TWI487661B - Method of modifying carbon-based electrode material and carbon-based electrode material formed thereby - Google Patents

Description

Method for modifying carbon material for electrode and carbon material for electrode made thereof

The present invention relates to a method for modifying a carbon material for an electrode, and more particularly to a method for forming titanium hydroxide and anatase crystal phase titanium dioxide fixed on a carbon material by a sol-gel method using a eutectic mixed liquid in combination with microwave heating.

At present, carbon-based materials have been widely used in the fields of fiber materials, lithium batteries, fuel cells, supercapacitors, capacitor desalination and hydrogen storage devices. Commonly used carbon materials include porous activated carbon powder, nano carbon fiber, carbon. Aerosols, carbon nanotubes, network-structured activated carbon, etc., in which porous activated carbon is often used on electrode materials.

However, when activated carbon is applied to the electrode material, it irreversibly physically adsorbs some components in the electrolyte, thereby reducing the capacitance and service life of the electrode material, so the activated carbon needs to be modified. At present, one of the reforming methods of activated carbon materials is chemical modification, such as adding alkali (such as KOH or NaOH), the main function of which is to modify the hydrophilicity of the activated carbon, so that the surface of the activated carbon contains polar functional groups and increases The surface is hydrophilic, so that the aqueous electrolyte solution is easy to access the carbon material electrode, but the increase of the polar functional group reduces the conductivity of the carbon material, is not conducive to the transfer of electrons in the electrode material, or may cause surface polarization of the carbon material. Moreover, this modification method cannot simultaneously improve the hydrophilicity and conductivity of the carbon material.

Another modification method is to add a nano metal oxide, and use a blending, a chemical precipitation method or a sol-gel method to add or fix a nano metal oxide to the activated carbon material. Remove carbon material surface a polar functional group to increase the conductivity of the carbon material, but this modification method tends to make the surface of the carbon material hydrophobic, and the mixing, chemical precipitation or sol-gel method may have uneven distribution of metal oxides and excessive particle size. Or the synthesis step is complicated, time-consuming, and requires post-treatment high temperature (200-500 ° C) winding and other problems, does not meet the environmental protection needs of energy saving and carbon reduction, and this modification method cannot simultaneously improve the hydrophilicity and conductivity of the carbon material.

The present disclosure provides a method for modifying a carbon material by a sol-gel method using deep eutectic solvents (DES) in combination with microwave heating, at a low temperature of 80 ° C to 100 ° C and at 1 atmosphere (atm) At normal pressure, in the short time of 30 to 120 minutes, the simultaneous formation of titanium hydroxide (TiOH) and anatase crystal phase titanium dioxide (anatase-TiO ₂ ) reacts with the carbon material to form a bond, and the formed hydrogen Titanium oxide (TiOH) and anatase phase titanium dioxide are uniformly distributed on the surface or inside the carbon material, which can simultaneously increase the hydrophilicity and electron transport of the carbon material. It is an environmentally friendly and low-cost carbon material modification. method.

At the same time, when the modified carbon material is applied to the electrode material, the capacitance capability and the service life of the electrode material can be improved, and the charge and discharge rate and the use efficiency of the electrode material can be increased.

According to an embodiment, a method for modifying a carbon material is provided, the method comprising: mixing a carbon material with a titanium dioxide precursor, a eutectic mixture (DES), water, and an alcohol solvent, and performing the first stage microwave heating, which is generated. Filtration of the first stage product; adding the aforementioned eutectic mixture, water and the aforementioned alcohol solvent to the filtered first stage product, and performing the second stage microwave heating to synthesize A composite carbon material comprising titanium hydroxide and anatase crystal phase titanium dioxide fixed on a carbon material.

In order to make the above objects, features, and advantages of the present invention more comprehensible, the following embodiments are described in detail below:

The implementation of the modified method of the present disclosure can be divided into two stages: (1) The first stage is to control the content of the eutectic mixture to inhibit the hydrolysis-condensation reaction of titanium dioxide (TiO ₂ ), thereby controlling The amount of titanium hydroxide (TiOH) formed; (2) The second stage is a crystallization reaction of titanium dioxide, thereby promoting crystallization of titanium dioxide to form anatase-TiO ₂ .

In the first stage of the step, the carbon material is uniformly dispersed in the solvent by using an alcohol solvent, and then a different ratio of the reagent prepared from the titanium dioxide precursor, the eutectic mixture (DES) and water is added. In one embodiment, the weight ratio of the carbon material to the alcohol solvent may be about 1:80, and the weight ratio of the carbon material to the titanium dioxide precursor may be about 4:1 to 2:1, and the titanium dioxide precursor and the incorporation The molar ratio of the mixed solution (DES) may be between about 1:0.25 and 1:1.5, and the molar ratio of the titanium dioxide precursor to water is between 1:5 and 1:30. The first stage of microwave heating is carried out at a low temperature (below 100 ° C) and at a normal pressure (1 atm). In one embodiment, the microwave heating time of the first stage may be about 30 minutes.

In the second stage of the step, after the first stage of the synthesis product is subjected to a filtration process, a reagent such as the aforementioned eutectic mixture (DES), water and an alcohol solvent is added. In one embodiment, after filtration, First stage synthesis The weight ratio of the product to the alcohol solvent is 1:30, and the molar ratio of the eutectic mixture (DES) to water can be between about 1:0 and 1:18, and the first stage after filtration The weight ratio of the synthesized product to the eutectic mixture (DES) may be about 1:3.6, and the second stage of microwave heating is performed at a low temperature (below 100 ° C) and at a normal pressure (1 atm). In one embodiment, the second The microwave heating time of the stage can be about 60 minutes.

The microwave power of the first stage and the second stage microwave heating may be 800 W, the microwave frequency may be 2.45 GHz, and the sum of the microwave heating time of the first stage and the second stage may be 30 to 120 minutes.

The eutectic mixture (DES) used in the present disclosure is composed of a quaternary ammonium salt and a hydrogen bond provider, wherein the quaternary amine salt halide is, for example, choline chloride (ChCl). The hydrogen bond provider includes polyalcohols, carboxylic acids, amines or amides, such as urea or glycerol, and quaternary amine salt halides and hydrogen. The molar ratio of the bond provider can be about 1:1 to 1:8. In this ratio range, the melting point of the quaternary amine salt halide and the hydrogen bond provider can be reduced to its inflection point, presenting a liquid mixture.

The carbon material modified in the present disclosure may be activated carbon, bamboo charcoal, carbon nanotube (CNT) or graphene. Further, the activated carbon may also be in the form of an activated carbon cloth. The carbon material has a specific surface area of more than 300 m ² /g, and the carbon material has a pore diameter of between 1 nm and 1000 nm.

The alcohol solvent used in the present disclosure may be ethanol or isopropanol. (isopropanol; IPA) or n-butanol, the titanium dioxide precursor used in the present disclosure is, for example, titanium tetraisopropoxide (TIP) or titanium butoxide.

The following examples illustrate the modification of the carbon material of the present disclosure and the related electrical characteristics of the electrode made of the modified carbon material:

[Preparation Example 1]

Ratio Control of Titanium Dioxide Precursor and Inorganic Mixture of Synthesized Anatase Crystalline Anatase-TiO ₂ Powder

The chelating ratio of choline chloride (ChCl) to glycerol (Glycerol) is 1:2 to prepare a eutectic mixture (DES), the titanium dioxide precursor is titanium tetraisopropoxide (TIP), and the alcohol solvent is different. Propanol (IPA).

Titanium dioxide precursor (TIP): alcohol solvent (IPA): water molar ratio of 1:3:100, and titanium dioxide precursor (TIP): eutectic mixture (DES) molar ratio of 1: 0.25, 1:0.50, 1:0.75, 1:1.0, 1:1.5, microwave heating at 80 to 85 ° C and 1 atm under normal pressure for 90 minutes.

The synthesized product prepared under the above conditions was analyzed by X-ray Diffraction (XRD), and the results are shown in Fig. 1. From the results of XRD analysis in Fig. 1, it can be known that the titanium dioxide precursor (TIP): eutectic mixture (DES) can synthesize anatase crystal phase titanium dioxide at a molar ratio of 1:0.25 to 1:1.5. Nanocrystals of (anatase-TiO ₂ ).

[Preparation Example 2]

Microwave heating time regulation of synthetic anatase crystal phase titanium dioxide (anatase-TiO ₂ ) powder

The chelating ratio of choline chloride (ChCl) to urea (Urea) is 1:2 to prepare a eutectic mixture (DES), the titanium dioxide precursor is titanium tetraisopropoxide (TIP), and the alcohol solvent is different. Propanol (IPA).

Titanium dioxide precursor (TIP): alcohol solvent (IPA): eutectic mixture (DES): water molar ratio of 1:3:1:100, at 80-85 ° C and 1 atm under normal pressure Microwave heating for 30, 60, 90, 120 minutes.

The synthesized product prepared under the above microwave heating time conditions was analyzed by X-ray diffractometer (XRD), and the results are shown in Fig. 2. From the results of XRD analysis in Fig. 2, it can be known that nanocrystals of anatase-TiO ₂ can be synthesized by microwave heating for 30 to 120 minutes.

[Preparation Example 3] Comparison of the effects of adding eutectic mixture (DES) on the synthesis of anatase-TiO ₂ powder

Use choline chloride (ChCl) and glycerol (Glycerol) mixed with a molar ratio of 1:2 to make the first fused mixture (DES-glycerol), using choline chloride (ChCl) and urea (Urea) The mixed molar ratio was 1:2 to prepare a second eucalyptus mixture (DES-urea), the titanium dioxide precursor was titanium tetraisopropoxide (TIP), and the alcohol solvent was isopropyl alcohol (IPA).

Titanium dioxide precursor (TIP): alcohol solvent (IPA): water molar ratio of 1:3:100, and the molar ratio of titanium dioxide precursor (TIP): eutectic mixture (DES) is 1 :0, Titanium Dioxide Precursor (TIP): The first eutectic mixture (DES-glycerol) has a molar ratio of 1:1, before titanium dioxide Drive (TIP): The second blended solution (DES-urea) has a molar ratio of 1:1 and is heated by microwave for 90 minutes at 80-85 ° C and 1 atm atmospheric pressure.

The synthesized product prepared under the above conditions was analyzed by X-ray diffractometer (XRD), and the results are shown in Fig. 3. From the results of XRD analysis in Fig. 3, it can be known that anatase crystal phase titanium dioxide (anatase-TiO ₂ ) cannot be synthesized without adding a eutectic mixture, and the first or second eutectic mixture can be synthesized. Anatase-TiO _{2 is} formed, so the addition of the eutectic mixture helps to form anatase crystal phase titanium dioxide at a low temperature.

[Examples 1-3 and Comparative Example 1] Comparison of activated carbon modified with anatase phase titanium dioxide and unmodified activated carbon

The chelating ratio of choline chloride (ChCl) to glycerol (Glycerol) is 1:2 to prepare a eutectic mixture (DES), the titanium dioxide precursor is titanium tetraisopropoxide (TIP), and the alcohol solvent is different. Propanol (IPA).

First, 2 g of activated carbon was placed in the reaction flask, and the activated carbon was uniformly dispersed by using 200 ml (mL) of isopropyl alcohol (IPA). The weight ratio of the carbon material to the alcohol solvent was about 1:80, followed by the addition of TIP. : The molar ratio of DES is 1:0.25, 1:0.75, 1:1, and the TIP:H ₂ O molar ratio is 1:15. The three reagents with different mixing ratios of TIP, DES and H ₂ O are The first stage of microwave heating was carried out at 80 to 85 ° C and 1 atm under normal pressure for 30 minutes, the microwave power was 800 W, and the frequency was 2.45 GHz, and the obtained first stage synthesis product was filtered.

Further, an alcohol solvent is further added to the synthesized product in the first stage after the filtration, wherein the weight ratio of the first stage synthesis product to the alcohol solvent after filtration is 1:30, and then the DES:H ₂ O molar is added. The ratio is 1:18 reagent, and wherein the weight ratio of the synthesized product of the first stage after filtration to DES is 1:3.6, and the second stage of microwave heating is performed for 60 minutes at 80-85 ° C and 1 atm atmospheric pressure. The microwave power was 800 W and the frequency was 2.45 GHz, and the preparation of the modified activated carbon of Examples 1-3 was completed.

Comparative Example 1 is an unmodified activated carbon.

The modified activated carbon AC/TiO ₂ -TIP of Examples 1-3 was analyzed by X-ray diffractometer (XRD): DES = 1:0.25, AC/TiO ₂ -TIP: DES = 1:0.75, AC/TiO ₂ -TIP: DES = 1:1 and unmodified activated carbon (AC) of Comparative Example 1, and the results are shown in Fig. 4. From the results of XRD analysis in Fig. 4, it was found that the unmodified activated carbon (AC) of Comparative Example 1 had no significant peak at an angle (2 θ) of 25.4°, and the modification activity of Examples 1-3 was obtained. The peak intensity of carbon at an angle (2 θ) of 25.4° is significantly increased. This result indicates that the modification of Examples 1-3 can effectively immobilize anatase-TiO ₂ on activated carbon. From the results of FIG. 4, it is found that when the molar ratio of TIP:DES used for modifying activated carbon is 1:0.75, the anatase crystal phase of titanium dioxide (anatase-TiO ₂ ) has the highest crystal strength, and the result is the same as Preparation Example 1 The results of synthesizing anatase crystal phase titanium dioxide (anatase-TiO ₂ ) powder were consistent.

[Embodiment 4] Activated carbon modified with anatase phase titanium dioxide

The chelating ratio of choline chloride (ChCl) to urea (Urea) is 1:2 to prepare a eutectic mixture (DES), and the titanium dioxide precursor is titanium tetraisopropoxide. (TIP), the alcohol solvent is isopropyl alcohol (IPA).

First, 2 g of activated carbon was placed in the reaction flask, and the activated carbon was uniformly dispersed by using 200 ml (mL) of isopropyl alcohol (IPA). The weight ratio of the carbon material to the alcohol solvent was about 1:80, followed by the addition of TIP. : DES has a Mohr ratio of 1:1, and the TIP:H ₂ O molar ratio of 1:15 TIP, DES and H ₂ O mixed reagents are carried out at 80-85 ° C and 1 atm atmospheric pressure. The first stage of the microwave was heated for 30 minutes, the microwave power was 800 W, and the frequency was 2.45 GHz. The obtained first stage synthesis product was subjected to a filtration procedure.

An alcohol solvent is further added to the first stage synthesis product after filtration, and the weight ratio of the first stage synthesis product to the alcohol solvent after filtration is 1:30, and then the molar ratio of DES:H ₂ O is 1 The reagent of 18: and the weight ratio of the first stage synthesis product to the DES after filtration is 1:3.6, and the second stage microwave heating is performed for 60 minutes at a normal pressure of 80 to 85 ° C and 1 atm, and the microwave power is 800 W. The preparation of the modified activated carbon of Example 4 was completed at a frequency of 2.45 GHz.

[Examples 5-7 and Comparative Example 2]

The anatase crystal phase titanium dioxide modified activated carbon of Example 1 and Example 3-4 was used to prepare an electrode with the unmodified activated carbon of Comparative Example 1, and the capacitance characteristics of the electrode were compared, wherein the modification of Example 3-4 was carried out. TIP used for the activated carbon: DES has a molar ratio of 1:1 and TIP:H ₂ O has a molar ratio of 1:15.

For the electrode preparation procedure, the modified activated carbon of Example 1 and Example 3-4 and the unmodified activated carbon of Comparative Example 1 were respectively mixed with polyvinylidene fluoride (PVDF, molecular weight 534 k, solid content 5). Wt%) And graphite powder (particle size 2.7 μm) mixed, wherein the modified activated carbon or unmodified activated carbon: polydifluoroethylene: graphite powder weight ratio of 80:10:10, N-methylrrolidone (N-methyl-2-pyrrolidone; NMP) solvent was added to the above mixture and uniformly stirred into a paste slurry, and the paste slurry was uniformly coated on a titanium foil having a thickness of 50 μm using a coater with a 200 μm doctor blade, and sent. The electrodes of Examples 5-7 and Comparative Example 2 were prepared by drying in an oven at 130 ° C for 2 hours, wherein the electrodes of Examples 5-7 were respectively made of modified activated carbon of Example 1 and Example 3-4. The electrode of Comparative Example 2 was prepared from the unmodified activated carbon of Comparative Example 1.

The electrodes of Examples 6-7 (made of the modified activated carbon of Example 3-4) and the electrode of Comparative Example 2 were evaluated for bulk resistivity (μΩ.cm) and specific capacitance (Fg ^{- 1} ), the results are shown in Table 1.

In addition, the modified activated carbon of Example 3-4 was detected by a thermogravimetric analyzer (TGA), and the temperature was raised from 30 ° C to 800 ° C at a temperature increase rate of 20 ° C per minute under oxygen, and the result of TGA analysis was analyzed. The content (% by weight, wt%) of anatase-TiO ₂ immobilized on the activated carbon in the modified activated carbon of Example 3-4 can be calculated, and the results are shown in Table 1. .

The results in Table 1 show that the contents of the anatase-TiO ₂ contained in the modified activated carbon of Example 3-4 prepared by the modification method of the present disclosure were 7.18% and 5.99%, respectively.

Further, the resistance value of the electrode prepared from the modified activated carbon of Example 3-4 was lowered to 95.0 as compared with the resistance value of the electrode prepared by the unmodified activated carbon of Comparative Example 1 of 107.3 μΩ·cm. μΩ.cm.

In terms of capacitance, the specific capacitance of the electrode prepared from the modified activated carbon of Example 3-4 can be improved by about the specific capacitance value of the electrode prepared by the unmodified activated carbon of Comparative Example 1. 1.3 times.

From the results of Table 1, it can be confirmed that the anatase crystal phase titanium dioxide (anatase-TiO ₂ ) can be immobilized on the activated carbon by the modification method of the present disclosure, and the modified activated carbon prepared by the modification method is applied to the electrode. When the material is used, the conductivity and capacitance of the electrode can be effectively improved.

Further, X-ray photoelectron spectroscopy (XPS) analysis was performed on the modified activated carbons of Example 1 and Example 3, and the modified activated carbons of Examples 1 and 3 were measured. The specific capacitance values of the electrodes (electrodes of Example 5 and Example 6) are shown in Table 2.

It can be seen from the results in Table 2 that by changing the amount of addition of the eutectic mixed solution (DES), the hydrolysis condensation reaction of anatase-TiO ₂ can be effectively controlled, and the amount of TiOH formed can be controlled. . When the addition amount of the eutectic mixed solution (DES) is increased, the content of anatase-TiO ₂ is not changed much, but the amount of formation of TiOH is relatively increased. The increase in the amount of TiOH produced makes the hydrated ions in the aqueous electrolyte solution easier to access the electrode surface, which in turn increases the specific capacitance of the electrode. As shown in the results of Table 2, when the fused mixture (DES) is added by 0.25 When the increase is 1, the specific capacitance of the electrode prepared by the modified activated carbon prepared is also increased from 46.4 Fg ^-1 to 53.4 Fg ^-1 .

The modification method of the present disclosure uses a eutectic liquid mixture in combination with microwave heating, and the eutectic mixture liquid absorbs microwaves and has a function of promoting crystallization of titanium dioxide, thereby contributing to low temperature (below 100 ° C), normal pressure (1 atm), and In a short time (less than 2 hours), simultaneous formation of titanium hydroxide (TiOH) and anatase crystal phase titanium dioxide (anatase-TiO ₂ ) nanocrystals are fixed on the carbon material, thereby simultaneously increasing the conductivity of the carbon material. With hydrophilicity.

In addition, it can be known from the analysis of thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS) of modified activated carbon that the composite carbon material prepared according to the modified method of the present disclosure contains anatase crystal The weight ratio of the titanium dioxide is about 4-10%, and the weight ratio of the titanium hydroxide is about 15-50%.

In addition, according to the modification method of the present disclosure, the hydration condensation reaction rate of the anatase crystal phase titanium dioxide can be controlled by the addition amount of the eutectic liquid mixture, and the titanium oxyhydroxide content in the modified composite carbon material can be regulated.

At the same time, the eutectic mixture used in the modification method of the present disclosure is a highly polar and non-volatile solvent, which has the advantages of biodegradability, non-toxicity, simple manufacture, low cost, etc., so the modification method of the present disclosure is green. Low-cost carbon material upgrading method.

The modified composite carbon material can be applied to an electrode material of a supercapacitor, a capacitor desalination or an energy storage device, reducing irreversible adsorption on the surface of the electrode material and increasing electron conductivity to enhance the ion absorption/desorption of the electrode, and It is also beneficial for the ions in the aqueous electrolyte to be easily close to the surface of the carbon electrode electrode, thereby improving the effect of the electrode capacitance, increasing the charge and discharge rate and the use efficiency of the electrode.

In addition, the modification method of the present disclosure is more conventional than the method of adding or fixing a nano metal oxide to activated carbon by means of blending, chemical precipitation or sol-gel. The effect of uniformly distributing titanium hydroxide and anatase crystal phase titanium dioxide on the surface of the carbon material or inside the pore can be achieved, and the aggregation phenomenon caused by nanocrystallization of the anatase crystal phase titanium oxide can be reduced.

Although the present invention has been disclosed in its preferred embodiments, it is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application attached.

Fig. 1 is a view showing an X-ray diffraction pattern (XRD) of the comparison of the effect of the addition ratio of the different inclusive mixture (DES) of the preparation example 1 on the synthesis of anatase-TiO ₂ powder. Fig. 2 is a view showing an X-ray diffraction pattern (XRD) of Comparative Example 2 using a different microwave heating time for synthesizing anatase-TiO ₂ powder; FIG. 3 is a view X-ray diffractometer (XRD) analysis pattern of the effect of adding and adding a co-melt mixture of Preparation Example 3 on the synthesis of anatase-TiO ₂ powder; and Figure 4 showing a comparative example An X-ray diffractometer (XRD) analysis pattern of the unmodified activated carbon of 1 and the modified activated carbon of Examples 1-3.

Claims (10)

A method for modifying a carbon material for an electrode comprises: mixing a carbon material with a titanium dioxide precursor, a eutectic mixture, water and an alcohol solvent, and performing a first stage of microwave heating to produce a first stage product, wherein the The eutectic mixture is composed of a quaternary amine salt halide and a hydrogen bond provider. In the first stage, the weight ratio of the carbon material to the alcohol solvent is 1:80, and the weight of the carbon material and the titanium dioxide precursor The molar ratio of the titanium dioxide precursor to the eutectic mixture is 1:0.25 to 1:1.5, and the molar ratio of the titanium dioxide precursor to water is 1:4 to 2:1. 5 to 1:30; and further adding the eutectic mixture, water and the alcohol solvent to the first stage product, performing a second stage of microwave heating to synthesize titanium hydroxide and anatase crystal phase a composite carbon material in which titanium dioxide is fixed on the carbon material. In the second stage, the weight ratio of the first stage product to the alcohol solvent is 1:30, and the amount of the eutectic mixture and the water added is not The ear ratio is 1:18, and the weight ratio of the first stage product to the eutectic mixture It is 1:3.6, and wherein the heating time of the second stage is longer than the heating time of the first stage. The method for modifying a carbon material for an electrode according to claim 1, wherein a molar ratio of the quaternary amine salt halide of the eutectic mixture to the hydrogen bond provider is 1:1 to 1: 8. The method for modifying a carbon material for an electrode according to claim 2, wherein the quaternary amine salt halide comprises choline chloride, and the hydrogen bond provider comprises a polyol, a carboxylic acid, an amine or a decylamine. The modification of the carbon material for electrodes as described in claim 1 of the patent application scope The method, wherein the microwave heating in the first stage and the second stage is performed at a normal temperature of 80-100 ° C and 1 atm, the microwave power is 800 W, the microwave frequency is 2.45 GHz, and the total microwave heating time is 30. Up to 120 minutes. The method for modifying a carbon material for an electrode according to claim 1, wherein the carbon material comprises activated carbon, bamboo carbon, carbon nanotubes or graphene, and the specific surface area of the carbon material is greater than 300 m ² /g. The carbon material has an average pore diameter of between 1 nm and 1000 nm. The method for modifying a carbon material for an electrode according to claim 1, wherein the alcohol solvent comprises ethanol, isopropanol or n-butanol. The method for modifying a carbon material for an electrode according to claim 1, wherein the titanium dioxide precursor comprises titanium tetraisopropoxide or titanium butoxide. The carbon material for an electrode is prepared by the method for modifying the carbon material for an electrode according to the first aspect of the patent application, and comprises titanium hydroxide and anatase crystal phase titanium dioxide fixed on a carbon material, which contains the sharp The weight ratio of the titanium ore phase titanium dioxide is 4-10%, and the composition ratio of the titanium hydroxide is 15-50%. The carbon material for an electrode according to claim 8, wherein the carbon material comprises activated carbon, bamboo carbon, carbon nanotubes or graphene, and the carbon material has a specific surface area of more than 300 m ² /g, the carbon material The pores have an average diameter between 1 nm and 1000 nm. The electrode carbon material according to claim 8 is used for an electrode material of a supercapacitor, a capacitor desalination or an energy storage device.