CN113571839B - Functional composite diaphragm suitable for secondary zinc-based battery and preparation method and application thereof - Google Patents

Functional composite diaphragm suitable for secondary zinc-based battery and preparation method and application thereof Download PDF

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CN113571839B
CN113571839B CN202111129656.XA CN202111129656A CN113571839B CN 113571839 B CN113571839 B CN 113571839B CN 202111129656 A CN202111129656 A CN 202111129656A CN 113571839 B CN113571839 B CN 113571839B
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battery
powder
zinc
diaphragm
negative electrode
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CN113571839A (en
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赵泽泉
钟澄
胡文彬
宋永江
刘丝靓
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Tianjin 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • Y02E60/10—Energy storage using batteries

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  • Battery Electrode And Active Subsutance (AREA)
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Abstract

The invention discloses a functional composite diaphragm suitable for a secondary zinc-based battery, a preparation method and application thereof, the functional composite diaphragm mainly comprises high molecular water-absorbent resin powder, a support body, a binder and a pore-forming agent, and is prepared into a film by adopting a physical rolling method.

Description

Functional composite diaphragm suitable for secondary zinc-based battery and preparation method and application thereof
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a functional composite diaphragm suitable for a secondary zinc-based battery, and a preparation method and application thereof.
Background
At present, energy storage batteries mainly comprise lithium batteries and lead-acid batteries, wherein the lithium batteries have the defects of high potential safety hazard, high cost and the like, and the lead-acid batteries have the defects of low energy density, low power density, high lead toxicity and the like. The metal zinc has the advantages of environmental protection, high specific capacity, low cost and the like, and secondary zinc-based batteries (such as zinc-nickel batteries, zinc-manganese batteries, zinc-air batteries and the like) are expected to replace lead-acid batteries to become the next-generation water system battery energy storage technology.
The secondary zinc-nickel battery generally has the problems that the negative electrode is easy to grow dendrite and deform, the electrolyte is easy to volatilize, the negative electrode is easy to be excessively oxidized by oxygen separated out from the positive electrode, and the like, and has negative influence on the cycle performance of the battery. Many studies have developed gel electrolytes to achieve the effects of suppressing dendrite growth and volatilization of electrolytes, such as polyvinyl alcohol (PVA) -based and polyacrylic acid (PAA) -based gel electrolytes. The gel electrolyte can be formed by polymerizing monomers, or can be formed by adding a certain proportion of polymer additives into the aqueous electrolyte. However, the gel electrolyte still has many technical problems in the actual production process, for example, the thickness of the gel electrolyte is difficult to adjust, the thickness is difficult to thin, the gel electrolyte has high viscosity and is difficult to be poured into the battery, so that the gel electrolyte must be used as a current battery, and cannot be stored as a battery component in advance, and the popularization is poor.
In addition, some researches have been made on improvement of a negative electrode in which an inorganic metal oxide is added as an additive or a negative electrode particle is surface-coated to play a role in suppressing growth of dendrites. However, the improvement process for the negative electrode is complicated, and the problems of zinc-nickel battery deformation, easy volatilization of electrolyte and easy excessive oxidation of the negative electrode cannot be solved.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide the preparation method of the diaphragm, which has simple preparation process and simple assembly. The technology combines the gel component in the gel electrolyte and the component of the inorganic additive of the negative electrode in the negative electrode modification process, so that the diaphragm is not limited to play the role of physically blocking dendritic crystals of the traditional diaphragm, the growth, deformation and volatilization of electrolyte of negative electrode dendritic crystals can be effectively inhibited in the secondary zinc-based battery, the functionalization of the diaphragm is realized, and the cycle life of the battery is effectively prolonged.
In order to solve the technical problems, the basic concept of the technical scheme of the invention is as follows:
the invention provides a functional composite diaphragm suitable for a secondary zinc-based battery, which mainly comprises the following components:
(1) The high molecular water-absorbing resin powder can be dissolved, diffused and cross-linked in an aqueous solution to finally form a quasi-solid gel with a certain viscosity, and the high molecular water-absorbing resin powder is used as a gel component to enable the diaphragm to have the characteristics of a gel electrolyte and mainly used for inhibiting growth, deformation and electrolyte loss of negative dendrites. The high-molecular water-absorbing resin powder can be selected from synthetic resin type high-water-absorbing resin (potassium polyacrylate, polyacrylamide, polyvinyl alcohol); starch-based super absorbent resins (wheat starch, corn starch, potato starch); cellulose-based super absorbent resin (lignin fiber), and the like.
(2) And a support for forming the separator and for forming pores by increasing the specific surface area of the separator. The support should be an insulating oxide powder that is electrochemically inert in a zinc-based cell, such as titanium dioxide (TiO) 2 ) Silicon dioxide (SiO) 2 ) Aluminum oxide (Al) 2 O 3 ）。
(3) The binder, which is intended to bind the components of the separator, should be selected from a polymer emulsion, such as Polytetrafluoroethylene (PTFE), polyvinylidene fluoride, which has stable properties, strong binding capacity, and moderate resistance.
(4) The pore-forming agent is selected from electrolyte additives soluble in aqueous solution, such as zinc sulfate, disodium hydrogen phosphate, thiourea and sodium dodecyl benzene sulfonate.
The invention also provides a preparation method of the functionalized composite diaphragm, which comprises the following specific processes:
(1) Mixing high-molecular water-absorbing resin powder, a support, a binder and a pore-forming agent according to a certain mass ratio range of (1-9) to (1-2) to (0.01-1), wherein the optimal ratio is 7:3:1:0.8, weighing and preparing materials, then placing the high polymer water-absorbent resin powder, the support body and the pore-forming agent in a mortar, and fully mixing the powder through mechanical stirring and grinding to uniformly disperse all components;
(2) Adding a binder and a proper amount of battery electrolyte (30 wt% KOH solution, and adding 1 ml-1.2 ml electrolyte for every 3.5g of the high polymer water-absorbent resin powder) into the mixed powder in the step (1), and fully stirring to form soft and elastic powder lumps;
(3) Tabletting the powder mass into a film by using a roller press, wherein the film thickness is 0.02-0.4 mm, and the preferable thickness is 0.04 mm;
(4) After the preparation is finished, drying is not needed, and the battery can be directly assembled or sealed for standby.
The preparation method is simple to operate, the diaphragm precursor suitable for pressing and film forming can be prepared by the agglomeration process through appropriate material proportion design and simple mechanical mixing, and the film forming process can realize diaphragm forming only through rolling equipment. The whole set of process equipment is simple, the operation is simplified, and additional spinning instruments, coating equipment, molding films and other equipment are not needed, so that the production efficiency is greatly improved, and the production cost and the equipment cost are reduced.
The invention also provides a secondary zinc-based battery comprising the functional composite diaphragm, wherein the functional composite diaphragm is attached between the positive electrode and the negative electrode of the battery and is in contact with the negative electrode and the positive electrode of the battery. The assembly method of the functional composite diaphragm in the secondary zinc-based battery is as follows: (1) Placing the functionalized composite diaphragm between the negative electrode and the positive electrode; (2) The whole is put into a battery shell (the shell material is not specially limited), then a proper amount of electrolyte is poured, and the battery is kept stand for more than 2 h to ensure that the electrolyte fully infiltrates a diaphragm and an electrode, so that the battery with the same effect as a quasi-solid electrolyte battery can be obtained. A schematic of the battery assembly is shown in figure 1.
After the technical scheme is adopted, compared with the prior art, the invention has the following beneficial effects.
The diaphragm of the invention is mainly composed of high molecular water-absorbing resin powder, inorganic supporting body, binder and pore-forming agent, and is prepared into a film by adopting a physical rolling method, the preparation process is simple, the diaphragm can play the role of gel electrolyte after being added into a battery, the growth and deformation of dendritic crystals of a negative electrode and the volatilization of the electrolyte can be effectively inhibited, the excessive oxidation of the negative electrode is avoided, and the proportion is 7:3:1:0.8, the effect is best, the diaphragm of the invention simultaneously keeps the characteristics of easy disassembly and assembly and easy carrying of the traditional diaphragm, and the cycle life of the secondary zinc-based battery assembled with the diaphragm can be greatly prolonged.
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the invention without limiting the invention to its proper form. It is obvious that the drawings in the following description are only some embodiments, and that for a person skilled in the art, other drawings can be derived from them without inventive effort. In the drawings:
FIG. 1 is a schematic view of the assembly of a separator in a battery according to an embodiment of the invention;
FIG. 2 is a battery cycling curve according to one embodiment of the present invention;
FIG. 3 is a photograph of a negative scan after testing in accordance with one embodiment of the present invention;
FIG. 4 is a membrane water retention curve according to an embodiment of the present invention;
FIG. 5 is a calendar life graph according to an embodiment of the present invention;
FIG. 6 is a float life curve of an embodiment of the present invention;
fig. 7 is a photograph of a negative electrode after testing in accordance with an embodiment of the present invention.
In the figure: 1-functionalized composite diaphragm, 2-cathode, and 3-anode.
It should be noted that the drawings and the description are not intended to limit the scope of the inventive concept in any way, but to illustrate it by a person skilled in the art with reference to specific embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention.
In the description of the present invention, it should be noted that the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; may be directly connected or indirectly connected through an intermediate. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Example 1:
(1) Mixing potassium Polyacrylate (PAAK) and TiO 2 Powder, 60 wt.% aqueous Polytetrafluoroethylene (PTFE) solution in 3:7:2, weighing and preparing materials, then placing the components except the PTFE aqueous solution into a mortar, and fully mixing the powder and uniformly dispersing the components through mechanical stirring and grinding;
(2) Adding a PTFE aqueous solution and a proper amount of electrolyte for a zinc-nickel battery (30 wt% KOH solution, and adding 1 ml-1.2 ml electrolyte for every 3.5g PAAK) into the mixed powder, and fully stirring to form soft and elastic powder clusters;
(3) And tabletting the powder dough by using a roller press to form a film, wherein the film forming thickness is 0.4mm, the external light of the diaphragm after film forming is smooth and white, the plasticity is low, the elasticity is low, and the film is suitable for assembling a battery with low expected gel proportion.
(4) The diaphragm is assembled into a secondary zinc-nickel battery according to the assembly method of the diaphragm in the secondary zinc-based battery, the cathode of the zinc-nickel battery is a ZnO powder cathode, the anode of the zinc-nickel battery is a Ni (OH) 2 powder anode, and the assembled zinc-nickel battery is activated and then is ready for testing;
(5) The zinc-nickel battery provided with the diaphragm is subjected to charge-discharge cycle test under the test conditions of high multiplying power of 10C and 10% of discharge depth to monitor the voltage change of the zinc-nickel battery. After the zinc-nickel battery is circulated 4500 circles, the voltage is stabilized to be around 1.0V, the discharge voltage platform is stable, and the short circuit phenomenon does not occur.
(6) And disassembling the battery which is tested for 4500 circles, observing the morphology of the negative electrode by using a scanning electrode, wherein most particles on the surface of the negative electrode are in a polygonal morphology, and the rest particles are in a rod-shaped morphology, so that a sharp dendritic crystal morphology is not observed. The surface particles are distributed uniformly, and obvious particle agglomeration or large-area active substance shedding is avoided, which shows that the diaphragm has an inhibiting effect on the problems of negative electrode deformation, dendritic crystal growth, active substance shedding and the like.
(7) The diaphragm is put into a 60 ℃ oven, is wetted by 10g of distilled water and then is subjected to a quick drying experiment, and the weight loss curve observation shows that the water loss speed of the diaphragm is obviously slower than that of the common diaphragm and the water retention property is excellent. Therefore, the battery assembled with the separator can maintain a longer calendar life, and the voltage is still higher than 1.62V when the battery is kept still for nearly 20 days under the high-temperature condition of 60 ℃.
(8) When the battery equipped with the separator was subjected to a 1.8V constant voltage float charge, it was found that a minute charging current was generated at the float charge stage, indicating that the negative electrode of the battery was not excited by excessive oxidation resulting in charging current. After one week the cell was removed and moderate swelling of the cell occurred. By observing the oxidation of the negative electrode, the battery is hardly oxidized, and most of the battery presents a gray black color of metallic zinc, which indicates that the negative electrode is not affected by excessive oxidation caused by oxygen generated by float charging.
Example 2:
(1) Mixing potassium polyacrylate particles and TiO 2 Powder, 60 wt.% aqueous PTFE solution in a ratio of 4:5:1, weighing and preparing materials, then placing other components except the PTFE aqueous solution in a mortar, and fully mixing powder and uniformly dispersing all the components through mechanical stirring and grinding;
(2) Adding a PTFE aqueous solution and a proper amount of electrolyte for a zinc-nickel battery (30 wt% KOH solution, and adding 1 ml-1.2 ml electrolyte for every 3.5g PAAK) into the mixed powder, and fully stirring to form soft and elastic powder clusters;
(3) The powder dough is pressed into a film by using a roller press, the film forming thickness is 0.15 mm, the external light of the film is smooth and white after the film is formed, the plasticity is moderate, the elasticity is moderate, and the method is suitable for assembling a battery with moderate expected gel proportion.
(4) The diaphragm is assembled into a secondary zinc-nickel battery according to the assembly method of the diaphragm in the secondary zinc-based battery, the cathode of the zinc-nickel battery is a ZnO powder cathode, the anode of the zinc-nickel battery is a Ni (OH) 2 powder anode, and the assembled zinc-nickel battery is activated and then is ready for testing;
(5) The zinc-nickel battery provided with the diaphragm is subjected to charge-discharge cycle test under the test conditions of high multiplying power of 10C and 10% of discharge depth to monitor the voltage change of the zinc-nickel battery. After the zinc-nickel battery is cycled for 3800 circles, the voltage is stabilized to be near 1.0V, the discharge voltage platform is stable, and the short circuit phenomenon does not occur.
(6) And disassembling the battery which is tested for 4500 circles, observing the morphology of the negative electrode by using a scanning electrode, wherein particles on the surface of the negative electrode partially present a polygonal morphology, and partially present a rod-shaped morphology, and no sharp dendritic crystal morphology is observed. The surface particles are distributed uniformly, and obvious particle agglomeration or large-area active substance shedding is avoided, which shows that the diaphragm has an inhibiting effect on the problems of negative electrode deformation, dendritic crystal growth, active substance shedding and the like.
(7) The diaphragm is put into a 60 ℃ drying oven, and is wetted by 10g of distilled water for a quick drying experiment, and the observation of a weight loss curve shows that the water loss speed of the diaphragm is obviously slower than that of a common diaphragm, and the water retention property is excellent. Therefore, the battery assembled with the separator can maintain a longer calendar life, and the voltage is still higher than 1.62V when the battery is kept still for nearly 20 days under the high-temperature condition of 60 ℃.
(8) When the battery equipped with the separator was subjected to a 1.8V constant voltage float charge, it was found that a minute charging current was generated at the float charge stage, indicating that the negative electrode of the battery was not excited by excessive oxidation resulting in charging current. After one week the cell was removed and moderate swelling of the cell occurred. By observing the oxidation of the negative electrode, the battery is hardly oxidized, and most of the battery is gray black with metal zinc, which indicates that the negative electrode is not affected by excessive oxidation caused by oxygen generated by float charging.
Example 3:
(1) Mixing potassium polyacrylate particles and TiO 2 Powder, 60 wt.% aqueous PTFE solution in a 7:3:1, weighing and preparing materials, then placing other components except the PTFE aqueous solution in a mortar, and fully mixing powder and uniformly dispersing all the components through mechanical stirring and grinding;
(2) Adding a PTFE aqueous solution and a proper amount of electrolyte for a zinc-nickel battery (30 wt percent KOH solution, and adding 1 ml-1.2 ml electrolyte for every 3.5g PAAK) into the mixed powder, and fully stirring to form a soft and elastic powder mass;
(3) The powder dough is pressed into a film by using a roller press, the film forming thickness is 0.04 mm, the external light of the diaphragm after film forming is smooth and white, the plasticity is high, the elasticity is good, and the film is suitable for assembling a battery with higher expected gel proportion.
(4) The diaphragm is assembled into a secondary zinc-nickel battery according to the invention part 'assembly method of the diaphragm in the secondary zinc-based battery', the cathode of the zinc-nickel battery is ZnO powder cathode, and the anode is Ni (OH) 2 A powder anode, namely activating the assembled zinc-nickel battery and preparing for testing;
(5) The zinc-nickel battery provided with the diaphragm is subjected to charge-discharge cycle test under the test conditions of high multiplying power of 10C and 10% of discharge depth to monitor the voltage change of the zinc-nickel battery. After the zinc-nickel battery is circulated 4500 circles, the voltage is stabilized to be around 1.0V, the discharge voltage platform is stable, and the short circuit phenomenon does not occur.
(6) And disassembling the battery for testing 4500 circles, observing the morphology of the negative electrode by using a scanning electrode, wherein most particles on the surface of the negative electrode are in a polygonal morphology, and a few particles are in a rod-shaped morphology, so that the sharp dendritic crystal morphology is not observed. The surface particles are distributed uniformly, and obvious particle agglomeration or large-area active substance shedding is avoided, which shows that the diaphragm has an inhibiting effect on the problems of negative electrode deformation, dendritic crystal growth, active substance shedding and the like.
(7) The diaphragm is put into a 60 ℃ oven, is wetted by 10g of distilled water and then is subjected to a quick drying experiment, and the weight loss curve observation shows that the water loss speed of the diaphragm is obviously slower than that of the common diaphragm and the water retention property is excellent. Therefore, the battery assembled with the separator can maintain a longer calendar life, and the voltage is still higher than 1.62V when the battery is kept still for nearly 20 days under the high-temperature condition of 60 ℃.
(8) When the battery equipped with the separator was subjected to a 1.8V constant voltage float charge, it was found that a minute charging current was generated at the float charge stage, indicating that the negative electrode of the battery was not excited by excessive oxidation resulting in charging current. After one week the cell was removed and moderate swelling of the cell occurred. By observing the oxidation of the negative electrode, the battery is hardly oxidized, and most of the battery presents a gray black color of metallic zinc, which indicates that the negative electrode is not affected by excessive oxidation caused by oxygen generated by float charging.
Example 4:
(1) Mixing wheat starch and TiO 2 Powder, 60 wt.% aqueous PTFE solution in a 7:3:1, weighing and preparing materials, then placing other components except the PTFE aqueous solution in a mortar, and fully mixing powder and uniformly dispersing all the components through mechanical stirring and grinding;
(2) Adding a PTFE aqueous solution and a proper amount of electrolyte for a zinc-nickel battery (30 wt% KOH solution, and adding 1 ml-1.2 ml electrolyte for every 3.5g of wheat starch) into the mixed powder, and fully stirring to form soft and elastic powder dough;
(3) The powder dough is pressed into a film by using a roller press, the film forming thickness is 0.04 mm, the film is smooth and white after being formed, the plasticity is moderate, and the elasticity is moderate.
(4) The diaphragm is assembled into a secondary zinc-nickel battery according to the invention part 'assembly method of the diaphragm in the secondary zinc-based battery', the cathode of the zinc-nickel battery is ZnO powder cathode, and the anode is Ni (OH) 2 A powder anode, namely activating the assembled zinc-nickel battery and preparing for testing;
(5) The zinc-nickel battery provided with the diaphragm is subjected to charge-discharge cycle test under the test conditions of high multiplying power of 10C and 10% of discharge depth to monitor the voltage change of the zinc-nickel battery. After 3500 cycles of the zinc-nickel battery, the voltage is stabilized near 1.0V, and the discharge voltage platform is stable without short circuit.
(6) And disassembling the battery for testing 3500 circles, observing the morphology of the negative electrode by using a scanning electrode, wherein the particle part on the surface of the negative electrode is in a polygonal morphology, the part of the particle part is in a rod-shaped morphology, and the part of the particle part is in a sharp dendritic crystal morphology. The surface particles are distributed uniformly, and obvious particle agglomeration or large-area active substance shedding is avoided, which indicates that the diaphragm has an inhibiting effect on the problems of negative electrode deformation, dendritic crystal growth, active substance shedding and the like.
(7) The diaphragm is put into a 60 ℃ oven, is wetted by 10g of distilled water and then is subjected to a quick drying experiment, and the weight loss curve is obtained. It can be seen that the water loss rate is slower but faster than in example 3, and the water retention is better. Therefore, the battery assembled with the separator can maintain moderate calendar life, and the voltage is still higher than 1.62V when the battery is kept still for nearly 16 days under the high-temperature condition of 60 ℃.
(8) When the battery equipped with the separator was subjected to a 1.8V constant voltage float charge, it was found that almost no charging current was generated at the float charge stage, indicating that the negative electrode of the battery was not excited by excessive oxidation resulting in charging current. After one week the cell was removed and moderate swelling of the cell occurred. By observing the oxidation condition of the negative electrode, the negative electrode is hardly oxidized, and the electrode mostly presents a gray black color of metal zinc, which shows that the negative electrode is not influenced by excessive oxidation caused by oxygen generated by floating charge.
Example 5:
(1) Mixing potassium polyacrylate and TiO 2 Powder, 60 wt.% aqueous PTFE solution, thiourea in 7:3:1:1, weighing and preparing materials, then placing other components except the PTFE aqueous solution in a mortar, and fully mixing powder and uniformly dispersing all the components through mechanical stirring and grinding;
(2) Adding a PTFE aqueous solution and a proper amount of electrolyte for a zinc-nickel battery (30 wt% KOH solution, and adding 1 ml-1.2 ml electrolyte for every 3.5g PAAK) into the mixed powder, and fully stirring to form soft and elastic powder clusters;
(3) The powder dough is pressed into a film by a roller press, the film thickness is 0.04 mm, and the film is smooth and white, high in plasticity and good in elasticity after being formed.
(4) The diaphragm is assembled into a secondary zinc-nickel battery according to the invention part 'assembly method of the diaphragm in the secondary zinc-based battery', the cathode of the zinc-nickel battery is ZnO powder cathode, and the anode is Ni (OH) 2 A powder anode, namely activating the assembled zinc-nickel battery and preparing for testing;
(5) The zinc-nickel battery provided with the diaphragm is subjected to charge-discharge cycle test under the test conditions of high multiplying power of 10C and 10% of discharge depth to monitor the voltage change of the zinc-nickel battery. After the zinc-nickel battery is cycled for 5500 circles, the voltage is stabilized to be near 1.0V, the discharge voltage platform is stable, and the short circuit phenomenon does not occur.
(6) Disassembling the battery with 5500 circles, observing the morphology of the negative electrode by using a scanning electrode, wherein most of particles on the surface of the negative electrode are in a polygonal morphology, almost no rod-shaped morphology exists, and no sharp dendritic crystal morphology is observed. The surface particles are distributed uniformly, and obvious particle agglomeration or large-area active substance shedding is avoided, which shows that the diaphragm has an inhibiting effect on the problems of negative electrode deformation, dendritic crystal growth, active substance shedding and the like.
(7) The diaphragm is put into a 60 ℃ oven, and is wetted by 10g of distilled water for a quick drying experiment, so that the weight loss curve shows that the water loss speed is very low and the water retention is very good. Therefore, the battery assembled with the separator can maintain a very long calendar life, and the voltage is still higher than 1.62V when the battery is kept still for nearly 25 days under the high-temperature condition of 60 ℃.
(8) When the battery assembled with the diaphragm is subjected to 1.8V constant-voltage floating charge, no charging current is generated in the floating charge stage, which indicates that the negative electrode of the battery is not excessively oxidized to cause excitation of the charging current. After one week, the cell was removed and a large bulge occurred. By observing the oxidation of the negative electrode, the electrode exhibited a majority of metallic zinc in a gray black color and a minority of zinc oxide in a white color, indicating that although the negative electrode was slightly passivated by oxidation with a small amount of oxygen, it was hardly affected by excessive oxidation by oxygen generated by float charging.
Example 6:
(1) Mixing potassium polyacrylate, wheat starch, and TiO 2 Powder, 60 wt.% aqueous PTFE solution, thiourea in 5:2:3:1:0.8, weighing and preparing materials, then placing the components except the PTFE aqueous solution into a mortar, and fully mixing the powder and uniformly dispersing the components through mechanical stirring and grinding;
(2) Adding a PTFE aqueous solution and a proper amount of electrolyte for a zinc-nickel battery (30 wt% KOH solution, and adding 1 ml-1.2 ml electrolyte for PAAK + wheat starch mixed with 3.5 g) into the mixed powder, and fully stirring to form soft and elastic powder dough;
(3) The powder dough is pressed into a film by a roller press, the film thickness is 0.04 mm, and the film is smooth and white, high in plasticity and good in elasticity after being formed.
(4) The diaphragm is assembled into a secondary zinc-nickel battery according to the invention part 'assembly method of the diaphragm in the secondary zinc-based battery', the cathode of the zinc-nickel battery is ZnO powder cathode, and the anode is Ni (OH) 2 A powder anode, namely activating the assembled zinc-nickel battery and preparing for testing;
(5) The zinc-nickel battery provided with the diaphragm is subjected to charge-discharge cycle test under the test conditions of high multiplying power of 10C and 10% of discharge depth to monitor the voltage change of the zinc-nickel battery. After 5000 cycles of the zinc-nickel battery are recycled as shown in FIG. 2, the voltage is stabilized near 1.0V, the discharge voltage platform is stable, the fluctuation is extremely small, and the short circuit phenomenon does not occur.
(6) Disassembling the battery with 5000 circles, observing the morphology of the negative electrode by using a scanning electrode, and as shown in fig. 3, observing that the surface of the negative electrode is polygonal, most particles on the surface of the negative electrode are polygonal, completely have no rod-shaped morphology, and completely have no sharp dendritic crystal morphology. The surface particles are distributed uniformly, and obvious particle agglomeration or large-area active substance shedding is avoided, so that the diaphragm effectively inhibits the problems of negative electrode deformation, dendritic crystal growth, active substance shedding and the like.
(7) The diaphragm is put into a 60 ℃ oven, and is wetted by 10g of distilled water to carry out a quick drying experiment, and the weight loss curve of the diaphragm is shown in figure 4. Therefore, the water loss speed is slow, and the water retention is good. Therefore, the battery equipped with the separator can maintain a high calendar life, and as shown in fig. 5, the battery is left to stand at a high temperature of 60 ℃ for approximately 23 days, and the voltage is still higher than 1.62V or more.
(8) The battery equipped with the present separator was subjected to a 1.8V constant voltage float charge, and it was found that almost no charging current was generated at the float charge stage, as shown in fig. 6, indicating that the negative electrode of the battery was not excessively oxidized to cause excitation of the charging current. After one week the cell was removed and slight swelling of the cell occurred. By observing the oxidation of the negative electrode, the electrode showed a gray black color of metallic zinc as shown in fig. 7, indicating that the negative electrode was not affected by excessive oxidation due to oxygen generated by float charging.
Comparative example 1: (without adding Water-absorbent resin powder)
(1) Adding TiO into the mixture 2 Powder, 60 wt.% aqueous PTFE solution in a 10:2, weighing and preparing materials, then placing the components except the PTFE aqueous solution into a mortar, and fully mixing the powder and uniformly dispersing the components through mechanical stirring and grinding;
(2) Adding a PTFE aqueous solution and a proper amount of electrolyte for a zinc-nickel battery (30 wt percent KOH solution, and adding 1 ml-2 ml electrolyte for every 3.5 zxft 3252 powder) into the mixed powder, and fully stirring to form a powder dough;
(3) The powder dough is pressed into a film by using a roller press, the film forming process is difficult, an additional binder is required, the film forming thickness is difficult to realize thinner thickness, the film forming thickness is 0.4mm, the external light of the diaphragm after film forming is smooth and white, and the plasticity is poor.
(4) The diaphragm is assembled into a secondary zinc-nickel battery according to the invention part 'assembly method of the diaphragm in the secondary zinc-based battery', the cathode of the zinc-nickel battery is ZnO powder cathode, and the anode is Ni (OH) 2 A powder anode, namely activating the assembled zinc-nickel battery and preparing for testing;
(5) The zinc-nickel battery assembled with the diaphragm is subjected to charge-discharge cycle test under the test conditions of high multiplying power of 10C and 10% of discharge depth to monitor the voltage change of the zinc-nickel battery. After the zinc-nickel battery is recycled for 2000 circles, the voltage drops to be below 1.0V, and the voltage dropping speed is high.
(6) And disassembling the battery for testing for 2000 circles, observing the morphology of the negative electrode by using a scanning electrode, and finding that the surface of the negative electrode diaphragm has deformation to a certain degree and has a little dendritic crystal morphology.
(7) The diaphragm is put into a 60 ℃ oven, is wetted by 10g of distilled water and then is subjected to a quick drying experiment, so that the diaphragm has high dehydration speed and weak water retention. Therefore, the battery equipped with the separator has a weak calendar life, and the battery is left to stand at a high temperature of 60 ℃ for approximately 14 days and has a voltage of less than 1.62V or more.
(8) The battery assembled with the diaphragm is subjected to 1.8V constant-voltage floating charge, and a certain charging current is generated in the floating charge stage, which indicates that the charging current is excited due to the excessive oxidation of the negative electrode of the battery. After one week the cell was removed and moderate swelling of the cell occurred. By observing the oxidation of the negative electrode, if the battery negative electrode is obviously oxidized and appears white like zinc oxide, the negative electrode is excessively oxidized by oxygen generated by floating charge.
Comparative example 2: (TiO without addition of a support 2 ）
(1) PAAK powder, 60 wt.% aqueous PTFE solution was mixed in a 10:1, weighing and preparing materials, then placing other components except the PTFE aqueous solution in a mortar, and fully mixing powder and uniformly dispersing all the components through mechanical stirring and grinding;
(2) Adding a PTFE aqueous solution and a proper amount of electrolyte for a zinc-nickel battery (30 wt% KOH solution, and adding 1 ml-1.2 ml electrolyte for every 3.5g PAAK) into the mixed powder, and fully stirring to form a powder dough;
(3) The powder dough is pressed into a film by using a roller press, the film forming process is easy, the film forming is easy to realize thinner thickness, the film forming thickness is 0.04 mm, the film is white after film forming, and the plasticity is better.
(4) The separator is assembled in the secondary zinc-based battery according to the inventionIs loaded into a secondary zinc-nickel battery, the cathode of the zinc-nickel battery is ZnO powder cathode, the anode is Ni (OH) 2 A powder anode, namely activating the assembled zinc-nickel battery and preparing for testing;
(5) The zinc-nickel battery provided with the diaphragm is subjected to charge-discharge cycle test under the test conditions of high multiplying power of 10C and 10% of discharge depth to monitor the voltage change of the zinc-nickel battery. After 3500 cycles of the zinc-nickel battery, the voltage drops to below 1.0V, and the voltage drop speed is moderate.
(6) And disassembling the battery tested for 3500 circles, observing the appearance of the negative electrode by using a scanning electrode, and finding that the surface deformation of the negative electrode diaphragm is relieved and the appearance of fresh dendritic crystals is generated.
(7) The diaphragm is put into a 60 ℃ oven, is wetted by 10g of distilled water and then is subjected to a quick drying experiment, and the diaphragm has very low water loss speed and very strong water retention. Therefore, the battery assembled with the separator can maintain a very long calendar life, and the voltage is still higher than 1.62V when the battery is still kept for nearly 28 days under the high-temperature condition of 60 ℃.
(8) When the battery equipped with the separator was subjected to a 1.8V constant voltage float charge, it was found that almost no charging current was generated at the float charge stage, indicating that the negative electrode of the battery was not excited by excessive oxidation resulting in charging current. After one week, the battery was removed and a large swelling occurred in the battery. By observing the oxidation of the negative electrode, the battery was found to be hardly oxidized and to exhibit a gray black color of metallic zinc, indicating that the negative electrode was not affected by excessive oxidation due to oxygen generated by float charging.
Comparative example 3: (ordinary PP separator)
(1) Assembling a double-layer common diaphragm (glass fiber, filter paper, polypropylene/polypropylene diaphragm and the like can be selected, and polypropylene Celgard series diaphragms are preferred) into a secondary zinc-nickel battery, wherein the cathode of the zinc-nickel battery is a ZnO powder cathode, the anode of the zinc-nickel battery is a Ni (OH) 2 powder anode, and the assembled zinc-nickel battery is activated and then is ready for testing;
(2) The zinc-nickel battery provided with the diaphragm is subjected to charge-discharge cycle test under the test conditions of high multiplying power of 10C and 10% of discharge depth to monitor the voltage change of the zinc-nickel battery. After 800 cycles of the zinc-nickel battery recycling, the voltage drops to below 0.5V, the voltage is in a sudden drop trend, and the zinc-nickel battery has obvious short circuit signs.
(3) Disassembling the battery which is tested for 800 turns, observing the morphology of the negative electrode by using a scanning electrode, and finding that the surface deformation of the negative electrode diaphragm has obvious dendritic morphology which causes the short circuit of the battery.
(4) The diaphragm is put into a 60 ℃ oven, is wetted by 10g of distilled water and then is subjected to a quick drying experiment, and the diaphragm has high dehydration speed and weak water retention. Therefore, the calendar life of the battery equipped with the separator was poor, and the battery was left to stand at a high temperature of 60 ℃ for approximately 12 days and the voltage was less than 1.62V.
(5) The battery assembled with the diaphragm is subjected to constant-voltage floating charge of 1.8V, and the fact that a large charging current is generated in the floating charge stage is found, which indicates that the excitation of the charging current is caused by serious over-oxidation of the negative electrode of the battery. After one week the cell was removed and moderate swelling of the cell occurred. By observing the oxidation of the negative electrode, if the negative electrode of the battery is obviously oxidized, the white color of zinc oxide is shown, which indicates that the negative electrode is excessively oxidized by oxygen generated by floating charge.
Comparative example 4: (polyvinyl alcohol instead of Potassium polyacrylate)
(1) Mixing polyvinyl alcohol, wheat starch and TiO 2 Powder, 60 wt.% aqueous PTFE solution, thiourea in 5:2:3:1:0.8, weighing and preparing materials, then placing the components except the PTFE aqueous solution into a mortar, and fully mixing the powder and uniformly dispersing the components through mechanical stirring and grinding;
(2) Adding a PTFE aqueous solution and a proper amount of electrolyte for a zinc-nickel battery (30 wt% KOH solution, and adding 1 ml-1.2 ml electrolyte for PAAK + wheat starch mixed with 3.5 g) into the mixed powder, and fully stirring to form soft and elastic powder dough;
(3) And tabletting the powder dough by using a roller press to form a film, wherein the film forming thickness is 0.04 mm, and the film after film forming is rough and white in appearance, poor in plasticity and poor in elasticity.
(4) The separator is partially' separator in a secondary zinc-based battery according to the inventionThe assembly method is' assembled into a secondary zinc-nickel battery, the cathode of the zinc-nickel battery is a ZnO powder cathode, and the anode is Ni (OH) 2 A powder anode, namely activating the assembled zinc-nickel battery and preparing for testing;
(5) The zinc-nickel battery provided with the diaphragm is subjected to charge-discharge cycle test under the test conditions of high multiplying power of 10C and 10% of discharge depth to monitor the voltage change of the zinc-nickel battery. After 2500 cycles of the zinc-nickel battery, the voltage is stabilized near 1.0V, the discharge voltage platform is stable, the fluctuation is large, and the short circuit phenomenon does not occur.
(6) And (3) disassembling the battery for testing 2500 circles, and observing the morphology of the negative electrode by using a scanning electrode, wherein a few particles on the surface of the negative electrode are polygonal, most of the particles are rod-shaped, and a few particles are sharp dendritic crystal morphologies. The surface particles are distributed uniformly, and local particle aggregation and small-area active substance shedding occur, which indicates that the diaphragm has the problems of negative electrode deformation, dendritic crystal growth, active substance shedding and the like.
(7) The diaphragm is put into a 60 ℃ oven, is wetted by 10g of distilled water and then is subjected to a quick drying experiment, so that the diaphragm has high dehydration speed and weak water retention. The calendar life of the battery assembled with the diaphragm is general, and the battery is kept still for nearly 12 days under the high-temperature condition of 60 ℃, and the voltage is lower than 1.62V.
(8) The battery equipped with the separator was subjected to a 1.8V constant voltage float charge, and it was found that a small amount of charging current was generated at the float charge stage, indicating that the negative electrode of the battery was slightly oxidized to cause excitation of the charging current. After one week the cell was removed and moderate swelling of the cell occurred. By observing the oxidation condition of the negative electrode, a part of the electrode presents grey black of metal zinc, and a part of the electrode is oxidized into zinc oxide to generate slight passivation, which shows that the negative electrode is influenced by oxidation caused by oxygen generated by floating charge.
Comparative example 5: (aluminum oxide instead of titanium dioxide)
(1) Mixing potassium polyacrylate, wheat starch, and Al 2 O 3 Powder, 60 wt.% aqueous PTFE solution, thiourea in 5:2:3:1:0.8 weight stock, then put other components except the aqueous PTFE solution into a mortarIn the middle, the powder is fully mixed and all components are uniformly dispersed through mechanical stirring and grinding;
(2) Adding a PTFE aqueous solution and a proper amount of electrolyte for a zinc-nickel battery (30 wt% KOH solution, and adding 1 ml-1.2 ml electrolyte for PAAK + wheat starch mixed with 3.5 g) into the mixed powder, and fully stirring to form soft and elastic powder dough;
(3) And tabletting the powder dough by using a roller press to form a film, wherein the film forming thickness is 0.04 mm, and the film has smooth appearance, dark color, better plasticity and better elasticity after film forming.
(4) The diaphragm is assembled into a secondary zinc-nickel battery according to the invention part 'assembly method of the diaphragm in the secondary zinc-based battery', the cathode of the zinc-nickel battery is ZnO powder cathode, and the anode is Ni (OH) 2 A powder anode, namely activating the assembled zinc-nickel battery and preparing for testing;
(5) The zinc-nickel battery provided with the diaphragm is subjected to charge-discharge cycle test under the test conditions of high multiplying power of 10C and 10% of discharge depth to monitor the voltage change of the zinc-nickel battery. After 3500 cycles of the zinc-nickel battery are recycled, the voltage is stabilized near 1.0V, the discharge voltage platform is stable, the fluctuation is large, and the short circuit phenomenon does not occur.
(6) The battery for testing 3500 circles is disassembled, the negative electrode morphology is observed by using a scanning electrode, and the negative electrode surface particle part shows a polygonal shape, the part shows a rod-shaped morphology, and the minority shows a sharp dendritic crystal morphology. The distribution of surface particles is uniform, a small part of particles are agglomerated and a small area of active substances falls off, and the diaphragm has certain inhibiting effects on negative electrode deformation, dendritic crystal growth, active substance falling and the like.
(7) The diaphragm is put into a 60 ℃ oven, is wetted by 10g of distilled water and then is subjected to a quick drying experiment, and the diaphragm has slow dehydration speed and good water retention. The battery assembled with the diaphragm can keep a longer calendar life, and the voltage is still higher than 1.62V when the battery stands for nearly 18 days at the high temperature of 60 ℃.
(8) The battery assembled with the diaphragm is subjected to constant-voltage floating charging at 1.8V, and a little charging current is generated in the floating charging stage, which indicates that the cathode of the battery is slightly oxidized to cause excitation of the charging current. After one week the cell was removed and moderate swelling of the cell occurred. By observing the oxidation condition of the negative electrode, a part of the electrode presents grey black of metal zinc, and a part of the electrode is oxidized into zinc oxide to generate slight passivation, which shows that the negative electrode is influenced by oxidation caused by oxygen generated by floating charge.
Comparative example 6: (aqueous solution of Potassium polyacrylate instead of aqueous solution of PTFE)
(1) Mixing potassium polyacrylate, wheat starch, and TiO 2 Powder, 60 wt% aqueous potassium polyacrylate, thiourea in 5:2:3:1:0.8, weighing and preparing materials, then placing the components except the PTFE aqueous solution into a mortar, and fully mixing the powder and uniformly dispersing the components through mechanical stirring and grinding;
(2) Adding a PTFE aqueous solution and a proper amount of electrolyte for a zinc-nickel battery (30 wt% KOH solution, and adding 1 ml-1.2 ml electrolyte for PAAK + wheat starch mixed with 3.5 g) into the mixed powder, and fully stirring to form soft and elastic powder dough;
(3) The powder dough is pressed into a film by using a roller press, the film forming thickness is 0.04 mm, the appearance of the diaphragm after film forming is smooth and white, the diaphragm after drying has almost no plasticity and poor elasticity, the powder on the diaphragm is found to fall off and suspend in electrolyte after being filled into a battery, the structure is damaged, and subsequent tests cannot be carried out.
Data comparison table for examples 1-6 and comparative examples 1-6:
Figure 586248DEST_PATH_IMAGE001
Figure 669873DEST_PATH_IMAGE002
and (4) conclusion: from the above examples and comparative examples, it can be seen that the optimum ratio of the separator is the mixture of potassium polyacrylate particles and TiO 2 Powder, 60 wt% aqueous PTFE solution, thiourea7:3:1: 1. potassium polyacrylate, wheat starch, tiO 2 Powder, 60 wt.% aqueous PTFE solution, thiourea 5:2:3:1:0.8. comparative example 1, if the high molecular water-absorbent resin powder is not added, tiO 2 The powder ratio is too high, which causes difficulty in film formation, and indicates that the high molecular water-absorbent resin powder has a positive effect on diaphragm molding. Comparative example 2, the sample with a higher proportion of the polymeric water-absorbent resin powder is not only easy to form, but also has a higher cycle number, which is probably because the polymeric water-absorbent resin powder component can form a quasi-solid interface on the surface of the negative electrode, and slows down the movement of zincate ions in the electrolyte, thereby inhibiting the generation of dendrites; however, too much of the high molecular water-absorbent resin powder component may lower the ionic conductivity to cause the voltage decay, so that TiO 2 The addition of a suitable amount of powder helps to increase the porosity of the separator, thereby increasing the overall conductivity, and in addition, tiO 2 The powder has larger binding energy to zincate ions, can effectively guide the uniform deposition of zinc, and is contrastively tested to obtain Al 2 O 3 The effect cannot be achieved. For water retention, the PAAK component plays a major role in improving water retention due to the chemisorption of hydrogen bonds, and secondly, tiO 2 The powder also has a small contribution due to the large specific surface area. To the isolated gas effect, PAAK is comparatively compact and can obstruct oxygen oxidation negative pole, but too excessive separation also can lead to oxygen can't be consumed by the negative pole and cause excessive bulging, and add inorganic powder of certain proportion, can let a small amount of oxygen carry out the oxygen recombination through going to the negative pole, and on the other hand can avoid excessively compounding again to cause the excessive oxidation of negative pole. The pore-forming agent can increase the porosity of the diaphragm, so that part of oxygen can permeate to the negative electrode for proper oxygen recombination, and can be dissolved in the electrolyte to play a role of a surfactant, polar groups of the pore-forming agent are adsorbed on the surface of the negative electrode to inhibit a hydrogen evolution reaction so as to further improve the calendar life, but the excessive pore-forming agent is dissolved in the electrolyte and can also cause slight passivation of the negative electrode. More than two kinds of water-absorbing resin are selected to generate the water-retaining effect of more kinds of hydrophilic groups, the water-retaining property is also improved, and in addition, the starch and PAAK with a certain proportion can beThe oxygen is isolated more favorably, and the starch can block micropores generated by the diaphragm, so that the cathode is further protected from excessive oxidation. Therefore, the appropriate ratio of the water-absorbent resin (potassium polyacrylate in combination with starch) + TiO 2 The separator of the powder support and the pore-forming agent is most beneficial to the performance of the battery.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (7)

1. A preparation method of a functionalized composite diaphragm suitable for a secondary zinc-based battery is characterized by comprising the following steps:
step 1, weighing and preparing high-molecular water-absorbent resin powder, a support, a binder and a pore-forming agent according to a ratio; the mass ratio of the high molecular water-absorbing resin powder, the support, the binder and the pore-forming agent is (1-9) to (1-2) to (0.01-1);
wherein, the high polymer water-absorbing resin powder is potassium polyacrylate, wheat starch or the combination of the potassium polyacrylate and the wheat starch, the support body is titanium dioxide, and the adhesive is polytetrafluoroethylene; the pore-forming agent is thiourea;
step 2, mixing the high-molecular water-absorbent resin powder, the support body and the pore-forming agent, putting the mixture into a mortar, fully mixing the powder through mechanical stirring and grinding, and uniformly dispersing all the components to obtain mixed powder;
step 3, adding a binder and battery electrolyte into the mixed powder, and fully stirring to form soft and elastic powder balls;
and 4, tabletting the powder dough into a film by using a roller press, and directly assembling the battery or sealing the battery for later use without drying after the preparation is finished.
2. The method for preparing the functionalized composite membrane suitable for the secondary zinc-based battery according to claim 1, characterized in that: the mass ratio of the high polymer water-absorbent resin powder, the support, the binder and the pore-forming agent is 7.
3. The method for preparing the functionalized composite membrane suitable for the secondary zinc-based battery according to claim 1, characterized in that: the thickness of the diaphragm is 0.02-0.4 mm.
4. The method for preparing the functionalized composite membrane suitable for the secondary zinc-based battery according to claim 1, characterized in that: the electrolyte for the battery is a KOH solution of 30 wt, and 1 ml-1.2 ml of electrolyte is required to be added for every 3.5g of the high polymer water-absorbent resin powder.
5. The method for preparing the functionalized composite membrane suitable for the secondary zinc-based battery according to claim 1, characterized in that: the high polymer water-absorbent resin powder consists of 5:2 mass ratio of potassium polyacrylate and wheat starch, and the mass ratio of the high polymer water-absorbent resin powder to the support to the binder to the pore-forming agent is (7).
6. A functionalized composite separator prepared according to the preparation method of any one of claims 1 to 5.
7. A secondary zinc-based battery comprising the functionalized composite separator prepared by the preparation method of any one of claims 1 to 5.
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