Alkali Metal-Sulfur Secondary Battery Containing a Nano Sulfur-Loaded Cathode and Manufacturing Method

Patent metadata

Field	Value
Publication number	US-2018233784-A1
Application number	US-201715431231-A
Country	US
Kind code	A1
Filing date	Feb 13, 2017
Priority date	Feb 13, 2017
Publication date	Aug 16, 2018
Grant date	—

Abstract

A rechargeable alkali metal-sulfur cell selected from lithium-sulfur cell, sodium-sulfur cell, or potassium-sulfur cell The alkali metal-sulfur cell comprises an anode active material layer, an optional anode current collector supporting the anode active material layer, a cathode active material layer, an electrolyte with an optional porous separator layer in ionic contact with the anode active material layer and the cathode active material layer, and an optional cathode current collector supporting the cathode active material layer, wherein the cathode active material layer contains a graphite or carbon material having expanded inter-graphene planar spaces with an inter-planar spacing d 002 from 0.43 nm to 2.0 nm, as measured by X-ray diffraction, and 1%-95% by weight of sulfur or a metal polysulfide residing in these expanded inter-graphene planar spaces. This battery exhibits an excellent combination of high sulfur content, high sulfur utilization efficiency, high energy density, and long cycle life.

First claim

1 . A rechargeable alkali metal-sulfur cell selected from lithium-sulfur cell, sodium-sulfur cell, or potassium-sulfur cell, said alkali metal-sulfur cell comprising an anode active material layer, an optional anode current collector supporting said anode active material layer, a cathode active material layer, an electrolyte with an optional porous separator layer in ionic contact with said anode active material layer and said cathode active material layer, and an optional cathode current collector supporting said cathode active material layer, wherein said cathode active material layer contains a graphite or carbon material having expanded inter-graphene planar spaces with an inter-planar spacing d 002 from 0.43 nm to 2.0 nm, as measured by X-ray diffraction, and 1%-95% by weight of sulfur or a metal polysulfide residing in said expanded inter-graphene planar spaces.

2 . The rechargeable alkali metal-sulfur cell of claim 1 , wherein said metal polysulfide contains M x S y , wherein x is an integer from 1 to 3 and y is an integer from 1 to 10, and M is a metal element selected from an alkali metal, an alkaline metal selected from Mg or Ca, a transition metal, a metal from groups 13 to 17 of the periodic table, or a combination thereof.

3 . The rechargeable alkali metal-sulfur cell of claim 2 , wherein said metal element M is selected from Li, Na, K, Mg, Zn, Cu, Ti, Ni, Co, Fe, or Al.

4 . The rechargeable alkali metal-sulfur cell of claim 1 , wherein said metal polysulfide contains Li 2 S 6 , Li 2 S 7 , Li 2 S 8 , Li 2 S 9 , Li 2 S 10 , Na 2 S 6 , Na 2 S 7 , Na 2 S 8 , Na 2 S 9 , Na 2 S 10 , K 2 S 6 , K 2 S 7 , K 2 S 8 , K 2 S 9 , or K 2 S 10 .

5 . The rechargeable alkali metal-sulfur cell of claim 1 , wherein said carbon or graphite material in said cathode active material layer is selected from meso-phase pitch, meso-phase carbon, meso carbon micro-beads (MCMB), coke particles, expanded graphite flakes, artificial graphite particles, natural graphite particles, highly oriented pyrolytic graphite, soft carbon particles, hard carbon particles, multi-walled carbon nanotubes, carbon nano-fibers, carbon fibers, graphite nano-fibers, graphite fibers, carbonized polymer fibers, carbon arogel, carbon xerogel, or a combination thereof, wherein said carbon or graphite material has an inter-planar spacing d 002 from 0.27 nm to 0.42 nm prior to a chemical or physical expansion treatment and the inter-planar spacing d 002 .is increased to from 0.43 nm to 2.0 nm after said expansion treatment.

6 . The rechargeable alkali metal-sulfur cell of claim 1 , wherein said carbon or graphite material is selected from graphite foam or graphene foam having pores and pore walls, wherein said pore walls contain a stack of bonded graphene planes having an expanded inter-planar spacing d 002 from 0.45 nm to 1.5 nm.

7 . The rechargeable alkali metal-sulfur cell of claim 6 , wherein said stack contains from 2 to 100 graphene planes.

8 . The rechargeable alkali metal-sulfur cell of claim 1 , wherein said inter-planar spacing d 002 .is from 0.5 nm to 1.2 nm.

9 . The rechargeable alkali metal-sulfur cell of claim 1 , wherein said inter-planar spacing d 002 .is from 1.2 nm to 2.0 nm.

10 . The rechargeable alkali metal-sulfur cell of claim 5 , wherein said expansion treatment includes an oxidation, fluorination, bromination, chlorination, nitrogenation, intercalation, combined oxidation-intercalation, combined fluorination-intercalation, combined bromination-intercalation, combined chlorination-intercalation, or combined nitrogenation-intercalation of said graphite or carbon material.

11 . The rechargeable alkali metal-sulfur cell of claim 10 , further comprising a constrained thermal expansion treatment.

12 . The rechargeable alkali metal-sulfur cell of claim 1 , wherein said carbon or graphite material contains a non-carbon element selected from oxygen, fluorine, chlorine, bromine, iodine, nitrogen, hydrogen, or boron.

13 . The rechargeable alkali metal-sulfur cell of claim 1 , wherein said cell has a sulfur utilization efficiency greater than 85%.

14 . A cathode active material layer for a rechargeable alkali metal-sulfur cell, wherein said cathode active material layer contains a graphite or carbon material having expanded inter-graphene planar spaces with an inter-planar spacing d 002 from 0.43 nm to 2.0 nm, as measured by X-ray diffraction, and 1%-95% by weight of sulfur or a metal polysulfide residing in said expanded inter-graphene planar spaces.

15 . The cathode active material layer of claim 14 , wherein said metal polysulfide contains M x S y , wherein x is an integer from 1 to 3 and y is an integer from 1 to 10, and M is a metal element selected from an alkali metal, an alkaline metal selected from Mg or Ca, a transition metal, a metal from groups 13 to 17 of the periodic table, and combinations thereof.

16 . The cathode active material layer of claim 15 , wherein said metal element M is selected from Li, Na, K, Mg, Zn, Cu, Ti, Ni, Co, Fe, or Al.

17 . The cathode active material layer of claim 14 , wherein said metal polysulfide contains Li 2 S 6 , Li 2 S 7 , Li 2 S 8 , Li 2 S 9 , Li 2 S 10 , Na 2 S 6 , Na 2 S 7 , Na 2 S 8 , Na 2 S 9 , Na 2 S 10 , K 2 S 6 , K 2 S 7 , K 2 S 8 , K 2 S 9 , or K 2 S 10 .

18 . The cathode active material layer of claim 14 , wherein said carbon or graphite material in said cathode active material layer is selected from meso-phase pitch, meso-phase carbon, meso carbon micro-beads (MCMB), coke particles, expanded graphite flakes, artificial graphite particles, natural graphite particles, highly oriented pyrolytic graphite, soft carbon particles, hard carbon particles, multi-walled carbon nanotubes, carbon nano-fibers, carbon fibers, graphite nano-fibers, graphite fibers, carbonized polymer fibers, carbon aerogel, carbon xerogel, or a combination thereof, wherein said carbon or graphite material has an inter-planar spacing d 002 from 0.27 nm to 0.42 nm prior to a chemical or physical expansion treatment and the inter-planar spacing d 002 .is increased to from 0.43 nm to 2.0 nm after said expansion treatment.

19 . The cathode active material layer of claim 14 , wherein said carbon or graphite material is selected from graphite foam or graphene foam having pores and pore walls, wherein said pore walls contain a stack of bonded graphene planes having an expanded inter-planar spacing d 002 from 0.45 nm to 1.5 nm.

20 . The cathode active material layer of claim 19 , wherein said stack contains from 2 to 100 graphene planes.

21 . The cathode active material layer of claim 14 , wherein said inter-planar spacing d 002 is from 0.5 nm to 1.2 nm.

22 . The cathode active material layer of claim 14 , wherein said inter-planar spacing d 002 is from 1.2 nm to 2.0 nm.

23 . The cathode active material layer of claim 18 , wherein said expansion treatment includes an oxidation, fluorination, bromination, chlorination, nitrogenation, intercalation, combined oxidation-intercalation, combined fluorination-intercalation, combined bromination-intercalation, combined chlorination-intercalation, or combined nitrogenation-intercalation of said graphite or carbon material.

24 . The cathode active material layer of claim 23 , further comprising a constrained thermal expansion treatment.

25 . The cathode active material layer of claim 14 , wherein said carbon or graphite material contains a non-carbon element selected from oxyg

Assignees

• Nanotek Instruments Inc

Inventors

• Zhamu Aruna
• Jang Bor Z

Classifications

• H01M4/5815

  Sulfides · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M4/625

  Carbon or graphite · CPC title

• H01M4/382 Primary

  Lithium (H01M4/405 takes precedence) · CPC title

• H01M4/38 Primary

  of elements or alloys · CPC title