Sulfate Containing Rechargeable Battery Cathode with Oxidized Surface

Patent metadata

Field	Value
Publication number	US-2016365571-A1
Application number	US-201515121439-A
Country	US
Kind code	A1
Filing date	Feb 25, 2015
Priority date	Feb 27, 2014
Publication date	Dec 15, 2016
Grant date	—

Abstract

A method for preparing a positive electrode material for a rechargeable lithium battery, comprising the steps of: providing a Li metal (M) oxide electroactive material, providing an inorganic oxidizing chemical compound, providing a chemical that is a Li-acceptor, mixing the Li metal (M) oxide, the oxidizing compound and the Li-acceptor, and heating the mixture at a N temperature between 200 and 800° C. in an oxygen comprising atmosphere. In an embodiment the positive electrode material comprises a Li metal (M) oxide electroactive material, and between 0.15 and 5 wt % of a LiNaSO4 secondary phase. The Li metal oxide may have the general formula Li 1+a′ M 1−a O 2 , with a′<a and 0.9≦(1+a′)/(1−a)≦1.15, and M═Ni 1−x−y M′xCo y , with M′═Mn i−z Al z , 0≦z≦1, 0.1≦y≦0.4 and x+y≦0.5.

First claim

1 - 19 . (canceled)

20 . A positive electrode material for a rechargeable lithium battery comprising a Li metal (M) oxide electroactive material, and between 0.15 and 5 wt % of a LiNaSO 4 secondary phase.

21 . The positive electrode material of claim 20 , wherein M═Ni 1−x−y M′ x Co y , with M′═Mn 1−z Al z , 0≦z≦1, 0.1≦y≦0.4 and x+y≦0.5.

22 . The positive electrode material of claim 21 , wherein 1−y−2x>0.2.

23 . The positive electrode material of claim 20 , wherein the Li metal oxide has the general formula Li 1+a′ M 1−a O 2 , with a′<a and 0.9≦(1+a′)/(1−a)≦1.15.

24 . The positive electrode material of claim 20 , wherein the mass fraction of the LiNaSO 4 secondary phase is between 0.2 and 2 wt %.

25 . The positive electrode material of claim 20 , wherein the material comprises a core comprising the Li metal (M) oxide and a coating comprising the LiNaSO 4 secondary phase.

26 . The positive electrode material of claim 20 , wherein the secondary phase further comprises up to 1 wt % of one or more compounds selected from the group consisting of Al 2 O 3 , LiAlO 2 , LiF, Li 3 PO 4 , MgO and Li 2 TiO 3 .

27 . The positive electrode material of claim 25 , wherein the LiNaSO 4 coating is covered by a second coating comprising one or more of Al 2 O 3 , LiAlO 2 , LiF or MgO, and wherein the second coating represents up to 1 wt % of the material.

28 . The positive electrode material of claim 20 , wherein the Li metal (M) oxide is doped with up to 2 mol % of one or more elements selected from the group consisting of Al, Ti, Mg and Zr.

29 . The positive electrode material of claim 20 , wherein the Li metal (M) oxide is doped with up to 0.2 mol % of one or more elements selected from the group consisting of Ca, Sr, Si, F, P and K.

30 . A method for preparing the positive electrode material of claim 20 , comprising:
providing a Li metal (M) oxide electroactive material, providing an inorganic oxidizing chemical compound, providing a chemical that is a Li-acceptor, mixing the Li metal (M) oxide, the oxidizing compound and the Li-acceptor, and heating the mixture at a temperature between 300 and 800° C. in an oxygen comprising atmosphere.

31 . The method according to claim 30 , wherein the Li metal oxide has the general formula Li 1+a′ M 1−a O 2 , with a′<a and 0.9≦(1+a′)/(1−a)<1.15, and M═Ni 1−x−y M′ x Co y , with M′═Mn 1−z Al z , 0≦z≦1, 0.1≦y≦0.4 and x+y≦0.5.

32 . The method according to claim 30 , wherein the inorganic oxidizing chemical compound comprises NaHSO 5 or either one of a chloride, a chlorate, a perchlorate or a hypochloride of either one of potassium, sodium, lithium, magnesium or calcium.

33 . The method according to claim 30 , wherein the Li-acceptor chemical comprises one of AlPO 4 , Li 3 AlF 6 or AlF 3 .

34 . The method according to claim 30 , wherein the inorganic oxidizing chemical compound and the Li-acceptor chemical are the same compound, being one of Li 2 S 2 O 8 , H 2 S 2 O 8 or Na 2 S 2 O 8 .

35 . The method according to claim 30 , wherein the mass fraction of the Li metal (M) oxide in the mixture is between 95 and 99.8 wt %.

36 . The method according to claim 30 , wherein the heating temperature is between 350 and 450° C.

37 . The method according to claim 34 , wherein the inorganic oxidizing chemical compound and the Li-acceptor chemical are Na 2 S 2 O 8 , and wherein Na 2 S 2 O 8 is mixed with the Li metal (M) oxide in a dry process.

38 . The method according to claim 34 , wherein a nanosized Al 2 O 3 powder is provided as a further Li-acceptor chemical.

Assignees

• Umicore Nv
• Umicore Korea Ltd

Inventors

• Kim Dae-Hyun
• Paulsen Jens

Classifications

• 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

• H01M4/366 Primary

  as layered products · CPC title

• H01M4/505

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

• H01M2004/028

  Positive electrodes · CPC title

• H01M10/0525

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