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

Patent metadata

Field	Value
Publication number	US-2023207808-A1
Application number	US-202218145348-A
Country	US
Kind code	A1
Filing date	Dec 22, 2022
Priority date	Dec 21, 2015
Publication date	Jun 29, 2023
Grant date	—

Abstract

Olivine-type compounds, their preparation and use in cathode materials for sodium-ion batteries. The olivine-type compounds may be obtained by a direct synthesis embodying a hydrothermal method. The method may include preparing an aqueous mixture including a M-containing compound, a M′-containing compound and a M″-containing compound to obtain a M-M′-M″ mixture; adding a P-containing compound to the mixture M-M′-M″ mixture to obtain a M-M′-M″-P mixture; adding a Na-containing compound to the M-M′-M″-P mixture to obtain a Na-M-M′-M″-P mixture; and introducing the Na-M-M′-M″-P mixture into an autoclave to perform crystal growth and obtain the compound of general formula NahMiM′jM″kPO4.

First claim

1 - 38 . (canceled)

39 . A method of preparing a sodium phospho-olivine compound, the method comprising a hydrothermal method.

40 . A method of preparing 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, the 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 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 .

41 . The method of claim 40 , further comprising the steps of:
(e) fast-cooling the crystals; and (f) drying the cooled crystals.

42 . The method of claim 41 , wherein step (f) is performed at a temperature of about 50-85° C. for a period of about 6-12 hours.

43 . The method of claim 41 , wherein step (f) is performed at a temperature of about 60-75° C. for a period of about 8-10 hours.

44 . The method of claim 40 , 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.

45 . The method of claim 40 , wherein each of steps (a)-(c) is performed under stirring.

46 . The method of claim 40 , wherein step (c) comprises preparing an aqueous solution of the Na-containing compound and adding the solution to the M-M′-M″-P mixture.

47 . The method of claim 40 , wherein step (d) is performed under an atmosphere of O 2 , N 2 or a combination thereof.

48 . The method of claim 40 , 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.

49 . The method of claim 40 , 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.

50 . The method of claim 40 , wherein the aqueous mixture comprises deionized water bubbled under N 2 .

51 . The method of claim 40 , 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 .

52 . The method of claim 40 , wherein the compounds are each independently a hydrated compound.

53 . The method of claim 40 , wherein the P-containing compound is H 3 PO 4 .

54 . The method of claim 40 , wherein the Na-containing compound is NaOH.

55 . The method of claim 40 , wherein the Na-containing compound is used in an excess amount.

56 . The method of claim 40 , 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
• Cic Energigune

Inventors

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

Classifications

• C01P2002/72

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

• C01P2002/77

  by unit-cell parameters, atom positions or structure diagrams · CPC title

• H01M4/364

  as mixtures · CPC title

• H01M2004/028

  Positive electrodes · CPC title

• C01P2002/76

  by a space-group or by other symmetry indications · CPC title