CN115611379A - Prussian blue carbon-based composite electrode and preparation method and application thereof - Google Patents
Prussian blue carbon-based composite electrode and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 229960003351 prussian blue Drugs 0.000 title claims abstract description 83
- 239000013225 prussian blue Substances 0.000 title claims abstract description 83
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 238000010612 desalination reaction Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 15
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- -1 potassium ferricyanide Chemical compound 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000006258 conductive agent Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 239000011267 electrode slurry Substances 0.000 claims abstract description 10
- 230000008929 regeneration Effects 0.000 claims abstract description 10
- 238000011069 regeneration method Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000741 silica gel Substances 0.000 claims description 21
- 229910002027 silica gel Inorganic materials 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 15
- 238000002242 deionisation method Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 13
- 239000004677 Nylon Substances 0.000 claims description 12
- 229920001778 nylon Polymers 0.000 claims description 12
- 239000004033 plastic Substances 0.000 claims description 9
- 238000005192 partition Methods 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000007790 scraping Methods 0.000 claims description 2
- 238000011033 desalting Methods 0.000 abstract description 15
- 239000007772 electrode material Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 9
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 238000002715 modification method Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000012266 salt solution Substances 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013505 freshwater Substances 0.000 description 4
- 230000002572 peristaltic effect Effects 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
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- 230000005686 electrostatic field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- BYGOPQKDHGXNCD-UHFFFAOYSA-N tripotassium;iron(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] BYGOPQKDHGXNCD-UHFFFAOYSA-N 0.000 description 1
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
Abstract
The invention provides a Prussian blue carbon-based composite electrode, a preparation method and application thereof, and belongs to the technical field of brackish water desalination. The method comprises the following steps: 1) Adding a potassium ferricyanide solution and a ferric chloride solution into the activated carbon powder, uniformly stirring, standing for layering, and drying a precipitate on a lower layer; 2) Calcining the dried product at high temperature to obtain a Prussian blue doped active carbon material; 3) Grinding the Prussian blue doped activated carbon material, adding a conductive agent, a binder and a solvent, and uniformly mixing to obtain electrode slurry; 4) And (4) coating the slurry on the surface of a current collector in a blade mode, and drying to obtain the Prussian blue carbon-based composite electrode. The electrode material can rapidly and efficiently complete the desalting and regeneration processes under the action of bipolar voltage, and the desalting effect is obviously superior to that of the traditional activated carbon electrode. According to the invention, the Prussian blue is doped on the activated carbon by a simple modification method, and sodium ions are rapidly embedded and removed by utilizing a Prussian blue three-dimensional framework structure, so that the electrode has good stability and high adsorption performance.
Description
Technical Field
The invention belongs to the technical field of brackish water desalination and desalination, and particularly relates to a Prussian blue carbon-based composite electrode, and a preparation method and application thereof.
Background
Along with the rapid development of the economic society and the continuous acceleration of the industrialization and urbanization processes, people face more and more serious water resource problems. Among them, the problem of water shortage is the most outstanding and urgent need to be solved. Fresh water resources on the earth mainly exist in glaciers and ice covers of two poles, and finally, surface water and shallow groundwater which can be utilized by human beings only account for 0.26 percent of the total water quantity of the earth, and the distribution is extremely uneven. Different from the situation of fresh water resource shortage, the brackish water resource in China is rich in content and distributed in many places, and the underground brackish water resource in China is about 200 hundred million meters 3 With a producible amount of 130 hundred million m 3 Most of the water exists at the underground 10-100 m, and is suitable for exploitation and utilization.
Aiming at the problem of shortage of fresh water resources, if abundant brackish water resources can be used for generating fresh water through a desalination technology, the problem of water resource shortage in China can be relieved to a certain extent.
The capacitive deionization technology is a new and rapidly developed environmental protection technology, and applies a voltage to two electrodes to generate an electrostatic field between the two electrodes. Under the electrostatic action, the positive and negative ions in the salt solution move to the positive and negative electrodes respectively and are adsorbed on the electrodes, and finally the effects of desalination and desalination are achieved. And the two electrodes are in short circuit or reverse connection, so that the regeneration and the utilization of the electrodes are realized.
The traditional activated carbon electrode is limited by the characteristics of the material of the traditional activated carbon electrode in the aspect of capacitive desalination performance, and the desalination effect is poor. Therefore, the technical personnel in the field need to solve the problem of how to improve the capacitive desalting performance of the activated carbon electrode by modifying the activated carbon material by a simple method.
Disclosure of Invention
The invention aims to provide a preparation method of a Prussian blue carbon-based composite electrode, which is used for effectively doping Prussian blue onto active carbon through a simple method so as to prepare an electrode material. Compared with the traditional active carbon electrode, the Prussian blue carbon-based composite electrode material adopts a Prussian blue three-dimensional frame structure which is beneficial to rapid embedding and removing of sodium ions, and can better perform sodium embedding and sodium removing, so that the Prussian blue carbon-based composite electrode material has good stability and good application prospect in the technical field of capacitive deionization. The prepared composite electrode material can complete the rapid and efficient desalting and regeneration process under the action of bipolar voltage.
In order to achieve the above object, the present invention provides a prussian blue carbon-based composite electrode, which specifically comprises the following steps:
1) Adding a potassium ferricyanide solution and a ferric chloride solution into the activated carbon powder, uniformly stirring to obtain a mixed solution, standing for layering, and drying a precipitate on a lower layer;
2) Calcining the dried product in the step 1) at high temperature in an inert atmosphere to obtain a Prussian blue doped activated carbon material;
3) Grinding the product obtained in the step 2) to obtain prussian blue doped active carbon fine powder, adding a conductive agent, a binder and a solvent, and uniformly mixing to obtain electrode slurry;
4) And (4) coating the slurry obtained in the step 3) on the surface of a current collector in a scraping manner, and drying to obtain the Prussian blue carbon-based composite electrode.
In a preferred embodiment, in step 1), the concentration of the potassium ferricyanide solution and the concentration of the ferric chloride solution are both 0.02-0.08mol/L, and the solvent of the solutions is deionized water.
In a preferred embodiment, in step 1), the mass-to-volume ratio of the activated carbon powder, the potassium ferricyanide solution and the ferric chloride solution is 1g: (8-12) ml: (8-12) ml.
In a preferred embodiment, in step 2), the high-temperature calcination temperature is 600-800 ℃, and the calcination time is 1-3h.
In a preferred embodiment, in the step 3), the mass volume ratio of the prussian blue doped activated carbon fine powder, the conductive agent, the binder and the solvent is 1g:0.1g: (0.73-0.74) ml: (2-4) ml.
The invention also aims to provide a Prussian blue carbon-based composite electrode, which is obtained by uniformly stirring the prepared Prussian blue doped active carbon electrode material with a conductive agent, an adhesive and a solvent, and coating the Prussian blue doped active carbon electrode material on a current collector, wherein the thickness of a coating area is 100-200 mu m, and the length and the width of the coating area are 6-7cm. According to the invention, the Prussian blue is effectively doped on the activated carbon through a simple method, and the traditional activated carbon electrode can be modified, so that the electron conduction is accelerated, and the adsorption capacity and the adsorption rate of the activated carbon electrode are improved.
The invention also aims to provide application of the Prussian blue carbon-based composite electrode, two prepared Prussian blue carbon-based composite electrodes are assembled into a capacitive deionization electrode module group, sodium chloride solution flows in from one end of the module group, flows through the two electrodes and flows out from the other end of the module group, and positive pressure and negative pressure are respectively applied to the two electrodes, so that solution desalination can be completed. After the desalination is finished, the regeneration of the electrodes can be realized in a mode of reversely connecting the positive electrode and the negative electrode, so that the aim of recycling is fulfilled. During desalting, the treated saline solution has high inlet water concentration and large desalting amount per unit mass, and has wide application prospect.
In a preferred embodiment, the capacitive deionization electrode module set sequentially comprises: a glass plate, a silica gel gasket, a Prussian blue carbon-based composite electrode, a nylon net, a silica gel gasket, a plastic partition plate, a silica gel gasket, a nylon net, a Prussian blue carbon-based composite electrode, a silica gel gasket and a glass plate; wherein, the glass plate is provided with a water inlet and a water outlet, the silica gel gasket and the plastic partition plate are hollow, and the positions corresponding to the Prussian blue carbon-based composite electrode are provided with small holes to ensure that the solution fully flows through the electrode coating area.
In a preferred embodiment, the applied voltage is in the range of 1-1.5V, the solution flow rate is 1-8mL/min, and the sodium chloride solution is 50-200mg/L.
In a preferred embodiment, in the capacitive deionization electrode module group, deionized water flows in from one end of the module group, flows through two electrodes, and flows out from the other end of the module group, and the two electrodes are connected in reverse at the same time, so that electrode regeneration can be completed.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. in the invention, all the used raw materials are low in cost and easy to purchase, the modification method of the carbon material is simple, the requirements on equipment and reaction conditions are low, and the method is suitable for large-scale production and preparation.
2. In the invention, the Prussian blue is used for doping the activated carbon powder so as to modify the activated carbon, and the Prussian blue has a three-dimensional framework structure which is beneficial to the embedding and the separation of sodium ions, so that the desalting performance of the activated carbon material can be improved.
Drawings
These and/or other aspects and advantages of the present invention will become more apparent and more readily appreciated from the following detailed description of the embodiments of the invention, taken in conjunction with the accompanying drawings of which:
fig. 1 is an SEM image of a prussian blue-doped activated carbon material provided in example 1 of the present invention.
Fig. 2 is an XRD chart of the prussian blue doped activated carbon material provided in example 1 of the present invention.
Fig. 3 is a diagram of a prussian blue carbon-based composite electrode under the capacitive deionization technology provided in embodiment 2 of the present invention.
Fig. 4 is a schematic diagram of an electrode module in the capacitive deionization technology provided in embodiment 2 of the present invention.
FIG. 5 is a graph showing the amount of desalted per unit mass of the electrodes obtained in example 2 of the present invention and comparative example 1.
FIG. 6 is a graph showing the desalination rate of the electrode obtained in example 2 of the present invention and that obtained in comparative example 1.
Description of the main reference numbers: 1-glass plate, 2-water inlet, 3-silica gel gasket, 4-tab, 5-Prussian blue carbon-based composite electrode, 6-nylon net, 7-plastic separator, 8-electrode coating and 9-water outlet.
Detailed Description
For a better understanding of the present invention for those skilled in the art, the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments, but it should be understood that the scope of the present invention is not limited to the specific embodiments.
The invention provides a preparation method of a Prussian blue carbon-based composite electrode, and solves the problems that in the prior art, the traditional activated carbon electrode is limited by the characteristics of the material of the electrode in the aspect of capacitive desalination performance, and the desalination effect is poor.
In order to solve the problems, the technical scheme of the invention has the following general idea:
the invention provides a Prussian blue carbon-based composite electrode, which specifically comprises the following steps:
1) Adding a potassium ferricyanide solution and a ferric chloride solution into the activated carbon powder, uniformly stirring to obtain a mixed solution, standing for layering, and drying a lower-layer precipitate;
2) Calcining the dried product in the step 1) at high temperature in an inert atmosphere to obtain a Prussian blue doped activated carbon material;
3) Grinding the product obtained in the step 2) to obtain prussian blue doped active carbon fine powder, adding a conductive agent, a binder and a solvent, and uniformly mixing to obtain electrode slurry;
4) And (3) blade-coating the slurry obtained in the step 3) on the surface of a current collector, and drying to obtain the Prussian blue carbon-based composite electrode.
In a preferred embodiment, before step 1), in order to improve the purity of the activated carbon and reduce the influence of impurities on the conductive capability, an activated carbon powder pretreatment step can be further included. The pretreatment of the activated carbon powder can be carried out in any manner known to those skilled in the art as long as impurities can be removed. The preferred pretreatment method is: dispersing activated carbon powder in deionized water, stirring and settling, taking the lower layer, washing with deionized water and/or ethanol, and drying to obtain the activated carbon. Wherein the stirring and settling conditions are as follows: stirring in deionized water at 30-40 deg.C at 50-100rpm for 2-4h; the optional mode of washing by the ionized water and/or the ethanol is as follows: washing with deionized water for 2-4 times, and washing with ethanol for 2-4 times; the drying conditions are as follows: drying in a vacuum oven at 60-80 deg.C for 1-2h.
In a preferred embodiment, in the step 1), the concentrations of the potassium ferricyanide solution and the ferric chloride solution are both 0.02-0.08mol/L, and the solvents of the solutions are deionized water; more preferably, the concentration of the potassium ferricyanide solution and the concentration of the ferric chloride solution are both 0.05mol/L. Tests show that the Prussian blue carbon-based composite material obtained by mixing the solution with the concentration and the active carbon has a better doping effect.
In a preferred embodiment, in step 1), the mass-to-volume ratio of the activated carbon powder, the potassium ferricyanide solution and the ferric chloride solution is 1g: (8-12) ml: (8-12) ml; more preferably, the mass volume ratio of the activated carbon powder to the potassium ferricyanide solution to the ferric chloride solution is 1g:10ml:10ml. Under the condition of the proportion, the dosage of the active carbon can be reduced, and the doping effect is better, so that the adsorption capacity and the adsorption rate of the electrode are effectively improved.
In a preferred embodiment, in step 1), the stirring conditions are: stirring at 100-200rpm for 1-2h; the standing and layering conditions are as follows: standing at normal temperature for 12-24h.
In a preferred embodiment, in step 1), in order to improve the doping effect, after standing and layering, the lower layer precipitate may be washed with deionized water for 2-6 times to wash away the potassium ferricyanide and ferric chloride which may remain, and then dried.
In a preferred embodiment, in step 1), the drying manner may be any manner known to those skilled in the art, and preferably, the drying conditions are as follows: drying in a vacuum oven at 60-80 deg.C for 8-16h.
In a preferred embodiment, in step 2), the inert atmosphere comprises nitrogen, the high-temperature calcination temperature is 600-800 ℃, and the calcination time is 1-3h; more preferably, the calcination temperature is 700 ℃ and the calcination time is 2h.
In a preferred embodiment, in the step 3), after grinding, the particle size of the Prussian blue doped activated carbon fine powder is less than or equal to 150 microns.
In a preferred embodiment, in the step 3), the mass volume ratio of the prussian blue doped activated carbon fine powder, the conductive agent, the binder and the solvent is 1g:0.1g: (0.73-0.74) ml: (2-4) ml; more preferably, the mass-volume ratio of the prussian blue doped activated carbon fine powder to the conductive agent to the binder to the solvent is 1g:0.1g:0.014g:0.73ml.
In a preferred embodiment, the conductive agent comprises acetylene black powder, and the binder is a solution of PVDF (polyvinylidene fluoride) dissolved in NMP (N-methyl pyrrolidone), wherein the mass fraction of PVDF is 2%; the solvent includes NMP (N-methylpyrrolidone).
In a preferred embodiment, in step 4), the slurry coating method can be any method known to those skilled in the art, and a linear coating bar is preferably used for coating. The current collector may be made of any material known to those skilled in the art, and a preferred current collector is graphite paper.
In a preferred embodiment, in step 4), the drying conditions may be any manner known to those skilled in the art, and preferably, the current collector with the slurry coated on the surface is placed in a vacuum drying oven and dried at 60-80 ℃ for 1-2h.
The invention also aims to provide a Prussian blue carbon-based composite electrode, which is obtained by uniformly stirring the prepared Prussian blue doped active carbon electrode material with a conductive agent, an adhesive and a solvent, and coating the Prussian blue doped active carbon electrode material on a current collector, wherein the thickness of a coating area is 100-200 mu m, and the length and the width of the coating area are 6-7cm. According to the invention, prussian blue is effectively doped on the activated carbon through a simple method, and the traditional activated carbon electrode can be modified, so that the electronic conduction is accelerated, and the adsorption capacity and the adsorption rate of the activated carbon electrode are improved.
The invention also aims to provide the application of the Prussian blue carbon-based composite electrode, two prepared Prussian blue carbon-based composite electrodes are assembled into a capacitance deionization electrode module group, sodium chloride solution flows in from one end of the module group, flows through the two electrodes and flows out from the other end of the module group, and positive pressure and negative pressure are respectively applied to the two electrodes at the same time, so that the solution desalination can be completed. After the desalination is finished, the regeneration of the electrodes can be realized in a mode of reversely connecting the positive electrode and the negative electrode, so that the aim of recycling is fulfilled. During desalting, the treated saline solution has high inlet water concentration and large desalting amount per unit mass, and has wide application prospect.
In a preferred embodiment, the capacitive deionization electrode module set sequentially comprises: a glass plate, a silica gel gasket, a Prussian blue carbon-based composite electrode, a nylon net, a silica gel gasket, a plastic partition plate, a silica gel gasket, a nylon net, a Prussian blue carbon-based composite electrode, a silica gel gasket and a glass plate; wherein, the glass plate is provided with a water inlet and a water outlet, the silica gel gasket and the plastic clapboard are hollow, and the positions corresponding to the Prussian blue carbon-based composite electrode are provided with small holes to ensure that the solution fully flows through the electrode coating area. When the electrode module is prepared, the surface of the Prussian blue carbon-based composite electrode is specially added with a nylon net, and the function of the nylon net is as follows: the firmness of the surface coating of the electrode plate is improved, and the surface coating is prevented from being washed away when the flow is too large; moreover, the nylon net is added, so that the contact surface of the water flow and the coating is more uniform, and the stability of the desalting effect is improved.
In a preferred embodiment, the applied voltage is in the range of 1-1.5V, the solution flow rate is 1-8mL/min, and the sodium chloride solution is 50-200mg/L.
In a preferred embodiment, in the capacitive deionization electrode module group, deionized water flows in from one end of the module group, flows through two electrodes, and flows out from the other end of the module group, and the two electrodes are connected in reverse at the same time, so that electrode regeneration can be completed.
The technical scheme of the application is explained in detail by the following specific embodiments:
unless otherwise specified, the technical means used in the present invention are conventional means well known to those skilled in the art, and various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods. The reagents used in the invention are analytically pure unless otherwise specified.
Example 1
Preparing a Prussian blue doped active carbon electrode material:
(1) Active carbon pretreatment: placing the activated carbon powder in deionized water at 40 ℃, heating and stirring for 4h, settling, taking the lower layer, washing with deionized water and ethanol for multiple times, placing in a vacuum oven, drying for 1h at 80 ℃ to obtain activated carbon powder, and grinding for later use;
(2) Respectively preparing 50mL of potassium ferricyanide solution and 50mL of ferric chloride solution at 0.05 mol/L;
(3) Placing 5g of pretreated activated carbon powder in a beaker, adding 50mL of each of 0.05mol/L of iron potassium cyanide solution and ferric chloride solution, stirring for 2h, standing and aging at normal temperature for 24h, repeatedly cleaning the lower-layer precipitate with deionized water and ethanol, and then placing in a vacuum oven for drying at 80 ℃ for 12h;
(4) And grinding the dried product into fine powder, filling the fine powder into a quartz boat, putting the quartz boat into a tube furnace, heating the quartz boat for 2 hours at 700 ℃ under nitrogen atmosphere, and taking the quartz boat out after the heating and cooling are finished to obtain the Prussian blue doped active carbon electrode material.
The obtained prussian blue doped activated carbon material is characterized, and the SEM image and the XRD image are respectively shown as figure 1 and figure 2. Both the agglomerated particles in fig. 1 and the diffraction peaks shown in fig. 2 indicate successful doping of prussian blue onto activated carbon.
Example 2
Preparing a Prussian blue carbon-based composite electrode:
(1) Grinding the Prussian blue doped activated carbon electrode material prepared in the example 1, sieving the ground Prussian blue doped activated carbon electrode material with a 100-mesh sieve to obtain Prussian blue doped activated carbon fine powder, adding a conductive agent, a binder and a solvent into the Prussian blue doped activated carbon fine powder, and uniformly mixing to obtain electrode slurry. The specific operation is as follows: uniformly mixing 2g of prussian blue doped active carbon fine powder and 0.2g of acetylene black powder (conductive agent), dropwise adding 1.468mL of NMP solution (binder) containing 2% of PVDF, uniformly stirring with the powder material, and then dropwise adding 6mL of N-methylpyrrolidone while oscillating to prepare uniform electrode slurry.
(2) And (3) coating the electrode slurry on the surface of a graphite paper current collector by using a linear coating rod, wherein the thickness of a coating area is 200 mu m, and the length and the width of the coating area are 7cm, placing the current collector coated with the electrode slurry on the surface in a vacuum drying box, and drying for 1h at 80 ℃ to obtain the Prussian blue carbon-based composite electrode. The physical diagram of the electrode is shown in figure 3.
Comparative example 1
Preparing a traditional activated carbon electrode:
the activated carbon pretreated in the step (1) in the embodiment 1 is used as a raw material to replace the electrode material of the Pulusblue-doped activated carbon in the embodiment 2, and the other steps of the method are completely consistent with those in the embodiment 2, so that the activated carbon electrode is obtained.
Examples of effects
The desalting performance test was performed using the electrodes obtained in example 2 and comparative example 1, respectively:
(1) Assembling the capacitive deionization electrode module device: according to the technical scheme, the glass plate, the silica gel gasket, the electrode, the nylon net, the silica gel gasket, the plastic partition plate, the silica gel gasket, the nylon net, the electrode, the silica gel gasket and the glass plate are adopted; wherein, the glass plate is provided with a water inlet and a water outlet, the silica gel gasket and the plastic partition plate are hollow, and small holes are arranged at corresponding positions, thereby achieving the purposes of facilitating the water inlet and outlet of the module and ensuring that the solution fully flows through the electrode coating area.
(2) Assembling a desalting test device: the device comprises a salt solution, a peristaltic pump, an electrode module, a multifunctional parameter tester and a direct current power supply. The peristaltic pump pumps the salt solution into the electrode module, and the salt solution flows through the two electrode coating areas, flows out of the electrode module through the water outlet and is pumped back into the original beaker by the other peristaltic pump. The direct current power supply applies direct current voltage to the two electrodes through the tabs of the current collector, and the multi-parameter tester determines and records the concentration of the salt solution in the beaker through the conductivity electrode.
(3) Desalination test method: the assembled electrode module (shown in fig. 4) was connected to a desalination performance testing apparatus. And then realizing the circulation of the salt solution in the desalting performance testing device by a peristaltic pump, inserting the conductivity electrode into a container filled with the salt solution, and continuously circulating the salt solution until the conductivity value is stable. And after the conductivity is stable, applying voltage to the two electrode lugs in the electrode module to start desalting, automatically recording the conductivity once every 30s by the multi-parameter tester, and finishing the desalting stage when the conductivity value of the salt solution is stable. Wherein the working voltage is 1-1.5V, the flow rate of inlet and outlet water of the saline solution is 8mL/min, and the inlet water concentration is 200mg/L.
(4) Electrode regeneration test method: the inlet and outlet water is deionized water, and the inlet and outlet water is realized by reversely connecting two electrodes, and the rest is completely consistent with the desalination test.
Results and discussion: the results of the test were shown in FIGS. 5 and 6, with "15min desalination +5min regeneration". It can be seen from the figure that under different voltage conditions, the prussian blue carbon-based composite electrode is obviously superior to the performance index of the traditional activated carbon electrode in both desalination amount and desalination rate, which indicates that the prussian blue doped activated carbon electrode material obtained by the simple method can be suitable for different operation conditions of the capacitive deionization technology and has better universality.
The foregoing description of specific exemplary embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. A preparation method of a Prussian blue carbon-based composite electrode is characterized by comprising the following steps:
1) Adding a potassium ferricyanide solution and a ferric chloride solution into the activated carbon powder, uniformly stirring to obtain a mixed solution, standing for layering, and drying a precipitate on a lower layer;
2) Calcining the dried product obtained in the step 1) at a high temperature in an inert atmosphere to obtain a Prussian blue doped activated carbon material;
3) Grinding the product obtained in the step 2) to obtain prussian blue doped active carbon fine powder, adding a conductive agent, a binder and a solvent, and uniformly mixing to obtain electrode slurry;
4) And (4) coating the slurry obtained in the step 3) on the surface of a current collector in a scraping manner, and drying to obtain the Prussian blue carbon-based composite electrode.
2. The method for preparing a prussian blue carbon-based composite electrode as claimed in claim 1, wherein in step 1), the concentrations of the potassium ferricyanide solution and the ferric chloride solution are both 0.02 to 0.08mo L/L, and the solvents of the solutions are deionized water.
3. The method for preparing the prussian blue carbon-based composite electrode as claimed in claim 1, wherein in step 1), the mass-to-volume ratio of the activated carbon powder, the potassium ferricyanide solution and the ferric chloride solution is 1g: (8-12) ml: (8-12) ml.
4. The method for preparing the prussian blue carbon-based composite electrode according to claim 1, wherein in the step 2), the high-temperature calcination temperature is 600 to 800 ℃, and the calcination time is 1 to 3 hours.
5. The method for preparing the prussian blue carbon-based composite electrode according to claim 1, wherein in step 3), the mass-to-volume ratio of the prussian blue-doped activated carbon fine powder, the conductive agent, the binder and the solvent is 1g:0.1g: (0.73-0.74) ml: (2-4) ml.
6. The Prussian blue carbon-based composite electrode obtained by the preparation method according to any one of claims 1 to 5, wherein the thickness of an electrode slurry region on the surface of the Prussian blue carbon-based composite electrode is 100 to 200 μm, and the length and the width of the electrode slurry region are 6 to 7cm.
7. The use of the prussian blue carbon-based composite electrode obtained by the preparation method according to any one of claims 1 to 5, wherein the two prussian blue carbon-based composite electrodes obtained by the preparation method are assembled into a capacitive deionization electrode module group, a sodium chloride solution flows in from one end of the module group, flows through the two electrodes, and flows out from the other end of the module group, and positive pressure and negative pressure are applied to the two electrodes respectively, thereby completing the solution desalination.
8. The use of a prussian blue carbon-based composite electrode as claimed in claim 7, wherein the set of capacitive deionization electrode modules comprises in order: glass plate, silica gel gasket, prussian blue carbon-based composite electrode, nylon net, silica gel gasket, plastic partition plate, silica gel gasket, nylon net, prussian blue carbon-based composite electrode, silica gel gasket and glass plate; wherein, the glass plate is provided with a water inlet and a water outlet, the silica gel gasket and the plastic clapboard are hollow, and the positions corresponding to the Prussian blue carbon-based composite electrode are provided with small holes to ensure that the solution fully flows through the electrode coating area.
9. The use of a prussian blue carbon-based composite electrode according to claim 8, wherein the applied voltage is in the range of 1-1.5V, the solution inlet and outlet flow rate is 1-8mL/min, and the sodium chloride solution is 50-200mg/L.
10. The use of the prussian blue carbon-based composite electrode as claimed in claim 7, wherein in the capacitive deionization electrode module group, deionized water is introduced from one end of the module group, flows through the two electrodes, and then flows out from the other end of the module group, and the two electrodes are connected in reverse, thereby completing electrode regeneration.
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