Methods for using atomic layer deposition to produce a film for solid state electrolytes and protective electrode coatings for lithium batteries

1. A method for using atomic layer deposition to produce a film configured for use in an anode, cathode, or solid-state electrolyte of a lithium-ion battery or a lithium-sulfur battery, the method comprising:

repeating a cycle for a predetermined number of times in an inert atmosphere, the cycle comprising:

exposing a substrate to a first precursor;

purging the substrate with inert gas;

exposing the substrate to a second precursor; and

purging the substrate with inert gas,

wherein the film comprises a metal sulfide, and

wherein the first precursor is selected from one of the following groups:

1) the group consisting of: lithium tert-butoxide, lithium acetylacetonate, 2,2,6,6-Tetramethyl-3,5-heptanedionato lithium, lithium cyclopentadienide, lithium pentamethylcyclopentadienide, and lithium 2-methyl-2-butoxide,

2) the group consisting of: hexakis(dimethylamido)digallium, hexakis(diethylamido)digallium, hexakis(ethyl-methylamido)digallium, gallium(III) acetylacetonate, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)gallium(III), gallium(III) hexafluoroacetylacetonate, and trimethylgallium, or

3) the group consisting of: tris(dimethylamido)aluminum, tris(dimethylamido)aluminum, tris(diethylamido)aluminum, tris(ethyl-methylamido)aluminum, aluminum(III) acetylacetonate, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)aluminum(III), aluminum(III) hexafluoroacetylacetonate, and trimethylaluminum.

2. The method of claim 1 , wherein the second precursor is hydrogen sulfide.

3. The method of claim 2 , wherein exposing the substrate to hydrogen sulfide comprises delivering 1% hydrogen sulfide pressure pulses of ˜0.2 Torr using at least one needle valve.

4. The method of 1 , wherein exposing the substrate to the first precursor comprises heating a solid form of the first precursor in a reservoir prior to exposure and diverting inert gas through the reservoir while exposing the substrate to the first precursor.

5. The method of claim 4 , wherein the inert gas comprises ultrahigh purity inert gas having a purity of 99.999%.

6. The method of claim 1 , wherein a duration of each exposing step and purging step of the cycle is 5 seconds.

7. The method of claim 1 ,

wherein the film is lithium sulfide and the first precursor is selected from the group consisting of: lithium tert-butoxide, lithium acetylacetonate, 2,2,6,6-Tetramethyl-3,5-heptanedionato lithium, lithium cyclopentadienide, lithium pentamethylcyclopentadienide, and lithium 2-methyl-2-butoxide, and

wherein a temperature at each step of the cycle is between 150-300° C.

8. The method of claim 1 , wherein the substrate is selected from the group consisting of Si(100), fused silica, micromachined Si trench wafers, copper foils, graphite particles, graphite laminates, Al 2 O 3 , and a combination thereof.

9. The method of claim 1 ,

wherein the film is gallium sulfide and the first precursor is selected from the group consisting of: hexakis(dimethylamido)digallium, hexakis(diethylamido)digallium, hexakis(ethyl-methylamido)digallium, gallium(III) acetylacetonate, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)gallium(III), gallium(III) hexafluoroacetylacetonate, and trimethylgallium, and

wherein the substrate is selected from the group consisting of Si wafers, fused silica, micromachined Si trenches, capillary glass arrays, copper foils, ZrO 2 nanopowder and a combination thereof.

10. The method of claim 1 , wherein a temperature at each step of the cycle is between 125-225° C.

11. The method of claim 1 , further comprising depositing the gallium sulfide film on a single-walled carbon nanotube powder to form a nano-composite material comprised of a conductive carbon core encapsulated by a uniform and conformal, amorphous, GaS x shell.

12. The method of claim 11 , wherein the cycle is repeated 50-150 times to produce a film with a thickness of 2.5 to 11.1 nm.

13. A method for using atomic layer deposition to produce a film configured for use in an anode, cathode, or solid-state electrolyte of a lithium-ion battery or a lithium-sulfur battery, the method comprising:

alternately repeating a first cycle and a second cycle for a predetermined number of times in an inert atmosphere,

wherein the first cycle comprises:

exposing a substrate to a first precursor,

purging the substrate with inert gas,

exposing the substrate to a second precursor, and

purging the substrate with inert gas,

wherein the second cycle comprises:

exposing the substrate to a third precursor different than the first precursor,

purging the substrate with inert gas,

exposing the substrate to a fourth precursor,

purging the substrate with inert gas, and

wherein the film comprises a metal sulfide.

14. The method of claim 13 , wherein

the film is Li x Al y S z ;

the first precursor is selected from the group consisting of: lithium tert-butoxide, lithium acetylacetonate, 2,2,6,6-Tetramethyl-3,5-heptanedionato lithium, lithium cyclopentadienide, lithium pentamethylcyclopentadienide, and lithium 2-methyl-2-butoxide;

the second precursor is hydrogen sulfide;

the third precursor is selected from the group consisting of: tris(dimethylamido)aluminum, tris(dimethylamido)aluminum, tris(diethylamido)aluminum, tris(ethyl-methylamido)aluminum, aluminum(III) acetylacetonate, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)aluminum(III), aluminum(III) hexafluoroacetylacetonate, and trimethylaluminum; and

the fourth precursor is hydrogen sulfide.

15. The method of claim 14 , wherein the first precursor is lithium tert-butoxide and the third precursor is tris(dimethylamido)aluminum.

16. The method of claim 13 , wherein

the film is Li x Ga y S z ;

the first precursor is selected from the group consisting of: lithium tert-butoxide, lithium acetylacetonate, 2,2,6,6-Tetramethyl-3,5-heptanedionato lithium, lithium cyclopentadienide, lithium pentamethylcyclopentadienide, and lithium 2-methyl-2-butoxide;

the second precursor is hydrogen sulfide;

the third precursor is selected from the group consisting of: hexakis(dimethylamido)digallium, hexakis(diethylamido)digallium, hexakis(ethyl-methylamido)digallium, gallium(III) acetylacetonate, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)gallium(III), gallium(III) hexafluoroacetylacetonate, and trimethylgallium; and

the fourth precursor is hydrogen sulfide.

17. The method of claim 16 , wherein the first precursor is lithium tert-butoxide and the third precursor is hexakis(dimethylamido)digallium.