Magnesium-sulfur secondary battery containing a metal polysulfide-preloaded active cathode layer

Patent metadata

Field	Value
Publication number	US-2016308208-A1
Application number	US-201514545279-A
Country	US
Kind code	A1
Filing date	Apr 17, 2015
Priority date	Apr 17, 2015
Publication date	Oct 20, 2016
Grant date	—

Abstract

A rechargeable magnesium-sulfur cell comprising an anode layer, an electrolyte, a metal polysulfide-preloaded active cathode layer, wherein the active cathode layer comprises: (a) an integral porous structure having massive surfaces (specific surface area >100 m 2 /g) or pores with a size from 1.0 nm to 100 nm and wherein multiple particles; and (b) a metal polysulfide, M x S y , preloaded in the pores or deposited on the massive surfaces, 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, a transition metal, a metal from groups 13 to 17 of the periodic table, or a combination thereof. The metal polysulfide is in a form of solid-state thin coating or small particles with a thickness or diameter less than 50 nm.

First claim

1 . A rechargeable magnesium-sulfur cell comprising an anode active material layer, an optional anode current collector, a porous separator and/or an electrolyte, a metal polysulfide-preloaded active cathode layer, and an optional cathode current collector, wherein said metal polysulfide-preloaded active cathode layer comprises:
(A) an integral porous structure of an electronically conductive material, wherein said integral porous structure has massive surfaces having a specific surface area greater than 100 m 2 /g or has pores with a size from 1.0 nm to 100 nm and wherein multiple particles, platelets or filaments of said conductive material form a 3-D network of electron-conducting paths; and (B) a sulfur-rich metal polysulfide, M x S y , preloaded in said pores or deposited on said massive surfaces, 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, a transition metal, a metal from groups 13 to 17 of the periodic table, or a combination thereof; wherein said metal polysulfide is in a form of solid-state thin coating or small particles with a thickness or diameter less than 50 nm and occupies a weight fraction of from 1% to 99% of the total weight of said porous structure and said metal polysulfide combined.

2 . The rechargeable magnesium-sulfur cell of claim 1 , wherein said metal element M is selected from Li, Na, K, Mg, Ca, Zn, Cu, Ti, Ni, Co, Fe, Mn, Mo, Nb, Ta, Zr, or Al.

3 . The rechargeable magnesium-sulfur cell of claim 1 , wherein said M x S y is selected from Li 2 S, Li 2 S 2 , Li 2 S 3 , Li 2 S 4 , Li 2 S 5 , Li 2 S 6 , Li 2 S 7 , Li 2 S 8 , Li 2 S 9 , Li 2 S 10 , Na 2 S, Na 2 S 2 , Na 2 S 3 , Na 2 S 4 , Na 2 S 5 , Na 2 S 6 , Na 2 S 7 , Na 2 S 8 , Na 2 S 9 , Na 2 S 10 , K 2 S, K 2 S 2 , K 2 S 3 , K 2 S 4 , K 2 S 5 , K 2 S 6 , K 2 S 7 , K 2 S 8 , K 2 S 9 , K 2 S 10 , MgS, MgS 2 , MgS 3 , MgS 4 , MgS 5 , MgS 6 , Mo 6 S 8 , Nb 6 S 8 , Zr 6 S 8 , or Ta 6 S 8 .

4 . The rechargeable magnesium-sulfur cell of claim 1 , wherein said M x S y is loaded in said pores or on said massive surfaces after said integral porous structure is made and before said cell is made.

5 . The rechargeable magnesium-sulfur cell of claim 1 , wherein said integral porous structure is a meso-porous structure formed of multiple particles, platelets, or filaments of a carbon, graphite, metal, or conductive polymer, wherein said meso-porous structure has meso-scaled pores of 2-50 nm and a specific surface area greater than 100 m 2 /g and wherein said carbon, graphite, metal, or conductive polymer is selected from chemically etched or expanded soft carbon, chemically etched or expanded hard carbon, exfoliated activated carbon, chemically etched or expanded carbon black, chemically etched multi-walled carbon nanotube, nitrogen-doped carbon nanotube, boron-doped carbon nanotube, chemically doped carbon nanotube, ion-implanted carbon nanotube, chemically treated multi-walled carbon nanotube with an inter-planar separation no less than 0.4 nm, chemically expanded carbon nano-fiber, chemically activated carbon nano-tube, chemically treated carbon fiber, chemically activated graphite fiber, chemically activated carbonized polymer fiber, chemically treated coke, activated meso-phase carbon, meso-porous carbon, electro-spun conductive nano fiber, highly separated vapor-grown carbon or graphite nano fiber, highly separated carbon nano-tube, carbon nanowire, metal nano wire, metal-coated nanowire or nano-fiber, conductive polymer-coated nanowire or nano-fiber, or a combination thereof, and wherein said particles or fibrils are optionally bonded to form said porous structure by a binder of from 0% to 30% by weight of a total porous structure weight not counting the metal polysulfide weight.

6 . The rechargeable magnesium-sulfur cell of claim 1 , wherein said integral porous structure is a porous graphene structure containing a graphene material or an exfoliated graphite material wherein the graphene material is selected from pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, or a combination thereof and wherein the exfoliated graphite material is selected from exfoliated graphite worms, expanded graphite flakes, or recompressed graphite worms or flakes, and wherein said graphene structure comprises multiple sheets of said graphene material or multiple flakes of said exfoliated graphite material that are intersected or interconnected to form said integral layer with or without a binder to bond said multiple sheets or flakes together, wherein said binder is from a resin, a conductive polymer, coal tar pitch, petroleum pitch, meso-phase pitch, coke, or a derivative thereof and occupies from 0% to 30% by weight of a total porous graphene structure weight not counting the metal polysulfide weight.

7 . The rechargeable magnesium-sulfur cell of claim 1 , wherein said integral porous structure is a porous, electrically conductive material selected from metal foam, carbon-coated metal foam, graphene-coated metal foam, metal web or screen, carbon-coated metal web or screen, graphene-coated metal web or screen, perforated metal sheet, carbon-coated porous metal sheet, graphene-coated porous metal sheet, metal fiber mat, carbon-coated metal-fiber mat, graphene-coated metal-fiber mat, metal nanowire mat, carbon-coated metal nanowire mat, graphene-coated metal nano-wire mat, surface-passivated porous metal, porous conductive polymer film, conductive polymer nano-fiber mat or paper, conductive polymer foam, carbon foam, graphitic foam, carbon aerogel, carbon xerox gel, or a combination thereof.

8 . The rechargeable magnesium-sulfur cell of claim 1 , which is a free-standing layer or is physically or chemically bonded to a current collector layer prior to being incorporated into said magnesium-sulfur cell.

9 . The rechargeable magnesium-sulfur cell of claim 1 , further comprising an element Z or a metal compound M x Z y deposited in said porous or on said massive surfaces wherein said element Z or M x Z y is mixed with said metal polysulfide or formed as discrete coating or particles having a dimension less than 100 nm and said Z element is selected from Sn, Sb, Bi, Se, and/or Te, and wherein x is an integer from 1 to 3, y is an integer from 1 to 10, and M is a metal element selected from an alkali metal, an alkaline metal, a transition metal, a metal from groups 13 to 17 of the periodic table, or a combination thereof, and the weight ratio of Z/M x S y or M x Z y /M x S y is less than 1.

10 . The rechargeable magnesium-sulfur cell of claim 1 , wherein said metal polysulfide occupies a weight fraction of at least 70% of the total weight of said porous structure and said metal polysulfide combined.

11 . The rechargeable magnesium-sulfur cell of claim 1 , wherein said metal polysulfide occupies a weight fraction of at least 90% of the total weight of said porous structure and said metal polysulfide combined.

12 . The rechargeable magnesium-sulfur cell of claim 1 , wherein said metal polysulfide thickness or diameter is smaller than 20 nm.

13 . The rechargeable magnesium-sulfur cell of claim 1 , wherein said metal polysulfide thickness or diameter is smaller than 10 nm.

14 . The rechargeable magnesium-sulfur cell of claim 1 , wherein said integral porous structure has massive surfaces having a specific surface area greater than 500 m 2 /g.

15 . The rechargeable magnesium-sulf

Assignees

• He Hui
• Zhamu Aruna
• Jang Bor Z

Inventors

• He Hui
• Zhamu Aruna
• Jang Bor Z

Classifications

• H01M2/1673

  Electricity · mapped topic

• H01M2220/20

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

• H01M2300/0037

  Mixture of solvents · CPC title

• H01M4/38

  of elements or alloys · CPC title

• H01M10/0568

  characterised by the solutes · CPC title