CN110240240B - Device and method for enhancing capacitive deionization performance of flow electrode - Google Patents
Device and method for enhancing capacitive deionization performance of flow electrode Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C—CHEMISTRY; METALLURGY
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
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Abstract
The invention belongs to the technical field of water treatment, and relates to a device and a method for enhancing the capacitive deionization performance of a flowing electrode. The method is based on the traditional FCDI (FCDI), namely, a clean conductive material is used as a current collector substrate, and the method of electrodeposition, hydrothermal synthesis, a polytetrafluoroethylene bonding method, a chemical reduction method, an ion sputtering method, a high-temperature sintering method and a metal powder sintering method is adopted to load a catalyst on the current collector substrate, so that the electrochemical reaction of a positive electrode chamber and a negative electrode chamber is enhanced, the speed of moving anions to an anode and the speed of moving cations to a cathode are accelerated, the speed of separating ions from a solution is accelerated, the removal efficiency can be improved, and the energy consumption under unit removal amount is reduced to a certain extent.
Description
Technical Field
The invention belongs to the technical field of water treatment, and relates to a device and a method for enhancing the capacitive deionization performance of a flowing electrode.
Background
Water is an absolute necessity of human life, and it is therefore extremely important to have enough safe, clean water. With the growing population and the growing industrialization, the demand for fresh water has become one of the most important global challenges in the 21 st century. United nations 'education, science and cultural organizations estimate that nearly one third of the world's population currently lives in water-deficient areas, and this figure is expected to double by 2025. In order to meet the urgent demand of fresh water, various seawater desalination technologies have been developed, but widely used desalination technologies have great technical defects, such as large flash evaporation energy consumption, expensive regeneration technology required by ion exchange and reverse osmosis technology, and secondary pollution caused in the regeneration process; electrodialysis systems, although commercialized, consume a large amount of power due to the very high voltages used. Capacitive Deionization (CDI) is a water treatment technology that has received much attention in recent years.
The capacitive deionization technology is to apply an electrostatic field to the treated solution containing ions to separate the ions from water, thereby obtaining water with low ion content. When the water treatment technology adopts the flowing electrode liquid as an electrode, because fresh electrode materials are continuously supplied, the continuous adsorption of ions can be realized, and further, the purification of the brine and the wastewater containing high-concentration ions is realized, and the CDI technology is called as Flowing Capacitance Deionization (FCDI) technology.
Compared with the traditional water treatment technology, the flow capacitance deionization technology has the advantages of low energy consumption, high water utilization rate, simple operation and the like. The technology can be used in the fields of seawater desalination, hard water softening, precious metal enrichment, high-purity water preparation and the like.
The existing flow capacitance deionization technology has the following problems: the migration speed of anions and cations in the water treatment chamber to the anode chamber and the cathode chamber respectively is slow, so that the ions can not be separated from the solution quickly. In order to solve the problems, a device and a method for enhancing the capacitive deionization performance of the flow electrode are provided.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a device and a method for enhancing the capacitive deionization performance of a flowing electrode.
In order to realize the purpose, the invention adopts the following technical scheme:
a current collector for a device for enhancing the capacitive deionization performance of a flowing electrode is a current collector loaded with a catalyst.
The current collector for the device for enhancing the capacitive deionization performance of the current collector is characterized in that the unit area load capacity of the current collector loaded catalyst is 0.05-200 mg/cm2。
The current collector for the device for enhancing the capacitive deionization performance of the flowing electrode is prepared from one or more of metal hydrochlorides, nitrates, sulfates, carbonates and acetates of nickel, cobalt, manganese, copper, iron, tungsten and molybdenum.
The current collector for the device for enhancing the capacitive deionization performance of the current collector comprises pure metals or alloys of titanium, nickel, copper, iron, aluminum, silver and lead, stainless steel, carbon cloth, a graphite plate and graphite paper.
The method for loading the catalyst on the current collector comprises the following steps: electrodeposition, hydrothermal synthesis, polytetrafluoroethylene bonding, chemical reduction, ion sputtering, high-temperature sintering, or metal powder sintering.
The method for loading the catalyst on the current collector comprises the following steps: (1) pretreatment:
performing ultrasonic treatment on a current collector substrate for 3-60min by using 0.1-5mol/L hydrochloric acid aqueous solution, performing ultrasonic treatment on acetone, ethanol and deionized water for 10-60min respectively, and drying at 25-100 ℃ for 3-24h for later use;
(2) preparing a solution:
dissolving one or more of metal hydrochloride, nitrate, sulfate, carbonate or acetate of nickel, cobalt, manganese, copper, iron, tungsten and molybdenum in deionized water to form a single or mixed metal salt solution 1 with metal ion concentration of 0.01-1 mol/L; (3) loading of the catalyst:
(electrodeposition method) the solution 1 in the step (2) and the clean current collector substrate in the step (1) are subjected to current density of 0.5-10A/dm2Carrying out catalyst loading by electrodeposition for 3-100min under constant current or constant voltage of 0.5-10V; or
(hydrothermal synthesis method) transferring the solution 1 in the step (2) and the clean current collector substrate in the step (1) into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting for 5-24 hours at 80-200 ℃ in an oven by using the hydrothermal synthesis method;
(4) cleaning and drying:
taking out the current collector loaded in the step (3), repeatedly washing the current collector with deionized water for 3-5 times, and drying the current collector at the temperature of 60-100 ℃ for 3-24 hours to obtain the anode current collector loaded with the catalyst, wherein the unit area load capacity of the catalyst is 0.05-200 mg/cm2；
(5) Preparing a cathode current collector:
repeating the steps (1) to (4) to obtain the cathode current collector loaded with the catalyst, wherein the unit area load capacity of the catalyst is 0.05-200 mg/cm2。
A device for enhancing the capacitive deionization performance of a flowing electrode comprises a water treatment chamber, a cation exchange membrane, an anion exchange membrane, a flowing electrode chamber, an anode current collector, a cathode current collector and an end plate; the anode current collector is the current collector described above, or the cathode current collector is the current collector described above, or both the cathode current collector and the anode current collector are the current collectors described above.
A method for enhancing the capacitive deionization performance of a flowing electrode is to load a current collector of an FCDI device with a catalyst.
The method for enhancing the capacitive deionization performance of the flow electrode is characterized in that a catalyst is loaded on an anode current collector, or a catalyst is loaded on a cathode current collector, or a catalyst is loaded on both anode and cathode current collectors.
The method for enhancing the capacitive deionization performance of the flow electrode and the method for loading the catalyst on the current collector are as described above.
The method for enhancing the capacitive deionization performance of the flow electrode comprises the steps of loading a catalyst on a current collector of the FCDI device, and then using an active carbon solution with a flow electrode of 1-200g/L under a constant voltage of 1-10V or a current density of 0.1-50A/m2The solution in the water treatment chamber is purified under constant flow.
The invention has the beneficial effects that:
aiming at the problem of low ion migration speed in the traditional FCDI technology, the invention provides a method for improving the electrochemical reaction of an anode chamber and a cathode chamber by loading a catalyst on a current collector on the basis of the traditional FCDI technology, so that the moving speed of anions to an anode and the moving speed of cations to a cathode are increased, the separation speed of ions from a solution is increased, the removal efficiency can be improved, and the energy consumption under the unit removal amount is reduced to a certain extent.
Drawings
FIG. 1 is a schematic illustration of the FCDI unit architecture; in the figure, the large arrow indicates the water flow direction, and the small arrow indicates the ion moving direction; 10. a water treatment chamber, 11a cation exchange membrane, 11b anion exchange membrane, 12 flowing electrode chamber, 13a cathode current collector, 13b anode current collector, 14 end plate;
FIG. 2 shows the nickel foam of example 1As current collector base map, a.nf11，b.NF12；
Fig. 3 is a schematic diagram of energy consumption for the catalyst-supported current collector and the catalyst-unsupported current collector in example 1;
FIG. 4 is a view of a titanium plate as a current collector substrate in example 2; a.Ti11，b.Ti12；
Fig. 5 is a schematic energy consumption diagram of the catalyst-supported current collector and the catalyst-unsupported current collector in example 2;
FIG. 6 is a drawing of a current collector substrate made of a cloth in example 3, a. CC11，b.CC12；
Fig. 7 is a schematic energy consumption diagram of the catalyst-supported current collector and the catalyst-unsupported current collector in example 3;
fig. 8 is a schematic energy consumption diagram for the catalyst-supported and unsupported collectors of example 4;
fig. 9 is a schematic diagram of energy consumption of the catalyst-supported collector and the catalyst-unsupported collector in example 5.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way. The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
A device for enhancing the capacitive deionization performance of a flowing electrode comprises a water treatment chamber, a cation exchange membrane, an anion exchange membrane, a flowing electrode chamber, an anode current collector, a cathode current collector and an end plate; the anode current collector is a current collector for loading a catalyst, or the cathode current collector and the anode current collector are current collectors for loading a catalyst. The raw material used by the catalyst is one or more of metal hydrochloride, nitrate, sulfate, carbonate and acetate of nickel, cobalt, manganese, copper, iron, tungsten and molybdenum. The base of the current collector is made of pure metal or alloy of titanium, nickel, copper, iron, aluminum, silver and lead, stainless steel, carbon cloth, graphite plate or graphite paper. The method for loading the catalyst on the current collector is an electrodeposition method, a hydrothermal synthesis method, a polytetrafluoroethylene bonding method, a chemical reduction method, an ion sputtering method, a high-temperature sintering method or a metal powder sintering method.
The method for loading the catalyst is taken as an example of electro-deposition and hydrothermal synthesis, and comprises the following steps:
step A, pretreatment:
performing ultrasonic treatment on a current collector substrate for 3-60min by using 0.1-5mol/L hydrochloric acid aqueous solution, performing ultrasonic treatment on acetone, ethanol and deionized water for 10-60min respectively, and drying at 25-100 ℃ for 3-24h for later use;
step B, preparation of a solution:
dissolving one or more of metal hydrochloride, nitrate, sulfate, carbonate or acetate of nickel, cobalt, manganese, copper, iron, tungsten, molybdenum and the like in deionized water to form a single or mixed metal salt solution 1 with the metal ion concentration of 0.01-1 mol/L;
step C, loading of the catalyst:
(electrodeposition method) the solution 1 in step B and the clean current collector substrate in step A are subjected to current density of 0.5-10A/dm2Carrying out catalyst loading by electrodeposition for 3-100min under constant current or constant voltage of 0.5-10V; or
(hydrothermal synthesis) transferring the solution 1 in the step B and the clean current collector substrate in the step A into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting for 5-24h at 80-200 ℃ in an oven by using the hydrothermal synthesis;
step D, cleaning and drying:
taking out the current collector loaded in the step C, repeatedly washing the current collector with deionized water for 3-5 times, and drying the current collector at the temperature of 60-100 ℃ for 3-24 hours to obtain the anode current collector loaded with the catalyst, wherein the unit area load capacity is 0.05-200 mg/cm2；
Step E, preparing a cathode current collector:
repeating the steps A-D to obtain a cathode current collector loaded with a catalyst, wherein the unit area load capacity is 0.05-200 mg/cm2。
A method for enhancing the capacitive deionization performance of a flowing electrode, which comprisesThe method comprises loading catalyst on anode current collector of FCDI device, or loading catalyst on cathode current collector, or loading catalyst on both cathode and anode current collectors, and loading catalyst in the same way, and treating with 1-200g/L active carbon solution at constant voltage of 1-10V or current density of 0.1-50A/m2The solution in the water treatment chamber is purified under constant flow.
Example 1
A device for enhancing the capacitive deionization performance of a flowing electrode comprises a water treatment chamber, a cation exchange membrane, an anion exchange membrane, a flowing electrode chamber, an anode current collector, a cathode current collector and an end plate; the current collectors of the cathode and the anode are both current collectors loaded with catalysts, the anode current collector loaded with catalysts is made of ferric nitrate and nickel nitrate, the cathode current collector loaded with catalysts is made of nickel nitrate and cobalt nitrate, and the current collector substrate is foamed nickel.
The method for loading the catalyst comprises the following steps:
(1) carrying out ultrasonic treatment on foamed nickel serving as a current collector substrate for 5min by using 1.0mol/L hydrochloric acid aqueous solution, respectively carrying out ultrasonic treatment on acetone, ethanol and deionized water for 15min, and drying at 60 ℃ for 6h for later use, wherein the mark is NF 0;
(2) dissolving ferric nitrate and nickel nitrate into 90mL of deionized water in sequence, wherein Fe and Ni are 2:1, and forming a mixed solution 1 with the metal ion concentration of 0.8 mol/L;
(3) transferring the solution 1 in the step (2) and the clean foamed nickel in the step (1) into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting for 16h at 120 ℃ in an oven by using a hydrothermal synthesis method;
(4) taking out the current collector loaded in the step (3), repeatedly washing the current collector with deionized water for 3-5 times, and drying the current collector at 60 ℃ for 12 hours to obtain the anode current collector NF1 loaded with the catalyst1The unit area load is 180mg/cm2；
(5) Repeating the steps (1) to (4), and replacing the metal salt in the step (2) with nickel nitrate and cobalt nitrate to obtain the catalyst-supported cathode current collector NF12The unit area load is 180mg/cm2；
(6) The catalyst-supporting current collector obtained by the steps (1) to (5).
The method for enhancing the capacitive deionization performance of the flowing electrode is characterized in that catalysts are loaded on the current collectors of the cathode and the anode of the FCDI device, and the method for loading the catalysts is the same as the method for loading the catalysts.
Comparative experimental example: the end plate and the current collector NF1 are sequentially connected by a screw and a nut2A flowing electrode chamber, a cation exchange membrane, a water treatment chamber, an anion exchange membrane, a flowing electrode chamber and a current collector NF11Assembling the end plate, performing circulating treatment on 100mL of a NaCl aqueous solution with the concentration of 1.0g/L under the condition of 2.0V voltage by using 10g/L of an activated carbon solution as a flowing electrode, testing at room temperature, and performing the experiment for 100min, wherein the salt concentration is 0.497g/L, and the salt concentration is reduced to 0.590g/L and the removal rate is obviously improved by using pure foam nickel without a catalyst as a current collector; also, as can be seen in fig. 3, the energy consumption is much lower than for the unsupported catalyst collector test procedure.
Example 2
A device for enhancing the deionization performance of a flowing electrode capacitor comprises a water treatment chamber, a cation exchange membrane, an anion exchange membrane, a flowing electrode chamber, an anode current collector, a cathode current collector and an end plate; the current collectors of the cathode and the anode are both current collectors loaded with catalysts, the anode current collector loaded with catalysts is made of ferric nitrate and nickel nitrate, the cathode current collector loaded with catalysts is made of nickel nitrate and cobalt nitrate, and the current collector substrate is a titanium plate.
The method for loading the catalyst comprises the following steps:
(1) carrying out ultrasonic treatment on a titanium plate serving as a current collector substrate for 5min by using 1.0mol/L hydrochloric acid aqueous solution, respectively carrying out ultrasonic treatment on acetone, ethanol and deionized water for 15min, and drying at 60 ℃ for 6h for later use, wherein the mark is Ti 0;
(2) dissolving ferric nitrate and nickel nitrate into 500mL of deionized water in sequence, wherein Fe and Ni are 2:1 to form a mixed solution 1 with the metal ion concentration of 0.3 mol/L;
(3) at a constant current of 1.0A/dm2Next, the clean current collector substrate in step (1) is subjected to electrodeposition in solution 160min；
(4) Taking out the current collector loaded in the step (3), repeatedly washing the current collector with deionized water for 3-5 times, and drying the current collector at 60 ℃ for 12 hours to obtain the anode current collector Ti1 loaded with the catalyst1The unit area load is 55mg/cm2；
(5) Repeating the steps (1) to (4), and replacing the ferric nitrate in the step (2) with cobalt nitrate to obtain the cathode current collector Ti1 of the supported catalyst2The unit area load is 55mg/cm2；
(6) The catalyst-supporting current collector obtained by the steps (1) to (5).
The method for enhancing the capacitive deionization performance of the flowing electrode is characterized in that catalysts are loaded on the current collectors of the cathode and the anode of the FCDI device, and the method for loading the catalysts is the same as the method for loading the catalysts.
Comparative experimental example: the end plate and the current collector Ti1 are sequentially butted by a screw and a nut2A flowing electrode chamber, a cation exchange membrane, a water treatment chamber, an anion exchange membrane, a flowing electrode chamber and a current collector Ti11The end plates were assembled and 10g/L of activated carbon solution was used as the flow electrode at 9.27A/m2Under the current density condition, 100mL of NaCl aqueous solution with the concentration of 1.0g/L is subjected to cyclic treatment, the room temperature test shows that after the cyclic treatment is carried out for 60min, the salt concentration is reduced to 0.615g/L, the removal rate of the salt solution is close to 40%, and when the cyclic treatment is carried out for 100min, the salt concentration is reduced to 0.356g/L, and the removal rate can reach 65%. When the pure titanium current collector without the supported catalyst is tested, the salt concentration is only reduced to 0.803g/L and the removal rate is only 20% in 100min, so that the removal efficiency of the current collector with the supported catalyst is obviously improved in the same time by modifying the current collector, and the energy consumption of the current collector with the supported catalyst is reduced compared with the current collector without the supported catalyst as can be seen from the graph 5.
Example 3
A device for enhancing the capacitive deionization performance of a flowing electrode comprises a water treatment chamber, a cation exchange membrane, an anion exchange membrane, a flowing electrode chamber, an anode current collector, a cathode current collector and an end plate; the current collectors of the cathode and the anode are both current collectors loaded with catalysts, the anode current collector loaded with catalysts is made of copper nitrate and cobalt nitrate, the cathode current collector loaded with catalysts is made of nickel nitrate and cobalt nitrate, and the current collector substrate is carbon cloth.
The method for loading the catalyst comprises the following steps:
(1) carrying out ultrasonic treatment on carbon cloth serving as a current collector substrate by using 1.0mol/L hydrochloric acid aqueous solution for 5min, respectively carrying out ultrasonic treatment on acetone, ethanol and deionized water for 15min, drying for 6h at 60 ℃, and keeping the carbon cloth for later use as CC 0;
(2) sequentially dissolving copper nitrate and cobalt nitrate in 500mL of deionized water, wherein Cu: co 1: 1, forming a mixed solution 1 with the metal ion concentration of 0.1 mol/L;
(3) at a constant current of 2.0A/dm2Next, performing electrodeposition on the clean current collector substrate in the step (1) in the solution 1 for 10 min;
(4) taking out the current collector loaded in the step 3, repeatedly washing the current collector with deionized water for 3-5 times, and drying the current collector at 60 ℃ for 12 hours to obtain the anode current collector CC1 loaded with the catalyst1The unit area load is 0.1mg/cm2；
(5) Repeating the steps (1) to (4), and replacing the copper nitrate in the step (2) with nickel nitrate to obtain a cathode current collector CC1 of the supported catalyst2The unit area load is 0.1mg/cm2；
(6) The catalyst-supporting current collector obtained by the steps (1) to (5).
The method for enhancing the capacitive deionization performance of the flowing electrode is characterized in that catalysts are loaded on the current collectors of the cathode and the anode of the FCDI device, and the method for loading the catalysts is the same as the method for loading the catalysts.
Comparative experimental example: the end plate and the current collector CC1 are sequentially butted by screws and nuts2A flow electrode chamber, a cation exchange membrane, a water treatment chamber, an anion exchange membrane, a flow electrode chamber, a current collector CC11The end plate is assembled, 100mL of NaCl aqueous solution with the concentration of 1.0g/L is circularly treated under the voltage condition of 1.8V by using 10g/L of activated carbon solution as a flowing electrode, and the salt concentration is reduced to 0.532g/L after 100min circular treatment according to the test result at room temperatureWhen the pure carbon cloth without the supported catalyst is tested, the salt concentration is reduced to 0.681g/L, the desalting effect of the supported catalyst is better, and as can be seen from the graph in FIG. 7, the energy consumption of the current collector loaded with the catalyst is much lower than that of the current collector without the supported catalyst while the removal efficiency is improved.
Example 4
A device for enhancing the capacitive deionization performance of a flowing electrode comprises a water treatment chamber, a cation exchange membrane, an anion exchange membrane, a flowing electrode chamber, an anode current collector, a cathode current collector and an end plate; the anode current collector is a current collector for loading a catalyst, the used raw materials are ferric nitrate and nickel nitrate, and the current collector substrate is a titanium plate.
The method for loading the catalyst comprises the following steps:
(1) carrying out ultrasonic treatment on a titanium plate serving as a current collector substrate for 5min by using 1.0mol/L hydrochloric acid aqueous solution, respectively carrying out ultrasonic treatment on acetone, ethanol and deionized water for 15min, and drying at 60 ℃ for 6h for later use, wherein the mark is Ti 0;
(2) dissolving ferric nitrate and nickel nitrate into 500mL of deionized water in sequence, wherein Fe and Ni are 2:1 to form a mixed solution 1 with the metal ion concentration of 0.3 mol/L;
(3) electrodepositing the clean current collector substrate in step (1) in solution 1 at a constant voltage of 7V for 30 min;
(4) taking out the current collector loaded in the step (3), repeatedly washing the current collector with deionized water for 3-5 times, and drying the current collector at 60 ℃ for 12 hours to obtain the anode current collector Ti1 loaded with the catalyst1The unit area load is 35mg/cm2；
(5) Directly using Ti0 in the step (1) as a cathode current collector;
(6) the catalyst-supporting current collector obtained by the steps (1) to (5).
A method for enhancing the capacitive deionization performance of a flowing electrode is to load a catalyst on an anode current collector of an FCDI device, and the method for loading the catalyst is the same as the method for enhancing the capacitive deionization performance of the flowing electrode.
Comparative experimental example: the end plate, the current collector Ti0, the flowing electrode chamber, the cation exchange membrane, the water treatment chamber, the anion exchange membrane and the flow are sequentially connected by a screw and a nutMoving electrode chamber and current collector Ti11The end plates were assembled and 10g/L of activated carbon solution was used as the flow electrode at 9.27A/m2Under the current density condition of (3), the concentration of Na to 100mL is 1.0g/L2SO4The water solution is circularly treated, and the test result at room temperature shows that when the treatment is carried out for 100min, the salt concentration is reduced to 0.606g/L, and the removal rate can reach 40%. When the pure titanium current collector without the supported catalyst is tested, the salt concentration is only reduced to 0.831g/L and the removal rate is only 17 percent when the pure titanium current collector is subjected to 100 min. It can be seen that the removal efficiency is improved by modifying the current collector, and it can be seen from fig. 8 that the energy consumption of the current collector loaded with the catalyst is reduced compared with the current collector not loaded with the catalyst.
Example 5
A device for enhancing the capacitive deionization performance of a flowing electrode comprises a water treatment chamber, a cation exchange membrane, an anion exchange membrane, a flowing electrode chamber, an anode current collector, a cathode current collector and an end plate; the cathode current collector is a current collector for loading a catalyst, the used raw materials are nickel nitrate and cobalt nitrate, and the current collector substrate is a titanium plate.
The method for loading the catalyst comprises the following steps:
(1) carrying out ultrasonic treatment on a titanium plate serving as a current collector substrate for 5min by using 1.0mol/L hydrochloric acid aqueous solution, respectively carrying out ultrasonic treatment on acetone, ethanol and deionized water for 15min, and drying at 60 ℃ for 6h for later use, wherein the mark is Ti 0;
(2) sequentially dissolving cobalt nitrate and nickel nitrate into 500mL of deionized water, wherein the ratio of Co to Ni is 2:1, and forming a mixed solution 1 with the metal ion concentration of 0.3 mol/L;
(3) performing electrodeposition on the clean current collector substrate in the step (1) in the solution 1 for 90min at a constant voltage of 5V;
(4) taking out the current collector loaded in the step (3), repeatedly washing the current collector with deionized water for 3-5 times, and drying the current collector at 60 ℃ for 12 hours to obtain the anode current collector Ti1 loaded with the catalyst2The unit area load is 65mg/cm2；
(5) Directly using Ti0 in the step (1) as an anode current collector;
(6) the catalyst-supporting current collector obtained by the steps (1) to (5).
A method for enhancing the capacitive deionization performance of a flowing electrode is to load a catalyst on a cathode current collector of an FCDI device, and the method for loading the catalyst is the same as the method for loading the catalyst.
Comparative experimental example: the end plate and the current collector Ti1 are sequentially butted by a screw and a nut2The flow electrode chamber, the cation exchange membrane, the water treatment chamber, the anion exchange membrane, the flow electrode chamber, the current collector Ti0 and the end plate are assembled, and 10g/L of activated carbon solution is used as the flow electrode at the rate of 9.27A/m2For 100mL of CaCl with a concentration of 0.5g/L2The water solution is circularly treated, and the test result at room temperature shows that when the treatment is carried out for 100min, the salt concentration is reduced to 0.204g/L, and the removal rate can reach 60 percent. And when the pure titanium without the supported catalyst is used as a current collector to be tested, the salt concentration is only reduced to 0.410g/L and the removal rate is only 18 percent when the test is carried out for 100 min. It can be seen that the removal efficiency is improved by modifying the current collector, and it can be seen from fig. 9 that the energy consumption of the current collector loaded with the catalyst is reduced compared to the current collector not loaded with the catalyst.
It will be apparent to those skilled in the art from this disclosure that many changes and modifications can be made, or equivalents modified, in the embodiments of the invention without departing from the scope of the invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention shall still fall within the protection scope of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.
Claims (3)
1. A device for enhancing the deionization performance of a flowing electrode capacitor comprises a water treatment chamber, a cation exchange membrane, an anion exchange membrane, a flowing electrode chamber, an anode current collector, a cathode current collector and an end plate, and is characterized in that the anode current collector is a current collector loaded with a catalyst, or the cathode current collector is a current collector loaded with a catalyst, or the current collectors of the anode and the cathode are current collectors loaded with a catalyst;
the raw materials used by the catalyst are one or more of metal hydrochloride, nitrate, sulfate, carbonate and acetate of nickel, cobalt, manganese, copper, iron, tungsten and molybdenum;
the method for loading the catalyst on the current collector comprises the following steps: electrodeposition, hydrothermal synthesis, polytetrafluoroethylene bonding, chemical reduction, ion sputtering, high-temperature sintering, or metal powder sintering;
the method for supporting the catalyst on the current collector comprises the following steps:
(1) pretreatment:
carrying out ultrasonic treatment on a current collector substrate for 3-60min by using 0.1-5mol/L hydrochloric acid aqueous solution, respectively carrying out ultrasonic treatment on acetone, ethanol and deionized water for 10-60min, and drying for 3-24h at 25-100 ℃ for later use;
(2) preparing a solution:
dissolving one or more of metal hydrochloride, nitrate, sulfate, carbonate or acetate of nickel, cobalt, manganese, copper, iron, tungsten and molybdenum in deionized water to form a single or mixed metal salt solution 1 with metal ion concentration of 0.01-1 mol/L;
(3) loading of the catalyst:
an electrodeposition method: subjecting the solution 1 in the step (2) and the clean current collector substrate in the step (1) to current density of 0.5-10A/dm2Carrying out catalyst loading by electrodeposition for 3-100min under constant current or constant voltage of 0.5-10V; or
Hydrothermal synthesis method: transferring the solution 1 in the step (2) and the clean current collector substrate in the step (1) into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting for 5-24 hours at 80-200 ℃ in an oven by using a hydrothermal synthesis method;
(4) cleaning and drying:
taking out the current collector loaded in the step (3), repeatedly washing the current collector with deionized water for 3-5 times, and drying the current collector at the temperature of 60-100 ℃ for 3-24 hours to obtain the anode current collector loaded with the catalyst, wherein the unit area load capacity of the catalyst is 0.05-200 mg/cm2；
(5) Preparing a cathode current collector:
repeating the steps (1) to (4) to obtain the catalyst-loaded catalystThe unit area load of the catalyst of the cathode current collector is 0.05-200 mg/cm2。
2. The device for enhancing capacitive deionization of current electrodes according to claim 1, wherein the loading amount per unit area of the current collector supported catalyst is 0.05-200 mg/cm2。
3. A method for enhancing the capacitive deionization performance of a flowing electrode, which comprises using the device of any one of claims 1 to 2, and using a flowing electrode which is a 1-200g/L activated carbon solution, at a constant voltage of 1-10V or at a current density of 0.1-50A/m2The solution in the water treatment chamber is purified under constant flow.
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| WO2010069065A1 (en) * | 2008-12-18 | 2010-06-24 | Enpar Technologies Inc. | Capacitive deionization cell with radial flow |
| CN102208652A (en) * | 2010-08-31 | 2011-10-05 | 中国科学院上海硅酸盐研究所 | Air electrode for lithium air battery and preparation method thereof |
| CN104437675A (en) * | 2013-09-24 | 2015-03-25 | 韩国能源研究技术研究所 | Ion exchange membrane for flow-electrode capacitive deionization device and flow-electrode capacitive deionization device including the same |
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| WO2010069065A1 (en) * | 2008-12-18 | 2010-06-24 | Enpar Technologies Inc. | Capacitive deionization cell with radial flow |
| CN102208652A (en) * | 2010-08-31 | 2011-10-05 | 中国科学院上海硅酸盐研究所 | Air electrode for lithium air battery and preparation method thereof |
| CN104437675A (en) * | 2013-09-24 | 2015-03-25 | 韩国能源研究技术研究所 | Ion exchange membrane for flow-electrode capacitive deionization device and flow-electrode capacitive deionization device including the same |
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