Phosphate‐functionalized Zirconium Metal–Organic Frameworks for Enhancing Lithium–Sulfur Battery Cycling

Liu, Bingqian; Baumann, Avery E.; Butala, Megan M.; Thoi, V. Sara

doi:10.1002/chem.202300821

Title: Phosphate‐functionalized Zirconium Metal–Organic Frameworks for Enhancing Lithium–Sulfur Battery Cycling

Journal Article · 29 May 2023 · Chemistry - A European Journal

DOI: https://doi.org/10.1002/chem.202300821 · OSTI ID:1983442

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Department of Chemistry Johns Hopkins University Baltimore MD 21218 United States
Department of Chemistry Johns Hopkins University Baltimore MD 21218 United States, National Institute of Standards and Technology Gaithersburg MD 20899 USA
National Institute of Standards and Technology Gaithersburg MD 20899 USA, Department of Materials Science and Engineering University of Florida Gainesville FL 32611 USA
Department of Chemistry Johns Hopkins University Baltimore MD 21218 United States, Department of Materials Science and Engineering Johns Hopkins University Baltimore MD 21218 United States

Abstract Lithium–sulfur batteries are promising candidates for next‐generation energy storage devices due to their outstanding theoretical energy density. However, they suffer from low sulfur utilization and poor cyclability, greatly limiting their practical implementation. Herein, we adopted a phosphate‐functionalized zirconium metal–organic framework (Zr‐MOF) as a sulfur host. With their porous structure, remarkable electrochemical stability, and synthetic versatility, Zr‐MOFs present great potential in preventing soluble polysulfides from leaching. Phosphate groups were introduced to the framework post‐synthetically since they have shown a strong affinity towards lithium polysulfides and an ability to facilitate Li ion transport. The successful incorporation of phosphate in MOF‐808 was demonstrated by a series of techniques including infrared spectroscopy, solid‐state nuclear magnetic resonance spectroscopy, and X‐ray pair distribution function analysis. When employed in batteries, phosphate‐functionalized Zr‐MOF (MOF‐808‐PO4) exhibits significantly enhanced sulfur utilization and ion diffusion compared to the parent framework, leading to higher capacity and rate capability. The improved capacity retention and inhibited self‐discharge rate also demonstrate effective polysulfide encapsulation utilizing MOF‐808‐PO4. Furthermore, we explored their potential towards high‐density batteries by examining the cycling performance at various sulfur loadings. Our approach to correlate structure with function using hybrid inorganic–organic materials offers new chemical design strategies for advancing battery materials.

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Sponsoring Organization:: USDOE

OSTI ID:: 1983442

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 40 Vol. 29; ISSN 0947-6539

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (64)

A Soft Approach to Encapsulate Sulfur: Polyaniline Nanotubes for Lithium-Sulfur Batteries with Long Cycle Life Xiao, Lifen; Cao, Yuliang; Xiao, Jie Advanced Materials, Vol. 24, Issue 9, p. 1176-1181 https://doi.org/10.1002/adma.201103392	journal	January 2012
Lithium-Sulfur Batteries: Progress and Prospects Manthiram, Arumugam; Chung, Sheng-Heng; Zu, Chenxi Advanced Materials, Vol. 27, Issue 12 https://doi.org/10.1002/adma.201405115	journal	February 2015
Creating Lithium-Ion Electrolytes with Biomimetic Ionic Channels in Metal-Organic Frameworks Shen, Li; Wu, Hao Bin; Liu, Fang Advanced Materials, Vol. 30, Issue 23 https://doi.org/10.1002/adma.201707476	journal	April 2018
A High Conductivity 1D π–d Conjugated Metal–Organic Framework with Efficient Polysulfide Trapping‐Diffusion‐Catalysis in Lithium–Sulfur Batteries Yang, Dawei; Liang, Zhifu; Tang, Pengyi Advanced Materials, Vol. 34, Issue 10 https://doi.org/10.1002/adma.202108835	journal	January 2022
Strongly Coupled Interfaces between a Heterogeneous Carbon Host and a Sulfur-Containing Guest for Highly Stable Lithium-Sulfur Batteries: Mechanistic Insight into Capacity Degradation Peng, Hong-Jie; Hou, Ting-Zheng; Zhang, Qiang Advanced Materials Interfaces, Vol. 1, Issue 7 https://doi.org/10.1002/admi.201400227	journal	July 2014
Lithium-Sulfur Cells: The Gap between the State-of-the-Art and the Requirements for High Energy Battery Cells Hagen, Markus; Hanselmann, Dominik; Ahlbrecht, Katharina Advanced Energy Materials, Vol. 5, Issue 16, 1401986 https://doi.org/10.1002/aenm.201401986	journal	April 2015
A Nonflammable and Thermotolerant Separator Suppresses Polysulfide Dissolution for Safe and Long-Cycle Lithium-Sulfur Batteries Lei, Tianyu; Chen, Wei; Hu, Yin Advanced Energy Materials, Vol. 8, Issue 32 https://doi.org/10.1002/aenm.201802441	journal	September 2018
Highly Solvating Electrolytes for Lithium–Sulfur Batteries Gupta, Abhay; Bhargav, Amruth; Manthiram, Arumugam Advanced Energy Materials, Vol. 9, Issue 6 https://doi.org/10.1002/aenm.201803096	journal	December 2018
Strategies toward High‐Loading Lithium–Sulfur Battery Hu, Yin; Chen, Wei; Lei, Tianyu Advanced Energy Materials, Vol. 10, Issue 17 https://doi.org/10.1002/aenm.202000082	journal	March 2020
Metal-Organic Frameworks for High Charge-Discharge Rates in Lithium-Sulfur Batteries Jiang, Haoqing; Liu, Xiao-Chen; Wu, Yushan Angewandte Chemie International Edition, Vol. 57, Issue 15 https://doi.org/10.1002/anie.201712872	journal	February 2018
A Metal–Organic Framework with Tetrahedral Aluminate Sites as a Single‐Ion Li ⁺ Solid Electrolyte Fischer, Sabrina; Roeser, Jérôme; Lin, Terri C. Angewandte Chemie International Edition, Vol. 57, Issue 51 https://doi.org/10.1002/anie.201808885	journal	December 2018
An Intrinsic Flame-Retardant Organic Electrolyte for Safe Lithium-Sulfur Batteries Yang, Huijun; Guo, Cheng; Chen, Jiahang Angewandte Chemie International Edition, Vol. 58, Issue 3 https://doi.org/10.1002/anie.201811291	journal	December 2018
The Chemistry of Nucleation: In Situ Pair Distribution Function Analysis of Secondary Building Units During UiO‐66 MOF Formation Xu, Hui; Sommer, Sanna; Broge, Nils Lau Nyborg Chemistry – A European Journal, Vol. 25, Issue 8 https://doi.org/10.1002/chem.201805024	journal	January 2019
2D Sandwich‐Like α‐Zirconium Phosphate/Polypyrrole: Moderate Catalytic Activity and True Sulfur Confinement for High‐Performance Lithium–Sulfur Batteries Liu, Ye; Yan, Wenjun; Zhang, Wei ChemSusChem, Vol. 12, Issue 23 https://doi.org/10.1002/cssc.201902227	journal	November 2019
Bimetallic Metal‐Organic Framework with High‐Adsorption Capacity toward Lithium Polysulfides for Lithium–sulfur Batteries Geng, Pengbiao; Du, Meng; Guo, Xiaotian ENERGY & ENVIRONMENTAL MATERIALS, Vol. 5, Issue 2 https://doi.org/10.1002/eem2.12196	journal	June 2021
A Highly Conductive MOF of Graphene Analogue Ni ₃ (HITP) ₂ as a Sulfur Host for High‐Performance Lithium–Sulfur Batteries Cai, Dong; Lu, Mengjie; Li, La Small, Vol. 15, Issue 44 https://doi.org/10.1002/smll.201902605	journal	September 2019
Charge/discharge characteristics of sulfurized polyacrylonitrile composite with different sulfur content in carbonate based electrolyte for lithium batteries Wang, Li; He, Xiangming; Li, Jianjun Electrochimica Acta, Vol. 72 https://doi.org/10.1016/j.electacta.2012.04.005	journal	June 2012
Dual-engineered separator for highly robust, all-climate lithium-sulfur batteries Ma, Cheng; Feng, Yiming; Liu, Xuejun Energy Storage Materials, Vol. 32 https://doi.org/10.1016/j.ensm.2020.07.034	journal	November 2020
Phosphate-dependent morphological evolution of hydroxyapatite and implication for biomineralisation Jiang, Shu-Dong; Yao, Qi-Zhi; Ma, Yi-Fei Gondwana Research, Vol. 28, Issue 2 https://doi.org/10.1016/j.gr.2014.04.005	journal	September 2015
A facile approach to fabricate an immobilized-phosphate zirconium-based metal-organic framework composite (UiO-66-P) and its activity in the adsorption and separation of organic dyes Yang, Ji-Min Journal of Colloid and Interface Science, Vol. 505 https://doi.org/10.1016/j.jcis.2017.05.040	journal	November 2017
Metal-Organic Frameworks for Batteries Zhao, Ruo; Liang, Zibin; Zou, Ruqiang Joule, Vol. 2, Issue 11 https://doi.org/10.1016/j.joule.2018.09.019	journal	November 2018
A study of the electrochemical processes in lithium–sulphur cells by impedance spectroscopy Kolosnitsyn, V. S.; Kuzmina, E. V.; Karaseva, E. V. Journal of Power Sources, Vol. 196, Issue 3 https://doi.org/10.1016/j.jpowsour.2010.08.105	journal	February 2011
Developing porous carbon with dihydrogen phosphate groups as sulfur host for high performance lithium sulfur batteries Cui, Yanhui; Zhang, Qi; Wu, Junwei Journal of Power Sources, Vol. 378 https://doi.org/10.1016/j.jpowsour.2017.12.027	journal	February 2018
Modulating charge transport in MOFs with zirconium oxide nodes and redox-active linkers for lithium sulfur batteries Liu, Bingqian; Baumann, Avery E.; Thoi, V. Sara Polyhedron, Vol. 170 https://doi.org/10.1016/j.poly.2019.06.044	journal	September 2019
Improving Charge Transfer in Metal–Organic Frameworks through Open Site Functionalization and Porosity Selection for Li–S Batteries Liu, Bingqian; Thoi, V. Sara Chemistry of Materials, Vol. 32, Issue 19 https://doi.org/10.1021/acs.chemmater.0c02438	journal	September 2020
Promises and Challenges of Next-Generation “Beyond Li-ion” Batteries for Electric Vehicles and Grid Decarbonization Tian, Yaosen; Zeng, Guobo; Rutt, Ann Chemical Reviews, Vol. 121, Issue 3 https://doi.org/10.1021/acs.chemrev.0c00767	journal	December 2020
Selective Metal–Organic Framework Catalysis of Glucose to 5-Hydroxymethylfurfural Using Phosphate-Modified NU-1000 Yabushita, Mizuho; Li, Peng; Islamoglu, Timur Industrial & Engineering Chemistry Research, Vol. 56, Issue 25 https://doi.org/10.1021/acs.iecr.7b01164	journal	June 2017
Realizing High Utilization of High-Mass-Loading Sulfur Cathode via Electrode Nanopore Regulation Tu, Shuibin; Chen, Zihe; Zhang, Bao Nano Letters, Vol. 22, Issue 14 https://doi.org/10.1021/acs.nanolett.2c02258	journal	July 2022
Graphene–Metal–Organic Framework Composite Sulfur Electrodes for Li–S Batteries with High Volumetric Capacity Baumann, Avery E.; Downing, Julia R.; Burns, David A. ACS Applied Materials & Interfaces, Vol. 12, Issue 33 https://doi.org/10.1021/acsami.0c09622	journal	August 2020
Chemical Sulfide Tethering Improves Low-Temperature Li–S Battery Cycling Burns, David A.; Baumann, Avery E.; Bennett, Kevin J. ACS Applied Materials & Interfaces, Vol. 13, Issue 43 https://doi.org/10.1021/acsami.1c12129	journal	October 2021
Mixed-Metal–Organic Framework with Effective Lewis Acidic Sites for Sulfur Confinement in High-Performance Lithium–Sulfur Batteries Wang, Ziqi; Wang, Buxue; Yang, Yu ACS Applied Materials & Interfaces, Vol. 7, Issue 37 https://doi.org/10.1021/acsami.5b07024	journal	September 2015
Dual Core–Shell-Structured S@C@MnO₂ Nanocomposite for Highly Stable Lithium–Sulfur Batteries Ni, Lubin; Zhao, Gangjin; Yang, Guang ACS Applied Materials & Interfaces, Vol. 9, Issue 40 https://doi.org/10.1021/acsami.7b07996	journal	September 2017
Lithiated Defect Sites in Zr Metal–Organic Framework for Enhanced Sulfur Utilization in Li–S Batteries Baumann, Avery E.; Burns, David A.; Díaz, José C. ACS Applied Materials & Interfaces, Vol. 11, Issue 2 https://doi.org/10.1021/acsami.8b19034	journal	December 2018
Highly Reversible Lithium-Metal Anode and Lithium–Sulfur Batteries Enabled by an Intrinsic Safe Electrolyte Chen, Jiahang; Yang, Huijun; Zhang, Xuan ACS Applied Materials & Interfaces, Vol. 11, Issue 36 https://doi.org/10.1021/acsami.9b09215	journal	August 2019
A Perspective toward Practical Lithium–Sulfur Batteries Zhao, Meng; Li, Bo-Quan; Zhang, Xue-Qiang ACS Central Science, Vol. 6, Issue 7 https://doi.org/10.1021/acscentsci.0c00449	journal	June 2020
An Aqueous Inorganic Polymer Binder for High Performance Lithium–Sulfur Batteries with Flame-Retardant Properties Zhou, Guangmin; Liu, Kai; Fan, Yanchen ACS Central Science, Vol. 4, Issue 2 https://doi.org/10.1021/acscentsci.7b00569	journal	February 2018
Conductive Porous Laminated Vanadium Nitride as Carbon-Free Hosts for High-Loading Sulfur Cathodes in Lithium–Sulfur Batteries Liu, Ruiqing; Liu, Wenhui; Bu, Yali ACS Nano, Vol. 14, Issue 12 https://doi.org/10.1021/acsnano.0c07415	journal	November 2020
Niobium Diboride Nanoparticles Accelerating Polysulfide Conversion and Directing Li₂S Nucleation Enabled High Areal Capacity Lithium–Sulfur Batteries Wang, Bin; Wang, Lu; Zhang, Bo ACS Nano, Vol. 16, Issue 3 https://doi.org/10.1021/acsnano.2c01179	journal	March 2022
Challenges and Prospects of Lithium–Sulfur Batteries Manthiram, Arumugam; Fu, Yongzhu; Su, Yu-Sheng Accounts of Chemical Research, Vol. 46, Issue 5 https://doi.org/10.1021/ar300179v	journal	June 2012
MOF Functionalization via Solvent-Assisted Ligand Incorporation: Phosphonates vs Carboxylates Deria, Pravas; Bury, Wojciech; Hod, Idan Inorganic Chemistry, Vol. 54, Issue 5 https://doi.org/10.1021/ic502639v	journal	February 2015
Superacidity in Sulfated Metal–Organic Framework-808 Jiang, Juncong; Gándara, Felipe; Zhang, Yue-Biao Journal of the American Chemical Society, Vol. 136, Issue 37 https://doi.org/10.1021/ja507119n	journal	September 2014
General and Direct Method for Preparing Oligonucleotide-Functionalized Metal–Organic Framework Nanoparticles Wang, Shunzhi; McGuirk, C. Michael; Ross, Michael B. Journal of the American Chemical Society, Vol. 139, Issue 29 https://doi.org/10.1021/jacs.7b05633	journal	July 2017
Lithium Thiophosphate Functionalized Zirconium MOFs for Li–S Batteries with Enhanced Rate Capabilities Baumann, Avery E.; Han, Xu; Butala, Megan M. Journal of the American Chemical Society, Vol. 141, Issue 44 https://doi.org/10.1021/jacs.9b09538	journal	October 2019
Employing Conductive Metal–Organic Frameworks for Voltammetric Detection of Neurochemicals Ko, Michael; Mendecki, Lukasz; Eagleton, Aileen M. Journal of the American Chemical Society, Vol. 142, Issue 27 https://doi.org/10.1021/jacs.9b13402	journal	March 2020
Amphiphilic Surface Modification of Hollow Carbon Nanofibers for Improved Cycle Life of Lithium Sulfur Batteries Zheng, Guangyuan; Zhang, Qianfan; Cha, Judy J. Nano Letters, Vol. 13, Issue 3, p. 1265-1270 https://doi.org/10.1021/nl304795g	journal	February 2013
Permselective Graphene Oxide Membrane for Highly Stable and Anti-Self-Discharge Lithium–Sulfur Batteries Huang, Jia-Qi; Zhuang, Ting-Zhou; Zhang, Qiang ACS Nano, Vol. 9, Issue 3 https://doi.org/10.1021/nn507178a	journal	February 2015
Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design Tao, Xinyong; Wang, Jianguo; Liu, Chong Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11203	journal	April 2016
Conductive MOF electrodes for stable supercapacitors with high areal capacitance Sheberla, Dennis; Bachman, John C.; Elias, Joseph S. Nature Materials, Vol. 16, Issue 2 https://doi.org/10.1038/nmat4766	journal	October 2016
U1 snRNP regulates cancer cell migration and invasion in vitro Oh, Jung-Min; Venters, Christopher C.; Di, Chao Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-019-13993-7	journal	January 2020
Understanding disorder and linker deficiency in porphyrinic zirconium-based metal–organic frameworks by resolving the Zr8O6 cluster conundrum in PCN-221 Koschnick, Charlotte; Stäglich, Robert; Scholz, Tanja Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23348-w	journal	May 2021
Metal-organic framework functionalization and design strategies for advanced electrochemical energy storage devices Baumann, Avery E.; Burns, David A.; Liu, Bingqian Communications Chemistry, Vol. 2, Issue 1 https://doi.org/10.1038/s42004-019-0184-6	journal	July 2019
Atomic resolution tracking of nerve-agent simulant decomposition and host metal–organic framework response in real space Terban, Maxwell W.; Ghose, Sanjit K.; Plonka, Anna M. Communications Chemistry, Vol. 4, Issue 1 https://doi.org/10.1038/s42004-020-00439-1	journal	January 2021
Rational design of a metal–organic framework host for sulfur storage in fast, long-cycle Li–S batteries Zhou, Junwen; Li, Rui; Fan, Xinxin Energy & Environmental Science, Vol. 7, Issue 8 https://doi.org/10.1039/C4EE01382D	journal	January 2014
Connecting defects and amorphization in UiO-66 and MIL-140 metal–organic frameworks: a combined experimental and computational study Bennett, Thomas D.; Todorova, Tanya K.; Baxter, Emma F. Physical Chemistry Chemical Physics, Vol. 18, Issue 3 https://doi.org/10.1039/C5CP06798G	journal	January 2016
Zr-based metal–organic frameworks: design, synthesis, structure, and applications Bai, Yan; Dou, Yibo; Xie, Lin-Hua Chemical Society Reviews, Vol. 45, Issue 8 https://doi.org/10.1039/C5CS00837A	journal	January 2016
A graphene-like metallic cathode host for long-life and high-loading lithium–sulfur batteries Pang, Quan; Kundu, Dipan; Nazar, Linda F. Materials Horizons, Vol. 3, Issue 2 https://doi.org/10.1039/C5MH00246J	journal	January 2016
A heterogenized Ni-doped zeolitic imidazolate framework to guide efficient trapping and catalytic conversion of polysulfides for greatly improved lithium–sulfur batteries Yang, Yuxiang; Wang, Zhenhua; Jiang, Taizhi Journal of Materials Chemistry A, Vol. 6, Issue 28 https://doi.org/10.1039/C8TA05176C	journal	January 2018
Metal–organic frameworks for lithium–sulfur batteries Zheng, Yan; Zheng, Shasha; Xue, Huaiguo Journal of Materials Chemistry A, Vol. 7, Issue 8 https://doi.org/10.1039/C8TA11075A	journal	January 2019
Tailored porous framework materials for advancing lithium–sulfur batteries Liu, Bingqian; Thoi, V. Sara Chemical Communications, Vol. 58, Issue 25 https://doi.org/10.1039/D1CC07087H	journal	January 2022
Zirconium phosphate supported tungsten oxide solid acid catalysts for the esterification of palmitic acid Rao, Katabathini Narasimha; Sridhar, Adapa; Lee, Adam F. Green Chemistry, Vol. 8, Issue 9 https://doi.org/10.1039/b606088a	journal	January 2006
Two-dimensional detector software: From real detector to idealised image or two-theta scan Hammersley, A. P.; Svensson, S. O.; Hanfland, M. High Pressure Research, Vol. 14, Issue 4-6, p. 235-248 https://doi.org/10.1080/08957959608201408	journal	January 1996
PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals Farrow, C. L.; Juhas, P.; Liu, J. W. Journal of Physics: Condensed Matter, Vol. 19, Issue 33 https://doi.org/10.1088/0953-8984/19/33/335219	journal	July 2007
PDFgetX3 : a rapid and highly automatable program for processing powder diffraction data into total scattering pair distribution functions Juhás, P.; Davis, T.; Farrow, C. L. Journal of Applied Crystallography, Vol. 46, Issue 2 https://doi.org/10.1107/S0021889813005190	journal	March 2013
Zr-Based MOF-808 as Meerwein–Ponndorf–Verley Reduction Catalyst for Challenging Carbonyl Compounds Plessers, Eva; Fu, Guangxia; Tan, Collin Catalysts, Vol. 6, Issue 7 https://doi.org/10.3390/catal6070104	journal	July 2016

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