A nano-tungsten trioxide loaded electrode material and a preparation method thereof

Abstract

The application discloses an electrode material loaded with nano tungsten trioxide, and preparation raw materials include, by weight, carbon cloth 40-50 parts, polyaniline 10-20 parts, metal oxide 1-3 parts, graphene 0.5-1.2 parts, butadiene styrene rubber 3-8 parts, cellulose 1-3 parts, carbon black 5-10 parts, tungsten-containing solution 1-5 parts, alcohol solution 5-10 parts, and water 20-40 parts. The carbon cloth can provide nucleation sites for the nano tungsten trioxide after pretreatment, so that the tungsten trioxide grows in situ on the carbon cloth, the electrode material has a good interface effect with the surface of the carbon cloth, and the cycle life and electronic conductivity of the electrode material are increased. Furthermore, the graphene with a thickness of 0.8-1.2 nm and a flake diameter of 0.5-5 microns is used together with the nano tungsten trioxide, so that the loading amount of the tungsten trioxide on the carbon cloth is increased, and the electrical performance of the electrode material is further improved.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of electrode material of load nano tungsten trioxide and its preparation method, it is related to H01G, specifically related to the powder with the structural features of material composition in electrode. BACKGROUND

[0002] Crystal nanometer tungsten material has relatively wide crystal interlayer spacing and high crystallinity, and has good charge storage performance in combination with carbon material. Capacitors are widely used in electric vehicles, new energy collection and conversion, and mobile electronic devices. Crystal nanometer tungsten material has a large specific surface area due to its unique crystal structure, has a high specific capacity under the same electric density, and has good cycle stability. However, it is difficult to combine nanometer tungsten material with carbon material, which is easily detached during the charging and discharging process of the capacitor, thereby reducing the cycle stability of the capacitor. Therefore, it is crucial to develop a good combination method of carbon material and tungsten material to improve the electrical performance of the capacitor.

[0003] Chinese invention patent CN201610365424.7 discloses a preparation method of tungsten trioxide nanobelt self-assembly into micro-nano star. High-purity orthorhombic tungsten trioxide nanobelt is synthesized by hydrothermal method using tungsten source, alcohol solvent and hydrogen peroxide as raw materials under mild conditions, and further self-assembled into three-dimensional structure tungsten trioxide micro-nano star with controllable size and uniform morphology. The method has the advantages of mild experimental conditions, low cost, no need for surfactants, and good reproducibility. However, it does not involve the combination with carbon material, and the cycle stability is poor when applied to capacitors. Chinese invention patent CN202210392686.8 discloses a preparation method of silk-based carbon nanotube / polyaniline / tungsten trioxide composite film and its application in flexible supercapacitors. The silk-based carbon nanotube / polyaniline / tungsten trioxide composite film material is prepared by adjusting the amount of carbon nanotubes and the concentration of tungsten peroxide through in-situ synchronous self-assembly method. The operation process is simple, easy to operate, environmentally friendly and safe, and low in cost. It has excellent mechanical flexibility and electrochemical energy storage performance. However, the combination of carbon nanotubes and tungsten trioxide is not good, and tungsten trioxide is easily detached during the use of the capacitor, which shortens the service life of the capacitor. SUMMARY

[0004] In order to improve the combination of nanometer tungsten trioxide and carbon material and improve the electrical performance applied in capacitors, the first aspect of the present application provides an electrode material loaded with nanometer tungsten trioxide, and the preparation raw materials include, by weight: carbon cloth 40-50 parts, polyaniline 10-20 parts, metal oxide 1-3 parts, graphene 0.5-1.2 parts, butadiene styrene rubber 3-8 parts, cellulose 1-3 parts, carbon black 5-10 parts, tungsten-containing solution 1-5 parts, alcohol solution 5-10 parts, and water 20-40 parts.

[0005] As a preferred embodiment, the metal oxide is selected from one or a combination of tin dioxide, lead dioxide, ruthenium oxide, yttrium oxide, iridium oxide, manganese dioxide.

[0006] As a preferred embodiment, the graphene is a modified graphene powder, the thickness of the graphene is 0.8-1.2nm, and the flake diameter is 0.5-5μm.

[0007] As a preferred embodiment, the graphene is a carboxyl modified graphene powder, the thickness of the graphene is 0.8-1.2nm, and the flake diameter is 0.5-5μm.

[0008] As a preferred embodiment, the block ratio of styrene and butadiene in the styrene-butadiene rubber is (30-40):(60-70).

[0009] As a preferred embodiment, the melt flow rate of the styrene-butadiene rubber at 220℃ is 3-5g / 10min.

[0010] As a preferred embodiment, the cellulose is selected from one or a combination of sodium carboxymethyl cellulose, sodium hydroxymethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, methyl cellulose.

[0011] As a preferred embodiment, the viscosity of the cellulose is 1000-2000cps.

[0012] As a preferred embodiment, the tungsten-containing solution is selected from one or a combination of sodium tungstate, peroxotungstic acid, nano-tungsten trioxide solution.

[0013] As a preferred embodiment, the particle size of tungsten trioxide in the nano-tungsten trioxide solution is 10-50nm.

[0014] The second aspect of the present application provides a preparation method of an electrode material loaded with nano-tungsten trioxide, comprising the following steps:

[0015] (1) uniformly mix and grind the metal oxide and the graphene, heat at 850-900℃ for 15-20min, cool, add an alcohol solution, add the tungsten-containing solution while stirring, stir for 3-4h, to obtain a mixture;

[0016] (2) mix water, the mixture, carbon black, styrene-butadiene rubber, and cellulose, ball mill with a ball mill for 0.5-1h to obtain a slurry;

[0017] (3) stir the carbon cloth in polyaniline in the dark for 0.5-1h, then immerse the carbon cloth in the slurry in the dark, react at 110-145℃ for 1-5h, take out and dry to obtain the electrode material.

[0018] The present application adopts polyaniline to pretreat carbon cloth, then soaks the carbon cloth into slurry, and reacts under high temperature and high pressure for a period of time, so that nano tungsten trioxide is loaded on the carbon cloth, the carbon cloth can provide nucleation sites for nano tungsten trioxide after pretreatment, so that tungsten trioxide grows in situ on the carbon cloth, the electrode material has good interface effect with the surface of the carbon cloth, and the cycle life and electronic conductivity of the electrode material are increased.

[0019] Compared with the prior art, the present application has the following beneficial effects:

[0020] (1) The electrode material loaded with nano tungsten trioxide, the carbon cloth can provide nucleation sites for nano tungsten trioxide after pretreatment, so that tungsten trioxide grows in situ on the carbon cloth, the electrode material has good interface effect with the surface of the carbon cloth, and the cycle life and electronic conductivity of the electrode material are increased.

[0021] (2) The electrode material loaded with nano tungsten trioxide, by using graphene with a thickness of 0.8-1.2 nm and a flake diameter of 0.5-5 μm together with nano tungsten trioxide, the loading amount of tungsten trioxide on the carbon cloth can be increased, and the electrical properties of the electrode material are further improved.

[0022] (3) The electrode material loaded with nano tungsten trioxide, by using butadiene-styrene rubber with a block ratio of (30-40):(60-70) of styrene and butadiene together with sodium hydroxymethyl cellulose, the bonding property of the carbon cloth and the slurry can be increased, the resistance of the electrode material is reduced, and the capacitor can be cycled multiple times, has high capacity retention rate, and has long service life. DETAILED DESCRIPTION

[0023] Example 1

[0024] An electrode material loaded with nano tungsten trioxide, the preparation raw materials include, by weight: carbon cloth 45 parts, polyaniline 15 parts, metal oxide 2 parts, graphene 1 part, butadiene-styrene rubber 5 parts, cellulose 2 parts, carbon black 8 parts, tungsten-containing solution 3 parts, ethanol 8 parts, and water 30 parts.

[0025] The carbon cloth is purchased from Henan Chanyu New Material Technology Co., Ltd., and the polyaniline is purchased from Wuhan Huaxiang Kejie Biological Technology Co., Ltd.

[0026] The metal oxide is tin dioxide.

[0027] The graphene is carboxyl-modified graphene powder with a thickness of 0.8-1.2 nm and a flake diameter of 0.5-5 μm, and is purchased from Jiangsu Xianfeng Nanometer Material Technology Co., Ltd. and has a model number of XF-004.

[0028] The styrene and butadiene in the styrene-butadiene rubber have a block ratio of 40:60, and a melt flow rate at 220℃ of 4 g / 10 min. The styrene-butadiene rubber is purchased from Shenzhen Yitian Chemical Co., Ltd. and has a model number of YH-792.

[0029] The cellulose is sodium hydroxymethyl cellulose with a viscosity of 2000 cps, and is purchased from Wuhan Kemik Biological Medicine Technology Co., Ltd.

[0030] The tungsten-containing solution is a nano tungsten trioxide solution, in which the particle size of the tungsten trioxide is 50 nm, and is purchased from Guangzhou Hongwu Material Technology Co., Ltd.

[0031] A preparation method of an electrode material loaded with nano tungsten trioxide, comprising the following steps:

[0032] (1) uniformly mixing and grinding a metal oxide and graphene, heating at 870℃ for 18 min, adding an alcohol solution after cooling, adding a tungsten-containing solution while stirring, and stirring for 3.5 h to obtain a mixture;

[0033] (2) mixing water, the mixture, carbon black, styrene-butadiene rubber, and cellulose, and ball milling for 1 h by using a ball mill to obtain a slurry;

[0034] (3) stirring carbon cloth in polyaniline in the dark for 1 h, then immersing the carbon cloth in the slurry in the dark, and reacting at 135℃ for 3.5 h, and taking out and drying to obtain the electrode material.

[0035] Example 2

[0036] An electrode material loaded with nano tungsten trioxide, and the preparation raw materials include, by weight, 40 parts of carbon cloth, 10 parts of polyaniline, 1 part of a metal oxide, 0.5 part of graphene, 3 parts of styrene-butadiene rubber, 1 part of cellulose, 5 parts of carbon black, 1 part of a tungsten-containing solution, 5 parts of ethanol, and 20 parts of water.

[0037] The carbon cloth is purchased from Henan Chanyu New Material Technology Co., Ltd., and the polyaniline is purchased from Wuhan Huaxiang Kejie Biological Technology Co., Ltd.

[0038] The metal oxide is manganese dioxide.

[0039] The graphene is carboxyl-modified graphene powder with a thickness of 0.8-1.2 nm and a flake diameter of 0.5-5 μm, and is purchased from Jiangsu Xianfeng Nanometer Material Technology Co., Ltd. and has a model number of XF-004.

[0040] The block ratio of styrene and butadiene in the styrene-butadiene rubber is 40:60, and the melt flow rate at 220℃ is 4g / 10min. It is purchased from Shenzhen Yida Chemical Co., Ltd., and the model is YH-792.

[0041] The cellulose is sodium carboxymethyl cellulose, which is purchased from Japan Dailu, and the model is CMC2200.

[0042] The tungsten-containing solution is a nano-tungsten trioxide solution, in which the particle size of tungsten trioxide is 50nm, and it is purchased from Guangzhou Hongwu Material Technology Co., Ltd.

[0043] A preparation method of an electrode material loaded with nano-tungsten trioxide, comprising the following steps:

[0044] (1) uniformly mix and grind the metal oxide and graphene, heat at 850℃ for 20min, cool, add an alcohol solution, add the tungsten-containing solution while stirring, and stir for 3h to obtain a mixture;

[0045] (2) mix water, the mixture, carbon black, styrene-butadiene rubber, and cellulose, and ball mill with a ball mill for 1h to obtain a slurry;

[0046] (3) stir the carbon cloth in polyaniline in the dark for 0.5h, then immerse the carbon cloth in the slurry in the dark, react at 130℃ for 5h, take out and dry to obtain the electrode material.

[0047] Example 3

[0048] An electrode material loaded with nano-tungsten trioxide, the preparation raw materials include, by weight: carbon cloth 40-50 parts, polyaniline 20 parts, metal oxide 3 parts, graphene 1.2 parts, styrene-butadiene rubber 8 parts, cellulose 3 parts, carbon black 10 parts, tungsten-containing solution 5 parts, ethanol 10 parts, and water 40 parts.

[0049] The carbon cloth is purchased from Henan Chanyu New Material Technology Co., Ltd., and the polyaniline is purchased from Wuhan Huaxiang Kejebio Technology Co., Ltd.

[0050] The metal oxide is yttrium dioxide.

[0051] The graphene is carboxyl-modified graphene powder, with a thickness of 0.8-1.2nm and a flake diameter of 0.5-5μm, which is purchased from Jiangsu Xianfeng Nanometer Material Technology Co., Ltd., and the model is XF-004.

[0052] The block ratio of styrene and butadiene in the styrene-butadiene rubber is 30:70, and the melt flow rate at 220℃ is 3.5g / 10min. It is purchased from Shenzhen Yida Chemical Co., Ltd., and the model is YH-791.

[0053] The cellulose is sodium hydroxymethyl cellulose with a viscosity of 2000cps, which is purchased from Wuhan Kemik Biomedical Technology Co., Ltd.

[0054] The tungsten-containing solution is a nano-tungsten trioxide solution, in which the particle size of the tungsten trioxide is 50nm, which is purchased from Guangzhou Hongwu Material Technology Co., Ltd.

[0055] A preparation method of an electrode material loaded with nano-tungsten trioxide, comprising the following steps:

[0056] (1) uniformly mixing and grinding a metal oxide and graphene, heating at 900℃ for 20min, cooling, adding an alcohol solution, stirring while adding a tungsten-containing solution, and stirring for 4h to obtain a mixture;

[0057] (2) mixing water, the mixture, carbon black, butadiene styrene rubber and cellulose, and ball milling for 1h by using a ball mill to obtain a slurry;

[0058] (3) stirring carbon cloth in polyaniline in the dark for 1h, then immersing the carbon cloth in the slurry in the dark, and reacting at 145℃ for 5h, and then taking out and drying to obtain the electrode material.

[0059] Example 4

[0060] An electrode material loaded with nano-tungsten trioxide, the specific steps of which are the same as those of Example 1, except that the tungsten-containing solution is a sodium tungstate aqueous solution with a mass fraction of 95%.

[0061] Example 5

[0062] An electrode material loaded with nano-tungsten trioxide, the specific steps of which are the same as those of Example 1, except that the graphene is an oxidized graphene powder, and the thickness of the graphene is 1-3nm and the flake diameter is 0.5-5μm.

[0063] Performance test

[0064] The electrode materials prepared in Examples 1-5 are assembled into capacitors, and the capacitance is tested at a current density of 5mA / cm 2 , and the maintenance rate of the capacitance is tested after 100 cycles.

[0065] The test results are shown in Table 1.

[0066] Table 1

[0067] Capacitance Wh / cm 2 ]]> Capacity retention rate / % Example 1 2.641 86.6 Example 2 2.539 86.3 Example 3 2.558 85.89 Example 4 2.487 83.21 Example 5 2.458 83.65

Claims

1. A nano tungsten trioxide-loaded electrode material, characterized in that, The preparation raw materials include, by weight parts: carbon cloth 40-50 parts, polyaniline 10-20 parts, metal oxide 1-3 parts, graphene 0.5-1.2 parts, butadiene styrene rubber 3-8 parts, cellulose 1-3 parts, carbon black 5-10 parts, tungsten-containing solution 1-5 parts, alcohol solution 5-10 parts, water 20-40 parts; The graphene is modified graphene powder, the thickness of the graphene is 0.8-1.2 nm, and the flake diameter is 0.5-5 μm; The block ratio of styrene and butadiene in the butadiene styrene rubber is (30-40):(60-70); The tungsten-containing solution is a nano tungsten trioxide solution, and the particle size of the tungsten trioxide in the nano tungsten trioxide solution is 10-50 nm; The preparation method of the electrode material loaded with nano tungsten trioxide comprises the following steps: (1) uniformly mix and grind the metal oxide and the graphene, heat at 850-900 ℃ for 15-20 min, cool, add the alcohol solution, add the tungsten-containing solution while stirring, and stir for 3-4 h to obtain a mixture; (2) mix the water, the mixture, the carbon black, the butadiene styrene rubber, and the cellulose, ball mill for 0.5-1 h with a ball mill to obtain a slurry; (3) stir the carbon cloth in the polyaniline in the dark for 0.5-1 h, then immerse the carbon cloth in the slurry in the dark, react at 110-145 ℃ for 1-5 h, take out and dry to obtain the electrode material.

2. The electrode material loaded with nano tungsten trioxide according to claim 1, characterized in that, The metal oxide is selected from one or a combination of several of tin dioxide, lead dioxide, ruthenium oxide, yttrium oxide, iridium oxide, and manganese dioxide.

3. The electrode material loaded with nano tungsten trioxide according to claim 1, characterized in that, The melt flow rate of the butadiene styrene rubber at 220 ℃ is 3-5 g / 10 min.

4. The electrode material loaded with nano tungsten trioxide according to claim 1, characterized in that, The cellulose is selected from one or a combination of several of sodium carboxymethyl cellulose, sodium hydroxymethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, and methyl cellulose.

5. The electrode material of claim 1, wherein the nano-W03 is loaded by 0.1- 10 wt%. The viscosity of the cellulose is 1000-2000 cps.

6. A method for preparing the electrode material loaded with nano tungsten trioxide according to any one of claims 1-5, characterized in that, The preparation method comprises the following steps: (1) uniformly mix and grind the metal oxide and the graphene, heat at 850-900 ℃ for 15-20 min, cool, add the alcohol solution, add the tungsten-containing solution while stirring, and stir for 3-4 h to obtain a mixture; (2) mix the water, the mixture, the carbon black, the butadiene styrene rubber, and the cellulose, ball mill for 0.5-1 h with a ball mill to obtain a slurry; (3) stir the carbon cloth in the polyaniline in the dark for 0.5-1 h, then immerse the carbon cloth in the slurry in the dark, react at 110-145 ℃ for 1-5 h, take out and dry to obtain the electrode material.