CN114709556B - Zinc ion battery diaphragm capable of inhibiting dendrite growth and preparation method thereof - Google Patents
Zinc ion battery diaphragm capable of inhibiting dendrite growth and preparation method thereof Download PDFInfo
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- CN114709556B CN114709556B CN202210436654.3A CN202210436654A CN114709556B CN 114709556 B CN114709556 B CN 114709556B CN 202210436654 A CN202210436654 A CN 202210436654A CN 114709556 B CN114709556 B CN 114709556B
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 210000001787 dendrite Anatomy 0.000 title claims abstract description 27
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 152
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 107
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000725 suspension Substances 0.000 claims abstract description 16
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000007710 freezing Methods 0.000 claims abstract description 7
- 230000008014 freezing Effects 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 5
- 239000011701 zinc Substances 0.000 description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 20
- 229910052725 zinc Inorganic materials 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000006185 dispersion Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 206010016807 Fluid retention Diseases 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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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
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a zinc ion battery diaphragm for inhibiting dendrite growth and a preparation method thereof. Firstly, mixing a solution of nano cellulose with sulfuric acid and potassium permanganate at 80-100 ℃ for continuous reaction to obtain nano cellulose/manganese dioxide suspension; filtering, washing and precipitating the nano cellulose/manganese dioxide suspension to obtain a nano cellulose/manganese dioxide film; finally, freezing the obtained nanocellulose/manganese dioxide film, and then vacuum freeze-drying to obtain the nanocellulose/manganese dioxide film, namely the zinc ion battery diaphragm for inhibiting dendrite growth. The battery diaphragm prepared by the invention can effectively inhibit the growth of dendrites of the zinc ion battery, and greatly prolongs the service life of the battery.
Description
Technical Field
The invention belongs to the field of new energy materials and electrochemistry, relates to a preparation method of a water-based zinc ion battery diaphragm material, and in particular relates to a zinc ion battery diaphragm for inhibiting zinc dendrites and a preparation method thereof.
Background
The wide application of lithium batteries brings great convenience to our lives, but the safety and environmental protection problems of lithium batteries are increasingly prominent. The zinc cathode has the advantages of high theoretical capacity (820 mAh/g and 5855mAh/cm 3), low oxidation-reduction potential (-0.76V vs. SHE), low cost, good safety and the like, so that the water-based zinc ion battery is regarded as one of ideal energy storage battery systems. The negative electrode of the battery adopts zinc metal which can generate two electron transfer reactions in neutral water-based electrolyte, so that higher storage energy can be provided for the battery; compared with the traditional alkaline electrolyte, the neutral water-based electrolyte has better environmental protection property, in particular better reversibility. However, in addition to the problems of self-discharge, hydrogen evolution and the like of the zinc cathode, the battery mainly generates zinc dendrites, namely dendritic zinc precipitates, in the charge-discharge cycle process, and the dendritic precipitates can sometimes puncture a diaphragm to cause internal short circuit of the battery, so that the service life of the battery is prolonged.
In order to prevent dendrites from penetrating through the diaphragm, a glass fiber membrane is mainly adopted in the industry at present, so that the penetration of dendrites can be effectively prevented, but the glass fiber membrane has low mechanical strength, does not have the function of preventing dendrites from generating, and has low water retention capacity, so that the longer service life of the zinc ion battery is not facilitated to be maintained. At present, people mainly focus on modifying a glass fiber membrane and a Nafion membrane to improve the strength and water retention of the glass fiber membrane and the Nafion membrane, but doing so improves the cost and the process complexity and weakens the advantages of the zinc ion battery.
It would be desirable to develop a separator for zinc ion batteries that is resistant to dendrite formation, puncture-resistant, and relatively inexpensive.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a dendrite inhibition diaphragm for a zinc ion battery and a preparation method thereof. The separator can effectively prevent dendrite formation of the zinc electrode in the charging process, prevent the separator from penetrating, and reduce internal short circuit and failure of the battery caused by the dendrite formation.
Through a great deal of experimental research, the manganese dioxide can induce zinc to be uniformly deposited, so that zinc dendrite formation and growth are inhibited. The nano cellulose has better mechanical strength, and the macroscopically compact nano cellulose film has good hydrophilic capability and is not easy to be pierced by dendrites. Based on the two points, we explore a method for growing manganese dioxide on nanocellulose, and a diaphragm for a zinc ion battery for inhibiting zinc dendrite growth is manufactured. The focus is on the growth of manganese dioxide on nanocellulose. The separator is composed of manganese dioxide and nanocellulose. The manganese dioxide is simple to prepare, has stable chemical properties, and is a common anode material of the water-based zinc ion battery. The multivalent manganese oxide has various crystal structures, wherein the manganese dioxide has the most abundant structure, most of the manganese dioxide has a tunnel structure or a layered structure, has good zinc ion transmission capacity and ion adsorption capacity, can regulate and control the internal transmission behavior of Zn 2+, can promote zinc deposition, and can promote the overall electrochemical performance of the battery. However, manganese dioxide and its product materials are difficult to uniformly disperse in the liquid phase during actual operation. The nanocellulose has low cost, reproducibility, good mechanical properties and excellent hydrophilicity, can realize good dispersion in a liquid phase, and is also a material with good mechanical properties and heat conduction properties. By the method of growing manganese dioxide on the nanocellulose, the nanocellulose/manganese dioxide composite material can be prepared, and the nanocellulose can automatically form a film after undergoing a dehydration process, so that a novel nanocellulose/manganese dioxide diaphragm can be prepared and used in the field of batteries. Based on the above thought, the present invention has been completed.
The invention provides a preparation method of a zinc ion battery diaphragm for inhibiting dendrite growth, which comprises the following steps:
step one, mixing a solution of nanocellulose with sulfuric acid and potassium permanganate at 80-100 ℃ for continuous reaction to obtain nanocellulose/manganese dioxide suspension;
step two, filtering and washing the nano cellulose/manganese dioxide suspension, and precipitating to obtain a nano cellulose/manganese dioxide film;
And thirdly, freezing the obtained nanocellulose/manganese dioxide film, and then vacuum freeze-drying to obtain the nanocellulose/manganese dioxide film, namely the zinc ion battery diaphragm for inhibiting dendrite growth.
Wherein, in the step one, the concentration of the nanocellulose in the solution of nanocellulose is (0.1+/-0.05)% g/mL; the mass ratio of the nanocellulose to the potassium permanganate is (1-3): 1, preferably (2.5 to 3): the mass concentration of sulfuric acid in the solution 1 is 0.05wt percent to 0.1wt percent. The proper concentration of the nanocellulose can provide good reaction sites for the reaction of sulfuric acid and potassium permanganate, reduce reaction kinetic obstruction and promote the original synthesis of manganese dioxide on the nanocellulose; in the reaction raw materials, potassium permanganate has strong oxidizing property, and sulfuric acid is an acid with strong corrosiveness, so that the upper concentration limit of sulfuric acid and potassium permanganate in a reaction system needs to be strictly controlled, the target manganese dioxide is obtained, meanwhile, the performance damage caused by strong oxidizing effect and strong acid effect on a nanocellulose diaphragm substrate is avoided, and meanwhile, the proportion and the total addition amount of the potassium permanganate and the potassium permanganate also need to be controlled so as to obtain a sufficient manganese dioxide product.
Wherein in the first step, the duration of the reaction is 40-60 minutes. The optimized reaction time can fully complete the reaction to obtain manganese dioxide, and meanwhile, the bad defects of unstable dispersion, agglomeration and the like of the nano cellulose solution caused by overlong reaction time are avoided.
In the third step, the freeze drying temperature is-40 to-20 ℃, and the vacuum degree is lower than 300Pa, so that the stability of the nanocellulose/manganese dioxide film in the drying process is facilitated, and the defects of excessive shrinkage, manganese dioxide desorption and the like are avoided.
In the third step, the freeze drying time is 24-48 hours.
Compared with the prior art, the invention has the following advantages:
1. the raw materials used in the invention have low price and no pollution, the preparation process does not generate pollution, and the preparation process is simple.
2. In the nano cellulose/manganese dioxide film prepared by the invention, the raw material of the nano cellulose can be wood pulp, is environment-friendly and renewable, has high tensile strength and excellent water retention capacity, can be used as a zinc ion battery diaphragm material to physically inhibit the growth of zinc dendrites, and can improve the cycle life of a zinc cathode; the manganese dioxide has good zinc ion transmission capability and ion adsorption capability, can regulate and control the internal transmission behavior of Zn 2+, and can promote zinc deposition; the nanocellulose/manganese dioxide film has the advantages of high mechanical strength, high porosity, strong water retention capacity and the like, and can improve the overall electrochemical performance of the water-based zinc ion battery.
Drawings
The technical scheme of the embodiment of the invention is further described in detail through the drawings and the embodiments.
FIG. 1 shows nanocellulose/manganese dioxide suspensions prepared in example (A) and comparative examples 1 (B) and 2 (C);
FIG. 2 is a graph showing the contact angle of the nanocellulose/manganese dioxide film obtained in the example with ZnSO 4 electrolyte;
FIG. 3 is a surface SEM photograph of nanocellulose/manganese dioxide film obtained in the example;
Fig. 4 shows the cycle curve at a current density of 1mA after the nanocellulose/manganese dioxide film (a) obtained in the example was assembled into a zinc symmetrical battery, compared with the nanocellulose separator (B) without manganese dioxide and the common glass fiber separator (C).
FIG. 5 is a comparison of the cycle curve at a current density of 5mA with a nanocellulose separator without manganese dioxide (B) after assembly of the nanocellulose/manganese dioxide film (A) obtained in the example into a zinc symmetrical cell;
FIG. 6 is a comparison of the cycle curve at a current density of 10mA with a nanocellulose separator without manganese dioxide (B) after assembly of the nanocellulose/manganese dioxide film (A) obtained in the example into a zinc symmetrical cell;
fig. 7 is an electrochemical impedance plot of the assembled nanocellulose/manganese dioxide separator cells obtained in the examples versus a conventional fiberglass separator cell.
Detailed Description
The invention is further illustrated by the drawings and the specific examples, which are to be understood as being for the purpose of more detailed description only and are not to be construed as limiting the invention in any way, i.e. not intended to limit the scope of the invention.
The invention is further described below with reference to examples. The following examples are presented only to aid in the understanding of the invention. It should be noted that it will be apparent to those skilled in the art that modifications can be made to the present invention without departing from the principles of the invention, and such modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
1. Examples of the embodiments
Examples
(1) Weighing 0.3g of nanocellulose, adding the nanocellulose into 10mL of deionized water, mechanically stirring for 30min, and uniformly dispersing the nanocellulose to form nanocellulose dispersion liquid;
(2) Adding the nanocellulose dispersion and 300mL of deionized water into a beaker, heating while stirring at 90 DEG C
Adding 0.4-0.6 mL sulfuric acid with concentration of 50wt% (concentration of 0.06-0.1 wt%) and 0.1g potassium permanganate, and keeping water bath at 90 ℃ for 50min to obtain nano cellulose/manganese dioxide suspension;
(3) Filtering and washing the nano cellulose/manganese dioxide suspension to obtain a nano cellulose/manganese dioxide film;
(4) Freezing the obtained nanocellulose/manganese dioxide film at the temperature of minus 40 ℃, and then freeze-drying for 48 hours under the vacuum of 200Pa to obtain the nanocellulose/manganese dioxide diaphragm.
Comparative example 1
(1) Weighing 0.3g of nanocellulose, adding the nanocellulose into 10mL of deionized water, mechanically stirring for 30min, and uniformly dispersing the nanocellulose to form nanocellulose dispersion liquid;
(2) Adding the nanocellulose dispersion and 300mL of deionized water into a beaker, heating while stirring at 95 DEG C
When 0.1mL of sulfuric acid with a concentration of 50wt% (concentration of 0.017 wt%) and 0.1g of potassium permanganate are added, 95 deg.C is maintained
Carrying out water bath for 50 minutes to obtain a nanocellulose/manganese dioxide suspension;
(3) Filtering and washing the nano cellulose/manganese dioxide suspension to obtain a nano cellulose/manganese dioxide film;
(4) Freezing the obtained nanocellulose/manganese dioxide film at the temperature of minus 40 ℃, and then freeze-drying for 48 hours under the vacuum of 200Pa to obtain the nanocellulose/manganese dioxide diaphragm.
Comparative example 2
(1) Weighing 0.3g of nanocellulose, adding the nanocellulose into 10mL of deionized water, mechanically stirring for 30min, and uniformly dispersing the nanocellulose to form nanocellulose dispersion liquid;
(2) Adding the nanocellulose dispersion and 300mL of deionized water into a beaker, heating while stirring at 95 DEG C
When 1mL of sulfuric acid with a concentration of 50wt% (concentration of 0.16 wt%) and 0.10g of potassium permanganate are added, 95 deg.C is maintained
Carrying out water bath for 50 minutes to obtain a nanocellulose/manganese dioxide suspension;
(3) Filtering and washing the nano cellulose/manganese dioxide suspension to obtain a nano cellulose/manganese dioxide film;
(4) Freezing the obtained nanocellulose/manganese dioxide film at the temperature of minus 40 ℃, and then freeze-drying for 48 hours under the vacuum of 200Pa to obtain the nanocellulose/manganese dioxide diaphragm.
Comparative example 3
(1) Weighing 0.3g of nanocellulose, adding the nanocellulose into 10mL of deionized water, mechanically stirring for 30min, and uniformly dispersing the nanocellulose to form nanocellulose dispersion liquid;
(2) Adding the nanocellulose dispersion liquid and 300mL of deionized water into a beaker, heating and stirring the mixture, and carrying out water bath at 90 ℃ for 50 minutes to obtain the nanocellulose suspension liquid;
(3) Filtering and washing the nano cellulose suspension to obtain a nano cellulose film;
(4) Freezing the obtained nanocellulose/manganese dioxide film at the temperature of minus 40 ℃, and then freeze-drying for 48 hours under the vacuum of 200Pa to obtain the nanocellulose diaphragm.
2. Results and characterization
FIG. 1 shows nanocellulose/manganese dioxide suspensions prepared in example (A) and comparative examples 1 (B) and 2 (C), from which it can be seen that the products of comparative examples 1 (B) and 2 (C) appear purplish red, and that the product obtained in example (A) is a turkish manganese dioxide. It is indicated that too much or too little sulfuric acid is detrimental to potassium permanganate growth of manganese dioxide on nanocellulose.
FIG. 2 shows that the nanocellulose/manganese dioxide membrane prepared in the example has good hydrophilicity and good ion adsorption capacity, and has a contact angle to a mixed solution of 2mol/L ZnSO 4 and 0.2mol/L MnSO 4.
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of the surface and cross section of a nanocellulose/manganese dioxide separator prepared in the example, and it can be seen that MnO 2 uniformly grows on the nanocellulose surface.
Nanocellulose/manganese dioxide separator performance test: the separator obtained after vacuum drying was cut into a wafer having a diameter of about 16mm, and the wafer was used as a separator for an aqueous zinc ion battery. Taking 2mol/L ZnSO 4 and 0.2mol/L MnSO 4 solution as electrolyte for testing, one drop of electrolyte is added to the surface of the nano-cellulose/manganese dioxide diaphragm, and an image of the electrolyte falling on the surface of the diaphragm is acquired; a zinc foil with the thickness of 0.1mm is used as a positive electrode and a negative electrode of the symmetrical battery, and 2mol/L ZnSO 4 and 0.2mol/L MnSO 4 solution are used as electrolyte for testing, so that the 2032 button battery is assembled. Constant current charge and discharge tests were carried out using a New Williams BTS7.6 battery test system with a current density of 1mAh cm -2 and a specific capacity of 1mAh cm -2.
Fig. 4 is a charge-discharge cycle curve of a symmetrical battery assembled by using the nanocellulose/manganese dioxide separator (a) prepared in the example at a current density of 1mA cm -2 and a specific capacity of 1mAh cm -2, and it can be seen from the figure that a low polarization voltage is maintained and no short circuit occurs after 800 hours of cycle, while the cycle lives of the battery assembled by the nanocellulose separator (B) without manganese dioxide and the commercially available common glass fiber separator (C) in the comparative example under the same condition are 350h and 85h, respectively, showing that the separator inhibits the growth of zinc dendrite and improves the cycle life of the battery.
Fig. 5 and 6 are graphs showing the effect of manganese dioxide grown on nanocellulose, respectively, after the nanocellulose/manganese dioxide films (5A, 6A) obtained in the examples are assembled into zinc symmetrical cells, when the cycle curves at current densities of 5mA (fig. 5), 10mA (fig. 6) are compared with the nanocellulose separator without manganese dioxide (5B, 6B) of comparative example 3, respectively. It can be seen that at high current densities, nanocellulose/manganese dioxide films can have a significant improvement in battery cycle life.
Fig. 7 is an electrochemical impedance plot of the assembled nanocellulose/manganese dioxide separator cell from the example versus a commercially available common glass fiber separator cell, showing better conductivity of the nanocellulose/manganese dioxide separator of the present invention.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (6)
1. A preparation method of a zinc ion battery diaphragm for inhibiting dendrite growth comprises the following steps:
step one, mixing a solution of nanocellulose with sulfuric acid and potassium permanganate at 80-100 ℃ for continuous reaction to obtain nanocellulose/manganese dioxide suspension;
The mass concentration of sulfuric acid in the solution is 0.05-0.1 wt%;
The mass ratio of the nanocellulose to the potassium permanganate is (1-3): 1, a step of;
the concentration of the nanocellulose in the solution of nanocellulose is (0.1+/-0.05) g/mL;
step two, filtering and washing the nano cellulose/manganese dioxide suspension, and precipitating to obtain a nano cellulose/manganese dioxide film;
And thirdly, freezing the obtained nanocellulose/manganese dioxide film, and then vacuum freeze-drying to obtain the nanocellulose/manganese dioxide film, namely the zinc ion battery diaphragm for inhibiting dendrite growth.
2. The preparation method of the zinc ion battery diaphragm for inhibiting dendrite growth according to claim 1, wherein the mass ratio of the nanocellulose to the potassium permanganate is (2.5-3): 1.
3. The method for preparing a zinc ion battery separator for inhibiting dendrite growth according to claim 1, wherein in the first step, the duration of the reaction is 40 to 60 minutes.
4. The method for preparing a zinc ion battery separator for inhibiting dendrite growth according to claim 1, wherein in the third step, the freeze-drying temperature is-40 to-20 ℃ and the vacuum degree is lower than 300Pa.
5. The method for preparing a zinc ion battery separator for inhibiting dendrite growth according to claim 1, wherein in the third step, the freeze-drying time is 24 to 48 hours.
6. A zinc ion battery separator obtainable by the process of any one of claims 1 to 5.
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| US6099987A (en) * | 1998-07-24 | 2000-08-08 | Battery Technologies Inc. | Cylindrical electrochemical cell with cup seal for separator |
| CN101974848B (en) * | 2010-08-27 | 2012-07-04 | 山东海龙股份有限公司 | Preparation method of cellulose-based ion exchange fiber |
| CN103437147A (en) * | 2013-09-18 | 2013-12-11 | 丛伟国 | Preparation method of cellulose-based ion exchange fibers |
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