CN112928322A - Hydrotalcite in-situ growth composite membrane and preparation method and application thereof - Google Patents
Hydrotalcite in-situ growth composite membrane and preparation method and application thereof Download PDFInfo
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0239—Organic resins; Organic polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
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Abstract
The application discloses a hydrotalcite in-situ growth composite membrane and a preparation method and application thereof, belonging to the field of alkaline and neutral-based secondary batteries. The hydrotalcite in-situ growth composite membrane comprises an ion-conducting membrane substrate and a hydrotalcite layer in-situ grown on the ion-conducting membrane. By effectively controlling the hydrotalcite synthesis conditions and the interface interaction, the distribution uniformity of the synthesized hydrotalcite layer can be effectively controlled, and the accurate size screening and the high-efficiency ion conductivity of the porous ion-conducting membrane can be realized. In addition, the in-situ grown hydrotalcite film has super-strong alkali-resistant stability and mechanical property, realizes an alkaline zinc-based flow battery with high performance and long service life, and shows good application prospect.
Description
Technical Field
The application relates to the field of alkaline and neutral-based secondary batteries, in particular to a hydrotalcite in-situ growth composite membrane and a preparation method and application thereof.
Background
The increasing energy consumption, especially the impact of the massive use of fossil fuels such as coal and petroleum on the environment and global climate, make the goal of human sustainable development face a serious threat. Therefore, the search for advanced methods for improving the energy utilization rate for the research and development of new energy and renewable energy has become a primary problem of global common attention. Energy storage technology is a key supporting technology of the energy revolution. The flow battery is a battery technology with great prospect in the field of large-scale energy storage, and has the advantages of high safety, independent design of output power and energy storage capacity, environmental friendliness and the like. The alkaline zinc-iron flow battery generally has the advantage of low cost of electrolyte, has better application prospect in large-scale flow batteries, and generates Zn (OH) after the zinc salt or/and the zinc oxide on the negative electrode side are dissolved in strong alkali 4 2- Then the electrochemical reaction of deposition and dissolution occurs on the electrode, and Fe (CN) occurs on the positive electrode 6 3- /Fe(CN) 6 4- The open-circuit voltage of the battery can reach 1.77V by the redox reaction, and the battery can run at normal temperature and normal pressure, has good safety and has no pollution to the environment.
As a core component of the cell structure, the separator, which acts to balance ions to complete the cell internal pathway and to block active material shuttling (positive and negative electrolytes), the proton conductivity, ion selectivity, and chemical stability of the membrane will directly affect the electrochemical performance and lifetime of the cell, and therefore the membrane is required to have a lower active material permeability (i.e., high ion selectivity) and a lower sheet resistance (higher ion conductivity). However, the current commercial separator still has a great bottleneck, and the development of a novel porous ion-conducting membrane is urgently needed.
In recent years, a porous ion exchange membrane is applied to a flow battery due to the advantages of adjustable pore size and low cost, but compared with a compact membrane, the porous membrane has the problem that the mutual connection problem of electrolytes is serious due to poor selectivity so that the performance of the battery is obviously reduced in the application of an alkaline zinc-iron flow battery system. For the porous ion-conducting membrane, the smaller the pore size is, the better the ion selectivity is, but the proton conductivity is reduced, and how to solve the balance between the selectivity and the conductivity of the porous ion-conducting membrane becomes a key bottleneck technology. Considering that the hydrotalcite nano material can be further stripped into single-layer nano sheets or chemically modified to improve the affinity and interaction with a polymer film, a new approach is provided for designing a next-generation high-performance diaphragm.
Disclosure of Invention
According to a first aspect of the present application, there is provided a hydrotalcite in-situ growth composite membrane comprising an ion-conducting membrane substrate and a hydrotalcite layer grown in-situ on the ion-conducting membrane. The appearance of the hydrotalcite in the pores of the base film and the in-situ growth on the surface of the base film can be seen through a scanning electron microscope, and the appropriate interlayer spacing in the hydrotalcite can effectively prevent the active substances from being connected with each other, so that the selectivity of the diaphragm is favorably improved, the good ion conductivity is kept, and the hydrotalcite shows good application prospects in alkaline and neutral-based battery systems.
Optionally, the thickness of the hydrotalcite layer is 1-2 μm, the interlayer distance is 0.6-0.8 nm, and the total thickness of the composite film is 110-120 μm.
Optionally, the ion-conducting membrane is selected from sulfonic acid group-containing polymer membranes.
Optionally, the ion conducting membrane is a blend membrane of sulfonated polyetheretherketone with at least one of the following polymers:
polyethersulfone, polysulfone or polyethylene.
Optionally, the ion conducting membrane is a blended membrane of polyethersulfone and sulfonated polyetheretherketone; wherein the mass ratio of the polyether sulfone to the sulfonated polyether ether ketone is 1-4: 1.
optionally, the ion-conducting membrane is a porous membrane; the pore diameter of the ion-conducting membrane is 0.3-70 nm, and the porosity is 30-60%.
Optionally, the divalent metal cation in the hydrotalcite layer is Mg 2+ 、Ni 2+ 、Co 2+ 、Zn 2+ Or Cu 2+ At least one of the trivalent metal cations is Al 3+ 、Cr 3+ 、Fe 3+ Or Sc 3+ At least one of, the anion being CO 3 2- 、NO 3 - 、Cl - 、OH - 、SO 4 2- Or PO 4 3- At least one of (1).
Optionally, the divalent metal cation in the hydrotalcite layer is Mg 2+ The trivalent metal cation is Al 3+ The anion is Cl - ；Mg 2+ With Al 3+ The molar ratio of (A) to (B) is 2 to 3.
According to a second aspect of the present application, there is provided a method for preparing a hydrotalcite in-situ growth composite membrane, comprising:
and (3) vertically growing a hydrotalcite layer on the surface of the ion-conducting membrane by a hydrothermal method to obtain the hydrotalcite in-situ growth composite membrane.
Optionally, the method comprises:
soaking the ion conduction membrane in a mixed solution of divalent metal salt and trivalent metal salt for a certain time;
adding a weak base solution into the mixed solution under the stirring condition to obtain a hydrotalcite precursor solution;
and vertically growing a hydrotalcite layer on the surface of the ion-conducting membrane by a hydrothermal method to obtain the hydrotalcite in-situ growth composite membrane.
Optionally, the ion-conducting membrane is soaked in the mixed solution of the divalent metal salt and the trivalent metal salt for at least 10 hours, preferably 10 to 12 hours.
Optionally, the cation in the divalent metal salt is Mg 2+ 、Ni 2+ 、Co 2+ 、Zn 2+ Or Cu 2+ At least one of (A) and (B), the anion being CO 3 2- 、NO 3 - 、Cl - 、OH - 、SO 4 2- Or PO 4 3- At least one of; the cation in the trivalent metal salt is Al 3+ 、Cr 3 + 、Fe 3+ Or Sc 3+ At least one of, the anion being CO 3 2- 、NO 3 - 、Cl - 、OH - 、SO 4 2- Or PO 4 3- At least one of (1).
Optionally, the divalent metal salt is MgCl 2 The trivalent metal salt is AlCl 3 (ii) a Wherein, mg 2+ With Al 3+ The molar ratio of (A) to (B) is 2 to 3.
Optionally, the preparation method further comprises:
dissolving an ion-conducting membrane raw material in an organic solvent to obtain a mixed solution;
and preparing the mixed solution into an ion conduction membrane by a phase inversion method.
The method can obtain the porous ion-conducting membrane with the aperture of 0.3-70 nm and the porosity of 30-60%.
Alternatively, the organic solvent may be selected from dimethylformamide, dimethylacetamide or N-methylpyrrolidinone.
Optionally, the ion-conducting membrane feedstock comprises a polymer containing sulfonic acid groups.
Optionally, the ion-conducting membrane feedstock is comprised of sulfonated polyetheretherketone with at least one polymer of:
polyethersulfone, polysulfone or polyethylene.
Optionally, the sulfonation degree of the sulfonated polyether ether ketone is 40-70%; the molecular weight of the sulfonated polyether ether ketone, the polyether sulfone, the polysulfone or the polyethylene is 3000-30000.
Optionally, the ion-conducting membrane feedstock consists of polyethersulfone and sulfonated polyetheretherketone; wherein the mass ratio of the polyether sulfone to the sulfonated polyether ether ketone is (1-4): 1
Optionally, the solid content in the mixed solution is 30wt% to 50wt%.
Optionally, the ion-conducting membrane is a porous membrane; the ion-conducting membrane has a pore diameter of 0.3-70 nm, a porosity of 30-60%, a lower limit of the pore diameter selected from 0.4nm, 0.5nm, 1nm, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm or 65nm, and an upper limit selected from 0.5nm, 1nm, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm or 70nm.
Optionally, the adding the weak base solution to the mixed solution under stirring includes:
and adding the weak base solution with the pH value of 7.1-8 into the mixed solution, and stirring for 8-15 min.
Optionally, the step of growing a hydrotalcite layer on the surface of the ion-conducting membrane by a hydrothermal method comprises:
carrying out hydrothermal reaction for 48-96 h at 70-100 ℃, and vertically growing a hydrotalcite layer on the surface of the ion-conducting membrane.
Optionally, the thickness of the hydrotalcite layer is 1-2 μm, and the total thickness of the composite film is 110-120 μm.
According to a third aspect of the present application, there is provided a use of the hydrotalcite in-situ growth composite membrane described in any one of the above, or the hydrotalcite in-situ growth composite membrane prepared by any one of the above methods, in an alkaline and neutral-based flow battery, wherein the alkaline-based flow battery comprises an alkaline-based zinc-iron flow battery, a zinc-nickel flow battery, a zinc-manganese flow battery, a zinc-silver flow battery; neutral-based flow batteries include neutral-based zinc-iron flow batteries or neutral-based zinc-iodine flow batteries.
In a specific embodiment, the present application discloses a novel hydrotalcite porous ion composite membrane, the preparation method of which comprises:
(1) Preparing porous base membranes with different PES/SPEEK ratios by using polyether sulfone PES/SPEEK (sulfonated polyether ether ketone) resin as a base material through an immersion phase conversion method;
(2) To prepare a hydrotalcite (LDH) membrane, the PES/SPEEK porous membrane obtained above is first soaked in MgCl 2 ：AlCl 3 Standing for 12h in a mixed salt solution of =2 (molar ratio) 1 for standby, preparing a weak base solution containing 0.5mol/L NaOH, adding the weak base solution into the salt solution containing the porous base membrane under the stirring action, and stirring for 10 minutes to obtain a hydrotalcite precursor solution; then transferring the base membrane and the hydrotalcite precursor solution into a stainless steel reaction kettle with a Teflon lining, carrying out hydrothermal reaction for 72 hours at 70 ℃, taking out the membrane, and washing the surface with ultrapure water to obtain a porous ion conduction membrane with hydrotalcite in-situ growth;
the PES/SPEEK base material of the polyether sulfone contains a certain amount of SO 3 - The functional group has the main function of being linked with metal cations (Mg) in a hydrotalcite structure 2+ ,Al 3+ ) Interaction to form a stable hydrotalcite film interface;
different PES/SPEEK ratios mainly include mass ratio PES: SPEEK =1, 2 3 - The functional groups interact with hydrotalcite metal ions to form a uniform and compact hydrotalcite layer, and PES is selected from SPEEK = 2;
al =1, determining that a synthesized hydrotalcite laminate is an Mg-Al laminate, and combining metal cations on the laminate by strong interaction of covalent bonds to regularly arrange the metal cations into a two-dimensional layered nano material; the anion selected is Cl - Used for compensating positive charges on hydrotalcite laminate to make hydrotalcite be neutral, and the anion Cl inserted between the layers acts on the layers with weak interaction force (electrostatic interaction, van der Waals interaction and hydrogen bond interaction) - The interlayer spacing for the expanded plywood increasing material is caused by the difference of the interlayer spacing caused by the difference of the sizes, the arrangement and the positioning directions of the anions among the layers, wherein the anions Cl - Determining the interval between the synthetic hydrotalcite material layers to be 0.76nm;
standing the mixed salt solution for 12 hours is the preferable time, too short standing time is not beneficial to promoting the interaction of the base membrane and the hydrotalcite membrane, so that the formed membrane has poor stability, and too long standing time is not beneficial to forming an upright hydrotalcite membrane structure;
the reaction temperature (70 ℃) and the reaction time (72 hours) are the preferable experimental conditions, and different reaction temperatures and reaction times can obtain grains with different grain sizes, different grain size distributions and different length-diameter ratios, and secondly, the structure and the performance of the hydrotalcite film can be influenced. Regulating and controlling the in-situ growth of the prepared and synthesized hydrotalcite in the interior of the finger-shaped macropores of the basal membrane and on the surface of the basal membrane by optimizing reaction conditions (as shown in figure 1);
finally preparing the vertical hydrotalcite porous ion-conducting membrane growing in situ.
Compared with the alkaline zinc-iron flow battery assembled by the traditional porous ion conducting membrane, the alkaline zinc-iron flow battery assembled by the in-situ grown hydrotalcite porous ion conducting membrane has better selectivity, corresponds to higher Coulombic Efficiency (CE), and simultaneously keeps excellent Voltage Efficiency (VE). The appearance of the hydrotalcite in the pores of the base film and the in-situ growth on the surface of the base film can be seen through a scanning electron microscope, and the appropriate interlayer spacing in the hydrotalcite can effectively prevent the active substances from being connected with each other, so that the selectivity of the diaphragm is improved, the good ionic conductivity is kept, and the hydrotalcite has a good application prospect in alkaline and neutral-based battery systems.
The beneficial effects that this application can produce include:
1. the two-dimensional material is introduced into the interior and the surface of the base membrane by using an in-situ growth method, so that the ion conductivity of the ion-conducting membrane is ensured while the selectivity of the ion-conducting membrane is effectively improved; the modified ion conduction composite membrane has low cost;
2. the application firstly provides that the hydrotalcite in-situ growth composite membrane is used in the alkaline zinc-iron flow battery, and the hydrotalcite in-situ growth composite membrane shows excellent performance in the alkaline zinc-iron flow battery, meets the requirement of large-scale application and shows good application prospect; compared with the traditional polyether sulfone porous membrane, the hydrotalcite-modified composite membrane shows higher ion selectivity in an alkaline electrolyte system, and simultaneously, OH is ensured due to the replaceability of anions in hydrotalcite - Thereby imparting high ionic conductivity to the composite membrane; similar effects are achieved in other alkaline-based batteries such as alkaline-based zinc-nickel batteries, zinc-manganese batteries, zinc-silver batteries, and in neutral-based zinc-iron batteries or neutral-based zinc-iodine batteries;
3. the method for introducing the layered hydrotalcite particles to the diaphragm and the inside of the diaphragm in an in-situ growth mode opens up a new strategy for introducing inorganic materials to the polymer diaphragm to improve the performance of the battery, the inorganic hydrotalcite materials are tightly combined to an organic polymer matrix in situ by utilizing the strong interaction of internal ions, and compared with physical action and other weak interactions, the composite membrane prepared by the method has more excellent mechanical properties and chemical stability.
4. The hydrotalcite particles grow on the surface of the porous base membrane in an upright mode, so that the ion selectivity and conductivity of the composite membrane are effectively guaranteed, the upright structure is more favorable for ion transmission, and the appropriate interlayer spacing guarantees high-efficiency ion selectivity. More importantly, when the base membrane is a porous membrane, the structure of the composite membrane is characterized in that hydrotalcite particles grow in the inner parts of the fingerlike macropores of the base membrane at the same time, and the mechanical stability and the non-collapse of the pore structure of the membrane are effectively guaranteed by the strong supporting effect. The porous ion conduction membrane with the special structure based on in-situ regulation has the characteristics of low cost, good stability and excellent performance.
Drawings
FIG. 1: a first morphology representation diagram of the hydrotalcite in-situ growth composite membrane provided in example 1, wherein a is a surface morphology SEM diagram of the hydrotalcite in-situ growth composite membrane, and b and c are both enlarged diagrams of a;
FIG. 2: a second appearance representation diagram of the hydrotalcite in-situ growth composite membrane in the embodiment 1 is shown, wherein a is a cross-sectional appearance SEM diagram of the hydrotalcite in-situ growth composite membrane, and b and c are both enlarged diagrams of a;
FIG. 3: a third appearance characterization diagram of the hydrotalcite in-situ growth composite membrane in the embodiment 1 is shown, wherein a is a cross-sectional pore appearance characterization SEM diagram of the hydrotalcite in-situ growth composite membrane, and b is an enlarged diagram of a;
FIG. 4 is a schematic view of: a is an alkaline zinc-iron flow battery assembled with LDHM-1 provided in example 1 at 80mA cm -2 A battery performance map of (a); b is the alkaline zinc-iron flow battery assembled with M-1 provided in comparative example 1 at 80mA cm -2 The battery performance of (a); c is a capacity fade curve of the batteries provided in example 1 and comparative example 1;
FIG. 5 is a schematic view of: a is an alkaline zinc-iron flow battery assembled with LDHM-2 provided in example 2 at 80mA cm -2 A battery performance map of (a); b is the M-2 assembled alkaline zinc-iron flow battery provided in comparative example 2 at 80mA cm -2 A battery performance map of (a);
FIG. 6: a is an alkaline zinc-iron flow battery assembled with LDHM-3 provided in example 3 at 80mA cm -2 A battery performance map of (a); b is the alkaline zinc-iron flow battery assembled by using the M-3 provided by the comparative example 3 at 80mA cm -2 The battery performance map of (a).
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The polyether sulfone, the sulfonated polyether ether ketone and the polyethylene high molecular polymer are all purchased from Beijing Wallich technology Limited.
The analytical methods in the examples of the present application are as follows:
and (4) testing the battery performance by using an Arbin charge-discharge tester.
Example 1
Taking polyether sulfone (PES)/SPEEK resin as a base material, dissolving PES/SPEEK in a DMAC (dimethylacetamide) solvent according to a mass ratio of 4.
The PES/SPEEK porous base membrane obtained above was immersed in 50mL of 0.6mol/L MgCl 2 And 0.3mol/L AlCl 3 The mixed salt solution is added for 12 hours to ensure SO in the diaphragm 3- Fully interacting with metal ions in a salt solution, preparing 40mL of alkali solution containing 0.45mol/L NaOH, adding the alkali solution into the salt solution containing the base film under the stirring action, stirring for 10 minutes, transferring the solution into a stainless steel reaction kettle with a Teflon lining, carrying out hydrothermal reaction at 70 ℃ for 72 hours, taking out a diaphragm, and washing the surface with ultrapure water to obtain a hydrotalcite in-situ growth composite membrane (recorded as LDHM-1) with the interlayer spacing of 0.76nm and the porosity of 40%. The layer thickness of hydrotalcite is 1.56 μm, saidThe total thickness of the composite membrane is 116 mu m, the aperture of the ion-conducting membrane is 0.5-50nm, and the porosity is 50%.
In order to verify the structural superiority of LDHM-1, the hydrotalcite in-situ growth composite membrane is dried for 30min at room temperature and then soaked in water for standby. As can be seen from the cross-sectional morphology (FIGS. 2 and 3) of the hydrotalcite in-situ growth composite membrane, the hydrotalcite nano-material not only grows in situ on the surface of the base membrane, but also grows in situ in the finger-shaped macropores inside the membrane. After drying for a certain time, the pores of the hydrotalcite in-situ growth composite membrane cannot be reduced in the drying process due to the supporting effect of the hydrotalcite in the pores, so that the high-efficiency ion transmission of the hydrotalcite membrane is ensured.
LDHM-1 is applied to an alkaline zinc-iron flow battery, the LDHM-1 is used as a diaphragm, positive and negative electrodes are carbon felts, and the positive electrolyte is 0.8mol/L Fe (CN) 6 4- +3mol/L OH - A solution; the negative electrode electrolyte is 0.4mol/L Zn (OH) 4 2- +3.8mol/L OH - A solution; the volumes of the positive electrolyte and the negative electrolyte are respectively 40mL; the battery adopts a constant current charge-discharge mode and is at 80mA cm -2 Under the condition of current density of (1), charging for 50min, and then cutting off the voltage to 80mA cm -2 Is discharged to 0.1V under the current density condition of (1). From the performance of the cell (FIG. 4 a) it can be seen that at 80mA cm -2 Under the current density, the initial Coulombic Efficiency (CE) of the battery assembled by the LDHM-1 is 96%, the Voltage Efficiency (VE) is 92%, and the Energy Efficiency (EE) can reach 88%. The analysis reason for the high coulombic efficiency of the battery is that due to the introduction of the high-selectivity layered hydrotalcite material on the surface, the mutual connection of the positive active substances is effectively blocked, so that the selectivity of the composite membrane is improved. Meanwhile, as the hydrotalcite is inserted into the finger-shaped holes of the porous membrane, the appearance of the holes is effectively ensured in the drying process, thereby ensuring the high voltage efficiency of the diaphragm. LDHM-1 assembled alkaline zinc-iron flow battery at 80mA cm -2 The high-performance lithium ion battery can still show high cycle stability under current density, and can complete 100 charge and discharge cycles without obvious performance attenuation.
The LDHM-1 is applied to a neutral zinc-iodine battery, the LDHM-1 is used as a diaphragm, positive and negative electrodes are carbon felts, and a positive electrolyte is a 2.5M KI solution; the electrolyte of the negative electrode is 4M ZnBr 2 A solution; the volumes of the positive electrolyte and the negative electrolyte are respectively 40mL; the battery adopts a constant current charge-discharge mode at 80mA cm -2 Is charged for 20min under the current density condition of (1). At 80mA cm -2 At current density, the initial Coulombic Efficiency (CE) of the cell assembled by the LDHM-1 is 97%, the Voltage Efficiency (VE) is 86%, and the Energy Efficiency (EE) can reach 83%.
Comparative example 1
The preparation method comprises the steps of taking polyether sulfone (PES)/SPEEK resin as a base material, dissolving PES/SPEEK in DMAC (dimethylacetamide) solvent according to the mass ratio of 4. Directly drying at room temperature for 10min to obtain the polyethersulfone porous ion-conducting membrane without hydrotalcite, wherein the aperture is 0.5-50nm, and the porosity is 50%. (denoted as M-1).
The electrolyte is applied to an alkaline zinc-iron flow battery, M-1 is taken as a diaphragm, positive and negative electrodes are carbon felts, and the positive electrolyte is 0.8mol/L Fe (CN) 6 4- +3mol/L OH - A solution; the negative electrode electrolyte is 0.4mol/L Zn (OH) 4 2- +3.8mol/L OH - A solution; the volumes of the positive electrolyte and the negative electrolyte are respectively 40mL; the battery adopts a constant current charge-discharge mode and is at 80mA cm -2 Under the condition of current density of (1), charging for 50min, and then cutting off the voltage to 80mA cm -2 Is discharged to 0.1V under the current density condition of (1). As can be seen from the performance of the cell (FIG. 4 b), the M-1 assembled cell was at 80mA cm -2 At the current density of (a), CE was only 93.5%, and VE was only 88% after drying for 10min, and a significant capacity fade occurred (fig. 4 c), because during the drying process, pores of the base film collapsed, resulting in a decrease in the ionic conductivity of the separator, and VE decreased, which is relatively low in the cell performance compared to LDHM-1, m-1 assembly, demonstrating the mechanism and performance advantages of hydrotalcite in-situ growth of porous ion-conducting membranes.
Applying M-1 to a neutral zinc-iodine battery, wherein M-1 is taken as a diaphragm, positive and negative electrodes are carbon felts, and a positive electrode electrolyte is a 2.5M KI solution; the electrolyte of the negative electrode is 4M ZnBr 2 A solution; the volumes of the positive electrolyte and the negative electrolyte are respectively 40mL; the battery adopts a constant current charge-discharge mode at 80mA cm -2 Is charged for 20min under the current density condition of (1). At 80mA cm -2 At current density, the initial Coulombic Efficiency (CE) of the LDHM-1 assembled cell was 92%, the Voltage Efficiency (VE) was 85%, and the Energy Efficiency (EE) was 80%.
Example 2
The preparation method comprises the steps of taking polyether sulfone (PES)/SPEEK resin as a base material, dissolving PES/SPEEK in a DMAC (dimethylacetamide) solvent according to a mass ratio of 2. The growth conditions and subsequent drying processes of the hydrotalcite film are the same as those in example 1, and finally the hydrotalcite in-situ growth composite film (marked as LDHM-2) with the interlayer spacing of 0.76nm and the porosity of 35% is obtained. The thickness of the hydrotalcite layer is 1.54 μm, the total thickness of the composite membrane is 114 μm, the aperture of the polyether sulfone porous ion conduction membrane is 0.5-50nm, and the porosity is 50%.
LDHM-2 was applied to the alkaline zinc-iron flow battery in the same manner as in example 1, except that LDHM-2 was used as the separator instead of LDHM-1.
The performance of the obtained composite membrane is tested by an alkaline zinc-iron flow battery, the test condition of the battery is the same as that of the battery in the embodiment 1, the performance of the obtained battery is shown in figure 5a, the coulombic efficiency of the LDHM-2 assembled battery can reach 97 percent compared with the CE of the battery with the LDHM-1 as a diaphragm, the voltage efficiency is basically unchanged, but the corresponding battery is 80mA cm -2 The cycle performance is greatly reduced under the current density, and only about 50 charge-discharge cycles can be realized. This is mainly due to the fact that an increase in the proportion of SPEEK in the base film substrate increases SO 3- Interaction with hydrotalcite induces the formation of a denser hydrotalcite layer, so that the CE of the cell is slightly improved, but the instability of the membrane in a strong alkaline solution is increased due to the increase of the SPEEK content of the base membrane, so that the cycle performance of the performance is reduced compared with that of example 1.
Comparative example 2.
Taking polyether sulfone PES/SPEEK resin as a base material, dissolving PES/SPEEK in a DMAC (dimethylacetamide) solvent according to a mass ratio of 2.
It was applied to an alkaline zinc-iron flow battery in the same manner as in comparative example 1, except that M2 was used as the separator instead of M1. And (3) carrying out performance test on the assembled alkaline zinc-iron flow battery, wherein the test method is the same as that of the comparative example 1. The cell performance is shown in fig. 5b, with an initial CE of only 88% and a voltage efficiency of only 85%. And along with the progress of charging and discharging, the efficiency of the battery is attenuated at a very fast speed, and after 40 cycles of charging and discharging, the performance of the battery is obviously attenuated. The analysis reason is that the membrane is not stably increased under the strong alkali condition along with the increase of the SPEEK proportion of the base membrane, so that the membrane is degraded, and meanwhile, under the supporting action of the anhydrous talc nano material, the internal pore structure of the membrane collapses in the drying process, so that the performance attenuation of the battery is obvious.
Example 3
Taking polyether sulfone PES/SPEEK resin as a base material, dissolving PES/SPEEK in a DMAC (dimethylacetamide) solvent according to a mass ratio of 1. The growth conditions and subsequent drying process of the hydrotalcite film are the same as those in example 1, and finally the hydrotalcite in-situ growth composite film (marked as LDHM-3) with the interlayer spacing of 0.76nm and the porosity of 30% is obtained. The thickness of the hydrotalcite layer is 1.56 μm, the total thickness of the composite membrane is 116 μm, the aperture of the polyether sulfone porous ion-conducting membrane is 0.5-50nm, and the porosity is 50%.
LDHM-3 was applied to the alkaline zinc-iron flow battery in the same manner as in example 1, except that LDHM-3 was used as the separator instead of LDHM-1.
The performance of the obtained alkaline zinc-iron flow battery is tested, the test conditions of the battery are the same as those of the battery in the example 1, the performance of the obtained battery is shown in figure 4, the coulombic efficiency of the LDHM-3 assembled battery is improved to 98 percent and the voltage efficiency is 91 percent compared with the CE of the battery with the LDHM-1 as a diaphragm, but the coulombic efficiency of the corresponding battery is 80mA cm -2 The current density of (a) is not good in cycle performance, and only about 10 charge-discharge cycles can be realized. This is because an increase in the proportion of SPEEK in the base film substrate increases SO 3 - Interaction with hydrotalcite induces a more compact hydrotalcite layer to slightly improve CE of the battery, but due to the fact that the SPEEK content of the base film is increased, instability of the base film is increased, and therefore cycle performance of the performance is reduced.
Comparative example 3
The preparation method comprises the steps of taking polyether sulfone (PES)/SPEEK resin as a base material, dissolving PES/SPEEK in a DMAC (dimethylacetamide) solvent according to a mass ratio of 1.
It was applied to an alkaline zinc-iron flow battery in the same manner as in comparative example 1, except that M3 was used as the separator instead of M1. And (3) carrying out performance test on the assembled alkaline zinc-iron flow battery, wherein the test method is the same as that of the comparative example 1. The cell performance is shown in fig. 4a, the initial CE is only 75%, and the voltage efficiency is only 80%. And along with the progress of charging and discharging, the efficiency of the battery is attenuated at the highest speed, and after 10 cycles of charging and discharging, the performance of the battery is obviously attenuated. The analysis reason is that the membrane is not stably increased under the strong alkali condition along with the increase of the SPEEK proportion of the base membrane, so that the membrane is degraded, and meanwhile, under the supporting action of the anhydrous talc nano material, the internal pore structure of the membrane collapses in the drying process, so that the performance attenuation of the battery is obvious.
Example 4
The composite membrane is basically the same as that in example 1, except that SPEEK resin is used as a base material, and is dissolved in a DMAC solvent to obtain a solution with the solid content of 35%, and the obtained composite membrane is recorded as LDHM-4. The thickness of the hydrotalcite layer is 1.55 mu m, the total thickness of the composite membrane is 115 mu m, the aperture of the ion-conducting membrane is 0.5-50nm, and the porosity is 50%. The composite membrane structure was similar to example 1, but the hydrotalcite layer was denser.
LDHM-4 was applied to the alkaline zinc-iron flow battery in the same manner as in example 1, except that LDHM-4 was used as the separator instead of LDHM-1.
The performance of the obtained alkaline zinc-iron flow battery is tested, the test conditions of the battery are the same as those of the example 1, the coulombic efficiency CE of the LDHM-4 assembled battery is 96%, the voltage efficiency is 80%, and the coulombic efficiency CE of the corresponding battery is 80mA cm -2 The cycle performance is greatly reduced under the current density, and only nearly 20 charge-discharge cycles can be realized.
Example 5
Basically the same as example 1, except that PES was replaced by polyethylene, the resulting composite film was designated as LDHM-5. The structure of the composite membrane is similar to that of the composite membrane in example 1, the interlayer spacing of the hydrotalcite is 0.76nm, the pore diameter of the ion-conducting membrane is 0.5-50nm, and the porosity is 50%.
LDHM-5 was applied to the alkaline zinc-iron flow battery in the same manner as in example 1, except that LDHM-5 was used as the separator instead of LDHM-1.
The performance of the obtained alkaline zinc-iron flow battery is tested, the test conditions of the battery are the same as those of the example 1, the coulombic efficiency CE of the LDHM-4 assembled battery is 95%, the voltage efficiency is 89%, and the coulombic efficiency at 80mA cm is higher than that of the LDHM-4 assembled battery -2 Can realize 80 charge and discharge cycles under the current density of (2).
Comparative example 4 is essentially the same as example 1, except that PES resin was used as the base material and dissolved in DMAC solvent to give a solution having a solids content of 35%, and the resulting film was designated M-4. The membrane structure is similar to example 1, but the PES-based membrane surface can not successfully grow the hydrotalcite layer in situ, the pore diameter of the ion-conducting membrane is 0.5-50nm, and the porosity is 50%.
M-4 was applied to an alkaline zinc-iron flow battery in the same manner as in example 1, except that M-4 was used as the separator instead of LDHM-1.
The performance of the obtained alkaline zinc-iron flow battery is tested, the test conditions of the battery are the same as those of the embodiment 1, the coulombic efficiency CE of the D-4 assembled battery is 80%, the voltage efficiency is 80%, and the coulombic efficiency is 80% at 80mA cm -2 Can realize 15 charge-discharge cycles under the current density of (2).
Comparative example 5
First, the conditions for preparing hydrotalcite particles were the same as in the examples. The preparation method comprises the steps of taking polyether sulfone (PES)/SPEEK resin as a base material, dissolving PES/SPEEK in DMAC (dimethylacetamide) solvent according to the mass ratio of 4. The pore diameter is 1nm, and the porosity is 40%. The hydrotalcite-polyether sulfone blend membrane obtained by the method (organic-inorganic blending) is assembled into the alkaline zinc-iron flow battery, the battery test condition is consistent with that of example 1, the membrane shows undesirable battery performance in the alkaline zinc-iron flow battery, and the battery performance is 80mA cm -2 The CE of the battery is only 92 percent, VE is only 65 percent, and the attenuation is rapid, the reason may be that the blended membrane obtained by the method is poor in ion conduction capability and low in voltage efficiency due to the fact that inorganic nanoparticles tightly block the pore channels of the porous membrane, the pore blocking effect can bring weak improvement of coulomb efficiency, and the overall performance of the battery is poor.
The hydrotalcite in-situ growth composite membrane provided by the application is used in the alkaline zinc-iron flow battery, compared with the traditional polyether sulfone porous membrane, the hydrotalcite-modified composite membrane shows higher ion selectivity in an alkaline electrolyte system, and meanwhile, due to the replaceability of anions in hydrotalcite, OH is guaranteed - Thereby endowing the composite membrane with high ion conductivity; similar effects are seen in other alkaline-based flow batteries, such as alkaline-based zinc-nickel flow batteries, zinc-manganese flow batteries, zinc-silver flow batteries, in neutral-based zinc-iron flow batteries or neutral-based zinc-iron flow batteriesSimilar effects are also observed in zinc-iodine based flow batteries.
Although the present invention has been described with reference to a few preferred embodiments, it should be understood that various changes and modifications can be made without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The hydrotalcite in-situ growth composite membrane is characterized by comprising an ion-conducting membrane substrate and a hydrotalcite layer in-situ grown on the ion-conducting membrane.
2. The hydrotalcite in-situ growth composite membrane according to claim 1, wherein the thickness of the hydrotalcite layer is 1-2 μm, the interlayer spacing is 0.6-0.8 nm, and the total thickness of the composite membrane is 110-120 μm.
3. The hydrotalcite in-situ growth composite membrane according to claim 1, wherein the ion-conducting membrane is selected from sulfonic acid group-containing polymer membranes;
preferably, the ion conducting membrane is a blend membrane of sulfonated polyetheretherketone with at least one of the following polymers: polyether sulfone, polysulfone or polyethylene;
preferably, the ion-conducting membrane is a blend membrane of polyethersulfone and sulfonated polyetheretherketone; wherein the mass ratio of the polyether sulfone to the sulfonated polyether ether ketone is (1-4): 1;
preferably, the ion-conducting membrane is a porous membrane; the ion-conducting membrane has a pore diameter of 0.3-70 nm and a porosity of 30-60%.
4. The hydrotalcite in-situ growth composite membrane according to claim 1, wherein the divalent metal cation in the hydrotalcite layer is Mg 2+ 、Ni 2+ 、Co 2+ 、Zn 2+ Or Cu 2+ In (1)At least one, trivalent metal cation is Al 3+ 、Cr 3+ 、Fe 3+ Or Sc 3 + At least one of, the anion being CO 3 2- 、NO 3 - 、Cl - 、OH - 、SO 4 2- Or PO 4 3- At least one of;
preferably, the divalent metal cation in the hydrotalcite layer is Mg 2+ The trivalent metal cation is Al 3+ The anion is Cl - ；Mg 2+ With Al 3+ The molar ratio of (A) to (B) is 2 to 3.
5. The method for preparing the hydrotalcite in-situ growth composite membrane according to any one of claims 1 to 4, comprising:
and (3) vertically growing a hydrotalcite layer on the surface of the ion-conducting membrane by a hydrothermal method to obtain the hydrotalcite in-situ growth composite membrane.
6. The method of manufacturing according to claim 5, comprising:
soaking the ion conduction membrane in a mixed solution of divalent metal salt and trivalent metal salt for a certain time;
adding a weak base solution into the mixed solution under the condition of stirring to obtain a hydrotalcite precursor solution;
vertically growing a hydrotalcite layer on the surface of the ion-conducting membrane by a hydrothermal method to obtain a hydrotalcite in-situ growth composite membrane;
preferably, the ion-conducting membrane is soaked in a mixed solution of a divalent metal salt and a trivalent metal salt for at least 10 hours;
preferably, the cation in the divalent metal salt is Mg 2+ 、Ni 2+ 、Co 2+ 、Zn 2+ Or Cu 2+ At least one of, the anion being CO 3 2- 、NO 3 - 、Cl - 、OH - 、SO 4 2- Or PO 4 3- At least one of (a); the cation in the trivalent metal salt is Al 3+ 、Cr 3+ 、Fe 3+ Or Sc 3+ At least one of, the anion being CO 3 2- 、NO 3 - 、Cl - 、OH - 、SO 4 2- Or PO 4 3- At least one of;
preferably, the divalent metal salt is MgCl 2 The trivalent metal salt is AlCl 3 (ii) a Wherein, mg 2+ With Al 3+ The molar ratio of (A) to (B) is 2 to 3.
7. The method of manufacturing according to claim 5, further comprising:
dissolving an ion-conducting membrane raw material in an organic solvent to obtain a mixed solution;
preparing the mixed solution into an ion conducting membrane by a phase inversion method;
preferably, the ion-conducting membrane feedstock comprises a polymer containing sulfonic acid groups;
preferably, the ion-conducting membrane raw material consists of sulfonated polyetheretherketone and at least one of the following polymers:
polyether sulfone, polysulfone or polyethylene;
preferably, the ion-conducting membrane raw material consists of polyethersulfone and sulfonated polyetheretherketone; wherein the mass ratio of the polyether sulfone to the sulfonated polyether ether ketone is 1-4: 1;
preferably, the solid content in the mixed solution is 30-50 wt%;
preferably, the ion-conducting membrane is a porous membrane; the ion-conducting membrane has a pore diameter of 0.3-70 nm and a porosity of 30-60%.
8. The method according to claim 6, wherein the adding the weak base solution to the mixed solution under stirring comprises:
and adding the weak base solution with the pH value of 7.1-8 into the mixed solution, and stirring for 8-15 min.
9. The method according to claim 5, wherein the step of growing the hydrotalcite layer on the surface of the ion-conducting membrane vertically by a hydrothermal method comprises:
carrying out hydrothermal reaction for 48-96 h at 70-100 ℃, and vertically growing a hydrotalcite layer on the surface of the ion-conducting membrane;
preferably, the thickness of the hydrotalcite layer is 1-2 μm, and the total thickness of the composite membrane is 110-120 μm.
10. Use of the hydrotalcite in-situ growth composite membrane according to any one of claims 1 to 4 or the hydrotalcite in-situ growth composite membrane prepared by the method according to any one of claims 5 to 9 in alkaline and neutral-based flow batteries.
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