CN113270686B - Preparation method of bacterial cellulose-based water-based zinc ion battery diaphragm material - Google Patents

Preparation method of bacterial cellulose-based water-based zinc ion battery diaphragm material Download PDF

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CN113270686B
CN113270686B CN202110573180.2A CN202110573180A CN113270686B CN 113270686 B CN113270686 B CN 113270686B CN 202110573180 A CN202110573180 A CN 202110573180A CN 113270686 B CN113270686 B CN 113270686B
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montmorillonite
bacterial cellulose
ion battery
suspension
zinc ion
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CN113270686A (en
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张乃庆
李欣
张宇
范立双
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Harbin Institute of Technology
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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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Abstract

The invention discloses a preparation method of a bacterial cellulose-based water-based zinc ion battery diaphragm material, which comprises the following steps: 1. adding montmorillonite into deionized water, and mechanically stirring to disperse uniformly; adding small molecular substances into the mixture, stirring the mixture at room temperature, and stripping the montmorillonite to obtain a suspension containing the interlayer montmorillonite; 2. centrifuging the suspension, washing and centrifuging the suspension for multiple times by using deionized water to obtain a lamellar montmorillonite solid precipitate; 3. freeze-drying the sheet montmorillonite solid precipitate to obtain sheet montmorillonite powder; 4. uniformly dispersing the lamellar montmorillonite powder and the bacterial cellulose homogenate in deionized water to obtain a homogeneous suspension; 5. the homogeneous suspension was suction filtered to obtain a wet film and dried in vacuo to obtain an MMT/BC film. The MMT/BC membrane prepared by the invention has the performances of high porosity, excellent mechanical strength, high liquid retention capacity and the like, and can improve the electrochemical performance of a zinc cathode in a water system zinc ion battery.

Description

Preparation method of bacterial cellulose-based water-based zinc ion battery diaphragm material
Technical Field
The invention belongs to the field of new energy materials and electrochemistry, relates to a preparation method of a zinc ion battery diaphragm material, and particularly relates to a preparation method of a bacterial cellulose-based water-based zinc ion battery diaphragm material.
Background
Lithium ion batteries dominate in the fields of portable mobile electronic devices, electric automobiles and the like, but due to the scarcity of lithium resources, safety problems caused by the use of toxic and flammable organic system electrolytes hinder further large-scale application of the lithium ion batteries. The water system zinc ion battery takes metal zinc as a negative electrode, and the zinc has high abundance, high water environment tolerance and high theoretical specific mass capacity (820 mAh g) -1 ）、The lithium ion battery has the advantages of low oxidation-reduction potential (-0.76V vs. SHE) and the like, and is considered as an alternative battery system of the lithium ion battery.
When the metal zinc is used as the negative electrode material of the zinc ion battery, the following three problems mainly exist: uncontrolled zinc dendrite growth, corrosion and hydrogen evolution reactions. Among them, the uncontrolled growth of zinc dendrites is the most widely studied problem. The near-neutral or weakly acidic zinc salt solution as an electrolyte in the water-based zinc ion battery can inhibit the growth of zinc dendrites to a certain extent, but the promotion of uniform deposition/dissolution of zinc is still a challenge. Because the surface of the metal zinc cathode has defects, the thermodynamic dislocation is more favorable for Zn 2+ Nucleation deposition, non-uniform nucleation and growth then lead to the formation of zinc dendrites, resulting in a decline in cell capacity. In addition, the common separator material in aqueous zinc ion batteries is glass fiber, which has poor mechanical strength and is insufficient to maintain its structural integrity during battery assembly and cycling. And the rigid zinc dendrite has high modulus, is easy to pierce through a glass fiber diaphragm and is directly contacted with the anode to cause the internal short circuit of the battery.
At present, researchers mainly aim at modifying the performance of glass fiber and commercial Nafion films in the research of zinc ion battery diaphragm materials, but the cost and the modification process are complex, the cost of the diaphragm materials is increased to a certain extent, and the low-cost advantage of the zinc ion battery is damaged. The bacterial cellulose has the advantages of low cost, reproducibility, high mechanical property, excellent hydrophilicity and the like, and can be used as a substrate material of a zinc ion battery diaphragm to improve the capability of the diaphragm in physically inhibiting the growth of zinc dendrites. And the montmorillonite has metal ion adsorption capacity and can regulate and control Zn 2+ The transmission action in the battery improves the whole electrochemical performance of the battery.
Disclosure of Invention
Aiming at the defects of the diaphragm material of the existing water-based zinc ion battery, the invention provides a preparation method of a diaphragm material of a bacterial cellulose-based water-based zinc ion battery. In the MMT/BC membrane prepared by the method, the bacterial cellulose is low in price, high in mechanical strength and good in liquid retention capacity, and can be kept in good contact with a zinc cathode and physically inhibit the growth of zinc dendrites when being used as a zinc ion battery diaphragm material; while coverThe removed soil can adsorb Zn due to its interlayer negative charge 2+ Thereby regulating Zn 2+ And the transmission in the separator improves the whole electrochemical performance of the battery.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a bacterial cellulose-based water-based zinc ion battery diaphragm material comprises the following steps:
step one, adding montmorillonite into deionized water, and uniformly dispersing through mechanical stirring; then adding small molecular substances into the mixture, stirring the mixture at room temperature, and stripping the montmorillonite to obtain a suspension containing lamellar montmorillonite, wherein: the small molecular substances are glycine, arginine or urea and the like, and the mass ratio of the montmorillonite to the small molecular substances is 4~6: 2~4;
and step two, centrifugally separating the suspension, washing and centrifuging for multiple times by using deionized water to obtain a lamellar montmorillonite solid precipitate, wherein: the rotation speed of the suspension liquid centrifugal separation is 1000 to 8000 rmp/min;
step three, freeze-drying the sheet montmorillonite solid precipitate to obtain sheet montmorillonite powder, wherein: the temperature of freeze drying is-30 to-10 ℃, and the vacuum degree is lower than 200 Pa;
step four, uniformly dispersing the lamellar montmorillonite powder and the bacterial cellulose homogenate in deionized water to obtain a homogeneous suspension, wherein: the mass ratio of the lamellar montmorillonite powder to the bacterial cellulose homogenate is 1 to 15 to 150, and the concentration of the bacterial cellulose homogenate is 1 to 3wt.%;
step five, carrying out suction filtration on the homogeneous suspension obtained in the step four to obtain a wet film, and carrying out vacuum drying to obtain a montmorillonite/bacterial cellulose (MMT/BC) film, wherein: the temperature of vacuum drying is 50 to 80 ℃, and the time is 10 to 15 hours.
Compared with the prior art, the invention has the following advantages:
1. the invention has the advantages of cheap raw materials, no pollution, clean and environment-friendly preparation process and simple synthetic route.
2. In the MMT/BC membrane prepared by the invention, the bacterial cellulose has high tensile strength, high elastic modulus and excellent water holding capacity and is used as a zinc ion battery separatorThe film material can physically inhibit the growth of zinc dendrites and prolong the cycle life of the zinc cathode; montmorillonite interlayer negative charge and can adsorb Zn 2+ Regulation of Zn 2+ Transport inside the membrane; the MMT/BC film has the performances of high porosity, excellent mechanical strength, high liquid retention capacity and the like, and can improve the electrochemical performance of a zinc cathode in a water-based zinc ion battery.
Drawings
FIG. 1 is a surface SEM photograph of the montmorillonite/bacterial cellulose membrane obtained in example 2;
FIG. 2 is a SEM photograph of a cross-section of the montmorillonite/bacterial cellulose membrane obtained in example 2;
FIG. 3 shows the ZnSO pair of montmorillonite/bacterial cellulose membrane obtained in example 2 4 A contact angle of the electrolyte;
FIG. 4 is a cycle curve of the montmorillonite/bacterial cellulose membrane obtained in example 2 as a zinc symmetric cell separator.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Example 1
(1) Weighing 500 mg montmorillonite, adding into 40 mL deionized water, mechanically stirring for 10 min, and uniformly dispersing the montmorillonite; adding 300 mg arginine, magnetically stirring at room temperature for 7 days, and stripping montmorillonite sufficiently to obtain tablet layer montmorillonite suspension;
(2) Centrifuging the mixed suspension containing the lamellar montmorillonite at 4000 rmp/min, washing and centrifuging for multiple times by using deionized water to obtain lamellar montmorillonite solid precipitate;
(3) Freeze-drying the sheet montmorillonite to obtain sheet montmorillonite powder;
(4) Respectively weighing 10 mg lamellar montmorillonite and 1.5 g bacterial cellulose homogenate with the mass concentration of 2 wt%, and uniformly dispersing in deionized water to obtain homogeneous suspension of the montmorillonite and the bacterial cellulose homogenate;
(5) Carrying out vacuum filtration on the homogeneous suspension to obtain an MMT/BC wet film; the MMT/BC wet film was dried under vacuum at 60 ℃ for 12 hours to obtain MMT/BC film.
Example 2
(1) Weighing 500 mg montmorillonite, adding into 40 mL deionized water, mechanically stirring for 10 min, and uniformly dispersing the montmorillonite; adding 300 mg glycine, magnetically stirring at room temperature for 7 days, and stripping montmorillonite sufficiently to obtain suspension containing sheet layer montmorillonite;
(2) Centrifuging the mixed suspension containing the lamellar montmorillonite at 4000 rmp/min, washing and centrifuging for multiple times by using deionized water to obtain lamellar montmorillonite solid precipitate;
(3) Freeze-drying the sheet montmorillonite to obtain sheet montmorillonite powder;
(4) Respectively weighing 20 mg lamellar montmorillonite and 1.5 g bacterial cellulose homogenate with the mass concentration of 2 wt%, and uniformly dispersing in deionized water to obtain a homogeneous suspension of the two;
(5) Carrying out vacuum filtration on the homogeneous suspension to obtain an MMT/BC wet film; the MMT/BC wet film was dried under vacuum at 60 ℃ for 12 hours to obtain MMT/BC film.
Preparing an MMT/BC diaphragm and testing the performance: the dry film obtained after vacuum drying was cut into circular sheets having a diameter of 16 mm, which were used as separators for aqueous zinc-ion batteries. At 3 mol/L ZnSO 4 The solution is used as a test liquid, 2 mu L of the solution is dripped on the surface of the MMT/BC membrane, and the liquid drop form of the liquid dripped on the surface of the diaphragm is collected; takes zinc sheets as positive and negative electrodes and ZnSO of 3 mol/L 4 Is used as electrolyte and is assembled into a button cell. Constant current charge and discharge test is carried out by adopting a Neware battery test system, and the current density is 0.5 mA cm -2 Specific capacity of 0.1 mAh cm -2 。
Fig. 1 and 2 are SEM photographs of the surface and cross-section of the MMT/BC membrane prepared in this example, and it can be seen from the photographs that MMT is uniformly distributed between the surface and the layers of the bacterial cellulose, and the MMT and the bacterial cellulose are uniformly mixed.
FIG. 3 shows the MMT/BC film pair prepared in this example with 3 mol/L ZnSO 4 Contact angle of the solution, M can be seen from the figureThe MT/BC membrane has good hydrophilicity.
FIG. 4 shows the current density of 0.5 mA cm/cm for the MMT/BC membrane assembled symmetrical cell prepared in this example -2 Specific capacity of 0.1 mAh cm -2 The charge-discharge cycle curve below shows that the zinc symmetrical battery can stably cycle for more than 4500 hours.
Example 3
(1) Weighing 500 mg montmorillonite, adding into 40 mL deionized water, mechanically stirring for 10 min, and uniformly dispersing the montmorillonite; adding 300 mg urea, magnetically stirring at room temperature for 7 days, and stripping montmorillonite to obtain suspension containing tablet layer montmorillonite;
(2) Centrifuging the mixed suspension containing the lamellar montmorillonite at 4000 rmp/min, washing and centrifuging for multiple times by using deionized water to obtain lamellar montmorillonite solid precipitate;
(3) Freeze-drying the sheet montmorillonite to obtain sheet montmorillonite powder;
(4) Respectively weighing 50 mg lamellar montmorillonite and 1.5 g bacterial cellulose homogenate with the mass concentration of 2 wt%, and uniformly dispersing in deionized water to obtain homogeneous suspension of the montmorillonite and the bacterial cellulose homogenate;
(5) Carrying out vacuum filtration on the homogeneous suspension to obtain an MMT/BC wet film; the MMT/BC wet film was dried under vacuum at 60 ℃ for 12 hours to obtain MMT/BC film.
Example 4
(1) Weighing 500 mg montmorillonite, adding into 40 mL deionized water, mechanically stirring for 10 min, and uniformly dispersing the montmorillonite; adding 300 mg glycine, magnetically stirring at room temperature for 7 days, and stripping montmorillonite sufficiently to obtain suspension containing sheet layer montmorillonite;
(2) Centrifuging the mixed suspension containing the lamellar montmorillonite at 4000 rmp/min, washing and centrifuging for multiple times by using deionized water to obtain lamellar montmorillonite solid precipitate;
(3) Freeze-drying the sheet montmorillonite to obtain sheet montmorillonite powder;
(4) Respectively weighing 100 mg lamellar montmorillonite and 1.5 g bacterial cellulose homogenate with the mass concentration of 2 wt%, and uniformly dispersing in deionized water to obtain homogeneous suspension of the montmorillonite and the bacterial cellulose homogenate;
(5) Carrying out vacuum filtration on the homogeneous suspension to obtain an MMT/BC wet film; the MMT/BC wet film was dried under vacuum at 60 ℃ for 12 hours to obtain MMT/BC film.
Example 5
(1) Weighing 500 mg montmorillonite, adding into 40 mL deionized water, mechanically stirring for 10 min, and uniformly dispersing the montmorillonite; adding 300 mg urea, magnetically stirring at room temperature for 7 days, and stripping montmorillonite to obtain suspension containing tablet layer montmorillonite;
(2) Centrifuging the mixed suspension containing the lamellar montmorillonite at 1000 rmp/min, washing with deionized water for multiple times, and centrifuging to obtain lamellar montmorillonite solid precipitate;
(3) Freeze-drying the sheet montmorillonite to obtain sheet montmorillonite powder;
(4) Respectively weighing 20 mg lamellar montmorillonite and 1.5 g bacterial cellulose homogenate with the mass concentration of 2 wt%, and uniformly dispersing in deionized water to obtain homogeneous suspension of the two;
(5) Carrying out vacuum filtration on the mixed and homogenized suspension to obtain an MMT/BC wet film; the MMT/BC wet film was dried under vacuum at 60 ℃ for 12 hours to obtain MMT/BC film.
Example 6
(1) Weighing 500 mg montmorillonite, adding into 40 mL deionized water, mechanically stirring for 10 min, and uniformly dispersing the montmorillonite; adding 300 mg arginine, magnetically stirring at room temperature for 7 days, and fully stripping montmorillonite to obtain a tablet layer montmorillonite suspension;
(2) Centrifuging the mixed suspension of the sheet montmorillonite at 8000 rmp/min, washing with deionized water for multiple times, and centrifuging to obtain solid precipitate of the sheet montmorillonite;
(3) Freeze-drying the sheet montmorillonite to obtain sheet montmorillonite powder;
(4) Respectively weighing 20 mg lamellar montmorillonite and 1.5 g bacterial cellulose homogenate with the mass concentration of 2 wt%, and uniformly dispersing in deionized water to obtain homogeneous suspension of the two;
(5) Carrying out vacuum filtration on the mixed and homogenized suspension to obtain an MMT/BC wet film; the MMT/BC wet film was dried under vacuum at 60 ℃ for 12 hours to obtain the MMT/BC film.

Claims (5)

1. A preparation method of a bacterial cellulose-based water-based zinc ion battery diaphragm material is characterized by comprising the following steps:
step one, adding montmorillonite into deionized water, and uniformly dispersing through mechanical stirring; then adding a small molecular substance into the mixture, stirring the mixture at room temperature, and stripping the montmorillonite to obtain a suspension of the montmorillonite in the tablet layer, wherein the small molecular substance is glycine, arginine or urea;
step two, centrifugally separating the suspension, washing and centrifuging for multiple times by using deionized water to obtain a lamellar montmorillonite solid precipitate;
step three, freeze-drying the sheet montmorillonite solid precipitate to obtain sheet montmorillonite powder;
dispersing the lamellar montmorillonite powder and the bacterial cellulose homogenate uniformly in deionized water to obtain a homogeneous suspension, wherein the mass ratio of the lamellar montmorillonite powder to the bacterial cellulose homogenate is 1 to 15-150;
and step five, carrying out suction filtration on the homogeneous suspension obtained in the step four to obtain a wet membrane, and carrying out vacuum drying to obtain the montmorillonite/bacterial cellulose membrane.
2. The preparation method of the bacterial cellulose based water-based zinc ion battery diaphragm material according to claim 1, wherein the mass ratio of the montmorillonite to the small molecular substance is 4~6:2~4.
3. The preparation method of the bacterial cellulose-based water-based zinc ion battery diaphragm material as claimed in claim 1, wherein the rotation speed of centrifugal separation of the suspension is 1000 to 8000 rmp/min.
4. The preparation method of the bacterial cellulose-based water-based zinc ion battery diaphragm material as claimed in claim 1, wherein the concentration of the bacterial cellulose homogenate is 1-3 wt.%.
5. The preparation method of the bacterial cellulose based water-based zinc ion battery diaphragm material as claimed in claim 1, wherein the temperature of vacuum drying is 50 to 80 ℃, and the time is 10 to 15 hours.
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