IP Library Granted Patent US 8,292,974
Granted Patent B2
US 8,292,974 · App. 13/397,319 · Granted Oct 23, 2012

Surface modification agents for lithium batteries

Assignee: UChicago Argonne, LLC
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Quick Facts
Patent No.
US 8,292,974
App. No.
13/397,319
Granted
Oct 23, 2012
Kind
B2
Abstract

A method includes modifying a surface of an electrode active material including providing a solution or a suspension of a surface modification agent; providing the electrode active material; preparing a slurry of the solution or suspension of the surface modification agent, the electrode active material, a polymeric binder, and a conductive filler; casting the slurry in a metallic current collector; and drying the cast slurry.

Claims (36)

1. A method of modifying a surface of an electrode active material, the method comprising:

providing a solution or a suspension of a surface modification agent;

providing the electrode active material;

preparing a slurry of the solution or suspension of the surface modification agent, the electrode active material, a polymeric binder, and a conductive filler;

casting the slurry in a metallic current collector; and

drying the cast slurry;

wherein

the surface modification agent is a silane, and the silane has Formula I, II, III, IV, or a mixture of any two or more thereof:

X 1 , X 2 , X 3 and X 4 are independently —Cl or —Br;

R 1 , R 2 , and R 3 are independently a halogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an OR 5 group, or a group of Formula V; and

R 5 is substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

2. The method of claim 1 , wherein the polymeric binder is PVDF, PVDF-HFP, or a mixture thereof.

3. The method of claim 1 , wherein the conductive filler is carbon black, carbon fiber, graphite, a metallic nano powder, or a mixture of any two or more thereof.

4. The method of claim 1 , wherein the concentration of the surface modification agent in the slurry is from about 0.00001 wt % to 5 wt %.

5. The method of claim 1 , wherein at least one of R 1 , R 2 , and R 3 is a substituted alkyl group that is an ethylene oxide moiety of Formula VI:

wherein:

m is an integer from 0 to 10;

n is an integer from 1 to 10; and

R 6 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a carbonate-based sub group of Formula VII:

wherein

R 7 is hydrogen, a substituted or unsubstituted alkyl group having from 1 to 12 carbon atoms; a substituted or unsubstituted alkenyl group having from 2 to 8 carbon atoms; and

q is an integer from 0 to 8.

6. The method of claim 5 , wherein the surface modification is a compound of Formula I; X 1 is Cl; R 6 is alkyl; m is 0; and n is from 1 to 5.

7. The method of claim 5 , wherein the surface modification is a compound of Formula I; X 1 is Cl; R 1 is an ethylene oxide of Formula VI; R 2 and R 3 are each alkyl; R 6 is alkyl; m is 0; and n is from 1 to 5.

8. The method of claim 5 , wherein the surface modification is a compound of Formula I; X 1 is Cl; R 1 is an ethylene oxide of Formula VI; R 2 and R 3 are each methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, or tert-butyl; R 6 is methyl or ethyl; m is 0; and n is from 1 to 5.

9. The method of claim 1 , wherein the surface modification agent is a compound of Formula I.

10. The method of claim 1 , wherein the electrode active material is a positive electrode active material selected from the group consisting of spinel, olivine, carbon-coated olivine, LiFePO 4 , Li x′ M′ y′ M″ z′ PO 4 , Li 1+x″ Ni α Mn β Co γ Met′ δ O 2−z″ F z″ , A n″ B 2 (XO 4 ) 3 , vanadium oxide, and mixtures of any two or more thereof; and further wherein

M′ is selected from the group consisting of V, Cr, Mg, Fe, Co, and Ni;

M″ is selected from group consisting of IIA, IIIA, IVA, VA, VIA and IIIB metals having an ionic radius less than the ionic radius of Fe 2+ ;

Met′ is selected from the group consisting of Mg, Zn, Al, Ga, B, Zr, and Ti; and

0≦x′≦1, 0≦y′≦1, 0≦z′≦1, 0≦x″≦0.4, 0≦α≦1, 0≦β≦1, 0≦γ≦2, 0≦δ≦0.2, 0≦z″≦0.5, and 0≦n″≦3.

11. The method of claim 1 , wherein the electrode active material is a negative electrode material selected from the group consisting of graphite, amorphous carbon, Li 4 Ti 5 O 12 , M 1−x A x Li 2−y B y Ti 6−z C z O 14−t Q t , tin alloys, silicon alloys, intermetallic compounds, lithium metal, or mixtures of any two or more such materials; and further wherein:

M is selected from the group consisting of Ba, Sr, Ca, Mg, Pb, and Sn;

0≦x≦0.5, 0≦y≦0.5, 0≦z≦0.5, 0<t≦0.5;

each of A, B and C are independently at least one divalent, trivalent or tetravalent metal; and

Q is a monovalent or divalent anion.

Assignments (1)
CONFIRMATORY LICENSE Recorded Apr 28, 2022
From: UCHICAGO ARGONNE, LLC
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 059761/0503 →
Continuity (3)
Continuation 12454173 · May 13, 2009
Provisional Application 61127901 · May 16, 2008
Related Publication 20120148731A1 · Jun 14, 2012