Supercapacitors comprising phosphonate and arsonate metal organic frameworks (MOFs) as active electrode materials

Patent metadata

Field	Value
Publication number	US-12170168-B2
Application number	US-202017637508-A
Country	US
Kind code	B2
Filing date	Jul 8, 2020
Priority date	Aug 23, 2019
Publication date	Dec 17, 2024
Grant date	Dec 17, 2024

Abstract

An electrode suitable for constructing an electrochemical double layer capacitor and/or supercapacitor is provided that includes an electrode material a metal organic framework (MOF), wherein the MOF includes an inorganic building unit including metal atoms selected from group 1 to group 12 elements, and functional groups of organic linkers including oxygen (O) and one or more atoms selected from the group comprising phosphorus (P), arsenic (As), antimony (Sb), silicon (Si), selenium (Se) and bismuth (Bi). The functional groups of the organic linkers can include phosphonate, arsonate, phosphonic acid, phosphinic acid, arsonic acids and/or arsenic acids, monoester and/or diester forms thereof. Further, the metal atoms may be selected from zinc (Zn), cadmium (Cd), copper (Cu), cobalt (Co), nickel (Ni), gold (Au) and silver (Ag). The use of the MOF as a semiconductor in semiconductor applications, a semiconductive device, such as a photovoltaic cell, including the MOF are also provided.

First claim

The invention claimed is:

1. An electrode suitable for constructing an electrochemical double layer capacitor and/or supercapacitor comprising as an electrode material a metal organic framework (MOF), wherein the MOF comprises an inorganic building unit comprising:
metal atoms selected from group 1 to group 12 elements, and
functional groups of organic linkers comprising oxygen (O) and one or more atoms selected from the group consisting of: phosphorus (P), arsenic (As), antimony (Sb), silicon (Si), selenium (Se) and bismuth (Bi).

2. The electrode according to claim 1 , wherein the metal atoms are selected form the group consisting of: zinc (Zn), cadmium (Cd), copper (Cu), cobalt (Co), nickel (Ni), gold (Au) and silver (Ag).

3. The electrode according to claim 1 , wherein the functional groups of the organic linkers are selected from the group consisting of: phosphonate, arsonate, phosphonic acid, phosphinic acid, arsonic acids and/or arsenic acids, monoester and/or diester forms thereof.

4. The electrode according to claim 1 , wherein the MOFs comprise auxiliary linkers.

5. The electrode according to claim 1 , wherein the functional groups of the organic linkers comprise arsonate and are synthetized using p-dimethylarsenato-phenylboronic acid.

6. The electrode according to claim 1 , wherein the metal atoms and the functional groups of the organic linkers are bound to each other through covalent bonding, coordinate covalent bonding and/or an ionic bonding.

7. The electrode according to claim 1 , wherein the MOF is porous.

8. The electrode according to claim 1 , wherein metal atoms comprise Cu, Ni, Fe, Cd, Zn, Zr, Ti, V, Cr and/or Co and the functional groups comprise phosphonate and/or arsonate.

9. The electrode according to claim 1 , wherein the MOF is [{Cu2 (4,4′-bpy) 0.5 } (1,4-naphthalenediphosphonate (NDPA))], [Co 2 (H 4 -MTPPA)]0.3NMP·H 2 O, [{Cu(H 2 O)} (2,6-NDPA) 0.5 ], [Zn{N(CH 3 ) 2 }(6-bromonapthalene-2-yl) phosphonate], Zn 2 H 4 MTPPA, Zn 2 H 4 STPPA, [Ni(Cu-H 4 TPPA)]·2(CH 3 ) 2 NH 2+ , Zn 2 (H 4 TPPA), Zn 2 (Cu-H 4 TPPA), Cu 3 (H 5 -MTPPA) 2 , K 6 (m-H 2 -TPPA)·2H 2 O, or [{Ca 2 (DMF)} (2,6-NDPA)].

10. The electrode according to claim 9 , wherein [Co 2 (H 4 -MTPPA)]·3NMP·H 2 O was prepared solvothermically from the tetrahedral linker tetraphenylmethane tetrakis-4-phosphonic acid (H8-MTPPA) and CoSO 47 H 2 O in N-methyl-2-pyrrolidone (NMP).

11. An electrochemical double layer capacitor or a supercapacitor comprising an electrode according to claim 1 .

12. The electrode according to claim 2 , wherein the metal atoms are at least one of Co, Cu and Ni.

13. The electrode according to claim 2 , wherein the metal atoms are at least one of Zn and Cu.

14. The electrode according to claim 3 , wherein the functional groups of the organic linkers are phosphonate and/or arsonate and/or monoester and/or diester forms thereof.

15. The electrode according to claim 4 , wherein the auxiliary linkers comprise organoimine groups.

16. The electrode according to claim 15 , wherein the organoimine groups are a Lewis base comprising a group 15 element.

17. The electrode according to claim 16 , wherein the Lewis base is 4,4′-bipyridine.

18. A semiconductor device or photovoltaic device comprising a metal organic framework (MOF), wherein the MOF comprises an inorganic building unit comprising:
metal atoms selected from group 1 to group 12 elements, and
functional groups of organic linkers comprising oxygen (O) and one or more atoms selected from the group consisting of: phosphorus (P), arsenic (As), antimony (Sb), silicon (Si), selenium (Se) and bismuth (Bi).

19. The photovoltaic device according to claim 18 , wherein the photovoltaic device is a photovoltaic cell comprising the MOF as a photoactive material.

Assignees

• Univ Berlin Tech

Inventors

• Yücesan Gündog

Classifications

• H01G11/30 Primary

  characterised by their material · CPC title

• H01G11/48 Primary

  Conductive polymers · CPC title

• H10F77/211

  for photovoltaic cells · CPC title

• H10K85/6572

  comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole · CPC title

• H10K85/331

  Metal complexes comprising an iron-series metal, e.g. Fe, Co, Ni · CPC title