CN117673378A - Rare earth doped material, preparation method and application thereof, and rare earth liquid flow energy storage battery - Google Patents
Rare earth doped material, preparation method and application thereof, and rare earth liquid flow energy storage battery Download PDFInfo
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- CN117673378A CN117673378A CN202311761408.6A CN202311761408A CN117673378A CN 117673378 A CN117673378 A CN 117673378A CN 202311761408 A CN202311761408 A CN 202311761408A CN 117673378 A CN117673378 A CN 117673378A
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- 239000007788 liquid Substances 0.000 title claims abstract description 96
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 74
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000004146 energy storage Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 263
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 146
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 116
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 27
- 238000007654 immersion Methods 0.000 claims abstract description 24
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 17
- 238000007772 electroless plating Methods 0.000 claims abstract description 17
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 16
- 230000004048 modification Effects 0.000 claims abstract description 15
- 238000012986 modification Methods 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000000084 colloidal system Substances 0.000 claims abstract description 14
- 239000010406 cathode material Substances 0.000 claims abstract description 7
- 230000003213 activating effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 85
- 238000010438 heat treatment Methods 0.000 claims description 52
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 51
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 51
- 238000007747 plating Methods 0.000 claims description 49
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 19
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 17
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 17
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 17
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 17
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 17
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 17
- 235000006408 oxalic acid Nutrition 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 230000009467 reduction Effects 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 13
- 230000004913 activation Effects 0.000 claims description 12
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 11
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- 239000001119 stannous chloride Substances 0.000 claims description 11
- 235000011150 stannous chloride Nutrition 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 7
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 229920000557 Nafion® Polymers 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003014 ion exchange membrane Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 108010010803 Gelatin Proteins 0.000 claims 1
- 229920000159 gelatin Polymers 0.000 claims 1
- 239000008273 gelatin Substances 0.000 claims 1
- 235000019322 gelatine Nutrition 0.000 claims 1
- 235000011852 gelatine desserts Nutrition 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052794 bromium Inorganic materials 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 6
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 abstract description 6
- 229920001021 polysulfide Polymers 0.000 abstract description 5
- 239000005077 polysulfide Substances 0.000 abstract description 5
- 150000008117 polysulfides Polymers 0.000 abstract description 5
- 238000006479 redox reaction Methods 0.000 abstract description 5
- 238000000151 deposition Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 12
- 230000006872 improvement Effects 0.000 description 8
- 229910052720 vanadium Inorganic materials 0.000 description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical class 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a rare earth doped material, a preparation method and application thereof and a rare earth liquid flow energy storage battery, and belongs to the technical field of liquid flow energy storage batteries. And after hydrophilizing the polyacrylonitrile carbon felt, coating a layer of wrinkled graphene oxide on the surface, sequentially carrying out surface modification by pre-immersion liquid, colloid palladium activating solution and dispergation liquid, depositing Nd/La/Y-Ni-B by electroless plating, and reducing by hydrazine hydrate to obtain the rare earth doped material. According to the invention, the catalyst and the rare earth elements are loaded on the cathode material of the liquid flow energy storage battery, so that the energy storage efficiency of the sodium polysulfide/bromine battery is improved, the catalyst has better catalytic activity on the oxidation-reduction reaction of polysulfide, and meanwhile, the energy efficiency and the cycle performance of the sodium polysulfide/bromine battery are improved.
Description
Technical Field
The invention relates to the technical field of liquid flow energy storage batteries, in particular to a rare earth doped material, a preparation method and application thereof, and a rare earth liquid flow energy storage battery.
Background
At present, the double-flow energy storage battery used in various countries in the world has the most mature technology and the most reliable performance, namely an all-vanadium flow battery (vanadium battery for short). The vanadium battery has high safety and long service life (the number of times of cyclic charge and discharge is more than 16000 times), and the capacity of the battery is large, and is mainly used for peak shaving of a power grid, such as a large-scale wind power station, a photovoltaic power station, a tidal power station and a thermal power station, and is suitable for an energy storage system of more than 100 MW. In addition, the zinc-nickel liquid flow energy storage battery belongs to a deposition type liquid flow battery, is a novel liquid flow energy storage battery with low price, excellent efficiency, safety, environmental protection, and has the advantages of high energy density and current efficiency, simple and easy operation of the device, long service life, low cost and the like, and is mainly applied to the fields of energy storage of renewable energy sources such as power grid peak shaving, wind energy, solar energy and the like, electric automobiles and the like.
The disadvantages of vanadium cells are mainly: the anode liquid is easy to separate out vanadium pentoxide sediment when the temperature is higher than 25 ℃ (the vanadium battery is easy to exceed 25 ℃ in operation); vanadium pentoxide is extremely toxic and harmful to the environment; graphite plates are susceptible to positive fluid etching and typically require maintenance for two months.
The zinc-nickel flow energy storage battery has the following main defects: the concentration of zinc ions in the solution in the zinc-nickel liquid flow energy storage battery determines the energy storage capacity and energy density of the battery system; the zinc deposited on the cathode is easy to generate self-corrosion hydrogen evolution, so that the cathode is fast in self-discharge and the overall charge holding capacity of the battery is poor.
Disclosure of Invention
The invention aims to provide a rare earth doped material, a preparation method and application thereof, and a rare earth liquid flow energy storage battery, wherein the energy storage efficiency of a sodium polysulfide/bromine battery is improved by loading a catalyst and rare earth elements on a cathode material of the liquid flow energy storage battery, the catalyst has better catalytic activity on redox reaction of polysulfide, and meanwhile, the energy efficiency and the cycle performance of the sodium polysulfide/bromine battery are improved.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of a rare earth doped material, which comprises the steps of coating a layer of wrinkled graphene oxide on the surface of a polyacrylonitrile carbon felt after hydrophilization treatment, sequentially carrying out surface modification by pre-immersion liquid, colloid palladium activating liquid and dispergation liquid, depositing Nd/La/Y-Ni-B by electroless plating, and carrying out hydrazine hydrate reduction to obtain the rare earth doped material.
As a further improvement of the invention, the method comprises the following steps:
s1, hydrophilizing treatment of carbon felt: heating polyacrylonitrile carbon felt in alkali liquor to prepare a hydrophilized carbon felt;
s2, coating the wrinkled graphene oxide: soaking the hydrophilized carbon felt prepared in the step S1 into graphene oxide aqueous dispersion liquid, covering the upper surface and the lower surface with glass sheets, heating in a resistance furnace, and drying to obtain a wrinkled graphene oxide coated carbon felt;
s3, surface modification: placing the wrinkled graphene oxide coated carbon felt prepared in the step S2 into pre-immersion liquid, performing room temperature treatment, then placing into colloid palladium activation liquid, performing heat treatment, then placing into glue solution, performing room temperature treatment, and washing to obtain the modified wrinkled graphene oxide coated carbon felt;
s4, electroless plating: dissolving nickel chloride in ethanol, adding lanthanum chloride, neodymium nitrate, yttrium chloride, citric acid and oxalic acid, stirring and mixing uniformly, regulating the pH value of the solution, adding borane dimethylamine, stirring and mixing uniformly to obtain a plating solution, adding the modified wrinkled graphene oxide-coated carbon felt prepared in the step S3 into the plating solution, performing chemical plating treatment, taking out, washing and drying to obtain the rare earth element doped wrinkled graphene oxide-coated carbon felt;
s5, reduction: and (3) reducing the rare earth element doped wrinkled graphene oxide coated carbon felt prepared in the step (S4) in hydrazine hydrate steam to prepare the rare earth doped material.
As a further improvement of the invention, the alkali liquor in the step S1 is 0.5-1.5mol/L NaOH or KOH solution, the temperature of the heating treatment is 90-100 ℃ and the time is 30-60min.
As a further improvement of the invention, the solid-to-liquid ratio of the hydrophilized carbon felt to the graphene oxide aqueous dispersion liquid in the step S2 is 1:4-7g/mL, the temperature of the heating treatment is 150-170 ℃ and the time is 2-4h.
As a further improvement of the invention, the formula of the pre-leaching solution in the step S3 comprises 35-40g/L of stannous chloride, 100-120mL/L of hydrochloric acid and the balance of water, wherein the temperature of the heating treatment is 40-50 ℃ for 5-10min, and the sol solution is 0.5-1.5mol/L of hydrochloric acid solution.
As a further improvement of the invention, the mass ratio of nickel chloride, lanthanum chloride, neodymium nitrate, yttrium chloride, citric acid, oxalic acid and borane dimethylamine in the step S4 is 0.8-1.2:0.05-0.1:0.03-0.05:0.02-0.04:0.3-0.5:0.2-0.4:1-1.5, wherein the pH value of the solution is regulated to 3.8-4.2, and the electroless plating treatment time is 1-3h.
As a further improvement of the invention, the pressure of the hydrazine hydrate vapor in the step S5 is 0.4-0.5kPa, and the time of the reduction is 5-7 hours.
As a further improvement of the invention, the method specifically comprises the following steps:
s1, hydrophilizing treatment of carbon felt: heating polyacrylonitrile carbon felt in 0.5-1.5mol/L NaOH or KOH solution to 90-100 ℃ and treating for 30-60min to obtain hydrophilized carbon felt;
s2, coating the wrinkled graphene oxide: soaking the hydrophilized carbon felt prepared in the step S1 into graphene oxide aqueous dispersion liquid, wherein the solid-to-liquid ratio of the hydrophilized carbon felt to the graphene oxide aqueous dispersion liquid is 1:4-7g/mL, covering the upper surface and the lower surface with glass sheets, heating to 150-170 ℃ in a resistance furnace, treating for 2-4h, and drying to obtain the wrinkled graphene oxide coated carbon felt;
s3, surface modification: placing 10 parts by weight of the wrinkled graphene oxide coated carbon felt prepared in the step S2 into 100 parts by weight of pre-immersion liquid, treating at room temperature for 2-4min, then placing into 100 parts by weight of colloid palladium activation liquid, heating to 40-50 ℃, treating for 5-10min, then placing into 100 parts by weight of 0.5-1.5mol/L hydrochloric acid solution, treating at room temperature for 3-5min, and washing to obtain a modified wrinkled graphene oxide coated carbon felt;
the formula of the pre-immersion liquid comprises 35-40g/L stannous chloride, 100-120mL/L hydrochloric acid and the balance of water;
s4, electroless plating: dissolving 0.8-1.2 parts by weight of nickel chloride in 100 parts by weight of ethanol, adding 0.05-0.1 part by weight of lanthanum chloride, 0.03-0.05 part by weight of neodymium nitrate, 0.02-0.04 part by weight of yttrium chloride, 0.3-0.5 part by weight of citric acid and 0.2-0.4 part by weight of oxalic acid, stirring and mixing uniformly, adjusting the pH value of the solution to 3.8-4.2, adding 1-1.5 parts by weight of borane dimethylamine, stirring and mixing uniformly to obtain a plating solution, adding 10 parts by weight of the modified wrinkled graphene oxide coated carbon felt prepared in the step S3 into 100 parts by weight of the plating solution, performing chemical plating treatment for 1-3 hours, taking out, cleaning, and drying to prepare the rare earth element doped wrinkled graphene oxide coated carbon felt;
s5, reduction: and (3) reducing the rare earth element doped wrinkled graphene oxide coated carbon felt prepared in the step (S4) in hydrazine hydrate steam with the pressure of 0.4-0.5kPa for 5-7 hours to prepare the rare earth doped material.
The invention further protects the rare earth doped material prepared by the preparation method.
The invention further protects a rare earth liquid flow energy storage battery, wherein the rare earth doped material is used as a battery cathode material, a battery anode material is polyacrylonitrile carbon felt, an anode electrolyte is 3-5mol/L NaBr aqueous solution, and the anode electrolyte is 1-2mol/L Na 2 S 4 The water solution and the ion exchange membrane are Nafion membranes.
The invention has the following beneficial effects: according to the invention, after the surface of the polyacrylonitrile carbon felt is subjected to hydrophilization treatment, rich hydroxyl groups are carried, and the surface of the polyacrylonitrile carbon felt can be combined with graphene oxide through hydrogen bond action, so that the fixation of the graphene oxide on the surface of the polyacrylonitrile carbon felt is facilitated, meanwhile, under the condition of intense heat, moisture in the graphene oxide aqueous dispersion liquid is quickly dissipated, and meanwhile, the glass sheet keeps the polyacrylonitrile carbon felt not deformed, so that a layer of wrinkled graphene oxide is loaded on the surface of the polyacrylonitrile carbon felt, the specific surface area of the surface of the polyacrylonitrile carbon felt is greatly improved, a larger active site is provided for the subsequent loading of rare earth elements, finally, the surface graphene oxide is reduced to graphene through hydrazine hydrate reduction, so that the electrical modification of the polyacrylonitrile carbon felt and the electroless plating deposition Nd/La/Y-Ni-B on the polyacrylonitrile carbon felt is greatly improved, and the redox reaction efficiency of polysulfide is also promoted.
The doping of rare earth metal element Nd/La/Y effectively improves the electron emission performance of the electrode material, greatly improves the capacitance of the electrode material, has paired d electrons and empty or half-full d orbit metal, generates a synergistic effect, is beneficial to electron transfer, promotes redox reaction catalysis of polysulfide, and has excellent conductivity when being chemically plated with Ni element, so that the mechanical property, corrosion resistance, stability and durability of the prepared electrode material are obviously improved.
According to the invention, the catalyst and the rare earth elements are loaded on the cathode material of the liquid flow energy storage battery, so that the energy storage efficiency of the sodium polysulfide/bromine battery is improved, the catalyst has better catalytic activity on the oxidation-reduction reaction of polysulfide, and meanwhile, the energy efficiency and the cycle performance of the sodium polysulfide/bromine battery are improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Colloidal palladium activation solution, bigley technology PL-5, specific gravity 1.4-1.45, purchased from Guangdong Bigley technology Co., ltd. Or self-made, the method is as follows: 5g of chloroauric acid was dissolved in 50mL of water, and the solution was stirred. 2mL of phosphoric acid and 10mL of hydrochloric acid are respectively dissolved in 50mL of water, the two solutions are uniformly stirred, 30mg of palladium powder is added and stirred, the stirring is kept until the palladium powder is completely dispersed, and the obtained mixed solution is filtered to obtain a colloidal palladium activated solution.
Example 1
The embodiment provides a preparation method of a rare earth doped material, which specifically comprises the following steps:
s1, hydrophilizing treatment of carbon felt: heating the polyacrylonitrile carbon felt in a NaOH solution with the concentration of 0.5mol/L to 100 ℃, and treating for 30min to obtain a hydrophilized carbon felt;
s2, coating the wrinkled graphene oxide: soaking the hydrophilized carbon felt prepared in the step S1 into graphene oxide aqueous dispersion liquid, wherein the solid-to-liquid ratio of the hydrophilized carbon felt to the graphene oxide aqueous dispersion liquid is 1:4g/mL, covering the upper surface and the lower surface with glass sheets, heating to 150 ℃ in a resistance furnace, treating for 2 hours, and drying to obtain the wrinkled graphene oxide coated carbon felt;
s3, surface modification: placing 10 parts by weight of the wrinkled graphene oxide coated carbon felt prepared in the step S2 into 100 parts by weight of pre-immersion liquid, treating at room temperature for 2min, then placing into 100 parts by weight of colloid palladium activation liquid, heating to 40 ℃, treating for 5min, then placing into 100 parts by weight of 0.5mol/L hydrochloric acid solution, treating at room temperature for 3min, and washing to obtain a modified wrinkled graphene oxide coated carbon felt;
the formula of the pre-immersion liquid comprises 35g/L of stannous chloride, 100mL/L of hydrochloric acid and the balance of water;
s4, electroless plating: dissolving 0.8 part by weight of nickel chloride in 100 parts by weight of ethanol, adding 0.05 part by weight of lanthanum chloride, 0.03 part by weight of neodymium nitrate, 0.02 part by weight of yttrium chloride, 0.3 part by weight of citric acid and 0.2 part by weight of oxalic acid, stirring and mixing for 20min, adjusting the pH value of the solution to 3.8, adding 1 part by weight of borane dimethylamine, stirring and mixing for 10min to obtain a plating solution, adding 10 parts by weight of the modified wrinkled graphene oxide coated carbon felt prepared in the step S3 into 100 parts by weight of the plating solution, heating to 70 ℃, carrying out chemical plating treatment for 1h, taking out, cleaning and drying to obtain the rare earth element doped wrinkled graphene oxide coated carbon felt;
s5, reduction: and (3) reducing the rare earth element doped wrinkled graphene oxide coated carbon felt prepared in the step (S4) in hydrazine hydrate steam with the pressure of 0.4kPa for 5 hours to prepare the rare earth doped material.
Example 2
The embodiment provides a preparation method of a rare earth doped material, which specifically comprises the following steps:
s1, hydrophilizing treatment of carbon felt: heating the polyacrylonitrile carbon felt to 90 ℃ in a KOH solution with the concentration of 1.5mol/L, and treating for 60min to obtain a hydrophilized carbon felt;
s2, coating the wrinkled graphene oxide: soaking the hydrophilized carbon felt prepared in the step S1 into graphene oxide aqueous dispersion liquid, wherein the solid-to-liquid ratio of the hydrophilized carbon felt to the graphene oxide aqueous dispersion liquid is 1:7g/mL, covering the upper surface and the lower surface with glass sheets, heating to 170 ℃ in a resistance furnace, treating for 4 hours, and drying to obtain the wrinkled graphene oxide coated carbon felt;
s3, surface modification: placing 10 parts by weight of the wrinkled graphene oxide coated carbon felt prepared in the step S2 into 100 parts by weight of pre-immersion liquid, treating for 4min at room temperature, then placing into 100 parts by weight of colloid palladium activation liquid, heating to 50 ℃, treating for 10min, then placing into 100 parts by weight of 1.5mol/L hydrochloric acid solution, treating for 5min at room temperature, and washing to obtain a modified wrinkled graphene oxide coated carbon felt;
the formula of the pre-immersion liquid comprises stannous chloride 40g/L, hydrochloric acid 120mL/L and water for the rest;
s4, electroless plating: dissolving 1.2 parts by weight of nickel chloride in 100 parts by weight of ethanol, adding 0.1 part by weight of lanthanum chloride, 0.05 part by weight of neodymium nitrate, 0.04 part by weight of yttrium chloride, 0.5 part by weight of citric acid and 0.4 part by weight of oxalic acid, stirring and mixing for 20min, adjusting the pH value of the solution to 4.2, adding 1.5 parts by weight of borane dimethylamine, stirring and mixing for 10min to obtain a plating solution, adding 10 parts by weight of the modified wrinkled graphene oxide coated carbon felt prepared in the step S3 into 100 parts by weight of the plating solution, heating to 70 ℃, carrying out chemical plating treatment for 3h, taking out, cleaning and drying to obtain the rare earth element doped wrinkled graphene oxide coated carbon felt;
s5, reduction: and (3) reducing the rare earth element doped wrinkled graphene oxide coated carbon felt prepared in the step (S4) in hydrazine hydrate steam with the pressure of 0.5kPa for 7 hours to prepare the rare earth doped material.
Example 3
The embodiment provides a preparation method of a rare earth doped material, which specifically comprises the following steps:
s1, hydrophilizing treatment of carbon felt: heating the polyacrylonitrile carbon felt in a 1mol/L NaOH solution to 95 ℃, and treating for 45min to obtain a hydrophilized carbon felt;
s2, coating the wrinkled graphene oxide: soaking the hydrophilized carbon felt prepared in the step S1 into graphene oxide aqueous dispersion liquid, wherein the solid-to-liquid ratio of the hydrophilized carbon felt to the graphene oxide aqueous dispersion liquid is 1:5g/mL, covering the upper surface and the lower surface with glass sheets, heating to 160 ℃ in a resistance furnace, treating for 3 hours, and drying to obtain the wrinkled graphene oxide coated carbon felt;
s3, surface modification: placing 10 parts by weight of the wrinkled graphene oxide coated carbon felt prepared in the step S2 into 100 parts by weight of pre-immersion liquid, treating for 3min at room temperature, then placing into 100 parts by weight of colloid palladium activation liquid, heating to 45 ℃, treating for 7min, then placing into 100 parts by weight of 1mol/L hydrochloric acid solution, treating for 4min at room temperature, and washing to obtain a modified wrinkled graphene oxide coated carbon felt;
the formula of the pre-immersion liquid comprises 37g/L of stannous chloride, 110mL/L of hydrochloric acid and the balance of water;
s4, electroless plating: dissolving 1 part by weight of nickel chloride in 100 parts by weight of ethanol, adding 0.07 part by weight of lanthanum chloride, 0.04 part by weight of neodymium nitrate, 0.03 part by weight of yttrium chloride, 0.4 part by weight of citric acid and 0.3 part by weight of oxalic acid, stirring and mixing for 20min, adjusting the pH value of the solution to 4, adding 1.2 parts by weight of borane dimethylamine, stirring and mixing for 10min to obtain a plating solution, adding 10 parts by weight of the modified wrinkled graphene oxide coated carbon felt prepared in the step S3 into 100 parts by weight of the plating solution, heating to 70 ℃, carrying out chemical plating treatment for 2h, taking out, cleaning and drying to obtain the rare earth element doped wrinkled graphene oxide coated carbon felt;
s5, reduction: and (3) reducing the rare earth element doped wrinkled graphene oxide coated carbon felt prepared in the step (S4) in hydrazine hydrate steam with the pressure of 0.45kPa for 6 hours to prepare the rare earth doped material.
Comparative example 1
In comparison with example 3, the difference is that step S1 is not performed.
The method comprises the following steps:
s1, coating the wrinkled graphene oxide: immersing a polyacrylonitrile carbon felt into graphene oxide aqueous dispersion liquid, wherein the solid-to-liquid ratio of the hydrophilization carbon felt to the graphene oxide aqueous dispersion liquid is 1:5g/mL, covering the upper surface and the lower surface with glass sheets, heating to 160 ℃ in a resistance furnace, treating for 3 hours, and drying to obtain a wrinkled graphene oxide coated carbon felt;
s2, surface modification: placing 10 parts by weight of the wrinkled graphene oxide coated carbon felt prepared in the step S1 into 100 parts by weight of pre-immersion liquid, treating for 3min at room temperature, then placing into 100 parts by weight of colloid palladium activation liquid, heating to 45 ℃, treating for 7min, then placing into 100 parts by weight of 1mol/L hydrochloric acid solution, treating for 4min at room temperature, and washing to obtain a modified wrinkled graphene oxide coated carbon felt;
the formula of the pre-immersion liquid comprises 37g/L of stannous chloride, 110mL/L of hydrochloric acid and the balance of water;
s3, electroless plating: dissolving 1 part by weight of nickel chloride in 100 parts by weight of ethanol, adding 0.07 part by weight of lanthanum chloride, 0.04 part by weight of neodymium nitrate, 0.03 part by weight of yttrium chloride, 0.4 part by weight of citric acid and 0.3 part by weight of oxalic acid, stirring and mixing for 20min, adjusting the pH value of the solution to 4, adding 1.2 parts by weight of borane dimethylamine, stirring and mixing for 10min to obtain a plating solution, adding 10 parts by weight of the modified wrinkled graphene oxide coated carbon felt prepared in the step S2 into 100 parts by weight of the plating solution, heating to 70 ℃, carrying out chemical plating treatment for 2h, taking out, cleaning and drying to obtain the rare earth element doped wrinkled graphene oxide coated carbon felt;
s4, reduction: and (3) reducing the rare earth element doped wrinkled graphene oxide coated carbon felt prepared in the step (S3) in hydrazine hydrate steam with the pressure of 0.45kPa for 6 hours to prepare the rare earth doped material.
Comparative example 2
In comparison with example 3, the difference is that steps S2 and S5 are not performed.
The method comprises the following steps:
s1, hydrophilizing treatment of carbon felt: heating the polyacrylonitrile carbon felt in a 1mol/L NaOH solution to 95 ℃, and treating for 45min to obtain a hydrophilized carbon felt;
s2, surface modification: putting 10 parts by weight of the hydrophilized carbon felt prepared in the step S1 into 100 parts by weight of pre-immersion liquid, treating at room temperature for 3min, then putting into 100 parts by weight of colloid palladium activation liquid, heating to 45 ℃, treating for 7min, then putting into 100 parts by weight of 1mol/L hydrochloric acid solution, treating at room temperature for 4min, and washing to obtain a modified carbon felt;
the formula of the pre-immersion liquid comprises 37g/L of stannous chloride, 110mL/L of hydrochloric acid and the balance of water;
s3, electroless plating: dissolving 1 part by weight of nickel chloride in 100 parts by weight of ethanol, adding 0.07 part by weight of lanthanum chloride, 0.04 part by weight of neodymium nitrate, 0.03 part by weight of yttrium chloride, 0.4 part by weight of citric acid and 0.3 part by weight of oxalic acid, stirring and mixing for 20min, adjusting the pH value of the solution to 4, adding 1.2 parts by weight of borane dimethylamine, stirring and mixing for 10min to obtain a plating solution, adding 10 parts by weight of the modified carbon felt prepared in the step S2 into 100 parts by weight of the plating solution, heating to 70 ℃, carrying out chemical plating treatment for 2h, taking out, cleaning and drying to obtain the rare earth element doped modified carbon felt, namely the rare earth doped material.
Comparative example 3
In comparison with example 3, the difference is that step S3 is not performed.
The method comprises the following steps:
s1, hydrophilizing treatment of carbon felt: heating the polyacrylonitrile carbon felt in a 1mol/L NaOH solution to 95 ℃, and treating for 45min to obtain a hydrophilized carbon felt;
s2, coating the wrinkled graphene oxide: soaking the hydrophilized carbon felt prepared in the step S1 into graphene oxide aqueous dispersion liquid, wherein the solid-to-liquid ratio of the hydrophilized carbon felt to the graphene oxide aqueous dispersion liquid is 1:5g/mL, covering the upper surface and the lower surface with glass sheets, heating to 160 ℃ in a resistance furnace, treating for 3 hours, and drying to obtain the wrinkled graphene oxide coated carbon felt;
s3, electroless plating: dissolving 1 part by weight of nickel chloride in 100 parts by weight of ethanol, adding 0.07 part by weight of lanthanum chloride, 0.04 part by weight of neodymium nitrate, 0.03 part by weight of yttrium chloride, 0.4 part by weight of citric acid and 0.3 part by weight of oxalic acid, stirring and mixing for 20min, adjusting the pH value of the solution to 4, adding 1.2 parts by weight of borane dimethylamine, stirring and mixing for 10min to obtain a plating solution, adding 10 parts by weight of the wrinkled graphene oxide coated carbon felt prepared in the step S2 into 100 parts by weight of the plating solution, heating to 70 ℃, carrying out chemical plating treatment for 2h, taking out, cleaning and drying to prepare the rare earth element doped wrinkled graphene oxide coated carbon felt;
s4, reduction: and (3) reducing the rare earth element doped wrinkled graphene oxide coated carbon felt prepared in the step (S3) in hydrazine hydrate steam with the pressure of 0.45kPa for 6 hours to prepare the rare earth doped material.
Comparative example 4
In comparison with example 3, the difference is that lanthanum chloride is not added in step S4.
The method comprises the following steps:
s4, preparing chemical plating: dissolving 1 part by weight of nickel chloride in 100 parts by weight of ethanol, adding 0.04 part by weight of neodymium nitrate, 0.03 part by weight of yttrium chloride, 0.4 part by weight of citric acid and 0.3 part by weight of oxalic acid, stirring and mixing for 20min, adjusting the pH value of the solution to be 4, adding 1.2 parts by weight of borane dimethylamine, stirring and mixing for 10min to obtain a plating solution, adding 10 parts by weight of the modified wrinkled graphene oxide coated carbon felt prepared in the step S3 into 100 parts by weight of the plating solution, heating to 70 ℃, carrying out chemical plating treatment for 2h, taking out, washing and drying to obtain the rare earth element doped wrinkled graphene oxide coated carbon felt.
Comparative example 5
In comparison with example 3, neodymium nitrate was not added in step S4.
The method comprises the following steps:
s4, preparing chemical plating: dissolving 1 part by weight of nickel chloride in 100 parts by weight of ethanol, adding 0.07 part by weight of lanthanum chloride, 0.03 part by weight of yttrium chloride, 0.4 part by weight of citric acid and 0.3 part by weight of oxalic acid, stirring and mixing for 20min, adjusting the pH value of the solution to be 4, adding 1.2 parts by weight of borane dimethylamine, stirring and mixing for 10min to obtain a plating solution, adding 10 parts by weight of the modified wrinkled graphene oxide coated carbon felt prepared in the step S3 into 100 parts by weight of the plating solution, heating to 70 ℃, carrying out chemical plating treatment for 2h, taking out, washing and drying to obtain the rare earth element doped wrinkled graphene oxide coated carbon felt.
Comparative example 6
In comparison with example 3, the difference is that yttrium chloride is not added in step S4.
The method comprises the following steps:
s4, preparing chemical plating: dissolving 1 part by weight of nickel chloride in 100 parts by weight of ethanol, adding 0.07 part by weight of lanthanum chloride, 0.04 part by weight of neodymium nitrate, 0.4 part by weight of citric acid and 0.3 part by weight of oxalic acid, stirring and mixing for 20min, adjusting the pH value of the solution to be 4, adding 1.2 parts by weight of borane dimethylamine, stirring and mixing for 10min to obtain a plating solution, adding 10 parts by weight of the modified wrinkled graphene oxide coated carbon felt prepared in the step S3 into 100 parts by weight of the plating solution, heating to 70 ℃, carrying out chemical plating treatment for 2h, taking out, washing and drying to obtain the rare earth element doped wrinkled graphene oxide coated carbon felt.
Comparative example 7
In comparison with example 3, the difference is that lanthanum chloride, neodymium nitrate and yttrium chloride are not added in step S4.
The method comprises the following steps:
s4, preparing chemical plating: dissolving 1 part by weight of nickel chloride in 100 parts by weight of ethanol, adding 0.4 part by weight of citric acid and 0.3 part by weight of oxalic acid, stirring and mixing for 20min, adjusting the pH value of the solution to be 4, adding 1.2 parts by weight of borane dimethylamine, stirring and mixing for 10min to obtain a plating solution, adding 10 parts by weight of the modified wrinkled graphene oxide coated carbon felt prepared in the step S3 into 100 parts by weight of the plating solution, heating to 70 ℃, carrying out chemical plating treatment for 2h, taking out, washing and drying to obtain the Ni-B doped wrinkled graphene oxide coated carbon felt.
Comparative example 8
In comparison with example 3, the difference is that step S4 is not performed.
The method comprises the following steps:
s1, hydrophilizing treatment of carbon felt: heating the polyacrylonitrile carbon felt in a 1mol/L NaOH solution to 95 ℃, and treating for 45min to obtain a hydrophilized carbon felt;
s2, coating the wrinkled graphene oxide: soaking the hydrophilized carbon felt prepared in the step S1 into graphene oxide aqueous dispersion liquid, wherein the solid-to-liquid ratio of the hydrophilized carbon felt to the graphene oxide aqueous dispersion liquid is 1:5g/mL, covering the upper surface and the lower surface with glass sheets, heating to 160 ℃ in a resistance furnace, treating for 3 hours, and drying to obtain the wrinkled graphene oxide coated carbon felt;
s3, surface modification: placing 10 parts by weight of the wrinkled graphene oxide coated carbon felt prepared in the step S2 into 100 parts by weight of pre-immersion liquid, treating for 3min at room temperature, then placing into 100 parts by weight of colloid palladium activation liquid, heating to 45 ℃, treating for 7min, then placing into 100 parts by weight of 1mol/L hydrochloric acid solution, treating for 4min at room temperature, and washing to obtain a modified wrinkled graphene oxide coated carbon felt;
the formula of the pre-immersion liquid comprises 37g/L of stannous chloride, 110mL/L of hydrochloric acid and the balance of water;
s4, reduction: and (3) reducing the modified wrinkled graphene oxide coated carbon felt prepared in the step (S3) in hydrazine hydrate steam with the pressure of 0.45kPa for 6 hours to prepare the rare earth doped material.
Comparative example 9
In comparison with example 3, the difference is that steps S3 and S4 are not performed.
The method comprises the following steps:
s1, hydrophilizing treatment of carbon felt: heating the polyacrylonitrile carbon felt in a 1mol/L NaOH solution to 95 ℃, and treating for 45min to obtain a hydrophilized carbon felt;
s2, coating the wrinkled graphene oxide: soaking the hydrophilized carbon felt prepared in the step S1 into graphene oxide aqueous dispersion liquid, wherein the solid-to-liquid ratio of the hydrophilized carbon felt to the graphene oxide aqueous dispersion liquid is 1:5g/mL, covering the upper surface and the lower surface with glass sheets, heating to 160 ℃ in a resistance furnace, treating for 3 hours, and drying to obtain the wrinkled graphene oxide coated carbon felt;
s3, reduction: and (3) reducing the wrinkled graphene oxide coated carbon felt prepared in the step (S2) in hydrazine hydrate steam with the pressure of 0.45kPa for 6 hours to prepare the rare earth doped material.
Comparative example 10
In comparison with example 3, the difference is that step S5 is not performed.
The method comprises the following steps:
s1, hydrophilizing treatment of carbon felt: heating the polyacrylonitrile carbon felt in a 1mol/L NaOH solution to 95 ℃, and treating for 45min to obtain a hydrophilized carbon felt;
s2, coating the wrinkled graphene oxide: soaking the hydrophilized carbon felt prepared in the step S1 into graphene oxide aqueous dispersion liquid, wherein the solid-to-liquid ratio of the hydrophilized carbon felt to the graphene oxide aqueous dispersion liquid is 1:5g/mL, covering the upper surface and the lower surface with glass sheets, heating to 160 ℃ in a resistance furnace, treating for 3 hours, and drying to obtain the wrinkled graphene oxide coated carbon felt;
s3, surface modification: placing 10 parts by weight of the wrinkled graphene oxide coated carbon felt prepared in the step S2 into 100 parts by weight of pre-immersion liquid, treating for 3min at room temperature, then placing into 100 parts by weight of colloid palladium activation liquid, heating to 45 ℃, treating for 7min, then placing into 100 parts by weight of 1mol/L hydrochloric acid solution, treating for 4min at room temperature, and washing to obtain a modified wrinkled graphene oxide coated carbon felt;
the formula of the pre-immersion liquid comprises 37g/L of stannous chloride, 110mL/L of hydrochloric acid and the balance of water;
s4, electroless plating: dissolving 1 part by weight of nickel chloride in 100 parts by weight of ethanol, adding 0.07 part by weight of lanthanum chloride, 0.04 part by weight of neodymium nitrate, 0.03 part by weight of yttrium chloride, 0.4 part by weight of citric acid and 0.3 part by weight of oxalic acid, stirring and mixing for 20min, adjusting the pH value of the solution to 4, adding 1.2 parts by weight of borane dimethylamine, stirring and mixing for 10min to obtain a plating solution, adding 10 parts by weight of the modified wrinkled graphene oxide coated carbon felt prepared in the step S3 into 100 parts by weight of the plating solution, heating to 70 ℃, carrying out chemical plating treatment for 2h, taking out, cleaning and drying to obtain the rare earth element doped wrinkled graphene oxide coated carbon felt, namely the rare earth doping material.
Test example 1
The specific surface area, total pore volume, macropore volume, mesopore and micropore volume parameters of the rare earth doped materials prepared in examples 1 to 3 and comparative examples 1 to 10 were measured using an ASAP2460 type full-automatic specific surface and porosity analyzer, and the results are shown in Table 1.
TABLE 1
As can be seen from the above table, the rare earth doped materials prepared in examples 1-3 of the present invention have a large specific surface area and a large total pore volume.
Examples 4 to 6 and comparative examples 11 to 20
A rare earth liquid flow energy storage battery is provided, rare earth doped materials are battery cathode materials, rare earth doped materials in examples 4-6 and comparative examples 11-20 are respectively prepared from examples 1-3 or comparative examples 1-10, battery cathode materials are polyacrylonitrile carbon felt, the size of the anode and the cathode is 20mm multiplied by 30 mm multiplied by 3.2mm, positive electrolyte is 50mL 4mol/L NaBr aqueous solution, and negative electrolyte is 50mL 1.3mol/L Na 2 S 4 The water solution and the ion exchange membrane are Nafion membranes. The flow rate of the positive electrode and the negative electrode of the battery electrolyte is 50mL/min, and the working temperature is normal temperature.
Test example 2
The rare earth flow energy storage batteries prepared in examples 4 to 6 and comparative examples 11 to 20 were subjected to battery performance evaluation by using an Arbin battery tester, wherein foam nickel was used as a negative electrode material as a control group. The results are shown in Table 2.
The energy efficiency of the battery is obtained by the ratio of the discharge energy and the charge energy measured by an Arbin instrument during the charge and discharge of the battery, constant current is adopted, the reverse direction is adopted, the charge control termination electric quantity is 1.34A/h, the discharge control termination voltage is 0.9V, and the current density is respectively measured to be 30mA/cm 2 、40mA/cm 2 、50mA/cm 2 。
The cycle performance of the battery is that the prepared rare earth liquid flow energy storage battery is at 40mA/cm 2 The battery energy efficiency retention was tested at a current density of 100 charge-discharge cycles.
TABLE 2
As can be seen from the above table, in the rare earth liquid flow energy storage batteries prepared in examples 4 to 6 of the present invention, the rare earth doped materials prepared in examples 1 to 3 are good negative electrode materials, and the charge-discharge current density is 30mA/cm 2 The energy efficiency of the battery can reach 95.22%, and the battery has good cycle performance.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. A preparation method of a rare earth doped material is characterized in that after hydrophilization treatment of polyacrylonitrile carbon felt, a layer of wrinkled graphene oxide is coated on the surface, the surface is modified by pre-immersion liquid, colloid palladium activating liquid and dispergation liquid in sequence, nd/La/Y-Ni-B is deposited by electroless plating, and hydrazine hydrate is used for reduction, so that the rare earth doped material is prepared.
2. The method of manufacturing according to claim 1, comprising the steps of:
s1, hydrophilizing treatment of carbon felt: heating polyacrylonitrile carbon felt in alkali liquor to prepare a hydrophilized carbon felt;
s2, coating the wrinkled graphene oxide: soaking the hydrophilized carbon felt prepared in the step S1 into graphene oxide aqueous dispersion liquid, covering the upper surface and the lower surface with glass sheets, heating in a resistance furnace, and drying to obtain a wrinkled graphene oxide coated carbon felt;
s3, surface modification: placing the wrinkled graphene oxide coated carbon felt prepared in the step S2 into pre-immersion liquid, performing room temperature treatment, then placing into colloid palladium activation liquid, performing heat treatment, then placing into glue solution, performing room temperature treatment, and washing to obtain the modified wrinkled graphene oxide coated carbon felt;
s4, electroless plating: dissolving nickel chloride in ethanol, adding lanthanum chloride, neodymium nitrate, yttrium chloride, citric acid and oxalic acid, stirring and mixing uniformly, regulating the pH value of the solution, adding borane dimethylamine, stirring and mixing uniformly to obtain a plating solution, adding the modified wrinkled graphene oxide-coated carbon felt prepared in the step S3 into the plating solution, performing chemical plating treatment, taking out, washing and drying to obtain the rare earth element doped wrinkled graphene oxide-coated carbon felt;
s5, reduction: and (3) reducing the rare earth element doped wrinkled graphene oxide coated carbon felt prepared in the step (S4) in hydrazine hydrate steam to prepare the rare earth doped material.
3. The method according to claim 2, wherein the alkali solution in step S1 is a solution of 0.5-1.5mol/L NaOH or KOH, and the heating treatment is carried out at a temperature of 90-100deg.C for 30-60min.
4. The method according to claim 2, wherein the solid-to-liquid ratio of the hydrophilized carbon felt and the graphene oxide aqueous dispersion in step S2 is 1:4-7g/mL, and the heating treatment is performed at a temperature of 150-170 ℃ for a time of 2-4h.
5. The preparation method according to claim 2, wherein the pre-immersion liquid in step S3 comprises 35-40g/L stannous chloride, 100-120mL/L hydrochloric acid and the balance water, the heating treatment is carried out at a temperature of 40-50 ℃ for 5-10min, and the solution of the gelatin is a hydrochloric acid solution of 0.5-1.5 mol/L.
6. The preparation method according to claim 2, wherein the mass ratio of nickel chloride, lanthanum chloride, neodymium nitrate, yttrium chloride, citric acid, oxalic acid and borane dimethylamine in step S4 is 0.8-1.2:0.05-0.1:0.03-0.05:0.02-0.04:0.3-0.5:0.2-0.4:1-1.5, wherein the pH value of the solution is regulated to 3.8-4.2, and the electroless plating treatment time is 1-3h.
7. The preparation method according to claim 2, wherein the pressure of the hydrazine hydrate vapor in step S5 is 0.4 to 0.5kPa, and the time for the reduction is 5 to 7 hours.
8. The preparation method according to claim 1, characterized by comprising the following steps:
s1, hydrophilizing treatment of carbon felt: heating polyacrylonitrile carbon felt in 0.5-1.5mol/L NaOH or KOH solution to 90-100 ℃ and treating for 30-60min to obtain hydrophilized carbon felt;
s2, coating the wrinkled graphene oxide: soaking the hydrophilized carbon felt prepared in the step S1 into graphene oxide aqueous dispersion liquid, wherein the solid-to-liquid ratio of the hydrophilized carbon felt to the graphene oxide aqueous dispersion liquid is 1:4-7g/mL, covering the upper surface and the lower surface with glass sheets, heating to 150-170 ℃ in a resistance furnace, treating for 2-4h, and drying to obtain the wrinkled graphene oxide coated carbon felt;
s3, surface modification: placing 10 parts by weight of the wrinkled graphene oxide coated carbon felt prepared in the step S2 into 100 parts by weight of pre-immersion liquid, treating at room temperature for 2-4min, then placing into 100 parts by weight of colloid palladium activation liquid, heating to 40-50 ℃, treating for 5-10min, then placing into 100 parts by weight of 0.5-1.5mol/L hydrochloric acid solution, treating at room temperature for 3-5min, and washing to obtain a modified wrinkled graphene oxide coated carbon felt;
the formula of the pre-immersion liquid comprises 35-40g/L stannous chloride, 100-120mL/L hydrochloric acid and the balance of water;
s4, electroless plating: dissolving 0.8-1.2 parts by weight of nickel chloride in 100 parts by weight of ethanol, adding 0.05-0.1 part by weight of lanthanum chloride, 0.03-0.05 part by weight of neodymium nitrate, 0.02-0.04 part by weight of yttrium chloride, 0.3-0.5 part by weight of citric acid and 0.2-0.4 part by weight of oxalic acid, stirring and mixing uniformly, adjusting the pH value of the solution to 3.8-4.2, adding 1-1.5 parts by weight of borane dimethylamine, stirring and mixing uniformly to obtain a plating solution, adding 10 parts by weight of the modified wrinkled graphene oxide coated carbon felt prepared in the step S3 into 100 parts by weight of the plating solution, performing chemical plating treatment for 1-3 hours, taking out, cleaning, and drying to prepare the rare earth element doped wrinkled graphene oxide coated carbon felt;
s5, reduction: and (3) reducing the rare earth element doped wrinkled graphene oxide coated carbon felt prepared in the step (S4) in hydrazine hydrate steam with the pressure of 0.4-0.5kPa for 5-7 hours to prepare the rare earth doped material.
9. A rare earth doped material produced by the production method according to any one of claims 1 to 8.
10. A rare earth liquid flow energy storage battery is characterized in that the rare earth doped material of claim 9 is used as a battery cathode material, a battery anode material is polyacrylonitrile carbon felt, an anode electrolyte is 3-5mol/L NaBr aqueous solution, and the anode electrolyte is 1-2mol/L Na 2 S 4 The water solution and the ion exchange membrane are Nafion membranes.
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| CN116836495A (en) * | 2023-04-11 | 2023-10-03 | 湖北中一科技股份有限公司 | Composite conductive film and preparation method thereof |
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