Highly electrical conductive composite material based on graphene-lithium polycarboxylate-nanoparticles

Patent metadata

Field	Value
Publication number	US-12084534-B2
Application number	US-202017920726-A
Country	US
Kind code	B2
Filing date	Apr 23, 2020
Priority date	Apr 23, 2020
Publication date	Sep 10, 2024
Grant date	Sep 10, 2024

Abstract

Herein presented is a high electrical conductivity, uniform, material based on nanoparticles-Li+-polycarboxylate grafted few-layer graphene oxide including perovskite type nanoparticles for filler in polymeric matrices, in direct and reverse osmosis membranes, in lithium batteries, among others. The material is obtained by a method comprising the step of: preparation of a composite material having polymers with mono- or di-acid groups covalently bonded to graphene; optionally further comprising the preparation of a composite material with graphene covalently bonded to polymers having mono- or di-acid groups that have been replaced by lithium ion; and optionally further comprising the preparation of a composite material with graphene covalently bonded to polymers having mono- or di-acid groups that have been replaced by lithium ion in addition to grafted nanoparticles, including nanoparticles perovskite type.

First claim

The invention claimed is:

1. A graphene-polycarboxylate type material comprising the Formula (I):

where,
X is H + or Li + ;
Y is H + , ABO 3 or functionalized ABO 3 ;
R 1 is methyl, ethyl, propyl, isopropyl, isobutyl ester or butyl carboxylate;
R 2 is chlorine or bromine;
A is Ca(II), Mg(II), Sr(II) or Ba (II) and B is: Ti(III), V(III), Mn(III), Fe(III), Co(III) or Ni(III); and
n: ranges from 1 to 300,
wherein said material is uniform and conductive.

2. The material of claim 1 , wherein said material is a graphene-polycarboxylate-nanoparticle type material.

3. The material of claim 2 , wherein said nanoparticle is a perovskite type nanoparticle.

4. The material of claim 1 , wherein said material is formed by a method comprising:
a. reacting the graphene oxide with a monomer of mono- or di-ester in presence of nitric acid and CuBr(II) in an organic solvent;
b. adding a polyamine to the mixture under inert atmosphere and evaporating the solvent after the reaction finishes.

5. The material of claim 4 , wherein said method further comprises:
c. mixing the functionalized graphene with distilled water to form a suspension;
d. adding lithium hydroxide under continuous agitation until reaching pH 8 to 11 and the suspension is allowed to dry.

6. The material of claim 5 , wherein said method further comprises:
e. dispersing by agitation the functionalized of polycarboxylate grafted few-layer graphene oxide graphene with lithium polycarboxylate in decalin, toluene, xylene, N,N-dimethylformamide, N-methyl-2-pyrrolidone or dioxane,
f. adding inorganic nanoparticles with functionalized organosilanes, in a ratio between 1: (0.5-3);
g. treating the mixture with ultrasound under an inert atmosphere;
h. removing and drying the resulting material.

7. The material of claim 6 , wherein the reaction time in (f) is between 2-24 hours.

8. The material of claim 6 , wherein the reaction temperature in (f) is between 100° C.-150° C.

9. The material of claim 6 , wherein the drying time in (h) is between 10-15 hours.

10. The material of claim 6 , wherein the drying temperature in (h) is between 65° C.-75° C.

11. The material of claim 5 , wherein the organic solvent in (e) is selected from decalin, toluene, xylene, N,N-dimethylformamide and N-methyl-2-pyrrolidone.

12. The material of claim 5 , wherein the concentration of the suspension in (c) is in a range between 1-10 wt %.

13. The material of claim 5 , wherein the concentration of lithium hydroxide in (d) range between 0.1-5 M.

14. The material of claim 5 , wherein the drying temperature in (d) is between 40° ° C.-120° ° C.

15. The material of claim 5 , wherein the drying time in (d) is between 19-23 hours.

16. The material of claim 4 , wherein the mono- or di- ester monomer is selected from cicatronic acid, mesanoic acid, itanoic acid and fumaric acid.

17. The material of claim 4 , wherein the organic solvent in (a) is selected from toluene, xylene, decalin and dioxane.

18. The material of claim 4 , wherein the polyamine in (a) is selected from bipyridine (bpy), tris[2-(dimethylamino)ethyl]amine (Me6TREN), tris(2-pyridylmethyl)amine (TPMA), 4,4′-Dinonyl-2,2′-dipyridyl (dNbpy) or N, N, N′, N “, N”-pentamethyldiethylenetriamine (PMDETA).

19. The material of claim 4 , wherein the evaporation step in (b) is carried out by rotary evaporator, laminar flow, fume hood, supercritical drying or oven with pressure control.

20. The material of claim 4 , wherein the evaporation temperature in step (a) is between 40° C. and 120° C.

21. The material of claim 4 or 6 , wherein the inert atmosphere is selected from nitrogen, helium, and argon.

22. The material of claim 4 , wherein the reaction step in (a) lasts 3 to 48 hours.

23. The material of claim 4 , wherein the reaction temperature in (a) is between 50 ºC and 100° ° C.

24. The material of claim 4 , wherein in step (a) the mixture is dried for 19 to 23 hours at 40° C. to 120° C.

Assignees

• Univ Chile

Inventors

• Aguilar Bolados Héctor Esteban
• Yazdani-Pedram Zobeiri Mehrdad
• Gallegos Cofre Moises De Jesus

Classifications

• C08K2201/011

  Nanostructured additives · CPC title

• C08K9/06

  with silicon-containing compounds · CPC title

• C08F2810/00

  Chemical modification of a polymer · CPC title

• C01P2004/64

  Nanometer sized, i.e. from 1-100 nanometer · CPC title

• C01P2004/04

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