CN114824278A - SEI film reaction liquid, modification method of zinc negative electrode and modified zinc negative electrode - Google Patents
SEI film reaction liquid, modification method of zinc negative electrode and modified zinc negative electrode Download PDFInfo
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- CN114824278A CN114824278A CN202210569090.0A CN202210569090A CN114824278A CN 114824278 A CN114824278 A CN 114824278A CN 202210569090 A CN202210569090 A CN 202210569090A CN 114824278 A CN114824278 A CN 114824278A
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- 239000011701 zinc Substances 0.000 title claims abstract description 78
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 78
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000012295 chemical reaction liquid Substances 0.000 title claims abstract description 29
- 150000003751 zinc Chemical class 0.000 title claims abstract description 18
- 238000002715 modification method Methods 0.000 title claims abstract description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 26
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical group [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 19
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000003990 capacitor Substances 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 9
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 9
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 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
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229950011008 tetrachloroethylene Drugs 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 230000002269 spontaneous effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 21
- 210000004027 cell Anatomy 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 description 6
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 5
- 229960001763 zinc sulfate Drugs 0.000 description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 description 5
- 210000001787 dendrite Anatomy 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- KGHAYBAGTGGGBA-UHFFFAOYSA-N [O--].[O--].[O--].[Na+].[V+5] Chemical compound [O--].[O--].[O--].[Na+].[V+5] KGHAYBAGTGGGBA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- -1 zinc carboxylate salt Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—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
- 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
- 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
- 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 discloses an SEI film reaction liquid, a modification method of a zinc cathode and a modified zinc cathode. The SEI film reaction liquid is used for generating an SEI film on the surface of a zinc negative electrode through reaction, and comprises organic carboxylic acid and an organic solvent, wherein the number of carbon atoms of the organic carboxylic acid is less than 10. The SEI film reaction liquid comprises organic carboxylic acid, and a SEI film is generated in situ through spontaneous reaction between the zinc cathode and the organic carboxylic acid, so that the generated SEI film is tightly connected with the zinc cathode through chemical bonding, can stably play a role in protection for a long time, and is difficult to fall off. The SEI film prepared from the SEI film reaction liquid is not easy to fall off in the circulation process and has good circulation stability.
Description
Technical Field
The invention relates to the field of electrochemical energy storage, in particular to an SEI film reaction solution, a zinc cathode modification method and a modified zinc cathode.
Background
Aqueous zinc ion secondary batteries (AZIBs) have high specific capacity (820mAh g) -1 ) The lithium ion battery has the unique advantages of low oxidation-reduction potential (-0.76V vs. SHE), low cost, high safety and the like, is unique among a plurality of novel aqueous rechargeable metal ion batteries, becomes the hottest research object in aqueous metal batteries, and is considered as an ideal substitute of the lithium ion battery. However, because of its special deposition mechanism, the aqueous zinc ion secondary battery is very vulnerable to the two problems of zinc dendrite growth and hydrogen evolution of the zinc cathode during the cycling process, and these two problems also become the biggest obstacles to the further development of the aqueous zinc ion secondary battery. Therefore, it is imperative to modify the battery system by a certain means to effectively suppress dendrites and hydrogen evolution problems.
Considering that the problems of dendritic crystal growth and hydrogen evolution of the zinc cathode are directly carried out on the interface of the zinc cathode/zinc cathode modification method, a certain method is adopted to modify the interface so as to realize the uniform deposition of zinc ions and reduce the side reaction of the interface including hydrogen evolution. At present, the most effective method is to artificially pre-prepare a protective film layer (SEI film) on a zinc cathode, and based on the SEI film, researchers have conducted a great deal of research from multiple angles such as the components, thickness, regulation and control mechanism and the like of the SEI film. However, the summary shows that most of the traditional SEI films have the problems of easy falling off, poor cycle stability and the like in the cycle process.
Disclosure of Invention
Based on this, there is a need for an SEI film reaction liquid that can solve the above problems.
In addition, a modification method of the zinc negative electrode adopting the SEI film reaction solution and a modified zinc negative electrode prepared by the modification method of the zinc negative electrode are also needed to be provided.
An SEI film reaction liquid is used for generating an SEI film on the surface of a zinc negative electrode in a reaction mode, and comprises an organic carboxylic acid and an organic solvent, wherein the number of carbon atoms of the organic carboxylic acid is less than 10.
In one embodiment, the organic carboxylic acid contains at least one CC double bond.
In one embodiment, the organic carboxylic acid has 3, 4, 5, or 6 carbon atoms.
In one embodiment, the organic carboxylic acid is selected from at least one of acrylic acid, methacrylic acid, and itaconic acid.
In one embodiment, the volume ratio of the organic carboxylic acid to the organic solvent is 1: 1 to 20.
In one embodiment, the organic solvent is selected from at least one of dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, tetrachloroethylene, and carbon tetrachloride.
A modification method of a zinc negative electrode comprises the following steps:
providing the SEI film reaction liquid; and
and (3) blade-coating the SEI reaction liquid to the zinc cathode, and generating an SEI film on the surface of the zinc cathode after full reaction to obtain the modified zinc cathode.
In one embodiment, the SEI reaction solution is blade-coated on a zinc negative electrode, an SEI film is generated on the surface of the zinc negative electrode after sufficient reaction, the reaction time is 6-12 h, and the thickness of the SEI film is 1-10 μm.
A modified zinc negative electrode used for an aqueous secondary battery or an aqueous capacitor is prepared by the modification method of the zinc negative electrode.
In one embodiment, the aqueous secondary battery is an aqueous zinc ion secondary battery.
The SEI film reaction liquid comprises organic carboxylic acid, and a SEI film is generated in situ through spontaneous reaction between the zinc cathode and the organic carboxylic acid, so that the generated SEI film is tightly connected with the zinc cathode through chemical bonding, can stably play a role in protection for a long time, and is difficult to fall off.
The SEI film prepared from the SEI film reaction liquid is not easy to fall off in the circulation process and has good circulation stability.
In addition, with reference to fig. 2 and 3, the surface of the SEI film prepared from the SEI film reaction solution of the present application has a cross-linked three-dimensional porous structure, so that electric field distribution can be balanced, abundant zinc nucleation sites can be provided, and the diffusion of zinc ions can be regulated.
The SEI film prepared from the SEI film reaction liquid can optimize the crystal orientation of the surface of the zinc cathode, and realize uniform deposition of zinc; the SEI film has rich oxygen-containing polar groups, can enhance the affinity with zinc ions, improve the hydrophilicity of the zinc cathode and optimize the cathode/electrolyte interface; as a stable SEI film layer, the compound can effectively inhibit negative Hydrogen Evolution (HER) and related side reactions.
The SEI film reaction liquid is used for modifying the zinc cathode to generate the SEI film, so that the problems of dendrite and hydrogen evolution of the cathode are effectively solved, the cycle life of the water system zinc ion secondary battery is prolonged, and the safety of the water system zinc ion secondary battery is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Wherein:
fig. 1 is a flowchart of a method for modifying a zinc negative electrode according to an embodiment.
FIG. 2 is a SEM surface image of the SEI film layer of AA/DMSO @ Zn prepared in example 1.
FIG. 3 is a SEM cross-sectional view of an SEI film layer of AA/DMSO @ Zn prepared in example 1.
Fig. 4 is a charge-discharge cycle performance test chart of button cell 1-1 prepared in example 1.
Fig. 5 is a comparative test chart of charge and discharge cycle performance of the button cell 1-1 and the button cell 1-2 prepared in example 1.
Fig. 6 is a charge-discharge cycle performance test chart of the button capacitor 1 prepared in example 2.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention discloses an SEI film reaction liquid which is used for generating an SEI film on the surface of a zinc cathode through reaction and comprises organic carboxylic acid and an organic solvent, wherein the carbon atom number of the organic carboxylic acid is less than 10.
In the present invention, the number of carbon atoms in the organic carboxylic acid is controlled to 10 or less, because the solubility of the organic carboxylic acid in the organic solvent is poor or even insoluble when the number of carbon atoms in the organic carboxylic acid exceeds 10.
The SEI film reaction liquid comprises organic carboxylic acid, an SEI film is generated in situ through spontaneous reaction between the zinc cathode and the organic carboxylic acid, and the generated SEI film is tightly connected with the zinc cathode through chemical bonding, can stably play a protective role for a long time and is difficult to fall off.
The SEI film prepared from the SEI film reaction liquid is not easy to fall off in the circulation process and has good circulation stability.
Preferably, in the present embodiment, the organic carboxylic acid contains at least one CC double bond.
When organic carboxylic acid reacts with zinc to generate zinc carboxylate salt, the zinc carboxylate salt can perform polyaddition reaction to form a crosslinked polymer due to the existence of CC double bonds, and the crosslinked three-dimensional porous structure of the generated SEI film is presented. The structure is formed, and the prepared SEI film can provide abundant nucleation sites for the deposition of zinc and regulate the deposition behavior of zinc ions.
With reference to fig. 2 and 3, the surface of the SEI film prepared from the SEI film reaction solution of the present application has a cross-linked three-dimensional porous structure, so that electric field distribution can be balanced, abundant zinc nucleation sites can be provided, and the diffusion of zinc ions and the deposition of zinc ions can be regulated.
Specifically, the SEI film prepared from the SEI film reaction liquid can optimize the crystal orientation of the surface of a zinc cathode and realize uniform deposition of zinc; the SEI film has rich oxygen-containing polar groups, can enhance the affinity with zinc ions, improve the hydrophilicity of the zinc cathode and optimize the cathode/electrolyte interface; in addition, as a stable SEI film layer, the negative electrode Hydrogen Evolution (HER) and related side reactions can be effectively inhibited.
More preferably, in the present embodiment, the number of carbon atoms of the organic carboxylic acid is 3, 4, 5 or 6.
Particularly preferably, in the present embodiment, the organic carboxylic acid is at least one selected from Acrylic Acid (AA), methacrylic acid (MAA), and itaconic acid (ITA).
In general, the volume ratio of organic carboxylic acid to organic solvent is 1: 1 to 20.
The organic solvent should be capable of uniformly dissolving the organic carboxylic acid so that it reacts uniformly with the zinc negative electrode.
Preferably, in the present embodiment, the organic solvent is at least one selected from the group consisting of dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), tetrachloroethylene, and carbon tetrachloride.
Experiments prove that the organic solvent can play a role in promoting film formation homogenization.
With reference to fig. 1, the present invention also discloses a modification method of a zinc negative electrode according to an embodiment, including the following steps:
and S10, providing the SEI film reaction liquid.
And S20, coating the SEI reaction liquid to the zinc negative electrode in a blade mode, and generating an SEI film on the surface of the zinc negative electrode after full reaction to obtain the modified zinc negative electrode.
Preferably, the SEI reaction solution is coated on the zinc negative electrode in a scraping manner, an SEI film is generated on the surface of the zinc negative electrode after sufficient reaction, and the reaction time is 6-12 h in the operation of obtaining the modified zinc negative electrode.
Preferably, the thickness of the SEI film is 1 to 10 μm.
The zinc cathode is modified by the SEI film reaction liquid to generate the SEI film, so that the problems of dendrite and hydrogen evolution of the cathode are effectively solved, the cycle life of the water system zinc ion battery is prolonged, and the safety of the water system zinc ion battery is improved.
The invention also discloses the modified zinc cathode of an embodiment, which is used for an aqueous secondary battery or an aqueous capacitor, and the modified zinc cathode is prepared by the modification method of the zinc cathode.
The modified zinc cathode can be matched with a cathode prepared from a vanadium-based cathode material for use.
Preferably, in the present embodiment, the aqueous secondary battery is an aqueous zinc ion secondary battery.
Specifically, when the modified zinc negative electrode is applied to an aqueous zinc ion secondary battery, the negative electrode material is the modified zinc negative electrode, the electrolyte adopts a zinc trifluoromethanesulfonate solution, a zinc sulfate solution or a zinc chloride solution, and the positive electrode active material adopts an electric double layer porous carbon material.
The electric double-layer porous carbon material is selected from at least one of activated carbon, graphene, carbon nanotubes and carbon fibers.
The following are specific examples.
Example 1
0.2mol of sodium sulfate is dissolved in 2000mL of water, and 0.3mol of citric acid which is a weak reducing agent is added and stirred to dissolve. Then adding 0.2mol (36.4g) of vanadium pentoxide solid, stirring and reacting for 24 hours at 60 ℃ to obtain the sodium ion pre-intercalated layered vanadium-based positive electrode material.
Uniformly mixing 70mg of sodium ion pre-intercalated layered vanadium-based positive electrode material, 20mg of conductive agent Keqin black and 10mg of binder PTFE to a plasticine state, passing through a roller press, cutting into a round sheet, and drying in a vacuum drying oven to obtain the vanadium-sodium oxide positive electrode sheet.
5mL of acrylic acid is dissolved in 75mL of dimethyl sulfoxide, stirred uniformly and then blade-coated on the surface of the zinc sheet cleaned by deionized water, and the zinc sheet protected by the SEI film layer (marked as AA/DMSO @ Zn) is obtained after standing for 12 hours.
Fig. 2 is a surface view of the SEI film layer, and fig. 3 is a cross-sectional view of the SEI film layer.
Referring to fig. 2 and 3, it can be seen that the surface of the SEI film prepared in example 1 has a cross-linked three-dimensional porous structure. The structure can balance electric field distribution, provide abundant zinc nucleation sites and regulate the diffusion of zinc ions.
A button cell 1-1 is assembled by taking AA/DMSO @ Zn as a negative electrode, 3mol/L zinc trifluoromethanesulfonate solution as electrolyte and the sodium vanadyl positive plate as a positive electrode, and a charge-discharge test is carried out to obtain a graph 4.
As can be seen from fig. 4, at 2A g -1 At a current density of 270mAh g, the button cell 1-1 can give off -1 The discharge specific capacity is realized, stable circulation of 2000 circles is realized, and the capacity retention rate is 60% after 2000 circles.
A bare chip is used as a negative electrode, 3mol/L zinc trifluoromethanesulfonate solution is used as electrolyte, the sodium vanadyl positive plate is used as a positive electrode to assemble the button cell 1-2, and the button cell 1-1 is assembled with the positive electrode to perform charge-discharge comparison test, so that a graph 5 is obtained.
As can be seen in fig. 5, at 2A g -1 The button cell 1-2 using the unprotected bare chip as the negative electrode can only maintain 20 stable cycles at the current density of (1).
Example 2
70mg of YP80 activated carbon, 20mg of conductive agent Keqin black and 10mg of binder PTFE are uniformly mixed to a plasticine state, the mixture is rolled by a roller press and cut into a circular sheet shape, and the circular sheet is dried in a vacuum drying box to obtain the YP80 positive plate.
5mL of acrylic acid is dissolved in 75mL of dimethyl sulfoxide, stirred uniformly and then blade-coated on the surface of the zinc sheet cleaned by deionized water, and the zinc sheet protected by the SEI film layer (marked as AA/DMSO @ Zn) is obtained after standing for 12 hours.
The button capacitor 1 was assembled with AA/DMSO @ Zn as the negative electrode, 3mol/L zinc trifluoromethanesulfonate solution as the electrolyte, and the YP80 positive electrode sheet as the positive electrode, and subjected to charge-discharge tests, to obtain fig. 6.
As can be seen in fig. 6, at 10A g -1 The button capacitor 1 can stably circulate 60000 cycles at the current density of (1), and the capacity retention rate is 100%.
Example 3
5mL of acrylic acid is dissolved in 25mL of dimethyl sulfoxide, stirred uniformly and then blade-coated on the surface of the zinc sheet cleaned by deionized water, and the zinc sheet protected by the SEI film layer (marked as AA/DMSO @ Zn) is obtained after standing for 12 hours.
A button cell 2 is assembled by taking AA/DMSO @ Zn as a negative electrode, 3mol/L zinc trifluoromethanesulfonate solution as electrolyte and the vanadium sodium oxide positive plate prepared in the embodiment 1 as a positive electrode, and a charge-discharge test is carried out.
The test results showed that the test was at 1A g -1 At a current density of (d), the button cell 2 can exert 307mAh g -1 The discharge specific capacity is improved, stable circulation of 2500 circles is achieved, and the capacity retention rate is 65% after 2500 circles.
Example 4
5mL of acrylic acid is dissolved in 25mL of dimethyl sulfoxide, stirred uniformly and then blade-coated on the surface of the zinc sheet cleaned by deionized water, and the zinc sheet is kept stand for 8 hours to obtain the prepared zinc sheet (marked as AA/DMSO @ Zn) protected by the SEI film layer.
The button capacitor 2 was assembled with AA/DMSO @ Zn as the negative electrode, 3mol/L zinc trifluoromethanesulfonate solution as the electrolyte, and the YP80 positive electrode sheet prepared in example 2 as the positive electrode, and a charge-discharge test was performed.
The test results showed that the test was at 1A g -1 The button capacitor 2 can stably circulate 20000 cycles at a current density of (g), and the capacity retention rate is 100%.
Example 5
5mL of methacrylic acid is dissolved in 75mL of N-methylpyrrolidone (NMP), stirred uniformly and then blade-coated on the surface of the zinc sheet cleaned by deionized water, and the zinc sheet is kept stand for 12 hours to obtain the prepared zinc sheet (marked as MAA/NMP @ Zn) protected by the SEI film layer.
The button cell 3 was assembled with MAA/NMP @ Zn as the negative electrode, 1mol/L zinc sulfate solution as the electrolyte, and the vanadyl-sodiumoxide positive plate prepared in example 1 as the positive electrode, and a charge-discharge test was performed.
The test results showed that the test was at 1A g -1 At current density of (2), the button cell battery 3 can exert 298mAh g -1 The discharge specific capacity is high, stable circulation of 1500 circles is achieved, and the capacity retention rate is 76% after 1500 circles.
Example 6
5mL of methacrylic acid is dissolved in 75mL of N-methylpyrrolidone (NMP), stirred uniformly and then blade-coated on the surface of the zinc sheet cleaned by deionized water, and the zinc sheet is kept stand for 12 hours to obtain the prepared zinc sheet (marked as MAA/NMP @ Zn) protected by the SEI film layer.
The YP80 positive electrode sheet obtained in example 2 was assembled into a button capacitor 3 using MAA/NMP @ Zn as the negative electrode and 1mol/L zinc sulfate solution as the electrolyte, and a charge-discharge test was performed.
The test results showed that the test was at 1A g -1 At a current density of (2), the button capacitor 3 can circulate 18000 cycles stably, and the capacity retention ratio is 100%.
Example 7
Dissolving 5mL of itaconic acid into 75mL of N-methylpyrrolidone (NMP), stirring uniformly, blade-coating the mixture to the surface of a zinc sheet cleaned by deionized water, and standing for 12 hours to obtain the prepared zinc sheet protected by an SEI film layer (named ITA/NMP @ Zn).
The button cell 4 was assembled with the ITA/NMP @ Zn as the negative electrode, 1mol/L zinc sulfate solution as the electrolyte, and the NaxOz positive electrode sheet obtained in example 1 as the positive electrode, and subjected to charge and discharge tests.
The test results showed that the test was at 1A g -1 At a current density of 264mAh g, the button cell 4 can exert -1 The discharge specific capacity is improved, stable circulation of 1000 circles is achieved, and the capacity retention rate is 83% after 1000 circles.
Example 8
Dissolving 5mL of itaconic acid into 75mL of N-methylpyrrolidone (NMP), stirring uniformly, blade-coating the mixture to the surface of a zinc sheet cleaned by deionized water, and standing for 6 hours to obtain the prepared zinc sheet protected by an SEI film layer (named ITA/NMP @ Zn).
The button capacitor 4 was assembled with MAA/NMP @ Zn as the negative electrode, 1mol/L zinc sulfate solution as the electrolyte, and YP80 positive electrode sheet prepared in example 2 as the positive electrode, and a charge and discharge test was performed.
The test results showed that the temperature was 10A g -1 At the current density of (3), the button capacitor 4 can stably circulate 126000 turns, and the capacity retention rate is 100%.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be construed as limiting the scope of the claims. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The SEI film reaction liquid is used for generating an SEI film on the surface of a zinc negative electrode through reaction and is characterized by comprising an organic carboxylic acid and an organic solvent, wherein the number of carbon atoms of the organic carboxylic acid is less than 10.
2. The SEI film reaction liquid as claimed in claim 1, wherein the organic carboxylic acid contains at least one CC double bond.
3. The SEI film reaction liquid as claimed in claim 2, wherein the organic carboxylic acid has 3, 4, 5 or 6 carbon atoms.
4. The SEI film reaction liquid according to claim 3, wherein the organic carboxylic acid is at least one selected from the group consisting of acrylic acid, methacrylic acid, and itaconic acid.
5. The SEI film reaction liquid according to any one of claims 1 to 4, wherein the volume ratio of the organic carboxylic acid to the organic solvent is 1: 1 to 20.
6. The SEI film reaction liquid according to claim 5, wherein the organic solvent is at least one selected from the group consisting of dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, tetrachloroethylene, and carbon tetrachloride.
7. A modification method of a zinc negative electrode is characterized by comprising the following steps:
providing the SEI film reaction liquid according to any one of claims 1 to 7; and
and (3) blade-coating the SEI reaction liquid to the zinc cathode, and generating an SEI film on the surface of the zinc cathode after full reaction to obtain the modified zinc cathode.
8. The method for modifying the zinc negative electrode according to claim 7, wherein the SEI reaction solution is blade-coated on the zinc negative electrode, an SEI film is generated on the surface of the zinc negative electrode after sufficient reaction, and the SEI film is 1-10 μm thick in the operation of obtaining the modified zinc negative electrode, wherein the reaction time is 6-12 h.
9. A modified zinc negative electrode for use in an aqueous secondary battery or an aqueous capacitor, characterized in that the modified zinc negative electrode is produced by the method for modifying a zinc negative electrode according to any one of claims 7 to 8.
10. The method for modifying a zinc negative electrode according to claim 9, wherein the aqueous secondary battery is a zinc ion battery.
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| CN115172647A (en) * | 2022-09-02 | 2022-10-11 | 中南大学 | Fatty acid zinc modified zinc metal negative electrode and preparation method and application thereof |
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