Journal Home > Volume 1 , Issue 1
Energy Materials and Devices 2023, 1(1): 9370004 https://doi.org/10.26599/EMD.2023.9370004
Research Article | Open Access | Issue | Published: 21 September 2023

Functional LiTaO3 filler with tandem conductivity and ferroelectricity for PVDF-based composite solid-state electrolyte

Show Author's Information Yu Yuan1,2,†,  Likun Chen1,2,†,  Yuhang Li1,2,  Xufei An1,2,  Jianshuai Lv1,2,  Shaoke Guo1,2,  Xing Cheng1,2,  Yang Zhao1,2,  Ming Liu1( ),  Yan-Bing He1( ),  Feiyu Kang1,2
Shenzhen All-Solid-State Lithium Battery Electrolyte Engineering Research Center, Institute of Materials Research (IMR), Tsinghua Shenzhen International Graduate School, Shenzhen 518055, China
School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China

† Yu Yuan and Likun Chen contributed equally to this work.

Keywords:
ferroelectric ion conductor, composite solid-state electrolytes, space charge layer, Li deposition
Cite this article:
Yuan Y, Chen L, Li Y, et al. Functional LiTaO3 filler with tandem conductivity and ferroelectricity for PVDF-based composite solid-state electrolyte. Energy Materials and Devices, 2023, 1(1): 9370004. https://doi.org/10.26599/EMD.2023.9370004
Download citation
EndNote(RIS)
BibTeX

5464

Views

1630

Downloads

Citations

7

Crossref

N/A

WoS

N/A

Scopus

N/A

CSCD

Abstract Full text Electronic supplementary material About this article

Composite solid-state electrolytes have received significant attention due to their combined advantages as inorganic and polymer electrolytes. However, conventional ceramic fillers offer limited ion conductivity enhancement for composite solid-state electrolytes due to the space-charge layer between the polymer matrix and ceramic phase. In this study, we develop a ferroelectric ceramic ion conductor (LiTaO3) as a functional filler to simultaneously alleviate the space-charge layer and provide an extra Li+ transport pathway. The obtained composite solid-state electrolyte comprising LiTaO3 filler and poly (vinylidene difluoride) matrix (P-LTO15) achieves an ionic conductivity of 4.90 × 10−4 S cm−1 and a Li+ transference number of 0.45. The polarized ferroelectric LiTaO3 creates a uniform electric field and promotes homogenous Li plating/stripping, providing the Li symmetrical batteries with an ultrastable cycle life for 4000 h at 0.1 mA cm−2 and a low polarization overpotential (~50 mV). Furthermore, the solid-state NCM811/P-LTO15/Li full batteries achieve an ultralong cycling performance (1400 cycles) at 1 C and a high discharge capacity of 102.1 mAh g−1 at 5 C. This work sheds light on the design of functional ceramic fillers for composite solid-state electrolytes to effectively enhance ion conductivity and battery performance.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

Functional LiTaO3 filler with tandem conductivity and ferroelectricity for PVDF-based composite solid-state electrolyte

Show Author's information Yu Yuan1,2,†, Likun Chen1,2,†, Yuhang Li1,2, Xufei An1,2, Jianshuai Lv1,2, Shaoke Guo1,2, Xing Cheng1,2, Yang Zhao1,2, Ming Liu1( ), Yan-Bing He1( ), Feiyu Kang1,2
Shenzhen All-Solid-State Lithium Battery Electrolyte Engineering Research Center, Institute of Materials Research (IMR), Tsinghua Shenzhen International Graduate School, Shenzhen 518055, China
School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China

† Yu Yuan and Likun Chen contributed equally to this work.

Abstract

Composite solid-state electrolytes have received significant attention due to their combined advantages as inorganic and polymer electrolytes. However, conventional ceramic fillers offer limited ion conductivity enhancement for composite solid-state electrolytes due to the space-charge layer between the polymer matrix and ceramic phase. In this study, we develop a ferroelectric ceramic ion conductor (LiTaO3) as a functional filler to simultaneously alleviate the space-charge layer and provide an extra Li+ transport pathway. The obtained composite solid-state electrolyte comprising LiTaO3 filler and poly (vinylidene difluoride) matrix (P-LTO15) achieves an ionic conductivity of 4.90 × 10−4 S cm−1 and a Li+ transference number of 0.45. The polarized ferroelectric LiTaO3 creates a uniform electric field and promotes homogenous Li plating/stripping, providing the Li symmetrical batteries with an ultrastable cycle life for 4000 h at 0.1 mA cm−2 and a low polarization overpotential (~50 mV). Furthermore, the solid-state NCM811/P-LTO15/Li full batteries achieve an ultralong cycling performance (1400 cycles) at 1 C and a high discharge capacity of 102.1 mAh g−1 at 5 C. This work sheds light on the design of functional ceramic fillers for composite solid-state electrolytes to effectively enhance ion conductivity and battery performance.

Keywords: ferroelectric ion conductor, composite solid-state electrolytes, space charge layer, Li deposition

References(40)

[1]
a) Zhao, Q., Stalin, S., Zhao, C. Z., Archer, L. A. (2020). Designing solid-state electrolytes for safe, energy-dense batteries. Nat. Rev. Mater. 5, 229–252. b) Famprikis, T., Canepa, P., Dawson, J. A., Islam, M. S., Masquelier, C. (2019). Fundamentals of inorganic solid-state electrolytes for batteries. Nat. Mater. 18, 1278–1291.
DOI
[2]

Tan, D. H. S., Banerjee, A., Chen, Z., Meng, Y. S. (2020). From nanoscale interface characterization to sustainable energy storage using all-solid-state batteries. Nat. Nanotechnol. 15, 170–180.
DOI Google Scholar
[3]

Chen, Z., Kim, G. T., Kim, J. K., Zarrabeitia, M., Kuenzel, M., Liang, H. P., Geiger, D., Kaiser, U., Passerini, S. (2021). Highly stable quasi-solid-state lithium metal batteries: reinforced Li1.3Al0.3Ti1.7(PO4)3/Li interface by a protection interlayer. Adv. Energy. Mater. 11, 2101339.
DOI Google Scholar
[4]

Yu, C., Zhao, F. P., Luo, J., Zhang, L., Sun, X. L. (2021). Recent development of lithium argyrodite solid-state electrolytes for solid-state batteries: synthesis, structure, stability and dynamics. Nano Energy. 83, 105858.
DOI Google Scholar
[5]

Wan, H. L., Liu, S. F., Deng, T., Xu, J. J., Zhang, J. X., He, X. Z., Ji, X., Yao, X. Y., Wang, C. S. (2021). Bifunctional interphase-enabled Li10GeP2S12 electrolytes for lithium-sulfur battery. ACS Energy Lett. 6, 862–868.
DOI Google Scholar
[6]

Xu, L. Q., Li, J. Y., Deng, W. T., Shuai, H. L., Li, S., Xu, Z. F., Li, J. H., Hou, H. S., Peng, H. J., Zou, G. Q., et al. (2021). Garnet solid electrolyte for advanced all-solid-state Li batteries. Adv. Energy Mater. 11, 2000648.
DOI Google Scholar
[7]

Liu, H., Cheng, X. B., Huang, J. Q., Yuan, H., Lu, Y., Yan, C., Zhu, G. L., Xu, R., Zhao, C. Z., Hou, L. P., et al. (2020). Controlling dendrite growth in solid-state electrolytes. ACS Energy Lett. 5, 833–843.
DOI Google Scholar
[8]

Nie, K. H., Wang, X. L., Qiu, J. L., Wang, Y., Yang, Q., Xu, J. J., Yu, X. Q., Li, H., Huang, X. J., Chen, L. Q. (2020). Increasing poly(ethylene oxide) stability to 4.5 V by surface coating of the cathode. ACS Energy Lett. 5, 826–832.
DOI Google Scholar
[9]

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. (2022). Topology crafting of polyvinylidene difluoride electrolyte creates ultra-long cycling high-voltage lithium metal solid-state batteries. Energy Storage Mater. 48, 375–383.
DOI Google Scholar
[10]

Zhou, D., He, Y. B., Liu, R. L., Liu, M., Du, H. D., Li, B. H., Cai, Q., Yang, Q. H., Kang, F. Y. (2015). In situ synthesis of a hierarchical all-solid-state electrolyte based on nitrile materials for high-performance lithium-ion batteries. Adv. Energy Mater. 5, 1500353.
DOI Google Scholar
[11]

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. (2021). 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. 60, 24668–24675.
DOI Google Scholar
[12]

Xin, S., You, Y., Wang, S. F., Gao, H. C., Yin, Y. X., Guo, Y. G. (2017). Solid-state lithium metal batteries promoted by nanotechnology: progress and prospects. ACS Energy Lett. 2, 1385–1394.
DOI Google Scholar
[13]

Yu, Q. J., Jiang, K. C., Yu, C. L., Chen, X. J., Zhang, C. J., Yao, Y., Jiang, B., Long, H. J. (2021). Recent progress of composite solid polymer electrolytes for all-solid-state lithium metal batteries. Chin. Chem. Lett. 32, 2659–2678.
DOI Google Scholar
[14]

Na, Y., Chen, Z., Xu, Z. K., An, Q., Zhang, X., Sun, X. H., Cai, S., Zheng, C. M. (2022). Novel fast lithium-ion conductor LiTa2PO8 enhances the performance of poly(ethylene oxide)-based polymer electrolytes in all-solid-state lithium metal batteries. Chin. Chem. Lett. 33, 4037–4042.
DOI Google Scholar
[15]

Liu, L., Zhang, D. C., Zhao, J. W., Shen, J. D., Li, F. K., Yang, Y., Liu, Z. B., He, W. X., Zhao, W. M., Liu, J. (2022). Synergistic effect of lithium salts with fillers and solvents in composite electrolytes for superior room-temperature solid-state lithium batteries. ACS Appl. Energy Mater. 5, 2484–2494.
DOI Google Scholar
[16]

Popovic, J., Hasegawa, G., Moudrakovski, I., Maier, J. (2016). Infiltrated porous oxide monoliths as high lithium transference number electrolytes. J. Mater. Chem. A. 4, 7135–7140.
DOI Google Scholar
[17]

Zhou, D., Liu, R. L., He, Y. B., Li, F. Y., Liu, M., Li, B. H., Yang, Q. H., Cai, Q., Kang, F. Y. (2016). SiO2 hollow nanosphere-based composite solid electrolyte for lithium metal batteries to suppress lithium dendrite growth and enhance cycle life. Adv. Energy Mater. 6, 1502214.
DOI Google Scholar
[18]
a) Lin, Z. X., Sheng, O. W., Cai, X. H., Duan, D., Yue, K., Nai, J. W., Wang, Y., Liu, T. F., Tao, X. Y., Liu, Y. J. (2023). Solid polymer electrolytes in all-solid-state lithium metal batteries: from microstructures to properties. J. Energy Chem. 81, 358–378. b) Zheng, J. F., Elgin, J., Shao, J. R., Wu, Y. Y. (2022). Differentiating grain and grain boundary ionic conductivities of Li-ion antiperovskite electrolytes. eScience 2, 639–645.
DOI
[19]

Zou, Z. Y., Li, Y. J., Lu, Z. H., Wang, D., Cui, Y. H., Guo, B. K., Li, Y. J., Liang, X. M., Feng, J. W., Li, H., et al. (2020). Mobile ions in composite solids. Chem. Rev. 120, 4169–4221.
DOI Google Scholar
[20]

Wang, L. L., Xie, R. C., Chen, B. B., Yu, X. R., Ma, J., Li, C., Hu, Z. W., Sun, X. W., Xu, C. J., Dong, S. M., et al. (2020). In-situ visualization of the space-charge-layer effect on interfacial lithium-ion transport in all-solid-state batteries. Nat. Commun. 11, 5889.
DOI Google Scholar
[21]
a) Jiang, B. B., Iocozzia, J., Zhao, L., Zhang, H. F., Harn, Y. W., Chen, Y. H., Lin, Z. Q. (2019). Barium titanate at the nanoscale: controlled synthesis and dielectric and ferroelectric properties. Chem. Soc. Rev. 48, 1194–1228. b) Guo, Y. P., Wang, R. Y., Cui, C., Xiong, R. D., Wei, Y. Q., Zhai, T. Y., Li, H. Q. (2020). Shaping Li deposits from wild dendrites to regular crystals via the ferroelectric effect. Nano Lett. 20, 7680–7687.
DOI
[22]
a) Gu, T., Chen, L. K., Huang, Y. F., Ma, J. B., Shi, P. R., Biao, J., Liu, M., Lv, W., He, Y. B. (2022). Engineering ferroelectric interlayer between Li1.3Al0.3Ti1.7(PO4)3 and lithium metal for stable solid-state batteries operating at room temperature. Energy Environ. Mater. in press. https://doi.org/10.1002/eem2.12531. b) Shi, P. R., Ma, J. B., Liu, M., Guo, S. K., Huang, Y. F., Wang, S. W., Zhang, L. H., Chen, L. K., Yang, K., Liu, X. T., et al. (2023). A dielectric electrolyte composite with high lithium-ion conductivity for high-voltage solid-state lithium metal batteries. Nat. Nanotechnol. 18, 602–610. https://doi.org/10.1038/s41565-023-01341-2.
DOI
[23]

Dai, Z. S., Wang, J. H., Zhao, H. L., Bai, Y. (2022). Surface coupling between mechanical and electric fields empowering Ni-rich cathodes with superior cyclabilities for lithium-ion batteries. Adv. Sci. 9, 2200622.
DOI Google Scholar
[24]

Glass, A. M., Lines, M. E., Nassau, K., Shiever, J. W. (1977). Anomalous dielectric behavior and reversible pyroelectricity in roller-quenched LiNbO3 and LiTaO3 glass. Appl. Phys. Lett. 31, 249–251.
DOI Google Scholar
[25]

Xue, D. F., Zhang, S. Y. (1998). Bond-charge calculation of nonlinear optical susceptibilities of LiXO3 type complex crystals. Chem. Phys. 226, 307–318.
DOI Google Scholar
[26]

Wang, W. M., Yi, E. Y., Fici, A. J., Laine, R. M., Kieffer, J. (2017). Lithium ion conducting poly(ethylene oxide)-based solid electrolytes containing active or passive ceramic nanoparticles. J. Phys. Chem. C. 121, 2563–2573.
DOI Google Scholar
[27]

Huo, H. Y., Chen, Y., Luo, J., Yang, X. F., Guo, X. X., Sun, X. L. (2019). Rational design of hierarchical "ceramic-in-polymer" and "polymer-in-ceramic" electrolytes for dendrite-free solid-state batteries. Adv. Energy Mater. 9, 1804004.
DOI Google Scholar
[28]

Zhang, Y., Wang, X. H., Feng, W., Zhen, Y. C., Zhao, P. Y., Li, L. T., Cai, Z. M. (2019). The effects of the size and content of BaTiO3 nanoparticles on solid polymer electrolytes for all-solid-state lithium-ion batteries. J. Solid State Electrochem. 23, 749–758.
DOI Google Scholar
[29]

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. (2017). 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. 139, 13779–13785.
DOI Google Scholar
[30]

Chen, L. K., Gu, T., Ma, J. B., Yang, K., Shi, P. R., Biao, J., Mi, J. S., Liu, M., Lv, W., He, Y. B. (2022). In situ construction of Li3N-enriched interface enabling ultra-stable solid-state LiNi0.8Co0.1Mn0.1O2/lithium metal batteries. Nano Energy. 100, 107470.
DOI Google Scholar
[31]

Martins, P., Lopes, A. C., Lanceros-Mendez, S. (2014). Electroactive phases of poly(vinylidene fluoride): determination, processing and applications. Prog. Polym. Sci. 39, 683–706.
DOI Google Scholar
[32]

Zhang, X., Han, J., Niu, X. F., Xin, C. Z., Xue, C. J., Wang, S., Shen, Y., Zhang, L., Li, L. L., Nan, C. W. (2020). High cycling stability for solid-state li metal batteries via regulating solvation effect in poly(vinylidene fluoride)-based electrolytes. Batteries Supercaps. 3, 876–883.
DOI Google Scholar
[33]

Quartarone, E., Mustarelli, P. (2011). Electrolytes for solid-state lithium rechargeable batteries: recent advances and perspectives. Chem. Soc. Rev. 40, 2525–2540.
DOI Google Scholar
[34]
a) Dong, G. H., Li, S. Z., Li, T., Wu, H. J., Nan, T. X., Wang, X. H., Liu, H. X., Cheng, Y. X., Zhou, Y. Q., Qu, W. B., et al. (2020). Periodic wrinkle-patterned single-crystalline ferroelectric oxide membranes with enhanced piezoelectricity. Adv. Mater. 32, 2004477. b) Feng, W. H., Yuan, J., Gao, F., Weng, B., Hu, W. T., Lei, Y. H., Huang, X. Y., Yang, L., Shen, J., Xu, D. F., et al. (2020). Piezopotential-driven simulated electrocatalytic nanosystem of ultrasmall MoC quantum dots encapsulated in ultrathin N-doped graphene vesicles for superhigh H2 production from pure water. Nano Energy 75, 104990. c) Zhang, H. Y., Chen, X. G., Tang, Y. Y., Liao, W. Q., Di, F. F., Mu, X., Peng, H., Xiong, R. G. (2021). PFM (piezoresponse force microscopy)-aided design for molecular ferroelectrics. Chem. Soc. Rev. 50, 8248–8278.
DOI
[35]

Liang, J. Y., Zeng, X. X., Zhang, X. D., Zuo, T. T., Yan, M., Yin, Y. X., Shi, J. L., Wu, X. W., Guo, Y. G., Wan, L. J. (2019). Engineering janus interfaces of ceramic electrolyte via distinct functional polymers for stable high-voltage li-metal batteries. J. Am. Chem. Soc. 141, 9165–9169.
DOI Google Scholar
[36]
a) Zhang, X., Wang, S., Xue, C. J., Xin, C. Z., Lin, Y. H., Shen, Y., Li, L. L., Nan, C. W. (2019). Self-suppression of lithium dendrite in all-solid-state lithium metal batteries with poly(vinylidene difluoride)-based solid electrolytes. Adv. Mater. 31, 1806082. b) Chen, J. H., Zhang, Y., Lu, H. C., Ding, J., Wang, X. C., Huang, Y. D., Ma, H. Y., Wang, J. L. (2023). Electrolyte solvation chemistry to construct an anion-tuned interphase for stable high-temperature lithium metal batteries. eScience 3, 100135.
DOI
[37]

Xia, S. H., Zhao, Y., Yan, J. H., Yu, J. Y., Ding, B. (2021). Dynamic regulation of lithium dendrite growth with electromechanical coupling effect of soft BaTiO3 ceramic nanofiber films. ACS Nano. 15, 3161–3170.
DOI Google Scholar
[38]

Liu, Y. Y., Xu, X. Y., Kapitanova, O. O., Evdokimov, P. V., Song, Z. X., Matic, A., Xiong, S. Z. (2022). Electro-chemo-mechanical modeling of artificial solid electrolyte interphase to enable uniform electrodeposition of lithium metal anodes. Adv. Energy Mater. 12, 2103589.
DOI Google Scholar
[39]

Manjunatha, H., Venkatesha, T. V., Suresh, G. S. (2012). Electrochemical studies of LiMnPO4 as aqueous rechargeable lithium-ion battery electrode. J. Solid State Electrochem. 16, 1941–1952.
DOI Google Scholar
[40]

Xu, F. L., Deng, S. G., Guo, Q. Y., Zhou, D., Yao, X. Y. (2021). Quasi-ionic liquid enabling single-phase poly(vinylidene fluoride)-based polymer electrolytes for solid-state LiNi0.6Co0.2Mn0.2O2 || Li batteries with rigid-flexible coupling interphase. Small Methods. 5, 2100262.
DOI Google Scholar
File
EMD-2023-0004-supplement-final.pdf (7.2 MB)
Publication history
Copyright
Acknowledgements
Rights and permissions

Publication history

Received: 04 August 2023
Revised: 26 August 2023
Accepted: 31 August 2023
Published: 21 September 2023
Issue date: September 2023

Copyright

© The Author(s) 2023. Published by Tsinghua University Press.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 52325206, U2001220 and 52203298), Key-Area Research and Development Program of Guangdong Province (No. 2020B090919001), Shenzhen. Shenzhen Outstanding Talents Training Fund. All-Solid-State Lithium Battery Electrolyte Engineering Research Center (XMHT20200203006), and Shenzhen Technical Plan Project (Nos. RCJC20200714114436091, YJ20220530143012027, JCYJ20220818101003007; JCYJ20220818101003008).

Rights and permissions

The articles published in this open access journal are distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

Return