AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article

Formatted PVDF in lamellar composite solid electrolyte for solid-state lithium metal battery

Xinji Zhang, Yafang Zhang, Shiyue Zhou, Jingchuan Dang( ), Chenye Wang, Wenjia Wu( ), Jingtao Wang
School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, China
Show Author Information

Graphical Abstract

A lamellar composite solid electrolyte with β-conformation polyvinylidene fluoride (PVDF) was prepared by confining PVDF in the interlayer channel of –NH2 modified vermiculite (Vr) lamellar framework, which imparts superior room-temperature ionic conductivity and lithium-ion transference number.

Abstract

Solid polymer electrolytes (SPEs) hold great application potential for solid-state lithium metal battery because of the excellent interfacial contact and processibility, but being hampered by the poor room-temperature conductivity (~ 10−7 S·cm−1) and low lithium-ion transference number ( tLi+). Here, a lamellar composite solid electrolyte (Vr-NH2@polyvinylidene fluoride (PVDF) LCSE) with β-conformation PVDF is fabricated by confining PVDF in the interlayer channel of –NH2 modified vermiculite lamellar framework. We demonstrate that the conformation of PVDF can be manipulated by the nanoconfinement effect and the interaction from channel wall. The presence of –NH2 groups could induce the formation of β-conformation PVDF through electrostatic interaction, which serves as continuous and rapid lithium-ion transfer pathway. As a result, a high room-temperature ionic conductivity of 1.77 × 10−4 S·cm−1 is achieved, 1–2 orders of magnitude higher than most SPEs. Furthermore, Vr-NH2@PVDF LCSE shows a high tLi+ of 0.68 because of the high dielectric constant, ~ 3 times of that of PVDF SPE, and surpassing most of reported SPEs. The LiNi0.8Co0.1Mn0.1O2||Li cell assembled by Vr-NH2@PVDF LCSE obtains a discharge specific capacity of 137.1 mAh·g−1 after 150 cycles with a capacity retention rate of 93% at 1 C and 25 °C. This study may pave a new avenue for high-performance SPEs.

Keywords

solid-state lithium metal batterylamellar composite solid electrolyteβ-conformation polyvinylidene fluoride (PVDF)room-temperature ionic conductivitylithium-ion transference number

Electronic Supplementary Material

Download File(s)
12274_2024_6439_MOESM1_ESM.pdf (3.7 MB)

References

[1]

Ye, L. H.; Li, X. A dynamic stability design strategy for lithium metal solid state batteries. Nature 2021, 593, 218–222.
Crossref Google Scholar
[2]

Bachman, J. C.; Muy, S.; Grimaud, A.; Chang, H. H.; Pour, N.; Lux, S. F.; Paschos, O.; Maglia, F.; Lupart, S.; Lamp, P. et al. Inorganic solid-state electrolytes for lithium batteries: Mechanisms and properties governing ion conduction. Chem. Rev. 2016, 116, 140–162.
Crossref Google Scholar
[3]

Lin, X. D.; Zhou, G. D.; Liu, J. P.; Yu, J.; Effat, M. B.; Wu, J. X.; Ciucci, F. Rechargeable battery electrolytes capable of operating over wide temperature windows and delivering high safety. Adv. Energy Mater. 2020, 10, 2001235.
Crossref Google Scholar
[4]

Qiu, J. L.; Liu, X. Y.; Chen, R. S.; Li, Q. H.; Wang, Y.; Chen, P. H.; Gan, L. Y.; Lee, S. J.; Nordlund, D.; Liu, Y. J. et al. Enabling stable cycling of 4.2 V high-voltage all-solid-state batteries with PEO-based solid electrolyte. Adv. Funct. Mater. 2020, 30, 1909392.
Crossref Google Scholar
[5]

Lu, X.; Wang, Y. M.; Xu, X. Y.; Yan, B. G.; Wu, T.; Lu, L. Polymer-based solid-state electrolytes for high-energy-density lithium-ion batteries—Review. Adv. Energy Mater. 2023, 13, 2301746.
Crossref Google Scholar
[6]

Yue, L. P.; Ma, J.; Zhang, J. J.; Zhao, J. W.; Dong, S. M.; Liu, Z. H.; Cui, G. L.; Chen, L. Q. All solid-state polymer electrolytes for high-performance lithium ion batteries. Energy Storage Mater. 2016, 5, 139–164.
Crossref Google Scholar
[7]

Xiao, Z. L.; Zhou, B. H.; Wang, J. R.; Zuo, C.; He, D.; Xie, X. L.; Xue, Z. G. PEO-based electrolytes blended with star polymers with precisely imprinted polymeric pseudo-crown ether cavities for alkali metal ion batteries. J. Membr. Sci. 2019, 576, 182–189.
Crossref Google Scholar
[8]

Liu, H. B.; Sun, Q.; Cheng, J.; Zhang, H. Q.; Xu, X.; Li, Y. Y.; Zeng, Z.; Zhao, Y.; Li, D. P.; Lu, J. Y. et al. Stable operation of polymer electrolyte-solid-state batteries via lone-pair electron fillers. Nano Res. 2023, 16, 12727–12737.
Crossref Google Scholar
[9]

Kumar, M.; Sekhon, S. S. Role of plasticizer’s dielectric constant on conductivity modification of PEO-NH4F polymer electrolytes. Eur. Polym. J. 2002, 38, 1297–1304.
Crossref Google Scholar
[10]

Su, Y. T.; Zhang, W. Q.; Lan, J. L.; Sui, G.; Zhang, H. T.; Yang, X. P. Flexible reduced graphene oxide/polyacrylonitrile dielectric nanocomposite films for high-temperature electronics applications. ACS Appl. Nano Mater. 2020, 3, 7005–7015.
Crossref Google Scholar
[11]

Patil, N.; Oh, J. H.; Khatri, S.; Saed, M. A.; Naraghi, M.; Green, M. J. Radio frequency heating response of polyacrylonitrile (PAN) films and nanofiber mats. ACS Appl. Polym. Mater. 2021, 3, 3125–3130.
Crossref Google Scholar
[12]

Ngai, K. S.; Ramesh, S.; Ramesh, K.; Juan, J. C. A review of polymer electrolytes: Fundamental, approaches and applications. Ionics 2016, 22, 1259–1279.
Crossref Google Scholar
[13]

Hu, P.; Chai, J. C.; Duan, Y. L.; Liu, Z. H.; Cui, G. L.; Chen, L. Q. Progress in nitrile-based polymer electrolytes for high performance lithium batteries. J. Mater. Chem. A 2016, 4, 10070–10083.
Crossref Google Scholar
[14]

Lopez, J.; Mackanic, D. G.; Cui, Y.; Bao, Z. N. Designing polymers for advanced battery chemistries. Nat. Rev. Mater. 2019, 4, 312–330.
Crossref Google Scholar
[15]

Lin, Y.; Wang, X. M.; Liu, J.; Miller, J. D. Natural halloysite nano-clay electrolyte for advanced all-solid-state lithium-sulfur batteries. Nano Energy 2017, 31, 478–485.
Crossref Google Scholar
[16]

Zhao, Q.; Stalin, S.; Zhao, C. Z.; Archer, L. A. Designing solid-state electrolytes for safe, energy-dense batteries. Nat. Rev. Mater. 2020, 5, 229–252.
Crossref Google Scholar
[17]

Zhou, Q.; Ma, J.; Dong, S. M.; Li, X. F.; Cui, G. L. Intermolecular chemistry in solid polymer electrolytes for high-energy-density lithium batteries. Adv. Mater. 2019, 31, 1902029.
Crossref Google Scholar
[18]

Zhang, Y.; Zhang, L.; Guo, P.; Zhang, C. Y.; Ren, X. C.; Jiang, Z.; Song, J. J.; Shi, C. Porous garnet as filler of solid polymer electrolytes to enhance the performance of solid-state lithium batteries. Nano Res. 2024, 17, 2663–2670
Crossref Google Scholar
[19]

Lu, G. L.; Zhang, Y. J.; Zhang, J. J.; Du, X. F.; Lv, Z. L.; Du, J. Z.; Zhao, Z. M.; Tang, Y.; Zhao, J. W.; Cui, G. L. Trade-offs between ion-conducting and mechanical properties: The case of polyacrylate electrolytes. Carbon Energy 2023, 5, e287.
Crossref Google Scholar
[20]

Zhou, Z. H.; Sun, T.; Cui, J.; Shen, X.; Shi, C.; Cao, S.; Zhao, J. B. A homogenous solid polymer electrolyte prepared by facile spray drying method is used for room-temperature solid lithium metal batteries. Nano Res. 2023, 16, 5080–5086.
Crossref Google Scholar
[21]

Bouchet, R.; Maria, S.; Meziane, R.; Aboulaich, A.; Lienafa, L.; Bonnet, J. P.; Phan, T. N. T.; Bertin, D.; Gigmes, D.; Devaux, D. et al. Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries. Nat. Mater. 2013, 12, 452–457.
Crossref Google Scholar
[22]

Ma, Q.; Zhang, H.; Zhou, C. W.; Zheng, L. P.; Cheng, P. F.; Nie, J.; Feng, W. F.; Hu, Y. S.; Li, H.; Huang, X. J. et al. Single lithium-ion conducting polymer electrolytes based on a super-delocalized polyanion. Angew. Chem., Int. Ed. 2016, 55, 2521–2525.
Crossref Google Scholar
[23]

Mi, J. S.; Ma, J. B.; Chen, L. K.; Lai, C.; Yang, K.; Biao, J.; Xia, H. Y.; Song, X.; Lv, W.; Zhong, G. M. et al. Topology crafting of polyvinylidene difluoride electrolyte creates ultra-long cycling high-voltage lithium metal solid-state batteries. Energy Storage Mater. 2022, 48, 375–383.
Crossref Google Scholar
[24]

Zhang, X.; Liu, T.; Zhang, S. F.; Huang, X.; Xu, B. Q.; Lin, Y. H.; Xu, B.; Li, L. L.; Nan, C. W.; Shen, Y. Synergistic coupling between Li6.75La3Zr1.75Ta0.25O12 and poly(vinylidene fluoride) induces high ionic conductivity, mechanical strength, and thermal stability of solid composite electrolytes. J. Am. Chem. Soc. 2017, 139, 13779–13785.
Crossref Google Scholar
[25]

Liu, J. F.; Wu, Z. Y.; Stadler, F. J.; Huang, Y. F. High dielectric poly(vinylidene fluoride)-based polymer enables uniform lithium-ion transport in solid-state ionogel electrolytes. Angew. Chem., Int. Ed. 2023, 62, e202300243.
Crossref Google Scholar
[26]

Huang, Y. F.; Zeng, J. P.; Li, S. F.; Dai, C.; Liu, J. F.; Liu, C.; He, Y. B. Conformational regulation of dielectric poly(vinylidene fluoride)-based solid-state electrolytes for efficient lithium salt dissociation and lithium-ion transportation. Adv. Energy Mater. 2023, 13, 2203888.
Crossref Google Scholar
[27]

Liu, Q. Y.; Yang, G. J.; Li, X. Y.; Zhang, S. M.; Chen, R. J.; Wang, X. F.; Gao, Y. R.; Wang, Z. X.; Chen, L. Q. Polymer electrolytes based on interactions between [solvent-Li+] complex and solvent-modified polymer. Energy Storage Mater. 2022, 51, 443–452.
Crossref Google Scholar
[28]

Liang, C. L.; Mai, Z. H.; Xie, Q.; Bao, R. Y.; Yang, W.; Xie, B. H.; Yang, M. B. Induced formation of dominating polar phases of poly(vinylidene fluoride): Positive ion-CF2 dipole or negative ion-CH2 dipole interaction. J. Phys. Chem. B 2014, 118, 9104–9111.
Crossref Google Scholar
[29]

Chu, Z. Z.; Zhao, R. J.; Wang, B.; Liu, L.; Ma, Z.; Li, Y. S. Effect of ions on the flow-induced crystallization of poly(vinylidene fluoride). Macromolecules 2021, 54, 3800–3809.
Crossref Google Scholar
[30]

Yu, S. S.; Zheng, W. T.; Yu, W. X.; Zhang, Y. J.; Jiang, Q.; Zhao, Z. D. Formation mechanism of β-phase in PVDF/CNT composite prepared by the sonication method. Macromolecules 2009, 42, 8870–8874.
Crossref Google Scholar
[31]

Nair, R. R.; Wu, H. A.; Jayaram, P. N.; Grigorieva, I. V.; Geim, A. K. Unimpeded permeation of water through helium-leak-tight graphene-based membranes. Science 2012, 335, 442–444.
Crossref Google Scholar
[32]

Wang, J. T.; Liu, Y. R.; Dang, J. C.; Zhou, G. L.; Wang, Y.; Zhang, Y. F.; Qu, L. B.; Wu, W. J. Lamellar composite membrane with acid-base pair anchored layer-by-layer structure towards highly enhanced conductivity and stability. J. Membr. Sci. 2020, 602, 117978.
Crossref Google Scholar
[33]

Ding, L.; Li, L. B.; Liu, Y. C.; Wu, Y.; Lu, Z.; Deng, J. J.; Wei, Y. Y.; Caro, J.; Wang, H. H. Effective ion sieving with Ti3C2T x MXene membranes for production of drinking water from seawater. Nat. Sustain. 2020, 3, 296–302.
Crossref Google Scholar
[34]

Zhang, Y. F.; Huang, J. J.; Liu, H.; Kou, W. J.; Dai, Y.; Dang, W.; Wu, W. J.; Wang, J. T.; Fu, Y. Z.; Jiang, Z. Y. Lamellar ionic liquid composite electrolyte for wide-temperature solid-state lithium-metal battery. Adv. Energy Mater. 2023, 13, 2300156.
Crossref Google Scholar
[35]

Zheng, Y. F.; Zhou, Z. F.; Jiao, M. Q.; Wang, L.; Zhang, J.; Wu, W. J.; Wang, J. T. Lamellar membrane with orderly aligned glycine molecules for efficient proton conduction. J. Membr. Sci. 2023, 672, 121433.
Crossref Google Scholar
[36]

Shao, J. J.; Raidongia, K.; Koltonow, A. R.; Huang, J. X. Self-assembled two-dimensional nanofluidic proton channels with high thermal stability. Nat. Commun. 2015, 6, 7602.
Crossref Google Scholar
[37]

Xiang, J. W.; Cheng, Z. X.; Zhao, Y.; Zhang, B.; Yuan, L. X.; Shen, Y.; Guo, Z. Z.; Zhang, Y.; Jiang, J. J.; Huang, Y. H. A lithium-ion pump based on piezoelectric effect for improved rechargeability of lithium metal anode. Adv. Sci. 2019, 6, 1901120.
Crossref Google Scholar
[38]

Martins, P.; Lopes, A. C.; Lanceros-Mendez, S. Electroactive phases of poly(vinylidene fluoride): Determination, processing and applications. Prog. Polym. Sci. 2014, 39, 683–706.
Crossref Google Scholar
[39]

Martins, P.; Nunes, J. S.; Hungerford, G.; Miranda, D.; Ferreira, A.; Sencadas, V.; Lanceros-Méndez, S. Local variation of the dielectric properties of poly(vinylidene fluoride) during the α- to β-phase transformation. Phys. Lett. A 2009, 373, 177–180.
Crossref Google Scholar
[40]

Zhang, M. C.; Mao, Y. Y.; Liu, G. Z.; Liu, G. P.; Fan, Y. Q.; Jin, W. Q. Molecular bridges stabilize graphene oxide membranes in water. Angew. Chem., Int. Ed. 2020, 59, 1689–1695.
Crossref Google Scholar
[41]

Liu, W. Y.; Yi, C. J.; Li, L. P.; Liu, S. L.; Gui, Q. Y.; Ba, D. L.; Li, Y. Y.; Peng, D. L.; Liu, J. P. Designing polymer-in-salt electrolyte and fully infiltrated 3D electrode for integrated solid-state lithium batteries. Angew. Chem., Int. Ed. 2021, 60, 12931–12940.
Crossref Google Scholar
[42]

Yang, K.; Chen, L. K.; Ma, J. B.; Lai, C.; Huang, Y. F.; Mi, J. S.; Biao, J.; Zhang, D. F.; Shi, P. R.; Xia, H. Y. et al. Stable interface chemistry and multiple ion transport of composite electrolyte contribute to ultra-long cycling solid-state LiNi0.8Co0.1Mn0.1O2/lithium metal batteries. Angew. Chem., Int. Ed. 2021, 60, 24668–24675.
Crossref Google Scholar
[43]

Zheng, J.; Tang, M. X.; Hu, Y. Y. Lithium ion pathway within Li7La3Zr2O12-polyethylene oxide composite electrolytes. Angew. Chem., Int. Ed. 2016, 55, 12538–12542.
Crossref Google Scholar
[44]

Zhao, Y.; Yang, X. F.; Sun, Q.; Gao, X. J.; Lin, X. T.; Wang, C. H.; Zhao, F. P.; Sun, Y. P.; Adair, K. R.; Li, R. Y. et al. Dendrite-free and minimum volume change Li metal anode achieved by three-dimensional artificial interlayers. Energy Storage Mater. 2018, 15, 415–421.
Crossref Google Scholar
[45]

Wu, M. J.; Song, J. P.; Lei, J. H.; Tang, H. L. An artificial interphase enables stable PVDF-based solid-state Li metal batteries. Nano Res. 2024, 17, 1482–1490
Crossref Google Scholar
[46]

Huang, Y. F.; Gu, T.; Rui, G. C.; Shi, P. R.; Fu, W. B.; Chen, L.; Liu, X. T.; Zeng, J. P.; Kang, B. H.; Yan, Z. C. et al. A relaxor ferroelectric polymer with an ultrahigh dielectric constant largely promotes the dissociation of lithium salts to achieve high ionic conductivity. Energy Environ. Sci. 2021, 14, 6021–6029.
Crossref Google Scholar
[47]

Ryu, H. H.; Namkoong, B.; Kim, J. H.; Belharouak, I.; Yoon, C. S.; Sun, Y. K. Capacity fading mechanisms in Ni-rich single-crystal NCM cathodes. ACS Energy Lett. 2021, 6, 2726–2734.
Crossref Google Scholar
Nano Research
Volume 17 Issue 6,
June 2024
Pages 5159-5167
DOI: 10.1007/s12274-024-6439-2
Cite this article:
Zhang X, Zhang Y, Zhou S, et al. Formatted PVDF in lamellar composite solid electrolyte for solid-state lithium metal battery. Nano Research, 2024, 17(6): 5159-5167. https://doi.org/10.1007/s12274-024-6439-2
Topics:
Lithium batteries

607

Views

3

Crossref

2

Web of Science

3

Scopus

0

CSCD

Altmetrics
Received: 05 November 2023
Revised: 19 December 2023
Accepted: 21 December 2023
Published: 01 February 2024
© Tsinghua University Press 2024
Return