Electroactive polymer based supercapacitors including a cathode having BBL or Pyr-BBL

Patent metadata

Field	Value
Publication number	US-9309440-B1
Application number	US-201514709758-A
Country	US
Kind code	B1
Filing date	May 12, 2015
Priority date	Nov 25, 2006
Publication date	Apr 12, 2016
Grant date	Apr 12, 2016

Abstract

A process used to cast films including; mixing Pyr-BBL and a room temperature molten salt from a range of about 35:65 weight ratio, dissolving the mixture in about 1% methanesulfonic acid to produce a Pyr-BBL solution, drop casting the solution onto glass or gold coated glass at 140° C. in air and heating for about 2 hours to produce films, drying the films in a vacuum oven at about 100° C. for at least 24 hours under dynamic vacuum, and rinsing the films to remove residual ionic liquid.

First claim

What is claimed is:

1. A Pyr-BBL film produced by the process, comprising:
mixing Pyr-BBL and a room temperature molten salt from a range of about 35:65 weight ratio;
dissolving said mixture in about 1% methanesulfonic acid to produce a Pyr-BBL solution;
drop casting said solution onto glass or gold coated glass at 140° C. in air and heating for about 2 hours to produce films;
drying said films in a vacuum oven at about 100° C. for at least 24 hours under dynamic vacuum; and
rinsing said films to remove residual ionic liquid.

2. The film according to claim 1 , wherein said rinsing utilized methanol or methylene chloride.

3. A process to synthesize Pyr-BBL, comprising:
deoxygenating polyphosphoric acid by heating to about 110° C. and stirring under a flow of nitrogen;
subliming 1,4,5,8-naphthalenetetracarboxylic acid dianhydride and adding said dianhydride to said polyphosphoric acid to produce a first reaction mixture;
adding pyridine to a solution of 1,3-phenylenediamine in anhydrous dichloromethane and cooled to about 0° C. under gas to produce a second reaction mixture;
adding p-Toluenesulfonyl chloride portion-wise to said second reaction mixture and allowing to warm to room temperature while stirring for about 12 hours;
extracting said reaction mixture with water;
extracting said reaction mixture with saturated aqueous sodium bicarbonate;
extracting said reaction mixture with brine to remove residual bulk water;
drying said organic layer over sodium sulfate;
filtering said organic layer;
concentrating said organic layer in vacuo to remove majority of said organic solvent;
pumping said material under high vacuum over about 48 hours;
dissolving said material in ethyl acetate and extracting at least twice with 1 M aqueous hydrochloric acid;
drying said material over sodium sulfate, filtering said material, and concentrating said material in vacuo;
adding dropwise 70% nitric acid at a rate to maintain the temp below 5° C. to a stirring solution of acetic anhydride;
adding 1,3-(p-toluenesulfamido)benzene to said solution at a rate to keep the temperature below 15° C.;
stirring said solution at room temperature for about 12 hours to about 24 hours to produce a precipitate;
collecting said precipitate by washing with water and recrystallizing said precipitate using acetone;
suspending 1,3-Dinitro-4,6-(p-toluenesulfamido)benzene in anhydrous ethanol in a pressure bomb and flushing with gas;
adding palladium on carbon;
emptying said gas in the pressure bomb via vacuum and flushing with a gas at least three times, filling the pressure bomb with gas to 50 psi and shaking said suspension;
suction-filtering said reaction mixture through Celite and washing with ethanol and acetone;
purifying said mixture by dissolving in a minimal amount of acetone and adding spatula tip amounts of sodium bicarbonate and activated charcoal and stirring for about 30 minutes to produce a solution;
filtering said solution through Celite, washing with an effective amount of acetone, and cooling said solution in refrigeration for an effective amount of time to precipitate a product;
isolating said product by filtering and washing with an effective amount of cold acetone;
protecting said product from light exposure;
adding to said product 1,4,5,8-naphthalenetetracarboxylic acid dianhydride and 1,3-diamino-4,6-(p-toluenesulfonamido)benzene and adding to polyphosphoric acid (PPA) at 90° C. for about 6 hours to produce a reaction mixture;
increasing temperature to said reaction mixture temperature to 180° C., and holding at said temperature for about 16 hours;
cooling said reaction mixture and precipitating in methanol to produce a residue;
dissolving said residue in methanesulfonic acid (MSA) and reprecipitating in methanol at least twice to produce a polymer; and
drying said polymer under vacuum without applying heat for about a week.

4. A Pyr-BBL film produced by the process, comprising:
deoxygenating polyphosphoric acid by heating to about 110° C. and stirring under a flow of nitrogen;
subliming 1,4,5,8-naphthalenetetracarboxylic acid dianhydride and adding said dianhydride to said polyphosphoric acid to produce a first reaction mixture;
adding pyridine to a solution of 1,3-phenylenediamine in anhydrous dichloromethane and cooled to about 0° C. under gas to produce a second reaction mixture;
adding p-Toluenesulfonyl chloride portion-wise to said second reaction mixture and allowing to warm to room temperature while stirring for about 12 hours;
extracting said reaction mixture with water;
extracting said reaction mixture with saturated aqueous sodium bicarbonate;
extracting said reaction mixture with brine to remove residual bulk water;
drying said organic layer over sodium sulfate;
filtering said organic layer;
concentrating said organic layer in vacuo to remove majority of said organic solvent;
pumping said material under high vacuum over about 48 hours;
dissolving said material in ethyl acetate and extracting at least twice with 1 M aqueous hydrochloric acid;
drying said material over sodium sulfate, filtering said material, and concentrating said material in vacuo;
adding dropwise 70% nitric acid at a rate to maintain the temp below 5° C. to a stirring solution of acetic anhydride;
adding 1,3-(p-toluenesulfamido)benzene to said solution at a rate to keep the temperature below 15° C.;
stirring said solution at room temperature for about 12 hours to about 24 hours to produce a precipitate;
collecting said precipitate by washing with water and recrystallizing said precipitate using acetone;
suspending 1,3-Dinitro-4,6-(p-toluenesulfamido)benzene in anhydrous ethanol in a pressure bomb and flushing with gas;
adding palladium on carbon;
emptying said gas in the pressure bomb via vacuum and flushing with a gas at least three times, filling the pressure bomb with gas to 50 psi and shaking said suspension;
suction-filtering said reaction mixture through Celite and washing with ethanol and acetone;
purifying said mixture by dissolving in a minimal amount of acetone and adding spatula tip amounts of sodium bicarbonate and activated charcoal and stirring for about 30 minutes to produce a solution;
filtering said solution through Celite, washing with an effective amount of acetone, and cooling said solution in refrigeration for an effective amount of time to precipitate a product;
isolating said product by filtering and washing with an effective amount of cold acetone;
protecting said product from light exposure;
adding to said product 1,4,5,8-naphthalenetetracarboxylic acid dianhydride and 1,3-diamino-4,6-(p-toluenesulfonamido)benzene and adding to polyphosphoric acid (PPA) at 90° C. for about 6 hours to produce a reaction mixture;
increasing temperature to said reaction mixture temperature to 180° C., and holding at said temperature for about 16 hours;
cooling said reaction mixture and precipitating in methanol to produce a residue;
dissolving said residue in methanesulfonic acid (MSA) and reprecipitating in methanol at least twice to produce a polymer; and
drying said polymer under vacuum without applying heat for about a week.

Assignees

• Us Navy
• Us Navy

Inventors

• Stenger-Smith John D
• Lai William W
• Irvin David
• Irvin Jennifer

Classifications

• C09D179/08 Primary

  Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors · CPC title

• H01G4/33

  Thin- or thick-film capacitors {(thin- or thick-film circuits; capacitors without a potential-jump or surface barrier specially adapted for integrated circuits, details thereof, multistep manufacturing processes therefor)} · CPC title

• C08G73/1067

  Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound · CPC title

• C07D409/04

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

• C07D333/22 Primary

  Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom · CPC title