CN116885303A - Multifunctional phase interface protective layer for negative electrode of water-based zinc ion battery and preparation method thereof - Google Patents
Multifunctional phase interface protective layer for negative electrode of water-based zinc ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN116885303A CN116885303A CN202310929272.9A CN202310929272A CN116885303A CN 116885303 A CN116885303 A CN 116885303A CN 202310929272 A CN202310929272 A CN 202310929272A CN 116885303 A CN116885303 A CN 116885303A
- Authority
- CN
- China
- Prior art keywords
- zinc
- negative electrode
- ion battery
- protective layer
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000011241 protective layer Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000005501 phase interface Effects 0.000 title claims abstract description 20
- 239000011701 zinc Substances 0.000 claims abstract description 91
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 68
- 239000010410 layer Substances 0.000 claims abstract description 26
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- GUNJVIDCYZYFGV-UHFFFAOYSA-K antimony trifluoride Chemical compound F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000000010 aprotic solvent Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 244000137852 Petrea volubilis Species 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 210000001787 dendrite Anatomy 0.000 abstract description 16
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 238000002161 passivation Methods 0.000 abstract description 4
- 238000005507 spraying Methods 0.000 abstract description 4
- 150000003751 zinc Chemical class 0.000 description 22
- 230000008021 deposition Effects 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 8
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000009396 hybridization Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000002000 Electrolyte additive Substances 0.000 description 2
- WQQLXQJZGCOECK-UHFFFAOYSA-N [Co][Cu]S[Zn] Chemical compound [Co][Cu]S[Zn] WQQLXQJZGCOECK-UHFFFAOYSA-N 0.000 description 2
- NHPHQYDQKATMFU-UHFFFAOYSA-N [Cu]=S.[Co] Chemical compound [Cu]=S.[Co] NHPHQYDQKATMFU-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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 relates to a multifunctional phase interface protective layer of a water system zinc ion battery cathode and a preparation method thereof, belonging to the technical field of zinc ion batteries. Will SbF 3 Spraying the solution onto the surface of a zinc negative electrode, and after a period of reaction, constructing compact and uniform ZnF on the surface of the zinc negative electrode in situ 2 /Zn 3 Sb 2 And (5) a hybridized interface protection layer. ZnF in the invention 2 And Zn 3 Sb 2 The hybrid interface has good compatibility with a zinc metal negative electrode as an artificial interface layer due to good mechanical property, high zinc ion conductivity and low electron conductivity, can promote zinc ions to uniformly deposit and nucleate at the negative electrode interface, and effectively inhibit growth of zinc negative electrode dendrites,Corrosion, passivation and capacity fade. In addition, the invention can improve the cycle stability of the water-based zinc ion battery, and the battery of the water-based zinc ion battery cathode with the surface covered with the interface protection layer has very stable cycle performance and also shows excellent rate performance after being cycled under different rates.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a multifunctional phase interface protective layer of a negative electrode of a water-based zinc ion battery and a preparation method thereof.
Background
The efficient clean utilization of new energy is urgent to develop a large-scale energy storage new technology with high safety, low cost and long service life. At present, a lithium ion battery occupies a main electrochemical energy storage market, but with the popularization and application of large-scale energy storage and electric automobile technology, potential safety hazards and lithium resource shortage can become key bottlenecks for restricting the large-scale application of the lithium ion battery. Compared with a lithium ion battery, the water-based zinc ion battery has the advantages of high safety, low cost and the like, and can fundamentally solve the problems of inflammability and high cost of the battery, so that the water-based zinc ion battery is expected to become an important alternative for a next-generation high-safety large-scale energy storage system.
However, the side reactions such as hydrogen evolution reaction, dendrite growth and the like at the interface of the zinc cathode/electrolyte are serious, so that the coulomb efficiency of the water-based zinc ion battery is reduced and the capacity decay is too fast in the charge and discharge process, thereby greatly influencing the rate capability and the cycle stability of the battery, and severely restricting the development and the commercial application of the water-based zinc ion battery.
In order to solve the problems of negative dendrite growth, hydrogen evolution, passivation corrosion and the like, researchers have conducted a great deal of research work, mainly including structural modification, surface modification, electrolyte additives and the like. The electrode structure is optimized to ensure that the modified zinc cathode has larger specific surface area, so that the deposition sites of zinc in the electrochemical reaction process can be increased, the growth of zinc dendrites and byproducts can be inhibited, and the reaction kinetics can be improved. However, electrodes composed of pure zinc lack a rigid support skeleton, the structure is subject to destruction during high depth of discharge and long term operation, and excessive zinc deposition still forms a zinc layer on the surface to promote dendrite growth. In addition, the type of electrolyte additive has obvious influence on electrochemical performance and morphological characteristics of the zinc cathode, can change polarization behavior, enable corrosion potential to shift negatively and reduce occurrence of hydrogen evolution reaction besides improving deposition/dissolution of zinc and inhibiting occurrence of zinc dendrite. However, the optimization of the electrolyte and the improvement of the structure still have the rapid growth of the negative dendrite under the high current density in the long-term circulation process, so that the problem of unstable negative circulation is difficult to fundamentally solve. In contrast, the surface modification is mainly to construct a functional layer on the surface of metallic zinc to block the direct contact between the electrode and the electrolyte. On one hand, the protective layer can effectively improve the zinc deposition mode and the dynamics, guide zinc to be uniformly deposited/dissolved and inhibit zinc dendrite growth; on the other hand, the protective layer can also reduce deformation of the zinc cathode and improve the utilization rate of metallic zinc, thereby improving the cycle stability and coulomb efficiency of the water-based zinc ion battery. However, the traditional organic polymer used as the negative electrode surface modification coating has higher preparation cost, and has potential safety hazards of inflammability, toxicity, environmental pollution and the like, thereby limiting the practical application of the organic polymer in the field of large-scale energy storage. Therefore, it is important to design a new zinc battery negative electrode protection layer. The development of a green and environment-friendly water-based zinc ion battery negative electrode protection layer becomes one of the current research hot spots. In view of the above, the invention provides a multifunctional phase interface protective layer for a negative electrode of a water-based zinc ion battery and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a multifunctional phase interface protective layer of a negative electrode of a water-based zinc ion battery and a preparation method thereof, so as to solve the problem of poor growth and cycling stability of dendrites of the negative electrode of the zinc ion battery in the prior art; the scheme provided by the invention can effectively regulate and control the deposition behavior of zinc ions in the interface layer of the negative electrode, inhibit the occurrence of side reactions on the surface of the negative electrode, effectively improve the cycle performance and coulomb efficiency of the water-based zinc ion battery, and greatly improve the safety of the water-based zinc ion battery.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in the scheme of the invention, the surface of the negative electrode of the water-based zinc ion battery is sprayed with an antimony fluoride material (SbF) 3 ) In-situ construction of compact and uniform ultrathin ZnF at negative electrode interface layer 2 /Zn 3 Sb 2 And (5) a hybridized interface protection layer. In situ constructed negative interface protective layer (ZnF) 2 /Zn 3 Sb 2 ) Due to good mechanical property, high zinc ion conductivity and low electron conductivity, the zinc-zinc composite material has good compatibility with a zinc metal negative electrode serving as an artificial interface layer, can promote zinc ions to be uniformly deposited and nucleated at the negative electrode interface, and effectively inhibits electrochemical side reactions on the surface of the zinc negative electrode, so that the problems of growth, corrosion, passivation and capacity attenuation of negative dendrites are effectively relieved. Therefore, for large-scale production of water-based zinc ion batteries with high cycle stability, sbF 3 ZnF in situ constructed with metallic zinc 2 /Zn 3 Sb 2 The hybrid interface protection layer has great application prospect, and specifically comprises the following contents.
A multifunctional phase interface protective layer of a negative electrode of a water-based zinc ion battery is ZnF 2 /Sb 2 Zn 3 Hybrid interface, composed of SbF 3 The material is produced on the surface of the zinc cathode by reaction.
A preparation method of a multifunctional phase interface protective layer of a water system zinc ion battery cathode comprises the following steps:
s1, preparation of an antimony fluoride solution: weighing a certain amount of antimony fluoride sample, dispersing the antimony fluoride sample in N-N dimethylacetamide aprotic solvent to prepare antimony fluoride solution, and then vigorously stirring the antimony fluoride solution for 1 hour;
s2, treating a metal zinc anode: selecting zinc sheets with different thicknesses as zinc cathodes, and polishing the surfaces of the zinc cathodes by using sand paper until a flat frosted surface appears; then soaking the polished zinc cathode in dilute hydrochloric acid to remove surface oxides; taking out the zinc sheet after soaking, washing and drying the zinc sheet;
s3, preparing a phase interface protective layer: placing the zinc cathode treated in the step S2 into the antimony fluoride solution prepared in the step S1, reacting for a period of time, and forming ZnF on the surface of the zinc cathode in situ 2 /Zn 3 Sb 2 Hybrid interface, znF 2 /Zn 3 Sb 2 The hybridized interface is an interface protection layer covering the surface of the zinc cathode.
Preferably, the concentration of the antimony fluoride solution prepared in the step S1 is 0.5-0.6M.
Preferably, the concentration of the dilute hydrochloric acid solution in S2 is 0.2 to 0.3M.
Preferably, the liquid used for washing the zinc cathode in S2 includes, but is not limited to, ethanol or acetone.
Preferably, the reaction time of the zinc electrode in the S3 in the antimony fluoride solution is 1-3 min, and more preferably 3min.
An application of a multifunctional phase interface protective layer of a water-based zinc ion battery cathode in preparing the water-based zinc ion battery cathode.
ZnF prepared by preparation method of multifunctional phase interface protective layer of negative electrode of water-based zinc ion battery 2 /Zn 3 Sb 2 The application of the hybrid interface in preparing a water-based zinc ion battery cathode comprises a zinc cathode and an interface protection layer covered on the surface of the zinc cathode.
Preferably, the specific preparation method for packaging the water-based zinc ion battery cathode with the surface covered by the interface protection layer into a full battery comprises the following steps: and placing the water-based zinc ion battery cathode with the surface covered with the interface protection layer into a cathode shell, placing a diaphragm, dripping electrolyte until the diaphragm is completely soaked, sequentially placing the water-based zinc ion battery cathode with the surface covered with the interface protection layer, a stainless steel gasket, a stainless steel spring plate and a positive electrode shell, and then placing into a press machine for pressure packaging to obtain the water-based zinc ion symmetrical battery.
Compared with the prior art, the invention provides the multifunctional phase interface protective layer of the negative electrode of the water-based zinc ion battery and the preparation method thereof, and has the following beneficial effects:
(1) The invention utilizes SbF 3 With metalZinc substitution reaction, in-situ generation of compact and uniform SEI at negative electrode interface, utilizing ZnF 2 /Zn 3 Sb 2 The hybridization interface regulates zinc ions to uniformly deposit and nucleate on the negative electrode, so that the problem of non-uniform deposition of the negative electrode is effectively solved;
(2) The water-based zinc ion battery cathode of the hybridized interface protective layer prepared by the invention effectively solves the problems of cathode dendrite growth and the like, improves the wettability of the zinc cathode to electrolyte, reduces the corrosion effect of water on the cathode, and greatly reduces the occurrence of side reaction of the cathode interface;
(3) ZnF prepared in the method of the invention 2 /Zn 3 Sb 2 The hybrid interface has excellent stability and high ionic conductivity, and effectively improves the stability of the battery in the long-acting cycle process;
(4) ZnF prepared by the invention 2 /Zn 3 Sb 2 The specific capacity and the multiplying power performance of the water-based zinc ion battery are improved by the water-based zinc ion battery cathode protected by the hybridization interface, and the symmetrical battery stably circulates for more than 100 hours; the specific capacity of the first circle of the zinc-cobalt copper sulfide full battery can reach 430mAh g -1 ；
In conclusion, the invention is realized by using SbF 3 Commercial zinc metal spraying for precursor, znF is constructed 2 /Zn 3 Sb 2 And (3) a hybrid interface layer. Due to ZnF 2 And Zn 3 Sb 2 The interfacial layer can effectively enhance uniform deposition of zinc ions and improve stability of electrolyte/anode interface. By using Zn in the interface layer 3 Sb 2 The uniform deposition of negative zinc ions is regulated and controlled, and dendrite growth and passivation of a negative interface layer are effectively relieved. In addition, znF 2 The interface layer has certain mechanical strength, can effectively limit dendrite growth and isolate corrosion of water to the cathode, thereby improving the cycle stability of the water system zinc ion battery, and is 1mA cm -2 Can be stably cycled for more than 100 hours at a current density of 0.1Ag -1 Is assembled into a zinc-cobalt copper sulfide battery under the current density, and the specific capacity of the first coil can reach 430mAh g -1 Has higher specific capacity and also shows excellent cycle at different multiplying powersIs a ratio of the rate performance of (2). The preparation process of the surface interface protective layer of the negative electrode of the water-based zinc ion battery is simple, the cost is low, the material is more environment-friendly, and the cycling stability of the negative electrode of the zinc ion battery is effectively prolonged.
Drawings
FIG. 1 shows unmodified zinc flakes and SbF according to example 1 of the present invention 3 A contrast chart of wettability of the modified zinc sheet to the electrolyte;
FIG. 2 shows SbF in example 1 of the present invention 3 Modified zinc cathode symmetrical battery with 1mA cm -2 /1mAh cm -2 Constant current charge and discharge data diagram under the condition;
FIG. 3 is a graph showing that the unmodified zinc anode symmetric cell of example 1 of the present invention was at 1mAcm -2 /1mAh cm -2 Constant current charge and discharge data diagram under the condition;
FIG. 4 shows SbF in example 1 of the present invention 3 Modified zinc cathode symmetrical battery with 1mAcm -2 /1mAh cm -2 Cycling the data graph under the condition;
FIG. 5 is a graph showing that the unmodified zinc anode symmetric cell of example 1 of the present invention was at 1mA cm -2 /1mAh cm -2 Cycling the data graph under the condition;
FIG. 6 shows SbF in example 1 of the present invention 3 Modified zinc cathode full cell is 0.1Ag -1 Constant current charge and discharge data diagram under current density;
FIG. 7 shows SbF in example 1 of the present invention 3 And modifying a multiplying power data graph of the zinc cathode full cell under different current densities.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. .
Example 1:
the present embodiment provides a SbF 3 The preparation method of the modified zinc cathode comprises the following steps:
S1、SbF 3 the preparation of the solution is as follows: weigh 1.788g SbF 3 This was dispersed in 20mL of N-N Dimethylacetamide (DMA) aprotic solvent and stirred vigorously for 1 hour.
And S2, spraying the solution on the zinc foil by using a small spray gun, and obtaining a stable protective layer after the surface color of the zinc metal is blackened. The method comprises the following steps: 20ml SbF 3 Placing the solution in a small spray gun, taking out the treated zinc sheet, spraying the solution on the surface of the zinc sheet, after the surface generates compact and uniform black SEI layer, flushing with absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ to obtain the surface-covered ZnF 2 /Zn 3 Sb 2 Is a zinc anode.
The reference negative electrode was a zinc sheet which was not surface modified, and a series of tests were performed.
The method comprises the following steps: surface pass SbF using contact angle experiments 3 Wettability of the modified zinc sheet and the unmodified zinc sheet to zinc sulfate electrolyte.
Referring to FIG. 1, as shown in FIG. 1, sbF 3 The wettability of the modified zinc sheet to the electrolyte is obviously better than that of the unmodified zinc sheet. The surface contains ZnF 2 /Zn 3 Sb 2 The hybrid interface can effectively improve the wettability of electrolyte on the negative electrode and optimize the ion beam on the surface of the negative electrode, thereby effectively relieving the non-uniform deposition behavior of the negative electrode ions and improving the cycle performance of the battery.
Referring to FIGS. 2-3, FIGS. 2-3 illustrate SbF prepared according to this example 3 The symmetric cell of the modified zinc cathode and the unmodified zinc cathode is 1mAcm -2 Constant current charge and discharge data diagram under current density. As shown in the figure, the deposition overpotential of the modified electrode in the charge-discharge process is stabilized between 35 mV and 40mV, and is obviously reduced compared with unmodified metallic zinc, which indicates that the surface-formed modified layer has better zinphilicity than the unmodified substrate, and the deposition of zinc is easier to realize, thereby being beneficial to inhibiting dendrite formation.
Referring to FIGS. 4-5, FIGS. 4-5 illustrate SbFs prepared in this example 3 Cycling data graph of modified zinc negative electrode and unmodified zinc negative electrode symmetric cell. As shown, sbF is used 3 The modified zinc cathode shows stable cycle performance at 1mAh cm -2 The stable circulation is carried out for more than 100 hours under the condition, compared with the zinc cathode without modification, the circulation time is improved by more than 2 times, and the circularity of the cathode is greatly improvedCan be used. The protective layer formed by in-situ self-assembly has strong acting force with the surface of the electrode, and can stably exist in the long-term use process after the battery is packaged.
Referring to FIG. 6, FIG. 6 shows that the surface of the negative electrode protection layer prepared in this example is ZnF 2 /Zn 3 Sb 2 The modified zinc cathode and cobalt copper sulfide assembled full cell is 0.1Ag -1 Constant current charge and discharge data diagram under current density. As shown in the figure, the first-turn specific capacity can reach 430mAh g -1 The modified zinc cathode exhibits a higher specific capacity.
Referring to FIG. 7, FIG. 7 shows that the surface of the negative electrode protection layer prepared in this example is ZnF 2 /Zn 3 Sb 2 And (3) multiplying power data graphs of the full battery assembled by the modified zinc cathode and the cobalt copper sulfide under different current densities. As shown, the effect of modification on full cell performance was investigated by rate capability testing. The modified zinc anode exhibits excellent rate capability at various current densities.
The invention selects SbF 3 Substitution reaction with metallic zinc, in situ generation of compact and uniform SEI at the interface of negative electrode, utilizing ZnF 2 /Zn 3 Sb 2 The hybridization interface regulates zinc ions to uniformly deposit and nucleate on the negative electrode, so that the problems of zinc metal negative electrode zinc ion deposition non-uniformity and zinc dendrite growth are solved. Has better affinity to electrolyte; the method is favorable for inducing uniform deposition of zinc ions on the surface of zinc metal, inhibiting zinc dendrites and preventing corrosion of the cathode; effectively improves the cycle performance of the zinc metal battery.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (7)
1. The multifunctional phase interface protective layer of the negative electrode of the water-based zinc ion battery is characterized by being ZnF 2 /Sb 2 Zn 3 Hybrid interface, composed of SbF 3 The material is produced on the surface of the zinc cathode by reaction.
2. The method for preparing the multifunctional phase interface protective layer for the negative electrode of the water-based zinc ion battery as claimed in claim 1, which is characterized by comprising the following steps:
s1, preparation of an antimony fluoride solution: weighing a certain amount of antimony fluoride sample, dispersing the antimony fluoride sample in N-N dimethylacetamide aprotic solvent to prepare antimony fluoride solution, and then vigorously stirring the antimony fluoride solution for 1 hour;
s2, treating a metal zinc anode: selecting zinc sheets with different thicknesses as zinc cathodes, and polishing the surfaces of the zinc cathodes by using sand paper until a flat frosted surface appears; then soaking the polished zinc cathode in dilute hydrochloric acid to remove surface oxides; taking out the zinc sheet after soaking, washing and drying the zinc sheet;
s3, preparing a phase interface protective layer: placing the zinc cathode treated in the step S2 into the antimony fluoride solution prepared in the step S1, reacting for a period of time, and forming ZnF on the surface of the zinc cathode in situ 2 /Zn 3 Sb 2 Hybrid interface, znF 2 /Zn 3 Sb 2 The hybridized interface is an interface protection layer covering the surface of the zinc cathode.
3. The aqueous zinc ion battery negative electrode multifunctional phase interface protective layer and the preparation method thereof according to claim 2, wherein the concentration of the antimony fluoride solution prepared in the step S1 is 0.5-0.6M.
4. The aqueous zinc ion battery negative electrode multifunctional phase interface protective layer and the preparation method thereof according to claim 2, wherein the concentration of the dilute hydrochloric acid solution in the S2 is 0.2-0.3M.
5. The multi-functional phase interface protective layer of the negative electrode of the water-based zinc-ion battery and the preparation method thereof according to claim 2, wherein the liquid used for washing the negative electrode of the zinc in S2 comprises but is not limited to ethanol or acetone.
6. The multi-functional phase interface protective layer of the negative electrode of the water-based zinc ion battery and the preparation method thereof according to claim 2, wherein the reaction time of the zinc electrode in the S3 in the antimony fluoride solution is 1-3 min.
7. The use of a multifunctional phase interface protective layer of a negative electrode of an aqueous zinc-ion battery according to claim 1 for the preparation of a negative electrode of an aqueous zinc-ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310929272.9A CN116885303A (en) | 2023-07-26 | 2023-07-26 | Multifunctional phase interface protective layer for negative electrode of water-based zinc ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310929272.9A CN116885303A (en) | 2023-07-26 | 2023-07-26 | Multifunctional phase interface protective layer for negative electrode of water-based zinc ion battery and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116885303A true CN116885303A (en) | 2023-10-13 |
Family
ID=88260273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310929272.9A Pending CN116885303A (en) | 2023-07-26 | 2023-07-26 | Multifunctional phase interface protective layer for negative electrode of water-based zinc ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116885303A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108807961A (en) * | 2018-06-06 | 2018-11-13 | 上海电力学院 | A kind of zinc-base cell negative electrode material and preparation method thereof |
| CN112635698A (en) * | 2020-12-22 | 2021-04-09 | 国家纳米科学中心 | Negative pole piece of zinc secondary battery and preparation method and application thereof |
| CN114551775A (en) * | 2022-02-24 | 2022-05-27 | 西安交通大学 | Metal zinc cathode protected by double-phase interface and preparation method and application thereof |
| CN114824236A (en) * | 2022-06-06 | 2022-07-29 | 安徽工业大学 | Water-based zinc ion battery cathode material with functional protective layer and preparation method thereof |
| CN115347140A (en) * | 2022-09-20 | 2022-11-15 | 浙江大学 | Surface-modified composite zinc-based negative electrode, preparation method and battery |
| CN116387485A (en) * | 2023-04-12 | 2023-07-04 | 昆明理工大学 | Method for inhibiting zinc dendrite growth in water-based zinc battery by using gallium-based liquid metal |
-
2023
- 2023-07-26 CN CN202310929272.9A patent/CN116885303A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108807961A (en) * | 2018-06-06 | 2018-11-13 | 上海电力学院 | A kind of zinc-base cell negative electrode material and preparation method thereof |
| CN112635698A (en) * | 2020-12-22 | 2021-04-09 | 国家纳米科学中心 | Negative pole piece of zinc secondary battery and preparation method and application thereof |
| CN114551775A (en) * | 2022-02-24 | 2022-05-27 | 西安交通大学 | Metal zinc cathode protected by double-phase interface and preparation method and application thereof |
| CN114824236A (en) * | 2022-06-06 | 2022-07-29 | 安徽工业大学 | Water-based zinc ion battery cathode material with functional protective layer and preparation method thereof |
| CN115347140A (en) * | 2022-09-20 | 2022-11-15 | 浙江大学 | Surface-modified composite zinc-based negative electrode, preparation method and battery |
| CN116387485A (en) * | 2023-04-12 | 2023-07-04 | 昆明理工大学 | Method for inhibiting zinc dendrite growth in water-based zinc battery by using gallium-based liquid metal |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111916744B (en) | Liquid metal composite cathode of zinc ion battery and preparation method and application thereof | |
| CN111900388A (en) | Zinc ion battery negative electrode material, preparation and application thereof | |
| CN113410453B (en) | Preparation method of metal-organic coordination film modified zinc cathode | |
| Wen et al. | Preliminary study on zinc–air battery using zinc regeneration electrolysis with propanol oxidation as a counter electrode reaction | |
| CN110148704A (en) | A kind of structure and preparation method of network-like pieces of light-gauge metal zinc electrode | |
| CN112331933A (en) | Long-cycle-life cathode of aqueous zinc secondary battery and preparation and application thereof | |
| CN113690397B (en) | Zinc cathode pole piece and preparation method and application thereof | |
| CN110137430A (en) | The Co of three-dimensional porous array structure3O4/ rGO/Ni foam combination electrode material and preparation method thereof | |
| CN114171726A (en) | Preparation method and application of metal zinc cathode of water-based zinc ion battery | |
| CN116314690A (en) | Preparation method of zinc ion battery anode material with three-dimensional structure | |
| CN116314861A (en) | High-performance composite electrode applied to zinc-based flow battery and preparation method thereof | |
| CN116885303A (en) | Multifunctional phase interface protective layer for negative electrode of water-based zinc ion battery and preparation method thereof | |
| CN114551775A (en) | Metal zinc cathode protected by double-phase interface and preparation method and application thereof | |
| CN114388901A (en) | Aqueous zinc ion battery electrolyte and battery | |
| CN113991086A (en) | Zinc ion battery cathode composite material and preparation method and application thereof | |
| CN109980226B (en) | Zinc cathode with polyamide brightener layer and preparation method and application thereof | |
| CN113998692A (en) | Graphene quantum dot, preparation method thereof, electrolyte containing graphene quantum dot and application of electrolyte in zinc ion battery | |
| CN116103614B (en) | Zinc fluoride modified porous lithium metal composite anode material and preparation method and application thereof | |
| CN111106398A (en) | Low-cost aqueous zinc-iron secondary battery | |
| CN113130956B (en) | Full-flow cerium-based redox flow battery | |
| CN115764007B (en) | Method for preparing zinc@vanadium oxide composite film in large area and application of zinc@vanadium oxide composite film in water-based zinc battery | |
| CN112670502B (en) | Antimony telluride nanosheet and application thereof in water-based zinc ion battery | |
| CN115332472A (en) | Preparation method and application of zinc phosphate film | |
| CN114824178A (en) | Composite modification method for lithium metal negative electrode | |
| CN116454279A (en) | Preparation method and application of nonionic surfactant modified zinc ion battery electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |