Cathode material for a lithium/sulfur cell

Patent metadata

Field	Value
Publication number	US-10177381-B2
Application number	US-201615168788-A
Country	US
Kind code	B2
Filing date	May 31, 2016
Priority date	Jun 5, 2015
Publication date	Jan 8, 2019
Grant date	Jan 8, 2019

Abstract

A cathode material for an alkali metal/sulfur cell, which encompasses at least one sulfur-containing cathode active material and at least one transition metal sulfide and/or at least one metal sulfide of at least one metal of the third, fourth, and/or fifth main group. Also described is a cell and a battery equipped therewith.

First claim

What is claimed is:

1. A cathode material for an alkali metal/sulfur cell, comprising:
at least one cathode active material that contains cyclic polyacrylonitrile with covalently bound sulfur; and
at least one metal sulfide, wherein the at least one metal sulfide is one of (i) at least one transition metal sulfide, or (ii) at least one metal sulfide of at least one metal of the third, fourth, and/or fifth main group.

2. The cathode material of claim 1 , wherein the at least one cathode active material contains a sulfur/carbon composite.

3. The cathode material of claim 1 , wherein the at least one metal sulfide is incorporated into the at least one cathode active material.

4. The cathode material of claim 2 , wherein the at least one cathode active material is surrounded by the at least one metal sulfide.

5. The cathode material of claim 1 , wherein the at least one metal sulfide has a standard electrode potential ≥1 V higher than the alkali metal of the cell.

6. The cathode material of claim 1 , wherein the at least one transition metal sulfide is a semiconductor.

7. The cathode material of claim 1 , wherein the at least one metal sulfide has more than one metal atom per sulfur atom, wherein the at least one metal sulfide has a hyperstoichiometric metal proportion.

8. The cathode material of claim 1 , wherein the at least one metal sulfide accounts in total for ≥25 wt % to ≤50 wt %, with reference to the weight of the at least one cathode active material and of the at least one metal sulfide.

9. The cathode material of claim 1 , wherein the at least one metal sulfide is the at least one transition metal sulfide and contains a sulfide of iron, copper, cobalt, nickel, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, zinc, manganese, and/or titanium.

10. The cathode material of claim 1 , wherein the at least one metal sulfide is selected from the group consisting of FeS, FeS 2 , CuS, Cu 2 S, CuS 2 , Cu 9 S 8 , Cu 7 S 4 , CoS, CoS 2 , Co 3 S 4 , Co 9 S 8 , NiS, NiS 2 , Ni 9 S 8 , Ni 3 S 2 , VS, VS 2 , V 2 S 3 , V 2 S 5 , VS 4 , NbS 2 , NbS 3 , NbS 4 , NbS 5 , Nb 2 S 3 , Nb 2 S 5 , TaS 2 , TaS 3 , TaS 4 , TaS 5 , Ta 2 S 3 , Ta 2 S 5 , Cr 2 S 3 , CrS 3 , MoS 2 , MoS 3 , MoS 4 , WS 2 , WS 3 , WS 4 , WS 5 , MnS, Mn 2 S 3 , TiS 2 , NiNb 3 S 6 , Cu 2 MoS 4 , and Cu 4 Mo 6 S 8 .

11. The cathode material of claim 1 , further comprising at least one electrically conducting metal oxide or at least one electrically conducting metal carbide, wherein the at least one electrically conducting metal oxide or the at least one electrically conducting metal carbide is incorporated into the at least one cathode active material.

12. The cathode material of claim 1 , further comprising at least one lithium ion-conducting or lithium ion-conductive polymer electrolyte and/or at least one inorganic ion conductor.

13. The cathode material of claim 12 , wherein the at least one polymer electrolyte has at least one repeating unit of the general chemical formula:

wherein:
-[A]- is a polymer-backbone-forming unit,
X is a spacer,
x is the quantity of spacer X and is 1 or 0, and
Q is
a negatively charged group Q − and a counter ion Z + , or
an uncharged group Q, or
a positively charged group Q + and a counter ion Z − .

14. The cathode material of claim 13 , wherein
the polymer-backbone-forming unit -[A]- includes one or more of an alkylene oxide unit, a unit encompassing a carbonate group, a siloxane unit, a phosphazene unit, a methyl methacrylate unit, a methacrylate unit, a phenylene unit, a phenylene oxide unit, a benzylene unit, and an alkylene unit.

15. The cathode material of claim 13 , wherein Q is the negatively charged group Q − and a counter ion Z + , wherein:
Q − is one of:
(i) a group based on a lithium conducting salt anion,
(ii) a group based on an anion of an ionic liquid, a sulfonate group, a sulfonylimide group, a sulfate group, or a carboxylate group,
(iii) a group based on a phosphoric acid-based anion,
(iv) a group based on an anion of an imide,
(v) a group based on an anion of an amide, or
(vi) a group based on an anion of a carboxylic acid amide; and

Z + is a lithium ion.

16. The cathode material of claim 13 , wherein the at least one inorganic ion conductor
is a sulfidic ion conductor,
has a garnet-like structure, or
is of the LISICON type, is of the NASICON type, or contains lithium phosphorus oxynitride.

17. The cathode material of claim 13 , wherein Q is the uncharged group Q, wherein the uncharged group Q is one of an alkylene oxide group, an acyclic carbonate group, a cyclic carbonate group, a lactone group, a cyclic carbamate group, an acyclic carboxylic acid ester group, an acyclic carbamate group, a hydrogen, or an alkyl group.

18. The cathode material of claim 13 , wherein Q is the positively charged group Q + and a counter ion Z − , wherein:
Q + includes at least one of a pyridinium group, an ammonium group, an imidazolium group, a piperidinium group, a pyrrolidinium group, a phosphonium group, a guanidinium group, a morpholinium group, a uronium group, or a thiouronium group; and
Z − is a lithium conducting salt anion.

19. The cathode material of claim 13 , wherein the spacer X includes at least one of the following:
(i) at least one oligoalkylene oxide group;
(ii) at least one other negatively charged group Q − that is either at least one sulfonylimide group and/or at least one sulfonate group, and a counter ion Z + that is a lithium ion;
(iii) at least one carbonyl group that is one or more of a cyclic carbonate group, a lactone group, a cyclic carbamate group, an acyclic carboxylic acid ester group, an acyclic carbamate group, and an acyclic carbonate group; and
(iv) at least one other positively charged group Q + that includes at least one of an ammonium group, a pyridinium group, an imidazolium group, a piperidinium group, a pyrrolidinium group, a phosphonium group, a guanidinium group, a morpholinium group, an uronium group, or a thiouronium group, and a counter ion Z − that is a lithium conducting salt anion.

20. The cathode material of claim 1 , wherein the at least one metal sulfide is the at least one metal sulfide of at least one metal of the third, fourth, and/or fifth main group and contains a sulfide of indium, gallium, aluminum, tin, germanium, antimony, and/or bismuth.

21. A cathode material for an alkali metal/sulfur cell, comprising:
at least one sulfur-containing cathode active material; and
at least one metal sulfide, wherein the at least one metal sulfide is one of (i) at least one transition metal sulfide, or (ii) at least one metal sulfide of at least one metal of the third, fourth, and/or fifth main group,
wherein the at least one metal sulfide contains electrochemically active sulfur and/or more than one sulfur atom per metal atom, wherein the at least one metal sulfide has at least one disulfide anion and/or polysulfide anion and/or a hyperstoichiometric sulfur proportion.

22. A cathode material for an alkali metal/sulfur cell, comprising:
at least one sulfur-containing cathode active material; and
at least one metal sulfide, wherein the at least one metal sulfide is one of (i) at least one transition metal sulfide, or (ii) at least one metal sulfide of at least one metal of the third, fourth, and/or fifth main group,
wherein the at least one metal sulfide contains at le

Assignees

• Bosch Gmbh Robert

Inventors

• Fanous Jean
• Thielen Joerg
• Schumann Bernd

Classifications

• H01M4/622

  being polymers · CPC title

• H01M4/364

  as mixtures · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M10/0562

  Solid materials · CPC title

• H01M4/624

  Electric conductive fillers · CPC title