Surface modifications for electrode compositions and their methods of making

Patent metadata

Field	Value
Publication number	US-10128489-B2
Application number	US-201615002528-A
Country	US
Kind code	B2
Filing date	Jan 21, 2016
Priority date	Oct 5, 2012
Publication date	Nov 13, 2018
Grant date	Nov 13, 2018

Abstract

Compositions and methods of making are provided for surface modified electrodes and batteries comprising the same. The compositions may comprise a base composition having an active material capable of intercalating the metal ions during a discharge cycle and deintercalating the metal ions during a charge cycle, wherein the active material is selected from the group consisting of LiCoO2, LiMn2O4, Li2MnO3, LiNiO2, LiMn1.5Ni0.5O4, LiFePO4, Li2FePO4F, Li3CoNiMnO6, Li(LiaNixMnyCoz)O2, LiaMn1.5-bNi0.5-cMdO4-x, and mixtures thereof. The compositions may also comprise an annealed composition covering a portion of the base composition, formed by a reaction of the base composition in a reducing atmosphere. The methods of making comprise providing the base composition and annealing the base electrode in a reducing atmosphere.

First claim

What is claimed is:

1. A cathode for a battery comprising:
a base composition having an active material capable of intercalating metal ions during a discharge cycle and deintercalating the metal ions during a charge cycle, wherein the active material comprises an active material selected from: Li 2 MnO 3 , LiMn 1.5 Ni 0.5 O 4 , Li 3 CoNiMnO 6 , Li a Mn 1.5-b Ni 0.5-c M d O 4-x , and mixtures thereof, wherein “a” is between 0.5-2 or 1-1.4, “b” is between 0-0.5, “c” is between 0-0.5 or 0-0.17, “d” is between 0-0.33, and “x” is 0 or 1, and wherein M is a metal selected from the group consisting of: Li, Na, K, Mg, Be, Ca, Sr, Ba, Si, Al, Ga, In, Tl, Sc, Ti, V, Cr, Fe, Pt, Os, Cu, and Zn; and
an annealed nitrogen-doped carbon coating composition covering a portion of the base composition, formed by a reaction of the base composition in a reducing atmosphere,
wherein the source of the nitrogen doping element in the nitrogen-doped carbon coating composition is selected from the group consisting of 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (EMIm-TFSI), 1-ethyl-3-methylimidazolium dicyanamide (EMIm-DCA), and mixtures thereof.

2. The cathode of claim 1 , wherein a capacity of the cathode is at least 125% greater at 3 C, 5 C, or 10 C when compared with an electrode having the same base composition without the annealed nitrogen-doped carbon coating composition.

3. The cathode of claim 1 , having a capacity of at least 120 mAh/g at a rate of C/10, 1 C, 3 C, 5 C, or 10 C.

4. A battery comprising:
an anode having a base composition;
the cathode of claim 1 ; and
an electrolyte capable of supporting reversible deposition and stripping of metal at the anode, and reversible intercalation and deintercalation of the metal at the cathode.

5. The battery of claim 4 , wherein a capacity of the battery is at least 125% greater at 3 C, 5 C, or 10 C when compared with an battery having the same anode, electrolyte, and base composition of the cathode without the annealed nitrogen-doped carbon coating composition.

6. The battery of claim 4 , wherein the base composition of the anode comprises at least 90 wt. % lithium as the primary electrochemically active material of the anode.

7. The battery of claim 4 , wherein the anode comprises mesoporous metal oxide microspheres, having (a) microspheres with an average diameter between 200 nm and 10 μm, and (b) mesopores on a surface and an interior of the microspheres, wherein the mesopores have an average diameter between 1 nm and 50 nm and the microspheres have a surface area between 50 m 2 /g and 500 m 2 /g.

8. The battery of claim 4 , wherein the battery is selected from the group consisting of the following battery types: lithium-ion, aluminum-ion, magnesium-ion, sodium-ion, metal-air, and metal-sulfur, wherein the metal is lithium, aluminum, magnesium, zinc, or sodium.

9. The battery of claim 4 having an ability to charge from 0% to 50% of the full range capacity in 6 minutes, or an ability to charge from 0% to 33% of full range capacity in 1 minute.

10. The battery of claim 4 having a functional discharge capacity of at least 90% of initial discharge capacity after 100 cycles.

11. The battery of claim 4 , wherein the battery is used in a grid storage application, vehicle battery application, military application, portable electronic device application, medical device application, or standard cell size battery application.

12. The cathode of claim 1 , wherein the annealed nitrogen-doped carbon coating over a surface of the cathode is between 1-100 nm in thickness and the coated cathode comprises 0.1- 20 wt. % carbon.

13. The cathode of claim 1 , wherein the active material is selected from: Li 2 MnO 3 , Li 3 CoNiMnO 6 , and mixtures thereof and
wherein the source of the nitrogen doping element in the nitrogen-doped carbon coating composition is selected from the group consisting of 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (EMIm-TFSI), 1-ethyl-3-methylimidazolium dicyanamide (EMIm-DCA), and mixtures thereof.

14. A method of forming a cathode, the method comprising:
providing a base cathode composition having an active material comprising LiMn 1.5 Ni 0.5 O 4 ;
annealing the base cathode composition in a reducing atmosphere to form a nitrogen-doped carbon coating composition, wherein the coating over a surface of the cathode is between 1-100 nm in thickness and the coated cathode comprises 0.1- 20 wt. % carbon; and
doping the base cathode composition with a metal oxide prior to the annealing step, therein forming a doped cathode composition comprising Li a Mn 1.5-b Ni 0.5-c M d O 4 , wherein “a” is between 0.5-2 or 1-1.4, “b” is between 0-0.5, “c” is between 0-0.5 or 0-0.17, and “d” is between 0-0.33, and wherein M is a metal selected from the group consisting of: Li, Na, K, Mg, Be, Ca, Sr, Ba, Si, Al, Ga, In, Tl, Sc, Ti, V, Cr, Fe, Pt, Os, Cu, and Zn;
wherein the source of the nitrogen doping element in the nitrogen-doped carbon coating composition is selected from the group consisting of 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (EMIm-TFSI), 1-ethyl-3-methylimidazolium dicyanamide (EMIm-DCA), and mixtures thereof.

15. The method of claim 14 , wherein the reducing atmosphere contains a flowing reducing gas selected from the group consisting of: hydrogen, argon, nitrogen, fluorine, sulfur, carbon monoxide, methane, ammonia, carbon dioxide, and mixtures thereof.

16. The method of claim 15 , wherein the flowing reducing gas is ammonia.

17. A cathode for a battery, the cathode comprising:
a base composition having an active material capable of intercalating the metal ions during a discharge cycle and deintercalating the metal ions during a charge cycle, wherein the active material is selected from the group consisting of Li 2 MnO 3 , LiMn 1.5 Ni 0.5 O 4 , Li 3 CoNiMnO 6 , Li a Mn 1.5-b Ni 0.5-c M d O 4-x , and mixtures thereof, wherein “a” is between 0.5-2 or 1-1.4, “b” is between 0-0.5, “c” is between 0-0.5 or 0-0.17, “d” is between 0-0.33, and “x” is 0 or 1, wherein M is a metal selected from the group consisting of: Li, Na, K, Mg, Be, Ca, Sr, Ba, Si, Al, Ga, In, Tl, Sc, Ti, V, Cr, Fe, Pt, Os, Cu, and Zn; and
an annealed nitrogen-doped carbon coating composition covering a portion of the base composition, formed by a reaction of the base composition in a flowing ammonia gas atmosphere, the annealed composition comprising uniformly dispersed oxy-nitride, metal nitride, or dissolved/adsorbed nitrogen.

18. The cathode of claim 17 , wherein the active material in the base composition of the cathode comprises LiMn 1.5 Ni 0.5 O 4.

19. The cathode of claim 17 , wherein the coated cathode comprises between 0.01-10 wt. %, 0.05-5 wt. %, or 0.1-1 wt. % nitrogen.

Assignees

• Ut Battelle Llc

Inventors

• Parans Paranthaman Mariappan
• Bridges Craig A
• Yoon Sukeun

Classifications

• H01M4/625

  Carbon or graphite · CPC title

• H01M4/0471

  involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis · CPC title

• H01M2220/20

  Batteries in motive systems, e.g. vehicle, ship, plane · CPC title

• H01M4/5825

  Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title