Title: Electrolyte design for Li metal-free Li batteries

Abstract

Li metal, with the lowest thermodynamically achievable negative electrochemical potential and the highest specific capacity (3860 mAh g^-1), is the ultimate anode choice for Li batteries. However, the highest reported Li plating/stripping Coulombic efficiency (CE) of 99.5% after extensive efforts is still too low for the Li metal-free (all the Li metal in cycling comes from cathode, without anode pre-lithiation) Li metal batteries. The low CE is attributed to both non-uniform Li plating/stripping on the lithiophobic Cu current collector and Li dendrite growth through lithiophilic organic–inorganic solid electrolyte interphase (SEI) formed in carbonate electrolytes. Here, we use a lithiophilic Bismuth graphite blend (Bi–Gr) substrate to replace lithiophobic Cu current collector to seed a uniform Li nucleation, and form a lithiophobic LiF-rich SEI rather than lithiophilic organic-rich SEI to suppress Li dendrite growth. Molecular dynamics simulations reveal the preferential reduction of anions in 2.0 M LiPF₆ in tetrahydrofuran/2-methyl tetrahydrofuran (2.0 M LiPF₆–mixTHF) electrolyte to generate LiF-rich SEI on plated Li. Bi–Gr substrate and 2.0 M LiPF₆–mixTHF electrolyte enable the Li anodes to achieve a record high CE of 99.83% at a high capacity of 1.0 mAh cm^-2 and current of 0.5 mA cm^-2. The Bi particles serve as dispersed nucleation centersmore » that promote uniform Li deposition with strong adhesion to the substrate to avoid dead Li, while the lithiophobic LiF-rich SEI promotes lateral Li growth and suppresses the vertical Li dendrite growth even at a high current density of 3.0 mA cm^-2 and high areal capacities of 3.0 mAh cm^-2. The regulation of Li nucleation and growth enables the Li metal-free LiFePO₄ full cells to achieve 100 cycles at a practical areal capacity of >2.0 mAh cm^-2. This article highlights the benefits of simultaneous substrate design to improve Li nucleation and electrolyte design to promote lithiophobic SEI growth, enabling a promising and practical route Li metal-free Li metal batteries.« less

Authors:

Chen, Ji ^[1]; Li, Qin ^[1]; Pollard, Travis P. ^[2]; Fan, Xiulin ^[1]; Borodin, Oleg ^[2]; Wang, Chunsheng ^[3]

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+ Show Author Affiliations

1. Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering
2. Army Research Lab., Adelphi, MD (United States). U.S. Army Combat Capabilities Development Command. Sensors and Electron Devices Directorate. Energy and Biomaterials Division. Battery Science Branch
3. Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Univ. of Maryland, College Park, MD (United States). Dept. of Chemistry and Biochemistry

Publication Date:

Sat Apr 25 00:00:00 EDT 2020

Research Org.:

Univ. of Maryland, College Park, MD (United States)

Sponsoring Org.:

USDOE Office of Energy Efficiency and Renewable Energy (EERE)

OSTI Identifier:

1848707

Alternate Identifier(s):

OSTI ID: 1690298

Grant/Contract Number:  

EE0008202

Resource Type:

Accepted Manuscript

Journal Name:

Materials Today

Additional Journal Information:

Journal Volume: 39; Journal Issue: C; Journal ID: ISSN 1369-7021

Publisher:

Elsevier

Country of Publication:

United States

Language:

English

Subject:

36 MATERIALS SCIENCE; Materials Science; Li metal; Electrolyte Design; Nucleation Design; Coulombic Efficiency; Density Functional Theory