WO2016074400A1

WO2016074400A1 - Carbon-supported catalyst and manufacturing method therefor

Info

Publication number: WO2016074400A1
Application number: PCT/CN2015/074427
Authority: WO
Inventors: 许加响
Original assignee: 温州晋航新能源科技有限公司
Priority date: 2014-11-10
Filing date: 2015-03-18
Publication date: 2016-05-19
Also published as: CN104409743B; CN104409743A

Abstract

The present invention relates to a catalyst, and particularly to a carbon-supported catalyst and a manufacturing method therefor. The carbon-supported catalyst comprises a cloth layer. A catalyst layer is arranged on the cloth layer, and a waterproof breathable layer is arranged on the catalyst layer. According to the carbon-supported catalyst in the present invention, a waterproof breathable layer is arranged on a catalyst layer; and when the carbon-supported catalyst participates in a cell reaction, the waterproof breathable layer can protect the catalyst, so that the catalyst is not easy to decompose while the catalytic effect of the catalyst is guaranteed, and the service life of a cell is greatly prolonged.

Description

Carbon-supported catalyst and preparation method thereof

Technical field

[0001] The present invention relates to a catalyst, and more particularly to a carbon supported catalyst and a method of making the same.

Background technique

[0002] Conventional hybrid type catalysts used in fuel cells are prone to decomposition due to direct contact between the catalyst layer and the electrolyte in the battery, which greatly affects the service life of the battery.

technical problem

[0003] An object of the present invention is to provide a carbon-supported catalyst which has the effect of being waterproof and gas permeable, can maintain the properties of the carbon-supported catalyst, and is not easily decomposed.

Problem solution

Technical solution

[0004] In order to achieve the above object, the present invention adopts the following technical solutions:

[0005] A carbon-supported catalyst comprising a cloth layer, a coating layer disposed on the cloth layer, and a waterproof gas permeable layer on the catalyst layer.

[0006] Preferably, the composition ratio of the catalyst layer is: mass ratio of carbon-supported copper oxide 80-120g, carbon-supported silver oxide catalyst 0.4-0.6g, carbon-supported platinum oxide catalyst 0.2-0.3g, glutinous rice glue 4 -6g.

Preferably, in the carbon supported copper oxide catalyst, the carbon supported silver oxide catalyst, and the carbon supported platinum oxide catalyst, the mass ratio of each of the three metal oxides to the activated carbon is 3:80-120.

Preferably, the composition of the waterproof gas permeable layer is in a mass ratio of 8-12 g of glutinous rice gum and 20 g of activated carbon 80-1.

[0009] The method for preparing the carbon-supported catalyst comprises the following steps:

[0010] A carbon-supported metal oxide catalyst comprising a carbon-supported copper oxide catalyst, a carbon-supported silver oxide catalyst and a carbon-supported platinum oxide catalyst;

[0011] B. Making the catalyst layer;

[0012] C. The waterproof gas permeable layer is fabricated. [0013] Preferably, in the step A, preparing the carbon-supported copper oxide catalyst 吋 comprises the following steps:

[0014] a) 400-600g of 400 mesh activated carbon was added to 100 ml of ethanol, and treated by ultrasonic dispersion;

[0015] b) 210g of a 20% copper nitrate solution was added to the treated activated carbon, stirred thoroughly with a stirrer, and placed 24 hours;

[0016] c) placing the activated carbon after standing in a dry box at 100 degrees Celsius until dry;

[0017] d) The dried material is wrapped with a glass cloth, placed in a stainless steel box, baked at 450 ° C, and kept for 1 hour to thermally decompose copper nitrate to produce copper oxide. After waiting for natural cooling, the activated carbon is obtained as a carrier. Copper oxide catalyst.

[0018] Preferably, in the step A, preparing the carbon-supported silver oxide catalyst 吋 comprises the following steps:

[0019] a) 400-600g of 400 mesh activated carbon was added to 100 ml of ethanol, and treated by ultrasonic dispersion;

[0020] b) 110g of a 20% silver nitrate solution was added to the treated activated carbon, fully stirred with a stirrer, and placed 24 hours;

[0021] c) placing the activated carbon after standing in a dry box at 100 degrees Celsius until drying;

[0022] d) The dried product is wrapped with a glass cloth, placed in a stainless steel box, baked at 450 ° C, and kept for 1 hour to thermally decompose the silver nitrate to produce silver oxide. After waiting for natural cooling, the activated carbon is obtained as a carrier. Silver oxide catalyst.

[0023] Preferably, in the step A, preparing the carbon-supported platinum oxide catalyst 吋 comprises the following steps:

[0024] a) 400-600 g of 400 mesh activated carbon was added to 100 ml of ethanol, and treated by ultrasonic dispersion;

[0025] b) 130g of a 20% by mass of platinum nitrate solution was added to the treated activated carbon, stirred thoroughly with a stirrer, and placed 24 hours;

[0026] 0 placing the activated carbon after standing in a dry box at 100 degrees Celsius until drying;

[0027] d) the dried material is wrapped with a glass cloth, placed in a stainless steel box, baked at 450 ° C, held for 1 hour, thermal decomposition of platinum nitrate to produce platinum oxide, waiting for natural cooling, obtained with activated carbon as a carrier Platinum oxide catalyst.

[0028] Preferably, the step B includes the following steps:

[0029] a) taking 80-120g of the prepared carbon-supported copper oxide catalyst, 0.4-0.6g of carbon-supported silver oxide catalyst, and 0.2-0.3g of carbon-supported platinum oxide catalyst mixed and stirred to form a ternary oxide catalyst, added 15 ml of ethanol, stirring constantly, adding 4-6 g of glutinous rice gel, stirring until viscous; [0030] b) Applying the viscous ternary oxide catalyst to a nonwoven fabric carrier and drying it in a drying oven to obtain the catalyst layer.

[0031] Preferably, the step C comprises: preparing 8-12 g of glutinous rice gel into a viscous state, adding 80-120 g of activated carbon, mixing, adding 100 ml of ethanol, diluting and stirring uniformly, and then uniformly coating with an animal brush. The cloth is coated on the catalyst layer and then dried in a drying oven to obtain the waterproof gas permeable layer.

Advantageous effects of the invention

Beneficial effect

[0032] In the carbon-supported catalyst of the present invention, a waterproof gas permeable layer is disposed on the catalyst layer, and the carbon-supported catalyst participates in the reaction of the battery, and the waterproof gas permeable layer can protect the catalyst, and the catalyst is not easily accommodated while ensuring the catalytic effect of the catalyst. Decomposition, greatly improving the battery life.

Embodiments of the invention

[0033] Specific embodiments of the technical solutions of the present invention are further described in detail below.

[0034] Embodiment 1 A carbon-supported catalyst comprising a cloth layer, a coating layer disposed on the cloth layer, and a waterproof gas permeable layer disposed on the catalyst layer. The composition of the catalyst layer is as follows: mass ratio of carbon-supported copper oxide catalyst 80g, carbon-supported silver oxide catalyst 0.6g, carbon-supported platinum oxide catalyst 0.25g, glutinous rice glue 5g, composition of the waterproof gas-permeable layer by mass The ratio is: 8 g of glutinous rice gelatin and 120 g of activated carbon.

[0035] The method for preparing the carbon-supported catalyst comprises the following steps:

[0036] A carbon-supported metal oxide catalyst, the carbon-supported metal oxide catalyst comprises a carbon-supported copper oxide catalyst, a carbon-supported silver oxide catalyst and a carbon-supported platinum oxide catalyst to produce carbon-supported copper oxide Catalyst 吋, including the following steps:

[0038] a) 400-600 g of 400 mesh activated carbon is added to 100 ml of ethanol and treated by ultrasonic dispersion; ultrasonic dispersion treatment allows ethanol to be fully loaded into the activated carbon;

[0039] b) 210 g of a 20% by mass copper nitrate solution was added to the treated activated carbon, stirred well with a stirrer, and left for 24 hours. The copper nitrate solution can obtain 15g of copper oxide after undergoing thermal decomposition reaction.

, maintaining the mass ratio of copper oxide to activated carbon at 3:80-120;

[0040] 0 The activated carbon after standing was placed in a dry box and treated at 100 degrees Celsius until dry. Ethanol can quickly evaporate water, making the drying process more rapid; [0041] d)

The dried product was wrapped in a glass cloth, placed in a stainless steel box, baked at 450 ° C, and kept for 1 hour to thermally decompose copper nitrate to produce copper oxide. After waiting for natural cooling, a copper oxide catalyst supported by activated carbon was obtained.

[0042] The preparation of the carbon-supported silver oxide catalyst 吋 includes the following steps:

[0043] a) 400-600 g of 400 mesh activated carbon was added to 100 ml of ethanol and treated by ultrasonic dispersion;

[0044] b) 110 g of a silver nitrate solution having a mass fraction of 20% was added to the treated activated carbon, stirred thoroughly with a stirrer, and left for 24 hours. The silver nitrate solution can obtain 15g of silver oxide after thermal decomposition reaction, so that the mass ratio of silver oxide to activated carbon is maintained at 3:80-120;

[0045] 0 The activated carbon after standing was placed in a dry box and treated at 100 ° C until dry.

[0046] d) The dried product is wrapped with a glass cloth, placed in a stainless steel box, baked at 450 degrees Celsius, and kept for 1 hour to thermally decompose the silver nitrate to produce silver oxide. After waiting for natural cooling, the activated carbon is obtained as a carrier. Silver oxide catalyst.

[0047] The preparation of the carbon-supported platinum oxide catalyst 吋 includes the following steps:

[0048] a) 400-600 g of 400 mesh activated carbon was added to 100 ml of ethanol and treated by ultrasonic dispersion;

[0049] b) 130 g of a 20% by mass platinum nitrate solution was added to the treated activated carbon, stirred thoroughly with a stirrer, and left for 24 hours. The platinum nitrate solution can obtain 15g of platinum oxide after thermal decomposition reaction, so that the mass ratio of platinum oxide to activated carbon is maintained at 3:80-120;

[0050] 0 placing the activated carbon after standing in a dry box at 100 degrees Celsius until drying;

[0051] d) The dried product is wrapped with a glass cloth, placed in a stainless steel box, baked at 450 ° C, and kept for 1 hour, to thermally decompose platinum nitrate to produce platinum oxide, and wait for natural cooling to obtain activated carbon as a carrier. Platinum oxide catalyst.

[0052] B. The catalyst layer is prepared, 80 prepared carbon-supported copper oxide catalyst, 0.6 g of carbon-supported silver oxide catalyst, and 0.25 g of carbon-supported platinum oxide catalyst are mixed and stirred to form a ternary oxide catalyst, 1 5 ml of ethanol was continuously stirred, 5 g of glutinous rice gum was added, and the mixture was stirred until it was viscous, and then it was applied onto a nonwoven fabric carrier, and dried by a drying oven to obtain the catalyst layer.

[0053] C. The waterproof gas permeable layer was prepared, 8 g of glutinous rice glue was prepared to be viscous, and 120 g of activated carbon was added and mixed, and then diluted with 100 ml of ethanol, stirred uniformly, and then uniformly coated with the animal hair brush. Catalyst layer Above, it is then dried in a dry box to obtain the waterproof gas permeable layer, and the carbon-supported catalyst is formed.

Example 2:

[0055] A carbon-supported catalyst comprising a cloth layer, a coating layer disposed on the cloth layer, and a waterproof gas permeable layer on the catalyst layer. The composition ratio of the catalyst layer is: 00g of carbon-supported copper oxide catalyst, 0.5g of carbon-supported silver oxide catalyst, 0.3g of carbon-supported platinum oxide catalyst, 4g of glutinous rice glue; the composition of the waterproof gas-permeable layer is The mass ratio is: 10 g of glutinous rice glue and 80 g of activated carbon.

[0056] The method for preparing the carbon-supported catalyst comprises the following steps:

[0057] A. Making a carbon-supported metal oxide catalyst, the carbon-supported metal oxide catalyst comprising carbon

[0058] The copper oxide catalyst, the carbon supported silver oxide catalyst and the carbon supported platinum oxide catalyst, the preparation process of the three metal oxides is similar to that described in the first embodiment, and will not be described again here.

[0059] B. The catalyst layer is prepared, and 100 g of the prepared carbon-supported copper oxide catalyst, 0.5 g of a carbon-supported silver oxide catalyst, and 0.3 g of a carbon-supported platinum oxide catalyst are mixed and stirred to form a ternary oxide catalyst.

15 ml of ethanol was continuously stirred, 4 g of glutinous rice gum was added, and the mixture was stirred until it was viscous, and then coated on a nonwoven fabric carrier, and dried by a drying oven to obtain the catalyst layer.

[0060] C. The waterproof gas permeable layer was prepared, 10 g of glutinous rice gelatin was prepared into a viscous shape, and 80 g of activated carbon was added and mixed, and then diluted with 100 ml of ethanol and uniformly stirred, followed by uniform coating with the animal hair brush. The catalyst layer is then dried on a drying oven to obtain the water-repellent gas permeable layer, and the carbon-supported catalyst is formed.

Example 3:

[0062] A carbon-supported catalyst comprising a cloth layer, a catalyst layer disposed on the cloth layer, and a waterproof gas permeable layer disposed on the catalyst layer. The composition of the catalyst layer is as follows: mass ratio of carbon-supported copper oxide catalyst 20g, carbon-supported silver oxide catalyst 0.4g, carbon-supported platinum oxide catalyst 0.2g, glutinous rice gum 6g; composition of the waterproof gas-permeable layer The mass ratio is: 9 g of glutinous rice gelatin and 100 g of activated carbon.

[0063] The method for preparing the carbon-supported catalyst comprises the following steps:

[0064] A. Making a carbon-supported metal oxide catalyst, the carbon-supporting metal oxide catalyst comprising carbon

[0065] The copper oxide-supporting catalyst, the carbon-supported silver oxide catalyst and the carbon-supported platinum oxide catalyst, the preparation process of the three metal oxides is similar to that described in the first embodiment, and will not be described again here.

[0066] B. The catalyst layer is prepared, 120 g of the prepared carbon-supported copper oxide catalyst, 0.4 g of carbon-supported silver oxide catalyst, and 0.2 g of carbon-supported platinum oxide catalyst are mixed and stirred to form a ternary oxide catalyst, 15 ml of ethanol was continuously stirred, 6 g of glutinous rice gum was added, and the mixture was stirred until it was viscous, and then it was applied onto a nonwoven fabric carrier, and dried by a drying oven to obtain the catalyst layer.

C. The waterproof gas-permeable layer is prepared, and 9 g of glutinous rice glue is prepared into a viscous shape. After adding 100 g of activated carbon, the mixture is diluted with 100 ml of ethanol, stirred uniformly, and then uniformly coated on the catalyst layer with an animal brush. Then, it is dried in a dry box to obtain the waterproof gas permeable layer, and the carbon-supported catalyst is formed.

Claims

Claim

[Claim 1] A carbon-supported catalyst comprising a cloth layer, a catalyst layer disposed on the cloth layer, and a waterproof gas permeable layer on the catalyst layer.

[Claim 2] A carbon-supported catalyst according to claim 1, wherein the composition of the catalyst layer is in a mass ratio: 80-120 g of a carbon-supported copper oxide catalyst, and a carbon-supported silver oxide catalyst .4-0.6g, carbon-supported platinum oxide catalyst 0.2-0.3g, glutinous rice glue 4-6g.

[Claim 3] A carbon-supported catalyst according to claim 1 or 2, wherein the carbon-supported copper oxide catalyst, the carbon-supported silver oxide catalyst, and the carbon-supported platinum oxide catalyst, three metal oxides The mass ratio of each and activated carbon is 3:80-120.

[Claim 4] A carbon-supported catalyst according to claim 3, wherein the composition of the waterproof gas-permeable layer is in a mass ratio of 8-12 g of glutinous rice gum and 80-120 g of activated carbon.

[Claim 5] A method for producing a carbon-supported catalyst according to claim 1, which comprises the steps of:

A. preparing a carbon supported metal oxide catalyst comprising a carbon supported copper oxide catalyst, a carbon supported silver oxide catalyst and a carbon supported platinum oxide catalyst;

B. fabricating the catalyst layer;

C. Making the waterproof gas permeable layer.

[Claim 6] The method for producing a carbon-supported catalyst according to claim 5, wherein in the step A, the carbon-supporting copper oxide catalyst is prepared, comprising the steps of:

a) Add 400-600g of 400 mesh activated carbon to 100ml of ethanol, disperse by ultrasonication b) Add 210g of copper nitrate solution of 20% by mass to the treated activated carbon, stir well with a stirrer, and place 24 small Inches;

c) Place the activated carbon after standing in a dry box at 100 ° C until dry; d) Wrap the dried material in a glass cloth, place it in a stainless steel box, and cook at 450 ° C for 1 hour. The copper nitrate is thermally decomposed to produce copper oxide, and after waiting for natural cooling, a copper oxide catalyst supported by activated carbon is obtained.

[Claim 7] A method for producing a carbon-supported catalyst according to claim 5, wherein In the step A, preparing the carbon-supported silver oxide catalyst 吋 comprises the following steps: a) adding 400-600 g of 400 mesh activated carbon to 100 ml of ethanol and dispersing with ultrasonic waves; b) adding 110 g of a silver nitrate solution having a mass fraction of 20% In the treated activated carbon, stir well with a stirrer and place it for 24 hours;

c) Place the activated carbon after standing in a dry box at 100 ° C until dry; d) Wrap the dried material in a glass cloth, place it in a stainless steel box, bake at 450 ° C, and keep it for 1 hour. Silver nitrate is thermally decomposed to produce silver oxide, and after waiting for natural cooling, a silver oxide catalyst supported on activated carbon is obtained.

[Claim 8] The method for producing a carbon-supported catalyst according to claim 5, wherein in the step A, the carbon-supporting platinum oxide catalyst is prepared, comprising the steps of:

a) Add 400-600g of 400 mesh activated carbon to 100ml of ethanol and disperse it by ultrasonic wave; b) Add 130g of 20% platinum nitrate solution to the treated activated carbon, stir well with a stirrer, and place 24 Xiao Yan;

c) Place the activated carbon after standing in a dry box at 100 ° C until dry; d) Wrap the dried material in a glass cloth, place it in a stainless steel box, bake at 450 ° C, and keep it for 1 hour. The platinum nitrate is thermally decomposed to produce platinum oxide, and after waiting for natural cooling, a platinum oxide catalyst supported by activated carbon is obtained.

[Claim 9] The method for fabricating a carbon-supported catalyst according to claim 5, wherein the step B comprises the following steps:

a) taking 80-120 g of prepared carbon-supported copper oxide catalyst, 0.4-0.6 g of carbon-supported silver oxide catalyst, and 0.2-0.3 g of carbon-supported platinum oxide catalyst, mixing and stirring to form a ternary oxide catalyst, adding 15 ml of ethanol Stirring was continued, 4-6 g of glutinous rice gum was added, and the mixture was stirred until it was viscous. b) The viscous ternary oxide catalyst was applied onto a nonwoven fabric carrier, and dried in a drying oven to obtain the catalyst layer.

[Claim 10] The method for producing a carbon-supported catalyst according to claim 5, wherein the step C comprises: preparing 8-12 g of glutinous rice gel into a viscous state, and adding 80-120 g of activated carbon to be mixed. After that, add 100 ml of ethanol to dilute and mix well, then apply evenly with animal hair brush. Above the catalyst layer, it is then dried in a drying oven to obtain the waterproof gas permeable layer, and the carbon-supported catalyst is formed.