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WO2025108190A1 - Membrane composite poreuse repoussant le zinc pour la mise en œuvre d'une manipulation de face cristalline, procédé de préparation et utilisation d'une membrane composite poreuse repoussant le zinc dans une batterie redox à base de zinc - Google Patents

Membrane composite poreuse repoussant le zinc pour la mise en œuvre d'une manipulation de face cristalline, procédé de préparation et utilisation d'une membrane composite poreuse repoussant le zinc dans une batterie redox à base de zinc Download PDF

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WO2025108190A1
WO2025108190A1 PCT/CN2024/132362 CN2024132362W WO2025108190A1 WO 2025108190 A1 WO2025108190 A1 WO 2025108190A1 CN 2024132362 W CN2024132362 W CN 2024132362W WO 2025108190 A1 WO2025108190 A1 WO 2025108190A1
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zinc
membrane
cmc
flow battery
porous base
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Chinese (zh)
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徐至
黄康
侯晓璇
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Nanjing Tech University
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Nanjing Tech University
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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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • 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
    • 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

Definitions

  • the present invention relates to a zinc-phobic porous composite membrane for realizing crystal plane manipulation, a preparation method and application thereof in a zinc-based liquid flow battery, and belongs to the technical field of liquid flow batteries.
  • ns-MFI loaded zeolite molecular sieve nanosheets
  • Non-patent literature 1 Hou
  • the technical problem to be solved by the present invention is that during the charge and discharge process of zinc-based liquid flow batteries, the generation of zinc dendrites leads to membrane damage, battery performance degradation and shortened cycle life; the rate at which electrically neutral porous membranes transmit OH - is slightly low.
  • the technical concept adopted by the present invention is: by spin coating carboxymethyl cellulose (CMC) on the surface of the porous composite membrane to perform functional modification on the membrane surface, the charge properties of the membrane surface are further improved, and a uniform Zn(OH) 4 2- distribution is obtained at the membrane-electrode interface, avoiding the phenomenon of excessive local zincate ion concentration caused by the "tip effect", thereby inducing zinc to expose more preferential crystal plane orientations (parallel (002) crystal planes) during the deposition process.
  • CMC carboxymethyl cellulose
  • the present invention provides a new solution for dendrite-free alkaline zinc-based liquid flow batteries, that is, by customizing and optimizing the charge properties of the composite membrane surface to adjust the microenvironment charge characteristics of the membrane electrode interface to achieve crystal plane manipulation.
  • a zinc-based liquid flow battery separator comprises a porous base membrane.
  • a modification layer is covered on the surface of the porous base membrane.
  • the material of the modification layer contains a modification material and a binder.
  • the modification material contains -COOH and -OH.
  • the charge property of one side of the porous base film is adjusted by introducing molecules with -COOH and -OH to construct a functional layer, so that the surface of the porous composite film has a strong negative charge.
  • the functional layer is evenly distributed on the surface of the porous base film, and repels zincate ions (Zn(OH) 4 2- ) with the same negative charge based on the Donnan effect, thereby constructing a zinc-phobic barrier for the porous film.
  • the base film is a porous base film with a thickness of 20 to 500 ⁇ m; the modification layer has a thickness of 0.1 to 10 ⁇ m.
  • the Zeta potential value of the surface of the zinc-based liquid flow battery separator is less than -10 mV, preferably less than -20 mV.
  • the material of the porous base membrane is selected from one or more of polysulfones, polyketones, polyimide, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, polyacrylonitrile, polybenzimidazole, polyvinyl pyridine, polyethylene, polypropylene, chitosan, and cellulose acetate; the polymer is preferably a mixture of one or more of polyethersulfone and sulfonated polyetheretherketone.
  • the modifying material is selected from one or a mixture of carboxymethyl cellulose, carboxyethyl cellulose, carboxypropyl cellulose, carboxylated carbon nanotubes or carboxylated chitosan;
  • the binder is selected from one or more of Nafion, sulfonated polyetheretherketone, polyvinylidene fluoride, polyacrylic acid, polytetrafluoroethylene and polyimide.
  • the above-mentioned method for preparing the zinc-based flow battery diaphragm comprises the following steps:
  • Step 1 obtaining a porous base membrane
  • Step 2 Disperse the modifying material and the binder in a solvent, and apply them on the surface of the porous base film, and obtain the zinc-based liquid flow battery separator after drying.
  • the base film is prepared by the following method: dispersing the polymer in an organic solvent as a casting liquid; coating the casting liquid on the surface of the substrate, and performing a film-forming treatment by a phase inversion method to obtain a porous base film;
  • the organic solvent is selected from one or more of N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, chloroform or dimethyl sulfoxide.
  • phase inversion method a poor solvent for the polymer is used as a coagulation bath, and the immersion time in the coagulation bath is 1-600s; in the phase inversion method, after the membrane is treated in the coagulation bath, it is treated with an extraction solvent at a set temperature for a certain time; the temperature is 20-200°C, and the treatment time is 0.5-24h.
  • step 2 the coating method is selected from flat blade coating, spray coating or spin coating; the mass ratio of the modifying material to the binder is 1:(3-8), and the binder accounts for 1-20% of the weight of the solvent.
  • the modified layer faces the negative electrode of the battery.
  • the application also includes a method for predicting battery VE performance, including the following steps:
  • the permeability or surface resistance of Fe(CN) 6 4- of battery separators obtained under different preparation conditions was measured, and the battery separator with the highest permeability or the lowest surface resistance was taken as the separator with the highest VE performance prediction.
  • the present invention also provides a method for regulating the crystal orientation of a zinc deposit layer (002) on the surface of a diaphragm during operation of a zinc-based liquid flow battery, comprising the following steps:
  • Step 1 obtaining a porous base membrane
  • Step 2 dispersing the modifying material and the binder in a solvent, and coating the resultant on the surface of the porous base film, and obtaining a zinc-based flow battery separator after drying;
  • Step 3 by increasing the loading amount of the modified material on the surface of the porous base film, the content of zinc with (002) crystal plane in the zinc deposition layer is increased.
  • the membrane surface and zincate ions are mutually repelled, which can effectively avoid their accumulation at certain tips, thereby achieving crystal plane manipulation.
  • the present invention selects carboxymethyl cellulose (CMC) with rich functional groups (-COOH, -OH), uses a small amount of binder, and evenly distributes it on the surface of the porous base membrane by spin coating, wherein the -COOH functional group gives the composite membrane surface a strong negative charge.
  • the electrostatic repulsion between the membrane and Zn(OH) 4 2- causes the zincate ions to follow the Donnan mechanism and stay away from the membrane surface, which in turn weakens the "tip effect" during zinc deposition, which is conducive to more exposure of the preferred orientation crystal plane ((002) crystal plane) of zinc deposition.
  • the ionic conductivity of the composite membrane is improved.
  • the battery equipped with the composite membrane exhibits excellent battery performance and long-term cycle stability.
  • FIG. 1 is a schematic diagram of constructing a porous composite membrane having a zinc-repellent functional layer by spin coating.
  • FIG3 shows a) porosity and b) FTIR of the porous composite membrane.
  • FIG4 shows a) water absorption and swelling rate, b) tensile strength and c) nanoindentation of the porous composite membrane.
  • FIG5 is a Fe(CN) 6 4- permeability test of a porous composite membrane: a) test apparatus, b) permeability curve.
  • FIG6 is an OH - permeability curve of the porous composite membrane.
  • FIG. 7 is an electrochemical impedance spectroscopy test of the porous composite membrane: a) conductivity, b) membrane surface resistance.
  • FIG. 8 is the electrochemical impedance spectroscopy test of Comparative Examples 1 and 2.
  • FIG. 9 shows the battery performance of the porous composite membrane at 80 mA cm -2 .
  • Figure 10 is a battery test of the porous composite membrane at 40-240 mA cm -2 .
  • Figure 11 is a battery cycle stability test of the porous composite membrane. a) Charge and discharge voltage curves of the battery equipped with P/S and P/S-Nf-CMC-400, b) an enlarged view of the charge and discharge voltage curves, and c) the discharge capacity of the battery.
  • FIG12 is a digital photograph, SEM image and EDX spectrum of the porous composite membrane surface after the battery cycle stability test: a) P/S, b) P/S-Nf-CMC-400.
  • Figure 13 shows the long cycle test of batteries equipped with different membranes at a current density of 80 mA cm -2 .
  • Figure 14 is an SEM image of zinc deposition on carbon felt after cycling of batteries equipped with different membranes for a period of time: a) P/S, b) P/S-Nf-CMC-400, c) P/S-Nf-CMC-500, d) P/S-Nf-CMC-800, e) P/S-Nf-CMC-1000.
  • Figure 15 is a Wiener scan of zinc deposition on carbon felt after cycling of batteries equipped with different membranes for a period of time: a) P/S, b) P/S-Nf-CMC-400, c) P/S-Nf-CMC-500, d) P/S-Nf-CMC-800, e) P/S-Nf-CMC-1000.
  • Figure 16 is a study of the zinc deposition orientation on the carbon felt of the battery equipped with different membranes at the end of the cycle. a) Schematic diagram of zinc deposition orientation, b) XRD test results, c) (002) crystal plane and (100) crystal plane XRD diffraction peak intensity ratio.
  • FIG. 17 is a Zeta potential test of the porous composite membrane surface.
  • FIG18 is a quartz crystal microbalance (QCM) test result of different film layers.
  • FIG. 19 is a potential energy scan between different molecules and zincate ions.
  • FIG. 20 is a schematic diagram showing the mechanism by which CMC regulates zinc deposition behavior.
  • the present invention selects carboxymethyl cellulose (CMC) with rich functional groups (-COOH, -OH), uses a small amount of binder, and evenly distributes it on the surface of the porous base film by spin coating ( Figure 1).
  • CMC carboxymethyl cellulose
  • -COOH rich functional groups
  • Figure 1 The presence of a large number of -COOH functional groups effectively regulates the surface charge properties of the composite membrane, making it have a strong negative charge.
  • the zincate ions follow the Donnan mechanism and repel each other with the negatively charged membrane surface, staying away from the membrane surface. This in turn weakens the "tip effect" during zinc deposition, which is conducive to more exposure of the preferentially oriented crystal plane ((002) crystal plane) of zinc deposition.
  • the good electrolyte wettability of hydrophilic CMC and its rich -OH functional groups have a positive effect on OH - transmission kinetics, which synergistically improves the ionic conductivity of the composite membrane.
  • the battery equipped with the composite membrane exhibits excellent battery performance and long-term cycle stability.
  • Sulfonated polyetherketone (SPEEK) is prepared by direct sulfonation of PEEK with sulfuric acid (98%) at 50° C. for 5 h (Non-Patent Document 2).
  • the degree of sulfonation (DS) of the prepared SPEEK is about 67% as measured by 1 H NMR.
  • Non-patent literature 2 J.Xi, Z.Li, L.Yu, B.Yin, L.Wang, L.Liu, X.Qiu, L.Chen Effect of degree of sulfonation and casting solvent on sulfonated poly(e ther ether ketone)membrane for vanadium redox flow battery J.Power Sources,285(2015),pp.195-204,10.1016/j.jpowsour.2015.03.104.
  • the porous base membrane was prepared by phase inversion method.
  • Polyethersulfone (PES) and sulfonated polyetherketone (SPEEK) were added to the solvent DMAc, and then the mixture was ball-milled and ultrasonically treated, and then left to stand for defoaming to form a uniform casting solution.
  • the total polymer concentration of the casting solution was 35wt%, of which SPEEK accounted for 20wt% and the rest was PES.
  • the casting solution was poured onto a flat glass plate and a flat film scraper was used to prepare the film at room temperature.
  • the glass plate was then immersed in water until the film was automatically peeled off after the phase inversion was completed.
  • the obtained film was soaked in isopropanol for 30 minutes and then evaporated at room temperature for 2 hours to ensure complete volatilization of the isopropanol. Finally, the film was stored in deionized water for use.
  • the thickness of the prepared porous base film was 70 ⁇ 5 ⁇ m.
  • the prepared P/S base membrane ( 3.5cm2 ) was coated with Nf-CMC by spin coating, and a series of porous composite membranes with different functional layer thicknesses were prepared by changing the spin coating amount of Nf-CMC (400, 500, 800, 1000 ⁇ L). Then it was placed in an oven to dry at 60°C for 6 hours, and finally stored in deionized water for use.
  • Example 3 The difference from Example 3 is that there is no zinc-repellent functional layer, that is, the original P/S film.
  • Example 3 The difference from Example 3 is that CMC is not added to the spin coating solution, and 5 wt % Nafion solution is directly used.
  • the preparation method is the same as that of Example 3.
  • Comparative Example 3 Using high-substituted CMC to construct a porous composite membrane with zinc-repellent functional layer
  • the Nf-CMC functional layer is beneficial to accelerate the selective transport of ions.
  • the barrier capacity of the P/S-Nf-CMC membrane for active ions is significantly enhanced compared with the P/S-based membrane.
  • the hydrophilic CMC and its rich -OH functional groups are conducive to the rapid transport of OH- through standard diffusion (car-borne mechanism) and proton hopping (Grotthuss mechanism).
  • the diffusion method ion permeability test process used is as follows:
  • the permeability of Fe(CN) 6 4- ions through the membrane was determined using a pair of diffusion cells separated by a membrane.
  • the left half cell was filled with 0.4 mol L -1 K 4 Fe(CN) 6 in 3 mol L -1 NaOH solution (volume: 50 mL), while the right half cell was filled with 0.4 mol L -1 K 2 SO 4 in 3 mol L -1 NaOH solution (volume: 50 mL) to balance the ionic strength on both sides.
  • the solutions in both half cells were vigorously stirred with a magnetic stirrer to avoid the influence of concentration polarization.
  • the permeability curve of Fe(CN) 6 4- measured by the diffusion method (a in FIG5 ) (b in FIG5 ) fully demonstrates that the barrier capacity of the P/S-Nf-CMC membrane for active ions is improved.
  • all P/S-Nf-CMC membranes exhibit faster OH - transmission rates than the P/S membranes ( FIG6 ).
  • Electrochemical impedance spectroscopy (EIS) experiments (a in FIG7 and b in FIG7 ) further reveal that the P/S-Nf-CMC membrane has higher ionic conductivity (a in FIG7 ) and lower surface resistance (b in FIG7 ) than the P/S-based membrane.
  • Nf-CMC Nf-CMC
  • the thickness of the functional layer thickens, which prolongs the OH - transmission path and reduces its transmission capacity.
  • the presence of more hydrophilic CMC enhances the wettability of the membrane to the electrolyte, thereby increasing the chance of active ions passing through the membrane, and the ion selectivity of the prepared membrane also decreases slightly.
  • the present invention also provides a method for predicting battery VE performance, comprising the following steps: determining the permeability or surface resistance of Fe(CN) 6 4- of battery separators obtained under different preparation conditions, and taking the battery separator with the highest permeability or the lowest surface resistance as the separator with the highest VE performance prediction.
  • the ionic conductivity of the composite membranes (denoted as P/S-Nf-CMC(H1)-500 and P/S-Nf-CMC(H2)-500) with Nf-CMC(H1) and Nf-CMC(H2) functional layers showed that the gradual reduction in the number of -OH functional groups did have a slight adverse effect on the transport kinetics of OH- through the Grotthuss mechanism.
  • the ionic conductivity of the composite membrane with Nf functional layer (denoted as P/S-Nf-500) is slightly higher than that of the P/S membrane, but much lower than that of the P/S-Nf-CMC-500 membrane.
  • a separator to be tested was sandwiched between two carbon felt electrodes, which were clamped by two graphite plates, and then all these parts were fixed between two acrylic plates to assemble a battery assembly.
  • the effective area of the electrode was 3 ⁇ 3 cm 2.
  • Solutions consisting of 10 mL 0.6M K 4 Fe(CN) 6 +5M NaOH and 10 mL 0.3M Zn(OH) 4 2- +5M NaOH were used as positive and negative electrolytes, respectively.
  • a peristaltic pump was used to force the positive and negative electrolytes to circulate in their respective reaction chambers to participate in the electrochemical reaction.
  • the charge and discharge cycle test was performed using ArbinBT 2000: the charging process was controlled by a fixed charging time to maintain a constant charging capacity, while the discharge process was terminated by setting a cut-off voltage of 0.1 V.
  • the coulombic efficiency (CE), voltage efficiency (VE) and energy efficiency (EE) of the battery were calculated by the following equations:
  • Cd and Cc are the discharge capacity and charge capacity respectively
  • Ed and Ec are the discharge energy and charge energy respectively.
  • the CE dropped sharply when the current density reached 200mA cm -2 . Even worse, when the current density dropped again to 80mA cm -2 , the battery performance showed an irreversible decline due to the complete destruction of the P/S membrane structure.
  • the battery equipped with P/S-Nf-CMC membrane maintained an ultra-long operating life at 80mA cm -2 ( Figure 13), and could be stably cycled for more than 3000 times (>1000 hours), which is much higher than the original P/S membrane ( ⁇ 500 times) and P/S-Nf-500 membrane ( ⁇ 900 times).
  • the average performance of the battery was stable at CE ⁇ 98.5%, EE ⁇ 79.9%, and VE ⁇ 81.1%.
  • Zinc metal is a typical hexagonal structure, and its main orientations are (002), (100) and (101) crystal planes ( Figure 16a), among which the (002) crystal plane is the preferred orientation for forming relatively flat zinc deposition.
  • X-ray diffractometer XRD was introduced to study the crystal plane orientation of zinc deposition on carbon felt.
  • Figure 16b for zinc deposition on battery carbon felt using P/S membrane, the diffraction peak intensity corresponding to the (100) and (101) crystal planes is relatively high.
  • the diffraction peak intensity corresponding to the (002) crystal plane is relatively high.
  • the quartz crystal microbalance (QCM) was used to capture the micro-changes in the adsorption of Zn(OH) 4 2- by different film layers.
  • the results show that there is a strong electrostatic repulsion between the -COOH functional group of CMC and Zn(OH) 4 2- , and the adsorption of zincate ions by the film layer decreases with the increase of CMC content in the film layer ( Figure 18).

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Abstract

La présente invention se rapporte au domaine technique des batteries redox, et concerne une membrane composite poreuse repoussant le zinc pour mettre en œuvre une manipulation de face cristalline, un procédé de préparation et une utilisation d'une membrane composite poreuse repoussant le zinc dans une batterie redox à base de zinc. De la carboxyméthylcellulose (CMC) est introduite pour effectuer une optimisation personnalisée sur les propriétés de charge de la surface de la membrane, et un projet d'interface repoussant le zinc à base de force de répulsion électrostatique est construit, de telle sorte que des ions zincate sont uniformément répartis le long d'une interface membrane-électrode. Le projet d'interface repoussant le zinc met en œuvre avec succès une manipulation de face cristalline, de telle sorte que l'exposition d'une face cristalline de préférence orientée côté dépôt de zinc (face cristalline (002)) est augmentée, ce qui permet d'obtenir un dépôt de zinc plus lisse, et de prolonger la durée de vie de la batterie redox à base de zinc. De plus, la bonne mouillabilité de la CMC hydrophile à un électrolyte et l'effet positif des groupes fonctionnels riches en -OH de la CMC hydrophile sur la cinétique de transport de porteurs de charge (OH-) garantissent de manière synergique que la membrane préparée présente une conductivité ionique élevée. La présente recherche fournit une nouvelle idée de manipulation de face cristalline pour résoudre le problème de dendrite de zinc, ce qui permet de favoriser le processus commercial de la batterie redox à base de zinc pour une accumulation d'énergie à long terme.
PCT/CN2024/132362 2023-11-23 2024-11-15 Membrane composite poreuse repoussant le zinc pour la mise en œuvre d'une manipulation de face cristalline, procédé de préparation et utilisation d'une membrane composite poreuse repoussant le zinc dans une batterie redox à base de zinc Pending WO2025108190A1 (fr)

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CN202311583199.0A CN117766830B (zh) 2023-11-23 2023-11-23 一种实现晶面操纵的疏锌多孔复合膜、制备方法及其在锌基液流电池中的应用

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CN117766830B (zh) * 2023-11-23 2024-12-27 南京工业大学 一种实现晶面操纵的疏锌多孔复合膜、制备方法及其在锌基液流电池中的应用

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