Olivine-type compounds: method for their preparation and use in cathode materials for sodium-ion batteries

Patent metadata

Field	Value
Publication number	US-2025260011-A1
Application number	US-202519193064-A
Country	US
Kind code	A1
Filing date	Apr 29, 2025
Priority date	Dec 21, 2015
Publication date	Aug 14, 2025
Grant date	—

Abstract

This disclosure provides for Olivine-type compounds, their preparation and use in cathode materials for sodium-ion batteries. The olivine-type compounds of the invention are obtained by a direct synthesis embodying a hydrothermal method.

First claim

1 . A cathode material for sodium-ion batteries, comprising:
a compound of general formula Na 1-x Li x Fe 1-y Mn y PO 4 or Na 1-x Li x Fe y Mn 1-y PO 4 , wherein: 0≤x<1 and 0<y<1; or a compound of general formula Na h M i M′ j M″PO 4 , wherein: 0<h≤1, 0≤i≤1, 0≤j≤1 and 0≤k≤1, and wherein M, M′ and M″ are each independently a metal selected from the group consisting of: Mg, Ca, Mn, Fe, Co, Ni, and Cu, and wherein i is not (1-h); or a compound of general formula NaMn 1-x Mg x PO 4 , wherein x≈0.1; or a compound of general formula Na 1-x Mg x MnPO 4 , wherein: 0<x≤1.

2 . The cathode material according to claim 1 , wherein the compound has the formula Na 0.9 Li 0.1 Fe 0.22 Mn 0.78 PO 4 or Na 0.9 Li 0.1 Fe 0.25 Mn 0.75 PO 4 .

3 . The cathode material according to claim 1 , further comprising a carbon material.

4 . A sodium-ion battery comprising the cathode material as defined in claim 1 .

5 . A sodium-ion battery, wherein a cathode material comprises a compound of general formula Na h M i M′ j M″ k PO 4 , wherein: 0<h≤1, 0<i≤1, 0<j≤1 and 0<k≤1, and wherein M, M′ and M″ are each independently a metal, and wherein the compound is prepared by a method comprising the steps of:
(a) preparing an aqueous mixture comprising a M-containing compound, a M′-containing compound, and a M″-containing compound to obtain a M-M′-M″ mixture;
(b) adding a P-containing compound to the mixture M-M′-M″ mixture to obtain a M-M′-M″-P mixture;
(c) adding a Na-containing compound to the M-M′-M″-P mixture to obtain a Na-M-M′-M″-P mixture;
(d) introducing the Na-M-M′-M″-P mixture into an autoclave to perform crystal growth and obtain the compound of general formula Na h M i M′ j M″ k PO 4 ;
(e) fast-cooling the crystals; and
(f) drying the cooled crystals.

6 . The sodium-ion battery according to claim 5 , wherein step (f) is performed at a temperature of about 50-85° C. for a period of about 6-12 hours.

7 . The sodium-ion battery according to claim 5 , wherein step (f) is performed at a temperature of about 60-75° C. for a period of about 8-10 hours.

8 . The sodium-ion battery according to claim 5 , wherein step (a) comprises preparing separate aqueous solutions of the M-containing compound, the M′-containing compound and the M″-containing compound, first mixing two of the three solutions and then adding the third solution to obtain the M-M′-M″ mixture.

9 . The sodium-ion battery according to claim 5 , wherein each of steps (a)-(c) is performed under stirring.

10 . The sodium-ion battery according to claim 5 , wherein step (b) comprises preparing an aqueous solution of the Na-containing compound and adding the solution to the M-M′-M″-P mixture.

11 . The sodium-ion battery according to claim 5 , wherein step (d) is performed under an atmosphere of O 2 , N 2 , or a combination thereof.

12 . A sodium-ion battery, wherein a cathode material comprises a compound of general formula Na h M i M′ j M″ k PO 4 , wherein: 0<h≤1, 0<i≤1, 0<j≤1 and 0<k≤1, and wherein M, M′ and M″ are each independently a metal, and wherein the compound is prepared by a method comprising the steps of:
(a) preparing an aqueous mixture comprising a M-containing compound, a M′-containing compound, and a M″-containing compound to obtain a M-M′-M″ mixture;
(b) adding a P-containing compound to the mixture M-M′-M″ mixture to obtain a M-M′-M″-P mixture;
(c) adding a Na-containing compound to the M-M′-M″-P mixture to obtain a Na-M-M′-M″-P mixture; and
(d) introducing the Na-M-M′-M″-P mixture into an autoclave to perform crystal growth and obtain the compound of general formula Na h M i M′ j M″ k PO 4 , wherein step (d) is performed at a temperature of about 150-250° C. for a period of about 2-6 hours under a pressure of about 1.5-2.5 Mpa.

13 . The sodium-ion battery according to claim 12 , wherein step (d) is performed at a temperature of about 200° C. for a period of about 4 hours under a pressure of about 2 MPa.

14 . The sodium-ion battery according to claim 12 , wherein the aqueous mixture comprises deionized water bubbled under N 2 .

15 . The sodium-ion battery according to claim 12 , wherein the M-containing compound, the M′-containing compound and the M″-containing compound are each independently selected from the group consisting of MnSO 4 , LiOH, FeSO 4 , and MgSO 4 .

16 . The sodium-ion battery according to claim 12 , wherein the compounds are each independently a hydrated compound.

17 . A sodium-ion battery, wherein a cathode material comprises a compound of general formula Na h M i M′ j M″ k PO 4 , wherein: 0<h≤1, 0<i≤1, 0<j≤1 and 0<k≤1, and wherein M, M′ and M″ are each independently a metal, and wherein the compound is prepared by a method comprising the steps of:
(a) preparing an aqueous mixture comprising a M-containing compound, a M′-containing compound, and a M″-containing compound to obtain a M-M′-M″ mixture;
(b) adding a P-containing compound to the mixture M-M′-M″ mixture to obtain a M-M′-M″-P mixture;
(c) adding a Na-containing compound to the M-M′-M″-P mixture to obtain a Na-M-M′-M″-P mixture; and
(d) introducing the Na-M-M′-M″-P mixture into an autoclave to perform crystal growth and obtain the compound of general formula Na h M i M′ j M″ k PO 4 , wherein the P-containing compound is H 3 PO 4 .

18 . The sodium-ion battery according to claim 17 , wherein the Na-containing compound is NaOH.

19 . The sodium-ion battery according to claim 17 , wherein the Na-containing compound is used in excess amount.

20 . The sodium-ion battery according to claim 17 , wherein, in the general formula Na h M i M′ j M″ k PO 4 , h=1 and 0≤i≤0.2 and 0≤j≤0.8 and 0.85≤i+j+k≤1.

Assignees

• Hydro Quebec

Inventors

• Galceran Mestres Montse
• Casas-Cabanas Montse
• Guerfi Abdelbast
• Armand Michel
• Rojo Teofilo
• Zaghib Karim
• Paolella Andrea

Classifications

• H01M2004/028

  Positive electrodes · CPC title

• H01M10/054

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

• H01M4/587

  for inserting or intercalating light metals · CPC title

• H01M4/364

  as mixtures · CPC title

• C01P2006/40

  Electric properties · CPC title