Redox couple for electrochemical and optoelectronic devices

Patent metadata

Field	Value
Publication number	US-9779879-B2
Application number	US-201214001062-A
Country	US
Kind code	B2
Filing date	Feb 24, 2012
Priority date	Feb 25, 2011
Publication date	Oct 3, 2017
Grant date	Oct 3, 2017

Abstract

The present invention provides an improved redox couple for electrochemical and optoelectronic devices. The redox couple is based on a complex of a first row transition metal, said complex containing at least one mono-, bi-, or tridentate ligand comprising a substituted or unsubstituted ring or ring system comprising a five-membered N-containing heteroring and/or a six-membered ring comprising at least two heteroatoms, at least one of which being a nitrogen atom, said five- or six-membered heteroring, respectively, comprising at least one double bond. The invention also relates to electrolytes and to the devices containing the complex, and to the use of the complex as a redox couple. The invention further provides electrochemical and/or optoelectronic devices comprising a first and a second electrode and, between said first and second electrode, a charge transport layer, said a charge transport layer comprising tetracyanoborate ([B(CN) 4 ] − ) and a cationic metal complex functioning as redox-couple.

First claim

The invention claimed is:

1. An electrochemical or optoelectronic device comprising a first and a second electrode and, between said first and second electrode, a charge transport layer, said a charge transport layer comprising a complex-based redox couple being added in the form of a salt of tetracyanoborate (B(CN) 4 ) having tetracyanoborate ([B(CN) 4 ] − ) as anion and a cationic metal complex of formula I:
M(La) n (Xb) m   (I)

wherein:
M is a 1 st row transition metal selected from the metals Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn;
n is an integer from 1 to 3 and a is a consecutive number of a first set consisting of the integers of 1 to n (1, . . . , n), so that there are n ligands L1, . . . , Ln;
m is 0 or an integer from 1 to 5 and b is a consecutive number of a second set consisting of 0 and integers of 1 to m (0, . . . , m), so that if m>0 there are m ligands X1, . . , Xm;
provided the sum of n and m equal the appropriate total number of ligands present on metal M;
each ligand La is independently selected from mono-, bi-, and tridentate ligands, comprising a substituted or unsubstituted ring or ring system, said ring or ring system comprising at least one nitrogen atom;
each co-ligand Xb is independently selected from H 2 O, Cl − , Br − , I − , CN − , NCO − , NCS − , NCSe − , NH 3 , NR 10 R 11 R 12 , PR 10 R 11 R 12 , R 10 , wherein R 10 , R 11 , and R 12 may be selected independently from substituted or unsubsituted alkyl, alkenyl, alkynyl and phenyl,
wherein each said La is independently selected from any one of compounds of formulae (2), (3), (64), (66) and (68) as shown below:

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 of formulae (2), (3), in as far as present, are selected independently from H, halogen (—F, —Cl, —Br, —I), —CN, and from C1-C6 alkyl and alkenyl, wherein any available hydrogen of said alkyl and alkenyl may or may not be replaced by halogen and/or —CN and from the substituents of formula (A-3), (A-5), (A-6), (B-5), (B-6), (B-8), (B-9), (B-10), (B-11), (B-12), (B-13), (B-14), (B-15), (B-17), (B-21), (B-22), (B-24), (B-25), (B-26), (B-27), (C-2), (C-3), (C-4), (C-5), (C-6), (C-7), (C-8), (C-9), (C-10), (C-11), (C-12), (C-13), (C-14), (C-15), (C-16), (C-17), (C-18), (C-19), (C-20), (C-21), (C-24), (C-25), (C-26), (C-27), (D-1), (D-2), (D-3), (E-1), (E-2), (E-3), (F-1), (F-2), (F-3), (F-4), (F-5), (F-6), (F-7), (F-9), (F-10), (G-1), (G-2) below:

wherein the dotted line represents the bond connecting the substituent of (A-1) to (G-2) on the respective compound of formula (2), (3), (64), (66) and (68); and, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 from formulae (A-3) to (G-2), in as far as present, are independently selected from H, hydrocarbons comprising 1 to 20 carbons and 0 to 20 heteroatoms, halogen, (—F, —Cl, —Br, —I), and —NO 2 ; and R′ of substituents (B-10), (C-9), (C-12), (C-14), and (C-16) is selected from H and from C1-C6 linear branched or cyclo alkyl, said alkyl being possibly and optionally substituted by halogen; and

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 of formulae (64), (66) and (68), in as far as applicable, are H, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 of formulae (64), (66) and (68), in as far as applicable, are selected from H, —CN, and —CF 3 .

2. The device according to claim 1 , wherein said charge transport layer comprises an organic solvent and/or comprises one or more ionic liquids.

3. The device according to claim 1 , wherein said first electrode is a semiconductor electrode comprising a surface facing the charge transport layer of the device, wherein a dye is adsorbed on said surface so as to form a layer on said surface, wherein said dye is selected from dyes carrying no charge or carrying a positive charge or carrying a negative charge when being adsorbed on said surface.

4. The device according to claim 3 , wherein said dye adsorbed on said surface lacks any negatively charged, free (non-anchored) anchoring group.

5. The device according to claim 3 , wherein said dye comprises a single anchoring group, by way of which said dye is attached to said surface.

6. The device according to claim 1 , which is selected from a photo-electrochemical device, an optoelectronic device, an electrochemical battery, (for example a lithium ion battery), a double layer capacitor, a light emitting device, an electrochromic or photo-electrochromic device, an electrochemical sensor, a biosensor, an electrochemical display and an electrochemical capacitor.

7. The device according to claim 1 , which is a photoelectric conversion device, preferably a dye-sensitized solar cell or photovoltaic cell.

8. The device according to claim 1 , wherein n is 3, m is 0 and/or wherein the ligands L1, L2, L3 are independently selected from compounds of formulae (2), (3) and (64).

9. The device according to claim 1 , wherein n is 2, m is 0 or 1, and/or wherein L1 and L2 are selected independently from the compounds of formulae (66) and (68).

10. A method of preparing a electrochemical device, the method comprising the steps of:
providing a first and a second electrode;
providing a charge transport layer;
adding to said charge transport layer a salt comprising tetracyanoborate ([B(CN) 4 ] − ) and a cationic metal complex of formula I:
M(La) n (Xb) m   (I)

wherein:
M, n, m, La and Xb are as defined in claim 1 .

11. The device according to claim 1 , wherein n is 2 and L1 and L2 is identical or wherein n is 3 and L1, L2 and L3 are identical.

Assignees

• Nazeeruddin Mohammad Khaja
• Graetzel Michael
• Baranoff Etienne
• Kessler Florian
• Yum Jun-Ho
• Yella Aswani
• Tsao Hoi Nok
• Zakeeruddin Shaik Mohammad
• Ecole Polytechnique Fed De Lausanne (Epfl)

Inventors

• Nazeeruddin Mohammad Khaja
• Graetzel Michael
• Baranoff Etienne
• Kessler Florian
• Yum Jun-Ho
• Yella Aswani
• Tsao Hoi Nok
• Zakeeruddin Shaik Mohammad

Classifications

• Y02E10/542

  Dye sensitized solar cells · CPC title

• H01L51/0083

  Electricity · mapped topic

• H01G9/2059

  comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution · CPC title

• C07D401/04 Primary

  directly linked by a ring-member-to-ring-member bond · CPC title

• C09B57/00

  Other synthetic dyes of known constitution · CPC title