Cathode material for lithium ion secondary battery, method of producing the same, and lithium ion secondary battery

Patent metadata

Field	Value
Publication number	US-2016049645-A1
Application number	US-201514815944-A
Country	US
Kind code	A1
Filing date	Jul 31, 2015
Priority date	Aug 13, 2014
Publication date	Feb 18, 2016
Grant date	—

Abstract

The present invention discloses a cathode material for lithium ion secondary battery. The cathode material is in the form of powder particles. The powder particle includes a bulk portion and a coating portion coated on the outer surface of the bulk portion. The bulk portion is formed of at least one first cathode material which is a lithium-nickel based composite oxide. The first cathode material has electrochemical activity and has high charging-discharging specific capacity at a charged voltage of 4.2V versus Li/Li + . The coating portion is formed of at least one second cathode material. The second cathode material has no electrochemical activity or has low charging-discharging specific capacity at a charged voltage of 4.2V versus Li/Li + . Lithium ion secondary battery using the cathode material has high energy density, cycling stability, security, and output power.

First claim

What is claimed is:

1 . A cathode material for a lithium ion secondary battery, wherein the cathode material is in the form of powder particles, the powder particle includes a bulk portion and a coating portion coated on the outer surface of the bulk portion, the bulk portion is formed of at least one first cathode material which is a lithium-nickel based composite oxide, the first cathode material has electrochemical activity and has high charging-discharging specific capacity at a charged voltage of 4.2V versus Li/Li + , the coating portion is formed of at least one second cathode material, the second cathode material has no electrochemical activity or has low charging-discharging specific capacity at a charged voltage of 4.2V versus Li/Li + .

2 . The cathode material for a lithium ion secondary battery of claim 1 , wherein the second cathode material is at least one of lithium transition metal oxides.

3 . The cathode material for a lithium ion secondary battery of claim 1 , wherein the first cathode material has a general formula of Li 1+δ [Ni 1−x−y Co x M y ]O 2 , wherein M is selected at least one metal element from Mn, Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Ge, Sn, Ti, V, Cr, Fe, Cu, Zn, Y, Zr, Nb, Mo, Cd, W, La, Ce, Nd and Sm, wherein 0≦δ≦0.2, 0≦x≦0.5, 0≦x+y≦0.5.

4 . The cathode material for a lithium ion secondary battery of claim 3 , wherein in the first cathode material with the general formula of Li 1+δ [Ni 1−x−y Co x M y ]O 2 , the valence of the metal element Ni and Co is +3, the valence of the metal element M is +2, +3, +4, +5, or +6.

5 . The cathode material for a lithium ion secondary battery of claim 1 , where in the first cathode material has a general formula of Li 1+δ [Ni 1−x−y Co x M y ]O 2−α P α , wherein M is selected at least one metal element from Mn, Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Ge, Sn, Ti, V, Cr, Fe, Cu, Zn, Y, Zr, Nb, Mo, Cd, W, La, Ce, Nd and Sm, P represents F or S, wherein 0≦δ≦0.2, 0≦x≦0.5, 0≦x+y≦0.5, 0<α≦0.2.

6 . The cathode material for a lithium ion secondary battery of claim 5 , wherein in the first cathode material with the general formula of Li 1+δ [Ni 1−x−y Co x M y ]O 2−α P α , the valence of the metal element Ni and Co is +3, the valence of the metal element M is +2, +3, +4, +5, or +6.

7 . The cathode material for a lithium ion secondary battery of claim 1 , wherein the second cathode material has a general formula of Li 1+η [Mn 2−a M′ a ]O 4 , wherein M′ is selected at least one metal element from Ni, Co, Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Ge, Sn, Ti, V, Cr, Fe, Cu, Zn, Y, Zr, Nb, Mo, Cd, W, La, Ce, Nd and Sm, wherein 0≦η≦0.2, 0<a≦1; or the second cathode material has a general formula of Li 2+γ [Mn 2−b M′ b ]O 3 , wherein M′ is selected at least one metal element from Ni, Co, Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Ge, Sn, Ti, V, Cr, Fe, Cu, Zn, Y, Zr, Nb, Mo, Cd, W, La, Ce, Nd and Sm, wherein 0≦γ≦0.4, 0≦b≦1.

8 . The cathode material for a lithium ion secondary battery of claim 7 , wherein in the second cathode material with the general formula of Li 1+η [Mn 2−a M′ a ]O 4 and the general formula of Li 2+γ [Mn 2−b M′ b ]O 3 , the valence of the metal element of Mn is +4, the valence of the metal element of M′ is +2, +3, +4, +5, or +6.

9 . The cathode material for a lithium ion secondary battery of claim 1 , wherein the second cathode material has a general formula of Li 1+η [Mn 2−a M′ a ]O 4−m P m , wherein M′ is selected at least one metal element from Ni, Co, Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Ge, Sn, Ti, V, Cr, Fe, Cu, Zn, Y, Zr, Nb, Mo, Cd, W, La, Ce, Nd and Sm, P represents F or S, wherein 0≦η≦0.2, 0<a≦1, 0<m≦0.5; or the second cathode material has a general formula of Li 2+γ [Mn 2−b M′ b ]O 3−n P n , wherein M′ is selected at least one metal element from Ni, Co, Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Ge, Sn, Ti, V, Cr, Fe, Cu, Zn, Y, Zr, Nb, Mo, Cd, W, La, Ce, Nd and Sm, P represents F or S, wherein 0≦γ≦0.4, 0≦b≦1, 0<n≦0.5.

10 . The cathode material for a lithium ion secondary battery of claim 9 , wherein in the second material with the general formula of Li 1+η [Mn 2−a M′ a ]O 4−m P m and the general formula of Li 2+γ [Mn 2−b M′ b ]O 3−n P n , the valence of the metal element Mn is +4, the valence of the metal element of M′ is +2, +3, +4, +5, or +6.

11 . The cathode material for a lithium ion secondary battery of claim 1 , wherein the weight of the coating portion accounts for 0.1˜10% of the weight of the powder particle.

12 . The cathode material for a lithium ion secondary battery of claim 1 , wherein an outer surface of the coating portion is dot coated or surface coated with at least one Lewis base.

13 . The cathode material for a lithium ion secondary battery of claim 12 , wherein the Lewis base is selected from at least one of ZnO, Al 2 O 3 , MgO, CaO, ZrO 2 , TiO 2 , SnO 2 and Sb 2 O 5 .

14 . The cathode material for a lithium ion secondary battery of claim 12 , wherein the weight of the Lewis base accounts for 0.1˜5% of the weight of the powder particle.

15 . The cathode material for a lithium ion secondary battery of claim 1 , wherein the powder particle is spherical or spheroidal, and the particle diameter is 0.5˜50 μm.

16 . A method of producing a cathode material for a lithium ion secondary battery, the cathode material being in the form of powder particles, the powder particle including a bulk portion and a coating portion coated on the outer surface of the bulk portion, the method comprising the following steps:
(1) providing nickel salt, further providing cobalt salt and/or at least one other salt of metal selected from Mn, Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Ge, Sn, Ti, V, Cr, Fe, Cu, Zn, Y, Zr, Nb, Mo, Cd, W, La, Ce, Nd and Sm, dissolving in water to form a precursor solution of the bulk portion; (2) providing manganese salt only, or providing manganese salt and at least one other salt of metal selected from Ni, Co, Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Ge, Sn, Ti, V, Cr, Fe, Cu, Zn, Y, Zr, Nb, Mo, Cd, W, La, Ce, Nd and Sm, dissolving in water to form a precursor solution of the coating portion; (3) feeding the precursor solution of the bulk portion, an aqueous solution of ammonia and an aqueous solution of alkali into a reactor for reaction; (4) when the bulk portions are formed in the reaction of step (3), stopping feeding the precursor solution of the bulk portion into the reactor, then feeding the precursor solution of the coating portion into the reactor for reaction with the aqueous solution of ammonia and the aqueous solution of alkali to form a precursor nickel complex compound of the cathode material, the precursor nickel complex compound being expressed as [(Ni 1−x−y Co x M y ) 1−z (Mn 2−a M′ a ) z ](OH) 2 or [(Ni 1−x−y Co x M y ) 1−z (Mn 0.5−b M′ b ) z ](OH) 2 or [(Ni 1−x−y Co x M y ) 1−z (Mn 2−a M′ a ) z ]CO 3 or [(Ni 1−x−y Co x M y ) 1−z (Mn 0.5−b M′ b ) z ]CO 3 , wherein 0≦x≦0.5, 0≦x+y≦0.5, 0≦a≦1, 0≦b≦0.25, 0<z≦0.2; (5) filtering, washing and drying the precursor nickel complex compound to obtain a nickel complex hydroxide or a nickel complex carbonate; or heat-treating the precursor nickel complex compound to obtain a nickel complex oxide; and (6) providing a lithium source compound, dry mixing or wet mixing the lithium source compound with the nickel complex hydroxide or the nickel complex carbonate or the nickel complex oxide to form a mixture, and sintering the mixture in air or oxygen to form the powder particles of the cathode material.

17 . The method of producing the cathode material for a lithium ion secondary battery of claim 16 , wherein in step (6), the mixture includes a non

Assignees

• Microvast Power Systems Co Ltd

Inventors

• Zheng Zhuoqun
• Qiu Jian
• Zhao Xiaozhen
• Nie Yunhua

Classifications

• H01M4/485

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title

• H01M4/366 Primary

  as layered products · CPC title

• H01M2004/028

  Positive electrodes · CPC title

• H01M4/525

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

• H01M4/505

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