CN116525751A - Preparation method of graphene/boron-alkene composite interface film modified zinc metal negative electrode and zinc ion battery - Google Patents
Preparation method of graphene/boron-alkene composite interface film modified zinc metal negative electrode and zinc ion battery Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 78
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 41
- 239000002184 metal Substances 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 150000003751 zinc Chemical class 0.000 title claims abstract description 36
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052796 boron Inorganic materials 0.000 claims abstract description 50
- -1 boron alkene Chemical class 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000004094 surface-active agent Substances 0.000 claims abstract description 18
- 230000008021 deposition Effects 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims description 38
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 238000000151 deposition Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 15
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229940069078 citric acid / sodium citrate Drugs 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- PSLWZOIUBRXAQW-UHFFFAOYSA-M dimethyl(dioctadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC PSLWZOIUBRXAQW-UHFFFAOYSA-M 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- 239000011701 zinc Substances 0.000 abstract description 28
- 229910052725 zinc Inorganic materials 0.000 abstract description 24
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 11
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 229910000085 borane Inorganic materials 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 5
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BGECDVWSWDRFSP-UHFFFAOYSA-N borazine Chemical compound B1NBNBN1 BGECDVWSWDRFSP-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/045—Electrochemical coating; Electrochemical impregnation
- H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
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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
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a preparation method of a graphene/boron-alkene composite interface film modified zinc metal negative electrode and a zinc ion battery, and belongs to the technical field of zinc ion battery negative electrodes. According to the method, graphene and boron alkene are selected as modified materials, and a layer of graphene and boron alkene composite interface film is formed on the surface of a zinc negative electrode through a constant current method under the action of a surfactant. The Zn symmetric battery assembled by the zinc metal cathode can be 5mAcm ‑2 Current density of 1mAhcm ‑2 Is reversible cycled for 1900h under the deposition capacity, and 105.95mAhg is charged and discharged for 50 circles under the current density of 1C in a zinc ion battery prepared by matching with a commercial lithium manganate anode ‑1 And exhibits excellent rate performance.
Description
Technical Field
The invention discloses a preparation method of a graphene/boron alkene composite interface film modified zinc metal negative electrode and a zinc ion battery, and belongs to the technical field of zinc ion battery negative electrodes.
Background
In the big background of the "two carbon" policy today, green energy construction has become the main investment direction for governments of various countries. The secondary battery is used as an important component of clean energy and is widely applied to the fields of power batteries, renewable energy sources, national defense and military industry and the like. Among the secondary batteries, zinc ion batteries have high safety due to the use of aqueous electrolyte. The zinc ion battery also has higher energy density, longer service life and competitive manufacturing cost, and is an ideal green battery system.
Although zinc ion batteries have wide application prospects, zinc metal directly used as a negative electrode has some problems: (1) In the repeated charge and discharge process of the battery, zinc ions and metallic zinc are repeatedly deposited and dissolved on the surface of the negative electrode, dendritic precipitates are formed, and the zinc dendrites are finally changed as the precipitates grow up. These zinc dendrites are extremely liable to pierce the separator to cause short circuit of the battery, and at the same time, cause uneven thickness distribution of the zinc electrode to cause deformation of the electrode, resulting in capacity reduction of the zinc ion battery; (2) The hydrogen evolution reaction is an unavoidable side reaction in the zinc metal battery, and can consume partial charge, so that the coulomb efficiency of the battery is reduced; the separated hydrogen can increase the pressure in a closed battery system, so that the battery expands; (3) The zinc metal in the electrolyte will undergo chemical and electrochemical corrosion. The above problems interact and interact, resulting in a further decrease in the electrochemical performance of the zinc ion battery.
In order to solve the above problems, it is common to inhibit the growth of zinc dendrites and the occurrence of interfacial side reactions through interfacial modification between an electrode and an electrolyte. Heretofore, many methods have been studied which can be used for modification of the negative electrode of a zinc ion battery, such as sol-gel method, drip coating method, immersion method, doctor blade method, chemical vapor deposition method, and the like. Sol-gel processes generally require a long time, often days or weeks, throughout the preparation process, and the gel will evolve many gases and organics during drying. The drip coating method realizes the purpose of modifying the performance by forming a film on the surface by reacting the solution with the zinc anode, but the liquid drops are unevenly distributed on the surface of the zinc anode in a physical falling mode, and the large-scale preparation of the zinc anode has a certain difficulty. The soaking method is used for soaking the zinc cathode in the solution for reaction, so that the residual solution on the surface is difficult to completely remove, and the performance of the finally prepared battery is affected. The doctor blade method has certain requirements on physical properties such as viscosity of modified substances, and the chemical vapor deposition method has more complicated steps. Compared with other methods, the electrodeposition method can realize mass production, has lower cost, simpler process and less pollution, and can effectively and accurately control the thickness of the modified layer by adjusting various parameters and electrochemical parameters of the electrodeposition liquid.
Graphene has remarkable properties in terms of carrier mobility, flexibility, thermal conductivity, and chemical resistivity. The boron alkene has a two-dimensional structure similar to graphene, with strong in-plane covalent bonds and weak interlayer van der Waals forces. At the same time, the boranes are used as a typical two-dimensional Dirac material consisting of the lightest solid elements, and have different surface configurations and complex multi-center double electronic bonds. The heterojunction structure of the graphene and the boron alkene is used as a coating to carry out interface modification on the zinc ion cathode, and the safety problem caused by zinc dendrite growth can be effectively relieved due to the synergistic effect of the heterojunction structure, so that the electrochemical performance of the battery can be improved.
Therefore, the interfacial film prepared from graphene and boron alkene can be controlled to be used as a surface modification coating of the zinc ion negative electrode by adopting an electrodeposition method, and the method has certain innovation and practicability.
Disclosure of Invention
In order to overcome the defects in the prior art, one of the purposes of the invention is to provide a preparation method of a graphene/boron-alkene composite interface film modified zinc metal anode.
The second object of the present invention is to provide a zinc ion battery.
In order to achieve the purpose of the invention, the following technical scheme is provided.
A preparation method of a graphene/boron alkene composite interface film modified zinc metal negative electrode comprises the following steps:
(1) Mixing graphene aqueous dispersion, boron aqueous dispersion and surfactant aqueous solution in a certain volume ratio, magnetically stirring, and adjusting pH by using citric acid/sodium citrate to obtain suspension;
the surfactant is one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, hexadecyl trimethyl ammonium bromide or dioctadecyl dimethyl ammonium bromide;
preferably, the size of the graphene sheet diameter is 50-200 nm;
preferably, the concentration of the graphene aqueous dispersion liquid is 0.5 mg/mL-2 mg/mL;
preferably, the particle size of the borazine is 1-10 nm;
preferably, the concentration of the borane aqueous dispersion is 0.5 mg/mL-2 mg/mL;
preferably, the concentration of the surfactant aqueous solution is 0.0001 mg/mL-0.2 mg/mL;
preferably, the volume ratio of the graphene aqueous dispersion to the boron aqueous dispersion to the surfactant aqueous solution is (0.5-2): 1-5.
Preferably, the pH value of the suspension is 3-6.
(2) Taking untreated zinc foil as a working electrode, taking a carbon rod as an electrode to form a two-electrode system, taking the suspension obtained in the previous step as a deposition solution, and simultaneously depositing graphene and boron alkene on the surface of the zinc foil by adopting a constant current method;
preferably, the zinc foil has a thickness of 100-500 μm;
preferably, the constant current is 0.0001A to 0.5A.
(3) Rinsing the zinc foil surface residual solution with deionized water;
(4) Transferring the treated zinc foil to a constant temperature oven, and drying at constant temperature to obtain the graphene/boron-alkene composite interface film modified zinc metal anode.
The zinc ion battery cathode is prepared by the preparation method of the graphene/boron-alkene composite interface film modified zinc metal cathode.
Advantageous effects
1. The invention provides a preparation method of a graphene/boron alkene composite interface film modified zinc metal negative electrode, which is characterized in that a layer of uniformly dispersed graphene/boron alkene interface film with high mechanical strength is formed on the surface of the zinc negative electrode. The interface film enables the zinc negative electrode to have higher stability and corrosion resistance in aqueous solution by utilizing the synergistic effect between the graphene and the boron, and the interface film is used as an interface passivation layer to avoid direct contact between the zinc negative electrode and electrolyte, so that the corrosion of the zinc negative electrode is obviously inhibited, and hydrogen evolution reaction and the formation of byproducts are inhibited.
2. The invention provides a preparation method of a graphene/boron-alkene composite interface film modified zinc metal negative electrode, which uses a surfactant to charge uncharged graphene and boron alkene in suspension, so that the graphene and the boron alkene are adsorbed on the zinc negative electrode under the action of an electric field force in a constant current electrodeposition method, and the surface of the zinc negative electrode is uniformly formed into a film. The constant current electrodeposition method can optimize the deposition speed and thickness by adjusting the current density and time, has the advantages of simple equipment, easy operation, mild reaction condition, high deposition speed, easy control of the deposition process and the like, and can be applied to large-scale processing and production, and has lower cost, simpler process and less pollution.
3. The invention provides a zinc ion battery, wherein the zinc ion battery cathode is prepared by the preparation method of the graphene/boron alkene composite interface film modified zinc metal cathode, and the assembled Zn symmetric battery can be in a range of 5mAcm -2 Is 1mAh cm -2 Is reversibly cycled 1900h at a deposition capacity of (c).
4. The invention provides a zinc ion battery, wherein the negative electrode of the zinc ion battery is prepared by the preparation method of the graphene/boron alkene composite interface film modified zinc metal negative electrode, and the positive electrode of the zinc ion battery is commercial lithium manganate. The charge-discharge cycle at a current density of 1C was 50 cycles with 105.95mAh g -1 Is a reversible discharge specific capacity of (a).
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of a graphene/boron alkene composite interfacial film modified zinc metal anode prepared in example 1.
FIG. 2 is an X-ray photoelectron spectroscopy (XPS) spectrum of a graphene/boron alkene composite interface film modified zinc metal anode prepared in example 1; wherein figure (a) is an XPS profile of C1 s; FIG. (b) shows an XPS profile of S2 p; FIG. (c) shows an XPS spectrum of B1S.
FIG. 3 is a graph showing that the graphene/boron-alkene composite interface film modified zinc metal anode prepared in example 1 is assembled into a Zn symmetric battery at 5mAcm -2 Is 1mAh cm -2 Voltage versus time curve for deposition capacity.
Fig. 4 is a constant current charge-discharge cycle curve of a graphene/boron alkene composite interface film modified zinc metal negative electrode matched lithium manganate positive electrode prepared in example 1 at a current density of 1C.
Fig. 5 is a graph showing the rate capability of the graphene/boron alkene composite interface film modified zinc metal negative electrode matching lithium manganate positive electrode prepared in example 1 at current densities of 0.5C, 1C, 2C and 4C.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples, but is not intended to limit the scope of the patent.
The reagents used, as well as other instruments, are conventional reagent products available commercially, without the manufacturer's knowledge.
An aqueous graphene dispersion: purchased from Jiangsu Xianfeng nanotechnology.
Aqueous boron ene dispersion: purchased from north family new materials technologies limited.
The following test was performed on a graphene/boron alkene composite interface film modified zinc metal anode prepared in the following example:
(1) X-ray photoelectron spectroscopy (XPS) test: the instrument model is Thermo Scientific.
(2) Scanning Electron Microscope (SEM) test: the instrument was a field emission scanning electron microscope, model S4800, japanese Hitachi.
(3) Button cell charge and discharge test: the instrument is a new Weir button cell charge-discharge tester, model CT-4008T-5V10Ma-164, purchased from Shenzhen New Wil electronic Co.
Example 1
A preparation method of a graphene/boron alkene composite interface film modified zinc metal negative electrode comprises the following steps:
(1) Mixing graphene aqueous dispersion, boron aqueous dispersion and sodium dodecyl sulfonate aqueous solution in a volume ratio of 4ml:4ml:12ml, magnetically stirring, and adjusting pH to 5 by using citric acid/sodium citrate to obtain a suspension;
the size of the graphene sheet is 50-200 nm;
the concentration of the graphene aqueous dispersion liquid is 1mg/mL;
the particle size of the boracene is 1-10 nm;
the concentration of the borane aqueous dispersion is 1mg/mL;
the concentration of the surfactant aqueous solution is 0.0005mg/mL;
the volume ratio of the graphene aqueous dispersion to the boron aqueous dispersion to the surfactant aqueous solution is 1:1:3.
(2) Taking untreated zinc foil as a working electrode, taking a carbon rod as an electrode to form a two-electrode system, taking the suspension obtained in the previous step as a deposition solution, and simultaneously depositing graphene and boron alkene on the surface of the zinc foil by adopting a constant current method;
the thickness of the zinc foil is 100 mu m;
the constant current is 0.0005A.
(3) Rinsing the zinc foil surface residual solution with deionized water;
(4) Transferring the treated zinc foil to a constant temperature oven, and drying at constant temperature to obtain the graphene/boron-alkene composite interface film modified zinc metal anode.
SEM characterization is carried out on the graphene/boron alkene composite interface film modified zinc metal anode prepared in the embodiment 1, and the result is shown in figure 1: it can be seen that layered deposits are obtained on the surface of the zinc foil, and the morphology is relatively uniform.
XPS characterization is carried out on the graphene/boron alkene composite interface film modified zinc metal anode prepared in the embodiment 1, and the result is shown in fig. 2: fig. (a) is an XPS spectrum of C1s, peaks of c—o bond and c=o bond can be observed, indicating that graphene is successfully adsorbed on the surface of zinc anode; FIG. b is an XPS spectrum of S2 p, illustrating the residue of sulfonate on the surface of zinc anode; fig. (c) is an XPS spectrum of B1S, illustrating successful adsorption of the boron alkene to the zinc anode surface.
The graphene/boron alkene composite interface film modified zinc metal negative electrode prepared in the embodiment 1 is assembled into a Zn metal symmetric battery with a concentration of 5mAcm -2 Is 1mAh cm -2 The voltage versus time curve results for the deposition capacity of (c) are shown in fig. 3: it was found that the cycle life exceeded 1900h.
For the graphene/boron alkene composite interface film modified zinc metal anode prepared in example 1, a commercial lithium manganate anode is assembled into a 2032 button cell, and a charge-discharge cycle curve under the current density of 1C is shown in fig. 4: the charge-discharge cycle at a current density of 1C was 50 cycles with 105.95mAh g -1 Is a reversible discharge specific capacity of (a).
The graphene/boron composite interface film modified zinc metal anode prepared in example 1 was assembled into 2032 button cell with the commercial lithium manganate anode, and the rate performance at 0.5C, 1C, 2C, 4C current densities was as shown in fig. 5: average capacities at corresponding rates were 137.36, 111.17, 98.16 and 81.01mAh g, respectively -1 When the cycle rate is gradually restored to the initial state (0.5C), the loss of capacity is almost negligible.
Example 2
A preparation method of a graphene/boron alkene composite interface film modified zinc metal negative electrode comprises the following steps:
(1) Mixing graphene aqueous dispersion, boron aqueous dispersion and sodium dodecyl benzene sulfonate aqueous solution in a volume ratio of 1ml to 4ml to 10ml, magnetically stirring, and adjusting pH to 3 by using citric acid/sodium citrate to obtain a suspension;
the size of the graphene sheet is 50-200 nm;
the concentration of the graphene aqueous dispersion liquid is 2mg/mL;
the particle size of the boracene is 1-10 nm;
the concentration of the borane aqueous dispersion is 0.5mg/mL;
the concentration of the surfactant aqueous solution is 0.0001mg/mL;
the volume ratio of the graphene aqueous dispersion to the boron aqueous dispersion to the surfactant aqueous solution is 0.5:2:5.
(2) Taking untreated zinc foil as a working electrode, taking a carbon rod as an electrode to form a two-electrode system, taking the suspension obtained in the previous step as a deposition solution, and simultaneously depositing graphene and boron alkene on the surface of the zinc foil by adopting a constant current method;
the zinc foil thickness is 300 μm;
the constant current is 0.0001A.
(3) Rinsing the zinc foil surface residual solution with deionized water;
(4) Transferring the treated zinc foil to a constant temperature oven, and drying at constant temperature to obtain the graphene/boron-alkene composite interface film modified zinc metal anode.
Example 3
A preparation method of a graphene/boron alkene composite interface film modified zinc metal negative electrode comprises the following steps:
(1) Mixing graphene aqueous dispersion, boron aqueous dispersion and hexadecyl trimethyl ammonium bromide aqueous solution in a volume ratio of 4ml to 1ml to 2ml, magnetically stirring, and adjusting pH to 4 by using citric acid/sodium citrate to obtain a suspension;
the size of the graphene sheet is 50-200 nm;
the concentration of the graphene aqueous dispersion solution is 0.5mg/mL;
the particle size of the boracene is 1-10 nm;
the concentration of the borane aqueous dispersion is 2mg/mL;
the concentration of the surfactant aqueous solution is 0.2mg/mL;
the volume ratio of the graphene aqueous dispersion to the boron aqueous dispersion to the surfactant aqueous solution is 2:0.5:1.
(2) Taking untreated zinc foil as a working electrode, taking a carbon rod as an electrode to form a two-electrode system, taking the suspension obtained in the previous step as a deposition solution, and simultaneously depositing graphene and boron alkene on the surface of the zinc foil by adopting a constant current method;
the thickness of the zinc foil is 500 mu m;
the constant current is 0.02A.
(3) Rinsing the zinc foil surface residual solution with deionized water;
(4) Transferring the treated zinc foil to a constant temperature oven, and drying at constant temperature to obtain the graphene/boron-alkene composite interface film modified zinc metal anode.
Example 4
A preparation method of a graphene/boron alkene composite interface film modified zinc metal negative electrode comprises the following steps:
(1) Mixing graphene aqueous dispersion, boron alkene aqueous dispersion and dioctadecyl dimethyl ammonium bromide aqueous solution in a volume ratio of 4ml to 1ml to 10ml, magnetically stirring, and adjusting pH to 6 by using citric acid/sodium citrate to obtain a suspension;
the size of the graphene sheet is 50-200 nm;
the concentration of the graphene aqueous dispersion liquid is 1mg/mL;
the particle size of the boracene is 1-10 nm;
the concentration of the borane aqueous dispersion is 2mg/mL;
the concentration of the surfactant aqueous solution is 0.1mg/mL;
the volume ratio of the graphene aqueous dispersion to the boron aqueous dispersion to the surfactant aqueous solution is 2:0.5:5.
(2) Taking untreated zinc foil as a working electrode, taking a carbon rod as an electrode to form a two-electrode system, taking the suspension obtained in the previous step as a deposition solution, and simultaneously depositing graphene and boron alkene on the surface of the zinc foil by adopting a constant current method;
the thickness of the zinc foil is 200 mu m;
the constant current is 0.5A.
(3) Rinsing the zinc foil surface residual solution with deionized water;
(4) Transferring the treated zinc foil to a constant temperature oven, and drying at constant temperature to obtain the graphene/boron-alkene composite interface film modified zinc metal anode.
Claims (5)
1. A preparation method of a graphene/boron alkene composite interface film modified zinc metal negative electrode is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing graphene aqueous dispersion, boron aqueous dispersion and surfactant aqueous solution in a certain volume ratio, magnetically stirring, and adjusting pH by using citric acid/sodium citrate to obtain suspension;
the surfactant is one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, hexadecyl trimethyl ammonium bromide or dioctadecyl dimethyl ammonium bromide;
(2) taking untreated zinc foil as a working electrode, taking a carbon rod as an electrode to form a two-electrode system, taking the suspension obtained in the previous step as a deposition solution, and simultaneously depositing graphene and boron alkene on the surface of the zinc foil by adopting a constant current method;
(3) rinsing the zinc foil surface residual solution with deionized water;
(4) transferring the treated zinc foil to a constant temperature oven, and drying at constant temperature to obtain the graphene/boron-alkene composite interface film modified zinc metal anode.
2. The preparation method of the graphene/boron-alkene composite interface film modified zinc metal anode, which is characterized by comprising the following steps of: the size of the graphene sheet is 50-200 nm; the concentration of the graphene aqueous dispersion liquid is 0.5 mg/mL-2 mg/mL; the particle size of the boracene is 1-10 nm; the concentration of the boron alkene water dispersion liquid is 0.5 mg/mL-2 mg/mL; the concentration of the surfactant aqueous solution is 0.0001 mg/mL-0.2 mg/mL; the volume ratio of the graphene aqueous dispersion to the boron aqueous dispersion to the surfactant aqueous solution is (0.5-2): (1-5); the pH value of the suspension is 3-6.
3. The preparation method of the graphene/boron-alkene composite interface film modified zinc metal anode, which is characterized by comprising the following steps of: the thickness of the zinc foil is 100-500 mu m.
4. The preparation method of the graphene/boron-alkene composite interface film modified zinc metal anode, which is characterized by comprising the following steps of: the constant current is 0.0001A-0.5A.
5. A zinc ion battery characterized in that: the negative electrode of the zinc ion battery is prepared by the method of any one of claims 1 to 4.
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