CN116053496B - Metal carbide-organic framework composite membrane for all-vanadium redox flow battery, preparation method and application thereof - Google Patents
Metal carbide-organic framework composite membrane for all-vanadium redox flow battery, preparation method and application thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 70
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 title description 2
- 239000002184 metal Substances 0.000 title description 2
- 239000013384 organic framework Substances 0.000 title description 2
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 32
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000003763 carbonization Methods 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000012924 metal-organic framework composite Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 27
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 22
- 239000011159 matrix material Substances 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 5
- 229920002530 polyetherether ketone Polymers 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 13
- 239000012621 metal-organic framework Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 7
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- 238000005266 casting Methods 0.000 abstract description 3
- 150000002736 metal compounds Chemical class 0.000 abstract description 3
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 239000012300 argon atmosphere Substances 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 229920002465 poly[5-(4-benzoylphenoxy)-2-hydroxybenzenesulfonic acid] polymer Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- 239000003792 electrolyte Substances 0.000 description 13
- 238000012546 transfer Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 229920000557 Nafion® Polymers 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- 230000010220 ion permeability Effects 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- 230000035699 permeability Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 239000013206 MIL-53 Substances 0.000 description 2
- 239000013132 MOF-5 Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000013207 UiO-66 Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- -1 ZIF-67 Substances 0.000 description 2
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- 238000001493 electron microscopy Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
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- 239000000945 filler Substances 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
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- 239000002159 nanocrystal Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 239000013251 zeolitic imidazolate framework-71 Substances 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000013153 zeolitic imidazolate framework 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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
-
- 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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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
The invention relates to a metal-organic framework composite membrane carbonized by an all-vanadium redox flow battery, and a preparation method and application thereof, and belongs to the technical field of all-vanadium redox flow batteries. The technical scheme adopted is as follows: the metal-organic framework material (ZIF-8) was pyrolyzed in an argon atmosphere at 600 ℃ to obtain a porous carbonized metal-organic framework material, which was then filled into a non-fluorine sulfonated polymer SPEEK, and a composite membrane was prepared by a solution casting method. In one aspect of the invention, ZIF-8 is converted to CZIF-8 consisting of a metal compound and carbon by carbonization, exhibiting enhanced acid stability; on the other hand, the addition of the carbonized material increases the interaction force in the base membrane, constructs additional proton transport channels, and exhibits enhanced proton conductivity. The composite membrane prepared from the two porous carbonized materials has the characteristics of stronger performance of the all-vanadium redox flow battery and good mechanical property, and is simple in process and low in cost.
Description
Technical Field
The invention relates to a metal-organic framework composite membrane carbonized by an all-vanadium redox flow battery, and a preparation method and application thereof, and belongs to the technical field of all-vanadium redox flow batteries.
Background
all-Vanadium Redox Flow Battery (VRFB), which is a large-scale energy storage technology, has been widely studied due to the advantages of recycling vanadium electrolyte, flexible design and layout, high response speed and the like, and has proved to be a large-scale energy storage system capable of being electrically used with renewable energy sources. The proton conducting film plays roles of separating positive and negative electrolytes, forming a closed loop, conducting protons and avoiding active ion cross-strings, is one of key components in a VRFB system, and the performance of the proton conducting film can influence the performance of a final battery. The Nafion series membrane produced by DuPont is the most commonly used proton conducting membrane at present, and has good proton conductivity and chemical stability, but the problems of high vanadium ion permeability, poor ion selectivity and high manufacturing cost generally exist, so that the further development of the membrane is severely limited. Therefore, there is a need to develop a new generation of high performance proton conducting membranes for VRFB.
The non-fluorosulfonic acid proton exchange membrane with simple manufacture and low cost can greatly reduce the production cost, and is commonly usedThe membrane material is a sulfonated aromatic polymer, wherein Sulfonated Polyetheretherketone (SPEEK) is considered as a high-performance membrane material promising to replace Nafion membranes, but the proton transmission capacity of the SPEEK membrane is weaker due to the weak acidity of the sulfonic acid group in the SPEEK. Thus, surface grafting, polymer blending, organic/inorganic hybridization, and the like methods have been widely used by researchers to improve film properties. The modification method of adding organic or inorganic filler can reconstruct the inner structure of the membrane and induce the formation of interfacial proton transmission channels, thus being an effective way for improving the performance of the membrane. To date, siO 2 、TiO 2 、WO 3 And inorganic nano particles such as SiC and the like have been used for improving the ion selectivity of the membrane, but the addition of inorganic nano ions fills the channels of the polymer matrix, so that the vanadium permeation is reduced, the ion selectivity is improved, meanwhile, the proton transmission channels are reduced, and the synchronous improvement of the ion selectivity and the proton transfer rate cannot be realized.
Compared with the traditional inorganic filler, the novel porous material of metal-organic frameworks (MOFs) has an adjustable nanoscale size window, and provides an additional proton transmission path while realizing effective screening of protons and vanadium ions. But the acid stability of the ZIF series MOFs is poor compared to other porous materials.
Disclosure of Invention
The invention converts it into a carbonized metal-organic framework material (CMOF) composed of metal compounds and carbon by direct pyrolysis to promote its acid stability. On one hand, CMOF can occupy part of vanadium ion transmission channels in the polymer matrix as a filler to block the passing of vanadium ions, and on the other hand, the increased pore channel size of carbonization reduces proton transmission resistance, so that the rapid passing of protons is facilitated. CMOF film has great potential in VRFB field as new film material.
The composite membrane comprises a polymer matrix and carbonized particles dispersed in the matrix, wherein the carbonized particles comprise a carbon skeleton with a polyhedral structure and ZnO particles loaded on the carbon skeleton; the particle size of the carbonized particles is 100-500nm, and the carbonized particles account for 0.5-10% of the mass ratio in the polymer matrix.
The polymer matrix is made of one or more of sulfonated polymer selected from sulfonated polyether ether ketone (SPEEK), sulfonated Polyimide (SPI) and sulfonated polyether sulfone (SPES).
The carbonized particles are formed by a structure with a regular dodecahedron.
The carbonized particles are obtained by carbonizing MOF materials.
The MOF material is selected from one or more of ZIF-8, ZIF-67, ZIF-71, MIL-53, MOF-5 and UiO-66.
The preparation method of the carbonized metal-organic framework composite membrane for the all-vanadium redox flow battery comprises the following steps of:
step 1, carbonizing MOF materials in inert gas atmosphere to obtain carbonized particles;
and 2, preparing a solution containing carbonized particles and a polymer matrix, coating the solution, and then drying, activating and cleaning to obtain the composite film.
In the step 1, the inert gas atmosphere refers to one of nitrogen and argon; the maximum temperature in carbonization treatment is 400-800 ℃, the residence time at the maximum temperature is 2-10h, and the rate of heating to the maximum temperature is 1-5 ℃/min.
In the step 2, the concentration of the polymer matrix in the solution is 0.05-0.5g/mL; the solution is an organic solvent.
In the step 2, the highest temperature in the drying process is 90-110 ℃, and the treatment time under the highest temperature condition is 5-20h.
In the step 2, the activation is carried out by adopting sulfuric acid solution.
The application of the composite membrane in the all-vanadium redox flow battery.
Advantageous effects
The invention introduces a porous carbonized material (CZIF-8) into a polymer matrix to optimize the performance of a composite membrane, including optimizing the mechanical properties, proton transfer rate and the like of the membrane, and develops a high-performance all-vanadium redox flow battery membrane. Through the addition of CZIF-8, the metal-organic framework material with an unstable framework structure in a strong acid environment can be used for the all-vanadium redox flow battery. CZIF-8 has improved mechanical and mass transfer properties of the membrane, and the composite membrane exhibits higher Voltage Efficiency (VE) and Energy Efficiency (EE) than a pure membrane.
Drawings
FIG. 1 is a) SEM, b) TEM and c) XRD patterns of ZIF-8. D) SEM of CZIF-8, e) TEM and f) XRD.
FIG. 2 is a graph of N at 77K for a) ZIF-8 and CZIF-8 2 Adsorption-desorption isotherms, b) ZIF-8 and c) CZIF-8.
FIG. 3 is a general spectrum of a) CZIF-8, and b) -d) XPS spectra of Zn2p, C1s and N1s, respectively.
FIG. 4 a) ZIF-8 addition 3M H 2 SO 4 Dissolution in solution, b) CZIF-8 soak 3M H 2 SO 4 SEM image after 48 hours of solution c) SEM image after CZIF-8 soaking in acid electrolyte containing vanadium ions.
FIG. 5 is a SEM sectional image of a composite film of a) SPEEK, b) S/CZIF-8-1%, c) S/CZIF-8-2%, d) S/CZIF-8-3%, e) S/CZIF-8-4% (inset is an SEM surface image). f) SEM image of CZIF-8/polymer interface in S/CZIF-8-3%.
FIG. 6 is a front and rear SEM sectional images of a) -b) S/ZIF-8-3% acid electrolyte containing vanadium ions. c) -d) a cross-sectional SEM image and a CZIF-8/polymer interface SEM image after soaking the acid electrolyte containing vanadium ions in S/CZIF-8-3%.
FIG. 7 is a graph of a) mechanical properties of S/CZIF-8-x (x=0, 1,2,3, 4%) films, and b) water absorption and swelling of S/CZIF-8-x (x=0, 1,2,3, 4%) films.
FIG. 8 is a) proton transfer rate of S/CZIF-8-x (x=0, 1,2,3, 4%), b) -c) vanadium ion concentration and vanadium ion permeability of S/CZIF-8-x (x=0, 1,2,3, 4%), d) ion selectivity of S/CZIF-8-x (x=0, 1,2,3, 4%).
FIG. 9 is a graph of S/ZIF-8-3% film, S/CZIF-8-3% film, SPEEK film and Nafion 212 at 20-100mA cm -2 All vanadium redox flow battery performance at current density graphs a) CE, b) VE, c) EE. d) Long cycle stability performance graph (current) for S/CZIF-8-3% film loaded cellDensity of 100mA cm -2 ). e) Battery cycle performance curve.
Detailed Description
Specifically screening out carbonized materials with acid stability, and mixing the carbonized materials with sulfonated polymer matrix according to a certain mass ratio to prepare the proton exchange membrane with excellent performance.
The invention adopts ZIF-8 which is unstable under acidic condition as carbonization precursor, and prepares CZIF-8 by pyrolysis in Ar atmosphere at 600 ℃ for 5 hours, and adds CZIF-8 as filler into sulfonated polymer, and prepares composite membrane by solution casting method. In one aspect of the invention, ZIF-8 is converted to CZIF-8 consisting of a metal compound and carbon by carbonization, exhibiting enhanced acid stability; on the other hand, the addition of the carbonized material increases the interaction force in the base membrane, constructs additional proton transport channels, and exhibits enhanced proton conductivity. The composite membrane prepared from the material has the characteristics of stronger performance of the all-vanadium redox flow battery and good mechanical property, and is simple in process and low in cost.
The MOF precursor used in the present invention is selected from ZIF-8, ZIF-67, ZIF-71, MIL-53, MOF-5 or UiO-66.
As the material in the present invention, sulfonated polymer is mainly used as the organic high molecular phase, and the sulfonated polymer which can be used is selected from sulfonated polyether ether ketone (SPEEK), sulfonated Polyimide (SPI) and sulfonated polyether sulfone (SPES).
The invention adopts ZIF-8 as a carbonization precursor material. In practical measurement, the maximum cavity size in ZIF-8 was 1.56nm. The size of the cavity of CZIF-8 after carbonization is increased and is larger than the diameter of hydrated vanadium ionResulting in small amounts of vanadium ions being able to pass through. Due to the structural stability of ZIF-8, the bad structural collapse of the frame in the carbonization process is reduced, the porous structure is reserved, and an additional path is provided for proton transmission; and ZIF-8 is converted to an acid stable material suitable for use in VRFB systems (CZIF-8).
Example 1 preparation of ZIF-8
0.744g of zinc nitrate hexahydrate was dissolved in 10mL of deionized water to form a homogeneous solution, 12.3g of 2-methylimidazole was dissolved in 90mL of deionized water to form another homogeneous solution, and then the two solutions were mixed and stirred at room temperature for 24 hours. ZIF-8 nanocrystals were collected by washing with excess methanol and centrifugation several times and then dried overnight at 80 ℃.
Example 2 preparation of CZIF-8
Obtained by directly carbonizing ZIF-8 under the argon flow at 600 ℃. Carbonization sets a series of temperature gradients: firstly, heating to 200 ℃ from 20 ℃ at a heating rate of 5 ℃/min, and preserving heat for 1h; then, the temperature is increased to 400 ℃ from 200 ℃ at the same heating rate, and the temperature is kept for 1h; finally heating to 600 ℃ from 400 ℃ at a heating rate of 3 ℃/min, and preserving heat for 5 hours to finally obtain the CZIF-8 nanocrystals.
Example 3 preparation of SPEEK/CZIF-8 hybrid Membrane
SPEEK was obtained by sulfonating PEEK powder in sulfuric acid (98 wt.%) at 50 ℃ for 5 h. The hybrid membrane was then prepared as follows.
A quantity of CZIF-8 was dispersed by sonication in 10mL DMF to form a mixed solution, and then 1.5g SPEEK was added to the mixed solution, followed by sonication for 30min and ball milling for 24h to form a homogeneous CMOF/SPEEK mixture. The resulting mixture was prepared into a film by a solution casting method, dried in an oven at 60 ℃ for 6 hours, and then dried in a vacuum oven at 100 ℃ for 12 hours. After the film was peeled from the glass plate, the film was peeled at 1M H 2 SO 4 Soaking in the solution for 24h for activation. Finally, the membrane was repeatedly rinsed with excess deionized water and stored in fresh deionized water prior to use. The CZIF-8 loading was controlled at 1-4% and the corresponding hybrid membrane was designated S/CMOF-x%, where S represents SPEEK and x% represents the mass ratio of CZIF-8 to SPEEK.
Example 4 Performance test
1) Scanning by electron microscope
ZIF-8 and CZIF-8 obtained in examples 1 and 2 were subjected to electron microscopy and transmission electron microscopy. As shown in figures 1 a, b, d and e, ZIF-8 has a typical dodecahedron structure with a particle size of about 300 nm. The carbonized CZIF-8 retains the original morphology, has highly symmetrical geometry, and reduces the average grain size to about 200 nm. The hybrid film obtained in example 3 was subjected to electron microscopy as shown in fig. 5. CZIF-8 particles are uniformly dispersed in the SPEEK matrix, and slight agglomeration occurs when the CZIF-8 loading exceeds 3%.
For VRFB systems, the acid stability of the material is critical. ZIF-8 was dispersed in 3M sulfuric acid solution, and it was observed that ZIF-8 particles dissolved immediately after 30s of the acid solution was added (FIG. 4 a). In contrast, CZIF-8 was dispersed in a 3M sulfuric acid solution and a vanadium ion-containing electrolyte, respectively, and the crystal shape and size were not significantly changed after storage of CZIF-8 in both solutions at room temperature for 48 hours, thanks to the structural stability of the powder of CZIF-8, showing excellent acid stability (b, c of FIG. 4).
The stability comparison was performed by adding the S/ZIF-8-3% membrane and the S/CZIF-8-3% membrane to the electrolyte containing vanadium ions. After 2d in the electrolyte containing vanadium ions, a film containing 3wt% ZIF-8 was observed to have significant pinholes due to the falling of ZIF-8 particles (fig. 6 a, b). While after 14 days the S/CZIF-8-3% film still showed a uniform distribution of CZIF-8 particles and a good CZIF-8/polymer interface (c, d, FIG. 6) from the SEM sectional view.
2) XRD detection
The phases of ZIF-8 and CZIF-8 were characterized. As can be seen from FIG. 1 c, the XRD pattern of ZIF-8 shows sharp and strong diffraction peaks, indicating that ZIF-8 was successfully synthesized and crystallized well. The characteristic peaks of ZIF-8 completely disappeared after carbonization, and there were three peaks near 2θ=24°,2θ=44° and 2θ=34.5°, corresponding to the (002) and (001) crystal plane diffraction peaks and the (002) characteristic peak of ZnO in the carbon material (f of fig. 1), respectively, indicating that ZIF-8 was completely converted into a composite material consisting of a carbon skeleton and zinc oxide at 600 ℃.
3) BET test
By N 2 Adsorption experiments explored the adsorption capacity and pore size of the crystals. As shown in FIG. 2, ZIF-8 exhibits a typical type I isotherm, and is a completely microporous material with high nitrogen adsorption at low relative pressures and low nitrogen adsorption at high relative pressures. CQIF-8 also exhibited a type I isotherm with a slight hysteresis loop, indicating that a small amount of mesopores was present in the sample. Value ofIt is noted that the pore size distribution becomes wider after carbonization and moves toward a larger pore size, which reduces proton transfer resistance to some extent, facilitating proton transfer.
4) XPS test
The composition and chemical state of the carbonized skeleton material were analyzed in detail by XPS (fig. 3). XPS spectra of Zn2p in FIG. 3 b show peaks around 1045.1 and 1022.2eV, corresponding to Zn2p, respectively 1/2 And 2p 3/2 Core energy level. C1s shows peaks around 284.6, 285.8, 288.1 and 299eV, corresponding in turn to the four forms of C-C, C-O, C =o and o=c-O (C of fig. 3). Furthermore, the N1s peak in d of fig. 3 corresponds to three different types of N: pyrindinic-N (398.4 eV), pyrroic-N (3.99.5 eV) and graphitic-N (400.7 eV).
5) Mechanical properties
At a drawing speed of 5mm/min -1 The mechanical properties of the films were obtained by the universal tester. The samples were cut into 50mm by 10mm strips and the film surface was wiped with filter paper prior to testing. The tensile strength of the sample was calculated by the following formula:
wherein F is max Is the maximum tension; w and D are the width and thickness, respectively, of the film sample. As shown in FIG. 5, the SPEEK film has a tensile strength of only 22.11MPa, and the tensile strength of the film is obviously improved after CZIF-8 is added, and particularly, the mechanical strength of the S/CZIF-8-3% film reaches 30.56MPa, which is the highest in all films. When the loading exceeds 3%, the tensile strength is reduced, but the tensile strength of the S/CZIF-8-4% film is also higher than that of the SPEEK film, and is 29.6MPa.
6) Water absorption and swelling ratio
The water absorption and swelling ratio of the hybrid film were calculated by the following formula:
wherein dwet and ddry are the diameters of the wet and dry films, respectively; wwet and Wdry are the mass of wet and dry films, respectively. Wet films were prepared by soaking in deionized water for 48h and wiping the film surface with filter paper prior to measurement. The measured wet film was then dried in a vacuum oven at 100 ℃ for 24 hours. FIG. 6 reflects the relationship between the amount of addition and the water absorption, and the result shows that the water absorption capacity of the composite film is greatly improved. The water absorption rate of the composite film added with CZIF-8 can reach 44% at most, which is 16% higher than that of a SPEEK pure film. In addition, CZIF-8 maintains the original rigid backbone structure of ZIF-8, and the introduction of CZIF-8 limits swelling of the SPEEK matrix to some extent, which is lower than that of pure SPEEK membranes.
7) Proton transfer rate
The membranes were tested for proton conductivity by an electrochemical workstation (Solartron analytical 1470E+1260A) using an alternating current impedance spectroscopy. The sample was sandwiched between two circular titanium plates and then secured with coin cell clips. The frequency range is 10 3 -10 6 Between Hz, the alternating current amplitude was 5mV. The proton transfer rate of the membrane was calculated according to the following formula:
R A ＝R×A
wherein σ is the proton conductivity of the membrane; l is the thickness of the sample; r and A are the resistance and effective area of the membrane, respectively; r is R A Is the area resistance of the film and the test results are shown in fig. 7. As can be seen from FIG. 7, the hybrid membrane exhibited a higher proton transfer rate than the SPEEK membrane, with the S/CZIF-8-3% membrane having the fastest proton transfer rate (0.078S cm) -1 ) (proton transfer rate of SPEEK film is 0.058S cm) -1 ) It was further demonstrated that the proton transfer rate of the hybrid membrane could be improved by incorporating a porous CZIF-8 material.
8)VO 2+ Permeability and ion selectivity
Vanadium (VO) using H-type membrane diffusion cell 2+ ) And (5) permeability test. The membrane to be measured is sandwiched between pairs of diffusion cells. 50mL of 1.5M VOSO was added to the left side of the diffusion cell 4 +3.0M H 2 SO 4 Solution, right side add 50mL 1.5M MgSO 4 +3.0M H 2 SO 4 The solution was magnetically stirred to eliminate concentration polarization in the diffusion cell. 4mL of the solution was taken out every 24h from the side containing MgSO4 solution and 4mL of 1.5M MgSO was added again 4 +3.0M H 2 SO 4 A solution. Measuring absorbance of the obtained solution by ultraviolet-visible spectrophotometer, and obtaining VO in the solution according to the standard curve of absorbance-concentration 2+ Concentration, VO was calculated using the formula 2+ Permeability (P):
wherein V is B Is the volume of the solution on one side (50 mL), C B (t) is VO in the solution at right side of t 2+ Concentration, C A Is VO in the solution of the diffusion cell on the left side 2+ Concentration (i.e., 1.5M), A and L are the effective areas of the membranes (1.77 cm, respectively 2 ) And film thickness.
The ion selectivity of a membrane is defined as the ratio of proton conductivity (σ) to vanadium ion permeability (P), which is calculated by the following equation:
as can be seen from FIG. 8, the hybrid membrane exhibited a lower vanadium ion permeation rate than the SPEEK membrane, since the introduced CZIF-8 extended the transport path and tortuosity of the vanadium ions within the membrane, the vanadium ion permeation rate of the S/CZIF-8-3% membrane was 8.14X10 -7 cm 2 min -1 Down to 4.23×10 -7 cm 2 min -1 . In addition, thanks to the excellent proton transfer rate and lower vanadium ion permeability of the S/CZIF-8-3% membrane, it shows good ion selectivity, much higher than SPEEK pure membrane.
Example 5 application of SPEEK/CZIF-8 hybrid Membrane
The all-vanadium redox flow battery consists of a self-made diaphragm (effective area is 3 multiplied by 3.5 cm) 2 ) The graphite felt electrode, the current collector, the electrolyte tanks and the like are formed, and the electrolyte tanks at the two ends are respectively provided with positive electrolyte (10 mL 1.5mol VO) 2+ /VO 2 + in 3M H 2 SO 4 ) And a negative electrode electrolyte (10 mL 1.5mol V) 2+ /V 3+ in 3M H 2 SO 4 ). Based on the test results, the S/CZIF-8-3% film was selected for battery performance testing. Charge and discharge experiments at 20, 40, 60, 80 and 100mA cm -2 Is carried out at a current density of 0.8V and 1.7V, respectively. The long-cycle performance of the battery is 100mA cm -2 And tested at current density. In order to avoid oxidation of vanadium ions in the electrolyte by oxygen in the air, N in the circuit is maintained during the test 2 And (3) unblocking.
Coulombic Efficiency (CE), energy Efficiency (EE), and Voltage Efficiency (VE) of all-vanadium redox flow batteries were calculated by the following formulas:
based on an all-vanadium redox flow battery with S/ZIF-8-3%, S/CZIF-8-3% and SPEEK membrane at 20-100mA cm -2 The following properties, as shown in FIG. 9, demonstrate that the addition of carbonized porous material to a polymer matrix is an effective way to improve VRFB performance, with higher Voltage Efficiency (VE) and Energy Efficiency (EE) than S/CZIF-8-3% and SPEEK films. As a control, commercial Nafion 212 membranes were tested under the same conditions (fig. 9 (a), (b), (c)). Carefully observeIt was found that as the current density increased, the charge and discharge time of the battery was shortened and the permeation amount of vanadium ions was reduced, so that CE was increased continuously and stabilized at about 99% at a high current density. Conversely, a high current density exacerbates the polarization effect, which causes VE to gradually decrease as the current density increases. At 20-100mA cm -2 At current density, CE of S/CZIF-8-3% membrane increased from 98.09% to 99.12% well above Nafion 212 and SPEEK membranes. Similarly, the S/CZIF-8-3% VE (83.39-96.23%) was also higher than Nafion 212 and SPEEK membranes. As a result of the combination of CE and VE, EE of VRFB is also significantly improved. At 80mA cm -2 The EE of the lower S/CZIF-8-3% membrane can reach 82.66%, which is significantly higher than that of Nafion 212 (77.03%) and SPEEK (76.49%). As shown in FIG. 9 (d), the S/CZIF-8-3% film was coated at 100mA cm -2 The current density is tested by long-term charge and discharge, the stable operation of the hybrid membrane is over 1000 circles, EE is slightly reduced from 84.26% to 79.95%, and the SPEEK pure membrane can only operate for about 390 circles, so that the stability of the hybrid membrane can be improved by adding CZIF-8.
Claims (5)
1. The application of carbonized particles in reducing the vanadium ion permeation quantity of a carbonized metal-organic framework composite membrane of an all-vanadium redox flow battery is characterized in that the composite membrane comprises a polymer matrix and carbonized particles, and the carbonized particles are dispersed in the polymer matrix;
the carbonized particles comprise carbon frameworks and ZnO particles, the ZnO particles are loaded on the carbon frameworks, and the carbon frameworks have a polyhedral structure; the particle size of the carbonized particles is 100-500nm, and the mass percentage of the carbonized particles in the polymer matrix is 0.5-10%;
the polymer matrix is made of one or more of sulfonated polyether-ether-ketone, sulfonated polyimide and sulfonated polyether sulfone;
the carbonized particles are obtained by carbonizing ZIF-8 materials;
the preparation method of the composite film comprises the following steps:
step 1, carbonizing ZIF-8 material in inert gas atmosphere to obtain carbonized particles;
step 2, preparing a solution containing carbonized particles and a polymer matrix, coating the solution, and then drying, activating and cleaning to obtain a composite membrane;
in the step 1, the inert gas atmosphere refers to one of nitrogen and argon; the maximum temperature in carbonization treatment is 400-800 ℃, the residence time at the maximum temperature is 2-10h, and the rate of heating to the maximum temperature is 1-5 ℃/min.
2. The use according to claim 1, wherein the carbon skeleton has a regular dodecahedron structure.
3. The use according to claim 1, wherein in step 2 the concentration of the polymer matrix in the solution is 0.05-0.5g/mL; the solvent in the solution is an organic solvent.
4. The use according to claim 1, wherein in step 2, the maximum temperature during drying is 90-110 ℃ and the treatment time under the maximum temperature condition is 5-20h.
5. The use according to claim 1, wherein in step 2, the activation is performed with a sulfuric acid solution.
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