Method for producing inorganic compounds

Patent metadata

Field	Value
Publication number	US-9590245-B2
Application number	US-200913124725-A
Country	US
Kind code	B2
Filing date	Oct 23, 2009
Priority date	Oct 23, 2008
Publication date	Mar 7, 2017
Grant date	Mar 7, 2017

Abstract

The present arrangement provides compounds (I) A a M m (YO4) y Z z (I) that are obtained from precursors of the constituent elements by a method having steps that can include dispersion of the precursors in a liquid support having one or more ionic liquids made up of a cation and an anion the electric charges of which balance out to give a suspension of the precursors in the liquid. The suspension is heated to a temperature of 25 to 380° C. and the ionic liquid and the inorganic oxide of formula (I) are separated from the reaction of the precursors.

First claim

The invention claimed is:

1. A process for preparing an inorganic oxide of formula (I) A a M m (YO 4 ) y Z z (I) in which:
A represents at least one element chosen from alkali metals, alkaline-earth metals, a dopant element and a space;
M represents (T 1-t ,T′ t ), T representing one or more transition metals and T′ representing at least one element chosen from Mg, Ca, Al and rare-earths, 0 ≦t<1;
Y represents at least one element chosen from S, Se, P, As, Si, Ge and Al;
Z represents at least one element chosen from F, O and OH;
a, m, y and z are stoichiometric coefficients and are real, zero or positive numbers, with the following conditions:
a, m, t, y and z are such that the electrical neutrality of the inorganic oxide of formula (I) is respected,
a≧0; m>0; y>0
z≧0;
starting with precursors of the constituent elements of the inorganic oxide of formula (I), said process comprises the following steps:
i) dispersion of said precursors in a support liquid consisting essentially of one or more ionic liquids formed from a cation and an anion whose electrical charges equilibrate, to obtain a suspension of said precursors in said liquid, said precursors having no solubility in said liquid support
ii) heating of said suspension to a temperature from 25 to 380° C.,
iii) separation of said ionic liquid and of the inorganic oxide of formula (I) derived from the reaction between said precursors.

2. The process as claimed in claim 1 , wherein the precursors of an alkali metal A are selected from the group consisting of the salts of thermolabile anions; the salts of volatile organic acids; and the salts of acids that can decompose when hot.

3. The process as claimed in claim 2 , wherein said precursors are selected fro the group consisting of Li 2 CO 3 , LiHCO 3 , LiOH, Li 2 O 2 , LiNO 3 , LiCH 3 CO 2 , LiCHO 2 , Li 2 C 2 O 4 , Li 3 C 6 H 5 O 7 , Na 2 CO 3 , NaOH, Na 2 O 2 , NaNO 3 , NaCH 3 CO 2 , NaCHO 2 , Na 2 C 2 O 4 , Na 3 C 6 H 5 O 7 , K 2 CO 3 , KOH, K 2 O 2 , KO 2 KNO 3 , KCH 3 CO 2 , KCHO 2 , K 2 C 2 O 4 , K 3 C 6 H 5 O 7 and hydrates thereof.

4. The process as claimed in claim 1 , wherein the precursors of a transition metal M are selected from the group consisting of the salts of volatile inorganic acids, the salts of volatile organic acids, the salts of acids that can decompose when hot, and the salts of inorganic acids.

5. The process as claimed in claim , wherein the precursors of the oxyanions YO 4 are chosen from the corresponding acids thermolabile ammonium, amine, imidazole or pyridine salts.

6. The process as claimed claim 1 , wherein the oxyanion YO 4 precursors are selected from the group consisting of AHSO 4 and A 2 SO 4 , in which A represents an alkali metal.

7. The process as claimed in claim 6 , wherein the oxyanion YO 4 precursors are selected from the group consisting of LiHSO 4 and Li 2 SO 4 .

8. The process as claimed in claim 1 , wherein the amount of precursors present in the ionic liquid during step i) is from 0.01% to 85% by mass.

9. The process as claimed in claim 1 , wherein the oxides of formula (I) are selected from the group consisting of the fluorosulfates A a M m SO 4 F and sulfates.

10. The process as claimed in claim 1 , wherein the cations of the ionic liquid are selected from the group consisting of the cations of the following formulae:

in which:
the radicals R 4 -R 17 , R 27 , R 24 , R 28 , R 29 , R 37 , R 34 , R 39 , R 43 and R 46 to R 57 , independently of each other, represent a C 1 -C 24 alkyl, C 1 -C 24 arylalkyl or (C 1 -C 24 )alkylaryl radical;
the radicals R 18 to R 22 , R 23 , R 25 ,R 26 ,R 30 to R 33 , R 35 , R 36 , R 38 , R 40 to R 42 , R 44 , and R 45 represent a hydrogen atom, a C 1 -C 24 alkyl radical, an aryl radical, a C 1 -C 24 oxaalkyl radical or a radical [(CH) 2 ] m Q in which Q represents OH, CN, C(═O)OR 58 , C(═O)NR 59 R 60 ,NR 61 R 62 or a 1-imidazoyl, 3-imidazoyl or 4-imidazoyl radical and m is a positive integer between 0 and 12 inclusive;
the radicals R 8 to R 16 may also denote a (C 1 -C 20 )alkylaryl radical or a group NR 63 R 64 ,
R 58 to R 64 , independently of each other, represent a hydrogen atom or a C 1 -C 20 alkyl, aryl or C 1 -C 20 oxaalkyl radical.

11. The process as claimed in claim 1 , wherein the anions of the ionic liquids are selected from the group consisting of: Cl, Br, I, RSO 3 31 , ROSO 3 − , [RPO 2 ] − , [R(R′O)PO 2 ] − , [(RO) 2 PO 2 ] − , BF 4 − , R f BF 3 − , PF 6 − , R f PF 5 − , (R f ) 2 PF 4 − , (R f ) 3 PF 3 − , R f CO 2 − , R f SO 3 − , [(R f SO 2 ) 2 N] − , [(R f SO 2 ) 2 CH] − , [(R f SO 2 ) 2 C(CN)] − , [R f SO 2 C(CN) 2 ] − , [(R f SO 2 ) 3 C] 31 , N(CN) 2 − , C(CN) 3 − , [(C 2 O 4 ) 2 B] − in which:
R and R′, which may be identical or different, represent a C 1 -C 24 alkyl, aryl or (C 1 -C 24 )alkylaryl radical,
R f is a fluoro radical chosen from C n F 2n+1 in which 0≦n≦8, CF 3 OCF 2 , HCF 2 CF 2 and C 6 F 5 .

12. The process as claimed in claim 1 , wherein the ionic liquid contains one or more carbon precursors chosen from simple carbohydrates and polymerized carbohydrates.

13. The process as claimed in claim 1 , wherein the heating step ii) is continued d beyond 380° C.

14. The process as claimed in clan wherein the heating step is performed under an inert atmosphere, at atmospheric pressure.

15. The process as claimed in claim 1 , wherein the duration of the heating step ii) ranges from 10 minutes to 200 hours.

16. The process as claimed in claim 2 , wherein the precursors of an alkali metal A are selected from the group consisting of carbonates, hydrogen carbonates, hydroxides, peroxides and nitrates; acetates and formates; oxalates, malonates and citrates.

17. The process as claimed in claim 4 , wherein the precursors of a transition metal M are selected from the group consisting of nitrates and carbonates, acetates and formates, oxalates, malonates and citrates, and sulfates, chlorides and bromides.

18. The process as claimed in claim 5 , wherein the precursors of the oxyanions YO 4 are chosen from H 2 SO 4 ; thermolabile ammonium, amine, imidazole or pyridine salts.

19. The process as claimed in claim 12 , wherein the ionic liquid contains one or more carbon precursors chosen from sugars and starch and cellulose.

Assignees

• Tarascon Jean-Marie
• Recham Nadir
• Armand Michel
• Centre Nat Rech Scient
• Uníversite De Picardie Jules Verne

Inventors

• Tarascon Jean-Marie
• Recham Nadir
• Armand Michel

Classifications

• C01G51/006

  Chemistry & Metallurgy · mapped topic

• C01G49/009

  Compounds containing iron, with or without oxygen or hydrogen, and containing two or more other elements · CPC title

• C01B25/37

  Phosphates of heavy metals · CPC title

• C01P2004/04

  obtained by TEM, STEM, STM or AFM · CPC title

• C01P2002/77

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