CN114613980A - Zinc ion battery composite negative electrode and preparation method and application thereof - Google Patents
Zinc ion battery composite negative electrode and preparation method and application thereof Download PDFInfo
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 106
- 239000011701 zinc Substances 0.000 claims abstract description 101
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 100
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000003792 electrolyte Substances 0.000 claims description 21
- 239000011159 matrix material Substances 0.000 claims description 20
- 229910001868 water Inorganic materials 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 12
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- 239000002904 solvent Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 11
- 229960001763 zinc sulfate Drugs 0.000 claims description 11
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
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- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- OEVRGZYFUKEZMX-UHFFFAOYSA-N C1(CCC(N1)=O)=O.FC(F)F.FC(F)F.[Zn] Chemical compound C1(CCC(N1)=O)=O.FC(F)F.FC(F)F.[Zn] OEVRGZYFUKEZMX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
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- 125000000524 functional group Chemical group 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
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- 239000007864 aqueous solution Substances 0.000 abstract description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
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- 229910001220 stainless steel Inorganic materials 0.000 description 4
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
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- VCPQWWKLNIMKND-UHFFFAOYSA-L zinc hydroxy sulfate Chemical compound [Zn++].OOS([O-])(=O)=O.OOS([O-])(=O)=O VCPQWWKLNIMKND-UHFFFAOYSA-L 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910019953 NaxV2O5 Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- -1 Zn2+ ions Chemical class 0.000 description 1
- KSHPUQQHKKJVIO-UHFFFAOYSA-N [Na].[Zn] Chemical compound [Na].[Zn] KSHPUQQHKKJVIO-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
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Images
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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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- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a zinc ion battery composite negative electrode and a preparation method and application thereof. The carbon dot coating provided by the invention has the advantages of easily available raw materials, low cost, low toxicity, safety and simple operation; the provided carbon dot coating is insoluble in aqueous solution but has strong zinc affinity, and can be used as an electrochemically inert solid coating material. Meanwhile, the functionalized carbon dot coating can be uniformly distributed with an electric field, and zinc ions are induced to be uniformly deposited under the carbon dot coating; and abundant functional groups on the surface of the functionalized carbon dots can promote charge transfer of zinc ions, reduce nucleation potential epitaxy, reduce corrosion and hydrogen evolution rate of a zinc cathode, and effectively inhibit formation and growth of zinc dendrites, so that the safety performance and the cycle performance of the battery are greatly improved.
Description
Technical Field
The invention relates to the related technical field of zinc ion batteries, in particular to a zinc ion battery composite negative electrode and a preparation method and application thereof.
Background
The lithium battery dominates the energy storage device market of portable devices and electric vehicles by virtue of the advantages of high working voltage, long cycle life, no memory effect, low self-discharge and the like. However, due to the high cost and potential safety hazard of combustible and explosive lithium ion batteries and the low abundance of lithium in natural resources, the future application prospect in large-scale storage still has certain limitations. In view of these limitations, rechargeable zinc-based batteries using aqueous zinc salt as electrolyte and zinc metal as negative electrode material have many unique advantages of safety, environmental protection, abundant resources, convenient preparation, etc., and have recently received scientific research attention, and they are considered to be one of the most promising next-generation batteries.
However, under weakly acidic or neutral conditions, zinc metal is prone to have problems of dendritic crystal growth, inevitable corrosion, hydrogen evolution and the like due to thermodynamic instability and uneven surface, so that coulombic efficiency in an electroplating/stripping process is low, cycle reversibility is poor, and the problems seriously affect the cycle stability of the zinc ion battery, so that the zinc ion battery cannot meet the requirement of long cycle life in the fields of power energy and scale energy storage. Similar to Li/Na metal batteries, Zn2+ ions tend to nucleate more at sites with higher potential, and then zinc ions deposit at initial nucleation sites with higher curvature and lower activation energy to further grow into projections, with the protruding tips with higher electric field as charge centers, which eventually leads to rapid dendritic growth after long-term accumulation. Although zinc has a high hydrogen evolution overpotential, inevitably, hydrogen gas is still precipitated due to the higher reactivity of zinc than water, which reduces the utilization rate of zinc and causes problems such as leakage of an inflation electrolyte. Most importantly, due to the generation of hydrogen, the local pH value of the zinc cathode is increased, OH < - > is gathered on the surface of the zinc cathode, and then basic zinc sulfate is generated as a by-product, and the non-conductive interface product can block the transportation of zinc ions, so that poorer rate performance and cycle performance are caused. The crazy growth of the dendritic crystal and the interface parasitic reaction mutually influence and promote each other, further seriously influence the stability of the zinc cathode, even pierce through the diaphragm to cause the short circuit of the battery, and cause the thorough failure of the battery.
In order to solve the above problems, researchers have proposed various modification strategies to inhibit dendrite growth to improve the cycle life of zinc negative electrodes, such as current collector design, novel separator development, zinc surface modification, electrolyte engineering, etc. The surface modification of the zinc cathode has obvious application advantages: the operation is simple, and the zinc metal is stable in the air and can be realized by a simple coating process; (2) the effect is obvious, and due to the existence of artificial SEI, the direct contact between the zinc cathode and the electrolyte can be avoided, and the side reaction of water participation is inhibited; (3) the interface layer of the fast ion conductor can effectively and uniformly homogenize zinc ion flow and inhibit the growth of dendritic crystals. Although some progress has been made in these studies, the surface modification reported at present has certain defects, which are represented by complicated preparation process, high cost and increased interface impedance.
Disclosure of Invention
Based on the above technical problems in the prior art, an object of the present invention is to provide a zinc ion battery composite negative electrode, in which a functional carbon dot is coated on the surface of a zinc metal substrate to form a coating, the formed coating serves as an artificial interface protection layer to achieve the effect of protecting the zinc metal substrate, and the surface of the added functional carbon dot has rich functional groups, and has stronger binding energy with zinc ions, so that the nucleation overpotential and the interface impedance can be effectively reduced, and the zinc ion current can be continuously adjusted to guide the zinc ions to be uniformly deposited on the surface of the composite negative electrode, thereby effectively inhibiting the generation of zinc dendrites or dendrites, and further improving the rate capability and cycle performance of the zinc ion battery.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a zinc ion battery composite negative electrode comprises a zinc metal matrix and a functionalized carbon dot layer, wherein the functionalized carbon dot layer is formed by mixing functionalized carbon dots, a binder and a solvent and then coating the mixture on the surface of the zinc metal matrix, and the functionalized carbon dots are carbon dots doped with at least one of nitrogen, oxygen and sulfur.
The functionalized carbon dots may be carbon dots doped with nitrogen, boron, or sulfur, or a mixture of carbon dots doped with at least one of nitrogen, boron, and sulfur.
In some embodiments, the mass ratio of the functionalized carbon dots to the binder is 1-3: 7 to 9.
In some embodiments, the zinc metal matrix layer has a thickness of 30 to 200 μm. Specifically, the zinc metal substrate is a zinc foil.
In some embodiments, the binder is at least one of carboxymethyl cellulose, polyvinylidene fluoride, sodium alginate, and sodium silicate.
In some embodiments, the solvent is one of water, 1-methyl-2-pyrrolidone, N-dimethylformamide.
Another object of the present invention is to provide a method for preparing a zinc ion battery composite negative electrode according to any one of the above embodiments, the method comprising the steps of:
s1, polishing, cleaning and drying the surface of the zinc metal matrix;
s2, uniformly mixing the binder and the solvent;
s3, adding the functionalized carbon dots into a mixture formed by the binder and the solvent, and uniformly mixing to obtain slurry;
and S4, coating the slurry on the surface of the zinc metal matrix, and drying to obtain the zinc ion battery composite negative electrode.
In some embodiments, the method comprises the steps of:
s1, polishing the surface of the zinc metal matrix by using sand paper, then cleaning by using deionized water and ethanol, and drying;
s2, adding the binder into a size mixing bottle, adding a part of solvent, and uniformly stirring;
s3, putting the functionalized carbon dots into a mortar, and forcibly grinding for 15-20min until the particles of the functionalized carbon dots are uniform and have no large particles;
s4, weighing the ground functionalized carbon dots, slowly adding the weighed functionalized carbon dots into the slurry mixing bottle in the step S2, adding the rest solvent, and stirring to obtain slurry with proper viscosity;
and S5, coating the slurry on the surface of a zinc metal substrate, and then putting the zinc metal substrate into a vacuum drying oven for drying.
In the scheme, the oxide layer on the surface of the zinc metal matrix is removed by polishing with sand paper, and the roughness of the zinc metal matrix is increased to enhance the bonding capability of the functionalized carbon dot coating on the surface of the matrix in the new technology.
In some embodiments, in step S4, the dried mixture is placed in a vacuum drying oven and dried at 60 to 120 ℃ for 8 to 12 hours. Preferably, the drying is carried out at 80 ℃ for 10 h.
In some embodiments, in step S3, the stirring time is 4 to 8 hours, preferably 6 hours.
It is a further object of the present invention to provide a zinc ion battery including the zinc ion composite negative electrode according to any one of the above embodiments.
In some embodiments, the zinc-ion battery further comprises a positive electrode, an electrolyte and a separator, wherein the electrolyte is at least one of zinc sulfate aqueous solution, zinc chloride aqueous solution and bis (trifluoromethane) succinimide zinc aqueous solution.
In some embodiments, the separator is a glass fiber.
In some embodiments, the positive electrode includes a positive active material that is manganese dioxide and/or sodium vanadate.
In some embodiments, the conductive agent is commonly used in the art, including but not limited to graphite-based conductive agents, carbon-based conductive agents, metal conductive agents.
Compared with the prior art, the invention has the following beneficial effects:
the invention can achieve the function of protecting the zinc cathode by coating the functionalized carbon dots doped with at least one of nitrogen, oxygen and sulfur on the surface of the zinc cathode to form a coating, and taking the functionalized carbon dot coating as an artificial interface protective layer. The carbon dots are novel zero-dimensional nano materials, the surfaces of the carbon dots contain various rich functional groups such as zinc-philic, oxygen-containing, nitrogen-containing, sulfur-containing and the like, on one hand, the functionalized carbon dots can reduce the over potential and interface impedance of nucleation and improve the reaction kinetics by virtue of the rich functional groups on the surfaces of the functionalized carbon dots and stronger binding energy of zinc ions, and can continuously adjust zinc ion flow and guide the zinc ions to be uniformly deposited on the surface of the composite cathode, so that the generation of zinc dendrites or dendrites is effectively inhibited, and the rate capability and the cycle performance of the water system zinc ion battery are obviously improved; on the other hand, the functionalized carbon dot coating can be used as an inert protective layer, so that the direct contact between free water and a zinc cathode is reduced, the corrosion resistance is enhanced, the hydrogen evolution reaction and the corrosion reaction of water are inhibited, and the stability and the coulombic efficiency of the composite cathode are improved.
Compared with the prior art, the composite cathode has the following advantages:
(1) the functionalized carbon dots provided by the invention have the advantages of easily available raw materials, low cost, low toxicity, safety, simple operation and obvious effect;
(2) at room temperature, no matter the electrochemical proceeding degree of the whole system, a carbon dot coating formed on the surface of the zinc metal matrix always exists stably and keeps electrochemical inertia, the corrosion resistance of the zinc metal matrix layer is improved, the problem that the zinc metal matrix layer is corroded due to the charge provided by a battery system is avoided, the utilization rate of a zinc cathode of the zinc ion battery is ensured, and therefore the safety cycle performance and the coulombic efficiency of the battery can be greatly improved;
(3) the nucleation potential barrier of zinc ions on the surface of the zinc metal matrix modified by the carbon points is greatly reduced, which is beneficial to the uniform distribution of zinc ion current on the surface of the composite cathode, thereby effectively inhibiting the generation of zinc dendrites or dendrites, avoiding the problem that the zinc dendrites formed on the surface of the zinc cathode pierce the diaphragm to cause short circuit in the use process of the zinc ion battery, and improving the use safety performance of the zinc ion battery;
(4) the carbon dot modified zinc cathode prepared by the preparation method provided by the invention has the advantages that the cycle efficiency of the zinc ion battery is obviously improved, the service life of the zinc ion battery can be prolonged under the condition of ensuring the use safety of the zinc ion battery, the technical requirement of electrochemical energy storage can be met, and the application prospect is wide.
Drawings
In fig. 1, (a) is a graph showing a contact angle of a Bare zinc negative electrode (barezn) of comparative example 1 and an electrolyte; (b) the figure shows the contact angle between the carbon point modified zinc negative electrode (Zn @ CDs) and the electrolyte in the example 1;
in FIG. 2, (a) - (c) are optical microscope images of button-type symmetrical batteries prepared in comparative example 1 after circulation; (d) the picture (b) is an optical microscope picture of the button symmetrical cell in the example 1;
in FIG. 3, (a) and (b) are scanning electron micrographs of button symmetrical cell prepared in comparative example 1 after circulation; (c) and (d) is a scanning electron microscope image of the button symmetrical battery of the embodiment 1 after circulation;
in fig. 4, (a) is an XRD spectrum of the zinc negative electrode after charge-discharge cycles of the button symmetrical cell in comparative example 1 and the button symmetrical cell in example 1; (b) the graph is a Tafel plot of the corrosion test results for the three-electrode system in comparative example 1 and example 1;
FIG. 5 shows the comparative example 1 button cell and the example 1 button cell at 1mA cm-2Current density of 1mAh cm-2Voltage-time curve at deposition amount;
fig. 6 is a voltage versus time plot for the symmetric button cell of comparative example 1 and the symmetric button cell of example 1 at different current densities;
fig. 7 shows the full cell button in comparative example 1 and the full cell button in example 1 at 1A g-1A cycle performance diagram and charge-discharge curves with different turns under current density;
fig. 8 is a graph of rate performance obtained by performing charge and discharge cycles under different conditions for the full cell button in comparative example 1 and the full cell button in example 1.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In the examples, the means used are conventional in the art unless otherwise specified.
The terms "comprises," "comprising," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental raw materials used in the examples of the present invention are all commercially available products.
Example 1
A zinc ion battery composite negative electrode is prepared by the following steps:
s1, polishing the surface of the zinc metal matrix by using 1000-mesh sand paper, then cleaning by using deionized water and ethanol, and drying;
s2, adding 30mg of carboxymethyl cellulose into a size mixing bottle at normal temperature, adding a proper amount of solvent, and stirring for 1 hour until the binder is uniformly dispersed;
s3, putting the functionalized carbon dots doped with nitrogen, oxygen and sulfur elements into a mortar, and forcibly grinding for 15-20min until the carbon dots are uniform in particle size and have no large particles;
s4, weighing 120mg of the functionalized carbon dots obtained in the step S3, slowly adding the weighed functionalized carbon dots into a size mixing bottle, adding the rest of solvent, and stirring for 6 hours until the viscosity of the mixed size is proper;
s5, coating the mixed slurry obtained in the step S4 on a zinc metal substrate through an automatic coating machine, adjusting the height to be 20 microns, then placing the zinc metal substrate into a vacuum drying oven, drying the zinc metal substrate for 10 hours at 80 ℃, and cutting the zinc metal substrate into pole pieces with the diameter of 14mm for later use.
Comparative example 1
Preparing a zinc metal negative electrode:
and (3) grinding the surface of the zinc foil (with the thickness of 100 mu m) for 10min by using 1000-mesh sand paper, then cleaning the zinc foil with deionized water and ethanol, drying the zinc foil to obtain the metal zinc foil (with the thickness of 90 mu m) with a smooth and clean surface and no zinc oxide, and cutting the metal zinc foil into pole pieces with the diameter of 14mm for later use.
The contact angle was measured with the pole pieces of example 1 and comparative example 1, respectively, and the results are shown in fig. 1. As can be seen from the graph (a) in fig. 1, the contact angle of Bare zinc (barre Zn) and zinc sulfate electrolyte is 104.5 °, which indicates that Bare zinc and electrolyte have poor wettability, which is not favorable for the migration of zinc ions on the surface of the electrode; in contrast, the carbon dot modified zinc cathode (Zn @ CDs) and the electrolyte have a contact angle of only 63.8 ° (as shown in (b) of fig. 1), which indicates that the introduction of the multifunctional carbon dot can significantly enhance the wettability of the interface, because the carbon dot surface contains abundant zinc-philic functional groups, the uniform zinc ion current can be adjusted, and the phenomenon of non-uniform interface electric field due to the tip effect is alleviated.
Preparing a battery:
preparing a zinc symmetrical battery:
and at room temperature, the pole pieces of the embodiment 1 and the comparative example 1 are used as positive and negative electrodes, the glass fiber is used as a diaphragm, and the zinc sulfate is used as electrolyte, so that the button type symmetrical battery assembly is completed in the air.
Preparing a zinc ion full battery:
at room temperature, the battery assembly of the button type zinc ion full battery is completed in the air by respectively using the pole pieces prepared in the example 1 and the comparative example 1 as a negative electrode, zinc sulfate as an electrolyte, sodium vanadate or manganese dioxide as a positive electrode and glass fiber as a diaphragm.
Wherein:
the preparation process of sodium vanadate comprises the following steps:
weigh 0.724g V2O5And 0.598g Na3C6H5O7·2H2Adding O into 60mL of deionized water, and stirring vigorously for 30 min;then transferring the mixed solution into a reaction kettle, reacting for 48h at 160 ℃, naturally cooling to room temperature, respectively washing the product with ethanol and deionized water, and finally drying in a vacuum drying oven for 10h to obtain the anode material NaxV2O5·nH2O。
The preparation process of the sodium vanadate anode comprises the following steps:
according to the mass ratio of 7: 2: 1 weighing 70mg of sodium vanadate, 20mg of carbon black conductive agent and 10mg of PVDF binder respectively, uniformly stirring in an agate mortar, then dripping 20 drops of NMP for stirring, grinding for 10min to uniform slurry, uniformly coating the slurry on the surface of a stainless steel net by using a scraper, then putting the stainless steel net into a vacuum drying oven for standing for 10h at 100 ℃, and taking out and cutting into a wafer with the diameter of 12 cm.
MnO2The preparation process of the positive electrode comprises the following steps:
according to the mass ratio of 7: 2: 1 separately weighing 70mg of MnO2Stirring the carbon black of 20mg and the PVDF of 10mg into an agate mortar uniformly, then dripping the NMP into the mortar to stir the slurry, grinding the slurry for 10min to uniform slurry, uniformly coating the slurry on the surface of a stainless steel net by using a scraper, then placing the stainless steel net into a vacuum drying oven for 10h at 100 ℃, and then taking out the cut pieces.
Performance test
The corrosion rate of the pole piece is tested by utilizing the Chenghua (Shanghai) electrochemical workstation, a three-electrode testing system (the pole piece is used as a working electrode, a zinc counter electrode and AgCl/Ag is used as a reference electrode) is adopted, and 1mv s is used-1The scanning speed of the device is-0.3V relative to the open circuit potential, and Tafel test of the zinc cathode is carried out; the prepared symmetrical battery is subjected to cycle performance test by using the Xinwei electrochemical test system, and the current density of the symmetrical battery is 1.0-4.0mA cm-2(ii) a The cycle performance of the zinc ion full cell is tested by using a Xinwei electrochemical testing system, and the voltage range of the zinc-sodium vanadate cell is as follows: 0.2-1.5V, and current density of 0.2-4A g-1。
Respectively taking the pole pieces of the example 1 and the comparative example 1 as positive and negative poles, zinc sulfate as electrolyte, glass fiber as a diaphragm, and after the CR2016 type battery shell is assembled and stands for 2 hours, the battery shell is placed at 1mAcm-2Current density of 1mAh cm-2Is not limited toAfter 10 cycles, the button cell was disassembled, the pole piece was washed with water and ethanol, the pole piece was sampled and photographed by an optical microscope, and the results are shown in fig. 2. Wherein the graphs (a) - (c) are photographs of the electrode sheet in comparative example 1, it can be seen that the bare zinc negative electrode surface is extremely uneven with a large number of uneven zinc deposition particles, and the three-dimensional height map shows the unevenness of the electrode sheet surface due to the large amount of zinc deposition at the initial nucleation sites, resulting in continuous zinc dendrite accumulation; (d) the picture (e) is a photograph of the pole piece of example 1, from which it can be seen that the pole piece has a flat surface with no significant dendrite formation, indicating that zinc is uniformly deposited on the surface of the composite negative electrode. According to the result of fig. 2, it can be seen that the carbon dot coating as an artificial interface protection layer can effectively inhibit the formation of zinc dendrites, greatly reduce the risk that the dendrites pierce the diaphragm, and thus improve the stability and cycle life of the composite cathode.
Respectively assembling the pole pieces of the embodiment 1 and the comparative example 1 as a positive pole and a negative pole, zinc sulfate as electrolyte, glass fiber as a diaphragm and a CR2016 type battery case to prepare a symmetrical battery; after completion and standing for 2h, at 1mAcm-2Current density of 1mAh cm-2After 25 and 50 cycles, the button cell was disassembled, washed with water and ethanol, the electrode plate was sampled, and the Scanning Electron Microscope (SEM) image of the sample was taken as shown in fig. 3. The figure (a) is a scanning diagram of 25 circles of zinc cathode circulation, (b) is a scanning diagram of 50 circles of zinc cathode circulation, (c) is a scanning diagram of 25 circles of composite cathode circulation, and (d) is a scanning diagram of 50 circles of composite cathode circulation. As can be seen from (a), zinc on the surface of the zinc cathode is randomly accumulated on the surface, and a large amount of block byproducts and dendritic dendrites are formed, and meanwhile, part of glass fibers are adhered on the surface of the zinc cathode due to the penetration of the diaphragm, as the number of cycles is increased to 50, as shown in (b), more glass fibers are present, and a large amount of dead zinc and dendrites begin to appear, which can cause the use rate of zinc to be sharply reduced, and the service life of the battery is seriously influenced. In contrast, as shown in (c) and (d), it is evident that very uniform zinc deposition, with no glass fibers and dendrites present on the composite anode surface. Go toThe carbon dot coating can alleviate the formation of interface by-products and successfully inhibit the formation of zinc dendrites, which leads to better cycling performance and greater stability of the zinc ion battery.
Respectively taking the pole pieces of the example 1 and the comparative example 1 as positive and negative poles, zinc sulfate as electrolyte, glass fiber as a diaphragm, and after the CR2016 type battery case is assembled and stands for 2 hours, the battery is placed at 1mA cm-2Current density of 1mAh cm-2After charge and discharge cycles, the button cell was disassembled, washed with water and ethanol, the electrode plate was sampled, and XRD test was performed, and the test result is shown in fig. 4. As can be seen from the graph (a) in FIG. 4, the XRD spectrum of the zinc negative electrode of the button cell of the pole piece in the comparative example 1 has a very obvious peak of the by-product zinc hydroxyl sulfate at about 9 degrees, while the XRD spectrum of the pole piece in the example 1 has a very obvious intensity reduction of the peak (by-product zinc hydroxyl sulfate) at 9 degrees, and the comparison analysis result of the graph (a) in FIG. 3 shows that the functionalized carbon dot coating can be used as a physical inert protective layer to isolate the direct contact between the electrolyte and the zinc negative electrode and effectively reduce H2O and Io SO4 2-The reaction activity of the zinc anode can inhibit the generation of byproducts and the occurrence of zinc corrosion, thereby prolonging the cycle life of the zinc anode; FIG. 4 (b) is a Tafel plot of the corrosion test results of the negative electrode plate of the button cell, which is calculated to show that the corrosion rate of the electrode plate in example 1 is 1.671mA cm-2Much lower than the corrosion rate (4.126mA cm) of the pole piece in comparative example 1-2) As can be seen from the results of the comparison analysis of the graph (b) in fig. 3, the functionalized carbon dot coating can reduce the corrosion rate of the zinc cathode, improve the coulombic efficiency of the zinc cathode, and improve the service efficiency of the zinc cathode.
In conclusion, based on abundant functional groups on the surfaces of the functionalized carbon dots, the functionalized carbon dots can be coordinated with zinc ions, so that the process of zinc deposition is regulated, and the uniform deposition of zinc is guided; meanwhile, the functional carbon dots which are insoluble in water can be used as an inert protective layer to reduce the direct contact of water and a zinc metal matrix, improve the stability of the zinc cathode and greatly prolong the cycle life of the zinc cathode.
The pole pieces in the comparative examples of the embodiments are used as positive and negative electrodes, zinc sulfate is used as electrolyte, glass fiber is used as a diaphragm, and the CR2016 type battery case is assembled into a water-based zinc ion symmetric battery, and after the assembly is completed and the battery is kept stand for 2 hours, an electrochemical test is carried out.
At 1mA cm-2Current density of 1mAh cm-2The test results are shown in fig. 5, in which a long charge-discharge cycle was performed at the capacity of (d). As can be seen from fig. 5, in the aqueous zinc ion symmetric battery using the pole piece in comparative example 1 as the positive and negative poles, after 50h of cycling, the polarization of the zinc negative pole is increased, which is caused by serious interface side reaction and formation of zinc dendrite, whereas the aqueous zinc ion symmetric battery using the composite pole piece in example 1 as the positive and negative poles can be stably cycled for more than 2000 hours, and maintain stable battery polarization, further showing that dendrite and side reaction can be reduced under the action of functionalized carbon points, thereby greatly improving the cycling stability of the zinc negative pole and prolonging the cycling life; in addition, as can be seen from the inset of fig. 5, the polarization potential of the water-based zinc ion symmetric cell in example 1 is significantly lower than that of the comparative water-based zinc ion symmetric cell, which shows that the addition of the carbon dots can reduce the nucleation overpotential and the interface charge transfer resistance by zinc, and is beneficial to improving the interface reaction kinetics, thereby improving the electrochemical performance of the cell.
At 0.2-4.0mA cm-2The charge-discharge cycle was performed at the current density of (a), and the voltage-time curve obtained is shown in fig. 6. As can be seen from the graph (a) of FIG. 6, the polarization potential of the zinc negative electrode in example 1 is steadily increased with the gradual increase of the current density, and there is no obvious polarization increase phenomenon, especially at 4mA cm-2Under high current density, stable operation can still be achieved, and the polarization potential is lower than that of the zinc cathode in the water-based zinc ion symmetric battery in the comparative example 1. Most importantly, as shown in FIG. 6 (a), when the current density returns to 1.0mA cm-2The aqueous zinc ion symmetric cell in the example can still work normally for 100h, while the aqueous zinc ion symmetric cell made with the electrode sheet in comparative example 1 failed due to short circuit (as shown in fig. 6 (b)), which is caused by large interfacial resistance and severe zinc dendrite growth, which is illustrated in the exampleThe symmetrical battery has more excellent rate performance and can be applied to different conditions.
Respectively taking the pole pieces of the example 1 and the comparative example 1 as negative electrodes, zinc sulfate as electrolyte, glass fiber as a diaphragm, sodium vanadate as a positive electrode material, and after the CR2016 type battery case is assembled and stands for 2 hours, the voltage interval is 0.2-1.5V, and the current density is 1A g-1The following charge and discharge cycles were performed, and the obtained cycle performance graph and the charge and discharge curves with different turns were shown in fig. 7. As can be seen from the graph (a) of fig. 7, the aqueous zinc ion full cell prepared by using the electrode sheet of example 1 as the negative electrode still has 234.6mAh g after 500 cycles of cycling-1The discharge specific capacity and the capacity retention rate of the battery are as high as 81.6 percent, and after the water system zinc ion full battery prepared by taking the pole piece of the comparative example 1 as the negative pole is circulated for 500 circles, the discharge specific capacity only remains 61.2mAh g-1And the capacity retention rate is only 44.4%, and it can be seen from the (b) diagram and the (c) diagram of the detailed voltage-specific capacity curve diagram 7 that the discharge plateau of the aqueous zinc ion full cell prepared from the pole piece in example 1 still maintains a good discharge plateau, while the discharge plateau of the aqueous zinc ion full cell prepared from the pole piece in comparative example 1 becomes smaller and smaller, which is caused by the capacity reduction of the zinc negative electrode due to the complicated side reaction (hydrogen evolution and zinc corrosion) of the zinc negative electrode and the formation of dendrites, so that the specific discharge capacity of the full cell sharply attenuates, and the cell fails.
The voltage interval is 0.2-1.5V, and the current density is 0.1-2A g-1The following charge-discharge cycles were performed, and the rate performance curve obtained is shown in fig. 8. As can be seen from fig. 8, the capacity of the aqueous zinc-ion full cell made from the electrode sheet of comparative example 1 decayed rapidly with increasing current density at 4A g-1Has a capacity of only 186.2mAh g at a current density of-1The specific capacity decayed very much, when the current density returned to 0.5A g-1Its capacity is only 307.4mAh g-1When the circulation is continued, the capacity is still continuously reduced; an aqueous zinc ion full cell assembled with the electrode sheets prepared in example 1 was rated at 4A g-1Current density of 204.7mAh g-1Has a specific discharge capacity of 0.5A g-1Still has a current density of 329.5mAh g-1The capacity retention rate is as high as 97.6%, and stable circulation can still be realized. The functionalized carbon dot coating can obviously inhibit the growth of dendritic crystals, relieve the interface side reaction and improve the cycling stability of the zinc cathode, thereby achieving the aim of improving the performance of the full battery.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The zinc ion battery composite cathode is characterized by comprising a zinc metal matrix and a functionalized carbon dot layer, wherein the functionalized carbon dot layer is formed by mixing functionalized carbon dots, a binder and a solvent and then coating the mixture on the surface of the zinc metal matrix, and the functionalized carbon dots are carbon dots doped with at least one of nitrogen, oxygen and sulfur.
2. The zinc ion battery composite negative electrode as claimed in claim 1, wherein the mass ratio of the functionalized carbon dots to the binder is 1-3: 7 to 9.
3. The zinc ion battery composite negative electrode as claimed in claim 1, wherein the thickness of the zinc metal matrix layer is 30 to 200 μm.
4. The zinc-ion battery composite anode of claim 1, wherein the binder is at least one of carboxymethyl cellulose, polyvinylidene fluoride, sodium alginate and sodium silicate.
5. The zinc-ion battery composite negative electrode according to claim 1, wherein the solvent is one of water, 1-methyl-2-pyrrolidone, and N, N-dimethylformamide.
6. The method for preparing the composite negative electrode of the zinc ion battery as recited in any one of claims 1 to 5, characterized by comprising the steps of:
s1, polishing, cleaning and drying the surface of the zinc metal matrix;
s2, uniformly mixing the binder and the solvent;
s3, adding the functionalized carbon dots into a mixture formed by the binder and the solvent, and uniformly mixing to obtain slurry;
and S4, coating the slurry on the surface of the zinc metal matrix, and drying to obtain the zinc ion battery composite negative electrode.
7. A zinc ion battery comprising the zinc ion battery composite negative electrode according to any one of claims 1 to 5.
8. The zinc-ion battery of claim 7, further comprising a positive electrode, an electrolyte and a separator, wherein the electrolyte is at least one of an aqueous zinc sulfate solution, an aqueous zinc chloride solution and an aqueous zinc bis (trifluoromethane) succinimide solution.
9. The zinc-ion battery of claim 8, wherein the separator is glass fiber.
10. The zinc-ion battery of claim 8, wherein the positive electrode comprises a positive active material that is manganese dioxide and/or sodium vanadate.
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