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Supporting Information

Hybrid Lithium-Sulfur Batteries with a Solid Electrolyte Membrane and Lithium

Polysulfide Catholyte

Xingwen Yu†, Zhonghe Bi

‡, Feng Zhao

‡*, and Arumugam Manthiram

†*

† Electrochemical Energy Laboratory, Materials Science and Engineering Program, The

University of Texas at Austin, Austin, TX 78712, USA

‡ Ceramatec, Inc., Salt Lake City, UT 84119, USA

*(A.M.) E-mail: manth@austin.utexas.edu.

*(F.Z.) E-mail: fzhao@ceramatec.com.

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Table S1. Specifications and operating conditions for the hybrid Li-PS cells with the

LiSICON membrane

Criterion Cell specifications and operating conditions

Cell configuration

Area of the cathode

Cathode matrix

Catholyte

Separator

Capacity density

Capacity of the cell

Charge/discharge rate

CR 2032 coin cell

1.13 cm-2

Carbon nanofiber paper

0.67 M Li2S6 (4.0 M sulfur)

LiSICON membrane

2.85 mAh cm-2

3.2 mAh

C/10, C/5, C/3

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Figure S1. (a) Schematic of a setup for polysulfide permeation experiments. (b) Photograph of

the sealed transparent tube with a piece of Celgard membrane embedded. (c) Photograph of the

sealed transparent tube with a piece of LiSICON membrane embedded.

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Figure S2. Polysulfide diffusion tests of the (a and b) Celgard membrane and (c, d, and e)

LiSICON membrane after various resting times.

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Figure S3. Electrochemical impedance spectroscopy (EIS) data of the three types of membrane-

electrode assemblies (MEAs) as illustrated in Figure 3a, b, and e in the paper. Black line: with

the application of a layer of liquid electrolyte at the Li-anode/LiSICON membrane interface;

blue line: with the application of a mechanical pressure to enhance the surface contact between

Li metal and the LiSICON membrane; pink line: with the insertion of a soft, facile Li-ion

transfer interlayer to accommodate the roughness at the Li anode/LiSICON membrane interface.

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Figure S4. Typical charge/discharge profiles of a Li-S cell prepared with a traditional sulfur-

carbon cathode and a Celgard separator.

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Figure S5. Schematic of the hybrid Li || LiSICON || polysulfide coin cell assembly.

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Figure S6. Charge/discharge profiles of the hybrid Li || LiSICON || polysulfide batteries at

different representative cycles at (a) C/10, (b) C/5, and (c) C/3 rates.

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Figure S7. (a) EIS spectra and (b) bulk resistance (RL) as a function of cycle number of the Li-S

cell with a LiSICON membrane solid electrolyte after various cycles at C/3 rate.