# US 10,121,971 B2 · Cellulose-polymer composites for solar cells

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- Number: US 10,121,971 B2
- Document ID: US10121971B2
- Status: Granted
- Kind: B2
- Application number: 14/409,821
- Filed: 2013-06-21
- Published: 2015-07-02
- Granted: 2018-11-06
- Earliest claimed: 2012-06-21
- Assignees: Chemgreen Innovation Inc.
- Applicants: Chemgreen Innovation Inc.
- Inventors: Khashayar Ghandi; Yang Tan; Fraser Burns; Sean Robertson; Zahid Shabbir Mahimwalla
- Web page: https://patentgrep.com/patent/US10121971B2

## CPC

- C08F 38/00: Homopolymers and copolymers of compounds having one or more carbon-to-carbon triple bonds
- B82Y 10/00: Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
- C08B 1/003: {Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids (solutions used in the manufacture of monocomponent artificial filaments or cellulose or derivatives thereof D01F2/02)}
- C08J 3/098: {Other compounds}
- C08L 1/02: Cellulose; Modified cellulose
- C08L 1/08: Cellulose derivatives
- C08L 25/06: Polystyrene
- C08L 65/00: Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C08L7/00 - C08L57/00, C08L61/00 take precedence); Compositions of derivatives of such polymers
- H01B 1/127: {comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes}
- H01B 1/128: {comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes}
- H10K 30/20: comprising organic-organic junctions, e.g. donor-acceptor junctions
- H10K 30/81: Electrodes
- H10K 85/10: Organic polymers or oligomers
- H10K 85/143: {Polyacetylene; Derivatives thereof}
- C08G 61/124: {with a five-membered ring containing one nitrogen atom in the ring}
- C08G 2261/312: Non-condensed aromatic systems, e.g. benzene
- C08G 2261/3142: fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
- C08G 2261/3221: containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
- C08G 2261/3223: containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
- C08G 2261/3241: containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
- C08G 2261/3422: conjugated, e.g. PPV-type
- C08J 2301/02: Cellulose; Modified cellulose
- H10K 30/50: Photovoltaic [PV] devices
- H10K 30/80: Constructional details
- H10K 85/761: {Biomolecules or bio-macromolecules, e.g. proteins, chlorophyl, lipids or enzymes}
- Y02E 10/549: Organic PV cells
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C08B: POLYSACCHARIDES; DERIVATIVES THEREOF (polysaccharides containing less than six saccharide radicals attached to each other by glycosidic linkages C07H; fermentation or enzyme-using processes C12P19/00; sugar industry C13; production of cellulose D21)
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K})
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The present disclosure relates to a cellulose-polymer composite solar cell that is substantially biodegradable and fabricated using environmentally friendly materials and methods. The polymer solar cell comprises an electrically conductive cellulose-polymer composite and an electrically semiconductive cellulose-polymer composite.

## Claims

### Claim 1

A composite polymer, comprising:
a) a cellulose composite comprising
i) cellulose or a cellulose derivative;
ii) a phosphonium ionic liquid; and
iii) a conductive polymer; and
b) optionally, an electrically conductive dopant,
wherein the cellulose or cellulose derivative is dissolved in the phosphonium ionic liquid and the phosphonium ionic liquid is incorporated into the cellulose or cellulose derivative, and the cellulose or cellulose derivative is bound to the conductive polymer.

### Claim 2 (depends on 1)

The composite polymer of claim 1, wherein the phosphonium ionic liquid has the structure
wherein
each R′ is independently or simultaneously C1-20alkyl and X is any suitable anionic ligand.

### Claim 3 (depends on 2)

The composite polymer of claim 2, wherein the phosphonium ionic liquid is tetradecyl(trihexyl)phosphonium chloride, tetradecyl(trihexyl)phosphonium bromide, tetradecyl(trihexyl)phosphonium decanoate, tetradecyl(trihexyl)phosphonium(bis 2,4,4-trimethylpentyl)phosphinate, tetradecyl(trihexyl)phosphonium dicyanamide, triisobutyl(methyl)phosphonium tosylate, tributyl(methyl)phosphonium methylsulfate, tetradecyl(trihexyl)phosphonium bistriflamide, tetradecyl(trihexyl)phosphonium hexafluorophosphate, tetradecyl(trihexyl)phosphonium tetrafluoroborate, tributyl(hexadecyl)phosphonium bromide, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetraoctylphosphonium bromide, tetradecyl(tributyl)phosphonium chloride, ethyltri(butyl)phosphonium diethylphosphate, tetradecyl(tributyl)phosphonium dodecylsulfonate or tetradecyl(trihexyl)phosphonium dodecylsulfonate.

### Claim 4 (depends on 1)

The composite polymer of claim 1, wherein the conductive polymer is polyaniline, polypyrrole, poly(p-phenylene-vinylene), poly(thiophene), poly(fluorene), polyphenylene, polypyrene, polyazulene, polynaphthalene, polycarbazole, polyindole, derivatives, or copolymers thereof.

### Claim 5 (depends on 1)

The composite polymer of claim 1, wherein the conductive polymer comprises an optionally substituted 5- or 6-membered heteroaromatic ring, wherein the optional substituents are selected independently or simultaneously from one, two or three of halo, (C1-6)-alkyl, or fluoro-substituted (C1-6)-alkyl.

### Claim 6 (depends on 5)

The composite polymer of claim 5, wherein the heteroaromatic polymer is of the formula (III)
wherein R′ is independently or simultaneously halo, (C1-6)-alkyl, or fluoro-substituted (C1-6)-alkyl;
q is 0, 1 or 2; and
m is an integer greater than or equal to 100.

### Claim 7 (depends on 6)

The composite polymer of claim 6, wherein the polymer of the formula (III) is
wherein m is an integer which is greater than or equal to 100.

### Claim 8 (depends on 1)

The composite polymer of claim 1, wherein the electrically conductive dopant is iodine (I2), iron trichloride (FeCl3), a metal naphtalide, AgClO4, gaseous O2, H2O2, benzoquinone, AsF5, metal powder, dodecylbenzenesulfonic acid (dbsa), indigo carmine, 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (abts), p-toluenesulfonic acid, and its sodium salt (ptsa and ptsa-na), benzenesulfonic acid (bsa), para-toluene sulphonate, or combinations thereof.

### Claim 9 (depends on 1)

A polymeric solar cell, comprising:
a. a first electrode comprising a composite polymer as defined in claim 1;
b. a second electrode comprising a composite polymer semiconductor,
wherein the composite polymer semiconductor comprises:
b.i. cellulose or a cellulose derivative;
b.ii. polyphenylacetylene or a derivative thereof, or a metal polystyrene nanoparticle; and
b.iii optionally, a second electrically conductive dopant.

### Claim 10 (depends on 9)

The polymeric solar cell of claim 9, wherein the first electrode is in contact with the second electrode.

### Claim 11 (depends on 9)

The polymeric solar cell according to claim 9, wherein the conductive polymer is polyaniline, poly(p-phenylene-vinylene), poly(thiophene), poly(fluorene), polyphenylene, polypyrene, polyazulene, polynaphthalene, polycarbazole, polyindole, poly(p-phenylene sulfide), derivatives, copolymers, or cellulose composites thereof.

### Claim 12 (depends on 9)

The polymeric solar cell according to claim 9, wherein the conductive polymer comprises an optionally substituted 5- or 6-membered heteroaromatic ring, wherein the optional substituents are selected independently or simultaneously from one, two or three of halo, (C1-6)-alkyl, or fluoro-substituted (C1-6)-alkyl.

### Claim 13 (depends on 11)

The polymeric solar cell according to claim 11, wherein the heteroaromatic polymer is of the formula (III)
wherein R′ is independently or simultaneously halo, (C1-6)-alkyl, or fluoro-substituted (C1-6)-alkyl;
q is 0, 1 or 2; and
m is an integer greater than or equal to 100.

### Claim 14 (depends on 9)

The polymeric solar cell according to claim 9, wherein the electrically conductive dopant is iodine (I2), iron trichloride (FeCl3), a metal naphtalide, AgClO4, gaseous O2, H2O2, benzoquinone, AsF5, metal powder, dodecylbenzenesulfonic acid (dbsa), indigo carmine, 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (abts), p-toluenesulfonic acid, and its sodium salt (ptsa and ptsa-na), benzenesulfonic acid (bsa), para-toluene sulphonate, or combinations thereof.

### Claim 15 (depends on 9)

The polymeric solar cell of claim 9, wherein the polystyrene or derivative thereof is of the formula (IV)
wherein R′ is independently or simultaneously halo or (C1-6)-alkyl, the latter group being optionally substituted by halo, (C1-2)-alkyl or fluoro-substituted (C1-2)-alkyl;
b is 0, 1, 2, 3 4, or 5;
w is an integer between 100 to 100,000; and the polymer includes metal nano particles; and wherein the polyphenylacetylene or polyphenylacetylene derivative is of the formula (V):
wherein Ph and the alkene is optionally substituted,
the optional substituents are simultaneously or independently selected from one to five of Si, Ge, halo, optionally substituted (C1-6)-alkyl, optionally substituted (C1-6)-alkoxy, optionally substituted (C6-14)-aryl, optionally substituted (C5-14)-heteroaryl, nitro, and —NR1R2 wherein R1 and R2 are independently or simultaneously H, (C1-6)-alkyl or (C6-14)-aryl, and
p is an integer between 100 to 50,000.

### Claim 16 (depends on 14)

The polymeric solar cell of claim 14, wherein the polystyrene has the structure
w is an integer between 100 to 100,000,
and polyphenylacetylene has the structure
or
wherein Ph is unsubstituted phenyl, and
p is an integer between 100 to 50,000.

### Claim 17 (depends on 9)

The polymeric solar cell according to claim 9, wherein the second electrically conductive dopant is iodine (I2), iron trichloride (FeCl3), a metal naphtalide, AgClO4, gaseous O2, H2O2, benzoquinone, AsF5, metal powder, dodecylbenzenesulfonic acid (dbsa), indigo carmine, 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (abts), p-toluenesulfonic acid, and its sodium salt (ptsa and ptsa-na), benzenesulfonic acid (bsa), para-toluene sulphonate, or combinations thereof.

### Claim 18 (depends on 9)

The polymeric solar cell of claim 9, wherein the first electrode has an electron conductivity of between 0.0001 and 10.0 S/cm.

### Claim 19 (depends on 9)

The polymeric solar cell of claim 9, wherein the polymeric solar cell is substantially biodegradable.

### Claim 20 (depends on 9)

The polymeric solar cell of claim 9, wherein the first electrode is coated with an ionic liquid layer, in which carbon nanotubes are optionally dissolved in the ionic liquid.

### Claim 21 (depends on 1)

A process for dissolving cellulose or a cellulose derivative in a phosphonium ionic liquid for the preparation of a composite polymer as claimed in claim 1, the process comprising:
(i) mixing the cellulose or cellulose derivative with the phosphonium ionic liquid under conditions for the dissolution of the cellulose or cellulose derivative in the ionic liquid,
(ii) obtaining a composite comprising the cellulose or cellulose derivative incorporated with the ionic liquid; and
(iii) mixing the composite with a monomer of a conductive polymer to obtain the composite polymer, wherein the cellulose or cellulose derivative is bound to the conductive polymer.

### Claim 22 (depends on 20)

The process of claim 20, wherein the ionic liquid is further mixed with a co-solvent, wherein the composite is also incorporated with the co-solvent, and wherein the co-solvent is dimethyl formamide (DMF).

### Claim 23 (depends on 20)

The process of claim 20, wherein the cellulose or cellulose derivative is mixed with the ionic liquid at a temperature between 50° C. and 100° C.

### Claim 24 (depends on 20)

The process of claim 20, wherein the cellulose or cellulose derivative is mixed with the ionic liquid for a time between 3-6 hours.

### Claim 25 (depends on 20)

The process of claim 20, wherein the phosphonium ionic liquid has the structure
wherein
each R′ is independently or simultaneously C1-20alkyl and X is any suitable anionic ligand.

### Claim 26 (depends on 20)

The process of claim 20, wherein the phosphonium ionic liquid is tetradecyl(trihexyl)phosphonium chloride, tetradecyl(trihexyl)phosphonium bromide, tetradecyl(trihexyl)phosphonium decanoate, tetradecyl(trihexyl)phosphonium(bis 2,4,4-trimethylpentyl)phosphinate, tetradecyl(trihexyl)phosphonium dicyanamide, triisobutyl(methyl)phosphonium tosylate, tributyl(methyl)phosphonium methylsulfate, tetradecyl(trihexyl)phosphonium bistriflamide, tetradecyl(trihexyl)phosphonium hexafluorophosphate, tetradecyl(trihexyl)phosphonium tetrafluoroborate, tributyl(hexadecyl)phosphonium bromide, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetraoctylphosphonium bromide, tetradecyl(tributyl)phosphonium chloride, ethyltri(butyl)phosphonium diethyiphosphate, tetradecyl(tributyl)phosphonium dodecylsulfonate or tetradecyl(trihexyl)phosphonium dodecylsulfonate.

### Claim 27 (depends on 20)

The process of claim 20, wherein the composite is further mixed with a free radical initiator.