High performance layered cathode materials for high voltage sodium-ion batteries

Patent metadata

Field	Value
Publication number	US-2018090758-A1
Application number	US-201615280753-A
Country	US
Kind code	A1
Filing date	Sep 29, 2016
Priority date	Sep 29, 2016
Publication date	Mar 29, 2018
Grant date	—

Abstract

A cathode active material includes Na x MO 2 having at least a first phase, a second phase different from the first phase, and a third phase that is different from the first and second phases, wherein each phase is independently selected from Pm or On, where m and n are individually an integer, M is a transition metal or a mixture of transition metals, and x is greater than 0 and less than or equal to 1.

First claim

What is claimed is:

1 . A cathode active material comprising integrated Na x MO 2 having at least a first phase, a second phase different from the first phase, and a third phase that is different from the first and second phases, wherein each phase is independently selected from Pm or On, where m and n are individually an integer, M is a transition metal or a mixture of transition metals, and x is greater than 0 and less than or equal to 1.

2 . The cathode active material of claim 1 , wherein m is 1, 2, 3, 4, 5, 6, 7, or 8; and n is 1, 2, 3, 4, 5, 6, 7, or 8.

3 . The cathode active material of claim 1 , wherein M is selected from the group consisting of Fe, Co, Ni, Mn, Cr, V, Cu, Ti, and a combination of any two or more thereof.

4 . The cathode active material of claim 1 further comprising a dopant such that an overall formula of the doped cathode active material is Na x M y M′ z O 2-δ F δ , wherein M′ is Li, Mg, Al, Ca, Sc, Zn, Y, Zr, Nb, Mo, Ru, Ag, Ba, Sb, or a combination of any two or more thereof; y is greater than 0 and less than or equal to 0.9; z is greater than 0 and less than or equal to 0.1; and δ is greater than 0 and less than or equal to 0.2.

5 . The cathode active material of claim 1 , wherein the M is a mixture of Co, Ni, and Mn.

6 . The cathode active material of claim 1 having the formula Na x Ni α Co β Mn γ O 2 , and α is greater than 0 and less than or equal to 1, β is greater than 0 and less than or equal to 1, and γ is greater than 0 and less than or equal to 1, where the total of α, β, and γ is equal to 1.

7 . The cathode active material of claim 1 , wherein the first phase is P2, the second phase is O1, and the third phase is O3.

8 . The cathode active material of claim 1 , further comprising a current collector, a conductive agent, a binder, or any combination thereof.

9 . The cathode active material of claim 1 further comprising a surface coating.

10 . The cathode active material of claim 9 , wherein the surface coating comprises a metal oxide, a metal fluoride, a metal phosphate, a conductive carbon coating, a metal oxyfluoride, or a combination of any two or more thereof.

11 . The cathode active material of claim 10 , wherein the surface coating comprises a metal oxide selected from the group consisting of MgO, Al 2 O 3 , ZrO 2 , MnO 2 , CeO 2 , TiO 2 , ZnO, SiO 2 , SnO 2 , Cr 2 O 3 , and a combination of any two or more thereof.

12 . The cathode active material of claim 10 , wherein the surface coating comprises a metal fluoride selected from the group consisting of AlF 3 , CaF 2 , CeF 3 , ZrF, ZrF 2 , ZrF 3 , ZrF 4 , LaF 3 , SrF 2 , and a combination of any two or more thereof.

13 . The cathode active material of claim 10 , wherein the surface coating comprises a metal phosphate selected from the group consisting of AlPO 4 , YPO 4 , Li 3 PO 4 , FePO 4 , Mg 3 (PO 4 ) 2 , Zn 3 (PO 4 ) 2 , Ca 3 (PO 4 ) 2 , Co 3 (PO 4 ) 2 , Ni 3 (PO 4 ) 2 , and a combination of any two or more thereof.

14 . The cathode active material of claim 10 , where the surface coating comprises a metal oxyfluoride selected from the group consisting of iron oxyfluoride, cerium oxyfluoride, magnesium oxyfluoride, zirconium oxyfluoride, aluminum oxyfluoride, vanadium oxyfluoride, silicon oxyfluoride, bismuth oxyfluoride, and a combination of any two or more thereof.

15 . A process of preparing integrated Na x MO 2 , the process comprising:
reacting under solvothermal or co-precipitation conditions salts of sodium and M in the presence of a precipitation agent and solvent to form a mixture; calcining at a first temperature the mixture to form a first calcined mixture; calcining at a second temperature the first calcined composition to form a second calcined composition; and thermally quenching the second calcined composition through rapid cooling to form the integrated Na x MO 2 ; wherein:
the integrated Na x MO 2 has at least a first phase, a second phase different from the first phase, and a third phase that is different from the first and second phases;
each phase is independently selected from Pm or On;
m is an integer;
n is an integer;
M is a transition metal; and
x is greater than 0 and less than or equal to 1.

16 . The process claim 15 , wherein:
the salts are sodium or transition metal salts selected from the group consisting of sulfates, sulfites, chlorates, nitrates, acetates, phosphates, citrates, carbonates and a mixture of any two or more thereof; the precipitation agent is selected from the group consisting of oxalic cid, sodium hydroxide, ammonium hydroxide, sodium carbonate, ammonium carbonate, ammonium hydrogen carbonate, and a mixture of any two or more thereof; the solvent is selected from the group consisting of ethanol, deionized water, acetone, acetonitrile, 1-butanol, 2-butanol, diethylene glycol, ethylene glycol, toluene, 1-propanol, 2-propanol, hexane, cyclohexane, diethyl ether, acetic acid, chlorobenzene, 1,2-dimethoxy-ethane, dimethyl-formamide, dimethyl sulfoxide, tetrahydrofuran, oleic acid, oleic amide, and a mixture of any two or more thereof.

17 . The process claim 15 , wherein the first calcination is conducted at about 400° C. to about 600° C. and for about 1 hour to about 20 hours; the second calcination is conducted at about 600° C. to about 1000° C. for about 1 hour to about 30 hours; and the thermal quenching is conducted by rapid cooling of the sample from a temperature of 300° C. to 1000° C. to room temperature.

18 . An electrochemical device comprising an anode, a non-aqueous electrolyte, and a cathode; wherein: the cathode comprises integrated Na x MO 2 having at least a first phase, a second phase different from the first phase, and a third phase that is different from the first and second phases; each phase is independently selected from Pm or On; m is an integer; n is an integer; M is a transition metal or a mixture of transition metals; and x is greater than 0 and less than or equal to 1.

19 . The electrochemical device of claim 18 , wherein the electrochemical device is a sodium-ion battery.

Assignees

• Uchicago Argonne Llc

Inventors

• Xu gui-liang
• Chen Zonghai
• Amine Khalil

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

• H01M10/054

  Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium · CPC title

• H01M4/0409

  by a doctor blade method, slip-casting or roller coating · CPC title

• H01M2004/028

  Positive electrodes · CPC title

• H01M4/366

  as layered products · CPC title