Self-assembled hydrated copper coordination compounds as ionic conductors for room temperature solid-state batteries

被引:64
作者
Zhan, Xiao [1 ]
Li, Miao [1 ]
Zhao, Xiaolin [2 ]
Wang, Yaning [2 ]
Li, Sha [1 ]
Wang, Weiwei [1 ]
Lin, Jiande [1 ]
Nan, Zi-Ang [1 ]
Yan, Jiawei [1 ]
Sun, Zhefei [1 ]
Liu, Haodong [3 ]
Wang, Fei [4 ]
Wan, Jiayu [5 ]
Liu, Jianjun [2 ]
Zhang, Qiaobao [1 ,6 ]
Zhang, Li [1 ]
机构
[1] Xiamen Univ, Collaborat Innovat Ctr Chem Energy Mat iChEM, State Key Lab Phys Chem Solid Surfaces, Tan Kah Kee Innovat Lab,Coll Chem & Chem Engn, Xiamen 361005, Peoples R China
[2] Chinese Acad Sci, Shanghai Inst Ceram, State Key Lab High Performance Ceram & Superfine M, Shanghai 200050, Peoples R China
[3] Univ Calif San Diego, Chem Engn, La Jolla, CA 92093 USA
[4] Fudan Univ, Dept Mat Sci, Shanghai 200433, Peoples R China
[5] Shanghai Jiao Tong Univ, Global Inst Future Technol, Future Battery Res Ctr, Shanghai 200240, Peoples R China
[6] Xiamen Univ, Shenzhen Res Inst, Shenzhen 518000, Peoples R China
基金
中国国家自然科学基金;
关键词
TOTAL-ENERGY CALCULATIONS; METAL BATTERIES; LITHIUM; OXIDATION; CHEMISTRY; EFFICIENT; CATALYST; CRYSTAL; CHAINS;
D O I
10.1038/s41467-024-45372-2
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
As the core component of solid-state batteries, neither current inorganic solid-state electrolytes nor solid polymer electrolytes can simultaneously possess satisfactory ionic conductivity, electrode compatibility and processability. By incorporating efficient Li+ diffusion channels found in inorganic solid-state electrolytes and polar functional groups present in solid polymer electrolytes, it is conceivable to design inorganic-organic hybrid solid-state electrolytes to achieve true fusion and synergy in performance. Herein, we demonstrate that traditional metal coordination compounds can serve as exceptional Li+ ion conductors at room temperature through rational structural design. Specifically, we synthesize copper maleate hydrate nanoflakes via bottom-up self-assembly featuring highly-ordered 1D channels that are interconnected by Cu2+/Cu+ nodes and maleic acid ligands, alongside rich COO- groups and structural water within the channels. Benefiting from the combination of ion-hopping and coupling-dissociation mechanisms, Li+ ions can preferably transport through these channels rapidly. Thus, the Li+-implanted copper maleate hydrate solid-state electrolytes shows remarkable ionic conductivity (1.17 x 10-4 S cm-1 at room temperature), high Li+ transference number (0.77), and a 4.7 V-wide operating window. More impressively, Li+-implanted copper maleate hydrate solid-state electrolytes are demonstrated to have exceptional compatibility with both cathode and Li anode, enabling long-term stability of more than 800 cycles. This work brings new insight on exploring superior room-temperature ionic conductors based on metal coordination compounds. The design of inorganic-organic hybrid solid-state electrolytes is expected to merge the merits of both inorganic and organic material. Here, the authors craft Li-ion-implanted copper maleate hydrate nanoflakes via a bottom-up self-assembly approach to reveal superior room-temperature Li-ion conductivity.
引用
收藏
页数:14
相关论文
共 79 条
[1]   Bond softness-sensitive bond valence parameters for crystal structure plausibility tests [J].
Adams, Stefan ;
Chen, Haomin .
ACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES, 2017, 73 :C381-C381
[2]  
Bai SY, 2016, NAT ENERGY, V1, DOI [10.1038/nenergy.2016.94, 10.1038/NENERGY.2016.94]
[3]  
Binitha MP, 2016, INDIAN J PURE AP PHY, V54, P453
[4]   PROJECTOR AUGMENTED-WAVE METHOD [J].
BLOCHL, PE .
PHYSICAL REVIEW B, 1994, 50 (24) :17953-17979
[5]   SoftBV - a software tool for screening the materials genome of inorganic fast ion conductors [J].
Chen, Haomin ;
Wong, Lee Loong ;
Adams, Stefan .
ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE CRYSTAL ENGINEERING AND MATERIALS, 2019, 75 (01) :18-33
[6]   Highly Stable Quasi-Solid-State Lithium Metal Batteries: Reinforced Li1.3Al0.3Ti1.7(PO4)3/Li Interface by a Protection Interlayer [J].
Chen, Zhen ;
Kim, Guk-Tae ;
Kim, Jae-Kwang ;
Zarrabeitia, Maider ;
Kuenzel, Matthias ;
Liang, Hai-Peng ;
Geiger, Dorin ;
Kaiser, Ute ;
Passerini, Stefano .
ADVANCED ENERGY MATERIALS, 2021, 11 (30)
[7]   Increasing the conductivity of crystalline polymer electrolytes [J].
Christie, AM ;
Lilley, SJ ;
Staunton, E ;
Andreev, YG ;
Bruce, PG .
NATURE, 2005, 433 (7021) :50-53
[8]   Structural Variation in Mellitate Complexes of First-Row Transition Metals: What Chance for Design? [J].
Clegg, William ;
Holcroft, James M. .
CRYSTAL GROWTH & DESIGN, 2014, 14 (12) :6282-6293
[9]   Protonated malonate:: the influence of the hydrogen bonds on the magnetic behaviour [J].
Delgado, FS ;
Sanchiz, J ;
Ruiz-Pérez, C ;
Lloret, F ;
Julve, M .
CRYSTENGCOMM, 2004, 6 :443-450
[10]   Active species of copper chromite catalyst in C-O hydrogenolysis of 5-methylfurfuryl alcohol [J].
Deutsch, Keenan L. ;
Shanks, Brent H. .
JOURNAL OF CATALYSIS, 2012, 285 (01) :235-241