Pre-sulfurized cathode for alkali metal-sulfur secondary battery and production process

Patent metadata

Field	Value
Publication number	US-2016240841-A1
Application number	US-201514544765-A
Country	US
Kind code	A1
Filing date	Feb 18, 2015
Priority date	Feb 18, 2015
Publication date	Aug 18, 2016
Grant date	—

Abstract

A method of producing a pre-sulfurized active cathode layer for a rechargeable alkali metal-sulfur cell; the method comprising: (a) Preparing an integral layer of porous graphene structure having a specific surface area greater than 100 m 2 /g; (b) Preparing an electrolyte comprising a solvent and a sulfur source; (c) Preparing an anode; and (d) Bringing the integral layer and the anode in ionic contact with the electrolyte and imposing an electric current between the anode and the integral layer (serving as a cathode) to electrochemically deposit nano-scaled sulfur particles or coating on the graphene surfaces. The sulfur particles or coating have a thickness or diameter smaller than 20 nm (preferably <10 nm, more preferably <5 nm or even <3 nm) and occupy a weight fraction of at least 70% (preferably >90% or even >95%).

First claim

1 . An electrochemical method of producing a pre-sulfurized active cathode layer for a rechargeable alkali metal-sulfur cell, said method comprising:
(a) Preparing an integral layer of porous graphene structure having massive graphene surfaces with a specific surface area greater than 100 m 2 /g, wherein said graphene structure contains 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 and with or without a conductive filler included in said integral layer, and wherein said porous graphene structure contains optional 0-49% by weight of sulfur or sulfur-containing compound pre-loaded therein and an optional binder material of 0-10% by weight; (b) Preparing an electrolyte comprising a non-aqueous solvent and a sulfur source dissolved or dispersed in said solvent; (c) Preparing an anode; and (d) Bringing said integral layer of porous graphene structure and said anode in ionic contact with said electrolyte and imposing an electric current between said anode and said integral layer of porous graphene structure, serving as a cathode, with a sufficient current density for a sufficient period of time to electrochemically deposit nano-scaled sulfur particles or coating directly on said graphene surfaces to form said pre-sulfurized active cathode layer, wherein said particles or coating have a thickness or diameter smaller than 20 nm.

2 . The method of claim 1 , wherein said sulfur source is selected from 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 method of claim 1 , wherein said anode comprises an anode active material 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.

4 . The method of claim 2 , wherein said metal element M is selected from Li, Na, K, Mg, Zn, Cu, Ti, Ni, Co, Fe, or Al.

5 . The method of claim 2 , wherein said M x S y is selected from 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 .

6 . The method of claim 1 , further comprising a procedure of depositing an element Z to said porous graphene structure wherein said element Z is mixed with sulfur or formed as discrete Z 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 the weight of element Z is less than the weight of sulfur.

7 . The method of claim 6 , wherein said procedure of depositing element Z includes electrochemical deposition, chemical deposition, or solution deposition.

8 . The method of claim 1 , wherein said nano-scaled sulfur particles or coating occupy a weight fraction of at least 70% based on the total weights of said sulfur particles or coating and said graphene material combined.

9 . The method of claim 1 , wherein said electrolyte further comprises a metal salt selected from lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro-metasulfonate (LiCF 3 SO 3 ), bis-trifluoromethyl sulfonylimide lithium (LiN(CF 3 SO 2 ) 2 ), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 O 4 ), lithium oxalyldifluoroborate (LiBF 2 C 2 O 4 ), lithium nitrate (LiNO 3 ), Li-Fluoroalkyl-Phosphates (LiPF 3 (CF 2 CF 3 ) 3 ), lithium bisperfluoro-ethysulfonylimide (LiBETI), lithium bis(trifluoromethanesulphonyl)imide, lithium bis(fluorosulphonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid-based lithium salt, sodium perchlorate (NaClO 4 ), potassium perchlorate (KClO 4 ), sodium hexafluorophosphate (NaPF 6 ), potassium hexafluorophosphate (KPF 6 ), sodium borofluoride (NaBF 4 ), potassium borofluoride (KBF 4 ), sodium hexafluoroarsenide, potassium hexafluoroarsenide, sodium trifluoro-metasulfonate (NaCF 3 SO 3 ), potassium trifluoro-metasulfonate (KCF 3 SO 3 ), bis-trifluoromethyl sulfonylimide sodium (NaN(CF 3 SO 2 ) 2 ), sodium trifluoromethanesulfonimide (NaTFSI), bis-trifluoromethyl sulfonylimide potassium (KN(CF 3 SO 2 ) 2 ), or a combination thereof.

10 . The method of claim 1 , wherein said solvent is selected from 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), tetraethylene glycol dimethylether (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), sulfone, sulfolane, ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), gamma-butyrolactone (γ-BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene, methyl acetate (MA), fluoroethylene carbonate (FEC), vinylene carbonate (VC), allyl ethyl carbonate (AEC), a hydrofluoroether, a room temperature ionic liquid solvent, or a combination thereof.

11 . The method of claim 1 , wherein said anode, said electrolyte, and said integral layer of porous graphene structure are disposed in an external container outside of a lithium-sulfur cell and said step of electrochemically depositing nano-scaled sulfur particles or coating on said graphene surfaces is conducted outside said lithium-sulfur cell.

12 . The method of claim 1 , wherein said anode, said electrolyte, and said integral layer of porous graphene structure are disposed inside a lithium-sulfur cell and said step of electrochemically depositing nano-scaled sulfur particles or coating on said graphene surfaces is conducted after said lithium-sulfur cell is fabricated.

13 . The method of claim 1 , wherein said anode, said electrolyte, and said integral layer of porous graphene structure are part of a lithium-sulfur cell and said step of electrochemically depositing nano-scaled sulfur particles or coating on said graphene surfaces occurs after said lithium-sulfur cell is fabricated and is conducted during a first charge cycle of said cell.

14 . The method of claim 1 , wherein said nano-scaled sulfur particles or coating occupy a weight fraction of at least 80%.

15 . The method of claim 1 , wherein said nano-scaled sulfur particles or coating occupy a weight fraction of at least 90%.

16 . The method of claim 1 , wherein said nano-scaled sulfur particles or coating have a thickness or diameter smaller than 10 nm.

17 . The method of claim 1 , wherein said nano-scaled sulfur particles or coating have a thickness or diameter smaller than 5 nm.

18 . The method of claim 1 , wherein said nano-scaled sulfur particles or coating have a thickness or diamete

Assignees

• He Hui
• Zhamu Aruna
• Jang Bor Z

Inventors

• He Hui
• Zhamu Aruna
• Jang Bor Z

Classifications

• H01M4/1397

  of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title

• H01M4/38

  of elements or alloys · CPC title

• H01M4/625

  Carbon or graphite · CPC title

• H01M4/0447

  of complete cells or cells stacks · CPC title

• H01M4/0452

  from solutions · CPC title