CN108493501B - Preparation method of sodium fluoride dual-ion battery and application of sodium fluoride dual-ion battery in electrochemical fluorine removal - Google Patents
Preparation method of sodium fluoride dual-ion battery and application of sodium fluoride dual-ion battery in electrochemical fluorine removal Download PDFInfo
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- CN108493501B CN108493501B CN201810294845.4A CN201810294845A CN108493501B CN 108493501 B CN108493501 B CN 108493501B CN 201810294845 A CN201810294845 A CN 201810294845A CN 108493501 B CN108493501 B CN 108493501B
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- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 title claims abstract description 118
- 239000011775 sodium fluoride Substances 0.000 title claims abstract description 59
- 235000013024 sodium fluoride Nutrition 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011737 fluorine Substances 0.000 title description 18
- 229910052731 fluorine Inorganic materials 0.000 title description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000006181 electrochemical material Substances 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 18
- 239000011734 sodium Substances 0.000 claims abstract description 11
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 11
- 238000006115 defluorination reaction Methods 0.000 claims abstract description 8
- 229910014485 Na0.44MnO2 Inorganic materials 0.000 claims abstract description 7
- 239000007772 electrode material Substances 0.000 claims abstract description 7
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 77
- 239000002041 carbon nanotube Substances 0.000 claims description 60
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 229910052797 bismuth Inorganic materials 0.000 claims description 39
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 38
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 22
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- 238000001354 calcination Methods 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 8
- 230000020477 pH reduction Effects 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- VZZHAYFWMLLWGG-UHFFFAOYSA-K triazanium;bismuth;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [NH4+].[NH4+].[NH4+].[Bi+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O VZZHAYFWMLLWGG-UHFFFAOYSA-K 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 claims description 3
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 27
- -1 fluoride ions Chemical class 0.000 abstract description 21
- 230000008569 process Effects 0.000 abstract description 10
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 239000003575 carbonaceous material Substances 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- 229910004589 Na2FeP2O7 Inorganic materials 0.000 abstract description 3
- 229910000665 Na2V6O16 Inorganic materials 0.000 abstract description 3
- 229910019441 NaTi2(PO4)3 Inorganic materials 0.000 abstract description 3
- FPHIOHCCQGUGKU-UHFFFAOYSA-L difluorolead Chemical compound F[Pb]F FPHIOHCCQGUGKU-UHFFFAOYSA-L 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract 1
- BNBLBRISEAQIHU-UHFFFAOYSA-N disodium dioxido(dioxo)manganese Chemical compound [Na+].[Na+].[O-][Mn]([O-])(=O)=O BNBLBRISEAQIHU-UHFFFAOYSA-N 0.000 description 27
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 238000007865 diluting Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
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- 238000002441 X-ray diffraction Methods 0.000 description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- QSBNOZODKXUXSP-UHFFFAOYSA-K bismuth;azane;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound N.[Bi+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QSBNOZODKXUXSP-UHFFFAOYSA-K 0.000 description 4
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 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 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 2
- VTGOHKSTWXHQJK-UHFFFAOYSA-N pyrimidin-2-ol Chemical compound OC1=NC=CC=N1 VTGOHKSTWXHQJK-UHFFFAOYSA-N 0.000 description 2
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- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910019898 NaxMnO2 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- 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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a preparation method of a sodium fluoride bi-ion battery and application of the sodium fluoride bi-ion battery in electrochemical defluorination. The sodium fluoride double-ion battery comprises a sodium ion electrochemical material, a fluorine ion electrochemical material and electrolyte; the sodium ion electrode material comprises Na0.44MnO2，Na2FeP2O7，Na2V6O16，NaTi2(PO4)3，Na0.44[Mn1‑xTix]O2Etc.; the fluoride ion electrochemical material comprises an electrochemical material or an electrochemical material coated by a carbon material; the electrochemical material comprises Bi, BiF3, Pb, PbF2, piperidine inorganic matters, bipyridinium salt and the like; the electrolyte is NaF solution. The sodium fluoride double-ion battery has high specific capacity and good cycle performance; meanwhile, in the charging and discharging process, the fluoride ion electrode material can remove fluoride ions in the solution by utilizing the electrochemical fluoride ion adsorption, and can be applied to fluoride-containing sewage treatment.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to a preparation method of a sodium fluoride double-ion battery and application of the sodium fluoride double-ion battery in electrochemical defluorination.
Background
Water is an important substance that humans rely on for survival and is indispensable. Although water resources on earth are abundant, the phenomenon of water shortage in many areas is still serious due to limited and uneven distribution of fresh water resources, sudden population increase and continuous increase of water consumption for industrial and agricultural use. Although water on earth is renewable and continuously circulated, water quality is increasingly deteriorated due to increasing environmental pollution. The global water resource crisis brings great harm to human beings. Water pollution is the reduction or loss of the value of water use caused by harmful chemicals. Water pollution can be mainly classified into chemical pollution, physical pollution and biological pollution according to different pollution impurities, wherein the chemical pollution is the most serious. Chemical contamination is the reduction or loss of value in the use of water caused by harmful chemicals.
Fluoride-containing industrial wastewater is discharged in the processes of manufacturing of micro-electrolysis filler fluorine-containing products, coke production, electronic component production, electroplating, glass and silicate production, steel and aluminum manufacturing, metal processing, wood corrosion prevention, pesticide and fertilizer production and the like. Fluoride has paradoxical properties for humans. Fluorine is one of the trace elements necessary for the human body. If the intake amount is too small, the caries can cause serious black to brown spots on the teeth of people and even damage the structure of the teeth; if the intake amount is too large, the bone fracture will be caused, the human bone will be deformed, the osteoporosis will be brittle, the toughness will be lost, the fracture will be easy, and the movement will be blocked. At present, the treatment method of fluoride-containing wastewater can be divided into two main types of precipitation method and adsorption method. The precipitation method is suitable for treating industrial wastewater with high fluoride content, but secondary treatment is often required when the precipitation method is not thorough in treatment, and chemical agents required for treatment comprise lime, alum, dolomite and the like. The adsorption method is suitable for treating industrial wastewater with low fluoride content or wastewater with fluoride concentration still not meeting relevant regulations after precipitation treatment, but the adsorption method has poor capability of removing fluoride ions and low efficiency.
Therefore, a brand-new defluorination method is needed, which not only consumes less energy in the preparation process, has strong ion removal capability, is environment-friendly and is simple and convenient to operate; but also can provide electric energy in the process of removing fluorine.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a sodium fluoride dual-ion battery.
The invention also aims to provide a preparation method of the sodium fluoride bi-ion battery.
The invention also aims to provide application of the sodium fluoride bi-ion battery.
The purpose of the invention is realized by the following technical scheme: a sodium fluoride dual-ion battery comprises a sodium ion electrochemical material (positive electrode material), a fluorine ion electrochemical material (negative electrode material) and electrolyte; wherein:
the sodium ion electrode material is Na0.44MnO2，K0.27MnO2，Na2FeP2O7，V2O5，Na3V2(PO4)3，Na2V6O16，NaTi2(PO4)3PTVE (Polytetrafluoroethylene), PBA (polybutyl acrylate), Na2C8H4O4PVAQ (polyvinyl alcohol) and Na0.44[Mn1-xTix]O2One or more of (1);
the fluoride ion electrochemical material is an electrochemical material or an electrochemical material coated by a carbon material; the electrochemical material comprises more than one of Bi, BiF3, Pb, PbF2, piperidine inorganic matters and bipyridinium salt;
the electrolyte is NaF solution.
The piperidine inorganic substance comprises 2-hydroxypyrimidine and the like.
The bipyridinium salt includes 4' -bipyridinium dichloride and the like.
The carbon material comprises carbon nano tubes, graphene, activated carbon, carbon black and the like.
The NaF solution is preferably NaF aqueous solution.
Said Na0.44MnO2The (sodium manganate cathode material) is preferably prepared by the following method:
(I) mixing sodium carbonate and manganese oxide, then carrying out ball milling, and calcining mixed powder obtained after ball milling to obtain a product J;
(II) ball-milling the product J obtained in the step (I) again, and then calcining the precursor obtained after ball-milling again to obtain Na0.44MnO2(sodium manganate positive electrode material).
The mol ratio of the sodium carbonate to the manganese oxide in the step (I) is preferably 0.4-0.5: 1.
The ball milling conditions in the step (I) and the step (II) are as follows: ball milling is carried out for 10-15 h at 250-270 r/min.
The conditions of the calcination described in step (I) are preferably: heating to 400-600 ℃ in air at a speed of 2-10 ℃/min, and keeping the temperature for 4-7 h.
The conditions of the calcination in step (II) are preferably: heating to 900-1200 ℃ in air at a speed of 2 ℃/min, and keeping the temperature for 10-14 h.
The fluoride ion electrochemical material (nano bismuth coated by the carboxylated carbon nanotube) is preferably prepared by the following method:
(1) adding a mixed solution of concentrated sulfuric acid and concentrated nitric acid into the carbon nano tube for acidification treatment, then adding water for dilution, cooling, filtering, and washing to be neutral to obtain a filter cake A;
(2) drying and grinding the filter cake A obtained in the step (1) to obtain powder B;
(3) adding a mixed acid solution of concentrated sulfuric acid and hydrogen peroxide into the powder B obtained in the step (2) for secondary acidification treatment, then adding water for dilution, cooling, filtering, and washing to be neutral to obtain a filter cake C;
(4) drying and grinding the filter cake C obtained in the step (3) to obtain a carboxylated carbon nano tube D;
(5) dispersing the carboxylated carbon nano tube D obtained in the step (4) into water to obtain a solution E;
(6) adding bismuth ammonium citrate into the solution E obtained in the step (5), and uniformly stirring to obtain a solution F;
(7) and (3) dropwise adding the sodium borohydride solution into the solution F obtained in the step (6), continuing stirring after dropwise adding is finished to obtain a solution G, performing centrifugal purification and rinsing, and then performing vacuum drying to obtain the fluoride ion electrochemical material (nano bismuth coated by the carboxylated carbon nanotube).
The volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed solution of the concentrated sulfuric acid and the concentrated nitric acid in the step (1) is preferably 1:2 to 4.
The concentrated sulfuric acid is preferably concentrated sulfuric acid with the mass fraction of 98%.
The concentrated nitric acid is preferably concentrated nitric acid with the mass fraction of 68%.
The dosage of the carbon nano tube in the step (1) is calculated according to the proportion of 0.014-0.025 g of carbon nano tube per milliliter (ml) of mixed solution.
Said acidification treatment described in step (1) is preferably achieved by: adding a mixed solution of concentrated sulfuric acid and concentrated nitric acid into the carbon nano tube, performing 300W ultrasonic treatment for 10-40 min to uniformly disperse the carbon nano tube, and then stirring for 0.5-2 h under the condition of 400-2000 r/min.
The water described in steps (1), (3) and (5) is preferably deionized water.
The filtration described in steps (1) and (3) is preferably filtration under reduced pressure; more preferably, the filtration is carried out under reduced pressure by using a suction filter, wherein the filter paper used in the filtration is 0.22 μm filter paper.
The drying in the step (2) is vacuum drying.
The drying conditions are preferably as follows: drying for 1-3 h at 60-100 ℃.
The dosage of the powder B in the step (3) is 0.014-0.025 g per milliliter (ml) of mixed solution.
The second acidification treatment in the step (3) is preferably realized by the following steps: and adding a mixed acid solution of concentrated sulfuric acid and hydrogen peroxide into the powder B, performing 300W ultrasonic treatment for 10-40 min to uniformly disperse the powder B, and then stirring for 0.5-2 h under the condition of 400-2000 r/min.
The volume ratio of the concentrated sulfuric acid to the hydrogen peroxide in the mixed solution of the concentrated sulfuric acid and the hydrogen peroxide in the step (3) is preferably 1:2 to 4.
The concentrated sulfuric acid is preferably concentrated sulfuric acid with the mass fraction of 98%.
The hydrogen peroxide is preferably hydrogen peroxide with the mass fraction of 36%.
The drying in the step (4) is vacuum drying.
The drying conditions are preferably as follows: drying for 10-14 h at 30-60 ℃.
The amount of the carboxylated carbon nanotube D in the step (5) is calculated by mixing 0.5mg of the carboxylated carbon nanotube D per milliliter (ml) of water.
The dispersion in step (5) is preferably ultrasonic dispersion.
The conditions of the ultrasound are preferably: carrying out 300W ultrasonic treatment for 10-40 min.
The mass ratio of the ammonium bismuth citrate in the step (6) to the carboxylated carbon nanotube D is preferably 1: 0.045-0.065.
The concentration of the sodium borohydride solution in the step (7) is preferably 0.8-1.2 mol/L.
The mass ratio of the mass of the sodium borohydride in the sodium borohydride solution in the step (7) to the mass of the bismuth ammonium citrate is 1.21-2.72.
The stirring conditions in the step (7) are as follows: stirring for 0.5-2 h at 400-2000 r/min; preferably: stirring at 1500r/min for 0.5-1 h.
The conditions for the centrifugation in the step (7) are preferably: centrifuge at 8000r for 15 min.
The rinsing described in step (7) is preferably performed with deionized water.
The vacuum drying conditions in step (7) are preferably: drying for 8-12 h at 50-70 ℃.
The concentration of the NaF solution is 0.75-0.85 mol/L; preferably 0.8 mol/L.
The preparation method of the sodium fluoride double-ion battery comprises the following steps:
(a) uniformly mixing a negative electrode material, a binder and a conductive agent, then mixing into slurry, coating the slurry on graphite paper, and drying to obtain a sodium fluoride bi-ion battery negative electrode plate;
(b) uniformly mixing a positive electrode material, a binder and a conductive agent, mixing into slurry, coating the slurry on graphite paper, and drying to obtain a sodium fluoride bi-ion battery positive plate;
(c) and (b) assembling the negative plate, the diaphragm and the electrolyte of the sodium fluoride double-ion battery obtained in the step (a) and the positive plate of the sodium fluoride double-ion battery obtained in the step (b) to obtain the sodium fluoride double-ion battery.
The mass ratio of the negative electrode material, the binder and the conductive agent in the step (a) is (70-84): (15-8): (15-8); the mass ratio is preferably 70:15: 15.
the binder in step (a) is preferably polyvinylidene fluoride (PVDF) or polyvinylpyrrolidone K30 (PVP-K30).
The conductive agent in step (a) is preferably conductive carbon black, Super-P.
The thickness of the coating in the step (a) is preferably 120 to 200 micrometers.
The drying in the step (a) and the step (b) is vacuum drying; preferably drying for 5-24 h under the vacuum condition of 50-100 ℃.
The graphite paper in the step (a) and the step (b) is preferably graphite paper with the thickness of 1 mm.
The step (a) and the step (b) are carried out by adding a solvent to prepare slurry.
The solvent is preferably N-methylpyrrolidone or dimethylformamide.
The using amount of the solvent is calculated according to the mass ratio of 1:2 of the solute to the solvent, wherein the solute is a negative electrode material (or a positive electrode material) of the sodium fluoride double-ion battery, a binder and a conductive agent.
The mass ratio of the positive electrode material, the binder and the conductive agent in the step (b) is (76-84): (12-8): (12-8); the mass ratio is preferably 70:15: 15.
the binder described in step (b) is preferably binder LA132 from genninderle.
The conductive agent in the step (b) is commercial conductive liquid which is generally purchased; conductive carbon black Super-P is preferred.
The thickness of the coating in the step (b) is preferably 100 to 180 micrometers.
The electrolyte in the step (c) is 0.75-0.85 mol/L NaF electrolyte; preferably 0.8mol/L NaF electrolyte.
The sodium fluoride double-ion battery is applied to the field of wastewater treatment or fluorine removal equipment.
The wastewater is preferably fluoride-containing wastewater, and the method utilizes the electrochemical reaction of an electrode material to adsorb fluoride ions.
The principle of the invention is as follows:
the invention provides an innovative fluorine removal concept, and fluorine removal is carried out by utilizing electrode materials of fluoride ions and sodium ions based on the chemical reaction principle of a battery, and the technology not only has strong deionization capacity, but also has stable periodic repeatability.
The prior methods for purifying water sources and removing fluoride ions comprise a precipitation method and an adsorption method, but the two methods have poor ion removal capability and low efficiency, and Na is selected to solve the problem0.44MnO2As a positive electrode material, because of NaxMnO2(X is 0.18-0.64), so Na0.44MnO2Sodium ions can be provided and accepted, nano bismuth is coated by carboxylated carbon nano tubes to serve as a negative electrode material, and 50ml of sodium fluoride solution existing in fluid is used as electrolyte. The innovative seawater desalination can not only achieve the aim of removing fluoride ions, but also provide stable electric energy in the process of seawater desalination.
The preparation of the cathode material has the defect of poor cycle performance of the cathode material of the battery due to the nano bismuth and the easy agglomeration phenomenon, and the conventional mode cannot well and uniformly disperse the nano bismuth. In order to solve the technical defects, the invention synthesizes carboxylated carbon nanotubes by performing two-step acidification treatment on the carbon nanotubes, and then coats the carboxylated carbon nanotubes with the nano bismuth, so that the nano bismuth can be fully dispersed, and the conductivity of the nano bismuth can be enhanced. In the aspect of anode materials, sodium manganate is prepared by adopting a solid-state reaction method. Then assembling the positive electrode and the negative electrode into a battery, and performing electrochemical test to obtain a sodium fluoride dual-ion full battery assembled by a sodium manganate positive electrode and a nano bismuth negative electrode coated by a carboxylated carbon nano tube, wherein the specific capacity is high and good in cycle performance, and the first specific capacity is more than 220 mAh/g; on the other hand, the anode and cathode materials and the electrolyte are assembled into a fluid device, and along with the removal capability of fluorine ions detected by an ion detector in the charge and discharge cycle, the device has a remarkable effect of removing the fluorine ions.
Compared with the prior art, the invention has the following advantages and effects:
(1) the cathode material of the invention adopts the carbon nano tube which is subjected to two-step acidification treatment to synthesize the carboxylated carbon nano tube, the carboxylated carbon nano tube has stronger hydrophilic capability, and then the carboxylated carbon nano tube coats the nano bismuth, so that the nano bismuth can be fully dispersed, and the conductivity of the cathode material can be increased.
(2) The anode material and the cathode material prepared by the invention have the advantages of excellent electrochemical performance, high specific capacity and good cycling stability. The positive electrode and the negative electrode are assembled into a battery, and the sodium fluoride dual-ion full battery assembled by the sodium manganate positive electrode and the nano bismuth negative electrode coated by the carboxylated carbon nano tube has high specific capacity and good cycle performance through electrochemical tests.
(3) The invention has low requirement on raw materials, less preparation process, simple process and simple and convenient operation, and is suitable for mass production; the prepared material is suitable for water-based batteries and meets the requirements of the active material of the new-generation high-performance water-based battery.
(4) Compared with the traditional defluorination technology, the invention provides an innovative defluorination concept, and the defluorination is carried out by utilizing the electrode material fluorine ions and sodium ions based on the chemical reaction principle of the battery. On one hand, the technology can not only remove fluoride ions, but also provide electric energy, and the first specific capacity reaches 220 mAh/g.
(5) The sodium fluoride double-ion full battery can be applied to the field of flow batteries, and can remove fluorine ions in electrolyte in the charging and discharging processes to achieve the purpose of purifying water sources. In semiconductor research and development, a large amount of HF is needed to treat a silicon material substrate in production, and a large amount of fluorine ions in waste liquid need to treat high-concentration waste water before being discharged; for example, some hospital and pharmaceutical waste liquids contain a large amount of fluoride ions, which also need to be treated before being discharged.
(6) The preparation process is simple, the operation is simple and convenient, the full-cell prepared by the method is suitable for large-scale production, and the prepared full-cell has the advantages of high specific capacity and good cycle performance, can meet the requirements of high-capacity electronic equipment, and can be applied to defluorination equipment.
Drawings
Fig. 1 is a XRD chart of the nano bismuth negative electrode material coated with carboxylated carbon nanotubes prepared in example 1.
Fig. 2 is an XRD chart of the sodium manganate positive electrode material prepared in example 1.
Fig. 3 is an SEM image of the nano bismuth negative electrode material coated with the carboxylated carbon nanotube prepared in example 2.
Fig. 4 is an SEM image of the sodium manganate positive electrode material prepared in example 2.
Fig. 5 is a graph of the long cycle performance of the sodium fluoride dual-ion full cell prepared in example 3.
Fig. 6 is a graph showing the change of voltage and fluoride ion conductivity with time during the charge and discharge processes of the sodium fluoride bi-ion full cell prepared in example 3.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
All raw materials and reagents in the present invention are conventional ones, unless otherwise specified.
Example 1
The preparation method of the nano bismuth anode material coated by the carboxylated carbon nanotube comprises the following specific steps:
(1) placing 1.5g of carbon nano tube in a round-bottom flask, adding 100ml of mixed solution of concentrated sulfuric acid with the mass fraction of 98% and concentrated nitric acid with the mass fraction of 68% in the volume ratio of 1:2 into the round-bottom flask, and performing ultrasonic dispersion with the power of 300W for 10 min; then carrying out magneton stirring at the rotating speed of 400r/min for 0.5 h; diluting with 1000ml of deionized water, cooling, filtering with 0.22 μm filter paper under reduced pressure (vacuum filtering with suction filter), and washing with deionized water for several times until pH is neutral to obtain filter cake A;
(2) carrying out vacuum drying on the filter cake A obtained in the step (1) for 1h at 60 ℃, and then grinding to obtain powder B;
(3) placing the powder B obtained in the step (2) into a round-bottom flask, and adding 120ml of the powder B in a volume ratio of: 1:2.5 of a mixed solution of 98% concentrated sulfuric acid and 36% hydrogen peroxide by mass percent, and carrying out ultrasonic treatment with the power of 300W for 15 min; then carrying out magneton stirring at the rotating speed of 500r/min for 1.5 h; diluting with 1000ml of deionized water, cooling, filtering with 0.22 μm filter paper under reduced pressure (vacuum filtering with suction filter), and washing with deionized water for several times until the filtrate is neutral to obtain filter cake C;
(4) carrying out vacuum drying and grinding on the filter cake C obtained in the step (3) at 60 ℃ for 12h to obtain a carboxylated carbon nanotube D;
(5) dissolving 20mg of D obtained in the step (4) in 500ml of deionized water, and performing ultrasonic dispersion with the power of 300W for 12 min; then carrying out magneton stirring at the rotating speed of 350r/min for 1.5h to obtain a solution E;
(6) dissolving 0.4g of ammonium bismuth citrate in the solution E obtained in the step (5), and stirring with magnetons at the rotating speed of 400r/min for 2 hours to obtain a solution F;
(7) dropwise adding 55ml of 1mol/L sodium borohydride solution into the solution F prepared in the step (6), continuing to stir for 2 hours by magnetic force after dropwise adding is finished to obtain a solution G, then carrying out centrifugal purification (8000r for 15 minutes), rinsing by deionized water, and then carrying out vacuum drying at 80 ℃ for 10 hours to obtain nano bismuth H coated by the carboxylated carbon nanotube of the required material;
the preparation method of the sodium (di) manganate anode material comprises the following specific steps:
(8) mixing sodium carbonate and manganese oxide according to the molar ratio of 0.45:1, and performing ball milling in a planetary ball mill for 10 hours and 260r/min to obtain mixed powder I;
(9) calcining the mixed powder I obtained in the step (8) in air, heating to 400 ℃ at the speed of 2 ℃/min, and keeping the constant temperature for 4 hours to obtain a product J;
(10) performing ball milling on the product J obtained in the step (9) for 12h again by using a planetary ball mill at 260r/min to obtain a precursor K;
(11) calcining the precursor K obtained in the step (10) in the air again; the calcination conditions were: heating to 900 ℃ at the speed of 2 ℃/min, and keeping the temperature for 10 hours to obtain the final material of sodium manganate J;
and (III) carrying out XRD spectrum detection on the nano bismuth anode material coated by the carboxylated carbon nano tube prepared in the step (I), wherein the detection result is shown in figure 1. As can be seen from fig. 1, the diffraction peak of nano bismuth is clearly shown in the spectrum, and the peak is completely matched with the standard PDF card, and in addition, a steamed bread peak appears at about 30 degrees, and the peak is the peak corresponding to the carboxylated carbon nanotube. And (5) carrying out XRD (X-ray diffraction) spectrum detection on the sodium manganate anode material prepared in the step (II), wherein the detection result is shown in figure 2. As can be seen from FIG. 2, the diffraction peak of the sodium manganate composition is clearly shown in the graph and is completely consistent with the standard PDF card.
(IV) preparing the electrode plate of the battery, which comprises the following specific steps:
(1) mixing the nano bismuth negative electrode material coated by the carboxylated carbon nano tube prepared in the step (I), the adhesive polyvinylidene fluoride and the conductive carbon black Super-P (conductive agent) according to the mass ratio of 70:15:15, mixing the mixture into slurry by taking N-methyl pyrrolidone as a solvent (the mass ratio of solute to solvent is 1:2), coating the slurry (the coating thickness is 100 mu m) on graphite paper with the thickness of 1mm, and performing vacuum drying at 80 ℃ for 10 hours. Preparing a nano bismuth negative plate 1 coated by the carboxylated carbon nano tube;
(2) and (2) uniformly mixing the sodium manganate positive electrode material prepared in the step (two), a binder LA132 (15% of binder solid content, available from Chengdu Dingle company) and conductive carbon black Super-P according to a weight ratio of 70:15:15, mixing the mixture into slurry by taking N-methylpyrrolidone as a solvent (the mass ratio of solute to solvent is 1:2), coating the slurry on graphite paper to a coating thickness of 100 mu m, and drying the slurry at 100 ℃ in vacuum for 10 hours to prepare a sodium manganate positive electrode sheet 1.
And (V) assembling the sodium fluoride double-ion full battery, which comprises the following specific steps:
the sodium fluoride double-ion full cell is assembled by an electrolytic cell: and (3) assembling the nano bismuth negative electrode sheet 1 coated by the carboxylated carbon nanotube prepared in the step (IV) (1), a diaphragm, an electrolyte (0.8mol/L NaF solution) and the sodium manganate positive electrode sheet 1 prepared in the step (IV) (2) by using a fluid device to obtain the sodium fluoride double-ion full cell. And the positive electrode clamp and the negative electrode clamp respectively clamp a sodium manganate positive electrode and a nano bismuth negative electrode coated by the carboxylated carbon nano tube, and the electrochemical performance is tested. And testing the conductivity of the ions by using a conductivity meter, and further obtaining the removal capacity of the fluorine ions.
Example 2
The preparation method of the nano bismuth anode material coated by the carboxylated carbon nanotube comprises the following specific steps:
(1) placing 2.5g of carbon nano tube in a round-bottom flask, adding 100ml of mixed solution of concentrated sulfuric acid with the mass fraction of 98% and concentrated nitric acid with the mass fraction of 68% in the volume ratio of 1:3 into the round-bottom flask, and performing ultrasonic dispersion with the power of 300W for 10 min; then carrying out magneton stirring for 1h at the rotating speed of 1500 r/min; diluting with a large amount (1000ml) of deionized water, cooling, filtering under reduced pressure with 0.22 μm filter paper, and washing with deionized water for multiple times until the pH value is neutral to obtain a filter cake A;
(2) carrying out vacuum drying on the filter cake A obtained in the step (1) at 100 ℃ for 2h, and then grinding to obtain powder B;
(3) placing the powder B obtained in the step (2) into a round-bottom flask, and adding 150ml of the powder B in a volume ratio of: 1:3, carrying out ultrasonic treatment with power of 300W for 10min, wherein the mixed solution of concentrated sulfuric acid with mass fraction of 98% and hydrogen peroxide with mass fraction of 36%; then carrying out magneton stirring at the rotation speed of 550r/min for 2.5 h; diluting with a large amount (1000ml) of deionized water, cooling, filtering under reduced pressure with 0.22 μm filter paper, and washing with deionized water for multiple times until the filtrate is neutral to obtain filter cake C;
(4) carrying out vacuum drying and grinding on the filter cake C obtained in the step (3) at 30 ℃ for 10h to obtain a carboxylated carbon nanotube D;
(5) dissolving 45mg of D obtained in the step (4) in 500ml of deionized water, and performing ultrasonic dispersion with the power of 300W for 15 min; then carrying out magneton stirring at the rotating speed of 450r/min for 2.5 h; obtaining a solution E;
(6) 1g of ammonium bismuth citrate is dissolved in the solution E obtained in step (5) and the rotation speed is carried out for 2 h: stirring with 500r/min magnetons to obtain a solution F;
(7) dropwise adding 40ml of 0.8mol/L sodium borohydride solution into the solution F prepared in the step (6), continuously stirring for 2.5 hours by magnetic force after dropwise adding is finished to obtain a solution G, performing centrifugal purification (8000r centrifugation for 15min), rinsing with deionized water, and then performing vacuum drying at 50 ℃ for 8 hours to obtain nano bismuth H coated by the carboxylated carbon nanotube of the required material;
the preparation method of the sodium (di) manganate anode material comprises the following specific steps:
(8) sodium carbonate and manganese sesquioxide are mixed according to the molar ratio: 0.45:1, and performing ball milling in a planetary ball mill for 10 hours and 250r/min to obtain mixed powder I;
(9) calcining the mixed powder I obtained in the step (8) in air, heating to 400 ℃ at the speed of 2 ℃/min, and keeping the constant temperature for 4 hours to obtain a product J;
(10) performing ball milling on the product J obtained in the step (9) for 10h again by using a 250r/min planetary ball mill to obtain a precursor K;
(11) and (4) calcining the precursor K obtained in the step (10) in air again, wherein the calcining conditions are as follows: heating to 900 ℃ at the speed of 2 ℃/min, and keeping the constant temperature for 14h to obtain the final material sodium manganate L;
and (III) carrying out scanning electron microscope detection on the nano bismuth cathode material coated by the carboxylated carbon nano tube prepared in the step (I), wherein the detection result is shown in figure 3. As can be seen from fig. 3, the nano bismuth particles are uniformly dispersed on the carbon nanotubes. And (5) carrying out scanning electron microscope detection on the sodium manganate cathode material prepared in the step (II), wherein the detection result is shown in figure 4. Figure 4 shows that the prepared sodium manganate particles have relatively low impurity content and uniform size.
(IV) preparing the electrode plate of the battery, which comprises the following specific steps:
(1) mixing the nano bismuth negative electrode material coated by the carboxylated carbon nano tube prepared in the step (I), the adhesive polyvinylidene fluoride and the conductive carbon black Super-P (conductive agent) according to the mass ratio of 70:15:15, mixing the mixture into slurry by taking N-methyl pyrrolidone as a solvent (the mass ratio of solute to solvent is 1:2), coating the slurry (the coating thickness is 120 mu m) on graphite paper with the thickness of 1mm, and performing vacuum drying for 5 hours at the temperature of 50 ℃ in vacuum. Preparing a nano bismuth negative plate 2 coated by the carboxylated carbon nano tube;
(2) and (2) uniformly mixing the sodium manganate positive electrode material prepared in the step (two), a binder LA132 (15% of binder solid content, available from Chengdu Dingle company) and conductive carbon black Super-P according to a weight ratio of 70:15:15, mixing the mixture into slurry by taking N-methylpyrrolidone as a solvent (the mass ratio of solute to solvent is 1:2), coating the slurry on graphite paper to a coating thickness of 150 mu m, and drying the slurry for 20 hours at a vacuum temperature of 80 ℃ to prepare a sodium manganate positive electrode sheet 2.
And (V) assembling the sodium fluoride double-ion full battery, which comprises the following specific steps:
the sodium fluoride double-ion full cell is assembled by an electrolytic cell: and (3) assembling the nano bismuth negative electrode sheet 2 coated by the carboxylated carbon nanotube prepared in the step (IV) and (1), a diaphragm, electrolyte (0.8mol/L NaF solution) and the sodium manganate positive electrode sheet 2 prepared in the step (IV) and (2) by using a fluid device to obtain the sodium fluoride double-ion full cell. And the positive electrode clamp and the negative electrode clamp respectively clamp a sodium manganate positive electrode and a nano bismuth negative electrode coated by the carboxylated carbon nano tube, and the electrochemical performance test is carried out. And testing the conductivity of the ions by using a conductivity meter, and further obtaining the removal capacity of the fluorine ions.
Example 3
The preparation method of the nano bismuth anode material coated by the carboxylated carbon nanotube comprises the following specific steps:
(1) placing 2.8g of carbon nanotubes in a round-bottom flask, adding 200ml of mixed solution of concentrated sulfuric acid with the mass fraction of 98% and concentrated nitric acid with the mass fraction of 68% in the volume ratio of 1:4 into the round-bottom flask, and performing ultrasonic dispersion with the power of 300W for 40 min; then carrying out magneton stirring for 2h at the rotating speed of 2000 r/min; diluting with a large amount (1000ml) of deionized water, cooling, filtering under reduced pressure with 0.22 μm filter paper, and washing with deionized water for multiple times until the pH value is neutral to obtain a filter cake A;
(2) carrying out vacuum drying on the filter cake A obtained in the step (1) for 3 hours at 100 ℃, and then grinding to obtain powder B;
(3) placing the powder B obtained in the step (2) into a round-bottom flask, and adding 150ml of the powder B in a volume ratio of: 1:4, carrying out ultrasonic treatment with the power of 300W for 40min on a mixed solution of 98% concentrated sulfuric acid and 36% hydrogen peroxide; then carrying out magneton stirring for 2h at the rotating speed of 2000 r/min; diluting with a large amount (1000ml) of deionized water, cooling, filtering under reduced pressure with 0.22 μm filter paper, and washing with deionized water for multiple times until the filtrate is neutral to obtain filter cake C;
(4) carrying out vacuum drying and grinding on the filter cake C obtained in the step (3) for 14h at 60 ℃ to obtain a carboxylated carbon nanotube D;
(5) dissolving 65mg of D obtained in the step (4) in 500ml of deionized water, and performing ultrasonic dispersion with the power of 300W for 35 min; then carrying out magneton stirring at the rotating speed of 1800r/min for 2.5 h; obtaining a solution E;
(6) dissolving 1g of ammonium bismuth citrate in the solution E obtained in the step (5), and stirring with magnetons at the rotating speed of 700r/min for 2 hours to obtain a solution F;
(7) dropwise adding 60ml of 1.2mol/L sodium borohydride solution into the solution F prepared in the step (6), continuing to magnetically stir for 2.5 hours after dropwise adding to obtain a solution G, performing centrifugal purification (8000r centrifugation for 15min), rinsing with deionized water, and then performing vacuum drying at 70 ℃ for 12 hours to obtain nano bismuth H coated by the carboxylated carbon nanotube of the required material;
the preparation method of the sodium (di) manganate anode material comprises the following specific steps:
(8) sodium carbonate and manganese sesquioxide are mixed according to the molar ratio: 0.5:1, and performing ball milling in a planetary ball mill for 15h and 270r/min to obtain mixed powder I;
(9) calcining the mixed powder I obtained in the step (8) in air, heating to 600 ℃ at the speed of 10 ℃/min, and keeping the constant temperature for 7 hours to obtain a product J;
(10) performing ball milling on the product J obtained in the step (9) for 15h again by using a 280r/min planetary ball mill to obtain a precursor K;
(11) calcining the precursor K obtained in the step (10) in the air again; the calcination conditions were: heating to 1200 ℃ at the speed of 2 ℃/min, and keeping the constant temperature for 14h to obtain the final material sodium manganate L;
(III) preparing the electrode plate of the battery, which comprises the following specific steps:
(1) mixing the nano bismuth negative electrode material coated by the carboxylated carbon nano tube prepared in the step (I), the adhesive polyvinylidene fluoride and the conductive carbon black Super-P (conductive agent) according to the mass ratio of 70:15:15, mixing the mixture into slurry by taking N-methyl pyrrolidone as a solvent (the mass ratio of solute to solvent is 1:2), coating the slurry (the coating thickness is 120 mu m) on graphite paper with the thickness of 1mm, and performing vacuum drying for 24 hours at the temperature of 100 ℃ in vacuum. Preparing a nano bismuth negative plate 3 coated by the carboxylated carbon nano tube;
(2) and (3) uniformly mixing the sodium manganate positive electrode material prepared in the step (two), a binder LA132 (15% of binder solid content, available from Chengdu Dingle company) and conductive carbon black Super-P according to a weight ratio of 70:15:15, mixing the mixture into slurry by taking N-methylpyrrolidone as a solvent (the mass ratio of solute to solvent is 1:2), coating the slurry on graphite paper to a coating thickness of 200 mu m, and drying the slurry for 24 hours at 100 ℃ in vacuum to prepare a sodium manganate positive electrode sheet 3.
(IV) assembling the whole battery and testing the battery performance, which comprises the following steps:
the sodium fluoride double-ion full cell is assembled by an electrolytic cell: and (3) assembling a fluid device on the nano bismuth negative electrode sheet 1 coated by the carboxylated carbon nanotube prepared in the step (III) and the step (1), a diaphragm, an electrolyte (0.8mol/L NaF solution) and the sodium manganate positive electrode sheet 1 prepared in the step (IV) and the step (2) to obtain the sodium fluoride double-ion full cell. The positive electrode clamp and the negative electrode clamp respectively clamp a sodium manganate positive electrode and a nano bismuth negative electrode coated by the carboxylated carbon nano tube. And carrying out electrochemical performance test after the precipitation is carried out for 12 h. And then testing the conductivity of the ions by using a conductivity meter, thereby obtaining the removal capability of the fluorine ions. The cyclic voltammetry test of the cell was performed at a potential range of 0 to 1.0V, and the results are shown in fig. 5. The initial charging specific capacity is 220mAh/g and shows good capacity performance after being tested under the current density of 100 mA/g. A graph of the voltage and fluoride ion conductivity over time during charge and discharge is shown in fig. 6. In the process of cross-flow charging, fluorine ions and sodium ions are separated out from the two electrodes, so that the electric conductivity in the solution is increased; however, during the cross-flow discharge, the fluorine ions are electrochemically adsorbed by one electrode, the sodium ions are electrochemically adsorbed by the other electrode, and the fluorine ion concentration in the solution is reduced, which is the most direct observation of the fluorine ion removal process. The electrochemical fluoride ion removing process can be regenerated through charging, and the regenerated electrochemical fluoride ion can be used for removing fluoride through next cycle of electrochemical discharge.
The sodium manganate anode material (Na) in the sodium fluoride double-ion full cell of the invention0.44MnO2 [1]) Can be replaced by K0.27MnO2 [2]，Na2FeP2O7 [3]，V2O5 [4]，Na3V2(PO4)3 [5]，Na2V6O16 [6]，NaTi2(PO4)3 [7]PTVE (Polytetrafluoroethylene), PBA (polybutyl acrylate), Na2C8H4O4 [8]PVAQ (polyvinyl alcohol), and/or Na0.44[Mn1-xTix]O2. The nano bismuth cathode material coated by the carboxylated carbon nano tube can be replaced by Bi, BiF3[9]，Pb，PbF2[10]Piperidine inorganic substances (e.g., 2-hydroxypyrimidine) and bipyridinium salts (e.g., 4' -bipyridinium dichloride), and carbon-coated mixtures thereof; the carbon material coating comprises carbon nano tubes, graphene, activated carbon, carbon black and the like. The electrolyte may be an aqueous solution of NaF.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Reference to the literature
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Claims (9)
1. A sodium fluoride bi-ion battery, characterized in that: the electrolyte comprises a sodium ion electrochemical material, a fluorine ion electrochemical material and electrolyte; wherein,
the sodium ion electrode material is Na0.44MnO2；
The fluoride ion electrochemical material is nano bismuth coated by carboxylated carbon nanotubes;
the electrolyte is NaF solution;
the concentration of the NaF solution is 0.75-0.85 mol/L.
2. The sodium fluoride bi-ion battery of claim 1, wherein the Na is0.44MnO2The preparation method comprises the following steps:
(I) mixing sodium carbonate and manganese oxide, then carrying out ball milling, and calcining mixed powder obtained after ball milling to obtain a product J;
(II) ball-milling the product J obtained in the step (I) again, and then calcining the precursor obtained after ball-milling again to obtain Na0.44MnO2。
3. The sodium fluoride bi-ion battery of claim 2, wherein:
the molar ratio of the sodium carbonate to the manganese sesquioxide in the step (I) is 0.4-0.5: 1.
4. The sodium fluoride bi-ion battery of claim 2, wherein:
the ball milling conditions in the step (I) and the step (II) are as follows: ball milling for 10-15 h at 250-270 r/min;
the calcining conditions in the step (I) are as follows: heating to 400-600 ℃ in the air at the speed of 2-10 ℃/min, and keeping the temperature for 4-7 h;
the calcining conditions in the step (II) are as follows: heating to 900-1200 ℃ in air at a speed of 2 ℃/min, and keeping the temperature for 10-14 h.
5. The sodium fluoride bi-ion battery of claim 1, wherein the fluoride electrochemical material is prepared by:
(1) adding a mixed solution of concentrated sulfuric acid and concentrated nitric acid into the carbon nano tube for acidification treatment, then adding water for dilution, cooling, filtering, and washing to be neutral to obtain a filter cake A;
(2) drying and grinding the filter cake A obtained in the step (1) to obtain powder B;
(3) adding a mixed acid solution of concentrated sulfuric acid and hydrogen peroxide into the powder B obtained in the step (2) for secondary acidification treatment, then adding water for dilution, cooling, filtering, and washing to be neutral to obtain a filter cake C;
(4) drying and grinding the filter cake C obtained in the step (3) to obtain a carboxylated carbon nano tube D;
(5) dispersing the carboxylated carbon nano tube D obtained in the step (4) into water to obtain a solution E;
(6) adding bismuth ammonium citrate into the solution E obtained in the step (5), and uniformly stirring to obtain a solution F;
(7) and (3) dropwise adding the sodium borohydride solution into the solution F obtained in the step (6), continuing stirring after dropwise adding is finished to obtain a solution G, performing centrifugal purification and rinsing, and then performing vacuum drying to obtain the fluoride ion electrochemical material.
6. The sodium fluoride bi-ion battery of claim 5, wherein:
the mass ratio of the bismuth ammonium citrate in the step (6) to the carboxylated carbon nanotube D is 1: 0.045-0.065;
the mass ratio of the mass of the sodium borohydride in the sodium borohydride solution in the step (7) to the mass of the bismuth ammonium citrate is 1.21-2.72.
7. The sodium fluoride bi-ion battery of claim 5, wherein:
the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed solution of the concentrated sulfuric acid and the concentrated nitric acid in the step (1) is 1: 2-4;
the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide in the mixed solution of the concentrated sulfuric acid and the hydrogen peroxide in the step (3) is 1:2 to 4.
8. The sodium fluoride bi-ion battery of claim 5, wherein:
the drying in the step (2) is vacuum drying; the drying conditions are as follows: drying for 1-3 h at 60-100 ℃;
the dispersion in the step (5) is ultrasonic dispersion; the ultrasonic conditions are as follows: carrying out 300W ultrasound for 10-40 min;
the vacuum drying conditions in the step (7) are as follows: drying for 8-12 h at 50-70 ℃.
9. Use of the sodium fluoride bi-ion battery of any one of claims 1 to 8 in the field of wastewater treatment or electrochemical defluorination equipment.
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| PCT/CN2019/079827 WO2019184939A1 (en) | 2018-03-28 | 2019-03-27 | Electrochemical- and photoelectrochemical-based ion removal device, preparation method thereof and application thereof |
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| KR101613435B1 (en) * | 2014-11-26 | 2016-04-20 | 한국생산기술연구원 | A manufacturing method of Na0.44MnO2 nano-rod for an electrode and a manufacturing method sodium rechargeable battery thereof |
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