CN113839144A - Diaphragm for water-based zinc ion battery and preparation method thereof - Google Patents

Diaphragm for water-based zinc ion battery and preparation method thereof Download PDF

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Publication number
CN113839144A
CN113839144A CN202111015944.2A CN202111015944A CN113839144A CN 113839144 A CN113839144 A CN 113839144A CN 202111015944 A CN202111015944 A CN 202111015944A CN 113839144 A CN113839144 A CN 113839144A
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China
Prior art keywords
diaphragm
membrane
zinc
acid
ion battery
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CN202111015944.2A
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Chinese (zh)
Inventor
神领弟
郭静
黎素宏
黄荣
何婧
张雨停
赖超
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Jiangsu Normal University
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Jiangsu Normal 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
    • H01M50/403—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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • 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
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • 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
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/423—Polyamide resins
    • 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
    • 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)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

A diaphragm for a water-based zinc ion battery comprises a commercial diaphragm or a self-made porous base film as a base body, wherein at least one surface of the base body is provided with a gelled high-molecular functional layer. According to the diaphragm for the water-based zinc ion battery, the organic polymer material can be combined with a large number of water molecules after being gelatinized on the substrate to form a communicated three-dimensional network structure, so that the corrosion of a zinc electrode caused by contacting with a water-based electrolyte can be reduced. The organic polymer material rich in functional groups can induce the uniform deposition of zinc ions, thereby effectively inhibiting the growth of zinc dendrites, preventing the diaphragm from being punctured by the dendrites, and improving the electrochemical performance and the cycle life of the water system zinc ion battery. The preparation method is simple, feasible, effective, environment-friendly and suitable for large-scale low-cost production.

Description

Diaphragm for water-based zinc ion battery and preparation method thereof
Technical Field
The invention relates to the technical field of water-system zinc ion batteries, in particular to a diaphragm for a water-system zinc ion battery and a preparation method thereof.
Background
In recent years, zinc ion batteries gradually enter the human vision due to the advantages of high discharge capacity, good cycle performance, rapid charge and discharge, low cost, environmental friendliness, high safety and the like, and have good development prospects in portable electronic equipment and large-scale energy storage. However, in the charging and discharging process, because zinc ions are repeatedly and unevenly deposited and dissolved on the surface of the metal zinc electrode, dendritic deposits can be formed on the surface of the metal zinc electrode, and the dendritic deposits are continuously increased along with the continuous charging and discharging to finally form zinc dendritic crystals, and the dendritic crystals can pierce through the diaphragm, so that the anode and the cathode in the battery are directly contacted, and the short circuit of the battery is caused. At present, the growth of zinc dendrites is one of the most difficult defects to overcome in an aqueous zinc ion battery.
The diaphragm is a vital component in the zinc ion battery, and prevents the direct contact between the positive electrode and the negative electrode of the battery, thereby avoiding thermal explosion caused by short circuit of the battery. Therefore, the performance of the diaphragm (such as mechanical strength, porosity, pore diameter, surface roughness, insulativity, thickness, ionic conductivity, electrolyte wettability and the like) has important influence on the overall performance of the zinc ion battery, so that the design and the regulation of the structure and the performance of the diaphragm are expected to solve the problem of zinc dendrite generation in the operation process of the zinc ion battery.
Disclosure of Invention
The invention aims to provide a diaphragm for a water system zinc ion battery, which takes gel-state functional polymers as an interface and realizes uniform transmission of zinc ions in an electrochemical cycle process, so that the overall performance of the battery is improved, and the problems of high capacity attenuation and short cycle life caused by the generation and pulverization of zinc dendrites in the traditional water system zinc ion battery in the prior art are solved.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a preparation method of a diaphragm for a water-based zinc ion battery comprises the steps of adopting a commercial diaphragm or a self-made porous base film as a substrate, and then preparing a gelled high-molecular functional layer on at least one surface of the substrate.
Further, the commercial membranes include, but are not limited to: glass fibers, perfluorosulfonic acid membranes, polyethylene membranes, polypropylene membranes, non-woven fabrics, and the like; the homemade porous base membrane includes, but is not limited to: electrostatic spinning nanofiber membranes, phase inversion porous membranes, membranes prepared by calendering, tape casting, blow molding, stretching, biaxial stretching and the like.
Further, the polymer materials used for the gelated polymer functional layer include, but are not limited to: polysaccharides and derivatives thereof (starch, cellulose, alginic acid, hyaluronic acid, chitosan, carboxymethyl cellulose, etc.), polypeptides (collagen, gelatin, poly-L-lysine, poly-L-glutamic acid, etc.), polyacrylic acid and derivatives thereof (polyacrylic acid, polymethacrylic acid, polyacrylamide, poly-N-polyacrylamide, etc.), polyethyleneimine, polyvinylamine, polyvinylpyridine, polydimethyldiallylammonium chloride, polyvinylpyrrolidone, polystyrene sulfonate, polyvinylsulfonic acid/salt, polyvinylphosphoric acid/salt, polyphosphate, polysilicic acid.
Further, the preparation method of the gelated polymer functional layer includes but is not limited to: suction filtration, coating, soaking, dipping, self-assembly and the like. Dissolving a functional polymer material (and a cross-linking agent) in water to form a uniform solution, preparing a polymer functional layer on a substrate by adopting the method, airing, soaking in a zinc sulfate solution for a period of time, taking out, and drying in the shade.
Further, the concentration of the solution prepared from the functional polymer material is 0.05 wt% -30 wt%, the concentration of the zinc sulfate solution is 0.1-20mol/L, and the time for soaking the zinc sulfate solution is 1-240 min.
Further, the method for gelling the gelling polymer functional layer includes, but is not limited to: chemical crosslinking and physical crosslinking. Chemical crosslinking is mainly achieved by forming chemical bonds; physical crosslinking is mainly achieved by the curling and winding of macromolecular chains, electrostatic action, hydrogen bonding action, van der waals force, and the like.
The invention also provides the separator for the water-based zinc ion battery prepared by the method.
Compared with the prior art, the invention has the beneficial technical effects that:
in the diaphragm for the water system zinc ion battery, the organic high polymer material can be combined with a large number of water molecules after being gelatinized on the substrate to form a communicated three-dimensional network structure, so that the corrosion of a zinc electrode caused by contacting with water system electrolyte can be reduced; the organic polymer material rich in functional groups can induce the uniform deposition of zinc ions, thereby effectively inhibiting the growth of zinc dendrites, preventing the diaphragm from being punctured by the dendrites, and improving the electrochemical performance and the cycle life of the water system zinc ion battery. The preparation method is simple, feasible, effective, environment-friendly and suitable for large-scale low-cost production.
Drawings
FIG. 1 is an SEM photograph of a Zn-PAA/GF composite membrane in example 1 (a, GF; b, Zn-PAA/GF);
fig. 2 is a graph of cycle times of the button type Zn | GF | Zn half-cell and the button type Zn | Zn-PAA/GF | Zn half-cell obtained in example 1.
FIG. 3 is a graph of cycle times for Zn | Zn-PAA/GF | Zn button half cells and Zn | Zn-PAA/GF | Zn button half cells obtained in example 3.
FIG. 4 is an SEM photograph of the separator obtained in example 5 (a, PES; b, CTS/PES).
FIG. 5 shows the buckled-type Zn PES V obtained in example 52O5Full cell and button type Zn (CTS)/PES (PES) V2O5Full cell at 2A g-1Long cycle performance of time。
Detailed Description
The present invention will be further illustrated with reference to the following examples.
Example 1
A preparation method of a zinc polyacrylate (Zn-PAA)/Glass Fiber (GF) composite diaphragm comprises the following steps:
1. sodium polyacrylate is dissolved in deionized water to prepare a uniform solution with the mass fraction of 0.1%.
2. Soaking a commercial glass fiber membrane in a zinc sulfate solution of 2mol/L, and airing until no obvious water drops exist on the surface.
3. And coating the prepared sodium polyacrylate solution on the surface of the glass fiber, controlling the thickness of the sodium polyacrylate by a scraper, and then airing.
4. And soaking the dried composite membrane in 2mol/L zinc sulfate solution for 1h to obtain the zinc polyacrylate/glass fiber composite membrane, wherein the structure of the zinc polyacrylate/glass fiber composite membrane is shown in figure 1.
5. Assembling the obtained glass fiber into a button Zn | GF | Zn half cell, assembling a Zn-PAA/GF diaphragm into a button Zn | Zn-PAA/GF | Zn half cell, and then using a zinc sulfate solution of 2mol/L as an electrolyte at 1m A/cm2The coulombic efficiency and the cycle number of the half-cell are tested under the current density, the test curve is shown in fig. 2, the Zn | Zn-PAA/GF | Zn half-cell shows good reversible performance, the final cycle fails for 430h, the final coulombic efficiency is 99.6%, and the Zn | GF | Zn half-cell fails after 13h of cycle (dendrites penetrate through a diaphragm and short circuit occurs).
Example 2
The method for preparing the Zn-PAA/GF membrane differs from example 1 in that a PAA concentration of 0.05 wt% is obtained, the final cycle of the assembled button Zn | Zn-PAA/GF | Zn half-cell is 98h failed, and the final coulombic efficiency is 98.8%.
Example 3
The method of preparing Zn-PAA/GF membrane differs from example 1 in that a PAA concentration of 0.2 wt% is obtained, assembled as a button Zn | Zn-PAA/GF | Zn half-cell with a final cycle of 330h failure as shown in fig. 3, and a final coulombic efficiency of 99.1%.
Example 4
The method of preparing the separator differs from example 1 in that the use of Sodium Alginate (SA) instead of PAA was obtained, the assembly shown being a button Zn | Zn-SA/GF | Zn half-cell with a final cycle of 352h failure and a final coulombic efficiency of 99.2%.
Example 5
A preparation method of a Chitosan (CTS)/polyether sulfone (PES) nanofiber membrane comprises the following steps:
1. dissolving polyether sulfone in an N, N-dimethylacetamide solvent to prepare a 25 wt% solution, preparing nanofibers through an electrostatic spinning mode, and obtaining a PES nanofiber base membrane after cold pressing.
2. Dissolving chitosan in 1 wt% acetic acid water solution to prepare solution with mass fraction of 1%.
3. And (3) coating the chitosan solution on one surface of the PES nanofiber basement membrane by adopting a dip coating method, and airing.
4. And soaking the surface of the CTS/PES composite membrane in 1mol/L zinc sulfate solution for two minutes, and then airing.
5. Repeating the steps for 3-4 times to obtain the CTS/PES nanofiber membrane, wherein the appearance of the CTS/PES nanofiber membrane is shown in figure 4.
6. Assembling the obtained PES nano-fibers into Zn PES V2O5The whole battery is assembled by a CTS/PES diaphragm into a button type Zn/PES V2O5The full cell is tested for the cycle performance under the current density of 2A/g by taking a zinc sulfate solution of 2mol/L as an electrolyte, the test curve is shown in figure 5, and Zn (CTS)/PES (V)2O5The full cell shows good cycle performance, the capacity is still maintained at a higher level after 400 cycles of cycle, and the capacity is far higher than Zn PES V2O5And (4) full cell.

Claims (8)

1. A method for producing a separator for an aqueous zinc-ion battery, comprising: a commercial diaphragm or a self-made porous base membrane is used as a matrix, and a gelled high-molecular functional layer is prepared on at least one surface of the matrix.
2. The method of claim 1, wherein the commercial membrane is a glass fiber, a perfluorosulfonic acid membrane, a polyethylene membrane, a polypropylene membrane, or a nonwoven fabric; the self-made porous base membrane is an electrostatic spinning nanofiber membrane or a phase-inversion porous membrane, or a membrane prepared by a calendering method, a tape casting method, a blow molding method, a stretching method or a biaxial stretching method.
3. The method according to claim 1, wherein the polymer material for the functional gelling polymer layer is at least one of polysaccharides and derivatives thereof, polypeptides, polyacrylic acid and derivatives thereof, polyethyleneimine, polyvinylamine, polyvinylpyridine, polydimethyldiallylammonium chloride, polyvinylpyrrolidone, polystyrene sulfonate, polyvinyl sulfonic acid, polyvinyl phosphoric acid, polyphosphate, and polysilicic acid; the polysaccharide and its derivatives are starch, cellulose, alginic acid, hyaluronic acid, chitosan or carboxymethyl cellulose; the polypeptide is collagen, gelatin, poly-L-lysine or poly-L-glutamic acid; the polyacrylic acid and the derivatives thereof are polyacrylic acid, polymethacrylic acid, polyacrylamide or poly-N-polyacrylamide.
4. The method according to claim 1, wherein the method for preparing the gelled polymeric functional layer is suction filtration, coating, dipping, or self-assembly.
5. The method of claim 4, wherein the method of preparing the gelled polymeric functional layer comprises: dissolving a functional polymer material and a cross-linking agent in water to form a uniform solution, then preparing a polymer functional layer on a substrate in a suction filtration, coating, soaking, dipping or self-assembly mode, soaking the substrate in a zinc sulfate solution for a period of time after the substrate is dried, and then taking out and drying in the shade to obtain the diaphragm for the water system zinc ion battery.
6. The method according to claim 4, wherein the functional polymer material is prepared in a solution concentration of 0.05 wt% to 30 wt%, the zinc sulfate solution concentration is 0.1 mol/L to 20mol/L, and the zinc sulfate solution soaking time is 1 min to 240 min.
7. The method according to claim 1, wherein the method for gelling the functional layer of gelled polymer is chemical crosslinking or physical crosslinking.
8. A separator for an aqueous zinc-ion battery produced by the method according to any one of claims 1 to 7.
CN202111015944.2A 2021-08-31 2021-08-31 Diaphragm for water-based zinc ion battery and preparation method thereof Withdrawn CN113839144A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114709554A (en) * 2022-03-31 2022-07-05 西北工业大学 Ion battery functionalized textile cotton cloth diaphragm and preparation method and application thereof
CN115275513A (en) * 2022-07-05 2022-11-01 天津工业大学 Polyamide 6 non-woven fabric battery diaphragm for zinc ion battery and preparation method thereof
CN116014164A (en) * 2023-02-10 2023-04-25 温州锌时代能源有限公司 Zinc-bromine flow battery diaphragm and preparation method thereof
CN117477168A (en) * 2023-12-26 2024-01-30 新乡华锐锂电新能源股份有限公司 Isolation film for sodium ion battery and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114709554A (en) * 2022-03-31 2022-07-05 西北工业大学 Ion battery functionalized textile cotton cloth diaphragm and preparation method and application thereof
CN115275513A (en) * 2022-07-05 2022-11-01 天津工业大学 Polyamide 6 non-woven fabric battery diaphragm for zinc ion battery and preparation method thereof
CN116014164A (en) * 2023-02-10 2023-04-25 温州锌时代能源有限公司 Zinc-bromine flow battery diaphragm and preparation method thereof
CN117477168A (en) * 2023-12-26 2024-01-30 新乡华锐锂电新能源股份有限公司 Isolation film for sodium ion battery and preparation method thereof
CN117477168B (en) * 2023-12-26 2024-03-08 新乡华锐锂电新能源股份有限公司 Isolation film for sodium ion battery and preparation method thereof

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