CN114520399A - Water-based battery composite diaphragm and preparation method and application thereof - Google Patents

Water-based battery composite diaphragm and preparation method and application thereof Download PDF

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Publication number
CN114520399A
CN114520399A CN202210028638.0A CN202210028638A CN114520399A CN 114520399 A CN114520399 A CN 114520399A CN 202210028638 A CN202210028638 A CN 202210028638A CN 114520399 A CN114520399 A CN 114520399A
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water
buffer layer
battery
polymer film
soluble polymer
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李享
罗小松
陈璞
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Ruihai Bo Changzhou Energy Technology Co ltd
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Priority to PCT/CN2022/144200 priority patent/WO2023134481A1/en
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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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • 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
    • H01M50/411—Organic material
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Cell Separators (AREA)

Abstract

The invention discloses a water system battery composite diaphragm and a preparation method and application thereof, wherein the composite diaphragm comprises: cellulose membrane and polymer film buffer layer, the polymer film buffer layer is established on the cellulose membrane. Therefore, the composite diaphragm can realize a thinner thickness, has good wettability, and can effectively inhibit dendritic crystals, thereby being beneficial to the improvement of the energy density, the electrochemical stability and the safety of a water system battery.

Description

Water-based battery composite diaphragm and preparation method and application thereof
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a composite diaphragm of a water-based battery, and a preparation method and application thereof.
Background
Currently, a glass fiber separator (AGM), a hydrophilic PP film, or a nonwoven fabric is generally used as a separator in an aqueous battery. The above separator has the following drawbacks: (1) the AGM and the non-woven fabric diaphragm are thick, so that the improvement of energy density is limited, the mechanical property is poor, and the blocking capability on metal dendrites is limited; (2) in a water system environment, the positive electrode material is easy to dissolve, and the dissolved positive electrode material is easy to block the pore channels of the PP film, so that the internal resistance is increased, and the electrical property is influenced.
Therefore, the existing water-based battery separator is in need of improvement.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a composite separator for a water-based battery, a method for preparing the same, and applications thereof, wherein the composite separator can achieve a thinner thickness, has good wettability, and can effectively inhibit dendrites, thereby facilitating improvement of energy density, electrochemical stability, and safety of the water-based battery.
In one aspect of the present invention, a water-based battery composite separator is provided. According to an embodiment of the invention, the composite membrane comprises: cellulose membrane and polymer film buffer layer, the polymer film buffer layer is established on the cellulose membrane.
According to the water-based battery composite diaphragm provided by the embodiment of the invention, the water-based battery composite diaphragm comprises the cellulose membrane and the polymer membrane buffer layer, the cellulose membrane and the polymer membrane buffer layer can be thinner, and the energy density of the battery can be favorably improved, wherein electrolyte cannot be stored in pores of the cellulose membrane, and zinc ions are difficult to enrich longitudinally, so that the longitudinal growth of the zinc ions can be effectively shielded, and the situation that negative metal dendrites penetrate through the diaphragm to cause short circuit is prevented; simultaneously through set up the polymer film buffer layer on the cellulose membrane, because the plumpness of polymer film buffer layer is better, can make electrolyte dispersion even, avoid the local deposit that local concentration too high leads to, can effectively solve the inhomogeneous phenomenon of electrolyte distribution between electrode and the diaphragm interface, and the polymer film buffer layer can also reduce interfacial impedance to be favorable to the promotion of electrochemistry stability. In conclusion, the composite diaphragm can achieve a thinner thickness, has good wettability, and can effectively inhibit dendritic crystals, thereby being beneficial to the improvement of the energy density, the electrochemical stability and the safety of a water system battery.
In addition, the water-based battery composite separator according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the polymeric membrane buffer layer is located on one or both surfaces of the cellulosic membrane. This is advantageous for improving the energy density, electrochemical stability, and safety of the aqueous battery.
In some embodiments of the present invention, the thickness of the polymer film buffer layer is 5 to 500 μm. This is advantageous for improving the energy density and electrochemical stability of the aqueous battery.
In some embodiments of the invention, the polymeric film buffer layer comprises at least one of PAM, CMC, HPMC, PVA, PEG, PAA and PAAs. This contributes to improvement in energy density and electrochemical stability of the aqueous battery.
In some embodiments of the present invention, the cellulose film has a thickness of 5 to 500. mu.m. This is advantageous for improving the energy density and safety of the aqueous battery.
In some embodiments of the invention, the cellulose membrane has a pore diameter of 1 to 10 nm. Therefore, the longitudinal growth of zinc ions can be effectively shielded, the negative metal dendrite is prevented from penetrating through the diaphragm to cause short circuit, and the safety of the water-based battery is improved.
In a second aspect of the present invention, the present invention proposes a method for producing the above-described water-based battery composite separator. According to an embodiment of the invention, the method comprises:
(1) mixing a water-soluble polymer with water to obtain a water-soluble polymer solution;
(2) applying the water-soluble polymer solution on one side surface of the substrate, drying and then peeling off to obtain a polymer film buffer layer;
(3) and laminating the polymer film buffer layer on a cellulose film so as to obtain the water-based battery composite diaphragm.
According to the method for preparing the above-mentioned water-based battery composite separator of the embodiment of the present invention, the water-soluble polymer is first mixed with water to dissolve the water-soluble polymer in the water, and then the resulting water-soluble polymer solution is applied to one surface of the substrate, dried and peeled off to obtain the polymer film buffer layer, and finally the polymer film buffer layer is laminated on the cellulose film, thereby obtaining the water-based battery composite separator. Electrolyte cannot be stored in pores of the cellulose membrane, and zinc ions are difficult to enrich longitudinally, so that longitudinal growth of the zinc ions can be effectively shielded, and short circuit caused by penetration of negative metal dendrites through the membrane is prevented; simultaneously through set up the polymer film buffer layer on the cellulose membrane, because the plumpness of polymer film buffer layer is better, can make electrolyte dispersion even, avoid the local deposit that local concentration too high leads to, can effectively solve the inhomogeneous phenomenon of electrolyte distribution between electrode and the diaphragm interface, and the polymer film buffer layer can also reduce interfacial impedance to be favorable to the promotion of electrochemistry stability. In addition, the cellulose membrane and the polymer membrane buffer layer can both realize thinner thickness, which is beneficial to the promotion of the energy density of the battery. In conclusion, the composite diaphragm prepared by the method can realize a thinner thickness, has good wettability, and can effectively inhibit dendritic crystals, thereby being beneficial to the improvement of the energy density, the electrochemical stability and the safety of a water system battery.
In addition, the method for manufacturing the above-described water-based battery composite separator according to the above-described embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, in the step (1), the water-soluble polymer solution contains 1 to 25% by mass of the water-soluble polymer. This is advantageous for improving the energy density and electrochemical stability of the aqueous battery.
In some embodiments of the invention, the water soluble polymer comprises at least one of PAM, CMC, HPMC, PVA, PEG, PAA and PAAs. This contributes to improvement in electrochemical stability of the aqueous battery.
In some embodiments of the invention, step (3) further comprises: the polymer film buffer layer is laminated on one side or both side surfaces of the cellulose film to obtain a water-based battery composite separator. This is advantageous for improving the energy density, electrochemical stability, and safety of the aqueous battery.
In some embodiments of the present invention, the lamination is press-fitting. This is advantageous for improving the energy density, electrochemical stability, and safety of the aqueous battery.
In a third aspect of the present invention, an aqueous battery is provided. According to the embodiment of the invention, the battery comprises a positive electrode, a negative electrode, electrolyte and a diaphragm, wherein the diaphragm comprises the composite diaphragm or the composite diaphragm prepared by the method, and at least one polymer film buffer layer is arranged on one side of the composite diaphragm, which is close to the positive electrode. Thus, the aqueous battery has high energy density, electrochemical stability and safety.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic structural view of a water-based battery composite separator according to one embodiment of the invention;
fig. 2 is a schematic structural view of a water-based battery composite separator according to still another embodiment of the invention;
fig. 3 is a schematic flow chart of a method for preparing the above-described water-based battery composite separator according to an embodiment of the present invention;
fig. 4 is a graph comparing the cycle performance of the assembled batteries of example 1 and comparative example 1.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "transverse," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, but are not intended to indicate or imply that the device or element so referred to must have a particular orientation, be constructed and operated in a particular orientation, and are not to be construed as limiting the invention.
In a first aspect of the present invention, a water-based battery composite separator is provided. According to an embodiment of the present invention, referring to fig. 1, the composite membrane includes: cellulose membrane 100 and polymer film buffer layer 200, polymer film buffer layer 200 is established on cellulose membrane 100.
The inventor finds that the cellulose membrane and the polymer membrane buffer layer can both realize thinner thickness, which is beneficial to the improvement of the energy density of the battery, wherein, electrolyte cannot be stored in the pores of the cellulose membrane, and zinc ions are difficult to enrich longitudinally, thereby effectively shielding the longitudinal growth of the zinc ions and preventing the negative metal dendrite from penetrating the diaphragm to cause short circuit; simultaneously through set up the polymer film buffer layer on the cellulose membrane, because the plumpness of polymer film buffer layer is better, can make electrolyte dispersion even, avoid the local deposit that local concentration too high leads to, can effectively solve the inhomogeneous phenomenon of electrolyte distribution between electrode and the diaphragm interface, and the polymer film buffer layer can also reduce interfacial impedance to be favorable to the promotion of electrochemistry stability. In conclusion, the composite diaphragm can achieve a small thickness, has good wettability, and can effectively inhibit dendritic crystals, thereby being beneficial to the improvement of the energy density, the electrochemical stability and the safety of the water system battery.
According to some embodiments of the present invention, the polymer film buffer layer 200 is disposed on one side (FIG. 1) or both sides (FIG. 2) of the cellulose film 100, and the cellulose film 100 has a thickness of 5 to 500 μm and a pore diameter of 1 to 10 nm. The inventor finds that electrolyte cannot be stored in the cellulose membrane with the pores, and zinc ions are difficult to enrich longitudinally, so that longitudinal growth of the zinc ions can be effectively shielded, and short circuit caused by penetration of negative metal dendrites through the membrane can be prevented. Meanwhile, the thickness of the polymer film buffer layer 200 is 5 to 500 μm. The inventor finds that if the thickness of the polymer film buffer layer is too small, the polymer film buffer layer cannot contain enough electrolyte, so that the local transfer of metal cations is not uniform, the effect of reducing the interfacial resistance is not obvious, and the electrochemical stability of the battery cannot be effectively improved; if the thickness of the polymer film buffer layer is too large, the ionic conductivity of the diaphragm is increased, the internal resistance of the battery is increased, and the capacity exertion is influenced. Therefore, by adopting the thickness of the polymer film buffer layer, the phenomenon of uneven distribution of electrolyte between the electrode and the diaphragm interface can be effectively solved, the electrochemical stability of the water system battery is improved, and the capacity is ensured to be exerted. It should be noted that the specific type of the polymer film buffer layer can be selected by those skilled in the art according to actual needs, for example, the polymer film buffer layer includes at least one of PAM, CMC, HPMC, PVA, PEG, PAA, and PAAs.
In a second aspect of the present invention, the present invention proposes a method for producing the above-described water-based battery composite separator. According to an embodiment of the invention, referring to fig. 3, the method comprises:
s100: mixing water-soluble polymer with water
In this step, the water-soluble polymer is completely dissolved in water by stirring and mixing the water-soluble polymer with water to obtain a water-soluble polymer solution. Specifically, the mixing process is carried out at 50-80 ℃. The inventors found that if the mixing temperature is too low, the water-soluble polymer is difficult to dissolve; if the mixing temperature is too high, the energy consumption is increased. Further, the mass fraction of the water-soluble polymer in the water-soluble polymer solution is 1 to 25%. It should be noted that the specific type of the above water-soluble polymer is not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the water-soluble polymer includes at least one of PAM, CMC, HPMC, PVA, PEG, PAA, and PAAs.
S200: applying a water-soluble polymer solution on one surface of the substrate, drying, and peeling
In this step, the water-soluble polymer solution obtained in step S100 is applied to one surface of the substrate, dried, and then peeled off to obtain the polymer film buffer layer. It should be noted that the specific type of the substrate is not particularly limited, and those skilled in the art can select the substrate according to actual needs, for example, the substrate may include at least one of plastic and glass. In addition, the specific application manner and the specific drying manner of the water-soluble polymer solution are conventional in the art, and are not described herein again.
S300: laminating a buffer layer of polymer film on the cellulose film
In this step, the polymer film buffer layer obtained in step S200 is laminated on the cellulose film, whereby the aqueous battery composite separator can be obtained. Specifically, the polymer film buffer layer is laminated on one side or both sides of the cellulose film to obtain the water-based battery composite diaphragm. In addition, the above-mentioned lamination mode can be that the macromolecule membrane buffer layer and the cellulose membrane are simply laminated together, or the macromolecule membrane buffer layer and the cellulose membrane are pressed together by applying a certain pressure. It should be noted that the specific thicknesses of the cellulose film and the polymer film buffer layer are the same as those described above, and are not described herein again.
The inventors have found that a composite separator for an aqueous battery can be obtained by mixing a water-soluble polymer with water to dissolve the water-soluble polymer in water, applying the resulting water-soluble polymer solution to one surface of a substrate, drying the solution, peeling the dried solution to obtain a polymer film buffer layer, and laminating the polymer film buffer layer on a cellulose film. Electrolyte cannot be stored in pores of the cellulose membrane, and zinc ions are difficult to enrich longitudinally, so that longitudinal growth of the zinc ions can be effectively shielded, and short circuit caused by penetration of negative metal dendrites through the membrane is prevented; simultaneously through set up the polymer film buffer layer on the cellulose membrane, because the plumpness of polymer film buffer layer is better, can make electrolyte dispersion even, avoid the local deposit that local concentration too high leads to, can effectively solve the inhomogeneous phenomenon of electrolyte distribution between electrode and the diaphragm interface, and the polymer film buffer layer can also reduce interfacial impedance to be favorable to the promotion of electrochemistry stability. In addition, the cellulose membrane and the polymer membrane buffer layer can both realize thinner thickness, which is beneficial to the improvement of the energy density of the battery. In conclusion, the composite diaphragm prepared by the method can realize a thinner thickness, has good wettability, and can effectively inhibit dendritic crystals, thereby being beneficial to the improvement of the energy density, the electrochemical stability and the safety of a water system battery.
In a third aspect of the present invention, an aqueous battery is provided. According to the embodiment of the invention, the battery comprises a positive electrode, a negative electrode, electrolyte and a diaphragm, wherein the diaphragm comprises the composite diaphragm or the composite diaphragm prepared by the method, and at least one polymer film buffer layer is arranged on one side of the composite diaphragm, which is close to the positive electrode. Specifically, only one side of the cellulose membrane is provided with a polymer membrane buffer layer, and the polymer membrane buffer layer is arranged on one side of the cellulose membrane close to the anode; or polymer film buffer layers are arranged on both sides of the cellulose film. The inventor finds that the polymer film buffer layer close to the positive electrode has a much more remarkable effect on improving the electrochemical performance of the battery than the polymer film buffer layer close to the negative electrode. Thus, the aqueous battery has high energy density, electrochemical stability and safety.
It should be noted that the specific types of the positive electrode, the negative electrode, and the electrolyte of the water-based battery and the specific assembly manner of the battery are conventional in the art, and the features and advantages described above for the water-based battery composite separator and the preparation method thereof are also applicable to the water-based battery, and are not described herein again.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
Step 1: mixing a water-soluble polymer PAM with deionized water according to a certain proportion, heating to 80 ℃, and stirring until the PAM is completely dissolved to obtain a water-soluble polymer solution (the mass fraction of the PAM is 2%);
step 2: coating the water-soluble polymer solution on a smooth and flat PET plastic plate, drying at room temperature for 12h, and stripping to obtain a polymer film buffer layer (with the thickness of 20 mu m);
and step 3: simply superposing the polymer film buffer layer on the two side surfaces of a cellulose film (the thickness is 15 mu m, and the pore diameter is 10nm) to obtain the water-system battery composite diaphragm;
and 4, step 4: using anodes as MnO2The negative electrode is Zn, and the electrolyte is 1.8M ZnSO4+0.2M MnSO4And the diaphragm is the composite diaphragm prepared above, and is assembled into a 5 Ah-grade battery, and the performance of the composite diaphragm is tested.
Electrical property data: after 10 cycles of activation, the initial gram capacity of the battery is 208mAh/g, after 200 cycles, the capacity is kept at 80% of the initial capacity, and a cycle performance chart is shown in figure 4. After the battery is disassembled, the surface of the negative electrode is smooth, and no obvious dendritic crystal is found.
Example 2
Step 1: mixing a water-soluble polymer HPMC and deionized water according to a certain proportion, heating to 50 ℃, and stirring until the HPMC is completely dissolved to obtain a water-soluble polymer solution (the mass fraction of the HPMC is 4%);
step 2: coating the water-soluble polymer solution on a smooth and flat PET plastic plate, drying at room temperature for 12h, and stripping to obtain a polymer film buffer layer (with the thickness of 50 μm);
and step 3: laminating a polymer membrane buffer layer on one side surface of a cellulose membrane (the thickness is 50 mu m, and the pore diameter is 10nm) to obtain a water-system battery composite diaphragm;
and 4, step 4: using anodes as MnO2The negative electrode is Zn, and the electrolyte is 1.8M ZnSO4+0.2M MnSO4The diaphragm is the composite diaphragm prepared above (the polymer film buffer layer is arranged on the side of the fiber film close to the anode), a 5 Ah-grade battery is assembled, and the performance of the composite diaphragm is tested.
Electrical property data: after 10 cycles of activation, the initial gram capacity of the battery was 205mAh/g, and after 195 cycles, the capacity remained 80% of the initial capacity. After the battery is disassembled, the surface of the negative electrode is smooth, and no obvious dendritic crystal is found.
Example 3
Step 1: mixing water-soluble polymer PAA and deionized water according to a certain proportion, heating to 60 ℃, and stirring until the water-soluble polymer PAA and the deionized water are completely dissolved to obtain a water-soluble polymer solution (the mass fraction of the PAA is 6%);
and 2, step: coating the water-soluble polymer solution on a smooth and flat PET plastic plate, drying at room temperature for 12h, and stripping to obtain a polymer film buffer layer (with the thickness of 200 mu m);
and step 3: laminating a polymer membrane buffer layer on one side surface of a cellulose membrane (the thickness is 100 mu m, and the pore diameter is 10nm) to obtain a water-system battery composite diaphragm;
and 4, step 4: using anodes as MnO2The negative electrode is Zn, and the electrolyte is 1.8M ZnSO4+0.2M MnSO4The diaphragm is the composite diaphragm prepared above (the polymer film buffer layer is arranged on the side of the fiber film close to the anode), a 5 Ah-grade battery is assembled, and the performance of the composite diaphragm is tested.
Electrical property data: after 10 cycles of activation, the initial gram capacity of the battery is 201mAh/g, and after 191 cycles, the capacity is kept to be 80% of the initial capacity. After the battery is disassembled, the surface of the negative electrode is smooth, and no obvious dendritic crystal is found.
Example 4
Step 1: mixing water-soluble polymer CMC and deionized water according to a certain proportion, heating to 65 ℃, and stirring until the CMC is completely dissolved to obtain a water-soluble polymer solution (the mass fraction of the CMC is 8%);
step 2: coating the water-soluble polymer solution on a smooth and flat glass plate, drying for 16h at room temperature, and stripping to obtain a polymer film buffer layer (with the thickness of 20 mu m);
and step 3: laminating a polymer membrane buffer layer on one side surface of a cellulose membrane (the thickness is 250 mu m, and the pore diameter is 10nm) to obtain a water-system battery composite diaphragm;
and 4, step 4: using anodes as MnO2The negative electrode is Zn, and the electrolyte is 1.8M ZnSO4+0.2M MnSO4The diaphragm is the composite diaphragm prepared in the above way (the polymer film buffer layer is arranged on the side, close to the anode, of the fiber film), a 5 Ah-level battery is assembled, and the performance of the composite diaphragm is tested.
Electrical property data: after 10 cycles of activation, the initial gram capacity of the battery was 204mAh/g, and after 192 cycles, the capacity remained 80% of the initial capacity. After the battery is disassembled, the surface of the negative electrode is smooth, and no obvious dendritic crystal is found.
Example 5
Step 1: mixing a water-soluble polymer PVA with deionized water according to a certain proportion, heating to 55 ℃, and stirring until the PVA is completely dissolved to obtain a water-soluble polymer solution (the mass fraction of the PVA is 15%);
step 2: coating the water-soluble polymer solution on a smooth and flat glass plate, drying for 16h at room temperature, and stripping to obtain a polymer film buffer layer (with the thickness of 5 mu m);
and 3, step 3: laminating the polymer membrane buffer layer on one side surface of a cellulose membrane (the thickness is 400 mu m, and the pore diameter is 10nm) to obtain the water-system battery composite diaphragm;
and 4, step 4: using anode being MnO2The negative electrode is Zn, and the electrolyte is 1.8M ZnSO4+0.2M MnSO4The diaphragm is the composite diaphragm prepared above (the polymer film buffer layer is arranged on the side of the fiber film close to the anode), a 5 Ah-grade battery is assembled, and the performance of the composite diaphragm is tested.
Electrical property data: after 10 cycles of activation, the initial gram capacity of the battery was 189mAh/g, and after 190 cycles, the capacity remained 80% of the initial capacity. After the battery is disassembled, the surface of the negative electrode is smooth, and no obvious dendritic crystal is found.
Example 6
Step 1: mixing a water-soluble polymer PEG and deionized water according to a certain proportion, heating to 70 ℃, and stirring until the PEG is completely dissolved to obtain a water-soluble polymer solution (the mass fraction of the PEG is 25%);
step 2: coating the water-soluble polymer solution on a smooth and flat PET plastic plate, drying at room temperature for 12h, and stripping to obtain a polymer film buffer layer (with the thickness of 20 mu m);
and step 3: pressing the polymer membrane buffer layer on the two side surfaces of a cellulose membrane (the thickness is 500 mu m, the pore diameter is 8nm) to obtain the water-system battery composite diaphragm;
and 4, step 4: using anodes as MnO2The negative electrode is Zn, and the electrolyte is 1.8M ZnSO4+0.2M MnSO4And the diaphragm is the composite diaphragm prepared above, and is assembled into a 5 Ah-grade battery, and the performance of the composite diaphragm is tested.
Electrical property data: after 10 cycles of activation, the initial gram capacity of the battery was 184mAh/g, and after 182 cycles, the capacity remained 80% of the initial capacity. After the battery is disassembled, the surface of the negative electrode is smooth, and no obvious dendritic crystal is found.
Example 7
Step 1: mixing a water-soluble polymer PAAS with deionized water according to a certain proportion, heating to 60 ℃, and stirring until the water-soluble polymer PAAS is completely dissolved to obtain a water-soluble polymer solution (the mass fraction of the PAAS is 7%);
step 2: coating the water-soluble polymer solution on a smooth and flat PET plastic plate, drying at room temperature for 18h, and stripping to obtain a polymer film buffer layer (with the thickness of 20 micrometers);
and step 3: pressing the polymer membrane buffer layer on the two side surfaces of a cellulose membrane (the thickness is 15 mu m, and the pore diameter is 5nm) to obtain the water-system battery composite diaphragm;
and 4, step 4: using anodes as MnO2The negative electrode is Zn, and the electrolyte is 1.8M ZnSO4+0.2M MnSO4And the diaphragm is the composite diaphragm prepared above, and is assembled into a 5 Ah-grade battery, and the performance of the composite diaphragm is tested.
Electrical property data: after 10 cycles of activation, the initial gram capacity of the battery was 204mAh/g, and after 197 cycles, the capacity remained 80% of the initial capacity. After the battery is disassembled, the surface of the negative electrode is smooth, and no obvious dendritic crystal is found.
Example 8
Step 1: mixing water-soluble polymer CMC and deionized water according to a certain proportion, heating to 75 ℃, and stirring until the CMC is completely dissolved to obtain a water-soluble polymer solution (the mass fraction of the CMC is 9%);
step 2: coating the water-soluble polymer solution on a smooth and flat glass plate, drying at room temperature for 20h, and stripping to obtain a polymer film buffer layer (with the thickness of 50 μm);
and step 3: pressing the polymer membrane buffer layer on the two side surfaces of a cellulose membrane (the thickness is 250 mu m, and the pore diameter is 10nm) to obtain the water-system battery composite diaphragm;
and 4, step 4: using anodes as MnO2Zn as negative electrode, and 1.8M ZnSO as electrolyte4+0.2M MnSO4And the diaphragm is the composite diaphragm prepared above, and is assembled into a 5 Ah-grade battery, and the performance of the composite diaphragm is tested.
Electrical property data: after 10 cycles of activation, the initial gram capacity of the battery was 203mAh/g, and after 195 cycles, the capacity remained 80% of the initial capacity. After the battery is disassembled, the surface of the negative electrode is smooth, and no obvious dendritic crystal is found.
Comparative example 1
The difference from example 1 was that AGM having a thickness of 0.5mm was used for the separator of the battery, and the rest was the same as example 1.
Electrical property data: after 10 cycles of activation, the initial gram capacity of the battery is 210mAh/g, and after only 85 cycles, the capacity is kept at 80% of the initial capacity, and a cycle performance chart is shown in FIG. 4. After the battery is disassembled, obvious dendrites are found on the surface of the negative electrode, and part of dendrites grow into the AGM.
Comparative example 2
The difference from example 1 was that a nonwoven fabric having a thickness of 0.4mm was used for the separator of the battery, and the rest was the same as example 1.
Electrical property data: after 10 cycles of activation, the initial gram capacity of the battery was 211mAh/g, and after 68 cycles only, the capacity remained 80% of the initial capacity. After the battery is disassembled, obvious dendritic crystals are found on the surface of the negative electrode, and part of the dendritic crystals grow into the non-woven fabric.
Comparative example 3
The difference from example 1 is that a PP film having a thickness of 0.1mm is used for the separator of the battery, and the rest is the same as example 1.
Electrical property data: after 10 cycles of activation, the initial gram capacity of the battery is 168mAh/g, and after 50 cycles, the battery is in short circuit. After the battery is disassembled, obvious dendritic crystals are found on the surface of the negative electrode and penetrate through the PP film.
Comparative example 4
The difference from example 2 is that the separator of the battery uses a cellulose film without a polymer film buffer layer, and the rest is the same as example 2.
Electrical property data: after 10 cycles of activation, the initial gram capacity of the battery was 191mAh/g, and after 145 cycles, the capacity remained 80% of the initial capacity. After the battery is disassembled, the surface of the negative electrode is smooth, and no obvious dendritic crystal is found.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. An aqueous battery composite separator, characterized by comprising: cellulose membrane and polymer film buffer layer, the polymer film buffer layer is established on the cellulose membrane.
2. The water-based battery composite separator according to claim 1, wherein the polymer film buffer layer is located on one or both side surfaces of the cellulose film.
3. The water-based battery composite separator according to claim 1 or 2, wherein the polymer film buffer layer has a thickness of 5 to 500 μm.
4. The water system battery composite separator according to claim 1 or 2, wherein the polymer film buffer layer comprises at least one of PAM, CMC, HPMC, PVA, PEG, PAA, and PAAs.
5. The water-based battery composite separator according to claim 4, wherein the cellulose film has a thickness of 5 to 500 μm.
6. The water-based battery composite separator according to claim 1 or 5, wherein the cellulose membrane has a pore diameter of 1 to 10 nm.
7. A method for producing the water-based battery composite separator according to any one of claims 1 to 6, comprising:
(1) mixing a water-soluble polymer with water to obtain a water-soluble polymer solution;
(2) applying the water-soluble polymer solution on one side surface of the substrate, drying and then peeling off to obtain a polymer film buffer layer;
(3) and laminating the polymer film buffer layer on a cellulose film so as to obtain the water-based battery composite diaphragm.
8. The method according to claim 7, wherein in the step (1), the mass fraction of the water-soluble polymer in the water-soluble polymer solution is 1-25%;
optionally, the water soluble polymer includes at least one of PAM, CMC, HPMC, PVA, PEG, PAA, and PAAs.
9. The method of claim 7, wherein step (3) further comprises: laminating the polymer membrane buffer layer on one side or two side surfaces of the cellulose membrane so as to obtain the water-system battery composite diaphragm;
optionally, the lamination is press-fitting.
10. An aqueous battery comprising a positive electrode, a negative electrode, an electrolyte, and a separator, wherein the separator comprises the composite separator according to any one of claims 1 to 6 or the composite separator produced by the method according to any one of claims 7 to 9, and at least a polymer film buffer layer is provided on the side of the composite separator adjacent to the positive electrode.
CN202210028638.0A 2022-01-11 2022-01-11 Water-based battery composite diaphragm and preparation method and application thereof Pending CN114520399A (en)

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Cited By (1)

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WO2023134481A1 (en) * 2022-01-11 2023-07-20 瑞海泊(常州)能源科技有限公司 Composite separator for aqueous battery, preparation method therefor, and application thereof

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CN108550767A (en) * 2018-04-28 2018-09-18 丹阳克帕斯特能源科技有限公司 A kind of zinc load battery diagram modification method
CN110350214B (en) * 2019-07-11 2021-02-02 佛山市金辉高科光电材料股份有限公司 Zinc-air battery diaphragm and preparation method thereof
CN114520399A (en) * 2022-01-11 2022-05-20 陈璞 Water-based battery composite diaphragm and preparation method and application thereof

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WO2023134481A1 (en) * 2022-01-11 2023-07-20 瑞海泊(常州)能源科技有限公司 Composite separator for aqueous battery, preparation method therefor, and application thereof

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