IP Library Granted Patent US 9,825,287
Granted Patent B2
US 9,825,287 · App. 14/744,433 · Granted Nov 21, 2017

Surface modification agents for lithium batteries

Inventors: Zonghai Chen (Bolingbrook, IL); Khalil Amine (Oakbrook, IL); Ilias Belharouak (Bolingbrook, IL)
Assignee: UCHICAGO ARGONNE, LLC
H01M4/366H01M4/0416H01M4/0421H01M4/13H01M4/139H01M4/485H01M4/604H01M4/62H01M4/623H01M4/625H01M10/052H01M10/0567H01M4/131H01M4/1391H01M4/505H01M10/0525Y02E60/122Y02P70/54Y02T10/7011Y10T29/49115
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Quick Facts
Patent No.
US 9,825,287
App. No.
14/744,433
Granted
Nov 21, 2017
Kind
B2
Abstract

An active material for an electrochemical device wherein a surface of the active material is modified by a surface modification agent, wherein the surface modification agent is an organometallic compound.

Claims (24)

1. An active material for an electrochemical device:

wherein:

a surface of the active material is modified by a first surface modification agent selected from the group consisting of aluminum sec-butoxide, diethylaluminum ethoxide, tris(ethylmethylamido)aluminum, triethylaluminum, triisobutylaluminum, trimethylaluminum, tris(diethylamido)aluminum, tris(ethylmethylamido)aluminum, trimethylarsine, diborane, trimethylboron, bis(N,N′-diisopropylacetaminato)cobalt (II), dicarbonyl(cyclopentadienyl)cobalt (I), (N,N′-diisopropylacetaminato)copper (II), bis(N,N′-di-tert-butylacetamidinato)iron (II), triethylgallium, triisopropylgallium, trimethylgallium, tri(dimethylamido)gallium, tri-tert-butylgallium, digermane, germane, tetramethylgermanium, hafnium (IV) tert-butoxide, tetrakis(diethylamido)hafnium (IV), tetrakis(dimethylamido)hafnium (IV), tetrakis(ethylmethylamido)hafnium (IV), indium acetylacetonate, triethylindium, tris(N,N′-Di-tert-butylacetamidinato)lanthanum (III), bis(pentaethylcyclopentadienyl)magnesium, molybdenum hexacarbonyl, niobium (V) ethoxide, bis(methylcyclopentadienyl)nickel (II), cyclopentadienyl(trimethyl)platinum (IV), bis(ethylcyclopentadienyl)ruthenium (II), trimethylantimony, tris(dimethylamido)antimony, pentakis(dimethylamido)tantalum (V), tantalum (V) ethoxide, tris(diethylamino)(tert-butylimido)tantalum (V), bis(diethylamido)bis(dimethylamido)titanium (IV), tetrakis(diethylamido)titanium (IV), tetrakis(dimethylamido)titanium (IV), tetrakis(ethylmethylamido)titanium (IV), titanium (IV) tert-butoxide, vanadium (V) oxytriisopropoxide, bis(tert-butylimido)bis(dimethylamido)tungsten (VI), tungsten hexacarbonyl, tris(N,N-bis(trimethylsilyl)amide)yttrium (III), yttrium (III) butoxide, diethylzinc, tetrakis(diethylamido)zirconium (IV), tetrakis(dimethylamido)zirconium (IV), tetrakis(ethylmethylamido)zirconium (IV), zirconium (IV) tert-butoxide, and a mixture of any two or more thereof.

2. The active material of claim 1 , wherein the surface active agent further comprises a second surface modification agent selected from the group consisting of: aluminum sec-butoxide, aluminum tribromide, aluminum trichloride, diethylaluminum ethoxide, tris(ethylmethylamido)aluminum, triethylaluminum, triisobutylaluminum, trimethylaluminum, tris(diethylamido)aluminum, tris(ethylmethylamido)aluminum, trimethylarsine, diborane, trimethylboron, bis(N,N′-diisopropylacetaminato)cobalt (II), dicarbonyl(cyclopentadienyl)cobalt (I), (N,N′-diisopropylacetaminato)copper (II), bis(N,N′-di-tert-butylacetamidinato)iron (II), gallium tribromide, gallium trichloride, triethylgallium, triisopropylgallium, trimethylgallium, tri(dimethylamido)gallium, tri-tert-butylgallium, digermane, germane, tetramethylgermanium, hafnium (IV) chloride, hafnium (IV) tert-butoxide, tetrakis(diethylamido)hafnium (IV), tetrakis(dimethylamido)hafnium (IV), tetrakis(ethylmethylamido)hafnium (IV), indium trichloride, indium(I) iodide, indium acetylacetonate, triethylindium, tris(N,N′-Di-tert-butylacetamidinato)lanthanum (III), bis(pentaethylcyclopentadienyl)magnesium, molybdenum hexacarbonyl, molybdenum (V) chloride, molybdenum (VI) fluoride, N,N-dimethylhydrazine, ammonia, azidotrimethylsilane, niobium (V) chloride, niobium (V) ethoxide, bis(methylcyclopentadienyl)nickel (II), phosphine, tert-butylphosphine, tris(trimethylsilyl)phosphine, cyclopentadienyl(trimethyl)platinum (IV), bis(ethylcyclopentadienyl)ruthenium (II), trimethylantimony, tris(dimethylamido)antimony, 2,4,6,8-tetramethylcyclotetrasiloxane, dimethoxydimethylsilane, disilane, methylsilane, octamethylcyclotetrasiloxane, silane, tris(isopropoxy)silanol, tris(tert-butoxy)silanol, tris(tert-pentoxy)silanol, pentakis(dimethylamido)tantalum (V), tantalum (V) chloride, tantalum (V) ethoxide, tris(diethylamino)(tert-butylimido)tantalum (V), bis(diethylamido)bis(dimethylamido)titanium (IV), tetrakis(diethylamido)titanium (IV), tetrakis(dimethylamido)titanium (IV), tetrakis(ethylmethylamido)titanium (IV), titanium (IV) bromide, titanium (IV) chloride, titanium (IV) tert-butoxide, vanadium (V) oxytriisopropoxide, bis(tert-butylimido)bis(dimethylamido)tungsten (VI), tungsten hexacarbonyl, tungsten (VI) chloride, tris(N,N-bis(trimethylsilyl)amide)yttrium (III), yttrium (III) butoxide, diethylzinc, tetrakis(diethylamido)zirconium (IV), tetrakis(dimethylamido)zirconium (IV), tetrakis(ethylmethylamido)zirconium (IV), zirconium (IV) bromide, zirconium (IV) chloride, zirconium (IV) tert-butoxide, and a mixture of any two or more thereof.

3. The active material of claim 1 , wherein the surface active agent further comprises a second surface modification agent selected from the group consisting of ammonia, phosphine, a halophosphine, a alkylphosphine, a haloalkylphosphine, an alkylamine, moisture, and a mixture of any two or more thereof.

4. An electrode comprising an active material for an electrochemical device, a current collector, and a binder;

wherein:

a surface of the active material is modified by a first surface modification agent selected from the group consisting of aluminum sec-butoxide, diethylaluminum ethoxide, tris(ethylmethylamido)aluminum, triethylaluminum, triisobutylaluminum, trimethylaluminum, tris(diethylamido)aluminum, tris(ethylmethylamido)aluminum, trimethylarsine, diborane, trimethylboron, bis(N,N′-diisopropylacetaminato)cobalt (II), dicarbonyl(cyclopentadienyl)cobalt (I), (N,N′-diisopropylacetaminato)copper (II), bis(N,N′-di-tert-butylacetamidinato)iron (II), triethylgallium, triisopropylgallium, trimethylgallium, tri(dimethylamido)gallium, tri-tert-butylgallium, digermane, germane, tetramethylgermanium, hafnium (IV) tert-butoxide, tetrakis(diethylamido)hafnium (IV), tetrakis(dimethylamido)hafnium (IV), tetrakis(ethylmethylamido)hafnium (IV), indium acetylacetonate, triethylindium, tris(N,N′-Di-tert-butylacetamidinato)lanthanum (III), bis(pentaethylcyclopentadienyl)magnesium, molybdenum hexacarbonyl, niobium (V) ethoxide, bis(methylcyclopentadienyl)nickel (II), cyclopentadienyl(trimethyl)platinum (IV), bis(ethylcyclopentadienyl)ruthenium (II), trimethylantimony, tris(dimethylamido)antimony, pentakis(dimethylamido)tantalum (V), tantalum (V) ethoxide, tris(diethylamino)(tert-butylimido)tantalum (V), bis(diethylamido)bis(dimethylamido)titanium (IV), tetrakis(diethylamido)titanium (IV), tetrakis(dimethylamido)titanium (IV), tetrakis(ethylmethylamido)titanium (IV), titanium (IV) tert-butoxide, vanadium (V) oxytriisopropoxide, bis(tert-butylimido)bis(dimethylamido)tungsten (VI), tungsten hexacarbonyl, tris(N,N-bis(trimethylsilyl)amide)yttrium (III), yttrium (III) butoxide, diethylzinc, tetrakis(diethylamido)zirconium (IV), tetrakis(dimethylamido)zirconium (IV), tetrakis(ethylmethylamido)zirconium (IV), zirconium (IV) tert-butoxide, and a mixture of any two or more thereof.

5. The electrode of claim 4 , wherein the surface active agent further comprises a second surface modification agent selected from the group consisting of: aluminum sec-butoxide, aluminum tribromide, aluminum trichloride, diethylaluminum ethoxide, tris(ethylmethylamido)aluminum, triethylaluminum, triisobutylaluminum, trimethylaluminum, tris(diethylamido)aluminum, tris(ethylmethylamido)aluminum, trimethylarsine, diborane, trimethylboron, bis(N,N′-diisopropylacetaminato)cobalt (II), dicarbonyl(cyclopentadienyl)cobalt (I), (N,N′-diisopropylacetaminato)copper (II), bis(N,N′-di-tert-butylacetamidinato)iron (II), gallium tribromide, gallium trichloride, triethylgallium, triisopropylgallium, trimethylgallium, tri(dimethylamido)gallium, tri-tert-butylgallium, digermane, germane, tetramethylgermanium, hafnium (IV) chloride, hafnium (IV) tert-butoxide, tetrakis(diethylamido)hafnium (IV), tetrakis(dimethylamido)hafnium (IV), tetrakis(ethylmethylamido)hafnium (IV), indium trichloride, indium(I) iodide, indium acetylacetonate, triethylindium, tris(N,N′-Di-tert-butylacetamidinato)lanthanum (III), bis(pentaethylcyclopentadienyl)magnesium, molybdenum hexacarbonyl, molybdenum (V) chloride, molybdenum (VI) fluoride, N,N-dimethylhydrazine, ammonia, azidotrimethylsilane, niobium (V) chloride, niobium (V) ethoxide, bis(methylcyclopentadienyl)nickel (II), phosphine, tert-butylphosphine, tris(trimethylsilyl)phosphine, cyclopentadienyl(trimethyl)platinum (IV), bis(ethylcyclopentadienyl)ruthenium (II), trimethylantimony, tris(dimethylamido)antimony, 2,4,6,8-tetramethylcyclotetrasiloxane, dimethoxydimethylsilane, disilane, methylsilane, octamethylcyclotetrasiloxane, silane, tris(isopropoxy)silanol, tris(tert-butoxy)silanol, tris(tert-pentoxy)silanol, pentakis(dimethylamido)tantalum (V), tantalum (V) chloride, tantalum (V) ethoxide, tris(diethylamino)(tert-butylimido)tantalum (V), bis(diethylamido)bis(dimethylamido)titanium (IV), tetrakis(diethylamido)titanium (IV), tetrakis(dimethylamido)titanium (IV), tetrakis(ethylmethylamido)titanium (IV), titanium (IV) bromide, titanium (IV) chloride, titanium (IV) tert-butoxide, vanadium (V) oxytriisopropoxide, bis(tert-butylimido)bis(dimethylamido)tungsten (VI), tungsten hexacarbonyl, tungsten (VI) chloride, tris(N,N-bis(trimethylsilyl)amide)yttrium (III), yttrium (III) butoxide, diethylzinc, tetrakis(diethylamido)zirconium (IV), tetrakis(dimethylamido)zirconium (IV), tetrakis(ethylmethylamido)zirconium (IV), zirconium (IV) bromide, zirconium (IV) chloride, zirconium (IV) tert-butoxide, and a mixture of any two or more thereof.

6. The electrode of claim 4 , wherein the surface active agent further comprises a second surface modification agent selected from the group consisting of ammonia, phosphine, a halophosphine, a alkylphosphine, a haloalkylphosphine, an alkylamine, moisture, and a mixture of any two or more thereof.

7. The electrode of claim 4 , wherein the binder is polyvinylidene difluoride, copolymer of polyvinylidene difluoride and hexafluoropropylene, or a mixture thereof.

8. The electrode of claim 4 further comprising a conductive filling selected from the group consisting of carbon black, carbon fiber, graphite, a metallic nano powder, and a mixture of any two or more thereof.

9. The electrode of claim 4 which is a negative electrode.

10. The electrode of claim 4 which is a positive electrode.

11. An active material for an electrochemical device:

wherein:

a surface of the active material is modified by a first surface modification agent and a second surface modification agent;

the first surface modification agent is a compound of Formula VIII, Formula IX, or a mixture thereof,

Formula VIII is M-(R 8 ) p ;

Formula IX is M-(O—R 9 ) p ;

M is a metal;

R 8 and R 9 are each independently hydrogen, alkoxy, alkyl, aryl, or aminoalkyl; and

p is an integer from 1 to 6; and

the second surface modification agent selected from the group consisting of: aluminum sec-butoxide, aluminum tribromide, aluminum trichloride, diethylaluminum ethoxide, tris(ethylmethylamido)aluminum, triethylaluminum, triisobutylaluminum, trimethylaluminum, tris(diethylamido)aluminum, tris(ethylmethylamido)aluminum, trimethylarsine, diborane, trimethylboron, bis(N,N′-diisopropylacetaminato)cobalt (II), dicarbonyl(cyclopentadienyl)cobalt (I), (N,N′-diisopropylacetaminato)copper (II), bis(N,N′-di-tert-butylacetamidinato)iron (II), gallium tribromide, gallium trichloride, triethylgallium, triisopropylgallium, trimethylgallium, tri(dimethylamido)gallium, tri-tert-butylgallium, digermane, germane, tetramethylgermanium, hafnium (IV) chloride, hafnium (IV) tert-butoxide, tetrakis(diethylamido)hafnium (IV), tetrakis(dimethylamido)hafnium (IV), tetrakis(ethylmethylamido)hafnium (IV), indium trichloride, indium(I) iodide, indium acetylacetonate, triethylindium, tris(N,N′-Di-tert-butylacetamidinato)lanthanum (III), bis(pentaethylcyclopentadienyl)magnesium, molybdenum hexacarbonyl, molybdenum (V) chloride, molybdenum (VI) fluoride, N,N-dimethylhydrazine, ammonia, azidotrimethylsilane, niobium (V) chloride, niobium (V) ethoxide, bis(methylcyclopentadienyl)nickel (II), phosphine, tert-butylphosphine, tris(trimethylsilyl)phosphine, cyclopentadienyl(trimethyl)platinum (IV), bis(ethylcyclopentadienyl)ruthenium (II), trimethylantimony, tris(dimethylamido)antimony, 2,4,6,8-tetramethylcyclotetrasiloxane, dimethoxydimethylsilane, disilane, methylsilane, octamethylcyclotetrasiloxane, silane, tris(isopropoxy)silanol, tris(tert-butoxy)silanol, tris(tert-pentoxy)silanol, pentakis(dimethylamido)tantalum (V), tantalum (V) chloride, tantalum (V) ethoxide, tris(diethylamino)(tert-butylimido)tantalum (V), bis(diethylamido)bis(dimethylamido)titanium (IV), tetrakis(diethylamido)titanium (IV), tetrakis(dimethylamido)titanium (IV), tetrakis(ethylmethylamido)titanium (IV), titanium (IV) bromide, titanium (IV) chloride, titanium (IV) tert-butoxide, vanadium (V) oxytriisopropoxide, bis(tert-butylimido)bis(dimethylamido)tungsten (VI), tungsten hexacarbonyl, tungsten (VI) chloride, tris(N,N-bis(trimethylsilyl)amide)yttrium (III), yttrium (III) butoxide, diethylzinc, tetrakis(diethylamido)zirconium (IV), tetrakis(dimethylamido)zirconium (IV), tetrakis(ethylmethylamido)zirconium (IV), zirconium (IV) bromide, zirconium (IV) chloride, zirconium (IV) tert-butoxide, and a mixture of any two or more thereof.

Assignments (1)
CONFIRMATORY LICENSE Recorded Oct 7, 2015
From: UCHICAGO ARGONNE, LLC
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 036815/0326 →
Continuity (5)
Continuation 13546440 · Jul 11, 2012
Continuation 13397319 · Feb 15, 2012
Continuation 12454173 · May 13, 2009
Provisional Application 61127901 · May 16, 2008
Related Publication 20150287987A1 · Oct 8, 2015