CN114835211B - Print type capacitor deionized electrode tablet and preparation method and application thereof - Google Patents
Print type capacitor deionized electrode tablet and preparation method and application thereof Download PDFInfo
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- CN114835211B CN114835211B CN202210522757.1A CN202210522757A CN114835211B CN 114835211 B CN114835211 B CN 114835211B CN 202210522757 A CN202210522757 A CN 202210522757A CN 114835211 B CN114835211 B CN 114835211B
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- 239000003990 capacitor Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 150000002500 ions Chemical class 0.000 claims abstract description 41
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 29
- SVJYFWHFQPBIOY-UHFFFAOYSA-N 7,8,16,17-tetrahydro-6h,15h-dibenzo[b,i][1,4,8,11]tetraoxacyclotetradecine Chemical compound O1CCCOC2=CC=CC=C2OCCCOC2=CC=CC=C21 SVJYFWHFQPBIOY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 230000002378 acidificating effect Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000006258 conductive agent Substances 0.000 claims abstract description 6
- 238000004132 cross linking Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 238000002242 deionisation method Methods 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 22
- 238000009210 therapy by ultrasound Methods 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 14
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 13
- 239000002033 PVDF binder Substances 0.000 claims description 13
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 6
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 2
- 150000003983 crown ethers Chemical class 0.000 abstract description 10
- 230000005684 electric field Effects 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
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- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 46
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 239000007772 electrode material Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 5
- 229920000128 polypyrrole Polymers 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
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- 239000007787 solid Substances 0.000 description 3
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
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- 230000004580 weight loss Effects 0.000 description 2
- ATWLRNODAYAMQS-UHFFFAOYSA-N 1,1-dibromopropane Chemical compound CCC(Br)Br ATWLRNODAYAMQS-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 238000000919 Fourier transform infrared map Methods 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 239000004020 conductor Substances 0.000 description 1
- 238000005421 electrostatic potential Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000004332 silver Substances 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
Images
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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
-
- 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
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- 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
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Abstract
The invention relates to a imprinting type capacitor deionized electrode tablet, and a preparation method and application thereof. The imprinting type capacitance deionized electrode is pressed into a tablet twoBenzo-14-crown-4 is used as a capturing agent, pyrrole is used as a conducting agent, and the compound is synthesized through a crosslinking method. The electrode tablet is prepared by firstly preparing an ion imprinted polymer by using dibenzo-14-crown-4 and multi-wall carbon nanotubes, and then preparing the electrode tablet by using pyrrole, the ion imprinted polymer and a conductive agent. The invention synthesizes a novel imprinted capacitor deionized electrode by combining ion imprinting and a capacitor deionized technology, and realizes Li in an acid solution by the synergistic effect of electric field driving and crown ether selective recognition + Good separation of ions. The invention has potential to develop into Li in an acidic environment + Excellent materials and methods for ion recovery.
Description
Technical Field
The invention belongs to the technical field of surface functionalization modification and application of carbon materials, and particularly relates to a imprinting type capacitor deionized electrode tablet applied to acidic environment lithium extraction, and a preparation method and application thereof.
Background
The surface ion imprinting technology can accurately identify target ions, and the target ions are expressed in Li + In the imprinting process, crown ether is generally adopted as a recognition unit, and Li is specifically recognized and captured through the size screening and chelating capacity of crown ether ring + . However, the traditional imprinting molecules are easy to generate protonation in an acidic environment, and high-concentration H+ damages the structural stability of the separating agent, so that the selective recognition capability of the separating agent is weakened, the grafting rate of the internal sites of the active group carrier is low, and the adsorption capacity is low.
Therefore, the capacitance deionization technology developed in recent years can well solve the adsorption capacity problem, but has low selectivity and can adsorb all ions with opposite charges. There is currently no technology to link the two together. Thus, the two challenges of extracting lithium from an acidic system mentioned above can overcome the respective disadvantages of the surface imprinting technique and the capacitive deionization technique in the present invention, and achieve both selectivity and adsorption capacity.
Disclosure of Invention
In order to solve the technical problems, the invention provides a imprinting type capacitance deionized electrode tabletting for extracting lithium in an acidic environment, which is synthesized by taking dibenzo-14-crown-4, pyrrole and multiwall carbon nanotubes as raw materials through a crosslinking reaction; in the electrode tablet, dibenzo-14-crown-4 is Li + Capturing agent, pyrrole and multi-wall carbon nano tube are Li + And a conductive agent.
Iron chloride, polyvinylidene fluoride PVDF and conductive graphite are also added into the imprinting type capacitive deionization electrode tabletting material, and the preparation method specifically comprises the following steps:
s1, preparing an ion imprinted polymer by using dibenzo-14-crown-4 and multi-wall carbon nanotubes;
s2, preparing a print capacitor deionized copolymer by utilizing pyrrole, an ion print polymer and ferric chloride solution, uniformly mixing the ion print polymer, polyvinylidene fluoride PVDF and conductive graphite, and tabletting to obtain the electrode tabletting.
Preferably, the S1 specifically includes:
s11, dispersing the multi-wall carbon nano tube in hydrochloric acid and performing 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-wall carbon nano tube without metal oxide on the surface;
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 multiwall carbon nanotubes in the step S11 into the mixed solution of the step S12, carrying out ultrasonic treatment for 5min, and then adding azodiisobutyronitrile and ethylene glycol dimethacrylate into the mixed solution subjected to ultrasonic treatment under the nitrogen atmosphere 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 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 ice bath condition to wait for reaction, washing the reacted product with nitric acid, and drying to obtain the print capacitance deionized copolymer;
s23, uniformly mixing the imprinted capacitor deionized copolymer, polyvinylidene fluoride and conductive graphite according to a mass ratio of 8:1:1, and tabletting under the set temperature and pressure conditions to obtain the needed imprinted capacitor deionized electrode tabletting.
Preferably, in the step S11, the usage ratio of the multiwall carbon nanotubes to the hydrochloric acid is 1g:100mL of hydrochloric acid with the concentration of 2mol/L, the ultrasonic treatment time of 5min, the water bath stirring temperature of 25 ℃, the drying condition of 100 ℃ and the vacuum degree of 0.05MPa, and the drying time of 6h.
Preferably, in the step S12, methanol, N-dimethylformamide, dibenzo-14-crown-4, lithium nitrate and alpha-methacrylic acid are used in a ratio of 20mL:40mL:0.3g:0.0689g:0.17mL.
Preferably, in the step S13, the reflux temperature is 70 ℃; in step S14, the drying condition is 70 ℃ and 0.05MPa vacuum degree, and the drying is carried out for 12 hours.
Preferably, in the step S21, the usage ratio of pyrrole, ion imprinted polymer, ferric chloride solution and absolute ethanol is 0.6mol:0.5g:15.15mL:25mL; the concentration of the ferric chloride solution is 1mol/L.
Preferably, in the step S21, the ultrasonic time is 5min; in the step S22, the ice bath time is 12 hours, and the drying condition is 100 ℃ and the vacuum degree is 0.05MPa, and the drying time is 6 hours.
Preferably, in the step S23, the temperature and pressure conditions are set to be maintained at 40 ℃ for 5min under 10 MPa.
The invention also provides a imprinting type capacitor deionization device applying the imprinting type capacitor deionization electrode tablet.
The assembly method of the device specifically comprises the following steps: pasting the imprinting type capacitance deionization electrode tabletting glue on a titanium sheet by using conductive silver glue, drying and fixing, respectively inserting a carbon rod and the titanium sheet with the imprinting type capacitance deionization electrode tabletting on two opposite sides of a capacitance 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 imprinting type capacitance deionization electrode tabletting to the negative electrode of the direct-current power supply through a negative electrode wire; and providing voltage and current of a set value by using the direct current power supply to obtain the imprinting type capacitive deionization device.
Preferably, the direct current power supply is used for providing voltage and current with set values, the voltage is 0.4V, and the current is 0.01mA.
The invention has the beneficial effects that:
aiming at the problem that the capture capacity of crown ether to lithium ions is weakened due to the protonation of oxygen atoms on crown ether ring in an acid system, the invention provides the imprinting type capacitance deionized electrode tablet applied to extracting lithium in an acid environment, and the electrode tablet is used for preparing an extraction device, so that the specific recognition capacity of crown ether weakened due to the protonation can be enhanced by applying external electrostatic potential, and the lithium extraction process under the acid condition can be realized.
Crown ethers, which are one type of ion imprinting, possess pore sizes that match the size of the cation diameter. Crown ether coordinates with alkali metal ions to form stable complex by virtue of 'macrocyclic effect', and the adsorbent loaded with crown ether can realize Li reaction + And (3) effective adsorption. The capacitive deionization technology has the advantages of simple operation, high adsorption capacity and easy regeneration. The invention realizes high-selectivity and high-capacity adsorption of lithium ions in an acidic complex multi-element solution system through the combination of the two.
The invention synthesizes Imprinting Capacitance Deionized (ICDI) by using dibenzo-14-crown-4 (DB 14C 4) as a capturing agent and pyrrole as a conductive agent through a crosslinking method. The proton resistance of the adsorbent in an acidic environment is improved, and the selective recognition capability of lithium ions under the interference of impurity ions is enhanced.
The electrode tabletting provided by the invention has almost unchanged adsorption capacity after five cycles after repeated experiments. The electrode tabletting is adsorbed in an acidic environment under the auxiliary action of electric field driving, and has remarkable progress compared with the adsorption under the conventional alkaline and neutral conditions. The lithium extraction method is an advanced imprinting type capacitance deionization method which can be applied to extracting lithium in an acidic environment.
Drawings
FIG. 1 is a schematic diagram of an apparatus for manufacturing by electrode tabletting according to the present invention;
FIG. 2 is a diagram of Li prepared according to the present invention + -NCDI、Li + -ICDI、Li + -field emission scanning electron microscopy of N/ICDI;
FIG. 3 is Li prepared according to the present invention + -NCDI、Li + -ICDI、Li + FTIR map of N/ICDI;
FIG. 4A is a schematic diagram of Li prepared according to the present invention + -NCDI、Li + -ICDI、Li + -an adsorption-desorption curve of N/ICDI, fig. 4B being a pore size distribution diagram thereof;
FIGS. 5A and 5B show Li prepared according to the present invention + -XPS spectra of ICDI in working and open potential;
FIGS. 6A-6C illustrate Li prepared according to the present invention + -NCDI、Li + -ICDI、Li + Adsorption kinetics of N/ICDI;
FIGS. 7A to 7C show Li prepared according to the present invention + -NCDI、Li + -ICDI、Li + -adsorption isotherms of N/ICDI;
FIG. 8 is Li prepared according to the present invention + -NCDI、Li + -ICDI、Li + -a graph of N/ICDI's selectivity for adsorption versus different ions;
FIG. 9 shows a print-type capacitive deionization electrode material Li prepared by the present invention + -NCDI、Li + -ICDI、Li + Influence of N/ICDI weight loss with pH;
FIG. 10 shows the cyclic adsorption regeneration curves of the imprinted capacitive deionization electrode materials Li+ -NCDI, li+ -ICDI, li+ -N/ICDI prepared in accordance with the present invention.
Detailed Description
The technical scheme of the invention is described in more detail below with reference to examples.
Deionized water as used in this application unless otherwise specified: liquid with purity of 99.99%; catechol: solid, 99% pure; alpha-methacrylic acid: purity 98%; n, N-dimethylformamide: purity 99.8%, lithium hydroxide monohydrate: purity 98%; multiwall carbon nanotubes: solid, 99.99%; KOH: purity 98%, solid state; dimethyl sulfoxide: liquid with purity of 99.95%; methanol: anhydrous methanol, liquid, 99.50%; ethanol: absolute ethanol, liquid, 99.50%; ethylene glycol dimethacrylate: liquid with purity of 98%; pyrrole: liquid with purity of 98%; dibromopropane: the purity of the liquid is 98%.
Example 1
The imprinting type capacitance deionized electrode tablet for extracting lithium in an acidic environment is synthesized by a crosslinking method by taking dibenzo-14-crown-4 as a capturing agent and pyrrole as a conductive agent.
The preparation method of the deionized electrode tablet comprises the following steps:
1. the procedure described in the reference synthesizes dibenzo-14-crown-4:
1.1, catechol, lithium hydroxide and 1,3 dibromopropane are sequentially dissolved in dimethyl sulfoxide according to the proportion of 5.5g to 4.4g to 5.3mL to 30mL, and are subjected to ultrasonic treatment to form uniform slurry;
1.2, filtering the slurry to obtain a filter cake, and respectively washing the filter cake by sodium hydroxide and deionized water with the mass concentration of 0.1 mol/L;
1.3 adding methanol for recrystallization, and drying after the reaction is finished to obtain dibenzo-14-crown-4; the drying temperature in the step is 60 ℃, the vacuum degree is 0.05MPa, and the drying time is 12 hours.
2. Preparation of ion imprinting polymer:
2.1 dispersing the multi-wall carbon nano tube in hydrochloric acid and carrying out ultrasonic treatment for 5min to obtain a mixed solution, stirring the mixed solution in a water bath (25 ℃) for 24h, filtering, washing to be neutral, and finally drying to obtain the multi-wall 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 to 100mL; the drying temperature is 100 ℃, the vacuum degree is 0.05MPa, and the drying time is 6 hours;
2.2 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; the use ratio of the methanol, the N, N-dimethylformamide, the dibenzo-14-crown-4, the lithium nitrate and the alpha-methacrylic acid is 20mL:40mL:0.3g:0.0689g:0.17mL;
2.3 adding the multiwall carbon nanotube in the step S11 into the mixed solution of the step S12, carrying out ultrasonic treatment for 5min, adding azodiisobutyronitrile and ethylene glycol dimethacrylate into the mixed solution subjected to ultrasonic treatment under the nitrogen atmosphere lasting for 15min, and stirring at the reflux stirring temperature of 70 ℃ 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. The drying temperature in the step is 70 ℃, the vacuum degree is 0.05MPa, and the drying time is 12 hours;
3. and preparing an electrode tabletting.
S21, adding the ion imprinted polymer into absolute ethyl alcohol, carrying out ultrasonic treatment for 5min, dropwise adding pyrrole and a conductive agent, namely ferric 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 ice bath condition, waiting for reaction to be carried out, washing the reacted product with nitric acid, and drying to obtain the imprinted capacitor deionized copolymer; in the step, the drying temperature is 100 ℃, the vacuum degree is 0.05MPa, and the drying time is 6 hours;
the usage ratio of the pyrrole, the ion imprinted polymer, the ferric chloride solution and the absolute ethyl alcohol is 0.6mol:0.5g:15.15mL:25mL; the concentration of the ferric chloride solution is 1mol/L.
S23, uniformly mixing the imprinted capacitor deionized copolymer, polyvinylidene fluoride and conductive graphite according to a mass ratio of 8:1:1, and maintaining the mixture at a temperature of 40 ℃ and a pressure of 10MPa for 5min by a tablet press to obtain the needed imprinted capacitor deionized electrode tablet.
The prepared electrode pressed sheet can be stored in a brown glass container, so that the moisture resistance, sun protection and acid-base salt corrosion resistance of a storage space are ensured, and 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 tabletting and is concretely characterized in that: coating the imprinting type capacitance deionization electrode pressing sheet on a titanium sheet, drying and fixing, respectively inserting a carbon rod and the titanium sheet with the imprinting type capacitance deionization electrode pressing sheet on two opposite sides of a capacitance 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 imprinting type capacitance deionization electrode pressing sheet to the negative electrode of the direct current power supply through a negative electrode wire; and providing voltage (0.4V) and current (0.01 mA) of a set value by using the direct current power supply to obtain the imprinting type capacitive deionization device.
As shown in fig. 1, the assembled device is schematically shown, and comprises a cuboid type electrolytic tank 10 for containing acidic medium solution, polytetrafluoroethylene magnetic particles 11 are arranged at the bottom of the electrolytic tank 10, a carbon rod 21 and a titanium sheet 22 with imprinting type capacitance deionizing electrode pressing sheets are immersed in the acidic solution. The DC power supply 30 is provided with a power switch 31, a current adjusting knob 32 and a voltage adjusting knob 33, the positive electrode 41 of the power supply is connected with the carbon rod 21, and the negative electrode 42 of the power supply is connected with the titanium sheet 22.
Example 2
With reference to the method of example 1, a stamped capacitive deionization electrode pellet was prepared:
1. synthesis of dibenzo-14-crown-4:
1.1 weighing 5.5g catechol and 4.4g lithium hydroxide, dissolving in 30mL dimethyl sulfoxide, dropwise adding 5.3 mL 1,3 dibromopropane, and performing ultrasonic treatment for 3 hours to form uniform slurry;
1.2, filtering the slurry to obtain a filter cake, and respectively washing the filter cake by using sodium hydroxide and deionized water with the mass concentration of 0.1 mol/L;
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 dibenzo-14-crown-4.
2. Preparation of ion imprinting polymer:
2.1 dispersing 1g of multi-wall carbon nano-tubes in 100mL of 2M hydrochloric acid for ultrasonic treatment for 15min to obtain a mixed solution, stirring the mixed solution in a water bath at 25 ℃ for 24h, filtering and washing to be neutral, and finally drying in a drying oven at 100 ℃ for 6h to obtain the multi-wall carbon nano-tubes without 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 for 30min at room temperature;
2.3 adding 0.5g of the multiwall carbon nanotube 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 subjected to ultrasonic treatment under the nitrogen atmosphere lasting for 15min, and stirring for 12h at the reflux stirring temperature of 70 ℃ to obtain a crude product;
2.4 reacting the mixed solution in a water bath at 70 ℃ for 12 hours, filtering the product, washing the product to be neutral by using methanol and ultrapure water in sequence, and drying the product in an oven at 70 ℃ for 12 hours to obtain the ion imprinted polymer.
3. Preparation of electrode pads
3.1 0.5g of the ion imprinted polymer in S2.4 was added to 25.0mL of absolute ethanol and sonicated for 5min, and stirred for 30min after adding a certain amount of deionized water. Then, 0.6mL of pyrrole was added dropwise to the solution, sonicated for 5min, and 15.15mL of ferric chloride solution at a concentration of 1mol/L was added dropwise. Reacting for 12h under ice bath condition, washing the product with 1mol/L nitric acid, and drying the obtained product in a 70 ℃ oven for 6h to obtain an active ingredient;
3.2 uniformly mixing the active ingredients, polyvinylidene fluoride (PVDF) and conductive graphite according to a mass ratio of 8:1:1, and maintaining the temperature at 40 ℃ and the pressure of 10MPa for 5min to obtain the imprinted capacitor deionized electrode tablet.
The electrode pressing sheet is stuck on the conductive material by utilizing conductive silver paste, and the lithium imprinting capacitor deionized electrode pressing sheet (Li + -ICDI)。
By Li + -ICDI-1、Li + -ICDI-2 is the electrode material at open circuit potential and working potential, respectively, li + ICDI-1 indicates the adsorbed material, li + -ICDI-2 represents desorbed material. Electrode pellets prepared herein were tested, analyzed and characterized and were prepared as Li, a material synthesized in a dispersion without dibenzo-14-crown-4 + -NCDI, material Li prepared with a content of dibenzo-14-crown-4 of 0.15g in the dispersion + -ICDI, dibenzo-14-crown-4 content of 0.15g in the dispersion + N/ICDI (i.e., the amount of different capture agents) was used as a comparison and the results are shown in FIGS. 2-9.
Li + -NCDI、Li + -ICDI、Li + The result of the field emission scanning electron microscopy of N/ICDI is shown in FIG. 2. It can be observed from figure a that the multi-walled carbon nanotubes MWCNTs are more densely connected, a dense coating is formed between the multi-walled carbon nanotubes and polypyrrole PPy, a part of the MWCNTs are mutually connected to form a dendritic connection, and the coating between the MWCNTs and PPy is probably caused by pi bond interaction in the polymerization process. In figures b and c it can be seen that a certain number of spherical PPy are distributed in the structure, indicating the formation of material aggregates. In the graph b, the surface is coarser to form petal-shaped polymer, the structural change is caused by the fact that DB14C4 is introduced, the inter-chain connection is increased, and a large number of nanoscale fissure pore channels are distributed on the surface, so that rapid transmission of lithium ions is facilitated.
Fourier transform infrared spectrum analysis is used for judging whether DB14C4 is grafted to a imprinting capacitance deionized electrode, and for Li+ -NCDI and Li + -ICDI-1、Li + -ICDI-1、Li + The groups present in the-N/ICDI and MWCNTs were FTIR characterized and the results are shown in FIG. 3. It can be seen that the characteristic spectrum of DB14C4 is also presented on the imprinted capacitive deionization electrode, which indicates that in Li + In ICDI Li is formed + Indicating successful doping of graphene oxide and polypyrrole.
Evaluation of Li by BET N2 adsorption method + Surface area and porosity type of ICDI, the results are shown in fig. 4. FIG. 4A shows that all N2 adsorption curves can be described as type IV, type H3 hysteresis loops, indicating the presence of mesopores in the prepared materialStructure is as follows. Pore size distribution figure 4B shows that the pore size distribution is predominantly between 2.5-10nm, consistent with SEM characterization. The mesopores can provide large surface area for adsorbing ions, shorten ion diffusion paths and produce the electrode material with high removal speed and stable circulation capacity.
XPS analysis of Li + The surface composition of ICDI at both the working and open potentials, and the XPS spectrum results are shown in FIG. 5. From the broad survey scan of FIG. 5A, li + The element O was observed in ICDI at an operating potential (O1 s,532.79 eV) and at an open potential (O1 s,532.14 eV), indicating that it was observed in DB14C4 and Li + And a reinforcing effect is formed between them. As shown in FIG. 5B, for Li appearing at the operating potential, it is shown that Li + ICDI adsorbs and rejects it at an operating potential and at an open potential, respectively.
Li + In Li + -ICDI、Li + -N/ICDI、Li + Adsorption behavior over contact time on NCDI, blotting capacitive deionization kinetic adsorption profile see fig. 6. As shown in FIG. 6A, li + The ICDI maintained a high adsorption rate in the first 20min, and the adsorption amount eventually tended to stabilize at approximately 2h, at which time Li was derived + The adsorption capacity of ICDI reached dynamic equilibrium and was 91.36. Mu. Mol/g. Meanwhile, under the same conditions, li can be derived from FIG. 6B and FIG. 6C, respectively + -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 + -ICDI; this is probably due to the excellent conductivity of-COOH functions and carbon nanotubes, but the overall difference is not large, li from the standpoint of selective adsorption + ICDI still has advantages. The adsorption capacity is from Li + ICDI angle analysis, possibly because the cross-linker partially covered the functional groups during the material synthesis. Li (Li) + When adsorbed on the blotting material, the inherent DB14C4 adsorption capacity of the material enables Li to be absorbed by + Is chelated. After 40min, li is simultaneously + 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 was 90.45. Mu. Mol/g, very close to the experimental value 91.36. Mu. Mol/g. The quasi-secondary kinetic model is more compatible,experimental data indicate that lithium ions are in Li + The adsorption process on ICDI is chemisorption.
The isothermal adsorption graph of the imprinted capacitive deionization electrode material is shown in FIG. 7 for evaluation of Li + Initial concentration vs. Li + -ICDI、Li + -N/ICDI、Li + Influence of NCDI adsorption, li at ph=2 and 25 ℃ + The adsorption experiment is carried out for 2 hours with the concentration of 40-700 mg/L, and the electrode material is obvious to Li + The adsorption capacity of (a) increases non-linearly with increasing concentration. As shown in fig. 7A, 7B and 7C, respectively, li + -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 + Compared with NCDI, li + N/ICDI showed better adsorption of lithium ions at the same initial concentration, indicating that the surface imprinted sites improved the adsorption capacity of the adsorbent. Li (Li) + NCDI adsorption capacity higher than Li + ICDI, possibly due to the coverage of the oxygen containing functional groups of the surface portion of the carbon nanotubes, leads to a reduced imprinted binding site. From the 7A graph, it can be seen that as the equilibrium concentration increases, the equilibrium adsorption capacity also increases gradually, and the Langmuir model more closely matches the experimental data to show that lithium ions are in Li + The adsorption process on ICDI is monolayer adsorption. This is also Li + -ICDI electrode pairs Li in solution + Ion adsorption is the primary reason for chemisorption rather than physisorption.
Li prepared by the invention + -NCDI、Li + -ICDI、Li + The results of the adsorption selectivity of N/ICDI for different ions are shown in FIG. 8. From the figure, it can be seen that the ion imprinting capacitance deionization electrode Li prepared by the invention + ICDI has significantly higher adsorption capacity for lithium ions than other ions, i.e. has the highest selective recognition for lithium ions, for Na + ,Mg 2+ ，Al 3+ K is as follows + The selected separation factors of (a) are 6.16, 46.92, 65.81,9.62, respectively.
The effect of weight loss of material with pH is shown in FIG. 9, and it can be seen that the dissolution rate of material with H + The decrease in concentration shows a decreaseTrend of (3). This is because the diffusion behavior of ions under an applied electric field generally causes an uneven concentration distribution, which causes uneven deformation, which in turn generates diffusion-induced stresses, leading to dissolution loss of the material. In addition, corrosion of the material by the acid medium is also an important cause.
The cycle adsorption regeneration curve of the imprinted capacitive deionization electrode material is shown in FIG. 10, from which it can be seen that Li + -ICDI electrode Material pair Li + There is no significant drop in cycle time increase. The adsorption capacity was reduced by only about 3.82% after five cycles compared to the first adsorption capacity, indicating Li + The imprinting sites can be effectively regenerated by electroelution under the potential of 1.0V, so that the cyclic adsorption is realized.
From the above series of test results, the invention synthesizes a novel imprinted capacitor deionized electrode (Li + ICDI), the amount of adsorption in the presence of an electric field is about 6 times that in the absence of an applied electric field. By the synergistic effect of electric field driving and crown ether selective recognition, li is shown + ICDI achieves Li in acidic solution + Good separation of ions. And after 5 cycles, the adsorption capacity was reduced by only about 3.82%, indicating that the obtained electrode material had excellent regeneration ability. Therefore, the invention provides Li + ICDI has the potential to develop into Li in an acidic environment + Excellent materials and methods for ion recovery.
The above embodiments are only for illustrating the technical scheme of the present invention, and are not limiting to the present invention; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A imprinting type capacitance deionization electrode tablet applied to extracting lithium in an acidic environment is characterized in that dibenzo-14-crown-type electrode tablet material is adopted4. Pyrrole and multi-wall carbon nano-tubes are used as raw materials and synthesized through a crosslinking reaction; in the electrode tablet, dibenzo-14-crown-4 is Li + Capturing agent, pyrrole and multi-wall carbon nano tube are Li + A conductive agent;
ferric chloride, polyvinylidene fluoride PVDF and conductive graphite are also added into the imprinting type capacitance deionized electrode tabletting material, and the preparation method comprises the following specific steps:
s1, preparing an ion imprinted polymer by using dibenzo-14-crown-4 and multi-wall carbon nano tubes;
s2, preparing a print capacitor deionized copolymer by utilizing pyrrole, an ion print polymer and ferric chloride solution, uniformly mixing the ion print polymer, polyvinylidene fluoride PVDF and conductive graphite, and tabletting to obtain the electrode tablet;
the S1 specifically comprises the following steps:
s11, dispersing the multi-wall carbon nano tube in hydrochloric acid and performing 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-wall carbon nano tube without metal oxide on the surface;
s12, methanol and N, N-dimethylformamide are mixed according to the volume ratio of 1:2, mixing, sequentially adding dibenzo-14-crown-4, lithium nitrate and alpha-methacrylic acid, and stirring to obtain a mixed solution;
s13, adding the multiwall carbon nanotubes in the step S11 into the mixed solution of the step S12, carrying out ultrasonic treatment for 5min, and then adding azodiisobutyronitrile and ethylene glycol dimethacrylate into the mixed solution subjected to ultrasonic treatment under the nitrogen atmosphere 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 an ion imprinted polymer;
the step S2 specifically comprises the following steps:
s21, adding the ion imprinted polymer into absolute ethyl alcohol, continuously dropwise adding 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 ice bath condition to wait for reaction, washing the reacted product with nitric acid, and drying to obtain the print capacitance deionized copolymer;
s23, uniformly mixing the imprinted capacitor deionized copolymer, polyvinylidene fluoride and conductive graphite according to a mass ratio of 8:1:1, and tabletting under the set temperature and pressure conditions to obtain the needed imprinted capacitor deionized electrode tabletting.
2. The imprinted capacitive deionization electrode tablet for extracting lithium in an acidic environment as claimed in claim 1, wherein in the step S11, the usage ratio of the multiwall carbon nanotubes to hydrochloric acid is 1g:100mL of hydrochloric acid with the concentration of 2mol/L, the ultrasonic treatment time of 5min, the water bath stirring temperature of 25 ℃, the drying condition of 100 ℃ and the vacuum degree of 0.05MPa, and the drying time of 6h.
3. The imprinted capacitor deionization electrode tablet for acidic environment lithium extraction of claim 1, wherein in step S12, methanol, N-dimethylformamide, dibenzo-14-crown-4, lithium nitrate and α -methacrylic acid are used in a ratio of 20ml:40ml:0.3g:0.0689g:0.17ml.
4. The imprinted capacitor deionization electrode tablet for extracting lithium in an acidic environment as claimed in claim 1, wherein in the step S13, the reflux temperature is 70 ℃; in step S14, the drying condition is 70 ℃ and a vacuum degree of 0.05MPa, and 12. 12h is dried.
5. The imprinted capacitive deionization electrode tablet for extracting lithium in an acidic environment according to claim 1, wherein in the step S21, the usage ratio of pyrrole, ion imprinted polymer, ferric chloride solution and absolute ethanol is 0.6mol:0.5g:15.15ml:25ml; the concentration of the ferric chloride solution is 1mol/L.
6. The imprinting type capacitor deionization electrode tablet for extracting lithium in an acidic environment according to claim 1, wherein in the step S21, the ultrasonic time is 5min; in step S22, the ice bath time was 12h, and the drying conditions were 100℃and a vacuum of 0.05MPa, and 6. 6h were dried.
7. The imprinted capacitor deionization electrode tablet for extracting lithium in an acidic environment as claimed in claim 1, wherein in the step S23, the set temperature and pressure conditions are that the tablet is maintained at 40 ℃ for 5min under 10 MPa.
8. A print-type capacitive deionization apparatus using the print-type capacitive deionization electrode pad of claim 1.
9. A method of assembling the device of claim 8, wherein the method of assembling comprises: attaching the imprinting type capacitance deionization electrode pressing sheet to a titanium sheet, drying and fixing, respectively inserting a carbon rod and the titanium sheet with the imprinting type capacitance deionization electrode pressing sheet at two opposite sides of a capacitance 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 imprinting type capacitance deionization electrode pressing sheet to the negative electrode of the direct-current power supply through a negative electrode wire; and providing voltage and current of a set value by using the direct current power supply to obtain the imprinting type capacitive deionization device.
10. The assembly method of claim 9, wherein the voltage is 0.4V and the current is 0.01mA.
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| US20090075171A1 (en) * | 2007-09-14 | 2009-03-19 | Tsinghua University | Anode of a lithium battery and method for fabricating the same |
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| 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 |
| 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 |
| 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 |
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