US2023253545A1PendingUtilityA1

Anodes, cathodes, and separators for batteries and methods to make and use same

77
Assignee: UNIV RICE WILLIAM MPriority: Aug 31, 2016Filed: Mar 8, 2023Published: Aug 10, 2023
Est. expiryAug 31, 2036(~10.1 yrs left)· nominal 20-yr term from priority
Inventors:James M. TourRodrigo Villegas SalvatierraGladys Anahi Lopez Silva
H01M 10/4235B82Y 40/00B82Y 30/00H01M 50/431H01M 50/403H01M 50/449H01M 4/134H01M 4/13H01M 4/133H01M 10/0525H01M 10/058H01M 4/583H01M 4/0404H01M 4/58H01M 4/625H01M 4/0471H01M 4/38H01M 4/136H01M 50/451Y02T10/70H01M 2004/028Y02E60/10
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Claims

Abstract

Anodes, cathodes, and separators for batteries (electrochemical energy storage devices). The anodes are Li metal anodes having lithiated carbon films (Li-MWCNT) (as dendrite suppressors and protective coatings for the Li metal anodes). The cathodes are sulfurized carbon cathodes. The separators are GNR-coated (or modified) separators. The invention includes each of these separately (as well as in combination both with each other and with other anodes, cathodes, and separators) and the methods of making each of these separately (and in combination). The invention further includes a battery that uses at least one of (a) the anode having a lithiated carbon film, (b) the sulfurized carbon cathode, and (c) the GNR-modified separator in the anode/cathode/separator arrangement. For instance, a full battery can include the sulfurized carbon cathode in combination with the Li-MWCNT anode or a full battery can include the sulfurized carbon cathode in combination with other anodes (such as a GCNT-Li anode).

Claims

exact text as granted — not AI-modified
What is claimed is: 
     
         1 . A lithium metal anode comprising a lithium metal coated with a lithiated carbon material. 
     
     
         2 . A cathode comprising a sulfurized carbon cathode. 
     
     
         3 . A GNR-modified separator comprising a polymer material coated with a layer of GNRs, wherein the GNR-modified separator is operable for use as a separator in a battery. 
     
     
         4 . A battery comprising an anode, a cathode, and a separator positioned between the anode and the cathode, wherein the battery comprises a component selected from the group consisting of:
 (a) anodes comprising the lithium metal anode of  claim 1 ;   (b) anodes comprising the sulfurized carbon cathode of  claim 2 ;   (c) separators comprising the GNR-modified separator of  claim 3 ; and   (d) combinations thereof.   
     
     
         5 . The battery of  claim 4 , wherein the anode comprises the lithium metal anode of  claim 1 . 
     
     
         6 . The battery of  claim 5 , wherein the cathode comprises the sulfurized carbon cathode of  claim 2 . 
     
     
         7 . The battery of  claim 6 , wherein the separator comprises the GNR-modified separator of  claim 3 . 
     
     
         8 . The battery of  claim 4 , wherein the cathode comprises the sulfurized carbon cathode of  claim 2 . 
     
     
         9 . The battery of  claim 8 , wherein the separator comprises the GNR-modified separator of  claim 3 . 
     
     
         10 . The battery of  claim 4 , wherein the separator comprises the GNR-modified separator of  claim 3 . 
     
     
         11 . A method comprising making a lithium metal anode, wherein the method includes the steps of:
 (a) selecting a lithium metal having a surface;   (b) coating the surface of the lithium metal with a carbon material and an electrolyte,   (c) performing a reaction involving the lithium metal, the carbon material, and the electrolyte to form a lithiated layer on the surface of the lithium metal.   
     
     
         12 . A method comprising making a sulfurized carbon cathode. 
     
     
         13 . A method comprising selecting a polymer material operable for use as a separator in a battery, and modifying the polymer material by adding a layer of GNRs to form a GNR-modified separator. 
     
     
         14 . A method of forming a battery comprising the steps of combining an anode, a cathode, and a separator positioned between the anode and cathode, wherein the method comprises the step selected from the group consisting of:
 (a) making the lithium metal anode of  claim 11 ;   (b) making the sulfurized carbon cathode of  claim 12 ;   (c) making the GNR-modified separator of  claim 13 ; and   (d) combinations thereof.   
     
     
         15 . The method of  claim 14 , wherein the method comprises making the lithium metal anode of  claim 11 . 
     
     
         16 . The method of  claim 15 , wherein the method comprises making the sulfurized carbon cathode of  claim 12 . 
     
     
         17 . The method of  claim 16 , wherein the method comprises making the GNR-modified separator of  claim 13 . 
     
     
         18 . The method of  claim 14 , wherein the method comprises making the sulfurized carbon cathode of  claim 12 . 
     
     
         19 . The method of  claim 18 , wherein the method comprises making the GNR-modified separator of  claim 13 . 
     
     
         20 . The method of  claim 14 , wherein the method comprises making the GNR-modified separator of  claim 13 . 
     
     
         21 . A method of forming a battery comprising the steps of combining an anode, a cathode, and a separator positioned between the anode and cathode, wherein the battery comprises a component selected from the group consisting of:
 (a) anodes comprising the lithium metal anode of  claim 1 ;   (b) anodes comprising the sulfurized carbon cathode of  claim 2 ;   (c) separators comprising the GNR-modified separator of  claim 3 ; and   (d) combinations thereof.   
     
     
         22 . The method of  claim 21 , wherein the anode comprises the lithium metal anode of  claim 1 . 
     
     
         23 . The method of  claim 22 , wherein the cathode comprises the sulfurized carbon cathode of  claim 2 . 
     
     
         24 . The method of  claim 23 , wherein the separator comprises the GNR-modified separator of  claim 3 . 
     
     
         25 . The method of  claim 21 , wherein the cathode comprises the sulfurized carbon cathode of  claim 2 . 
     
     
         26 . The method of  claim 25 , wherein the separator comprises the GNR-modified separator of  claim 3 . 
     
     
         27 . The method of  claim 25 , wherein the sulfurized carbon cathode comprises a seamless hybrid of nanotubes grown from a graphene layer. 
     
     
         28 . The method of  claim 21 , wherein the separator comprises the GNR-modified separator of  claim 3 . 
     
     
         29 . The lithium metal anode of  claim 1  or the method of  claim 11 , wherein the lithium metal is in the form of a lithium foil. 
     
     
         30 . The method of  claim 11 , wherein the carbon material comprises multi-walled carbon nanotubes. 
     
     
         31 . The method of  claim 30 , wherein the multi-walled carbon nanotubes are in the form of a bucky paper. 
     
     
         32 . The method of  claim 11 , wherein the carbon material comprises graphene nanoribbons. 
     
     
         33 . The method of  claim 32 , wherein the nanoribbons are in the form of a filtered nanoribbon paper. 
     
     
         34 . The method of  claim 11 , wherein the carbon material is selected from a group consisting of multi-walled carbon nanotubes, single-walled carbon nanotubes, few-walled carbon nanotubes, graphene nanoribbons, graphene oxide, graphene oxide nanoribbons, graphoil, graphene nanoplatelets, graphite, activated carbon, thermally treated asphalt, amorphous carbon, carbon black, and mixtures thereof. 
     
     
         35 . The method of  claim 34 , wherein the carbon materials are further treated with a polymer to make the carbon materials more flexible without cracking. 
     
     
         36 . The method of  claim 35 , wherein the polymer comprises polydimethylsiloxane. 
     
     
         37 . The method of  claim 35 , wherein the polymer is selected from a group consisting of polydimethylsiloxane, polyurethane, thermoplastic polyurethane, polybutadiene, poly(styrene butadiene), poly(styrene butadiene styrene), polyacrylonitrile, polyaniline, poly fluorinated systems, poly(methyl methacrylate), poly(ethylene glycol), poly(ethylene oxide), polyacrylates, vinyl polymers, chain growth polymers, step growth polymers, condensation polymers, and mixtures thereof. 
     
     
         38 . The method of  claim 11 , wherein the electrolyte is selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), dimethoxyethane (DME), and 1,3-dioxolane (DOL), and mixtures thereof. 
     
     
         39 . The method of  claim 38 , wherein the electrolyte comprises a mixture of the 1 mol L −1  lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in a ratio of 1:1 of the dimethoxyethane (DME) and the 1,3-dioxolane (DOL). 
     
     
         40 . The method of  claim 11 , wherein the electrolyte is an ionic liquid or a mixture of the ionic liquid with an organic solvent. 
     
     
         41 . The method of  claim 11 , wherein the electrolyte is formed from a salt in a solvent, wherein
 (a) the salt is selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, lithium bis(fluorosulfonyl)imide, lithium bis(oxalato)borate, lithium tetrafluoroborate, and combinations thereof, and   (b) the solvent is selected from the group consisting of ethlylene carbonate, propylene carbonate, butylene carbonate, vinyl ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethylene carbonate, tetraethylene glycol dimethyl ether, and combinations thereof.   
     
     
         42 . The method of  claim 11 , wherein the electrolyte is placed on or between the carbon material and the lithium metal in the initial phases of the method. 
     
     
         43 . The method of  claim 41 , wherein the electrolyte is in a high concentration. 
     
     
         44 . The method of  claim 11 , wherein the electrolyte is between 0.5 and 10 mol/L of lithium bis(fluorosulfonyl)imide (LIFSI) in dimethoxyethane (DME). 
     
     
         45 . The method of  claim 44 , wherein the electrolyte is between 2 and 8 mol/L of the lithium bis(fluorosulfonyl)imide (LIFSI) in the dimethoxyethane (DME). 
     
     
         46 . The method of  claim 44 , wherein the electrolyte is between 3 and 5 mol/L of the lithium bis(fluorosulfonyl)imide (LIFSI) in the dimethoxyethane (DME). 
     
     
         47 . The method of  claim 44 , wherein the electrolyte is 4 mol/L of the lithium bis(fluorosulfonyl)imide (LIFSI) in the dimethoxyethane (DME). 
     
     
         48 . The method of  claim 22 , wherein an electrolyte is added to the battery in combination with the anode. 
     
     
         49 . The method of  claim 48 , wherein the electrolyte is between 0.5 and 10 mol/L of lithium bis(fluorosulfonyl)imide (LIFSI) in dimethoxyethane (DME). 
     
     
         50 . The method of  claim 11 , wherein the lithium metal dopes the carbon material. 
     
     
         51 . The method of  claim 11 , wherein the carbon material becomes red or silver in color. 
     
     
         52 . The method of  claim 11 , wherein the carbon material is operable to suppress lithium dendrite formation of the lithium metal anode. 
     
     
         53 . The method of  claim 50 , wherein the doped carbon material becomes the source of lithium ions injected across into the electrolyte and then into a cathode. 
     
     
         54 . The method of  claim 50 , wherein
 (a) the lithium metal is a metallic Li foil, and   (b) the doped carbon material acts as a buffer between an SEI layer and the metallic Li foil.   
     
     
         55 . The method of  claim 54 , wherein the buffer eliminates any gap formation between the SEI layer and the metallic Li foil. 
     
     
         56 . The method  claim 11 , wherein the lithium metal, the carbon material, and the electrolyte are part of a battery. 
     
     
         57 . The method of  claim 11 , wherein the lithium metal, the carbon material, and the electrolyte are part of a battery anode. 
     
     
         58 . The method of  claim 57 , where the battery comprises a sulfur cathode. 
     
     
         59 . The method of  claim 11 , wherein the reaction involving the lithium metal, the carbon material, and the electrolyte to form the lithiated layer on the surface of the lithium metal comprises a solid state reaction. 
     
     
         60 . The method of  claim 12 , wherein the sulfurized carbon cathode comprises sulfur, carbon, and thermally treated polyacrylonitrile. 
     
     
         61 . The cathode of  claim 2  or the method of  claim 12 , wherein the sulfurized carbon cathode comprises sulfur in an amount between about 47% and about 60 wt %. 
     
     
         62 . The cathode of  claim 61  or the method of  claim 61 , wherein the amount of the sulfur in the sulfurized carbon cathode is between about 47% and about 57 wt %. 
     
     
         63 . The cathode of  claim 61  or the method of  claim 61 , wherein the amount of the sulfur in the sulfurized carbon cathode is between about 55% and about 60 wt %. 
     
     
         64 . The cathode of  claim 2  or the method of  claim 12 , wherein the cathode lacks elemental sulfur. 
     
     
         65 . The cathode of  claim 2  or the method of  claim 12 , wherein the cathode comprises a carbon additive that is a conductive filler. 
     
     
         66 . The cathode of  claim 65  or the method of  claim 65 , wherein the carbon additive is selected from the group consisting of carbon black, graphene, carbon nanotubes, graphene nanoribbons, and combinations thereof. 
     
     
         67 . The method of  claim 12 , wherein the method of making the sulfurized carbon cathode comprises heat treating elemental sulfur with a carbon source. 
     
     
         68 . The method of  claim 67 , wherein the carbon source comprises PAN. 
     
     
         69 . The method of  claim 67 , wherein the step of heat treating occurs in the presence of an additive. 
     
     
         70 . The method of  claim 69 , wherein the additive is selected from a group consisting of carbon black, graphene, carbon nanotubes, graphene nanoribbons, and combinations thereof. 
     
     
         71 . The method of  claim 67 , wherein the step of heat treating occurs at a temperature of at least about 100° C. 
     
     
         72 . The method of  claim 71 , wherein the step of heat treating occurs at a temperature of at least about 450° C. 
     
     
         73 . The method of  claim 67 , wherein the step of heat treating occurs for at least about 3 hours. 
     
     
         74 . The method of  claim 12 , wherein the method of making the sulfurized carbon cathode comprises:
 (a) forming a powder comprising elemental sulfur, a carbon source, and an additive;   (b) heat treating the powder at a temperature of at least about 450° C. for at least three hours.   
     
     
         75 . The method of  claim 74 , wherein
 (a) the carbon source comprises PAN; and   (b) the additive comprises graphene nanoribbons.   
     
     
         76 . The method of  claim 12 , wherein the sulfurized carbon cathode is part of a seamless hybrid of nanotubes grown from a graphene layer. 
     
     
         77 . The method of  claim 13 , wherein the polymer materials comprise at least one of polypropylene (PP) and polyethylene (PE). 
     
     
         78 . A method to form an anode comprising:
 (a) selecting a lithium metal having a surface;   (b) coating the surface of the lithium metal with a carbon material and an electrolyte; and   (c) forming a lithiated carbon material by lithiating the carbon material with lithium from the lithium metal.   
     
     
         79 . The method of  claim 78 , wherein the method further comprises continuing the step of lithiating the carbon material until there is no remaining lithium in the lithium metal, wherein the lithiated carbon material is the anode. 
     
     
         80 . A lithium metal anode, wherein the lithium metal is coated with a thin film material and an electrolyte.

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