Surface stabilized cathode material for lithium ion batteries and synthesizing method of the same

Patent metadata

Field	Value
Publication number	US-2018257947-A9
Application number	US-201715710540-A
Country	US
Kind code	A9
Filing date	Sep 20, 2017
Priority date	Sep 21, 2016
Publication date	Sep 13, 2018
Grant date	—

Abstract

A compound represented by Li α Co (1-x-2y) Me x (M1M2) y O δ , (Formula (I)) wherein Me, is one or more of Li, Mg, Al, Ca, Ti, Zr, V, Cr, Mn, Fe, Ni, Cu, Zn, Ru and Sn, and wherein 0≤x≤0.3, 0<y≤0.4, 0.95≤α≤1.4, and 1.90≤δ≤2.10 is disclosed. Further, particles including such compounds are described.

First claim

What is claimed is:

1 . A compound represented by Formula (I):
Li α Co (1-x-2y) Me x (M1M2) y O δ   Formula (I)
wherein Me is selected from one or more of Li, Mg, Al, Ca, Ti, Zr, V, Cr, Mn, Fe, Ni, Cu, Zn, Ru and Sn; wherein M1 is a metal having a +2 oxidation state; wherein M2 is a metal having a +4 oxidation state; wherein M1M2 represents pairs of M1 and M2; and wherein 0≤x≤0.3, 0<y≤0.4, 0.95≤α≤1.4, and 1.90≤δ≤2.10.

2 . The compound of claim 1 , wherein M1 is Ni and M2 is Mn.

3 . The compound of claim 1 , characterized by a trigonal crystal structure.

4 . The compound of any one preceding claim, wherein x is 0.

5 . The compound of any one preceding claim, wherein 0<y≤0.25.

6 . The compound of claim 5 , wherein 0.02≤y≤0.06.

7 . The compound of claim 6 , y is about 0.04.

8 . The compound of claim 5 , wherein 0.05≤y≤0.09.

9 . The compound of claim 8 , y is about 0.07.

10 . The compound of claim 5 , wherein 0.08≤y≤0.12.

11 . The compound of claim 10 , y is about 0.10.

12 . The compound of any of claim 5 , wherein 0.14≤y≤0.18.

13 . The compound of claim 12 , y is about 0.16.

14 . The compound of claim 5 , wherein 0.20≤y≤0.25.

15 . The compound of claim 14 , y is about 0.22.

16 . A particle comprising compounds represented by:
(a) Li a Co b M6 c O δ   Formula (V)
wherein M6 is one or more of manganese (Mn), nickel (Ni), aluminum (Al), magnesium (Mg), titanium (Ti), zirconium (Zr), calcium (Ca), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), and ruthenium (Ru); and wherein 0.90≤a≤1.1, wherein 0.5≤b≤1.0, wherein 0<c≤0.5, and wherein 1.90≤δ≤2.10; and
(b) Li α Co β M3 γ (M4M5) ϵ O δ   Formula (III)

wherein M3 is one or more of Mn, Ni, Al, Mg, Ti, Zr, Ca, C, Cr, Fe, Cu, Zn, Ru, wherein M4 is a metal having a +2 oxidation state, wherein M5 is a metal having a +4 oxidation state, wherein M4M5 represents pairs of M4 and M5, and wherein 0.95≤α≤1.4, 0.3≤β≤1.0, 0≤γ≤0.7, 0<ϵ≤0.4, and 1.90≤δ≤2.10.

17 . A particle comprising compounds represented by:
(a) Li α Co (1-x-2y) Me x (M1M2) y O δ   Formula (I)
wherein Me is selected from one or more of Li, Mg, Al, Ca, Ti, Zr, V, Cr, Mn, Fe, Ni, Cu, Zn, Ru and Sn, wherein M1 is a metal having a +2 oxidation state, wherein M2 is a metal having a +4 oxidation state, wherein M1M2 represents pairs of M1 and M2, and wherein 0≤x≤0.3, 0<y≤0.4, 0.95≤α≤1.4, and 1.90≤δ≤2.10; and
(b) Li α Co β M3 γ (M4M5) ϵ O δ   Formula (III)

wherein M3 is one or more of Mn, Ni, Al, Mg, Ti, Zr, Ca, C, Cr, Fe, Cu, Zn, Ru, wherein M4 is a metal having a +2 oxidation state, wherein M5 is a metal having a +4 oxidation state, wherein M4M5 represents pairs of M4 and M5, and wherein 0.95≤α≤1.4, 0.3≤β≤1.0, 0≤γ≤0.7, 0<ϵ≤0.4, and 1.90≤δ≤2.10.

18 . The particle of claim 16 , wherein 0.95≤α≤1.1.

19 . The particle of claim 16 , wherein 0<x≤0.3.

20 . The particle of claim 16 , wherein x is 0.

21 . The particle of claim 16 , wherein 0<γ≤0.7.

22 . The particle of claim 16 , wherein γ=0.

23 . The particle of claim 16 , wherein M4 is one or more of nickel, magnesium, and zinc.

24 . The particle of claim 16 , wherein M5 is one or more of manganese, titanium, zirconium, and vanadium.

25 . The particle of claim 16 ,
wherein γ=0; wherein M4 is one or more of nickel, magnesium, and zinc; and wherein M5 is one or more of manganese, titanium, zirconium, and vanadium.

26 . The particle of claim 16 , wherein the particle has an energy density higher at an interior of the particle than at a surface of the particle.

27 . The particle of claim 16 , wherein the particle has energy retentive properties higher at the surface of the particle than at an interior of the particle.

28 . The particle of claim 16 , comprising a core comprising the compound represented by Formula (I), and a coating comprising the compound represented by Formula (III).

29 . A cathode comprising a cathode current collector and a cathode active material disposed over the cathode current collector, the cathode active material comprising the composition of claim 1 .

30 . A battery cell comprising:
an anode comprising an anode current collector and an anode active material disposed over the anode current collector; and the cathode of claim 29 .

31 . A portable electronic device comprising:
a set of components powered by the battery cell of claim 30 .

32 . A method of synthesizing a lithium-oxide cathode active material for a lithium-ion battery, the method comprising:
reacting a metal sulfate feed solution with a chelate agent and an oxidizing agent at an alkaline pH to form a particulate solution through a coprecipitation process; washing, filtering and drying the particulate solution to collect hydroxide precursor particles; blending the collected particles with a lithium salt; reacting the blended particles at a first elevated temperature to produce base particles of a hydroxide precursor.

33 . The method of claim 32 , further comprising:
milling the base particles to produce sub-micron particles; and filtering and drying the sub-micron particles.

34 . The method of claim 33 , further comprising:
blending the sub-micron particles with the lithium salt and the base particles; and calcining the blended particles in air at a first elevated temperature.

35 . The method of claim 32 , further comprising:
blending the base particles with the lithium salt; calcining the blended base particles at a desired temperature; producing the calcined case particles; blending the produced particles with sub-micron particles and the lithium salt; heat-treating the blended particles with the sub-micro particles; and sintering the heat-treated particles with the blended base particles.

36 . The method of claim 33 , further comprising:
separately calcining the base particles and the sub-micron particles at a second elevated temperature; and heat-treating the calcined sub-micron particles with the calcined base particles at s third temperature higher than the second temperature.

37 . The method of claim 35 , further comprising:
preparing acetates and/or nitrates solution containing Li α Co 1-x-y-z (Mn x Ni y Al z )O σ , wherein 0<y≤x≤0.2, 0.98≤α≤1.02, 1.99≤δ≤2.01; and mixing the base particles and the prepared solution; forming a wet mixture; and drying and calcined the formed mixture.

38 . The method of claim 32 , further comprising:
growing and densifying the base particles to have near-optimum properties through a batch process; changing the metal sulfate feed solution to produce acetates and/or nitrates solution containing Li α Co 1-x-y-z (Mn x Ni y Al z )O σ , wherein 0<y≤x≤0.2, 0.98≤α≤1.02, 1.99≤δ≤2.01; performing the coprecipitation process until the base particles are overlaid with a desired amount; drying and calcining the particles with the lithium salt; and producing the lithium-oxide cathode active material.

39 . The method of claim 32 , wherein the hydroxide precursor has the following formula:
Co a Mn b (OH) 2 , wherein 0≤a≤1, 0≤b≤1, and a +b=1.

40 . The meth

Assignees

• Apple Inc

Inventors

• Dai Hongli
• Wang Dapeng
• Wu Huiming
• Strobridge Fiona Claire
• Carter John David
• Johnson Christopher S
• Wang Xiaoping
• Iddir Hakim H
• Kropf Arthur Jeremy
• Li Yan
• Maroni Victor A
• Vu Anh D
• Yang Zhenzhen
• Gutierrez Arturo
• Cui Yanjie

Classifications

• C01P2002/82

  by IR- or Raman-data · CPC title

• H01M4/525 Primary

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title

• H01M10/0525

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

• H01M4/505

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