CN115028237B - Electrode material for electrochemical desalination and preparation method thereof - Google Patents
Electrode material for electrochemical desalination and preparation method thereof Download PDFInfo
- Publication number
- CN115028237B CN115028237B CN202110246425.0A CN202110246425A CN115028237B CN 115028237 B CN115028237 B CN 115028237B CN 202110246425 A CN202110246425 A CN 202110246425A CN 115028237 B CN115028237 B CN 115028237B
- Authority
- CN
- China
- Prior art keywords
- gdfeo
- perovskite
- preparation
- electrode material
- electrochemical desalination
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000010612 desalination reaction Methods 0.000 title claims abstract description 28
- 239000007772 electrode material Substances 0.000 title claims abstract description 21
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 239000006260 foam Substances 0.000 claims abstract description 13
- 229910052709 silver Inorganic materials 0.000 claims abstract description 9
- 239000004332 silver Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 21
- 235000021110 pickles Nutrition 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 18
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- 239000002699 waste material Substances 0.000 claims description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 229940120146 EDTMP Drugs 0.000 claims description 4
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000002738 chelating agent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011033 desalting Methods 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F2001/46133—Electrodes characterised by the material
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses an electrode material for electrochemical desalination and a preparation method thereof, and belongs to the technical field of electrochemical desalination. The technical proposal is as follows: an electrode material for electrochemical desalination comprises a substrate and a catalytic film covered on the surface of the substrate, wherein the substrate is made of composite foam nickel doped with silver, and the catalytic film is made of GdFeO 3 perovskite-supported composite manganese dioxide. The beneficial effects of the invention are as follows: the electrode material for electrochemical desalination provided by the invention has the advantages of high corrosion resistance, good conductivity, high magnetic property, high industrial circulation external drainage electrochemical desalination efficiency improvement under complex conditions, high recovery rate, high preparation efficiency, economy, reasonability, good stability of the prepared electrode, high desalination efficiency, long service life and high recovery rate.
Description
Technical Field
The invention relates to the technical field of electrochemical desalination, in particular to an electrode material for electrochemical desalination and a preparation method thereof.
Background
The circulating water system is one of the indispensable energy media of the air conditioning system of the metallurgical industry, the petroleum industry, the chemical industry and the building. The improvement of the utilization rate of the circulating water greatly slows down the water pressure, but reduces the discharge of the circulating water, improves the concentration multiple of the circulating water, and inevitably causes the problems of scaling, corrosion, mass breeding of microorganisms and the like of pipelines and equipment. At present, for an industrial circulating water treatment system, in order to reduce adverse effects on pipelines and equipment caused by concentration of salts and the like in circulating water, a method of adding chemical agents is generally used for keeping water quality stable so as to improve the concentration multiple of the circulating water system. However, the method has certain disadvantages in the aspects of high medicament cost, high operation cost, pollution to the environment caused by phosphorus contained in the sewage and wastewater discharged from the system, and the like.
Although the novel agent can prevent the scaling and sterilization of the circulating water and improve the concentration multiple of the circulating water, the addition of the agent can increase COD, inorganic ions and the like of the water body, so that the water quality is continuously deteriorated. The electrochemical treatment technology can greatly reduce the addition of the medicament, not only saves a great amount of medicament cost, but also reduces the addition of harmful components in the water body, and is a real green environment-friendly technology.
Although electrochemical technology has been applied to industry on a large scale, forming a huge electrochemical industry, electrochemical desalination treatment technology is an effective green water treatment technology, and has not yet been widely applied to industrial circulating water systems, mainly because of low efficiency and unreasonable economy. Wherein, how to improve the stability, the service life and the recovery rate of the electrode is a difficulty of further improving the electrochemical desalination treatment technology.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the electrode material for electrochemical desalination, which has high corrosion resistance, good conductivity, high magnetic property, high recovery rate and high electrochemical desalination efficiency of industrial circulating external drainage under complex conditions, and simultaneously provides the preparation method of the electrode material for electrochemical desalination, which has high preparation efficiency, economy, rationality, good stability of the prepared electrode, high desalination efficiency, long service life and high recovery rate.
In order to achieve the above object, the present invention provides an electrode material for electrochemical desalination, which comprises a substrate and a catalytic film covered on the surface of the substrate, wherein the substrate is made of composite foam nickel doped with silver, and the catalytic film is made of composite manganese dioxide supported by GdFeO 3 perovskite. The silver electrode is doped in the foam nickel, so that the corrosion resistance and the conductivity of the electrode are obviously improved, the composite manganese dioxide prepared by using the composite transition metal in the waste lithium battery pickle liquor has high desalination efficiency, and the GdFeO 3 perovskite loaded composite manganese dioxide enables the electrode to have strong magnetic property, and has positive effects on recycling electrode materials.
The preparation method of the electrode material for electrochemical desalination comprises the following steps:
Step S1: preparation of GdFeO 3 perovskite: mixing gadolinium nitrate, ferric nitrate and a chelating agent, dissolving in deionized water, and mixing and stirring; heating in water bath at 90deg.C for 12 hr to form gel substance; heating in an air blast drying oven at 120 ℃ for 24 hours, transferring to a muffle furnace, and calcining for 6 hours to form GdFeO 3 perovskite;
Step S2: preparation of GdFeO 3 perovskite loaded composite manganese dioxide material:
Step S201: preparing a waste lithium battery pickle liquor and adjusting the pH of the pickle liquor to be slightly acidic or neutral, wherein the anode material of the waste lithium battery comprises LiMn 2O4 and Li (Ni xCoyMnz)O2, wherein x: y: z=1:1:1 or x: y: z=5:2:3 or x: y: z=6:2:2, and further, the mole ratio of transition metal and strong oxidant in the pickle liquor is set to be 1:2-1:4;
Step S202: mixing the waste lithium battery pickle liquor regulated in the step S201 with a strong oxidant, and adding the mixed liquor into the GdFeO 3 perovskite prepared in the step S1 to form mixed liquor, wherein the strong oxidant is preferably KMnO 4 or (NH 4）S2O8;
Step S203: placing the mixed solution prepared in the step S202 into a polytetrafluoroethylene hydrothermal reaction kettle for heating treatment, and then washing, filtering and drying to prepare the GdFeO 3 perovskite loaded composite manganese dioxide material with stronger electrochemical desalting performance;
Step S3: preparation of an electrode: mixing the GdFeO 3 perovskite loaded composite manganese dioxide material prepared in the step S2, carbon black and polytetrafluoroethylene according to the mol ratio of 7:2:1, adding organic acid or alcohol, specifically, selecting acetic acid or propionic acid when the organic acid is selected, selecting ethanol or propanol when the alcohol is selected, carrying out ultrasonic and drying, carrying out hydrothermal reaction by taking silver-doped composite foam nickel as a conductive matrix, washing and drying a product, so that the electrode has stronger corrosion resistance and conductivity.
Also a particular feature of the invention is that in said step S1, said chelating agent is provided as a salt of a hydroxy carboxylic acid or an organic phosphonic acid, preferably ethylenediamine tetramethylene phosphonic acid or diethylenetriamine pentamethylene phosphonic acid, or an organic acid, preferably citric acid.
The invention is characterized in that in the step S1, gadolinium nitrate, ferric nitrate and chelating agent are mixed and dissolved in deionized water to form a solution, and the mass ratio of the gadolinium nitrate, the ferric nitrate and the chelating agent in the solution is respectively set to be 20-40%.
The invention is also characterized in that in the step S1, the molar ratio of gadolinium nitrate, ferric nitrate and chelating agent is 1:1 (1.5-3.0).
The invention is also characterized in that in the step S1, the temperature range of the calcination treatment is set to 800-1000 ℃.
The invention is also characterized in that the mass ratio of the transition metal to GdFeO 3 perovskite in the pickle liquor of the waste lithium battery in the step S202 is not more than 20 percent.
The invention is also characterized in that in the step S3, the mass proportion of the doped silver in the silver-doped composite foam nickel is set to be 1-5%.
The invention is also characterized in that in step S203, the heat treatment temperature is 90-160 ℃, and the heat treatment time is preferably 12-24 hours.
The invention is also characterized in that in the step S3, the hydrothermal reaction temperature is 120-180 ℃, and the preferable hydrothermal reaction time is 6-12h.
The electrode prepared by the invention is applied to electrochemical desalination of industrial circulating external drainage, and has high desalination efficiency and strong corrosion resistance.
The beneficial effects of the invention are as follows: the electrode material prepared by the invention not only has better corrosion resistance and conductivity, but also has higher magnetic property, and has important significance for realizing improvement of the electrochemical desalination efficiency of the industrial circulating external drainage under complex conditions and recycling of the electrode material, and has obvious environmental protection advantage. The preparation method of the electrode material for electrochemical desalination provided by the invention can be used for preparing the electrode material with high corrosion resistance, high conductivity and strong magnetism, and has the advantages of high preparation efficiency, economy, rationality, good stability, long service life and high recovery rate of the prepared electrode, and has good industrial application prospect.
Detailed Description
In order to clearly illustrate the technical characteristics of the scheme, the scheme is explained below through a specific embodiment.
Example 1
The embodiment of the invention provides an electrode material for electrochemical desalination, which comprises a substrate and a catalytic film covered on the surface of the substrate, wherein the substrate is made of composite foam nickel doped with silver, and the catalytic film is made of GdFeO 3 perovskite-loaded composite manganese dioxide.
The composite foam nickel doped with silver is used as a substrate, and the GdFeO 3 perovskite loaded composite manganese dioxide material grows on the surface of the composite foam nickel, so that the corrosion performance and the conductivity of an electrode can be enhanced, and the composite foam nickel has higher magnetic performance, and has important significance for improving the electrochemical desalting efficiency of industrial circulating external drainage and recycling the electrode material under complex conditions.
Example 2
The embodiment of the invention provides a preparation method of an electrode material for electrochemical desalination, which comprises the following steps:
Step S1: preparation of GdFeO 3 perovskite: the molar ratio was set to 1:1:1.5, mixing gadolinium nitrate, ferric nitrate and ethylenediamine tetramethylene phosphonic acid, dissolving in deionized water, wherein the mass ratio of the gadolinium nitrate in the solution is 20%, and mixing and stirring; heating in water bath at 90deg.C for 12 hr to form gel substance; heating in an air blast drying oven at 120 ℃ for 24 hours, transferring to a muffle furnace, and calcining at 900 ℃ for 6 hours to form GdFeO 3 perovskite;
Step S2: preparation of GdFeO 3 perovskite loaded composite manganese dioxide material:
Step S201: the method comprises the steps of preparing waste lithium battery pickle liquor by using a positive electrode material Li (waste lithium battery of Ni 5Co3Mn2)O2 and pickle liquor of which the mole ratio of transition metal to strong oxidant is 1:2, and regulating the pH value to be slightly acidic;
Step S202: mixing the waste lithium battery pickle liquor regulated in the step S201 with KMnO 4, adding the mixture into the GdFeO 3 perovskite prepared in the step S1 to form mixed liquor, wherein the mass ratio of transition metal to GdFeO 3 perovskite in the waste lithium battery pickle liquor is 10%;
Step S203: placing the mixed solution prepared in the step S202 into a polytetrafluoroethylene hydrothermal reaction kettle, heating at 160 ℃ for 12 hours, and then washing, filtering and drying;
Step S3: preparation of an electrode: mixing the GdFeO 3 perovskite loaded composite manganese dioxide material prepared in the step S2, carbon black and polytetrafluoroethylene according to the mol ratio of 7:2:1, adding acetic acid, performing ultrasonic treatment and drying, performing hydrothermal reaction by taking composite foam nickel doped with 1% silver as a conductive matrix, performing hydrothermal reaction for 6 hours at the temperature of 140 ℃, and washing and drying the product.
Example 3
The embodiment of the invention provides a preparation method of an electrode material for electrochemical desalination, which comprises the following steps:
Step S1: preparation of GdFeO 3 perovskite: the molar ratio was set to 1:1:2, mixing gadolinium nitrate, ferric nitrate and ethylenediamine tetramethylene phosphonic acid, dissolving in deionized water, wherein the mass ratio of gadolinium nitrate in the solution is 20%, and mixing and stirring; heating in water bath at 90deg.C for 12 hr to form gel substance; heating in an air blast drying oven at 120 ℃ for 24 hours, transferring to a muffle furnace, and calcining at 850 ℃ for 6 hours to form GdFeO 3 perovskite;
Step S2: preparation of GdFeO 3 perovskite loaded composite manganese dioxide material:
step S201: the method comprises the steps of selecting a waste lithium battery with a positive electrode material of LiMn 2O4, and a mole ratio of transition metal to strong oxidant is 1:2, preparing waste lithium battery pickle liquor by the pickle liquor, and regulating the pH value of the waste lithium battery pickle liquor to be neutral;
Step S202: mixing the waste lithium battery pickle liquor regulated in the step S201 with (NH 4）S2O8), adding the mixed liquor into the GdFeO 3 perovskite prepared in the step S1 to form mixed liquor, wherein the mass ratio of transition metal to GdFeO 3 perovskite in the waste lithium battery pickle liquor is 10%;
Step S203: placing the mixed solution prepared in the step S202 into a polytetrafluoroethylene hydrothermal reaction kettle, heating at 140 ℃ for 12 hours, and then washing, filtering and drying;
Step S3: preparation of an electrode: mixing the GdFeO 3 perovskite loaded composite manganese dioxide material prepared in the step S2, carbon black and polytetrafluoroethylene according to the mol ratio of 7:2:1, adding acetic acid, performing ultrasonic treatment and drying, performing hydrothermal reaction by taking composite foam nickel doped with 1% silver as a conductive matrix, performing hydrothermal reaction for 6 hours at the temperature of 140 ℃, and washing and drying the product.
Comparative example 1
The preparation method comprises the following steps:
(1) Preparing manganese dioxide material: mixing MnSO 4·H2 O with KMnO 4, wherein the mol ratio of MnSO 4·H2 O to KMnO 4 is 1:2, placing the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, heating at 160 ℃ for 12h, washing, filtering and drying.
(2) Preparation of an electrode: manganese dioxide material, carbon black and polytetrafluoroethylene are mixed according to a molar ratio of 7:2:1, and acetic acid is added. And (3) performing ultrasonic treatment, drying, performing hydrothermal reaction by taking foam nickel as a conductive matrix, treating 6h at the temperature of 140 ℃, washing and drying the product, and preparing the manganese dioxide electrode.
Comparative example 2
The preparation method comprises the following steps:
(1) Preparing manganese dioxide material: mnSO 4·H2 O and (NH 4）S2O8) are mixed, the mol ratio of MnSO 4·H2 O and (NH 4）S2O8 is 1:2), and the mixture is heated in a tetrafluoroethylene hydrothermal reaction kettle at 140 ℃ for 12 hours, washed, filtered and dried.
(2) Preparation of an electrode: manganese dioxide material, carbon black and polytetrafluoroethylene are mixed according to a molar ratio of 7:2:1, and acetic acid is added. Ultrasonic treatment, drying, using foamed nickel as conductive matrix, hydrothermal reaction, treating at 140 deg.C for 6h, washing and drying the product, and manganese dioxide electrode.
The electrode prepared in the embodiment 2 and 3 of the invention has the desalination efficiency reaching 97% -98%, and the specific capacitance reaching 210F/g-225F/g at 0.5A/g;
The electrode prepared in comparative example 1 had a desalting efficiency of 81% and a specific capacitance of 49.44F/g at 0.5A/g;
the electrode prepared in comparative example 2 had a desalting efficiency of 83% and a specific capacitance of 50.67F/g at 0.5A/g.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (1)
1. The application of the electrode material in electrochemical desalination of a circulating water system is characterized in that the preparation method of the electrode material comprises the following steps:
step S1: preparation of GdFeO 3 perovskite: the molar ratio was set to 1:1:1.5 or 1:1:2, mixing gadolinium nitrate, ferric nitrate and ethylenediamine tetramethylene phosphonic acid, dissolving in deionized water, wherein the mass ratio of gadolinium nitrate in the solution is 20%, and mixing and stirring; heating in water bath at 90deg.C for 12 hr to form gel substance; heating in an air blast drying oven at 120 ℃ for 24 hours, transferring to a muffle furnace, and calcining at 900 ℃ for 6 hours to form GdFeO 3 perovskite;
Step S2: preparation of GdFeO 3 perovskite loaded composite manganese dioxide material:
Step S201: the method comprises the steps of preparing waste lithium battery pickle liquor by using a positive electrode material Li (waste lithium battery of Ni 5Co3Mn2)O2 and pickle liquor of which the mole ratio of transition metal to strong oxidant is 1:2, and regulating the pH value to be slightly acidic;
Step S202: mixing the waste lithium battery pickle liquor regulated in the step S201 with KMnO 4, adding the mixture into the GdFeO 3 perovskite prepared in the step S1 to form mixed liquor, wherein the mass ratio of transition metal to GdFeO 3 perovskite in the waste lithium battery pickle liquor is 10%;
Step S203: placing the mixed solution prepared in the step S202 into a polytetrafluoroethylene hydrothermal reaction kettle, heating at 160 ℃ for 12 hours, and then washing, filtering and drying;
Step S3: preparation of an electrode: mixing the GdFeO 3 perovskite loaded composite manganese dioxide material prepared in the step S2, carbon black and polytetrafluoroethylene according to the mol ratio of 7:2:1, adding acetic acid, performing ultrasonic treatment and drying, performing hydrothermal reaction by taking composite foam nickel doped with 1% silver as a conductive matrix, performing hydrothermal reaction for 6 hours at the temperature of 140 ℃, and washing and drying the product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110246425.0A CN115028237B (en) | 2021-03-05 | 2021-03-05 | Electrode material for electrochemical desalination and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110246425.0A CN115028237B (en) | 2021-03-05 | 2021-03-05 | Electrode material for electrochemical desalination and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115028237A CN115028237A (en) | 2022-09-09 |
| CN115028237B true CN115028237B (en) | 2024-06-07 |
Family
ID=83117947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110246425.0A Active CN115028237B (en) | 2021-03-05 | 2021-03-05 | Electrode material for electrochemical desalination and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115028237B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116411302B (en) * | 2022-10-28 | 2023-11-14 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Perovskite type foam metal composite electrode and synthesis method of linear carbonate |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002219363A (en) * | 2001-01-26 | 2002-08-06 | Matsushita Electric Ind Co Ltd | Catalyst for cleaning volatile organic compound and method for preparing the same |
| JP2014194898A (en) * | 2013-03-29 | 2014-10-09 | Hitachi Zosen Corp | Electrode and secondary battery |
| CN106241880A (en) * | 2016-06-21 | 2016-12-21 | 中国石油大学(华东) | Method for recovering high-purity manganese dioxide from waste manganese dry batteries and application |
| CN108285195A (en) * | 2018-01-10 | 2018-07-17 | 大连理工大学 | The preparation and application of the electrode material of carbon aerogel load manganese dioxide |
| CN108808147A (en) * | 2018-05-21 | 2018-11-13 | 金川集团股份有限公司 | A kind of method that manganese is recycled in waste and old lithium ion battery |
| CN108878901A (en) * | 2018-06-21 | 2018-11-23 | 北京创能惠通新能源科技有限公司 | Air electrode preparation method and aluminium-air cell |
| CN109364915A (en) * | 2018-11-23 | 2019-02-22 | 江苏中创清源科技有限公司 | A kind of Ca-Ti ore type O composite metallic oxide catalyst and preparation method thereof |
| RU2690496C1 (en) * | 2018-12-27 | 2019-06-04 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский государственный университет" (СПбГУ)" | Method of producing catalysts for synthesis gas production by carbon dioxide conversion of methane |
| CN110247063A (en) * | 2019-06-26 | 2019-09-17 | 太原理工大学 | A kind of preparation method and application of nano molybdenum disulfide/nitrogen-doped carbon nanometer pipe array hybridization compounding electrode |
| CN110306204A (en) * | 2019-04-04 | 2019-10-08 | 武汉工程大学 | A kind of stratiform nickel hydroxide composite electrode material of silver-doped and the preparation method and application thereof |
| CN110444778A (en) * | 2019-07-11 | 2019-11-12 | 桂林理工大学 | A method of double-perovskite oxide catalyst performance is improved using manganese dioxide |
| CN111530470A (en) * | 2020-05-06 | 2020-08-14 | 合肥工业大学 | Preparation method of manganese dioxide and composite material thereof and degradation method of sulfadiazine |
| CN112320899A (en) * | 2020-10-12 | 2021-02-05 | 浙江树人学院（浙江树人大学） | Nickel/zinc-manganese dioxide electrode and application thereof in wastewater treatment |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100569239B1 (en) * | 2003-10-25 | 2006-04-07 | 한국과학기술연구원 | Solid Oxide Fuel CellSOFC for coproducing syngas and electricity by the internal reforming of carbon dioxide by hydrocarbons and Electrochemical membrane reactor system for application |
-
2021
- 2021-03-05 CN CN202110246425.0A patent/CN115028237B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002219363A (en) * | 2001-01-26 | 2002-08-06 | Matsushita Electric Ind Co Ltd | Catalyst for cleaning volatile organic compound and method for preparing the same |
| JP2014194898A (en) * | 2013-03-29 | 2014-10-09 | Hitachi Zosen Corp | Electrode and secondary battery |
| CN106241880A (en) * | 2016-06-21 | 2016-12-21 | 中国石油大学(华东) | Method for recovering high-purity manganese dioxide from waste manganese dry batteries and application |
| CN108285195A (en) * | 2018-01-10 | 2018-07-17 | 大连理工大学 | The preparation and application of the electrode material of carbon aerogel load manganese dioxide |
| CN108808147A (en) * | 2018-05-21 | 2018-11-13 | 金川集团股份有限公司 | A kind of method that manganese is recycled in waste and old lithium ion battery |
| CN108878901A (en) * | 2018-06-21 | 2018-11-23 | 北京创能惠通新能源科技有限公司 | Air electrode preparation method and aluminium-air cell |
| CN109364915A (en) * | 2018-11-23 | 2019-02-22 | 江苏中创清源科技有限公司 | A kind of Ca-Ti ore type O composite metallic oxide catalyst and preparation method thereof |
| RU2690496C1 (en) * | 2018-12-27 | 2019-06-04 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский государственный университет" (СПбГУ)" | Method of producing catalysts for synthesis gas production by carbon dioxide conversion of methane |
| CN110306204A (en) * | 2019-04-04 | 2019-10-08 | 武汉工程大学 | A kind of stratiform nickel hydroxide composite electrode material of silver-doped and the preparation method and application thereof |
| CN110247063A (en) * | 2019-06-26 | 2019-09-17 | 太原理工大学 | A kind of preparation method and application of nano molybdenum disulfide/nitrogen-doped carbon nanometer pipe array hybridization compounding electrode |
| CN110444778A (en) * | 2019-07-11 | 2019-11-12 | 桂林理工大学 | A method of double-perovskite oxide catalyst performance is improved using manganese dioxide |
| CN111530470A (en) * | 2020-05-06 | 2020-08-14 | 合肥工业大学 | Preparation method of manganese dioxide and composite material thereof and degradation method of sulfadiazine |
| CN112320899A (en) * | 2020-10-12 | 2021-02-05 | 浙江树人学院（浙江树人大学） | Nickel/zinc-manganese dioxide electrode and application thereof in wastewater treatment |
Non-Patent Citations (3)
| Title |
|---|
| Manganese Dioxide-based Bifunctional Oxygen Reduction/Evolution Electrocatalysts: Effect of Perovskite Doping and Potassium Ion Insertion;P.Hosseini Benhangi;Electrochimica Acta;第Volume 123卷;第42-50页 * |
| The Influence of Fe Substitution in GdFeO3 on Redox and Catalytic Properties;L. V. Yafarova;Russian Journal of Physical Chemistry A;第94卷;2679–2684 * |
| 李娜.中温固体氧化物燃料电池双钙钛矿结构阴极材料的性能研究与改进.哈尔滨工业大学出版社,2021,第13页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115028237A (en) | 2022-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110482512A (en) | A kind of preparation method of battery-grade iron phosphate | |
| CN104628206B (en) | A kind of recycling treatment process of LiFePO4 factory effluent | |
| CN113171779B (en) | Preparation method and application of B-site five-membered high-entropy perovskite catalyst | |
| CN109289857B (en) | Rare earth element doped layered composite metal hydroxide and preparation and application thereof | |
| CN103606694A (en) | Preparation method for commercial vanadium battery electrolyte | |
| CN110240207A (en) | A kind of method that waste lithium cell recycling prepares tertiary cathode material | |
| CN110215921B (en) | Preparation method and application of magnetic nano composite catalyst with core-shell structure | |
| CN115028237B (en) | Electrode material for electrochemical desalination and preparation method thereof | |
| CN108400329A (en) | A kind of preparation method of precious metal simple substance adulterated vanadate nano-electrode material | |
| CN103904343B (en) | The preparation method of all-vanadium redox flow battery electrolytic solution | |
| CN103496777B (en) | Pretreatment method of ammonia-nitrogen wastewater | |
| CN111777149A (en) | Method for preparing polymeric ferric sulfate flocculant by using dye waste acid and application thereof | |
| CN110771627B (en) | Magnetic composite antibacterial material and preparation method thereof | |
| CN113200584A (en) | Electrode material and device for electrochemically treating circulating cooling water | |
| CN115215411A (en) | MOF-Ti doped with rare earth metal 4 O 7 Preparation method of composite electrode | |
| CN105668813B (en) | A kind of antisludging agent and preparation method thereof | |
| CN102963983A (en) | Vertical flow artificial wetland substrate modified based on LDHs (layered double hydroxides) coating film and preparation method of substrate | |
| CN116960425A (en) | Preparation method of iron-chromium flow battery electrolyte | |
| CN105645557B (en) | A kind of catalytic wet oxidation processing method of recirculated water | |
| CN110272111A (en) | A kind of oxidant and preparation method thereof removing high-salt wastewater COD organic matter | |
| CN115188958A (en) | Spherical porous sodium-ion battery material and preparation method thereof | |
| CN104495957A (en) | Preparation method of doped poly(nickel aluminophosphate) hydrotalcite | |
| CN105645558A (en) | Catalytic wet air oxidation treatment method of industrial circulating water | |
| CN107311294B (en) | Device and method for simultaneously treating park sludge and electroplating wastewater in electroplating industrial park | |
| CN110523406A (en) | A kind of solid carbon-based Anderson type catalyst containing molybdenum heteropolyacid and its application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |