CN112349893A - Method for inhibiting growth of zinc dendrite by polydopamine film - Google Patents
Method for inhibiting growth of zinc dendrite by polydopamine film Download PDFInfo
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- CN112349893A CN112349893A CN202011030473.8A CN202011030473A CN112349893A CN 112349893 A CN112349893 A CN 112349893A CN 202011030473 A CN202011030473 A CN 202011030473A CN 112349893 A CN112349893 A CN 112349893A
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000011701 zinc Substances 0.000 title claims abstract description 66
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 64
- 229920001690 polydopamine Polymers 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 20
- 210000001787 dendrite Anatomy 0.000 title claims abstract description 12
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 8
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229960003638 dopamine Drugs 0.000 claims abstract description 20
- 238000002791 soaking Methods 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 9
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 8
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007853 buffer solution Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 2
- -1 dopamine modified zinc foil Chemical class 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000005457 optimization Methods 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000011241 protective layer Substances 0.000 abstract 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
-
- 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 Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A method of inhibiting zinc dendrite growth in a polydopamine film comprising: and (3) soaking the zinc foil into a dopamine solution, and forming a polydopamine film layer on the surface of the zinc by adjusting the concentration of the dopamine, the pH value of the solution, the polymerization time and the reaction temperature. The dopamine modified zinc foil is used as the negative electrode of the secondary battery, and structural representation after charge and discharge cycles shows that the electrode surface is smooth and no obvious dendritic crystal is generated. The polydopamine is utilized to have strong affinity, a stable protective layer is formed on the surface of the zinc foil, and the deposition of zinc is limited in a limited space, so that the growth of zinc dendrites is effectively inhibited, and the cycle life of a zinc cathode is prolonged. The method has the advantages of simple process, easily controlled reaction conditions and environmental protection, and is favorable for performance optimization and practical application of the zinc cathode.
Description
Technical Field
The invention belongs to the field of water-based zinc ion batteries, and particularly relates to a method for inhibiting zinc dendrites through a polydopamine membrane.
Background
The rapid development of new energy vehicles, large-scale energy storage and other industries puts more stringent requirements on the energy density, power density, cycle life, safety and the like of an energy storage system. Commercial lithium ionThe battery has high output voltage and high energy density, but the lithium resource is limited, the cost is high, and the organic electrolyte safety is poor, so the research of a novel secondary battery system becomes a research focus. Wherein, the water system rechargeable zinc ion battery has the following characteristics: the zinc storage capacity is rich, the safety of the water system electrolyte is high, and the low-cost manufacture and safe use of the battery are expected to be realized at the same time; the zinc has lower oxidation-reduction potential (-0.76V, vs. SHE), and the theoretical mass specific capacity of the zinc can reach 820mAh g-1The volume specific capacity is up to 5855mAh cm-3(about 3 times of lithium) which is beneficial to the light weight and the miniaturization of the energy storage system; the aqueous electrolyte has high ionic conductivity (usually more than 1.0S cm)-1Three orders of magnitude higher than organic electrolytes) so that the zinc ion battery has potential high-rate characteristics. Based on the advantages, the water system zinc ion battery is distinguished from various energy storage systems.
The energy storage and release of zinc ion batteries is by Zn2+The migration between the anode and the cathode is realized, and the cathode material is mainly zinc foil. However, the zinc foil negative electrode has a fatal disadvantage of short cycle life, mainly because zinc generates a large amount of dendrites during repeated deposition/peeling on the surface of the negative electrode, easily pierces a separator, causes short-circuiting of a battery, and even causes a safety problem. For this purpose, researchers have adopted the construction of three-dimensional zinc foams, the application of inorganic protective films (CaCO)3、TiO2Etc.) and optimizing the electrolyte, etc. to inhibit the growth of zinc dendrites. However, the above methods have the problems of complicated process, high cost, difficult scale-up, etc., and thus the practical application of the zinc ion battery still faces a serious challenge.
Disclosure of Invention
The invention aims to provide a method for inhibiting zinc dendrite, which has simple process, low cost and easy realization of scale, so as to overcome the defects in the prior art.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a method for inhibiting zinc dendritic crystal growth of polydopamine film comprises the steps of taking zinc foil and dopamine as raw materials, soaking the zinc foil into dopamine solution, and constructing the polydopamine film layer on the surface of zincAnd preparing the zinc/polydopamine electrode. The preparation method of the dopamine solution comprises the step of dissolving dopamine hydrochloride into deionized water, wherein the concentration of the dopamine hydrochloride is 0.001-0.5 mol L-1. The pH value of the dopamine solution is 4-12, and a reagent for adjusting the pH value is one of HCl, ammonia water, sodium hydroxide or Tris-HCl buffer solution. When the zinc foil is soaked in the dopamine solution, stirring is not needed, the time is 0.2-72 hours, and dopamine is polymerized in the process to generate polydopamine. The thickness of the formed polydopamine membrane is 20 nm-1 mu m, the surface appearance is nano-particles, and the polydopamine membrane has a multi-pore channel structure. And (3) soaking the zinc foil in the dopamine solution, washing the zinc foil with deionized water for 3-6 times, and drying the zinc foil under a vacuum condition at the temperature of 30-60 ℃. And cutting the dopamine film layer modified zinc foil into 1 cm-1 cm pieces to obtain the zinc ion battery cathode.
Compared with the prior art, the invention has the beneficial technical effects that:
the method for modifying the polydopamine film on the surface of the zinc foil is simple to operate, controllable in conditions and easy for large-scale production. A large number of functional groups on the surface of the polydopamine have strong metallicity, and a uniform and stable polymer protective film can be formed on the surface of the zinc. In addition, the polymerization reaction condition of dopamine is easy to control, and the thickness of the polydopamine film can be effectively regulated and controlled.
The zinc/polydopamine composite negative electrode obtained by the invention has good electrochemical cycling stability. Meanwhile, the raw materials adopted by the material for inhibiting the growth of the zinc dendrite are cheap and easily available, are green and environment-friendly, and are a negative electrode material with application potential.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the Zn/polydopamine composite electrode prepared in example 1;
FIG. 2 is a graph of deposition/exfoliation cycle performance of the zinc/polydopamine composite electrode and zinc foil prepared in example 1 in a symmetrical cell;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the zinc/polydopamine electrode and zinc foil prepared in example 1 after cycling in a symmetrical cell (a) zinc foil, (b) zinc/polydopamine electrode;
FIG. 4 shows the Zn/poly obtained in example 1The total battery assembled by the dopamine negative electrode and the vanadium pentoxide positive electrode is 2 A.g-1Cycle performance plot under charge and discharge current density.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples. The experimental methods in the examples, in which the specific conditions are not specified, are generally performed under the conditions described in the manual and the conventional conditions, or under the conditions recommended by the manufacturer. The reagents used are all commercially available.
Example 1:
dissolving 0.25mmol of dopamine hydrochloride in 100mL of deionized water, adjusting the pH value to 8.5 by using a Tris-HCl buffer solution, then immersing a 2cm by 2cm zinc sheet into the solution for keeping for 4 hours, then taking out the zinc sheet, washing the zinc sheet for 3 times by using the deionized water, and drying the zinc sheet for 12 hours in vacuum at the temperature of 40 ℃ to obtain the zinc/poly-dopamine composite electrode.
The surface morphology of the zinc/polydopamine composite electrode is characterized by adopting SEM, as shown in figure 1, the polydopamine film is uniformly adsorbed on the surface of the zinc foil, and the surface of the composite electrode is flat.
The electrochemical performance test is carried out on the symmetrical battery assembled by the pure zinc foil and the zinc/polydopamine composite electrode, and the electrolyte is 2mol L-1The zinc sulfate solution has a current density of 1mA cm-2The deposition amount is 1mAh cm-2。
As shown in fig. 2, the zinc/polydopamine composite electrode exhibits superior cycle performance compared to a pure zinc electrode, and the cycle life of the zinc/polydopamine composite electrode can be as long as 500 hours.
SEM test is carried out on the electrode 100h after circulation, as shown in figure 3, the surface of the pure zinc foil electrode after circulation has a large amount of zinc dendrites, and the surface of the zinc/polydopamine composite electrode after circulation is smooth and has no obvious dendrite generation.
As shown in FIG. 4, using zinc/polydopamine as the negative electrode, V2O5The electrochemical performance test of the assembled full cell with the nano wire as the positive electrode is carried out at 2A g-1The capacity of the battery is up to 125mAh g at the current density of-1And the cycling stability is superior to that of pure zinc foil/V2O5A battery.
Example 2:
dissolving 0.5mmol of dopamine hydrochloride in 100mL of deionized water, adjusting the pH value to 11 by using a Tris-HCl buffer solution, then immersing a 2cm x 2cm zinc sheet into the solution for keeping for 4 hours, then taking out the zinc sheet, washing the zinc sheet for 3 times by using the deionized water, and drying the zinc sheet for 12 hours in vacuum at the temperature of 40 ℃ to obtain the zinc/poly-dopamine composite electrode.
Example 3:
dissolving 0.2mmol of dopamine hydrochloride in 100mL of deionized water, adjusting the pH value to 11 by using a Tris-HCl buffer solution, then immersing a 2cm x 2cm zinc sheet into the solution for keeping for 4 hours, then taking out the zinc sheet, washing the zinc sheet for 3 times by using the deionized water, and drying the zinc sheet for 12 hours in vacuum at the temperature of 40 ℃ to obtain the zinc/poly-dopamine composite electrode.
Example 4:
dissolving 0.5mmol of dopamine hydrochloride in 100mL of deionized water, adjusting the pH value to 11 by using a Tris-HCl buffer solution, then immersing a 2cm x 2cm zinc sheet into the solution for keeping for 4 hours, then taking out the zinc sheet, washing the zinc sheet for 3 times by using the deionized water, and drying the zinc sheet for 12 hours in vacuum at the temperature of 40 ℃ to obtain the zinc/poly-dopamine composite electrode.
Example 5:
dissolving 0.5mmol of dopamine hydrochloride in 100mL of deionized water, adjusting the pH value to 8.5 by using a Tris-HCl buffer solution, then immersing a 2cm x 2cm zinc sheet into the solution for keeping for 4 hours, then taking out the zinc sheet, washing the zinc sheet for 3 times by using the deionized water, and drying the zinc sheet for 12 hours in vacuum at the temperature of 40 ℃ to obtain the zinc/poly-dopamine composite electrode.
The zinc/polydopamine composite electrodes prepared in examples 2 to 5 were tested according to the test method of example 1, and the results show that the polydopamine films of the zinc/polydopamine composite electrodes prepared in examples 2 to 5 were uniformly adsorbed on the surface of the zinc foil, and the surface of the composite electrode was flat. After circulation, each zinc/polydopamine composite electrode has a smooth surface without obvious dendritic crystal generation, and the circulation stability is superior to that of pure zinc foil/V2O5A battery.
Claims (7)
1. A method of inhibiting zinc dendrite growth in a polydopamine film comprising: and soaking the zinc foil into a dopamine solution to form a polydopamine film layer on the surface of the zinc.
2. The method of claim 1, wherein the dopamine solution is formulated by a method comprising: dissolving dopamine hydrochloride in deionized water to form L with the concentration of 0.001-0.5 mol-1The dopamine solution of (1).
3. The method according to claim 2, wherein the dopamine solution has a pH of 4-12, and the reagent used for adjusting the pH is one of HCl, ammonia, sodium hydroxide or Tris-HCl buffer solution.
4. The method according to claim 1, wherein the zinc foil is soaked in the dopamine solution for 0.2 to 72 hours.
5. The method of claim 1, wherein the polydopamine membrane has a thickness of 20nm to 1 μm.
6. The method of claim 1, further comprising: and (3) soaking the zinc foil in the dopamine solution, washing the zinc foil with deionized water for 3-6 times, and drying the zinc foil under a vacuum condition, wherein the drying temperature is 30-60 ℃.
7. A preparation method of a zinc/polydopamine film composite electrode is characterized by comprising the following steps: cutting the zinc foil modified with the dopamine film layer in the claim 1 into 1cm by 1cm pieces to be used as a negative electrode of a zinc ion battery, and obtaining the zinc/polydopamine electrode.
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Cited By (6)
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| CN113314773A (en) * | 2021-05-12 | 2021-08-27 | 江苏师范大学 | Aqueous zinc ion battery electrolyte and preparation method and application thereof |
| CN113410453A (en) * | 2021-07-05 | 2021-09-17 | 西北工业大学 | Preparation method of metal-organic coordination film modified zinc cathode |
| CN113745675A (en) * | 2021-09-07 | 2021-12-03 | 中新国际联合研究院 | Zinc electrode protected by negative electricity skeleton hydrogel as modification layer and preparation method thereof |
| CN114597407A (en) * | 2020-12-07 | 2022-06-07 | 中国科学院大连化学物理研究所 | Zinc cathode and preparation method and application thereof |
| CN114824278A (en) * | 2022-05-24 | 2022-07-29 | 北京大学深圳研究生院 | SEI film reaction liquid, modification method of zinc negative electrode and modified zinc negative electrode |
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| CN113410453A (en) * | 2021-07-05 | 2021-09-17 | 西北工业大学 | Preparation method of metal-organic coordination film modified zinc cathode |
| CN113410453B (en) * | 2021-07-05 | 2023-02-28 | 西北工业大学 | Preparation method of metal-organic coordination film modified zinc cathode |
| CN113745675A (en) * | 2021-09-07 | 2021-12-03 | 中新国际联合研究院 | Zinc electrode protected by negative electricity skeleton hydrogel as modification layer and preparation method thereof |
| CN113745675B (en) * | 2021-09-07 | 2023-05-16 | 中新国际联合研究院 | Zinc electrode protected by negative framework hydrogel as modification layer and preparation method thereof |
| CN114824278A (en) * | 2022-05-24 | 2022-07-29 | 北京大学深圳研究生院 | SEI film reaction liquid, modification method of zinc negative electrode and modified zinc negative electrode |
| CN117174937A (en) * | 2023-09-14 | 2023-12-05 | 北京科技大学 | Preparation method and application of functional diaphragm for improving discharge capacity of zinc-based flow battery |
| CN117174937B (en) * | 2023-09-14 | 2024-06-11 | 北京科技大学 | Preparation method and application of functional diaphragm for improving discharge capacity of zinc-based flow battery |
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