CN115411292B - Molecular cross-linked molecular sieve nanosheet hybrid membrane, preparation method and application thereof in flow battery - Google Patents

Molecular cross-linked molecular sieve nanosheet hybrid membrane, preparation method and application thereof in flow battery Download PDF

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CN115411292B
CN115411292B CN202211064782.6A CN202211064782A CN115411292B CN 115411292 B CN115411292 B CN 115411292B CN 202211064782 A CN202211064782 A CN 202211064782A CN 115411292 B CN115411292 B CN 115411292B
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徐至
黄康
夏永生
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Abstract

The invention belongs to the technical field of new materials, and relates to a preparation method and application of a molecular cross-linked molecular sieve nanosheet hybrid membrane. The method adopts surface functional molecular crosslinking to introduce a catalyst with-SO on the surface of the two-dimensional molecular sieve 3 H、‑NH 2 And (3) dispersing molecular sieve nano-sheets crosslinked by functional molecules in a polymer solution to obtain uniform casting solution, and then preparing the hybrid membrane by solution casting. The molecular cross-linked organic side chain effectively improves the organic-inorganic interface compatibility and the stress transmission of the inorganic filler and the polymer phase, can be combined with the ion exchange groups on the polymer chain and induces the rearrangement thereof to form a continuous ion transmission channel, and enhances the mechanical strength, the stability, the ion selectivity and the proton conductivity of the membrane.

Description

Molecular cross-linked molecular sieve nanosheet hybrid membrane, preparation method and application thereof in flow battery
Technical Field
The invention belongs to the technical field of new materials, and relates to a preparation method and application of a molecular cross-linked molecular sieve nanosheet hybrid membrane.
Background
With the evolution of world energy structures, how to efficiently utilize renewable energy sources has become a major challenge to our face in coping with global climate change issues. As a large-scale energy storage technology, the flow battery has the characteristics of environmental friendliness, high efficiency, adjustable power and capacity, long cycle life, low maintenance cost and the like, and can be proved to effectively utilize renewable energy sources to realize the effect of peak clipping and valley filling. Proton conducting membranes, which serve as important components in flow batteries, serve the primary function of separating the electrolyte from the anode and transporting protons, and their performance can greatly affect the performance of the battery system. Therefore, development of the proton conducting membrane material with low cost and high performance has important significance for development of a large-scale energy storage flow battery system
In recent years, sulfonated non-fluorine polymers have been widely studied as a low-cost ion exchange membrane material, which can adjust proton conductivity of a membrane by adjusting sulfonation degree, but too high sulfonation degree tends to cause a more serious swelling phenomenon and poor ion selectivity and mechanical properties. By co-blending the functional inorganic filler with the polymer matrix is a general strategy to enhance the performance of the separator, which enables a good integration of the processing properties of organic polymers and the diverse functional properties of nanofillers. Porous materials such as zeolite, metal Organic Framework (MOF), covalent Organic Framework (COF) and the like are novel functional fillers for preparing high-performance proton conducting membranes, and inherent regular pore channels of the porous materials can effectively intercept active substances with larger sizes and can allow carriers such as protons to pass through rapidly. Notably, zeolite molecular sieves have three-dimensional interconnected rigid, regular channels that recognize ions or molecules in the emma size range. Films based on two-dimensional Zeolite Nanoplatelets (ZN) exhibit excellent performance in terms of ion and molecular separation due to the large lateral dimensions and the preferred nanoscale thickness in the straight-through channel direction. The high aspect ratio ZN can maximize ion discrimination and reduce proton transport paths, and has great potential as a functional member for developing a novel proton conducting membrane (non-patent documents 1 to 54). Although such inorganic porous materials show great promise as basic building blocks for proton conducting membranes, challenges remain in practical applications, such as poor compatibility at the organic-inorganic interface, and the tendency of extraneous fillers to alter the ion exchange group distribution in the polymer phase, resulting in difficulties in forming continuous proton transfer channels. Therefore, developing a suitable strategy to fully exploit the application potential of such inorganic nanofillers has great practical significance.
Non-patent document 1: kim D, jeon MY, stottrup BL, tssatsis M.para-Xylene ultra-selective zeolite MFI membranes fabricated from nanosheet monolayers at the air-water interface, angew Chem IntEd.2018;57:480-485.
Non-patent document 2: min B, yang S, korde A, kwon YH, jones CW, nair S.Continuous zeolite MFI membranes fabricated from 2D MFI nanosheets on ceramic hollow fibers.Angew Chem Int Ed.2019;58:8201-8205.
Non-patent document 3: dai L, xu F, huang K, et al Ultrafast water transport in two-dimensional channels enabled by spherical polyelectrolyte brushes with controllable flexbile, angew Chem IntEd.2021;60:19933-19941.
Non-patent document 4: liu Y, qiang W, ji T, et al, united hierarchical MFI nanosheets prepared via anisotropic etching for solution-based sub-100-nm-thick oriented MFI layer fabric Sci adv 2020; eaay5993.
Disclosure of Invention
The purpose of the invention is that: solves the problems of poor compatibility and low battery performance of the common two-dimensional zeolite molecular sieve nanosheets when applied to the diaphragm materials of the flow batteries. The method adopts surface functional molecular crosslinking to introduce a catalyst with-SO on the surface of the two-dimensional molecular sieve 3 H、-NH 2 And (3) dispersing molecular sieve nano-sheets crosslinked by functional molecules in a polymer solution to obtain uniform casting solution, and then preparing the hybrid membrane by solution casting. The molecular cross-linked organic side chain effectively improves the organic-inorganic interface compatibility and the stress transmission of the inorganic filler and the polymer phase, can be combined with the ion exchange groups on the polymer chain and induces the rearrangement thereof to form a continuous ion transmission channel, and enhances the mechanical strength, the stability, the ion selectivity and the proton conductivity of the membrane.
A molecular cross-linked molecular sieve nano-sheet hybrid membrane comprises a polymer and a molecular sieve nano-sheet, wherein a silane coupling agent is grafted on the surface of the molecular sieve nano-sheet, and the silane coupling agent is provided with one or more of amino, sulfonic acid group, mercapto, hydroxymethyl, ureido or ethoxy, methoxy or isocyanato functional groups.
The polymer is sulfonated polyether ether ketone, perfluorinated sulfonic acid resin, polyether block polyamide, polydimethylsiloxane, polyether sulfone, sulfonated polyether sulfone, polybenzimidazole or polyimide.
The molecular sieve nanosheets are selected from ZSM-5 molecular sieve nanosheets, ZSM-35 molecular sieve nanosheets or ZSM-22 nanosheets.
The silane coupling agent is 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, hydroxymethyl triethoxysilane, ethyl triethoxysilane, ureidopropyl triethoxysilane, trimethoxysilane or isocyanatopropyl triethoxysilane.
The weight ratio of molecular sieve nano-sheet to polymer is 0.1: 100-30: 100.
the thickness of the hybridized film is 20-150 mu m.
The preparation method of the molecular cross-linked molecular sieve nanosheet hybrid membrane comprises the following steps:
step 1, carrying out a crosslinking reaction on molecular sieve nano-sheets and a silane coupling agent in a first solvent, washing a product, and drying;
step 2, dispersing the molecular cross-linked molecular sieve nano-sheets and the polymer obtained in the step 1 in a second solvent to obtain a casting solution;
and step 3, performing film forming treatment on the film casting solution to obtain the hybrid film.
In the step 1, the weight ratio of the molecular sieve nanosheets to the silane coupling agent is 1:0.1 to 1:1.
the condition of the crosslinking reaction is that the condensation reflux is carried out for 24-48 hours at the temperature of 80-120 ℃.
The first solvent is selected from toluene, benzene or xylene.
In the step 2, the second solvent is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, water, ethanol, propanol, butanol, propylene glycol, dimethyl sulfoxide, isopropyl acetate and tetrahydrofuran.
The mass fraction of the polymer in the casting film liquid is 1-30%.
Advantageous effects
The invention successfully carries out a series of surface functionalization modification on the two-dimensional molecular sieve nanosheets through molecular crosslinking, and prepares the molecular sieve nanosheets hybridized film crosslinked by functional molecules by taking the molecular sieve nanosheets as fillers. The molecular cross-linked molecular sieve nano-sheet effectively enhances the mechanical strength, ion selectivity and proton conductivity of the diaphragm. The method fully exerts the selective screening effect of the molecular sieve nano-sheet, improves the compatibility between the molecular sieve nano-sheet and a polymer phase through molecular crosslinking, and provides a new thought and strategy for fully excavating the proton selective transmission advantage of the molecular sieve nano-sheet and the application of the molecular sieve nano-sheet in a battery diaphragm.
Drawings
FIG. 1 is a schematic diagram of the preparation and structure of a functional molecular crosslinked Zeolite Nanoplatelet (ZN) reinforced membrane. (a) Amino-functionalized ZN (ZN-NH) 2 ) And sulfonic acid functionalized ZN (ZN-SO) 3 H) A functional design mixing method schematic diagram of (a). (b) (i) SPEEK film and intercalation (ii) ZN-NH 2 And (iii) ZN-SO 3 Schematic structure of proton channel in mixed membrane of H.
Fig. 2 is a characterization of ZN. (a) ZN, (b) ZN-SO 3 H and (c) ZN-NH 2 Transmission Electron Microscope (TEM) images and energy dispersive X-ray spectroscopy (EDS) results (inset). (d) X-ray photoelectron spectroscopy (XPS) results, (e) thermogravimetric analysis (TG) curves, (f) X-ray diffraction (XRD) patterns, (g) adsorption-desorption isotherms of N2 at 77K, (h) pore size distribution curves, and (i) Ion Exchange Capacity (IEC) results of ZNs.
FIG. 3 is a hybrid film morphology incorporating ZN. Surface, cross-section and partial magnified Scanning Electron Microscope (SEM) images of (a) SPEEK films and hybrid films incorporating (b) ZN, (c) ZN-NH2 and (d) ZN-SO 3H. From left to right: surface images, cross-sectional images, and locally enlarged images. The ZN loading was 4wt%.
Fig. 4 is a film property. (a) water absorption and swelling ratio, (b) tensile strength, (c) TG curve, (d) diffusion concentration of permeate side vo2+ versus time, (e) proton conductivity and sheet resistance, and (f) ion selectivity of different membranes.
Fig. 5 is a battery performance. (a) Coulombic Efficiency (CE), voltage Efficiency (VE), and Energy Efficiency (EE) of VFB cells equipped with different membranes. (b) Comparison of EE for S/ZN-SO3H-4% membranes with reported SPEEK-based membranes applied to VFB at different current densities. Organic and inorganic represent SPEEK-based films modified by blending organic polymers and inorganic nanofillers, respectively. (c) CE, VE and EE of VFB cells equipped with different membranes were tested for long cycles at a current density of 120mA cm-2. (d) The discharge capacity retention rates of the different films were measured in a long cycle test with a current density of 120mA cm-2.
Detailed Description
The preparation steps of the hybrid membrane of the invention are detailed as follows:
step (1), preparing molecular cross-linked molecular sieve nano-sheets: sequentially adding molecular sieve nanosheets and silane coupling agents into the solvent A, stirring at a rotating speed of 100-500 rpm, heating to 80-120 ℃ under inert atmosphere, condensing and refluxing for 24-48 h, cooling the reaction mixture to room temperature, centrifuging the reaction mixture at a rotating speed of 5000-10000 rpm, pouring out supernatant, washing the collected reaction product with absolute ethyl alcohol for 3-5 times, and drying in a drying oven at 80 ℃ to obtain the molecular crosslinked molecular sieve nanosheets.
Step (2), preparing molecular cross-linked molecular sieve nanosheet casting solution: adding the molecular crosslinked molecular sieve nano-sheets prepared in the step (1) into the solvent B, and carrying out ultrasonic treatment for 12 hours to uniformly disperse the molecular crosslinked molecular sieve nano-sheets to obtain a dispersion liquid. Then adding polymer into the dispersion liquid, and stirring for 24 hours at 50-350 rpm after ultrasonic treatment for 6 hours to fully dissolve the polymer, thus obtaining the molecular cross-linked molecular sieve nanosheet casting solution.
Step (3), preparing a molecular cross-linked molecular sieve nanosheet hybrid membrane: spreading the molecular crosslinked molecular sieve nanosheet casting solution prepared in the step (2) on a glass plate, drying at 60 ℃ for 6 hours to volatilize the solvent, and transferring the glass plate to a vacuum drying oven for drying at 100-140 ℃ for 12 hours to obtain the molecular crosslinked molecular sieve nanosheet hybridization film.
In the step (1), the solvent A is toluene, benzene or xylene.
In the step (1), the molecular sieve nanosheets are ZSM-5 molecular sieve nanosheets, ZSM-35 molecular sieve nanosheets or ZSM-22 nanosheets.
In step (1), the following
In the step (1), the inert atmosphere is nitrogen, helium or argon.
In the step (2), the solvent B is one or more of N, N-dimethylformamide, N-dimethylacetamide, water, ethanol, propanol, butanol, propylene glycol, dimethyl sulfoxide, isopropyl acetate and tetrahydrofuran.
In the step (2), the polymer is sulfonated polyether ether ketone, perfluorinated sulfonic acid resin, polyether block polyamide, polydimethylsiloxane, polyether sulfone, sulfonated polyether sulfone, polybenzimidazole or polyimide.
In the step (1), the weight ratio of the molecular sieve nano-sheet to the silane coupling agent is 1:0.1 to 1:1.
in the step (2), the weight ratio of the molecular crosslinked molecular sieve nano-sheet to the polymer is 0.1: 100-30: 100.
in the step (2), the mass fraction of the polymer in the casting solution is 1-30%.
In the step (3), the thickness of the hybridized film is 20-150 mu m.
EXAMPLE 1 Synthesis of ZSM-5 Zeolite Nanosheets (ZNs)
ZN is synthesized by a two-step hydrothermal reaction. In a molar ratio of 10SiO 2 :2.4TPAOH:0.87NaOH:114H 2 O configures the precursor sol. The mixture was stirred at room temperature overnight, then reacted hydrothermally at 50℃for 6 days at normal pressure, followed by heating to 100℃for three more days. After the reaction is finished, washing the zeolite nano seed crystal with deionized water, and centrifugally collecting. The template bis-1, 5 tripropylpentamethylene diimmonium iodide (dC 5) is synthesized by thorough alkylation of 1, 5-diaminopentane and 1-iodopropane, and then purified by ethanol, 2-butanone and ethyl acetate. Second, the mole ratio of 80TEOS to 3.75dC5 to 20KOH to 9500H 2 O preparing a precursor sol, hydrolyzing the precursor sol at room temperature overnight and then mixing the precursor sol with zeolite nano-crystal seeds synthesized in the first step, wherein the silicon dioxide ratio of the zeolite nano-crystal seeds to the precursor sol is 1:800. after the mixture was hydrothermally reacted at 140℃for 3.5 days, 1MNaAlO was added thereto 2 (Si/Al is 25) and then the hydrothermal reaction is continuedAnd 0.5 days. The reaction product was treated with an alkali salt solution to remove amorphous silica, then washed with deionized water, and collected by centrifugation to obtain ZN. Calcining the synthesized ZN in air at 500 deg.C for 6 hr to remove template agent and activate, and heating at 1 deg.C for 1 min -1 。
EXAMPLE 2ZN-SO 3 Synthesis of H
0.5g of activated ZN was added with 15mL of toluene to a three-necked flask and stirred well. To the mixture was added 0.25g of 3-mercaptopropyl triethoxysilane under nitrogen atmosphere, and after reflux reaction was slowly heated to 110℃for 48 hours, the reaction product was obtained by washing with toluene and ethanol several times, centrifuging and drying at 60℃for 6 hours. Under nitrogen atmosphere, the product was purified under H 2 O 2 The mixture was oxidized in aqueous solution at room temperature for 24H with stirring, and then the product was oxidized in 10mL of 0.1M H 2 SO 4 Soaking for 6h to protonate the sulfonic acid group. Finally centrifuging, washing and drying the product at 80 ℃ overnight to obtain ZN-SO 3 H powder.
EXAMPLE 3ZN-NH 2 Is synthesized by the following steps:
0.5g of activated ZN was added with 15mL of toluene to a three-necked flask and stirred well. Under nitrogen atmosphere, 0.25g of 3-aminopropyl triethoxysilane is added into the mixture, and after reflux reaction is carried out for 48h by slowly heating to 110 ℃, ZN-NH is obtained by repeated washing with toluene and ethanol, centrifuging and drying at 80 ℃ overnight 2 And (3) powder.
Example 4 preparation of SPEEK/molecular sieve hybrid Membrane
SPEEK was prepared by sulfonating PEEK in sulfuric acid (98 wt.%) at 50 ℃ for 5 h. The SPEEK/MOF hybrid membrane is then prepared as follows.
ZN, ZN-SO in examples 1-3, respectively 3 H、ZN-NH 2 Dissolving SPEEK in N, N-dimethylformamide to give a SPEEK concentration of ZN, ZN-SO 3 H or ZN-NH 2 1-5% of the SPEEK by mass, and the concentration of the SPEEK in the N, N-dimethylformamide is about 14wt%, and the SPEEK is used as casting solution after being uniformly mixed. Spreading the film casting liquid on a glass plate, drying at 60 ℃ for 6 hours to volatilize the solvent, and then transferring the glass plate to a vacuum drying oven for drying at 100-140 DEG CAnd (3) 12h, obtaining the molecular cross-linked molecular sieve nanosheet hybrid membrane.
Test method
1. Swelling and Water absorption
The SR (swelling ratio) and WU (water absorption) of the film are obtained from the following two equations, respectively:
where d and W are the diameter and mass of the film in wet and dry states, respectively.
2. Mechanical properties
At a pulling speed of 10mm min -1 The mechanical properties of the films are obtained on a universal testing machine. The samples were cut into 20mm by 5mm strips and the wet film surface was wiped with water prior to testing. To reduce test errors, three samples of each film were tested and the resulting data averaged. The tensile strength of the film sample was calculated as follows:
wherein F is Max Is the maximum tension; w and D are the width and thickness of the sample film, respectively.
3. Proton transfer rate
The proton transfer rate of the membrane was measured on an electrochemical workstation (Solartron analytical 1470E+1260A) using an alternating current impedance spectroscopy test. The sample is clamped between two round titanium sheets, and the titanium sheets are fixed by button cell clamps. Test frequency at 10 3 To 10 6 Between hertz, the ac amplitude was 5mV. The proton transfer rate of the membrane was measured using the latest method of the professor plum team and the calculation formula is as follows:
where σ is the proton transfer rate of the membrane. L is the thickness of the sample. R is the impedance of the film. A is the effective area of the film, i.e. the area of the titanium plate.
The sheet resistance can be calculated by the following formula:
R A ＝R×A
R A is the film surface resistance.
4. Vanadium ion permeation rate and ion selectivity
At an effective area of 1.77em 2 Is tested in a diffusion cell. Side diffusion Chi Zhongzhuang has 50mL 1.5MVOSO 4 /3.0M H 2 SO 4 The solution, the other side diffusion cell was loaded with the same volume of 1.5M MgSO 4 /3.0M H 2 SO 4 The solution was equilibrated for ionic strength and osmotic pressure and was magnetically stirred to reduce concentration polarization during the test. Every 24h at MgSO 4 /H 2 SO 4 The solution was measured and absorbance was measured at 762nm with an ultraviolet-visible spectrophotometer. Determination of VO with a standard absorbance/concentration curve 2+ Is a concentration of (3). The vanadium permeation rate can be calculated by the following formula:
wherein V is B Is MgSO 4 /H 2 SO 4 The volume of the solution was 50ml in this experiment; c (C) B (t) is time t MgSO 4 /H 2 SO 4 VO in solution 2+ The concentration of ions; c (C) A Is VOSO 4 /H 2 SO 4 VO in solution 2+ The concentration, in the case where the test time is not too long, can be regarded as a constant to simplify the calculation; A. l is the effective film area and film thickness, respectively; p is the permeation rate of vanadium ions.
Ion selectivity is defined as proton transfer rate and VO 2+ The ratio of the permeation rates is calculated as follows:
5. ion exchange capacity
The ion exchange capacity is tested by adopting a traditional titration method, a sample is soaked in saturated NaCl solution for 24 hours, the solution containing H+ obtained by replacement is titrated by using 0.03M NaOH solution, and the ion exchange capacity can be calculated according to the following formula:
c NaOH is the concentration of NaOH solution; v (V) NaOH Is the volume of NaOH solution; w is the mass of the sample
6. Cell performance
Performance of VRFB was tested using a self-contained flow battery system consisting of a sheet of membrane (effective area 4cm 2 ) Two carbon felt electrodes, two graphite plate current collectors and a pair of shells. Membrane separation negative electrode electrolyte (10 ml 1.5M V) 2+ /V 3+ 3MH 2 SO 4 ) And a positive electrode electrolyte (10 ml 1.5M VO 2+ /VO2+3M H 2 SO 4 ) And is sandwiched between the two electrodes. For charge and discharge tests, the cut-off voltages of charge and discharge were 1.7V and 0.8V, respectively, and the current densities tested were 40-200mA cm -2 . For the cyclic test, the constant current density was 120mA cm -2 Tested at the same cut-off voltage. During the test, nitrogen protection was used. The Coulombic Efficiency (CE), voltage Efficiency (VE) and Energy Efficiency (EE) of the battery were calculated by the following formulas:
wherein C is d And C c Discharge capacity and charge capacity, respectively; e (E) d And E is c The discharge energy and the charge energy, respectively.
Characterization of molecular sieve nanoplatelets (ZN)
As shown in the a-c region of FIG. 2, the original ZN, ZN-NH 2 And ZN-SO 3 H each exhibits typical characteristics of single-or multi-layer two-dimensional nanoplatelets. Detection of ZN-NH by energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS), respectively 2 And ZN-SO 3 The nitrogen and sulfur elements of H, except the molecular sieve intrinsic elements, were not detected in ZN (regions a-d of FIG. 2), demonstrating-NH 2 and-SO 3 Successful grafting of the H functional group. Thermogravimetric analysis (TGA) showed that ZN has excellent thermal stability and ZN-NH 2 And ZN-SO 3 The weight loss behavior of H can be attributed to the decomposition of the organic side chains grafted onto the ZN surface (region e of fig. 2). X-ray diffraction (XRD) pattern, N 2 Adsorption-desorption isotherms and pore size distribution curves indicate that the crystal structure and intrinsic pore channels of ZN are well preserved after surface function modification (f-h region of fig. 2). In addition, ZN-NH 2 (0.45mmolg -1 ) And ZN-SO 3 H (0.57 mmolgs-1) showed a ratio ZN (0.27 mmolgs -1 ) Higher Ion Exchange Capacity (IEC) (region i of fig. 2) is expected to provide more exchange sites for proton transport.
Morphology of the film
The ZN, ZN-NH 2 And ZN-SO 3 H is respectively doped into SPEEK matrix to prepare proton conducting membrane, and the molecular sieve loading is controlled to be 1-5 wt%. The corresponding film is denoted S/Z-X, where S is SPEEK and Z represents ZN, ZN-NH 2 Or ZN-SO 3 H, X% is the weight ratio of nanoplatelets to SPEEK. The thickness of the different films was well controlled at 49±2 μm, and the thickness of the hybrid film increased with increasing ZN content. Due to the uniform dispersion of ZN in the polymer matrix, all hybrid films are almost identical to pure SPEEK films in apparent physical properties like color, opacity and flexibility. By scanning electron microscopy(SEM) characterization of cross-sectional morphology. SPEEK membranes and ZN-containing hybrid membranes were homogeneous, dense and defect-free, with the incorporated ZN homogeneously suspended in the polymer phase (fig. 3). Unlike the smooth cross section of a pure SPEEK membrane (region a of fig. 3), the ZN-incorporated membrane exhibits a coarser cross section with a specific corrugated network structure that becomes denser with increasing ZN loading (region b-d of fig. 3) due to the even distribution of ZN and rich interfacial interactions. Importantly, in the incorporation of ZN-NH 2 And ZN-SO 3 No significant gaps between ZN and polymer phases due to interfacial incompatibility (region b of fig. 3) were observed in the H film (regions c, d of fig. 3), indicating that by grafting-NH 2 and-SO 3 The H functional groups effectively enhance the surface affinity between ZN and the polymer.
Properties of the film
The water absorption and swelling ratio are two key parameters of proton-conducting membranes for flow batteries, the former being related to proton transport and the latter reflecting the dimensional stability of the membrane. Due to the inherent microporous structure of the molecular sieve (region a of fig. 4), the water absorption capacity of ZN-embedded membranes is higher than that of pure SPEEK membranes (region a of fig. 4), and the water absorption of hybrid membranes increases with increasing ZN loading. In addition, due to the introduction of hydrophilic-SO 3 H functional group, with ZN and ZN-NH 2 In contrast, when ZN-SO is doped 3 This enhancement in water absorption capacity is more pronounced in the H film. Meanwhile, the swelling rate of the polymer with water adsorption is well limited due to the steric confinement effect of the rigid molecular sieve framework (region a of fig. 4). As ZN loading increases, the swelling ratio of all mixed films decreases. In particular, due to-SO in the SPEEK matrix 3 H groups and ZN-NH 2 In (C) NH 2 Acid-base pairs are formed between the functional groups, thus incorporating ZN-NH 2 The dimensional stability of the membrane of (2) is further enhanced, thus the ZN-doped membrane-NH 2 Exhibit ratios ZN and ZN-SO 3 H is higher in resistance to swelling.
The stability of the membrane, including mechanical stability, chemical stability and thermal stability, is a parameter that determines the long term stability during battery assembly and operation. The addition of ZN increases the tensile strength of the film compared to a pure SPEEK filmDegree, which is due to the dispersion strengthening effect of ZN filler addition. In addition, ZN-NH is embedded under the same ZN load 2 The membrane of (C) shows advantages over ZN and ZN-SO 3 The tensile strength of the H film, because of the synergistic effect of the acid-base pair, contributes to better stress transfer from the polymer matrix to the nanofiller (region b of fig. 4). Due to VO inclusion 2+ Chemical stability is another key parameter of the VFB application film. The degradation of the membrane is usually caused by VO during charge and discharge 2+ The strong oxidation of ions causes. Absorption spectra showed that the film was immersed in the solution containing VO 2+ After 15 days in the ionic solution, there was no detectable change in the vanadium species in the soak solution, indicating that the membrane had excellent chemical stability. Furthermore, the thermal stability (region c of fig. 4) was assessed by thermogravimetric analysis (TGA). There was little apparent difference in the weight loss behavior of the membranes, indicating that the incorporation of ZN did not alter the thermodynamic properties of the membranes.
The ion selectivity and conductivity of the membrane are two of the most important parameters that directly determine the performance of the cell. The diaphragm with higher ion selectivity can effectively prevent cross contamination of active substances in the positive and negative electrolyte and slow down self discharge of the battery. First, the vanadium permeability of the membrane was studied by a vanadium ion permeation experiment. As shown in region d of fig. 4, the beneficial effect of the intercalation ZN on barrier to vanadium ion permeation is apparent. Once ZN is incorporated into the SPEEK polymer matrix, the vanadium permeation rate of all membranes decreases significantly, decreasing with increasing ZN loading. The enhancement of the vanadium ion barrier effect can be attributed to the complete barrier of the molecular sieve rigid channels to vanadium ions with diameters greater than 0.6nm and a significantly prolonged diffusion path for vanadium ions. Notably, ZN-NH incorporation was carried out at 4wt% ZN loading 2 The vanadium permeability of the membrane is slightly lower than that of the membrane doped with ZN and ZN-SO 3 H membrane, because of ZN-NH 2 The interface interaction with SPEEK further prevents the formation of large ion channels (region d of fig. 4).
Compared to pure SPEEK membranes and commercial Nafion212, ZN-NH intercalation 2 Or ZN-SO 3 All membranes of H exhibited lower sheet resistance and higher proton conductivity (region e of fig. 4). Proton conductivity presentation for membranes incorporating different species of ZNSimilar trend of change was seen, the proton conductivity increased with increasing ZNs content, reaching a maximum at 4wt% and then decreasing. The increased conductivity of the hybrid membrane is attributed to the hydrophilic ionization surface and b-axis straight channels of the incorporated ZN, which provides another internal channel for rapid capture and transport of protons. However, too much ZN can lead to severe aggregation and impede proton transport. In addition, the interfacial interaction between the polymer matrix and the surface functional groups creates a continuous long-range and low-energy barrier proton transfer channel along the interface between SPEEK and ZN (region b of fig. 1). Thus, ZN-NH was used at the same 4wt% ZN loading 2 And ZN-SO 3 H as filler causes an increase in proton conductivity above ZN, following S/ZN-SO 3 H-4% film>S/ZN-NH 2 -4% film>S/ZN-4% membrane order. S/ZN-SO 3 The proton conductivity of the H-4% membrane reaches 92.4mS cm -1 Is a pure SPEEK film (56.7 mS cm) -1 ) About 1.6 times that of the commercial Nafion212 membrane (39.3 mS cm) -1 ). Ion selectivity, defined as the ratio of proton conductivity to vanadium permeability, generally reflects the overall performance of the membrane. Due to the remarkable enhancement of vanadium ion barrier capability and proton conductivity, all hybrid membranes exhibited higher ion selectivity and corresponded well to the trend of proton conductivity (region f of FIG. 4). S/ZN-SO 3 H-4% membranes showed the highest ion selectivity among all membranes of this patent (6.0X10) 5 S min cm -3 ) Far higher than pure SPEEK film (1.6x10 5 S min cm -3 ) And commercial Nafion212 membranes (0.8x10) 5 S min cm -3 )。
Cell performance
Membranes incorporating 4wt% zn exhibit the most attractive combination of properties such as enhanced water absorption, better resistance to swelling, higher ion selectivity and conductivity, good stability in harsh environments, and hopefully excellent battery performance. To further verify the availability and superiority of the hybrid membranes, the S/ZN-4% membranes, S/ZN-NH 2 -4% membrane, S/ZN-SO 3 H-4% membrane, SPEEK membrane, were tested for VFB single cell and commercial Nafion212 membrane. At 40 to 200mA cm -2 At a current density of (3)With incorporation of ZN, ZN-NH 2 Or ZN-SO 3 The H membranes all showed better CE, VE and EE than the pure SPEEK membranes (region a of fig. 5). Notably, the CE of ZN-embedded membranes was significantly higher than that of pure SPEEK membranes and Nafion212 throughout the entire range of testing, especially at low current densities, consistent with vanadium permeation results (region d of fig. 4). Due to the high overpotential and ohmic polarization at high current density, VE of the film gradually decreases with increasing current density (region a of fig. 5). Nonetheless, VFB equipped with ZN-embedded membranes still exhibited significantly higher VE than VFB equipped with pure SPEEK membranes, because high proton conductivity effectively reduced ohmic polarization. VE for cells incorporating different types of ZN films still follows S/ZN-SO at the same current density 3 H-4% film>S/ZN-NH 2 -4% film>S/ZN-4% membrane order. This is well in agreement with the proton conductivity results (region e of fig. 4). Overall, excellent CE and VE demonstrate that the addition of ZN simultaneously improves vanadium ion barrier capability and proton conductivity and breaks the tradeoff between ion selectivity and proton conductivity. Thus, all ZN-doped membranes showed enhanced EE (region a of FIG. 5), where S/ZN-SO 3 EE is highest for H-4% membranes. S/ZN-SO 3 CE and EE of H-4% film cell at 120mAc m-2 99.0% and 85.0% in sharp contrast to 97.8% and 78.4% for pure SPEEK films, 96.3% and 80.1% for Nafion212 films, respectively.
The b region of fig. 5 summarizes the leading edge reports of SPEEK films modified by organic blending and inorganic nanofiller blending for VFB applications. It is evident that in the large current density range, the EE of cells with S/ZN-SO3H-4% membranes is superior to most reported membranes, thanks to the incorporation of functional ZNs while improving ion selectivity and conductivity.
To further confirm the stability and reliability of the mixed film, it was equipped with S/ZN-SO 3 H-4% membrane, S/ZN-NH 2 VFB cell with 4% film and SPEEK film at 120mA cm -2 Is run for long cycle testing (region c of fig. 5). S/ZN-SO 3 H-4% membrane and S/ZN-NH 2 The cell efficiency of the 4% film was relatively stable, with no visible appearance throughout the testA significant drop in SPEEK membrane efficiency after 80 cycles was drastically reduced due to membrane rupture during operation. In addition, compared to SPEEK membranes, ZN-embedded membranes, in particular ZN-NH 2 Shows significantly higher capacity retention because membranes with high ion selectivity can effectively resist cross-contamination of the electrolyte (region d of FIG. 5). The SPEEK film had a capacity retention of 74.3% after 80 cycles, a capacity fade of 0.32% per cycle and 6.36% per day. In contrast, S/ZN-SO 3 H-4% membrane and S/ZN-NH 2 The capacity retention of the 4% membrane after 250 cycles was 57.0% and 64.0%, respectively, indicating a significant reduction in capacity fade over the SPEEK membrane (0.17% and 3.35S/ZN-SO per cycle) 3 H-4% daily, 0.14% per cycle and S/ZN-NH 2 -4% 2.54% per day).

Claims (1)

1. The flow battery is characterized in that a molecular cross-linked molecular sieve nano-sheet hybrid membrane is adopted as a diaphragm, the molecular cross-linked molecular sieve nano-sheet hybrid membrane is a proton conduction membrane, the molecular cross-linked molecular sieve nano-sheet hybrid membrane comprises a polymer and a molecular sieve nano-sheet, and a silane coupling agent is grafted on the surface of the molecular sieve nano-sheet; the silane coupling agent is 3-mercaptopropyl triethoxysilane; the polymer is sulfonated polyether-ether-ketone; the molecular sieve nanosheets are selected from ZSM-5 molecular sieve nanosheets; the molecular sieve nano-sheet accounts for 1-5% of the mass of the polymer; the thickness of the hybridized film of the molecular cross-linked molecular sieve nano-sheet is 20-150 mu m; the preparation of the molecular cross-linked molecular sieve nanosheet hybrid membrane comprises the following steps:
(1) Synthesis of ZSM-5 zeolite nanosheets:
first, siO is added according to the mole ratio 2 :TPAOH:NaOH:H 2 O=10:2.4:0.87:114 configuring the first precursor sol; stirring the precursor sol at room temperature overnight, then carrying out hydrothermal reaction at 50 ℃ for 6 days under normal pressure, and then raising the temperature to 100 ℃ for 3 days; washing the obtained zeolite nano seed crystal with deionized water after the reaction is finished, and centrifugally collecting; the second step is that TEOS is used as template agent of bis-1, 5 tripropyl pentamethylene diimmonium iodide, KOH is used as H 2 O=80:3.75:20:9500Preparing a second precursor sol, hydrolyzing the second precursor sol at room temperature overnight, mixing with the zeolite nano-seed crystal synthesized in the first step, performing hydrothermal reaction at 140 ℃ for 3.5 days, and adding 1M NaAlO 2 Then the hydrothermal reaction is continued for 0.5 days; treating the reaction product with alkali salt solution to remove amorphous silica, washing with deionized water, centrifuging, collecting to obtain ZSM-5 zeolite nanosheets, calcining the synthesized ZSM-5 zeolite nanosheets in air at 500 ℃ for 6h to remove template agent and activate, and heating at a rate of 1 ℃ for min -1 ；
Wherein, the template agent of bis-1, 5-tripropyl pentamethylene ammonium diiodo is synthesized by thorough alkylation reaction of 1, 5-diaminopentane and 1-iodopropane, and then purified by ethanol, 2-butanone and ethyl acetate;
(2) Synthesis of sulfonic acid functionalized ZSM-5 zeolite nanoplatelets:
adding 0.5g of the activated ZSM-5 zeolite nano-plate and 15mL of toluene into a three-necked flask, and fully stirring; under nitrogen atmosphere, 0.25g of 3-mercaptopropyl triethoxysilane is added into the mixture, the mixture is slowly heated to 110 ℃ for reflux reaction for 48 hours, and then the reaction product is obtained by repeated washing with toluene and ethanol, centrifugation and drying at 60 ℃ for 6 hours; under nitrogen atmosphere, the product was purified under H 2 O 2 The mixture was oxidized in aqueous solution at room temperature for 24H with stirring, and then the product was oxidized in 10mL of 0.1M H 2 SO 4 Soaking for 6h to protonate the sulfonic acid group; finally, centrifuging and washing the product, and drying overnight at 80 ℃ to obtain sulfonic acid functionalized ZSM-5 zeolite nano-sheets;
(3) Preparation of molecular cross-linked molecular sieve nanosheet hybrid membrane:
dissolving sulfonic acid functionalized ZSM-5 zeolite nano sheets and SPEEK in N, N-dimethylformamide, enabling the sulfonic acid functionalized ZSM-5 zeolite nano sheets to account for 1-5% of the SPEEK in weight, enabling the concentration of the SPEEK in the N, N-dimethylformamide to be 14% by weight, uniformly mixing, then spreading the obtained mixture as casting solution on a glass plate, drying the casting solution at 60 ℃ for 6 hours to volatilize a solvent, transferring the glass plate to a vacuum drying oven for drying at 100-140 ℃ for 12 hours, and obtaining the molecular crosslinked molecular sieve nano sheet hybrid membrane; the molecular cross-linked molecular sieveProton conductivity of the nano-sheet hybrid membrane reaches 92.4 mS.cm -1 。
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