhao, L., & Gao, L.-M. (2024) · Chemical Engineering Journal · doi:10.1016/j.cej.2024.151616 · Cited by 7
Self-citation
Recent Progress of Potassium Metal Anodes: How to Regulate the Growth of Dendrite
Baek, S., Jung, T., Jie, S., Kim, M., & Lee, B. (2023) · International Journal of Energy Research · doi:10.1155/2023/6680001 · Cited by 8
Electrolytic construction of nanosphere‐assembled protective layer toward stable lithium metal anode
Lu, G.-X., Li, S., Yue, K., Yuan, H.-D., Luo, J.-M., Liu, Y.-J., Wang, Y., Tao, X.-Y., & Nai, J. (2023) · Battery Energy · doi:10.1002/bte2.20230044 · Cited by 7
Recent Progress on Nanomodification Applied in Anodes of Rechargeable Li Metal Batteries
Yao, Z., Li, W., Chen, T.-T., Xu, X., & Xiao, Q.-F. (2023) · ACS Applied Energy Materials · doi:10.1021/acsaem.3c01657 · Cited by 7
Building Optimal Sei Through Control of Morphology and Chemical Composition for High-Performance Lithium-Ion Batteries
Yang, H.-W., Maniyazagan, M., Naveenkumar, P., Kang, W., & Kim, S.-J. (2023) · Social Science Research Network · doi:10.2139/ssrn.4235886 · Cited by 7
Stabilizing Li metal anode by constructing lithiophilic N-doped carbon nanotubes on flexible carbon felt host
Li, T.-H., Jiang, J.-J., Zhou, H.-X., Shang, H., Huang, M., Gao, J.-J., Qu, M.-Z., Liu, W.-J., Zhang, H., & Peng, G.-C. (2022) · Diamond and related materials · doi:10.1016/j.diamond.2022.109391 · Cited by 7
Fluorine-Rich Interphase and Desolvation Regulation for a Long-Life and High-Rate TiS2-Based Li-Metal Battery
Cao, T.-Q., Huang, S., Sun, Y.-G., Wang, S.-J., Wu, Y., Ma, H., Chai, Y., Chen, R., Zhang, H.-R., Chen, D.-Y., et al. (2022) · Journal of Physical Chemistry C · doi:10.1021/acs.jpcc.2c00580 · Cited by 7
High-Performance Lithium Metal Battery Realized by Regulating Li+ Flux Distribution on Artificial-Solid-Electrolyte-Interphase Functionalized 3D Carbon Framework-Li Anode
Shi, X.-W., Qiao, Y., Xing, C., Zhang, Y., Liu, J., Wang, Y.-L., Wang, G., Liu, X.-C., & Li, L. (2022) · Materials today physics · doi:10.1016/j.mtphys.2022.100672 · Cited by 7
Realizing Compact Lithium Deposition via Elaborative Nucleation and Growth Regulation for Stable Lithium-Metal Batteries.
Wang, M., Ren, Z.-M., Lin, H., Peng, Z., Li, Z.-D., Li, H., Shen, Y., He, H., Wang, D.-Y., Zheng, J.-Y., et al. (2021) · ACS Applied Materials and Interfaces · doi:10.1021/acsami.1c07624 · Cited by 7
Avoiding dendrite formation by confining lithium deposition underneath Li–Sn coatings
Whang, G., Yan, Q., Li, D., Wei, Z., Butts, D. M., Sautet, P., Luo, J., & Dunn, B. (2020) · Journal of Materials Research · doi:10.1557/s43578-020-00047-8 · Cited by 7
“Due to the inherently low reduction potential of Li, the SEI formed at the Li surface upon contact with electrolyte results in the immediate electrolyte decomposition and formation of both organic and inorganic decomposition products[4–6].”
BackgroundInfluential
Roadmaps for dendrite suppression in next generation lithium-ion batteries: Toward sustainable energy solutions
Li, Y., Poudel, S., Sweta, K., Azqadan, E., Kunwar, A., & Nele Moelans, B. (2026) · Energy storage materials · doi:10.1016/j.ensm.2026.105000 · Cited by 3
Online Mass Spectrometry Investigation of SEI Formation on Carbon Electrode Surfaces in Sodium-Ion Batteries: Oxygen and Additive Effects
Zhang, P.-H., Nakahata, S., Peng, B., Li, B.-B., Zhang, D., Inoue, K.-I., Wang, L., Honma, I., & Ye, S. (2025) · ACS Applied Energy Materials · doi:10.1021/acsaem.5c03054 · Cited by 6
Interfacial Atomistic Evolution in Sodium-Ion Battery using a Graph-Theoretic Approach.
Gong, Y., Fan, Y.-X., Chen, Y.-L., Bonilla, M. R., Cortes, H. A., Gao, C.-L., Huang, Y.-H., & Yang, M.-H. (2025) · Small · doi:10.1002/smll.202511841 · Cited by 6
Homogeneous Li Flux and Mechanical Stable Solid‐Electrolyte Interphase Enabled by Different Solvation Chemistry for Lithium Metal Batteries
Zhao, Z., Joe, H., Desalegn, B. Z., Kim, S. K., Wang, D.-Y., & Seo, J. G. (2025) · Advanced Functional Materials · doi:10.1002/adfm.202508653 · Cited by 6
Achieving a Superior Lithium Metal Anode by a Hollow Nanocubic Carbon with an Inside-Out Lithiophilic Gradient.
Zhu, H., Xie, T., Liang, B., Lin, Z., Zheng, W., He, J.-L., Xiong, S.-Y., Li, Y.-J., & Huang, S.-M. (2025) · ACS Applied Materials and Interfaces · doi:10.1021/acsami.5c03058 · Cited by 6
Acrylic copolymers membrane synthesized through polymerization-induced phase separation as solid polymer electrolytes for Lithium metal batteries
Ho, N.-X., Viet, C. D., Thi, D. P., Dao, V.-D., Do, L. T., & Vu, N. H. (2025) · Journal of Alloys and Compounds · doi:10.1016/j.jallcom.2025.180525 · Cited by 6
Bis(2,2,2-trifluoroethyl) Carbonate As a Fire Suppressant Candidate for Lithium-Ion Batteries
Khan-Ghauri, M., Diévart, P., Grégoire, C., Kanayama, K., Almarzooq, Y. M., Takahashi, S., Tezuka, T., Nakamura, H., Catoire, L., Maruta, K., et al. (2025) · Energy & Fuels · doi:10.1021/acs.energyfuels.4c05359 · Cited by 6
Construction of robust solid electrolyte interface using [Cu(SCN2H4)n]Cl nanowires for stable lithium metal anodes
Lee, C., Kim, S., Cho, K.-Y., Sim, K., Jo, J., & Eom, K. (2024) · Chemical Engineering Journal · doi:10.1016/j.cej.2024.158005 · Cited by 6

Authors: Zhang, X., Cheng, X., Chen, X., Yan, C., & Zhang, Q.
Affiliations: Tsinghua University (CN)
Corresponding author: Zhang, Qiang
ORCID: Zhang, Xue‐Qiang
Cheng, Xin‐Bing
Chen, Xiang
Yan, Chong
Zhang, Qiang
Venue: Advanced Functional Materials
Publisher: Wiley
Published: 2017-01-20
Volume: 27
Issue: 10
ISSN: 1616-301X (ISSN-L)
1616-3028
DOI: 10.1002/adfm.201605989
OpenAlex: W2579562509
Cited by: 1,699
References: 0
Citations by year: 2026: 81 · 2025: 135 · 2024: 161 · 2023: 203 · 2022: 230 · 2021: 228 · 2020: 242 · 2019: 231 · 2018: 130 · 2017: 58
FWCI: 75.16
Type: journal article
Language: en
Open access: closed
Licence: onlinelibrary.wiley.com/termsAndConditions#vor (vor)
Locations: Advanced Functional Materials (publishedVersion)
Funders: National Key Research and Development Program (2016YFA0202500)
Natural Scientific Foundation of China (21422604, 21676160, 21561130151)
Topics: Physical Sciences › Engineering › Electrical and Electronic Engineering › Advanced Battery Materials and Technologies
Physical Sciences › Engineering › Electrical and Electronic Engineering › Advancements in Battery Materials
Physical Sciences › Engineering › Automotive Engineering › Battery Modeling and Management
Keywords: lithium metal batteries, fluoroethylene carbonate, electrolyte additives, lithium dendrite suppression, solid electrolyte interphase, LiF-rich SEI, lithium deposition uniformity, lithium metal anode, NCM cathode, Coulombic efficiency, high energy density

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Fluoroethylene Carbonate Additives to Render Uniform Li Deposits in Lithium Metal Batteries

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