CN114613980B - 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 68
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000011701 zinc Substances 0.000 claims abstract description 103
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 102
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 99
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 31
- 239000011159 matrix material Substances 0.000 claims description 24
- 239000003792 electrolyte Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 16
- 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
- 239000002904 solvent Substances 0.000 claims description 12
- 238000001035 drying 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
- 239000000203 mixture Substances 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
- 238000000034 method Methods 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
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 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
- RWSZBRJIXVNMFQ-UHFFFAOYSA-N FC(F)F.FC(F)F.[Zn] Chemical compound FC(F)F.FC(F)F.[Zn] RWSZBRJIXVNMFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 150000003949 imides Chemical class 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
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011152 fibreglass Substances 0.000 claims 1
- 210000001787 dendrite Anatomy 0.000 abstract description 26
- 238000005260 corrosion Methods 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 230000006911 nucleation Effects 0.000 abstract description 7
- 238000010899 nucleation Methods 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 6
- 230000005684 electric field Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000000407 epitaxy Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 28
- 210000004027 cell Anatomy 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000003365 glass fiber Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 244000137852 Petrea volubilis Species 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 150000003751 zinc Chemical class 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-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
- 238000009825 accumulation Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VCPQWWKLNIMKND-UHFFFAOYSA-L zinc hydroxy sulfate Chemical compound [Zn++].OOS([O-])(=O)=O.OOS([O-])(=O)=O VCPQWWKLNIMKND-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 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
- 230000004913 activation Effects 0.000 description 1
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
Abstract
The invention provides a zinc ion battery composite negative electrode, 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 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 in an electric field, and zinc ions are induced to be uniformly deposited under the carbon dot coating; and the abundant functional groups on the surface of the functionalized carbon point can promote the charge transfer of zinc ions, reduce nucleation potential epitaxy, reduce zinc cathode corrosion and hydrogen evolution rate, and effectively inhibit the formation and growth of zinc dendrites, thereby greatly improving the safety performance and cycle performance of the battery.
Description
Technical Field
The invention relates to the technical field related to zinc ion batteries, in particular to a zinc ion battery composite negative electrode, a preparation method and application thereof.
Background
The ambitious blue plot of achieving carbon neutralization has greatly stimulated people's enthusiasm for facilitating the popularity of large-scale energy storage devices that are eco-friendly, cost-effective and safe. Although lithium batteries have the advantages of high operating voltage, long cycle life, no memory effect, low self-discharge and the like, the market for portable devices and energy storage devices of electric automobiles is dominant. However, due to the high cost and the potential safety hazard of combustibility and explosiveness of lithium ion batteries, and the low abundance of lithium in natural resources, the future application prospect of lithium ion batteries in large-scale storage still has a certain limit. In view of these limitations, rechargeable zinc-based batteries using aqueous zinc salts as the electrolyte and zinc metal as the negative electrode material have unique advantages of safety, environmental protection, abundant resources, convenient preparation, and the like, and have been regarded as one of the most promising next-generation batteries in recent years due to the attention of scientific research.
However, under weak acidic or neutral conditions, zinc metal is prone to problems such as dendrite growth, unavoidable corrosion and hydrogen evolution due to thermodynamic instability and surface unevenness, so that coulomb efficiency is low and cycle reversibility is poor in an electroplating/stripping process, and the problems seriously affect the frontal cycle stability of a zinc ion battery, so that the zinc ion battery cannot meet the requirements of long cycle life in the fields of power energy and large-scale energy storage. Similar to Li/Na metal cells, zn2+ ions tend to nucleate more at sites with higher potential, then zinc ions deposit at initial nucleation sites with higher curvature and lower activation energy, grow further into protrusions, with protruding tips with higher electric field as charge centers, and eventually lead to rapid dendrite growth through long-term accumulation. Although zinc has a high hydrogen evolution overpotential, it is unavoidable that hydrogen is still evolved because zinc has a higher reactivity than water, which reduces zinc usage, resulting in problems such as leakage of the expanding electrolyte. Most importantly, due to the generation of hydrogen, the local pH value of the zinc cathode can be increased, OH < - > is accumulated on the surface of the zinc cathode, basic zinc sulfate byproducts are further generated, and the non-conductive interface products can obstruct the transportation of zinc ions, so that the zinc cathode has poorer rate performance and cycle performance. The crazy growth of dendrites and interface parasitic reactions mutually affect each other and promote each other, further seriously affect the stability of a zinc cathode, and even puncture a diaphragm to cause short circuit of a battery, so that the battery is completely failed.
In order to solve the above problems, various modification strategies are currently proposed by researchers to inhibit dendrite growth to improve the cycle life of zinc anode, such as current collector design, novel separator development, zinc surface modification, electrolyte engineering, etc. The zinc anode surface modification has obvious application advantages: (1) The operation is simple, and because zinc metal is stable in air, the zinc metal 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 evenly flow zinc ions and inhibit the growth of dendrites. Although some progress has been made in these studies, the surface modification reported so far still has certain drawbacks, particularly in terms of complicated preparation process, high cost and increased interfacial resistance.
Disclosure of Invention
Based on the technical problems in the prior art, one of the purposes of the invention is to provide a zinc ion battery composite negative electrode, wherein functionalized carbon dots are coated on the surface of a zinc metal matrix to form a coating, the formed coating can be used as an artificial interface protection layer to protect the zinc metal matrix, the added functionalized carbon dots have rich functional groups on the surface and have stronger binding energy with zinc ions, the nucleation overpotential and interface impedance can be effectively reduced, the zinc ion flow can be continuously regulated, and zinc ions are guided to be uniformly deposited on the surface of the composite negative electrode, so that zinc dendrite or dendrite generation can be effectively inhibited, and the multiplying power performance and the cycle performance of the zinc ion battery can be further improved.
In order to achieve the above object, the technical scheme of the present invention is as follows:
The composite negative electrode of the zinc ion battery 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 and sulfur at the same time, or may be 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 to 3:7 to 9.
In some embodiments, the zinc metal matrix layer has a thickness of 30 to 200 μm. Specifically, the zinc metal matrix is 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.
The second object of the present invention is to provide the method for preparing a zinc ion battery composite anode according to any one of the above embodiments, 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 anode.
In some embodiments, the method comprises the steps of:
s1, polishing the surface of a zinc metal matrix by sand paper, cleaning by deionized water and ethanol, and drying;
s2, adding the binder into a slurry mixing bottle, adding part of solvent, and uniformly stirring;
s3, placing the functionalized carbon dots into a mortar, and forcefully grinding for 15-20 min until the functionalized carbon dots are uniform in particles and have no large particles;
S4, weighing the ground functionalized carbon dots, slowly adding the carbon dots into the slurry mixing bottle in the step S2, and then adding the rest solvent and stirring to obtain slurry with proper viscosity;
s5, coating the slurry on the surface of the zinc metal matrix, and then placing the zinc metal matrix into a vacuum drying oven for drying.
In the scheme, sand paper is used for polishing, on one hand, an oxide layer on the surface of the zinc metal matrix is removed, and on the other hand, the roughness of the zinc metal matrix is increased to enhance the binding capacity of the functionalized carbon dot coating on the surface of the new technical matrix.
In some embodiments, in step S4, the mixture is placed in a vacuum drying oven and dried at 60-120 ℃ for 8-12 hours. Preferably, the drying is carried out at 80 ℃ for 10 hours.
In some embodiments, in step S3, the stirring time is 4 to 8 hours, preferably 6 hours.
A third object of the present invention is to provide a zinc ion battery comprising the zinc ion composite anode 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, the electrolyte being at least one of an aqueous zinc sulfate solution, an aqueous zinc chloride solution, and an aqueous zinc bistrifluoromethane yellow imide solution.
In some embodiments, the separator is a glass fiber.
In some embodiments, the positive electrode includes a positive electrode active material that is manganese dioxide and/or sodium vanadate.
In some embodiments, the conductive agents commonly used in the art include, but are not limited to, graphite-based conductive agents, carbon-based conductive agents, metallic conductive agents.
Compared with the prior art, the invention has the following beneficial effects:
According to the invention, the functional carbon dots doped with at least one of nitrogen, oxygen and sulfur are coated on the surface of the zinc anode to form a coating, and the functional carbon dot coating is used as an artificial interface protective layer to achieve the effect of protecting the zinc anode. The carbon dots are novel zero-dimensional nano materials, and the surfaces of the carbon dots contain various functional groups such as rich zinc-philic oxygen-containing, nitrogen-containing, sulfur-containing and the like, so that on one hand, the functional carbon dots can reduce nucleation overpotential and interface impedance by virtue of the strong binding energy of the rich functional groups on the surfaces of the carbon dots and zinc ions, improve reaction kinetics, continuously adjust zinc ion flow, guide zinc ions to uniformly deposit on the surfaces of the composite negative electrodes, effectively inhibit zinc dendrites or dendrites, and further remarkably improve the rate capability and cycle performance of the water-based zinc ion battery; 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 negative electrode is reduced, the corrosion resistance is enhanced, the hydrogen evolution reaction and the corrosion reaction which are participated by the water are inhibited, and the stability and the coulomb efficiency of the composite negative electrode are improved.
Compared with the prior art, the composite negative electrode has the following advantages:
(1) The functional carbon dot provided by the invention has the advantages of easily available raw materials, low cost, low toxicity, safety, simple operation and obvious action effect;
(2) At room temperature, no matter how much electrochemistry is carried out in the whole system, a carbon dot coating formed on the surface of the zinc metal matrix always exists stably and keeps electrochemical inertia, so that the corrosion resistance of the zinc metal matrix layer is improved, the problem that the zinc metal matrix layer is corroded due to the fact that a battery system provides charges is avoided, the utilization rate of a zinc cathode of a zinc ion battery is guaranteed, and the safety and circulation performance and coulombic efficiency of the battery can be greatly improved;
(3) The nucleation barrier of zinc ions on the surface of the zinc metal matrix modified by carbon points is greatly reduced, so that the distribution of uniform zinc ion flow on the surface of the composite negative electrode is facilitated, thereby effectively inhibiting the generation of zinc dendrites or dendrites, avoiding the problem of short circuit caused by the fact that zinc dendrites are formed on the surface of the zinc negative electrode to pierce through a diaphragm 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 obviously improves the cycle efficiency of the zinc ion battery, can prolong the service life of the zinc ion battery under the condition of ensuring the use safety of the zinc ion battery, can meet the technical requirements of electrochemical energy storage, and has a wide application prospect.
Drawings
In fig. 1, (a) is a graph showing contact angles between a bare zinc anode (Bare Zn) of comparative example 1 and an electrolyte; (b) FIG. 1 shows contact angles between carbon-point-modified zinc cathodes (Zn@CDs) and an electrolyte;
In fig. 2, (a) - (c) are optical microscope images of the button-type symmetrical cell prepared in comparative example 1 after cycling; (d) - (f) drawing is an optical microscope image of the button cell of example 1;
in fig. 3, (a) and (b) are scanning electron microscope images of the button type symmetrical cell prepared in comparative example 1 after cycling; (c) FIG. s (d) are the scanning electron microscope images of the button-type symmetrical cell of example 1 after cycling;
in fig. 4, (a) is a graph showing XRD spectra of the button symmetric battery in comparative example 1 and the zinc anode after charge-discharge cycles of the button symmetric battery in example 1; (b) FIG. is a Tafil curve showing the results of corrosion tests of the three electrode systems of comparative example 1 and example 1;
FIG. 5 is a plot of voltage versus time for the coin symmetric cell of comparative example 1 and the coin symmetric cell of example 1 at a current density of 1mAh cm -2, a deposition of 1mAh cm -2;
FIG. 6 is a graph of voltage versus time for the button cell of comparative example 1 and the button cell of example 1 at different current densities;
FIG. 7 is a graph of cycle performance and charge and discharge curves for different turns for the button cell of comparative example 1 and the button cell of example 1 at a current density of 1Ag -1;
fig. 8 is a graph showing the rate performance obtained by performing charge and discharge cycles under different conditions for the button cell of comparative example 1 and the button cell of 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. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
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 herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In the examples, all means used are conventional in the art unless otherwise specified.
The terms "comprising," "including," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, 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, step, method, article, or apparatus.
In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The experimental raw materials used in the examples of the invention are all commercial products.
Example 1
The preparation method of the zinc ion battery composite negative electrode comprises the following steps:
s1, polishing the surface of a zinc metal matrix by 1000-mesh sand paper, cleaning by deionized water and ethanol, and drying;
s2, adding 30mg of carboxymethyl cellulose into a slurry mixing bottle at normal temperature, adding a proper amount of solvent, and stirring for 1h until the binder is uniformly dispersed;
s3, placing the functionalized carbon dots doped with nitrogen, oxygen and sulfur elements into a mortar, and forcefully grinding for 15-20min until the carbon dots are uniform in particles and have no massive particles;
S4, weighing 120mg of the functionalized carbon dots in the step S3, slowly adding the functionalized carbon dots into a slurry mixing bottle, adding the rest of solvent, and stirring for 6 hours until the viscosity of the mixed slurry 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 20 mu m, then placing the zinc metal substrate into a vacuum drying oven, drying at 80 ℃ for 10 hours, and cutting into pole pieces with the diameter of 14mm for standby.
Comparative example 1
Preparation of zinc metal negative electrode:
Polishing the surface of zinc foil (thickness of 100 μm) by 1000-mesh sand paper for 10min, cleaning with deionized water and ethanol, drying to obtain metal zinc foil (thickness of 90 μm) with smooth and clean surface and no zinc oxide, and cutting into pole pieces with diameter of 14mm for use.
Contact angles were measured with the pole pieces of example 1 and comparative example 1, respectively, and the measurement results are shown in fig. 1. As can be seen from fig. 1 (a), the contact angle between the bare zinc (Bare Zn) and the zinc sulfate electrolyte is 104.5 °, which indicates that the bare zinc and the electrolyte have poor wettability, which is disadvantageous for migration of zinc ions on the electrode surface; in contrast, the carbon-point-modified zinc anode (Zn@CDs) and the electrolyte have a contact angle of only 63.8 degrees (as shown in (b) diagram in fig. 1), which shows that the introduction of the multifunctional carbon points can remarkably enhance the wettability of the interface, and the carbon point surface contains abundant zinc-philic functional groups, so that uniform zinc ion flow can be regulated, and the phenomenon of nonuniform interface electric field caused by a tip effect is relieved.
Preparation of a battery:
Preparation of zinc symmetrical cell:
at room temperature, button type symmetrical battery assembly is completed in air by taking the pole pieces of the example 1 and the comparative example 1 as positive and negative electrodes, glass fiber as a diaphragm and zinc sulfate as electrolyte.
Preparation of a zinc ion full cell:
at room temperature, the battery assembly of the button type zinc ion full battery is completed in the air by taking the pole piece prepared in the example 1 and the comparative example 1 as a negative electrode, zinc sulfate as electrolyte, sodium vanadate or manganese dioxide as a positive electrode and glass fiber as a diaphragm.
Wherein:
The preparation process of the sodium vanadate comprises the following steps:
0.724g V 2O5 and 0.598g of Na 3C6H5O7·2H2 O are weighed and added into 60mL of deionized water, and stirring is carried out vigorously for 30min; and transferring the mixed solution into a reaction kettle, reacting for 48 hours 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 10 hours to obtain the anode material Na xV2O5·nH2 O.
The preparation process of the sodium vanadate anode is as follows:
according to the mass ratio of 7:2:1, respectively weighing 70mg of sodium vanadate, 20mg of carbon black conductive agent and 10mg of PVDF binder to an agate mortar, uniformly stirring, then dripping 20 drops of NMP to perform slurry stirring, grinding for 10min to uniform slurry, uniformly coating the slurry on the surface of a stainless steel mesh by using a scraper, then placing the stainless steel mesh in a vacuum drying oven at 100 ℃ for 10h, and then taking out a wafer with the diameter of 12 cm.
The preparation flow of the MnO 2 positive electrode is as follows:
According to the mass ratio of 7:2:1, respectively weighing 70mg of MnO 2, 20mg of carbon black and 10mg of PVDF to an agate mortar, uniformly stirring, then dripping NMP to stir slurry, grinding for 10min to uniform slurry, uniformly coating the slurry on the surface of a stainless steel mesh by using a scraper, placing the stainless steel mesh in a vacuum drying oven at 100 ℃ for 10h, and taking out cut pieces.
Performance testing
The corrosion speed of a pole piece is tested by using a Chenhua (Shanghai) electrochemical workstation, a three-electrode testing system (a pole piece is used as a working electrode, zinc is used as a counter electrode, agCl/Ag is used as a reference electrode), and Tafel testing of a zinc cathode is carried out at a scanning speed of 1mv s -1 relative to an open-circuit potential of-0.3V; the prepared symmetrical battery is subjected to cycle performance test by utilizing a Xinwei electrochemical test system, and the current density of the symmetrical battery is 1.0-4.0mA cm -2; and (3) carrying out cycle performance test on the zinc ion full battery by using a Xinwei electrochemical test system, wherein the voltage range of the zinc-sodium vanadate battery is as follows: 0.2-1.5V, and current density of 0.2-4A g -1.
The pole pieces of example 1 and comparative example 1 were used as the positive and negative electrodes, zinc sulfate was used as the electrolyte, glass fiber was used as the separator, and after the assembly of the CR2016 type battery case and standing for 2 hours, charge and discharge cycles were performed at a current density of 1mAh -2 and a capacity of 1mAh cm -2, after 10 cycles, the button cell was disassembled, the pole pieces were washed with water and ethanol, the pole pieces were sampled, and photographing by an optical microscope was performed, and the results were shown in fig. 2. Wherein (a) - (c) are photographs of the pole pieces of comparative example 1, from which it can be seen that the bare zinc anode surface is extremely uneven with a large number of non-uniform zinc deposition particles, and the three-dimensional height map shows the pole piece surface roughness due to the large amount of zinc deposited at the initial nucleation sites, resulting in continuous zinc dendrite accumulation; (d) The- (e) plot is a photograph of the pole piece of example 1, from which it can be seen that the pole piece surface is flat and no significant dendrite formation occurs, indicating that zinc is uniformly deposited on the composite anode surface. According to the results of fig. 2, it can be seen that the carbon dot coating can effectively inhibit zinc dendrite formation as an artificial interface protective layer, and greatly reduce the risk of dendrite penetrating through the separator, thereby improving the stability and cycle life of the composite negative electrode.
The electrode sheets of the example 1 and the comparative example 1 are respectively taken as an anode and a cathode, zinc sulfate is taken as electrolyte, glass fiber is taken as a diaphragm, and a CR2016 type battery shell is assembled to prepare a symmetrical battery; after completion and standing for 2 hours, charge-discharge cycle was performed at a current density of 1mAcm -2 and a capacity of 1mAh cm -2, after 25 and 50 cycles of cycle, the coin cell was disassembled, washed with water and ethanol, the pole piece was sampled, and the result of Scanning Electron Microscope (SEM) photographing was shown in FIG. 3. Wherein, (a) the figure is a scanning figure of 25 circles of the zinc cathode cycle, (b) the figure is a scanning figure of 50 circles of the zinc cathode cycle, (c) the figure is a scanning figure of 25 circles of the composite cathode cycle, and (d) the figure is a scanning figure of 50 circles of the composite cathode cycle. It can be seen from the graph (a) that zinc on the surface of the zinc anode is randomly deposited on the surface, and a large amount of block byproducts and dendrites are formed, and at the same time, part of glass fibers are adhered to the surface of the zinc anode due to the penetration of a diaphragm, and as the number of cycles increases to 50, as in the graph (b), more glass fibers appear, a large amount of dead zinc and dendrites begin to appear, which can lead to rapid reduction of zinc utilization rate and seriously affect the service life of the battery. In contrast, as shown in figures (c) and (d), it is evident that very uniform zinc deposition occurs without glass fibers and dendrites appearing on the composite anode surface. It is further shown that carbon spot coating can mitigate the formation of interfacial byproducts and successfully inhibit the formation of zinc dendrites, which will lead to zinc ion batteries with better cycling performance and greater stability.
The pole pieces of example 1 and comparative example 1 were used as the positive and negative electrodes, zinc sulfate was used as the electrolyte, glass fiber was used as the separator, and after the CR2016 type battery case was assembled and left to stand for 2 hours, the button cell was disassembled after charge and discharge cycles were performed at a current density of 1mAh cm -2 and a capacity of 1mAh cm -2, the pole piece was sampled by washing with water and ethanol, and XRD test was performed, and the test results are shown in FIG. 4. As can be seen from fig. 4 (a), in the XRD spectrum of the zinc negative electrode of the button cell of the pole piece in comparative example 1, there is a significant peak of byproduct zinc hydroxysulfate at about 9 °, while in the XRD spectrum of the pole piece in example 1, the intensity of the peak at 9 ° (byproduct zinc hydroxysulfate) is significantly reduced, and as can be seen from the result of comparing the graph (a) in fig. 3, the functionalized carbon dot coating can be used as a physical inert protective layer to isolate direct contact between the electrolyte and the zinc negative electrode, thereby effectively reducing the reactivity of H 2 O and SO 4 2-, SO as to inhibit the generation of byproducts and zinc corrosion, and further improve the cycle life of the zinc negative electrode; the graph (b) in fig. 4 shows tafel curves of corrosion test results of the negative electrode sheet of the button cell, and the corrosion rate of the electrode sheet in example 1 is 1.671mA cm -2, which is far lower than that of the electrode sheet in comparative example 1 (4.126 mA cm -2), and the comparison analysis of the results of the graph (b) in fig. 3 shows that the functionalized carbon dot coating can relieve the corrosion rate of the zinc negative electrode, improve the coulombic efficiency of the zinc negative electrode and improve the service efficiency of the zinc negative electrode.
In summary, based on the abundant functional groups on the surface of the functionalized carbon dots, the functionalized carbon dots can coordinate with zinc ions, thereby adjusting the zinc deposition process and guiding the uniform deposition of zinc; meanwhile, the water-insoluble functionalized carbon point can be used as an inert protective layer to reduce direct contact between water and a zinc metal matrix, improve the stability of the zinc negative electrode and greatly prolong the cycle life of the zinc negative electrode.
The electrode plates in the comparative examples are respectively adopted as positive and negative electrodes, zinc sulfate is adopted as electrolyte, glass fiber is adopted as a diaphragm, a CR2016 type battery shell is assembled into a water system zinc ion symmetrical battery, and electrochemical test is carried out after the assembly is completed and the battery is kept stand for 2 hours.
The long charge and discharge cycles were performed at a current density of 1mAh cm -2 and a capacity of 1mAh cm -2, and the test results are shown in FIG. 5. As can be seen from fig. 5, the aqueous zinc ion symmetric battery using the electrode sheet in comparative example 1 as the positive electrode and the negative electrode, after 50 hours of circulation, the polarization of the zinc negative electrode increases due to serious interface side reaction and formation of zinc dendrite, which results in failure of the battery, while the aqueous zinc ion symmetric battery using the composite electrode sheet in example 1 as the positive electrode and the negative electrode can stably circulate for more than 2000 hours and maintain stable polarization of the battery, further showing that dendrite and side reaction can be reduced under the action of functionalized carbon points, thereby greatly improving the circulation stability of the zinc negative electrode and prolonging the circulation life; in addition, as can be seen from the inset of fig. 5, the polarization potential of the aqueous zinc ion symmetric battery in example 1 is significantly lower than that of the aqueous zinc ion symmetric battery in the comparative example, which indicates that the addition of carbon dots can reduce the nucleation overpotential and the interfacial charge transfer resistance by zinc, which is beneficial to improving the interfacial reaction kinetics, thereby improving the electrochemical performance of the battery.
The charge-discharge cycle was performed at a current density of 0.2-4.0mA cm -2 and the voltage-time curve obtained is shown in FIG. 6. As can be seen from fig. 6 (a), the polarization potential of the zinc anode in example 1 was steadily increased with increasing current density, and no significant polarization increase phenomenon was observed, and particularly, the zinc anode in the aqueous zinc ion symmetric cell in comparative example 1 was still stably operated at a current density of 4mA cm -2. Most importantly, as shown in fig. 6 (a), the aqueous zinc ion symmetric battery of the example can still work normally for 100 hours when the current density is returned to 1.0mA cm -2, while the aqueous zinc ion symmetric battery prepared by the pole piece of comparative example 1 is short-circuited to cause the battery to fail (as shown in fig. 6 (b)), which is caused by the large interface resistance and serious zinc dendrite growth, which indicates that the symmetric battery of the example has more excellent rate performance and can be applied to the condition of no use.
The pole pieces of the example 1 and the comparative example 1 are respectively taken as a negative electrode, zinc sulfate is taken as an electrolyte, glass fiber is taken as a diaphragm, sodium vanadate is taken as a positive electrode material, after the CR2016 type battery case is assembled and stood for 2 hours, charge and discharge cycles are carried out under the conditions that the voltage interval is 0.2-1.5V and the current density is 1A g -1, and the obtained cycle performance diagram and the charge and discharge curves with different circles are shown in figure 7. As can be seen from fig. 7 (a), the aqueous zinc ion full battery prepared by taking the pole piece of example 1 as the negative electrode still has a specific discharge capacity of 234.6mAh g -1 after 500 circles, the capacity retention rate is as high as 81.6%, while the aqueous zinc ion full battery prepared by taking the pole piece of comparative example 1 as the negative electrode only has 61.2mAh g -1 after 500 circles, the capacity retention rate is only 44.4%, as can be seen from the detailed voltage-specific capacity graph 7 (b) and (c), the aqueous zinc ion full battery prepared by taking the pole piece of example 1 still maintains a better discharge platform, while the aqueous zinc ion full battery prepared by taking the pole piece of comparative example 1 becomes smaller and smaller, because the specific discharge capacity of the full battery is rapidly attenuated due to the reduction of the capacity of the zinc negative electrode caused by complex side reactions (hydrogen evolution and zinc corrosion) and dendrite formation of the zinc negative electrode, and the battery is further disabled.
The charge-discharge cycle is carried out under the conditions that the voltage interval is 0.2-1.5V and the current density is 0.1-2A g -1, and the obtained rate performance curve is shown in figure 8. As can be seen from fig. 8, with the gradual increase of the current density, the capacity of the aqueous zinc ion full cell prepared by the pole piece in comparative example 1 rapidly decays, the capacity at the current density of 4A g -1 is only 186.2mAh g -1, the specific capacity decays greatly, and when the current density returns to 0.5A g -1, the capacity is only 307.4mAh g -1, and when the circulation is continued, the capacity is still continuously declined; the water-based zinc ion full battery assembled by the pole piece prepared in the embodiment 1 still has the discharge specific capacity of 204.7mAh g -1 under the current density of 4A g -1, still has the capacity of 329.5mAh g -1 under the current density of 0.5Ag -1, has the capacity retention rate of 97.6 percent, and can still stably circulate. The functional carbon dot coating can obviously inhibit the growth of dendrites, relieve interface side reactions and improve the cycling stability of the zinc cathode, thereby achieving the purpose of improving the performance of the full battery.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (9)
1. The zinc ion battery composite negative electrode 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;
the mass ratio of the functionalized carbon dots to the binder is 1-3: 7-9;
The thickness of the functionalized carbon dot layer is 20 μm.
2. The zinc-ion battery composite anode according to claim 1, wherein the zinc metal base layer has a thickness of 30 to 200 μm.
3. The zinc ion battery composite anode according to claim 1, wherein the binder is at least one of carboxymethyl cellulose, polyvinylidene fluoride, sodium alginate and sodium silicate.
4. The composite negative electrode of zinc ion battery according to claim 1, wherein the solvent is one of water, 1-methyl-2-pyrrolidone, and N, N-dimethylformamide.
5. The method for preparing the zinc ion battery composite anode according to any one of claims 1 to 4, 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 anode.
6. A zinc ion battery comprising the zinc ion battery composite anode of any one of claims 1-4.
7. The zinc-ion battery of claim 6, 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 bistrifluoromethane yellow imide solution.
8. The zinc-ion battery of claim 7, wherein the separator is fiberglass.
9. The zinc-ion battery of claim 7, wherein the positive electrode comprises a positive electrode active material that is manganese dioxide and/or sodium vanadate.
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