CN111573792A - Preparation method of capacitive deionization electrode active material, capacitive deionization electrode and application of capacitive deionization electrode - Google Patents
Preparation method of capacitive deionization electrode active material, capacitive deionization electrode and application of capacitive deionization electrode Download PDFInfo
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- CN111573792A CN111573792A CN201910746910.7A CN201910746910A CN111573792A CN 111573792 A CN111573792 A CN 111573792A CN 201910746910 A CN201910746910 A CN 201910746910A CN 111573792 A CN111573792 A CN 111573792A
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4691—Capacitive deionisation
Abstract
The invention discloses a preparation method of a capacitive deionization electrode active material, a capacitive deionization electrode and application thereof. The capacitive deionization electrode is prepared by taking an active material of the capacitive deionization electrode as a raw material. The preparation method has the advantages of simple preparation process, low preparation cost, high preparation yield and the like, and the prepared capacitive deionization electrode active material has the advantages of high specific surface area, high micropore content and the like, and has high use value and good application prospect. The capacitive deionization electrode has the advantages of high conductivity, high capacitance, good stability and the like, can be widely used for water body desalination or water body purification, has the advantages of high removal speed, good removal effect, environmental friendliness and the like, and provides a new way for capacitive deionization desalination.
Description
Technical Field
The invention belongs to the technical field of active carbon material modification, and relates to a preparation method of a capacitive deionization electrode active material, a capacitive deionization electrode and application thereof.
Background
With climate change, population growth, industrial development, water pollution and limited availability of fresh water, the pressure to obtain affordable clean water worldwide is increasing and is recognized as one of the most important global problems. In order to solve the problem of shortage of fresh water and increase the supply of fresh water, several techniques for desalinating sea water have been developed and applied in the past decades.
Capacitive Deionization (CDI) is an electrochemical technique that uses porous carbon materials as electrodes to achieve desalination. Due to the advantages of low energy consumption, easy operation, no secondary pollution and the like, the method draws wide attention and is considered as a promising high-efficiency, energy-saving, green and environment-friendly desalination technology. Based on the theory of electric double layers, CDI electrostatically adsorbs charged ions in water to porous electrode materials to remove salts from solution. The desalting quantity is a key index for measuring the capacitive deionization performance, namely the quality of salt adsorbed by a unit mass of electrode material. The electrode material is a key component of the capacitive deionization device, and the performance of the electrode material is directly related to the desalination performance and stability of CDI. Porous carbon materials with high conductivity, high specific surface area and high capacitance are ideal CDI electrode materials. Currently, various carbon electrode materials are used for CDI electrodes, including carbon aerogel, activated carbon, mesoporous carbon, carbon nanotubes, graphene, and the like, but most of these carbon materials have the disadvantages of high manufacturing cost, low yield, low desalination amount, and the like, and the development of capacitive deionization is restricted.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art, provide a preparation method of the capacitive deionization electrode active material with simple preparation process, low preparation cost and high preparation yield, and also provide a capacitive deionization electrode with high desalination amount and application of the capacitive deionization electrode as an electrode material of a capacitive deionization device in water body desalination or water body purification.
In order to solve the technical problems, the invention adopts the technical scheme that:
a method for preparing a capacitive deionization electrode active material, comprising the steps of:
(1) pyrolyzing pine nuts to obtain pine nut biochar;
(2) mixing the pine cone biochar obtained in the step (1) with a phosphoric acid solution for phosphoric acid modification, and drying to obtain phosphorus-doped pine cone biochar;
(3) and (3) activating the phosphorus-doped pine cone biochar obtained in the step (2) to obtain the capacitive deionization electrode active material.
In the above method for preparing a capacitive deionization electrode active material, it is further improved that in the step (1), the pyrolysis is performed under vacuum and inert atmosphere; the heating rate in the pyrolysis process is 5 ℃ min-1～10℃·min-1(ii) a The pyrolysis temperature is 550-600 ℃; the pyrolysis time is 2-3 h; naturally cooling the pyrolysis product after the pyrolysis is finished; the method also comprises the steps of cleaning, drying and crushing the pine cone before pyrolysis.
In the preparation method of the capacitive deionization electrode active material, the mass ratio of the pine cone biochar to the phosphoric acid solution in the step (2) is further improved to be 1: 2-1: 3; the mass fraction of the phosphoric acid solution is 85%; the drying temperature is 85 ℃; the drying time is 12 h.
In the above method for preparing a capacitive deionization electrode active material, it is further improved that in the step (3), the activation is performed under vacuum and inert atmosphere; the heating rate in the activation process is 5 ℃ min-1～10℃·min-1(ii) a The activation temperature is 800-900 ℃; the activation time is 2-2.5 h; and after the activation is finished, naturally cooling the activated product.
In the above method for preparing a capacitive deionization electrode active material, the step (3) further comprises the following steps after the activation: soaking the activated product in a hydrochloric acid solution, washing the activated product to be neutral by deionized water, filtering and drying to obtain the capacitive deionization electrode active material; the concentration of the hydrochloric acid solution is 2mol L-1(ii) a The soaking time is 24 hours; what is needed isThe drying temperature is 85 ℃; the drying time is 12 h.
As a general inventive concept, the invention also provides a capacitive deionization electrode, which is prepared by uniformly mixing the capacitive deionization electrode active material prepared by the preparation method, carbon black and a binder under the action of 1-methyl 2-pyrrolidone.
In a further improvement of the capacitive deionization electrode, the preparation method of the capacitive deionization electrode comprises the following steps: mixing the capacitive deionization electrode active material, carbon black and a binder, uniformly grinding, adding 1-methyl 2-pyrrolidone, and uniformly mixing to obtain a mixture; and coating the mixture on a substrate, and drying to obtain the capacitive deionization electrode.
In the capacitive deionization electrode, the mass ratio of the active material to the carbon black to the binder is 8: 1; the mass ratio of the capacitive deionization electrode active material to the 1-methyl 2-pyrrolidone is 0.07-0.13; the binder is polyvinylidene fluoride; the substrate is a current collector graphite sheet; the drying is carried out under vacuum conditions; the drying temperature is 60 ℃; the drying time is 12 h.
As a general inventive concept, the invention also provides an application of the capacitive deionization electrode in water body desalination or water body purification.
In the application, the voltage between the capacitive deionization electrodes is controlled to be 0.9V-1.5V in the water body desalting or water body purifying process.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a preparation method of a capacitive deionization electrode active material, which is characterized in that pine nuts are used as raw materials, phosphorus-doped pine nut biochar is prepared by pyrolysis and phosphoric acid modification, and then the phosphorus-doped pine nut biochar is activated to prepare the capacitive deionization electrode active material. According to the invention, pine cone is used as a raw material, the pine cone is rich in source, cheap and easy to obtain, and pyrolysis, phosphoric acid modification and activation are carried out on the pine cone, so that the specific surface area of the material is improved, and the micropore content of the material is also improved, therefore, the prepared capacitive deionization electrode active material has the advantages of high specific surface area, high micropore content and the like, is a porous carbon material, and can be better applied to the field of capacitive deionization; meanwhile, the capacitive deionization electrode active material prepared by the method is beneficial to enhancing the capacitive performance of the capacitive deionization electrode and improving the conductivity of the capacitive deionization electrode, so that the desalination amount of the capacitive deionization electrode can be effectively improved, and the capacitive deionization electrode active material has very important significance for improving the desalination or purification effect of a capacitive deionization technology. The preparation method of the capacitive deionization electrode active material has the advantages of simple preparation process, low preparation cost, high preparation yield and the like, can effectively realize the application of the capacitive deionization electrode active material to the industrial production of capacitive deionization desalination, and the prepared capacitive deionization electrode active material has the advantages of high specific surface area, high micropore content and the like, and has higher use value and better application prospect.
(2) The invention provides a capacitive deionization electrode, which is prepared by uniformly mixing a capacitive deionization electrode active material, carbon black and a binder in 1-methyl 2-pyrrolidone, wherein the carbon black is used for enhancing the conductivity, and the binder can be better dissolved in the 1-methyl 2-pyrrolidone, so that the binding property of the capacitive deionization electrode active material and the carbon black is enhanced, and the capacitive deionization electrode is kept stable in a water body and is not easy to fall off. The capacitive deionization electrode has the advantages of high conductivity, high capacitance, good stability and the like, and the capacitive deionization electrode has the advantages of simple preparation method, convenient operation, low cost and the like, is suitable for large-scale preparation, and is beneficial to industrial production and application.
(3) The invention provides an application of a capacitive deionization electrode as an electrode material of a capacitive deionization device in water body desalination or water body purification, and the capacitive deionization electrode is used as the electrode material of the capacitive deionization device for treating a target solution, so that a target substance in the target solution can be effectively removed, the aim of desalination or purification is fulfilled, and the capacitive deionization device has the advantages of high removal speed, good removal effect, environmental friendliness and the like, and provides a new way for capacitive deionization desalination.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Fig. 1 is SEM images of a phosphorus-doped pine cone activated carbon capacitive deionization electrode active material (PCP) prepared in example 1 of the present invention and a pine cone activated carbon capacitive deionization electrode active material (PC) prepared in comparative example 1.
Fig. 2 is a graph showing pore diameter-specific surface area distribution of a phosphorus-doped pine cone activated carbon capacitive deionization electrode active material (PCP) prepared in example 1 of the present invention and a pine cone activated carbon capacitive deionization electrode active material (PC) prepared in comparative example 1.
FIG. 3 is a CV diagram of a phosphorus-doped pine cone activated carbon capacitive deionization electrode (PCP-CDI) prepared in example 2 of the present invention and a pine cone activated carbon capacitive deionization electrode (PC-CDI) prepared in comparative example 2.
Fig. 4 is a schematic view of a capacitive deionization cycle system in embodiment 2 of the present invention.
FIG. 5 is a calibration graph of concentration versus conductivity of a solution in example 2 of the present invention.
FIG. 6 is a graph showing the change of conductivity at a voltage of 0.9V when the phosphorus-doped pine cone activated carbon capacitive deionization electrode (PCP-CDI) manufactured in example 2 according to the present invention and the phosphorus-doped pine cone activated carbon capacitive deionization electrode (PC-CDI) manufactured in comparative example 2 are used for desalting water.
FIG. 7 is a graph showing the change of concentration of phosphorus-doped pine cone activated carbon capacitive deionization electrode (PCP-CDI) prepared in example 2 of the present invention and pine cone activated carbon capacitive deionization electrode (PC-CDI) prepared in comparative example 2 at a voltage of 1.2V when they are used for desalination of water.
FIG. 8 is a graph showing the change of conductivity at a voltage of 1.5V when the phosphorus-doped pine cone activated carbon capacitive deionization electrode (PCP-CDI) manufactured in example 2 according to the present invention and the phosphorus-doped pine cone activated carbon capacitive deionization electrode (PC-CDI) manufactured in comparative example 2 are used for desalting water.
FIG. 9 is a bar graph of the amount of Salt Adsorbed (SAC) at different voltages when the phosphorus-doped pine cone activated carbon capacitive deionization electrode (PCP-CDI) prepared in example 2 of the present invention and the pine cone activated carbon capacitive deionization electrode (PC-CDI) prepared in comparative example 2 are used for desalination of water.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available. In the invention, phosphoric acid, hydrochloric acid, sodium chloride and analytical pure reagents produced by chemical reagents of national medicine group Limited are used; 1-methyl-2-pyrrolidone (NMP) is a chemical reagent with the purity of 99 percent produced by the company Aladdin; polyvinylidene fluoride (PVDF) is a chemical agent produced by the Aladdin company; the peristaltic pump (BT-300) is produced by Baoding Shenchen pump industry Co Ltd; the conductivity meter is produced by Shanghai mine magnetic instrument factory (DDS-307).
Example 1
A method for preparing a capacitive deionization electrode active material, comprising the steps of:
(1) washing the pine cone with tap water to remove attached dirt, washing with distilled water, drying in a forced air drying oven, and mechanically pulverizing into powder to obtain pine cone powder. Transferring the obtained pine cone powder into a quartz ark in a vacuum tube furnace, continuously introducing Ar into the vacuum tube furnace, and ensuring the air tightness of the whole device in the process to ensure that the whole device is completely in a vacuum state, namely, the temperature rise rate is 10 ℃ per minute under the vacuum and Ar atmosphere-1And heating the mixture from room temperature to 600 ℃ for pyrolysis for 3h, and then naturally cooling the mixture to obtain the pine cone biochar.
(2) Mixing the pine cone biochar obtained in the step (1) with a phosphoric acid solution with the mass fraction of 85% according to the mass ratio of the pine cone biochar to the phosphoric acid solution of 1: 2 for phosphoric acid modification, and then drying the modified product in a forced air drying oven at the temperature of 85 ℃ for 12 hours to obtain the phosphorus-doped pine cone biochar.
(3) The phosphorus-doped pine cone obtained in the step (2) is grownMoving the charcoal into a quartz boat in a vacuum tube furnace, continuously introducing Ar into the vacuum tube furnace, and ensuring the air tightness of the whole device in the process to ensure that the whole device is completely in a vacuum state, namely under the vacuum and Ar atmosphere, the temperature rise rate is 10 ℃ per minute-1Heating from room temperature to 800 ℃ for activation for 2h, then naturally cooling, and adding the obtained activated product to 2mol L-1And (3) soaking in a hydrochloric acid solution for 24h, washing with deionized water to be neutral, filtering to remove impurities so as to completely open a pore channel, and then drying in a blast drying oven at the temperature of 85 ℃ for 12h to obtain the phosphorus-doped pine cone activated carbon capacitive deionization electrode active material, which is marked as PCP.
Comparative example 1
A preparation method of a pine cone active capacitance deionization electrode active material comprises the following steps:
(1) washing the pine cone with tap water to remove attached dirt, washing with distilled water, drying in a forced air drying oven, and mechanically pulverizing into powder to obtain pine cone powder. Transferring the obtained pine cone powder into a quartz ark in a vacuum tube furnace, continuously introducing Ar into the vacuum tube furnace, and ensuring the air tightness of the whole device in the process to ensure that the whole device is completely in a vacuum state, namely, the temperature rise rate is 10 ℃ per minute under the vacuum and Ar atmosphere-1And heating the mixture from room temperature to 600 ℃ for pyrolysis for 3h, and then naturally cooling the mixture to obtain the pine cone biochar.
(2) Transferring the pine cone biochar obtained in the step (1) into a quartz ark and placing the quartz ark into a vacuum tube furnace, continuously introducing Ar into the vacuum tube furnace, and ensuring the air tightness of the whole device in the process so as to ensure that the whole device is completely in a vacuum state, namely the whole device is in a vacuum and Ar atmosphere at the temperature rise rate of 10 ℃ min-1Heating from room temperature to 900 ℃ for activation for 2h, then naturally cooling, and adding the obtained activated product to 2mol L-1Soaking in hydrochloric acid solution for 24 hr, washing with deionized water to neutrality, filtering to remove impurities and open pore channels, and drying at 85 deg.C in a blast drying ovenAnd drying for 12 hours to obtain the pine cone activated carbon capacitive deionization electrode active material which is marked as PC.
The phosphorus-doped pine cone activated carbon capacitive deionization electrode active material (PCP) prepared in example 1 and the pine cone activated carbon capacitive deionization electrode active material (PC) prepared in comparative example 1 were characterized by a scanning electron microscope, and the results are shown in fig. 1. Fig. 1 is SEM images of a phosphorus-doped pine cone activated carbon capacitive deionization electrode active material (PCP) prepared in example 1 of the present invention and a pine cone activated carbon capacitive deionization electrode active material (PC) prepared in comparative example 1. As can be seen from fig. 1, the phosphorus-doped pinecone activated carbon capacitive deionization electrode active material (PCP) and the pinecone activated carbon capacitive deionization electrode active material (PC) both have a porous structure, and the addition of phosphorus results in less agglomeration of the phosphorus-doped pinecone activated carbon capacitive deionization electrode active material.
The phosphorus-doped pine cone activated carbon capacitive deionization electrode active material (PCP) prepared in example 1 and the pine cone activated carbon capacitive deionization electrode active material (PC) prepared in comparative example 1 were tested using a nitrogen desorption-adsorption experiment, and the results are shown in fig. 2. Fig. 2 is a graph showing pore diameter-specific surface area distribution of a phosphorus-doped pine cone activated carbon capacitive deionization electrode active material (PCP) prepared in example 1 of the present invention and a pine cone activated carbon capacitive deionization electrode active material (PC) prepared in comparative example 1. As can be seen from FIG. 2, the specific surface areas of the phosphorus-doped pine cone activated carbon capacitive deionization electrode active material (PCP) and the pine cone activated carbon capacitive deionization electrode active material (PC) prepared in comparative example 1 were 1062m, respectively2g-1、726m2g-1It is shown that the specific surface area of the phosphorus-doped pinecone activated carbon capacitive deionization electrode active material (PCP) prepared in embodiment 1 of the present invention is greatly increased, and mainly the specific surface area of micropores is significantly increased, so that the capacitive deionization performance of the phosphorus-doped pinecone activated carbon is advantageously improved, which greatly provides possibility for the phosphorus-doped pinecone activated carbon to be used as an electrode of a high-efficiency CDI module.
Example 2
A capacitive deionization electrode is prepared by uniformly mixing the phosphorus-doped pinecone activated carbon capacitive deionization electrode active material (PCP) prepared in example 1, carbon black and a binder under the action of 1-methyl 2-pyrrolidone, and comprises the following steps:
according to the mass ratio of the capacitive deionization electrode active material to the carbon black to the binder of 8: 1, 80mg of the phosphorus-doped pinecone activated carbon capacitive deionization electrode active material prepared in the example 1, the carbon black and the polyvinylidene fluoride are mixed, uniformly ground in an agate mortar, 0.75mL of 1-methyl 2-pyrrolidone is dropwise added, and uniformly mixed to obtain a mixture; and (3) coating the mixture on a current collector graphite sheet (9cm multiplied by 9cm), and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain a capacitive deionization electrode prepared from the phosphorus-doped pinecone activated carbon capacitive deionization electrode active material, and marking as a phosphorus-doped pinecone activated carbon capacitive deionization electrode (PCP-CDI).
Comparative example 2
A capacitance deionization electrode of pine cone activated carbon is prepared by uniformly mixing the active material of the capacitance deionization electrode of pine cone activated carbon prepared in comparative example 1, carbon black and a binder under the action of 1-methyl 2-pyrrolidone, and comprises the following steps:
according to the mass ratio of the capacitive deionization electrode active material to the carbon black to the binder of 8: 1, 80mg of the capacitive deionization electrode active material prepared in the comparative example 1, the carbon black and the polyvinylidene fluoride are mixed, uniformly ground in an agate mortar, 0.75mL of 1-methyl 2-pyrrolidone is dropwise added, and uniformly mixed to obtain a mixture; and (3) coating the mixture on a current collector graphite sheet (9cm multiplied by 9cm), and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain a capacitive deionization electrode made of the pine cone activated carbon capacitive deionization electrode active material, and marking as a pine cone activated carbon capacitive deionization electrode (PC-CDI).
The phosphorus-doped pinecone activated carbon capacitive deionization electrode (1 × 1 cm) prepared in example 2 was subjected to a three-electrode system (working electrode, platinum electrode as counter electrode, calomel electrode as reference electrode)2Area) and the capacitive deionization electrode of pine cone activated carbon (1 × 1 cm) prepared in comparative example 2 (1 cm × cm)2Area) was tested and the results are shown in fig. 3. FIG. 3 shows phosphorus doping obtained in example 2 of the present inventionCV graphs of the heteroclite pine cone activated carbon capacitive deionization electrode (PCP-CDI) and the pine cone activated carbon capacitive deionization electrode (PC-CDI) prepared in comparative example 2. As can be seen from FIG. 3, the capacitance of the phosphorus-doped pine cone activated carbon capacitive deionization electrode (PCP-CDI) is significantly increased, indicating that the phosphorus-doped pine cone activated carbon capacitive deionization electrode (PCP-CDI) of the present invention has good capacitance performance.
The phosphorus-doped pine cone activated carbon capacitive deionization electrode (PCP-CDI) prepared in example 2 and the pine cone activated carbon capacitive deionization electrode (PC-CDI) prepared in comparative example 2 were used for water desalination, and included the following steps:
(1) the phosphorus-doped pine cone activated carbon capacitive deionization electrode (PCP-CDI) prepared in example 2 and the pine cone activated carbon capacitive deionization electrode (PC-CDI) prepared in comparative example 2 were used as electrode materials of a capacitive deionization apparatus, respectively, and assembled with an acrylic plate (with water inlet and outlet holes left), a nylon cloth diaphragm, and a rubber pad to form a capacitive deionization apparatus (CDI apparatus), as shown in fig. 4.
(2) At a flow rate of 32-44 mL min-1Rinsing the CDI apparatus with deionized water until the conductivity meter reads less than 5 μ S cm-1The conductivity of the aqueous solution was measured in real time by a conductivity meter, as shown in fig. 4.
(3) The CDI apparatus, peristaltic pump and NaCl solution (volume 50mL, initial concentration 500mg L)-1) The beaker of (1) was used for desalting water body by constituting a circulation system through a rubber hose as shown in FIG. 4, wherein the voltage between the electrode materials was 0.9V and the flow rate of the target solution was 32mL min-1And measuring the conductivity of the salt solution in real time by a conductivity meter.
According to the relationship between the conductivity and the concentration of the solution calibrated before the experiment, the change of the conductivity is utilized to obtain the change of the concentration Delta C according to the formula:
the adsorption capacity (mg g) of the CDI apparatus was calculated-1)
The relationship between conductivity and concentration of the NaCl solution calibrated before the experiment, e.g.As shown in fig. 5. As can be seen from fig. 5, G — 0.5011C, R20.9998, where G is NaCl solution conductivity (μ S cm)-1) And C is NaCl solution concentration (mg L)-1)，R2Is the variance.
The conductivity curves of the solutions in which the phosphorus-doped pine cone activated carbon capacitive deionization electrode (PCP-CDI) prepared in example 2 and the pine cone activated carbon capacitive deionization electrode (PC-CDI) prepared in comparative example 2 were subjected to capacitive deionization, as shown in fig. 6. FIG. 6 is a graph showing the change of conductivity at a voltage of 0.9V when the phosphorus-doped pine cone activated carbon capacitive deionization electrode (PCP-CDI) manufactured in example 2 according to the present invention and the phosphorus-doped pine cone activated carbon capacitive deionization electrode (PC-CDI) manufactured in comparative example 2 are used for desalting water. Meanwhile, the invention also considers the corresponding conductivity change curves when the voltage between the electrode materials is 1.2V and 1.5V, as shown in fig. 7 and 8. FIG. 7 is a graph showing the change of concentration of phosphorus-doped pine cone activated carbon capacitive deionization electrode (PCP-CDI) prepared in example 2 of the present invention and pine cone activated carbon capacitive deionization electrode (PC-CDI) prepared in comparative example 2 at a voltage of 1.2V when they are used for desalination of water. FIG. 8 is a graph showing the change of conductivity at a voltage of 1.5V when the phosphorus-doped pine cone activated carbon capacitive deionization electrode (PCP-CDI) manufactured in example 2 according to the present invention and the phosphorus-doped pine cone activated carbon capacitive deionization electrode (PC-CDI) manufactured in comparative example 2 are used for desalting water. As can be seen from FIGS. 6-8, the conductivity of the solution gradually becomes stable after rapidly decreasing with time, and the desalting performance of the phosphorus-doped pinecone activated carbon capacitive deionization electrode (PCP-CDI) is remarkably improved; meanwhile, as can be seen from fig. 6 to 8, the higher the voltage is, the faster the conductivity of the solution decreases, and the larger the decrease value is, which indicates that the larger the voltage is, the faster the salt in the water body is removed, so that the salt content in the water body is lower.
FIG. 9 is a bar graph of the amount of Salt Adsorbed (SAC) at different voltages when the phosphorus-doped pine cone activated carbon capacitive deionization electrode (PCP-CDI) prepared in example 2 of the present invention and the pine cone activated carbon capacitive deionization electrode (PC-CDI) prepared in comparative example 2 are used for desalination of water. As can be seen from fig. 9, the higher the voltage, the higher the salt adsorption amount of the phosphorus-doped pinecone activated carbon capacitive deionization electrode (PCP-CDI); phosphorus-doped pine cone activated carbon at 0.9VThe salt adsorption amounts of the capacitive deionization electrode (PCP-CDI) and the capacitive deionization electrode of pine cone activated carbon (PC-CDI) were 1.46mg g-1、9.23mg g-1(ii) a Under the voltage of 1.2V, the salt adsorption capacity of the phosphorus-doped pine cone activated carbon capacitive deionization electrode (PCP-CDI) and the salt adsorption capacity of the phosphorus-doped pine cone activated carbon capacitive deionization electrode (PC-CDI) are respectively 3.08mg g-1、13.46mg g-1(ii) a Under the voltage of 1.5V, the salt adsorption capacity of the phosphorus-doped pine cone activated carbon capacitive deionization electrode (PCP-CDI) and the salt adsorption capacity of the phosphorus-doped pine cone activated carbon capacitive deionization electrode (PC-CDI) are respectively 5.36mg g-1、16.92mg g-1. Therefore, the phosphorus-doped pine cone activated carbon capacitive deionization electrode (PCP-CDI) prepared by the phosphorus-doped activated carbon capacitive deionization electrode active material (PCP) has greatly improved desalting performance, and achieves the aim of the invention.
The foregoing is merely a preferred embodiment of the invention, which is not to be construed as limiting the invention. Many possible variations and modifications of the present invention may be made by one of ordinary skill in the art using the above disclosure. Therefore, any simple modification of the above embodiments according to the technical essence of the present invention is within the protection scope of the technical solution of the present invention.
Claims (10)
1. A method for preparing a capacitive deionization electrode active material, comprising the steps of:
(1) pyrolyzing pine nuts to obtain pine nut biochar;
(2) mixing the pine cone biochar obtained in the step (1) with a phosphoric acid solution for phosphoric acid modification, and drying to obtain phosphorus-doped pine cone biochar;
(3) and (3) activating the phosphorus-doped pine cone biochar obtained in the step (2) to obtain the capacitive deionization electrode active material.
2. The method for preparing a capacitive deionization electrode active material according to claim 1, wherein in the step (1), the pyrolysis is performed under a vacuum, inert atmosphere; in the pyrolysis processThe temperature rise rate of (2) is 5 ℃ min-1～10℃·min-1(ii) a The pyrolysis temperature is 550-600 ℃; the pyrolysis time is 2-3 h; naturally cooling the pyrolysis product after the pyrolysis is finished; the method also comprises the steps of cleaning, drying and crushing the pine cone before pyrolysis.
3. The method for preparing the capacitive deionization electrode active material according to claim 1, wherein in the step (2), the mass ratio of the pine cone biochar to the phosphoric acid solution is 1: 2 to 1: 3; the mass fraction of the phosphoric acid solution is 85%; the drying temperature is 85 ℃; the drying time is 12 h.
4. The method for producing a capacitive deionization electrode active material according to claim 1, wherein in the step (3), the activation is performed under a vacuum, an inert atmosphere; the heating rate in the activation process is 5 ℃ min-1～10℃·min-1(ii) a The activation temperature is 800-900 ℃; the activation time is 2-2.5 h; and after the activation is finished, naturally cooling the activated product.
5. The method for producing a capacitive deionization electrode active material according to any one of claims 1 to 4, wherein the step (3) further comprises the following steps after the activation: soaking the activated product in a hydrochloric acid solution, washing the activated product to be neutral by deionized water, filtering and drying to obtain the capacitive deionization electrode active material; the concentration of the hydrochloric acid solution is 2molL-1(ii) a The soaking time is 24 hours; the drying temperature is 85 ℃; the drying time is 12 h.
6. A capacitive deionization electrode is characterized in that the capacitive deionization electrode is prepared by uniformly mixing the active material of the capacitive deionization electrode prepared by the preparation method of any one of claims 1 to 5, carbon black and a binder under the action of 1-methyl 2-pyrrolidone.
7. The capacitive deionization electrode according to claim 6, wherein the preparation method of the capacitive deionization electrode comprises the steps of: mixing the capacitive deionization electrode active material, carbon black and a binder, uniformly grinding, adding 1-methyl 2-pyrrolidone, and uniformly mixing to obtain a mixture; and coating the mixture on a substrate, and drying to obtain the capacitive deionization electrode.
8. The capacitive deionization electrode according to claim 7, wherein the mass ratio of the capacitive deionization electrode active material, carbon black and binder is 8: 1; the mass ratio of the capacitive deionization electrode active material to the 1-methyl 2-pyrrolidone is 0.07-0.13; the binder is polyvinylidene fluoride; the substrate is a current collector graphite sheet; the drying is carried out under vacuum conditions; the drying temperature is 60 ℃; the drying time is 12 h.
9. Use of a capacitive deionization electrode according to any one of claims 6 to 8 in water desalination or water purification.
10. The use of claim 9, wherein the voltage between the capacitive deionization electrodes is controlled to be 0.9V to 1.5V in the water desalination or water purification process.
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