LIPON COATINGS FOR HIGH VOLTAGE AND HIGH TEMPERATURE Li-ION BATTERY CATHODES

Patent metadata

Field	Value
Publication number	US-2017200952-A1
Application number	US-201715416500-A
Country	US
Kind code	A1
Filing date	Jan 26, 2017
Priority date	Oct 12, 2012
Publication date	Jul 13, 2017
Grant date	—

Abstract

A lithium ion battery includes an anode and a cathode. The cathode includes a lithium, manganese, nickel, and oxygen containing compound. An electrolyte is disposed between the anode and the cathode. A protective layer is deposited between the cathode and the electrolyte. The protective layer includes pure lithium phosphorus oxynitride and variations that include metal dopants such as Fe, Ti, Ni, V, Cr, Cu, and Co. A method for making a cathode and a method for operating a battery are also disclosed.

First claim

1 .- 19 . (canceled)

20 . A method of making a cathode for a lithium ion battery, comprising the steps of:
providing a cathode material comprising a lithium, manganese, nickel and oxygen containing compound; providing a lithium phosphate target; sputtering the lithium phosphorus oxynitride in a nitrogen plasma to coat the lithium, manganese, nickel and oxygen containing compound with at least a 1 nm coating of lithium phosphorus oxynitride.

21 . The method of claim 20 , wherein the sputtering is RF magnetron sputtering.

22 . The method of claim 20 , wherein the cathode material is provided as particles.

23 . The method of claim 22 , further comprising the step of agitating or flowing the particles during the sputtering step.

24 . The method of claim 20 , further comprising the step of applying a lithium salt electrolyte layer in operable contact with the cathode, the electrolyte layer being free of lithium phosphorus oxynitride.

25 . The method of claim 24 , further comprising the step of applying an anode layer in operable contact with the electrolyte layer.

26 .- 40 . (canceled)

41 . The method of claim 25 , wherein the protective layer comprising lithium phosphorus oxynitride, and the protective layer is provided as a uniform coating from 0.5 to 10 nm on all sides of the of the particles prior to the electrode preparation, the coated particles being unannealed;
the battery having capacity retention at 60° C.

42 . A method of making protected, free-flowing cathode material for a lithium ion battery operable at an upper voltage of 4.5 Volts vs. Li/Li + or higher, comprising the steps of:
a) providing a cathode material comprising a lithium, manganese and oxygen containing compound as dry, free-flowing particles;
b) providing precursor sources suitable for the vapor deposition of lithium phosphorous oxynitride;
c) vapor depositing a uniform lithium phosphorus oxynitride protective layer of 0.5 to 10 nm onto said particles;
wherein said protected, free-flowing cathode material remains dry and suitable for use as a cathode material without annealing.

43 . The method of claim 42 , wherein the cathode material further comprises nickel.

44 . The method of claim 43 , wherein the cathode material comprises Li[Ni x Mn 2-x ]O 4 , where x is 0.5±0.1.

45 . The method of claim 43 , wherein the cathode compound comprises LiMn 1.5 Ni 0.5 O 4 .

46 . The method of claim 43 , wherein the cathode material further comprises cobalt.

47 . The method of claim 46 , wherein the cathode material comprises Li 1+w [Mn x Ni y Co z ]O 2 , where w+x+y+z=1.

48 . The method of claim 42 , wherein the cathode material comprises particles comprised of Li 1+x Mn 2-y O 4 , where x and y are independently 0 to 0.2.

49 . The method of claim 48 , wherein the cathode material also comprises particles comprised of Li 1+w [Mn x Ni y Co z ]O 2 , where w+x+y+z=1.

50 . The method of claim 42 , wherein the cathode compound comprises xLi 2 MnO 3 .(1-x)LiMO 2 , where M is at least one selected from the group consisting of Mn, Co, and Ni, and x is 0.2-0.7.

51 . The method of claim 42 , further comprising the step of agitating or flowing the particles during the vapor deposition step.

52 . The method of claim 42 , wherein the lithium phosphorous oxynitride layer is produced using a plasma precursor source.

53 . The method of claim 42 , wherein the vapor deposition is a sputtering process.

54 . A method of making protected, free-flowing cathode material for a lithium ion battery operable at an upper voltage of 4.5 Volts vs. Li/Li + or higher, comprising the steps of:
a) providing a cathode material comprising a lithium, manganese and oxygen containing compound as dry, free-flowing particles;
b) providing precursor sources suitable for the vapor deposition of lithium phosphorous oxynitride;
c) providing at least one additional dopant precursor source suitable for the vapor deposition of Ti, Fe, Ni, V, Cr, Cu or Co
d) vapor depositing a uniform, doped lithium phosphorus oxynitride protective layer onto said particles;

wherein the dopant to phosphorous ratio ranges from 1% to 100%, and
wherein the protected cathode material particles remain dry and suitable for use as a cathode material without annealing.

55 . The method of claim 54 , wherein the cathode compound comprises xLi 2 MnO 3 .(1-x)LiMO 2 , where M is at least one selected from the group consisting of Mn, Co, and Ni, and x is 0.2-0.7.

56 . The method of claim 54 , wherein the cathode material comprises one or more compounds selected from i) Li 1+x Mn 2-y O 4 , where x and y are independently 0 to 0.2; ii) Li[Ni x Mn 2-x ]O 4 , where x is 0.5±0.1; iii) Li 1+w [Mn x Ni y Co z ]O 2 , where w+x+y+z=1 and iv) Li[Mn x Ni y Co z ]O 2 , where x+y+z=1.

57 . A free-flowing cathode material protected with a lithium phosphorous oxynitride layer produced using the vapor deposition method of claim 42 .

58 . An electrode produced using the material of claim 57 , further comprising the steps of:
e) mixing said material with a binder and conductive additives to make a slurry; f) casting said slurry onto a current collector; g) drying said cast slurry to form said electrode, and h) optionally pressing or calendaring said electrode.

59 . A free-flowing cathode material protected with a doped lithium phosphorous oxynitride layer produced using the vapor deposition method of claim 54 .

60 . An electrode produced using the material of claim 59 , further comprising the steps of:
e) mixing said material with a binder and conductive additives to make a slurry; f) casting said slurry onto a current collector; g) drying said cast slurry to form said electrode, and h) optionally pressing or calendaring said electrode.

Assignees

• Ut Battelle Llc

Inventors

• Dudney Nancy J
• Liang Chengdu
• Nanda Jagjit
• Veith Gabriel M
• Kim Yoongu
• Martha Surendra Kumar

Classifications

• H01M10/42

  Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells (H01M10/60 takes precedence) · CPC title

• H01M4/628 Primary

  Inhibitors, e.g. gassing inhibitors, corrosion inhibitors · CPC title

• H01M4/0426 Primary

  Sputtering · CPC title

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• H01M4/62

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title