Plasticizer-inclusive polymeric-inorganic hybrid layer for a lithium anode in a lithium-sulfur battery

Patent metadata

Field	Value
Publication number	US-2022271291-A1
Application number	US-202217672960-A
Country	US
Kind code	A1
Filing date	Feb 16, 2022
Priority date	Feb 16, 2021
Publication date	Aug 25, 2022
Grant date	—

Abstract

A lithium-sulfur battery including an anode structure, a cathode, a separator, and an electrolyte is provided. A protective layer may form within the anode structure responsive to operational discharge-charge cycling of the lithium-sulfur battery. The protective layer may include a polymeric backbone chain formed of interconnected carbon atoms collectively defining a segmental motion of the protective layer. Additional polymeric chains may be cross-linked to one another and at least some carbon atoms of the polymeric backbone chain. Each additional polymeric chain may be formed of interconnected monomer units. A plasticizer may be dispersed throughout the protective layer without covalently bonding to the polymeric backbone chain. The plasticizer may separate adjacent monomer units of at least some additional polymeric chains. Increasing separation of adjacent monomer units increases a cooperative segmental mobility of the additional polymeric chains and ionic conductivity of the protective layer.

First claim

What is claimed is:

1 . A lithium-sulfur battery comprising:
a cathode; an anode structure positioned opposite to the cathode, the anode structure comprising:
a single layer of solid lithium configured to output a plurality of lithium ions;
a solid-electrolyte interphase layer formed on the single layer of solid lithium;
a protective layer formed on and at least partially disposed within the solid-electrolyte interphase layer responsive to operational discharge-charge cycling of the lithium-sulfur battery, the protective layer comprising:
a polymeric backbone chain formed of interconnected carbon atoms collectively defining a cooperative segmental mobility of the protective layer;
a plurality of additional polymeric chains cross-linked to one another and to at least some carbon atoms of the polymeric backbone chain, each polymeric chain formed of interconnected monomer units; and
a plasticizer dispersed throughout the protective layer without covalently bonding to the polymeric backbone chain, the plasticizer configured to separate adjacent monomer units of at least some of the plurality of additional polymeric chains, wherein an increased separation of adjacent monomer units is associated with an increase in the cooperative segmental mobility of the protective layer;

a separator positioned between the anode structure and the cathode; and an electrolyte dispersed throughout the cathode and in contact with the anode structure.

2 . The lithium-sulfur battery of claim 1 , wherein the protective layer is configured to melt at a glass transition temperature.

3 . The lithium-sulfur battery of claim 2 , wherein an increase in the glass transition temperature is associated with a reduction in the cooperative segmental mobility of the plurality of additional polymeric chains.

4 . The lithium-sulfur battery of claim 3 , wherein a decrease in the cooperative segmental mobility of the plurality of additional polymeric chains is associated with a decrease in lithium ion (Li + ) conductivity through the protective layer.

5 . The lithium-sulfur battery of claim 1 , wherein an increase in an amount of the plasticizer in the protective layer is associated with an increase in a lithium ion (Li + ) conductivity through the protective layer.

6 . A lithium-sulfur battery comprising:
a cathode; an anode positioned opposite to the cathode: a protective layer formed on the anode, the protective layer comprising:
a three-dimensional (3D) polymeric lattice comprising:
a first polymeric chain and a second polymeric chain positioned opposite one another, each of the first and second polymeric chains including carbon atoms at least temporarily chemically bonded to one or more of oxide ions (O 2− ), fluorine ions (F − ), or nitrate ions (NO 3− ); and
lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) dispersed throughout the 3D polymeric lattice and configured to dissociate into lithium ions (Li+) and TFSI − anions, the first and second polymeric chains configured to form the 3D polymeric lattice with a cross-linking density sufficient to trap TFSI − anions by cross-linking with each other upon exposure to an energetic environment including ultraviolet (UV) energy and LiTFSI configured to serve as a polymerization co-initiator compound;

a separator positioned between the anode and the cathode; and an electrolyte dispersed throughout the cathode and in contact with the anode.

7 . The lithium-sulfur battery of claim 6 , wherein the first and second polymeric chains are configured to form the 3D polymeric lattice through one or more cross-linking polymerization reactions.

8 . The lithium-sulfur battery of claim 7 , wherein one or more of the cross-linking polymerization reactions comprises a ultraviolet (UV) curing.

9 . The lithium-sulfur battery of claim 8 , wherein the UV curing is configured to progress at a curing rate.

10 . The lithium-sulfur battery of claim 9 , wherein the polymerization co-initiator compound is configured to increase the curing rate.

11 . The lithium-sulfur battery of claim 6 , further comprising a plurality of additives dispersed uniformly throughout the 3D polymeric lattice, each of the plurality of additives including:
lithium nitrate (LiNO 3 ); a plurality of inorganic ionically-conductive ceramics comprising one or more of lithium lanthanum zirconium oxide (LLZO), NASICON-type oxide Li 1+x Al x Ti 2-x (PO 4 ) 3 (LATP) or lithium tin phosphorus sulfide (LSPS); or a plurality of nitrogen-oxygen containing additives.

12 . The lithium-sulfur battery of claim 11 , wherein the plurality of inorganic ionically-conductive ceramics are uniformly embedded in the 3D polymeric lattice.

13 . The lithium-sulfur battery of claim 11 , wherein the plurality of inorganic ionically-conductive ceramics are uniformly distributed throughput the protective layer.

14 . The lithium-sulfur battery of claim 6 , wherein the protective layer includes one or more desiccated solvents.

15 . A lithium-sulfur battery comprising:
a cathode; an anode positioned opposite to the cathode: a protective layer configured to trap one or more types of anions, the protective layer including a plurality of ingredients comprising:
one or more relatively pliable oligomeric epoxy based compounds or relatively pliable oligomeric polyol based compounds;
a relatively rigid polymeric epoxy based compound;
one or more photo-initiator molecules; and
one or more lithium-containing salts configured to dissociate into a plurality of lithium (Li+) cations and at least one type of anion;
a separator positioned between the anode and the cathode; and an electrolyte dispersed throughout the cathode and in contact with the anode.

16 . The lithium-sulfur battery of claim 15 , wherein the protective layer is formed on the anode responsive to ultraviolet (UV) curing of at least some of the plurality of ingredients.

17 . The lithium-sulfur battery of claim 15 , wherein the protective layer includes one or more non-reactive diluents comprising 1,2-Dimethoxyethane (DME), tetrahydrofuran (THF), triethylene glycol dimethyl ether (TEGDME), or 2-Methyl-2-oxazoline (MOZ).

18 . The lithium-sulfur battery of claim 17 , wherein the protective layer includes one or more reactive diluents comprising 1,3-Dioxolane (DOL), 3,3-Dimethyloxetane (DMO), 2-Ethyl-2-oxazoline (EOZ), or ε-Caprolactone (CL).

19 . The lithium-sulfur battery of claim 18 , wherein a per-unit formulation weight of the protective layer is based on a concentration level of one or more non-reactive diluents or reactive diluents relative to the plurality of ingredients of the protective layer.

20 . The lithium-sulfur battery of claim 18 , wherein the one or more reactive diluents are configured to reduce mechanical stress of at least some of cross-linking within the protective layer.

21 . The lithium-sulfur battery of claim 15 , wherein the one or more relatively pliable oligomeric epoxy based compounds or relatively pliable oligomeric polyol based compounds are configured to eliminate formation of pinholes in the protective layer.

22 . The lithium-sulfur battery of claim 18 , wherein the one or more reactive diluents are configured to be removed from the protective layer.

23 . The lithium-sulfur battery of claim 18 , wherein the one or more reactive diluents are configured to remain in the protective layer after cross-linking of at least some of the plurality of ingredients.

Assignees

• Lyten Inc

Inventors

• Li You
• Baucom Jesse
• Rogojina Elena
• Kc Chandra B
• Shan Jingning
• Gazda Jerzy
• Bugga Ratnakumar

Classifications

• H01M2004/021

  Physical characteristics, e.g. porosity, surface area · CPC title

• H01M2220/20

  Batteries in motive systems, e.g. vehicle, ship, plane · CPC title

• H01M10/0525 Primary

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M4/62 Primary

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title

• H01M2300/0068

  inorganic · CPC title