CN114835211A - Imprinted capacitive deionization electrode tablet and preparation method and application thereof - Google Patents
Imprinted capacitive deionization electrode tablet and preparation method and application thereof Download PDFInfo
- Publication number
- CN114835211A CN114835211A CN202210522757.1A CN202210522757A CN114835211A CN 114835211 A CN114835211 A CN 114835211A CN 202210522757 A CN202210522757 A CN 202210522757A CN 114835211 A CN114835211 A CN 114835211A
- Authority
- CN
- China
- Prior art keywords
- imprinted
- capacitive deionization
- preparing
- electrode
- deionization electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to an imprinted capacitive deionization electrode tablet and a preparation method and application thereof. The imprinted capacitive deionization electrode tablet is synthesized by a cross-linking method by taking dibenzo-14-crown-4 as a capture agent and pyrrole as a conductive agent. The electrode pressing sheet is prepared by preparing an ion imprinted polymer by using dibenzo-14-crown-4 and a multi-wall carbon nano tube, and then preparing the electrode pressing sheet by using pyrrole, the ion imprinted polymer and a conductive agent. The invention synthesizes a novel imprinted capacitive deionization electrode by combining the ion imprinting and capacitive deionization technologies, and realizes the Li in an acid solution through the synergistic effect of electric field driving and crown ether selective recognition + Good separation of ions. The invention has the potential to develop into Li in an acid environment + Excellent materials and methods for ion recovery.
Description
Technical Field
The invention belongs to the technical field of surface functional modification and application of carbon materials, and particularly relates to an imprinted capacitive deionization electrode tablet applied to lithium extraction in an acidic environment, and a preparation method and application thereof.
Background
The surface ion imprinting technology can accurately identify target ions, namely in Li + In the imprinting process, crown ether is generally adopted as a recognition unit, and Li is specifically recognized and captured through size screening and chelating capacity of a crown ether ring + . However, the traditional imprinted molecules are easily protonated in an acidic environment, high-concentration H & lt + & gt destroys the structural stability of the separating agent, weakens the selective recognition capability of the separating agent, and causes low grafting rate of internal sites of the acting group carrier and low adsorption capacity.
Therefore, the capacitance deionization technology emerging in recent years can solve the problem of adsorption capacity well, but has low selectivity and can adsorb all ions with opposite charges. There is currently no technique to link the two together. Therefore, the above-mentioned two challenges of extracting lithium from an acidic system can be overcome by combining the surface imprinting technology and the capacitive deionization technology in the present invention, and both selectivity and adsorption capacity can be achieved.
Disclosure of Invention
In order to solve the technical problems, the invention provides a blotting type capacitive deionization electrode pressing sheet applied to extracting lithium in an acidic environment, wherein the blotting type capacitive deionization electrode pressing sheet is synthesized by cross-linking reaction by using dibenzo-14-crown-4, pyrrole and a multi-wall carbon nano tube as raw materials; in the electrode tablet, dibenzo-14-crown-4 is Li + Trapping agent, pyrrole and multi-walled carbon nanotube being Li + A conductive agent.
The trace type capacitive deionization electrode pressing sheet material is also added with ferric chloride, polyvinylidene fluoride (PVDF) and conductive graphite, and the preparation method comprises the following specific steps:
s1, preparing an ion imprinted polymer by using dibenzo-14-crown-4 and a multi-wall carbon nanotube;
s2, preparing imprinted capacitive deionization copolymer by using pyrrole, ion imprinted polymer and ferric chloride solution, uniformly mixing the ion imprinted polymer, polyvinylidene fluoride (PVDF) and conductive graphite, and tabletting to obtain the electrode tablet.
Preferably, the S1 specifically includes:
s11, dispersing the multi-walled carbon nano-tubes in hydrochloric acid, carrying out ultrasonic treatment to obtain a mixed solution, stirring the mixed solution in a water bath for 24 hours, filtering, washing to be neutral, and finally drying to obtain the multi-walled carbon nano-tubes without metal oxides on the surfaces;
s12, mixing methanol and N, N-dimethylformamide according to a volume ratio of 1:2, sequentially adding dibenzo-14-crown-4, lithium nitrate and alpha-methacrylic acid, and stirring to obtain a mixed solution;
s13, adding the multi-walled carbon nanotube in the S11 into the mixed solution of the S12, carrying out ultrasonic treatment for 5min, adding azobisisobutyronitrile and ethylene glycol dimethacrylate into the mixed solution after ultrasonic treatment in a nitrogen atmosphere lasting for 15min, and carrying out reflux stirring for 12h to obtain a crude product;
s14, washing the crude product to be neutral by using anhydrous methanol and ultrapure water in sequence, and drying to obtain the ion imprinted polymer.
Preferably, the S2 specifically includes:
s21, adding the ion imprinted polymer into absolute ethyl alcohol, continuously dropwise adding a pyrrole and ferric chloride solution after ultrasonic treatment, and performing ultrasonic treatment for the second time to obtain a uniform solution;
s22, standing the uniform solution under an ice bath condition for a reaction, washing a product after the reaction with nitric acid, and drying to obtain the imprinted capacitive deionization copolymer;
s23, uniformly mixing the imprinted capacitive deionization copolymer, polyvinylidene fluoride and conductive graphite according to the mass ratio of 8:1:1, and tabletting under the set temperature and pressure conditions to obtain the imprinted capacitive deionization electrode tablet.
Preferably, in step S11, the ratio of the multi-walled carbon nanotubes to the hydrochloric acid is 1g:100mL, the concentration of hydrochloric acid is 2mol/L, the ultrasonic treatment time is 5min, the water bath stirring temperature is 25 ℃, the drying condition is 100 ℃ and the vacuum degree is 0.05MPa, and the drying is carried out for 6 h.
Preferably, in the step S12, the ratio of methanol to N, N-dimethylformamide to dibenzo-14-crown-4 to lithium nitrate to alpha-methacrylic acid is 20mL to 40mL to 0.3g to 0.0689g to 0.17 mL.
Preferably, in the step S13, the reflux temperature is 70 ℃; in step S14, the drying is performed for 12 hours under the conditions of 70 ℃ and 0.05MPa of vacuum degree.
Preferably, in the step S21, the pyrrole, the ion imprinted polymer, the ferric chloride solution and the absolute ethyl alcohol are used in a ratio of 0.6mol:0.5g:15.15mL:25 mL; the concentration of the ferric chloride solution is 1 mol/L.
Preferably, in step S21, the ultrasound time is 5 min; in step S22, the ice-bath time is 12h, and the drying condition is 100 ℃ and 0.05MPa vacuum degree, and the drying is carried out for 6 h.
Preferably, in step S23, the temperature and pressure conditions are set to be 40 ℃ and 10MPa for 5min.
The invention also provides an imprinting type capacitive deionization device applying the imprinting type capacitive deionization electrode pressing sheet.
The assembling method of the device comprises the following steps: adhering a print type capacitive deionization electrode pressing sheet on a titanium sheet by conductive silver adhesive, drying and fixing, respectively inserting a carbon rod and the titanium sheet with the print type capacitive deionization electrode pressing sheet on two opposite sides of a capacitive deionization device, connecting the carbon rod to the anode of a direct-current power supply through a positive electrode wire, and connecting the titanium sheet with the print type capacitive deionization electrode pressing sheet to the cathode of the direct-current power supply through a negative electrode wire; and providing a set value of voltage and current by using the direct current power supply to obtain the imprinted capacitive deionization device.
Preferably, the voltage and the current of the set value are provided by the direct current power supply, the voltage is 0.4V, and the current is 0.01 mA.
The invention has the beneficial effects that:
the invention provides an imprinted capacitive deionization electrode tablet applied to acid environment lithium extraction, aiming at the problem that the lithium ion capture capacity of crown ether is weakened due to protonation of oxygen atoms on a crown ether ring in an acid system.
Crown ethers, as one type of ion imprinting, possess pore sizes that match the size of the cation diameter. Crown ether is coordinated with alkali metal ions to form a stable complex by virtue of a macrocyclic effect, and the adsorption of Li can be realized by adopting the crown ether-loaded adsorbent + Effectively adsorb. The capacitance deionization technology has simple operation, high adsorption capacity and easy regeneration. According to the invention, through the combination of the two, the high-selectivity and high-capacity adsorption of lithium ions is realized in an acidic complex multi-element solution system.
The Imprinting Capacitance Deionization (ICDI) is synthesized by a cross-linking method by taking dibenzo-14-crown-4 (DB14C4) as a capture agent and pyrrole as a conductive agent. The proton resistance of the adsorbent in an acidic environment is improved, and the selective recognition capability of the adsorbent to lithium ions under the interference of impurity ions is enhanced.
After the electrode pressing sheet provided by the invention is subjected to a repeatability experiment, the adsorption capacity is almost kept unchanged after five times of circulation. The electrode tablet is adsorbed in an acidic environment under the auxiliary action of electric field driving, and has remarkable improvement compared with the adsorption under the conventional alkaline and neutral conditions. The lithium extraction method is an advanced imprinting type capacitive deionization method which can be applied to the lithium extraction in the acidic environment.
Drawings
FIG. 1 is a schematic view of an apparatus for preparing electrode pellets according to the present invention;
FIG. 2 shows Li prepared by the present invention + -NCDI、Li + -ICDI、Li + -field emission scanning electron microscopy of N/ICDI;
FIG. 3 shows Li prepared by the present invention + -NCDI、Li + -ICDI、Li + -FTIR profile of N/ICDI;
FIG. 4A shows Li prepared by the present invention + -NCDI、Li + -ICDI、Li + Aspiration of N/ICDIDesorption curve, fig. 4B is its aperture distribution diagram;
FIGS. 5A and 5B are Li prepared by the present invention + -XPS spectra of ICDI in operating and open potential;
FIGS. 6A-6C are Li prepared by the present invention + -NCDI、Li + -ICDI、Li + Adsorption kinetics of N/ICDI;
FIGS. 7A-7C are Li prepared by the present invention + -NCDI、Li + -ICDI、Li + -adsorption isotherm of N/ICDI;
FIG. 8 shows Li prepared by the present invention + -NCDI、Li + -ICDI、Li + -graph of adsorption selectivity versus different ions for N/ICDI;
FIG. 9 shows a imprinted capacitive deionization electrode material Li prepared by the present invention + -NCDI、Li + -ICDI、Li + -effect of weight loss of N/ICDI as a function of pH;
FIG. 10 is the cyclic adsorption regeneration curves of the imprinted capacitive deionization electrode materials Li + -NCDI, Li + -ICDI and Li + -N/ICDI prepared by the present invention.
Detailed Description
The technical solution of the present invention is described in more detail with reference to the following embodiments.
Deionized water as used herein, unless otherwise specified: liquid with purity of 99.99%; catechol: solid, purity 99%; α -methacrylic acid: the purity is 98 percent; n, N-dimethylformamide: purity 99.8%, lithium hydroxide monohydrate: the purity is 98 percent; multi-walled carbon nanotubes: solid solids, 99.99%; KOH: purity 98%, solid; dimethyl sulfoxide: liquid with purity of 99.95%; methanol: anhydrous methanol, liquid, 99.50%; ethanol: absolute ethyl alcohol, liquid, 99.50%; ethylene glycol dimethacrylate: liquid with purity of 98%; pyrrole: liquid with purity of 98%; dibromopropane: liquid with purity of 98%.
Example 1
An imprinted capacitive deionization electrode tablet for extracting lithium in an acidic environment is synthesized by a cross-linking method by using dibenzo-14-crown-4 as a capture agent and pyrrole as a conductive agent.
The preparation method of the deionization electrode tablet comprises the following steps:
1. the synthesis of dibenzo-14-crown-4, described in the literature:
1.1, sequentially dissolving catechol, lithium hydroxide and 1, 3-dibromopropane in dimethyl sulfoxide according to the proportion of 5.5g to 4.4g to 5.3mL to 30mL, and carrying out ultrasonic treatment to form uniform slurry;
1.2 filtering the slurry to obtain a filter cake, and washing the filter cake by sodium hydroxide and deionized water with the mass concentration of 0.1mol/L respectively;
1.3 adding methanol for recrystallization, and drying after the reaction is finished to obtain dibenzo-14-crown-4; in the step, the drying temperature is 60 ℃, the vacuum degree is 0.05MPa, and the drying time is 12 h.
2. Preparation of ion imprinted polymer:
2.1 dispersing the multi-walled carbon nano-tube in hydrochloric acid, carrying out ultrasonic treatment for 5min to obtain a mixed solution, stirring the mixed solution in water bath (25 ℃) for 24h, filtering, washing to be neutral, and finally drying to obtain the multi-walled carbon nano-tube without metal oxide on the surface; in the step, the concentration of hydrochloric acid is 2mol/L, and the use ratio of the multi-wall carbon nano tube to the hydrochloric acid is 1g:100 mL; the drying temperature is 100 ℃, the vacuum degree is 0.05MPa, and the drying time is 6 h;
2.2 mixing methanol and N, N-dimethylformamide according to the volume ratio of 1:2, then sequentially adding dibenzo-14-crown-4, lithium nitrate and alpha-methacrylic acid, and stirring to obtain a mixed solution; the using ratio of the methanol, the N, N-dimethylformamide, the dibenzo-14-crown-4, the lithium nitrate and the alpha-methacrylic acid is 20mL to 40mL to 0.3g to 0.0689g to 0.17 mL;
2.3 adding the multi-walled carbon nanotube in the S11 into the mixed solution of the S12, carrying out ultrasonic treatment for 5min, adding azobisisobutyronitrile and ethylene glycol dimethacrylate into the mixed solution after ultrasonic treatment in a nitrogen atmosphere lasting for 15min, carrying out reflux stirring at the temperature of 70 ℃, and stirring for 12h to obtain a crude product;
s14, washing the crude product to be neutral by using methanol, nitric acid and ultrapure water in sequence, and drying to obtain the ion imprinted polymer. In the step, the drying temperature is 70 ℃, the vacuum degree is 0.05MPa, and the drying time is 12 h;
3. and preparing an electrode pressing sheet.
S21, adding the ion imprinted polymer into absolute ethyl alcohol, carrying out ultrasonic treatment for 5min, dropwise adding pyrrole and a conductive agent, namely an iron chloride solution, and carrying out ultrasonic treatment for 5min for the second time to obtain a uniform solution;
s22, standing the uniform solution for 12 hours under an ice bath condition, waiting for reaction, washing a product after the reaction with nitric acid, and drying to obtain an imprinted capacitive deionization copolymer; in the step, the drying temperature is 100 ℃, the vacuum degree is 0.05MPa, and the drying time is 6 h;
the pyrrole, the ion imprinted polymer, the ferric chloride solution and the absolute ethyl alcohol are used in a ratio of 0.6mol:0.5g:15.15mL:25 mL; the concentration of the ferric chloride solution is 1 mol/L.
S23, uniformly mixing the imprinted capacitive deionization copolymer, polyvinylidene fluoride and conductive graphite according to the mass ratio of 8:1:1, and maintaining the mixture for 5min at 40 ℃ and 10MPa by using a tablet press to obtain the imprinted capacitive deionization electrode tablet.
The prepared electrode pressing sheet can be stored in a brown glass container, so that the moisture resistance, the sun protection and the acid-base salt corrosion resistance of a storage space are ensured, the storage temperature is kept at 20 ℃, and the relative humidity is kept at 10%.
The imprinting type capacitive deionization device is obtained by utilizing the electrode pressing sheet, and specifically comprises the following steps: coating a print type capacitive deionization electrode pressing sheet on a titanium sheet, drying and fixing, respectively inserting a carbon rod and the titanium sheet with the print type capacitive deionization electrode pressing sheet on two opposite sides of a capacitive deionization device, connecting the carbon rod to the positive electrode of a direct-current power supply through a positive electrode wire, and connecting the titanium sheet with the print type capacitive deionization electrode pressing sheet to the negative electrode of the direct-current power supply through a negative electrode wire; and (3) providing a voltage (0.4V) and a current (0.01mA) with set values by using the direct current power supply to obtain the imprinting type capacitive deionization device.
Fig. 1 shows a schematic diagram of an assembled device, which has a cuboid electrolytic tank 10 for containing an acidic medium solution, a polytetrafluoroethylene magneton 11 is arranged at the bottom of the electrolytic tank 10, and a carbon rod 21 and a titanium sheet 22 with a printed trace type capacitive deionization electrode pressing sheet are immersed in the acidic solution. The direct current power supply 30 is provided with a power switch 31, a current adjusting knob 32 and a voltage adjusting knob 33, wherein the anode 41 of the power supply is connected with the carbon rod 21, and the cathode 42 of the power supply is connected with the titanium plate 22.
Example 2
Referring to the method of example 1, an imprinted capacitive deionization electrode pellet was prepared:
1. synthesis of dibenzo-14-crown-4:
1.1 weighing 5.5g of catechol and 4.4g of lithium hydroxide, dissolving in 30mL of dimethyl sulfoxide, dropwise adding 5.3mL of 1, 3-dibromopropane, and carrying out ultrasonic treatment for 3 hours to form uniform slurry;
1.2 filtering the slurry to obtain filter cakes, and washing the filter cakes by using sodium hydroxide and deionized water with the mass concentration of 0.1mol/L respectively;
1.3 adding methanol for recrystallization, filtering and washing after the reaction is finished, and drying a filter cake in a 60 ℃ oven to obtain the dibenzo-14-crown-4.
2. Preparation of ion imprinted polymer:
2.1 in order to eliminate the influence of residual metal oxides, dispersing 1g of multi-walled carbon nanotubes in 100mL of 2M hydrochloric acid, carrying out ultrasonic treatment for 15min to obtain a mixed solution, stirring the mixed solution in a water bath at 25 ℃ for 24h, filtering and washing the mixed solution to be neutral, and finally drying the mixed solution in a drying oven at 100 ℃ for 6h to obtain the multi-walled carbon nanotubes without the metal oxides on the surfaces;
2.2 weighing 0.3g of prepared dibenzo-14-crown-4, 0.0689g of lithium nitrate and 0.17mL of alpha-methacrylic acid, dissolving in a mixed solution of 20mL of methanol and 40mL of N, N-dimethylformamide, and stirring at room temperature for 30 min;
2.3, adding 0.5g of multi-walled carbon nano-tube in S11 into the mixed solution of S12, carrying out ultrasonic treatment for 5min, adding 12.5mg of azodiisobutyronitrile and 3.96g of ethylene glycol dimethacrylate into the mixed solution after ultrasonic treatment under the nitrogen atmosphere lasting for 15min, carrying out reflux stirring at the temperature of 70 ℃, and stirring for 12h to obtain a crude product;
2.4 the mixed solution reacts in a water bath at 70 ℃ for 12h, the product is filtered, washed to be neutral by methanol and ultrapure water in sequence, and dried in an oven at 70 ℃ for 12h to obtain the ion imprinted polymer.
3. Preparation of electrode pellets
3.1 adding 0.5g S2.4.4 of ion imprinted polymer into 25.0mL of absolute ethyl alcohol and carrying out ultrasonic treatment for 5min, adding a certain amount of deionized water and stirring for 30 min. Then 0.6mL of pyrrole was added dropwise to the solution, sonicated for 5min, and 15.15mL of 1mol/L ferric chloride solution was added dropwise. Reacting for 12 hours under the ice bath condition, washing with 1mol/L nitric acid to obtain a product, and drying the obtained product in a 70 ℃ oven for 6 hours to obtain an active ingredient;
3.2 mixing the active ingredients, polyvinylidene fluoride (PVDF) and conductive graphite uniformly according to the mass ratio of 8:1:1, and maintaining at 40 ℃ and 10MPa for 5min to obtain the imprinted capacitive deionization electrode tablet.
The electrode pressing sheet is pasted on the conductive material by utilizing conductive silver adhesive to obtain the lithium imprinting capacitance deionization electrode pressing sheet (Li) + -ICDI)。
With Li + -ICDI-1、Li + ICDI-2 is the electrode material for the open circuit potential and the working potential, respectively, then Li + ICDI-1 denotes adsorbed material, Li + ICDI-2 represents the desorbed material. Electrode pellets prepared in this application were examined, analyzed, and characterized, and as a material synthesized in a dispersion free of dibenzo-14-crown-4, Li + -NCDI, Material Li with a Dibenzo-14-crown-4 content in the Dispersion of 0.15g + ICDI, and Li, a material prepared with a dibenzo-14-crown-4 content of 0.15g in the dispersion + N/ICDI (i.e. the amount of different capture agents) as a comparison, the results are shown in FIGS. 2-9.
Li + -NCDI、Li + -ICDI、Li + The results of the field emission scanning electron microscopy of the-N/ICDI are shown in FIG. 2. From a in the figure, it can be observed that the connection between the multi-wall carbon nanotube MWCNT is more compact, a dense coating is formed between the MWCNT and the polypyrrole PPy, a part of the MWCNT is connected with each other to form a branched shape, and the coating between the MWCNT and PPy is probably caused by the interaction of pi bonds in the polymerization process.In the figures b and c it can be seen that a certain number of spherical PPy shapes are distributed in the structure, indicating the formation of a polymer of the material. The surface of the graph b is rougher, a petal-shaped polymer is formed, the structural change is caused by the introduction of DB14C4, the interchain connection is increased, and a large number of nanoscale fissured pores are distributed on the surface, so that the rapid transmission of lithium ions is facilitated.
Fourier transform infrared spectroscopy is used for analyzing whether DB14C4 is grafted to the imprinted capacitive deionization electrode or not, and Li < + > -NCDI and Li are detected + -ICDI-1、Li + -ICDI-1、Li + FTIR characterization of the groups present in the-N/ICDI and MWCNT is shown in FIG. 3. It can be seen that the characteristic spectrum of DB14C4 is also present on the imprinted capacitive deionization electrode, which indicates that Li + Formation of Li in ICDI + Indicating that the graphene oxide and the polypyrrole are successfully doped.
Evaluation of Li by BET N2 adsorption method + Surface area and porosity type of ICDI, results are shown in fig. 4. As can be seen in fig. 4A, all N2 adsorption curves can be described as type IV, H3 hysteresis loops, indicating the presence of mesoporous structures in the prepared material. Pore size distribution figure 4B shows that the pore size distribution is mainly distributed between 2.5 and 10nm, consistent with the SEM characterization. The mesopores can provide a large surface area to adsorb ions, shorten the ion diffusion path, and produce an electrode material with high removal rate and stable cycle capacity.
XPS analysis of Li + Surface composition of ICDI at operating and open potential, XPS spectrogram results are shown in fig. 5. From the broad survey scan of FIG. 5A, Li + The observation in ICDI of the element O at the working potential (O1s,532.79eV) and at the open potential (O1s,532.14eV) indicates that DB14C4 reacts with Li + An enhancement effect is formed in between. As shown in FIG. 5B, for Li present at the operating potential, indicating Li + ICDI adsorbs and desorbs it at the operating and open potentials, respectively.
Li + In Li + -ICDI、Li + -N/ICDI、Li + Adsorption behavior on NCDI over contact time, imprinted capacitive deionization kinetic adsorption profile see figure 6. As shown in FIG. 6A, Li + ICDI maintained high adsorption during the first 20minThe rate and the adsorption capacity finally tend to be stable in the time of approaching 2h, and Li at the moment can be obtained + The adsorption of ICDI reached a dynamic equilibrium with an adsorption of 91.36. mu. mol/g. Meanwhile, under the same conditions, Li can be obtained from FIGS. 6B and 6C + N/ICDI and Li + The adsorption capacities of NCDI were 98.89. mu. mol/g and 101.57. mu. mol/g, respectively, higher than Li + -an ICDI; this is probably due to the excellent conductivity of the-COOH functional groups and the carbon nanotubes, but the overall difference is not great, Li from the viewpoint of selective adsorption + ICDI still has advantages. The above adsorption capacity is derived from Li + ICDI angle analysis, probably because the crosslinker partially covers the functional groups during the material synthesis. Li + When adsorbed on the imprinting material, the inherent DB14C4 adsorption capacity of the material enables Li + Is sequestered. After 40min, with Li + The decrease in ion concentration results in an increase in diffusion resistance, resulting in a relatively slow adsorption process. Further, as shown in FIG. 6A, Li + The theoretical adsorption capacity of ICDI in the quasi-secondary model is 90.45. mu. mol/g, very close to the experimental value of 91.36. mu. mol/g. Therefore, the quasi-secondary kinetic model is more fit, and experimental data shows that the lithium ions are in Li + The adsorption process on ICDI is chemisorption.
FIG. 7 shows the isothermal adsorption profile of imprinted capacitive deionization electrode materials for evaluation of Li + Initial concentration vs. Li + -ICDI、Li + -N/ICDI、Li + Influence of NCDI adsorption, at pH 2 and 25 ℃ Li + The concentration is 40-700 mg/L, and the adsorption experiment is carried out for 2h, so that the electrode material can obviously adsorb Li + The adsorption capacity of (a) increases non-linearly with increasing concentration. Li is shown in FIG. 7A, FIG. 7B and FIG. 7C + -NCDI,Li + -ICDI and Li + The maximum adsorption capacities of N/ICDI were 2289.36. mu. mol/g, 2047.71. mu. mol/g and 2508.15. mu. mol/g, respectively. With Li + Comparison of-NCDI, Li + The N/ICDI showed better adsorption performance for lithium ions at the same initial concentration, which indicates that the surface imprinted sites improve the adsorption capacity of the adsorbent. Li + -NCDI adsorption capacity higher than Li + ICDI, possibly due to partial coverage of the surface of the carbon nanotubes with oxygen-containing functional groups,resulting in a reduction of its imprinted binding sites. From the 7A graph, it can be seen that the equilibrium adsorption capacity is gradually increased along with the increase of the equilibrium concentration, and the Langmuir model is more fit with the experimental data to indicate that the lithium ions are in Li + The adsorption process on ICDI is monolayer adsorption. This is also Li + ICDI electrode vs. Li in solution + Adsorption of ions is the main cause of chemisorption rather than physisorption.
Li prepared by the invention + -NCDI、Li + -ICDI、Li + The adsorption selectivity results for different ions for-N/ICDI are shown in FIG. 8. It can be seen from the figure that the ion imprinting capacitance deionization electrode Li prepared by the invention + The adsorption capacity of ICDI to lithium ion is obviously higher than that of other ions, namely the ICDI has the highest selective identification to lithium ion and has the highest selective identification to Na + ,Mg 2+ ，Al 3+ And K + Are selected to have separation factors of 6.16, 46.92, 65.81, 9.62, respectively.
The effect of material weight loss as a function of pH is shown in FIG. 9, where it can be seen that the material dissolution rate as a function of H + The decrease in concentration shows a tendency to decline. This is because the diffusion behavior of ions under the applied electric field generally causes uneven concentration distribution, and uneven concentration causes uneven deformation, which in turn causes diffusion-induced stress and hence dissolution loss of the material. In addition, corrosion of the material by the acid medium is also an important cause.
The cyclic adsorption regeneration curve of the imprinted capacitive deionization electrode material is shown in FIG. 10, from which Li can be seen + -ICDI electrode Material Pair Li + There was no significant decrease with increasing cycle time. The adsorption capacity decreased only about 3.82% after five cycles compared to the first adsorption capacity, indicating that Li + The imprinting sites can be effectively regenerated by electroelution under the potential of 1.0V, so that cyclic adsorption is realized.
From the series of test results, the invention synthesizes a novel imprinted capacitive deionization electrode (Li) by combining the ion imprinting and the capacitive deionization technology + ICDI), the adsorption capacity in the presence of an electric field is about 6 times that in the absence of an electric field. Driven by electric fieldSynergy of kinetic and crown ether selective recognition, indicating Li + ICDI achieves the effect on Li in acidic solution + Good separation of ions. And after 5 cycles, the adsorption capacity is only reduced by about 3.82%, which shows that the obtained electrode material has excellent regeneration capacity. Thus, the present invention provides Li + The potential development of ICDI as Li in acidic environments + Excellent materials and methods for ion recovery.
The above embodiments are only used to illustrate the technical solutions of the present invention, and do not limit the present invention; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that: any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (13)
1. The imprinting type capacitive deionization electrode pressing sheet is characterized by being synthesized by cross-linking reaction by taking dibenzo-14-crown-4, pyrrole and a multi-walled carbon nanotube as raw materials; in the electrode tablet, dibenzo-14-crown-4 is Li + Trapping agent, pyrrole and multi-walled carbon nanotube being Li + A conductive agent.
2. The preparation method of the imprinted capacitive deionization electrode sheet according to claim 1, wherein the imprinted capacitive deionization electrode sheet material is further added with ferric chloride, polyvinylidene fluoride (PVDF) and conductive graphite, and the preparation method specifically comprises the following steps:
s1, preparing an ion imprinted polymer by using dibenzo-14-crown-4 and a multi-wall carbon nanotube;
s2, preparing imprinted capacitive deionization copolymer by using pyrrole, ion imprinted polymer and ferric chloride solution, uniformly mixing the ion imprinted polymer, polyvinylidene fluoride (PVDF) and conductive graphite, and tabletting to obtain the electrode tablet.
3. The method for preparing the imprinted capacitive deionization electrode sheet for extracting lithium in an acidic environment according to claim 2, wherein S1 specifically comprises:
s11, dispersing the multi-walled carbon nano-tubes in hydrochloric acid, carrying out ultrasonic treatment to obtain a mixed solution, stirring the mixed solution in a water bath for 24 hours, filtering, washing, and finally drying to obtain the multi-walled carbon nano-tubes without metal oxides on the surfaces;
s12, mixing methanol and N, N-dimethylformamide in a volume ratio of 1:2, sequentially adding dibenzo-14-crown-4, lithium nitrate and alpha-methacrylic acid, and stirring to obtain a mixed solution;
s13, adding the multi-walled carbon nanotube in the S11 into the mixed solution of the S12, carrying out ultrasonic treatment for 5min, adding azobisisobutyronitrile and ethylene glycol dimethacrylate into the mixed solution after ultrasonic treatment in a nitrogen atmosphere lasting for 15min, and carrying out reflux stirring for 12h to obtain a crude product;
s14, washing the crude product to be neutral by using anhydrous methanol and ultrapure water in sequence, and drying to obtain the ion imprinted polymer.
4. The method for preparing the imprinted capacitive deionization electrode sheet for extracting lithium in an acidic environment according to claim 2, wherein S2 specifically comprises:
s21, adding the ion imprinted polymer into absolute ethyl alcohol, continuously dropwise adding a pyrrole and ferric chloride solution after ultrasonic treatment, and performing ultrasonic treatment for the second time to obtain a uniform solution;
s22, standing the uniform solution under an ice bath condition for a reaction, washing a product after the reaction with nitric acid, and drying to obtain the imprinted capacitive deionization copolymer;
s23, uniformly mixing the imprinted capacitive deionization copolymer, polyvinylidene fluoride and conductive graphite according to the mass ratio of 8:1:1, and tabletting under the set temperature and pressure conditions to obtain the imprinted capacitive deionization electrode tablet.
5. The method for preparing the imprinted capacitive deionization electrode sheet applied to the acidic environment lithium extraction as claimed in claim 3, wherein in step S11, the ratio of the multi-walled carbon nanotubes to hydrochloric acid is 1g:100mL, the concentration of hydrochloric acid is 2mol/L, the ultrasonic treatment time is 5min, the water bath stirring temperature is 25 ℃, the drying condition is 100 ℃ and the vacuum degree is 0.05MPa, and the drying is carried out for 6 h.
6. The method for preparing the imprinted capacitive deionization electrode tablet for extracting lithium in an acidic environment according to claim 3, wherein the ratio of methanol, N-dimethylformamide, dibenzo-14-crown-4, lithium nitrate and α -methacrylic acid used in step S12 is 20mL:40mL:0.3g:0.0689g:0.17 mL.
7. The method for preparing the imprinted capacitive deionization electrode tablet for extracting lithium in an acidic environment according to claim 3, wherein the reflux temperature is 70 ℃ in the step S13; in step S14, the drying is performed for 12 hours under the conditions of 70 ℃ and 0.05MPa of vacuum degree.
8. The method for preparing the imprinted capacitive deionization electrode tablet for extracting lithium in the acidic environment according to claim 4, wherein in step S21, pyrrole, the ionic imprinted polymer, the ferric chloride solution and absolute ethyl alcohol are used in a ratio of 0.6mol:0.5g:15.15mL:25 mL; the concentration of the ferric chloride solution is 1 mol/L.
9. The method for preparing the imprinted capacitive deionization electrode tablet for extracting lithium in the acidic environment according to claim 4, wherein in step S21, the ultrasonic time is 5 min; in step S22, the ice-bath time is 12h, and the drying condition is 100 ℃ and 0.05MPa vacuum degree, and the drying is carried out for 6 h.
10. The method for preparing a imprinted capacitive deionization electrode sheet according to claim 4, wherein the temperature and pressure conditions are set at 40 ℃ and 10MPa for 5min in step S23.
11. An imprinted capacitive deionization apparatus using the imprinted capacitive deionization electrode pad of claim 1.
12. A method of assembling the device of claim 11, the method comprising: attaching the imprinting type capacitive deionization electrode pressing sheet to a titanium sheet, drying and fixing, respectively inserting a carbon rod and the titanium sheet with the imprinting type capacitive deionization electrode pressing sheet into two opposite sides of a capacitive deionization device, connecting the carbon rod to the anode of a direct-current power supply through an anode wire, and connecting the titanium sheet with the imprinting type capacitive deionization electrode pressing sheet to the cathode of the direct-current power supply through a cathode wire; and providing a set value of voltage and current by using the direct current power supply to obtain the imprinted capacitive deionization device.
13. The method of claim 12, wherein the voltage is 0.4V and the current is 0.01 mA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210522757.1A CN114835211B (en) | 2022-05-13 | 2022-05-13 | Print type capacitor deionized electrode tablet and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210522757.1A CN114835211B (en) | 2022-05-13 | 2022-05-13 | Print type capacitor deionized electrode tablet and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114835211A true CN114835211A (en) | 2022-08-02 |
| CN114835211B CN114835211B (en) | 2023-07-07 |
Family
ID=82569294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210522757.1A Active CN114835211B (en) | 2022-05-13 | 2022-05-13 | Print type capacitor deionized electrode tablet and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114835211B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1591934A (en) * | 2003-08-29 | 2005-03-09 | 三星Sdi株式会社 | Positive electrode with polymer film and lithium-sulfur cell using the positive electrode |
| KR100723919B1 (en) * | 2006-02-16 | 2007-08-10 | 성균관대학교산학협력단 | Selective separation of heavy metal ion using the metal ion imprinted polymer(miip) |
| CN101195483A (en) * | 2007-12-19 | 2008-06-11 | 清华大学 | Method for mass production of bamboo joint shaped carbon nano-tube by adopting chemical vapor deposition method |
| US20090075171A1 (en) * | 2007-09-14 | 2009-03-19 | Tsinghua University | Anode of a lithium battery and method for fabricating the same |
| CN103137344A (en) * | 2011-11-28 | 2013-06-05 | 洛阳沃德节电科技开发有限公司 | Carbon nano tube (CNT) extra large (XL) capacitor manufacturing method |
| CN104698050A (en) * | 2015-02-10 | 2015-06-10 | 西安工程大学 | 2,4-diaminotoluene imprinted polymer film electrode and preparation method and application thereof |
| CN110078873A (en) * | 2019-04-20 | 2019-08-02 | 太原理工大学 | A kind of preparation method of magnetism carbon-based lithium ion imprinted material |
| CN110681367A (en) * | 2019-09-04 | 2020-01-14 | 太原理工大学 | Preparation method of nitrogen-doped carbon microsphere graphene composite aerogel lithium imprinted membrane for extracting lithium from acidic system |
-
2022
- 2022-05-13 CN CN202210522757.1A patent/CN114835211B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1591934A (en) * | 2003-08-29 | 2005-03-09 | 三星Sdi株式会社 | Positive electrode with polymer film and lithium-sulfur cell using the positive electrode |
| KR100723919B1 (en) * | 2006-02-16 | 2007-08-10 | 성균관대학교산학협력단 | Selective separation of heavy metal ion using the metal ion imprinted polymer(miip) |
| US20090075171A1 (en) * | 2007-09-14 | 2009-03-19 | Tsinghua University | Anode of a lithium battery and method for fabricating the same |
| CN101195483A (en) * | 2007-12-19 | 2008-06-11 | 清华大学 | Method for mass production of bamboo joint shaped carbon nano-tube by adopting chemical vapor deposition method |
| CN103137344A (en) * | 2011-11-28 | 2013-06-05 | 洛阳沃德节电科技开发有限公司 | Carbon nano tube (CNT) extra large (XL) capacitor manufacturing method |
| CN104698050A (en) * | 2015-02-10 | 2015-06-10 | 西安工程大学 | 2,4-diaminotoluene imprinted polymer film electrode and preparation method and application thereof |
| CN110078873A (en) * | 2019-04-20 | 2019-08-02 | 太原理工大学 | A kind of preparation method of magnetism carbon-based lithium ion imprinted material |
| CN110681367A (en) * | 2019-09-04 | 2020-01-14 | 太原理工大学 | Preparation method of nitrogen-doped carbon microsphere graphene composite aerogel lithium imprinted membrane for extracting lithium from acidic system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114835211B (en) | 2023-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Senthilkumar et al. | Electric double layer capacitor and its improved specific capacitance using redox additive electrolyte | |
| Peng et al. | Promising activated carbons derived from waste tea-leaves and their application in high performance supercapacitors electrodes | |
| Tanaka et al. | Surface modification of soft-templated ordered mesoporous carbon for electrochemical supercapacitors | |
| WO2001056924A1 (en) | Method for preparing porous carbon material, porous carbon material and electrical double layer capacitor using the same | |
| WO2013132388A1 (en) | Aerogel based on doped graphene | |
| CN110085433B (en) | Electrode material of China fir carbon sheet based on carbon nano tube and manganese dioxide, preparation method and super capacitor | |
| Kurniawan et al. | Carbon microsphere from water hyacinth for supercapacitor electrode | |
| CN113363086B (en) | MnO for supercapacitor 2 Nanobelt/nitrogen-doped graphene aerogel composite material and preparation method and application thereof | |
| CN110937601A (en) | Walnut shell based activated carbon, preparation method and application thereof | |
| Zhu et al. | Influence of nitric acid acitivation on structure and capacitive performances of ordered mesoporous carbon | |
| CN103641114A (en) | Preparation method and application of petroleum coke based activated carbon with zinc oxide and aluminium oxide as templates | |
| Xu et al. | Facile hydrothermal synthesis of tubular kapok fiber/MnO 2 composites and application in supercapacitors | |
| Le Van et al. | Activated Carbon by KOH and NaOH Activation: Preparation and Electrochemical Performance in K 2 SO 4 and Na 2 SO 4 Electrolytes | |
| US6940706B2 (en) | Electrode material and capacitor | |
| Chang et al. | Nitrogen and sulfur co-doped glucose-based porous carbon materials with excellent electrochemical performance for supercapacitors | |
| Li et al. | Polyaniline-decorated porous carbons with engineered meso/macrochannels for high performance capacitive deionization | |
| Yang et al. | Dissected carbon nanotubes functionalized by 1-hydroxyanthraquinone for high-performance asymmetric supercapacitors | |
| CN111554521A (en) | Preparation method of graphene/polyaniline flexible thin film electrode material | |
| Choi et al. | Assembly of graphene-wrapped ZIF-8 microspheres and confined carbonization for energy storage applications | |
| Zhang et al. | Trimetallic layered double hydroxides with a hierarchical heterostructure for high-performance supercapcitors | |
| CN113072066B (en) | Porous carbon material, preparation method thereof and supercapacitor | |
| Jia et al. | A simple synthetic route of N-doped mesoporous carbon derived from casein extracted with cobalt ions for high rate performance supercapacitors | |
| Nam et al. | Amorphous Mn oxide-ordered mesoporous carbon hybrids as a high performance electrode material for supercapacitors | |
| CN114835211B (en) | Print type capacitor deionized electrode tablet and preparation method and application thereof | |
| CN110002433B (en) | Preparation method of graphene aerogel with high specific surface area and high compressive strength |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |