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Atomically defined two-dimensional assembled nanoclusters for Li-ion batteries

Nature Synthesis (2025)Cite this article

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Abstract

When nanoclusters crystallize, weak supramolecular interactions lead to the formation of independent monomers (zero-dimensional molecular nodes), while strong intermolecular coordination promotes omnidirectional crystal packing into three-dimensional superstructures. However, achieving two-dimensional (2D) crystalline assembly, such as 2D grid networks, is more challenging. Here we achieve the 2D crystalline assembly of atomically precise metal nanoclusters by establishing intermolecular interactions between the peripheral carboxyl groups of cluster-based nodes and introduced alkali metal cations, forming an alkali metal-dependent and solvent-dependent 2D crystalline assembly. We also observe that the intercluster or interlayer alkali metal cations are mobile, allowing the materials to serve as cation sponges. The high ionic mobility of the cluster-based crystalline materials renders them efficient electrolytes for Li-ion batteries. Overall, these 2D assemblies of atomically precise crystalline nanoclusters provide a versatile platform for ion conduction and energy transmission.

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Fig. 1: Illustration of the construction of Ag29 nanocluster-assembled 2D crystal structures and a cluster-based 2D cation sponge.
Fig. 2: Construction of a cluster-assembled 2D crystal structure based on the Ag29-COOLi nanocluster in MeOH.
Fig. 3: Topology of 2D crystals of Ag29 nanoclusters.
Fig. 4: Prediction of the Li+ diffusion coefficient in Ag29-COOLi and Ag29-Li.
Fig. 5: Cluster-based crystalline materials as electrolytes.

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Data availability

All data supporting the findings of this study are included within the Article and its Supplementary Information. Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2370566 (Ag29-PPh3), 2370567 (Ag29-dimer), 2370568 (Ag29-Li), 2370781 (Ag29-COOLi-DMF), 2106345 (Ag29-COONa-DMF), 2370782 (Ag29-COOK-DMF), 2370587 (Ag29-COORb-DMF), 2370586 (Ag29-COOCs-DMF), 2370588 (Ag29-COOLi-MeOH), 2370591 (Ag29-COONa-MeOH), 2370592 (Ag29-COOK-MeOH), 2370593 (Ag29-COORb-MeOH) and 2370590 (Ag29-COOCs-MeOH). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. Source data are provided with this paper.

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Acknowledgements

We acknowledge the financial support of the NSFC (22371003, 22101001, 22471001, U24A20480 and 22473017), the Ministry of Education, Natural Science Foundation of Anhui Province (2408085Y006), the University Synergy Innovation Program of Anhui Province (GXXT-2020-053) and the Scientific Research Program of Universities in Anhui Province (2022AH030009).

Author information

Author notes

  1. These authors contributed equally: Xiao Wei, Zhou Huang.

Authors and Affiliations

  1. Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Anhui University, Hefei, China

    Xiao Wei, Haoqi Li, Xi Kang & Manzhou Zhu

  2. School of Materials Science and Engineering, Anhui University, Hefei, China

    Xiao Wei, Ximei Sun, Zhenjie Sun, Lingyun Zhu, Xi Kang & Manzhou Zhu

  3. School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Chemical Theory and Mechanism, Chongqing University, Chongqing, China

    Zhou Huang & Qing Tang

  4. National Key Laboratory of Opto-Electronic Information Acquisition and Protection Technology, Anhui University, Hefei, China

    Manzhou Zhu

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Contributions

X.K. and M.Z. conceived the initial idea. X.W. designed the research. X.W. and H.L. performed materials preparation, structural determination and characterization. L.Z., X.S. and Z.S. conducted the electrochemical performance tests. Q.T. and Z.H carried out the theoretical calculations. X.W., X.K., Q.T., L.Z. and M.Z. wrote the paper and all authors commented on it.

Corresponding authors

Correspondence to Qing Tang, Lingyun Zhu, Xi Kang or Manzhou Zhu.

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The authors declare no competing interests.

Peer review

Peer review information

Nature Synthesis thanks Puru Jena and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Peter Seavill, in collaboration with the Nature Synthesis team.

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Extended data

Extended Data Fig. 1 Quantitative estimation of the activation energy.

(a) Arrhenius plots of the Ag29-COOLi and Ag29-Li electrolytes. (b and c) Chronoamperometric profiles for extracting the electronic conductivity.

Source data

Supplementary information

Supplementary Information

Supplementary Figs. 1–78, Tables 1–13, Experiment and Characterization, ORTEP view of Ag29 nanoclusters system structure, Explanations for A and B alerts in Ag29 nanoclusters system structure.

Supplementary Data 1

Crystallographic data for Ag29-PPh3.

Supplementary Data 2

Crystallographic data for Ag29-dimer.

Supplementary Data 3

Crystallographic data for Ag29-Li.

Supplementary Data 4

Crystallographic data for Ag29-COOLi-DMF.

Supplementary Data 5

Crystallographic data for Ag29-COONa-DMF.

Supplementary Data 6

Crystallographic data for Ag29-COOK-DMF.

Supplementary Data 7

Crystallographic data for Ag29-COORb-DMF.

Supplementary Data 8

Crystallographic data for Ag29-COOCs-DMF.

Supplementary Data 9

Crystallographic data for Ag29-COOLi-MeOH.

Supplementary Data 10

Crystallographic data for Ag29-COONa-MeOH.

Supplementary Data 11

Crystallographic data for Ag29-COOK-MeOH.

Supplementary Data 12

Crystallographic data for Ag29-COORb-MeOH.

Supplementary Data 13

Crystallographic data for Ag29-COOCs-MeOH.

Source data

Source Data Fig. 4

NMR, DFT.

Source Data Fig. 5

EIS, LSV, Coulombic efficiency.

Source Data Extended Data Fig. 1

Arrhenius plots, chronoamperometric profiles.

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Wei, X., Huang, Z., Sun, X. et al. Atomically defined two-dimensional assembled nanoclusters for Li-ion batteries. Nat. Synth (2025). https://doi.org/10.1038/s44160-025-00852-1

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