CN113745520A - Preparation method and application of zinc cathode material for inhibiting zinc dendrites - Google Patents

Preparation method and application of zinc cathode material for inhibiting zinc dendrites Download PDF

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CN113745520A
CN113745520A CN202111035061.8A CN202111035061A CN113745520A CN 113745520 A CN113745520 A CN 113745520A CN 202111035061 A CN202111035061 A CN 202111035061A CN 113745520 A CN113745520 A CN 113745520A
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zinc
surfactant
electrode
oxide
zinc oxide
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CN113745520B (en
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刘宾虹
毛煜博
李洲鹏
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Zhejiang University ZJU
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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
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

Abstract

The invention relates to a zinc-nickel battery technology, and aims to provide a preparation method and application of a zinc cathode material for inhibiting zinc dendrites. The method comprises the following steps: dripping the nano zinc oxide suspension into the cyclodextrin inclusion compound solution of the triphenylphosphine oxide, uniformly stirring, and then carrying out spray drying; placing in a tube furnace, N2Carbonizing at constant temperature in the atmosphere to obtain phosphorus-doped carbon-coated zinc oxide; and placing the mixture into a hydrothermal kettle containing a surfactant aqueous solution, filtering and drying after hydrothermal treatment to obtain the zinc cathode material filled with the surfactant and used for inhibiting zinc dendrites. The invention overcomes the defects of the traditional method, the surfactant is arranged in the electrode, and the carbon film plays a role of preventing the surfactant from escaping carbon coated zinc oxide, so the suppression effect of the surfactant on dendritic crystal generation is fully exerted, and the effect is obvious compared with the prior art.

Description

Preparation method and application of zinc cathode material for inhibiting zinc dendrites
Technical Field
The invention relates to a zinc-nickel battery technology, in particular to a zinc electrode material for inhibiting zinc dendrite, a preparation method thereof and a use method in a zinc-nickel battery. In particular to a zinc electrode material which is filled with a surfactant in phosphorus-doped carbon-coated zinc oxide and a preparation method thereof.
Background
The zinc-nickel battery is an alkaline secondary battery which is formed by stacking a zinc cathode and a nickel electrode in sequence, arranging a diaphragm in the middle and taking a potassium hydroxide aqueous solution as an electrolyte. The zinc-nickel battery is applied to small loads such as household appliances, electric toys, electric doors and windows and has good commercial prospect in the fields of electric bicycles, electric automobiles, high-speed rail power supplies, energy storage base station standby power supplies and the like with high safety requirements.
The zinc oxide has abundant reserves, has better cost advantage compared with lead-acid batteries, lithium ion batteries and the like, and is environment-friendly. The invention of the zinc-nickel battery has been for hundreds of years till now, however, the key problem that the cycle performance is poor due to zinc dendrite of the negative electrode is not solved fundamentally till now.
When the zinc-nickel battery discharges, zinc in the zinc electrode is oxidized to form zinc oxide or zinc hydroxide. Because the electrolyte of the zinc-nickel battery is a high-concentration KOH solution, zinc oxide or zinc hydroxide is converted into zincate Zn (OH) in alkali liquor4 2-And dissolved. When the zinc-nickel battery is charged, the porous zinc electrode is controlled by liquid phase diffusion mass transfer, the ion concentration near the surface of the electrode is lower, and larger concentration polarization is generated, so that Zn (OH) dissolved in electrolyte is caused4 2-Is more easily reduced at the dendritic site to form dendritic dendrites. As charging and discharging progresses, zinc deposition at the dendrite portion of the electrode accelerates and dendrite develops. In addition, if the thickness distribution of the zinc electrode surface is not uniform due to the manufacturing process, the zinc electrode surface is also one of the causes of dendrite generation. After zinc dendrite is generated, the zinc dendrite can fall off from the electrode to cause capacity reduction, and if the zinc dendrite continues to grow up and pierces the diaphragm to be in contact with the positive electrode, a short circuit is formed, and the battery fails.
Factors influencing zinc dendrites mainly include current density, concentration of zincate in the electrolyte and the like. When the zinc electrode is charged, when the current density is lower than 30% of the maximum limiting current, the zinc dendrite mainly grows from the root to become whisker-shaped dendrite, the penetrating power of the whisker-shaped dendrite is weaker, and the whisker-shaped dendrite is blocked by a diaphragm; when the current exceeds the limiting current, the deposition of the metal zinc is limited by a diffusion link, the metal zinc is mainly deposited at the top of the dendritic crystal, the growth of the dendritic crystal presents a deer-horn shape, and the fine diameter can penetrate through micropores on the diaphragm to cause short circuit; when the current density is between the two, the deposition speed of the metal zinc is high, so that the SEI film is broken from multiple points to generate a plurality of growing points, meanwhile, the positions where the SEI film is not damaged can still generate whisker-shaped dendrites, and a very rough metal zinc interface is generated by the formation of various types of zinc dendrites. The generation of zinc dendrites is also closely related to the zincate content of the electrolyte. Research shows that zinc dendrites are more easily generated due to low concentration of zincate in the electrolyte, and the formation of the zinc dendrites is aggravated by factors blocking the transfer of the zincate.
The surfactant is a substance which can cause the surface tension of the solution to be remarkably reduced, has fixed hydrophilic and hydrophobic groups and can be directionally arranged on the surface of the solution. This property of the surfactant is determined by the characteristic molecular structure of the surfactant, which has a hydrophilic group at one end and a hydrophobic group at the other end. The hydrophilic group is usually a polar group, and carboxylic acid, sulfonic acid, sulfuric acid, amino group or amino group and ammonium salt ion thereof, hydroxyl group, amide group, ether bond and the like can also be used as the polar hydrophilic group. And the hydrophobic group is often a non-polar hydrocarbon chain, such as a hydrocarbon chain of 8 or more carbon atoms.
The surfactant can reduce the tension of water on the solid surface through the adsorption on the solid-liquid two-phase interface, also can reduce the oil-water interfacial tension through the adsorption between the liquid interfaces, and a plurality of surfactants can be aggregated into aggregates in the solution to form capsules or micelles. The concentration at which the surfactant begins to form micelles is called the critical micelle concentration or CMC. Solutions above the critical micelle concentration contain an ordered phase (micelles) and a disordered phase (free surfactant molecules and/or ions). The oleophylic tail end of the surfactant molecule of the micelle is gathered in the micelle, so that the contact with polar water molecules is avoided; the polar hydrophilic head end of the molecule is exposed outside, and reacts with polar water molecules to form a shell, so that the shell is kept in contact with water and the hydrophobic groups in the micelle are protected.
The presence of the surfactant in the solution increases the wettability of the liquid on the solid surface, the emulsifiability of the liquid (gas) liquid two-phase and the foamability of the gas-liquid two-phase. Monolayer adsorption of surfactant molecules occurs primarily on the non-polar solid surface, while multilayer adsorption of surfactant may occur on the polar solid surface. The required hydrophilic-lipophilic balance can be achieved by changing the types and the occupied portions of the hydrophilic groups or the lipophilic groups and the positions of the hydrophilic groups or the lipophilic groups in the molecular structure, and the wetting degree between liquid and solid is controlled.
Conventional surfactants are classified into ionic surfactants (including cationic surfactants and anionic surfactants), nonionic surfactants, amphoteric surfactants, complex surfactants, and the like. Anionic surfactants are those whose surface-active part is negatively charged after ionization in water, while those which do not generate ions in aqueous solutions are called nonionic surfactants, which can be subdivided into mono-and poly-surfactants. The amphoteric surfactant is a surfactant having both anionic and cationic hydrophilic groups such as betaine surfactant (R-N)+(CH3)2—CH2—CH2—COO-) For divalent cations such as Ca2+And Mg2+All show excellent stability, have excellent dispersing ability to divalent cations, prevent the precipitation of the divalent cations and improve the using effect.
The surfactant can be adsorbed on the surface of the metal zinc to form a compact adsorption layer, has a certain retardation effect on the passing of current, leads to the rise of overpotential, reduces the electrode reaction rate, inhibits dendritic crystals from occurring, and forms a bright, compact and smooth zinc deposition layer. The hydrophilic end of the surfactant molecule is usually provided with an unbonded lone pair of electrons, and the electronic configuration of the metal zinc is d10I.e. the d sublayer is completely filled, by sp3The hybridization and the ligand form a coordination compound with a tetrahedral structure to form a multi-layer chemical adsorption layer, and the spatial configuration of the ligand is a key factor for stabilizing the adsorption layer and passivating the front edge of zinc dendrites. When the surfactant is adsorbed on the surface of the metal zinc by electrostatic force, single-layer adsorption is formed, and an electric double layer is formed by the electric-rich state of the metal surface of the zinc and cations in an electrolyte system. The cationic surfactant is added into the electrolyte, which is favorable for the stability of the double-electric-layer structureForming a monomolecular adsorption layer, and the zinc surface passivation effect is weaker. However, it has been found that the addition of a cationic surfactant such as cetyltriethylammonium bromide (CTAB) to the electrolyte may be combined with the zincate ion Zn (OH)4 2-Form a multi-ionic associate (CTAB)+)2Zn(OH)4 2-The overpotential is obviously improved, and the occurrence of dendrite is reduced. Adding anionic surfactant such as citrate and sodium gluconate to form [ ZnHcit]-And [ ZnGlu ]]+Similarly, the overpotential is increased to suppress the generation of zinc dendrite.
In summary, suppression of zinc dendrites must be accomplished by reducing both the metal zinc/electrolyte interfacial activity and the reactivity of the zincate ion. The high-activity surfactant is used to form a stable adsorption layer on the surface of the metal zinc, and the stable adsorption layer and zincate ions form large-size composite ions, so that the over potential is improved by utilizing the steric hindrance effect, the crystal growth is retarded, and the occurrence of dendritic crystals is inhibited.
Because the electrolyte of the zinc-nickel battery is a strong alkaline solution, the solubility of the ionic surfactant is limited. The salt resistance of the anionic surfactant is poor, and the anionic surfactant is precipitated due to the existence of high-valence metal ions. While the non-ionic surface active agent such as gelatin, polyvinyl alcohol (PVA), polyethylene glycol (PEG) and polyvinylpyrrolidone (PVP) is not influenced by inorganic electrolyte because the polar group is uncharged, and can be reacted with H through hydrogen bond2O and H3O+The nonionic surfactant is bonded so as to be positively charged and have an electrical action similar to that of a hetero-electric surfactant. The nonionic surfactant is added into the ionic surfactant, so that the surface activity is improved, and the surface tension is obviously reduced. The interaction between the anionic surfactant and the nonionic surfactant is strong, and the complex formulation of the anionic surfactant and the nonionic surfactant can effectively improve the tolerance of the surfactant to high-valence cations, such as the complex formulation of the anionic surfactant-sodium alkenyl sulfonate and tween-80 (nonionic surfactant), and can be used for reducing the surface tension of hard water. When anionic surfactant and nonionic surfactant are compounded, the hydrophobic chain length, and its symmetry, amphiphobicThe more asymmetric the water chain length, the better the solubility of the mixed system. The nonionic surfactant can also be compounded with micromolecular surfactant molecules such as fatty alcohol with carbon atoms below 12, the nonionic surfactant has adsorption effect on the micromolecular surfactant molecules, the number of free surfactant molecules in the solution is reduced, and the critical micelle concentration is increased.
The fluorocarbon surfactant is a nonionic surfactant with the highest surface activity in all the surfactants at present, has the best chemical stability and thermal stability, and has special purposes which cannot be replaced by a plurality of hydrocarbon surfactants. However, the fluorocarbon surfactant is difficult to synthesize and expensive, and the practical application is greatly limited. Through compounding of the surfactants, the dosage of the fluorocarbon surfactant can be reduced, the surface activity of the fluorocarbon surfactant is kept, a strong synergistic effect is shown, and the effect which cannot be achieved by a single fluorocarbon surfactant is achieved.
The traditional method for inhibiting dendritic crystal growth is to dissolve a surfactant in an electrolyte, however, in the process of charging and discharging of a zinc electrode, a large amount of zincate ions are dissociated outside the zinc electrode, the zincate ions have high density and exist at the bottom of the battery, while the surfactant has low density and exists at the upper part of the battery, and concentration difference is formed in the battery, so that the dendritic crystal inhibition effect is not obvious.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a preparation method and application of a zinc cathode material for inhibiting zinc dendrites.
In order to solve the technical problem, the technical scheme of the invention is as follows:
the preparation method of the zinc anode material for inhibiting the zinc dendrites comprises the following steps:
(1) dissolving 0.1-0.5 g of triphenylphosphine oxide in 50mL of tetrahydropyran at 90 ℃, and performing ultrasonic vibration dispersion for 5 minutes to obtain a triphenylphosphine oxide solution; dissolving 2-5 g of beta-cyclodextrin in 50mL of deionized water at 90 ℃, and dropwise adding the deionized water into a triphenylphosphine oxide solution; after ultrasonic vibration dispersion for 30 minutes, stirring and cooling to ensure that the phenyl group enters a cyclodextrin cavity, thereby obtaining a cyclodextrin inclusion compound solution of the triphenylphosphine oxide;
(2) adding 25g of nano zinc oxide into 100mL of deionized water, and stirring to form zinc oxide suspension; then dropwise adding the solution into a cyclodextrin inclusion compound solution of triphenylphosphine oxide, uniformly stirring, and then carrying out spray drying to obtain a precursor;
(3) the precursor is placed in a tube furnace at N2Heating to 250 ℃ under the atmosphere protection, and pre-carbonizing for 2 h; then heating to 700 ℃, and carbonizing for 4h at constant temperature; then cooling to room temperature to obtain phosphorus-doped carbon-coated zinc oxide;
(4) taking 10g of phosphorus-doped carbon-coated zinc oxide, placing the 10g of phosphorus-doped carbon-coated zinc oxide in 80mL of hydrothermal kettle containing 10-50 wt.% of surfactant aqueous solution, and carrying out hydrothermal treatment at 80-160 ℃ for 20-60 minutes; and filtering and drying to obtain the zinc cathode material filled with the surfactant and used for inhibiting the zinc dendrites.
Preferably, in the step (1), the temperature is reduced by stirring at a cooling rate of 1 ℃/min.
Preferably, in the step (3), the temperature rise rates of two successive times are respectively 20 ℃/min and 10 ℃/min.
Preferably, the surfactant is at least one of an ionic surfactant, a nonionic surfactant, and an amphoteric surfactant.
The invention further provides a method for preparing a zinc electrode by using the zinc cathode material for inhibiting zinc dendrites, which comprises the following steps:
(1) taking a zinc cathode material and a binder PTFE according to the mass ratio of 9: 1, and carrying out mechanical grinding, mixing and repeated rolling to obtain an electrode blank material;
(2) covering the upper and lower surfaces of the galvanized copper mesh with the electrode blank material at 100Kg cm-2Is pressed and molded under the pressure of the pressure to obtain the zinc electrode.
The invention also provides a zinc-nickel battery, which comprises a diaphragm, an anode, a cathode and electrolyte, wherein the anode and the cathode are respectively arranged on two sides of the diaphragm in opposite directions to form a sandwich structure, and the electrolyte is arranged in the sandwich structure;
the negative electrode is a zinc electrode prepared by the method;
the positive electrode passes throughThe preparation method comprises the following steps: taking nickel hydroxide, nickel carbonyl powder and binder sodium carboxymethyl cellulose according to the mass ratio of 8:1:1, adding deionized water, grinding and blending into paste, and coating the paste on foamed nickel; drying at 100Kg cm-2Is pressed and molded under the pressure of (3) to obtain the positive electrode.
Preferably, in the zinc-nickel battery, the electrolyte is 6-12 mol/L KOH solution, and the diaphragm is a microporous polypropylene film.
Description of the inventive principles:
1. when the cyclodextrin solution is dripped into the triphenylphosphine oxide solution, benzene rings on the triphenylphosphine oxide enter the inner cavity of cyclodextrin molecules to form the triphenyl-oxyphosphorus cyclodextrin inclusion compound. The triphenyl-based oxygen-phosphorus cyclodextrin inclusion compound has the advantages that the cyclodextrin outer side of the triphenyl-based oxygen-phosphorus cyclodextrin inclusion compound is rich in hydroxyl groups, the affinity to zinc oxide is excellent, when zinc oxide suspension liquid drops are added to triphenyl-based oxygen-phosphorus cyclodextrin inclusion compound solution, the triphenyl-based oxygen-phosphorus cyclodextrin inclusion compound is effectively adsorbed on the surfaces of nano zinc oxide particles, the triphenyl-based oxygen-phosphorus cyclodextrin inclusion compound is continuously deposited on the surfaces of the zinc oxide particles in the spray drying process, and a triphenyl-based oxygen-phosphorus cyclodextrin inclusion compound shell is formed on the surfaces of the nano zinc oxide particles after drying, so that the obtained precursor is the triphenyl-based oxygen-phosphorus cyclodextrin inclusion compound coated zinc oxide with a core-shell structure.
In the calcining process, the triphenyl oxyphosphorus cyclodextrin inclusion compound is pre-carbonized at 250 ℃ to form a framework, then the framework is cracked and carbonized at the temperature of over 700 ℃ to obtain phosphorus-doped carbon-coated zinc oxide, and pores are formed between the zinc oxide and the carbon film due to the generation of cracking gas in the forming process of the phosphorus-doped carbon-coated layer. When the phosphorus-doped carbon-coated zinc oxide is placed in a hydrothermal kettle of a surfactant aqueous solution for hydrothermal treatment, the hydrophilic end of the surfactant is adsorbed on the surface of the zinc oxide, the hydrophobic end of the surfactant is adsorbed on the inner side of the carbon film, and a three-layer concentric core-shell structure of ZnO/surfactant/carbon film is formed after drying.
2. The triphenyl oxyphosphorous cyclodextrin inclusion compound is beneficial to the dispersion of zinc oxide, and a phosphorus-doped carbon film with uniform thickness is obtained on the surface of the nano zinc oxide after carbonization. The negative electrode material with the three-layer concentric core-shell structure of ZnO/surfactant/carbon film inhibits the formation of zinc dendrites in the carbon film due to the presence of the surfactant during the charging process. In the discharging process, the zincate ions and the surfactant form large-size composite ions, and the existence of the carbon film inhibits the composite ions from escaping from the carbon-coated zinc oxide, so that the generation and the development of zinc dendrites are avoided. The carbon film with uniform thickness ensures that the impedance distribution of the carbon-coated zinc oxide is uniform, and eliminates the tendency of dendrite caused by nonuniform electric field distribution.
3. After phosphorus-doped carbon films, phosphorus becomes an electricity-rich center in the carbon film because the outermost layer of phosphorus atoms has 5 electrons and the carbon atoms have only 4 electrons. The existence of phosphorus in the carbon film not only improves the conductivity of the carbon film, but also reduces the zincate compound ions which preferentially obtain electrons at the electricity-rich center during charging. The carbon film with uniformly distributed phosphorus effectively improves the nucleation rate of metal zinc, thereby reducing the possibility of zinc dendrite occurrence in the aspect of crystallography, and being an ideal dendrite-preventing zinc electrode material.
Compared with the prior art, the invention has the following beneficial effects:
the traditional method for inhibiting the dendritic crystal is to add a surfactant into an electrolyte, only has a function of inhibiting the dendritic crystal growth of zincate ions on the surface of an electrode and is difficult to diffuse into a porous electrode, so the dendritic crystal growth inhibition in the electrode is weak.
The invention overcomes the defects of the traditional method, the surfactant is arranged in the electrode, and the carbon film plays a role of preventing the surfactant from escaping carbon coated zinc oxide, so the suppression effect of the surfactant on dendritic crystal generation is fully exerted, and the effect is obvious compared with the prior art.
Drawings
Fig. 1 shows the charged morphology of the fluorocarbon surfactant-filled phosphorus-doped carbon-coated zinc oxide obtained in example six.
Fig. 2 is a graph showing the cycle performance of the zinc-nickel battery of the present invention obtained in example ten compared with the performance stability of a conventional zinc-nickel battery.
The reference numbers in the figures are: 1 a zinc-nickel battery assembled by a zinc electrode prepared by taking phosphorus-doped carbon-coated zinc oxide filled with octadecyl propyl hydroxysulfobetaine as a negative electrode material; 2 zinc-nickel battery with octadecyl propyl hydroxy sulfobetaine added into electrolyte, wherein zinc electrode prepared by phosphorus doped carbon coated zinc oxide as negative electrode material.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments:
the first embodiment is as follows: preparation of triphenylphosphine oxide solution
0.1g of triphenylphosphine oxide is dissolved in 50mL of tetrahydropyran at 90 ℃, and the solution is dispersed for 5 minutes by ultrasonic vibration to obtain the triphenylphosphine oxide solution.
Example two: preparation of cyclodextrin inclusion compound solution of triphenylphosphine oxide
Dissolving 0.3g of triphenylphosphine oxide in 50mL of tetrahydropyran at 90 ℃, and performing ultrasonic vibration dispersion for 5 minutes to obtain a triphenylphosphine oxide solution; dissolving 2g of beta-cyclodextrin in 50mL of deionized water at 90 ℃, and slowly dropwise adding the deionized water into a triphenylphosphine oxide solution; after ultrasonic vibration dispersion for 30 minutes, stirring and cooling at the cooling speed of 1 ℃/min to ensure that the phenyl group of the triphenylphosphine oxide molecule enters a cyclodextrin cavity, thus obtaining the cyclodextrin inclusion compound solution of the triphenylphosphine oxide.
Example three: precursor preparation
Dissolving 0.5g of triphenylphosphine oxide in 50mL of tetrahydropyran at 90 ℃, and performing ultrasonic vibration dispersion for 5 minutes to obtain a triphenylphosphine oxide solution; dissolving 3.5g of beta-cyclodextrin in 50mL of deionized water at 90 ℃, and slowly dropwise adding the deionized water into a triphenylphosphine oxide solution; after ultrasonic vibration dispersion for 30 minutes, stirring and cooling at a cooling speed of 1 ℃/min to enable the phenyl group of the triphenylphosphine oxide molecule to enter a cyclodextrin cavity, so as to obtain a cyclodextrin inclusion compound solution of the triphenylphosphine oxide;
adding 100mL of deionized water into 25g of vendor nano zinc oxide, stirring to form a zinc oxide suspension, dropwise adding the zinc oxide suspension into the triphenyl oxyphosphorus cyclodextrin inclusion compound solution, uniformly stirring, and then performing spray drying to obtain a precursor.
Example four: preparation of phosphorus-doped carbon-coated zinc oxide
Dissolving 0.5g of triphenylphosphine oxide in 50mL of tetrahydropyran at 90 ℃, and performing ultrasonic vibration dispersion for 5 minutes to obtain a triphenylphosphine oxide solution; dissolving 5g of beta-cyclodextrin in 50mL of deionized water at 90 ℃, and slowly dropwise adding the deionized water into a triphenylphosphine oxide solution; after ultrasonic vibration dispersion for 30 minutes, stirring and cooling at a cooling speed of 1 ℃/min to enable the phenyl group of the triphenylphosphine oxide molecule to enter a cyclodextrin cavity, so as to obtain a cyclodextrin inclusion compound solution of the triphenylphosphine oxide;
adding 100mL of deionized water into 25g of vendor nano zinc oxide, stirring to form a zinc oxide suspension, dropwise adding the zinc oxide suspension into the triphenyl oxyphosphorus cyclodextrin inclusion compound solution, uniformly stirring, and then performing spray drying to obtain a precursor;
the precursor is placed in a tube furnace at N2Under the protection of atmosphere at 20 deg.C for min-1Is heated to 250 ℃ at a speed of 2 hours for pre-carbonization, and then is heated for 10 min-1The temperature is raised to 700 ℃, the mixture is carbonized for 4 hours at constant temperature, and the mixture is cooled to room temperature to obtain the phosphorus-doped carbon-coated zinc oxide.
Example five: non-ionic surfactant filling of phosphorus-doped carbon-coated zinc oxide
And (3) taking 10g of phosphorus-doped carbon-coated zinc oxide obtained in the fourth embodiment, placing the 10g of phosphorus-doped carbon-coated zinc oxide into 80mL of a hydrothermal kettle containing 50 wt.% of Tween-80 aqueous solution, carrying out hydrothermal treatment at 80 ℃ for 60 minutes, filtering, and drying to obtain the Tween-80-filled zinc electrode material.
Example six: fluorocarbon surfactant filling of phosphorus-doped carbon-coated zinc oxide
The GS-FC327 fluorocarbon surfactant is a nonionic modified fluorocarbon surfactant obtained by ring-opening polymerization of perfluorooctyl sulfonyl fluoride, propylene oxide and ethylene oxide, has very low surface tension and interface tension, has extremely low critical micelle concentration, can resist high temperature, high mineralization and acid and alkali, and has good water solubility.
10g of the phosphorus-doped carbon-coated zinc oxide obtained in example four was placed in a 80mL hydrothermal kettle containing 30 wt.% of a water solution of vendor GS-FC327 fluorocarbon surfactant (GS chemical), subjected to hydrothermal treatment at 120 ℃ for 40 minutes, filtered, and dried to obtain a fluorocarbon surfactant-filled zinc electrode material, and the morphology after charging is shown in fig. 1.
Example seven: zinc electrode preparation
10g of phosphorus-doped carbon-coated zinc oxide obtained in example four was placed in an 80mL hydrothermal kettle containing 10 wt.% of a potassium dodecylbenzenesulfonate (yunnanlien Lilian biological) aqueous solution, subjected to hydrothermal treatment at 160 ℃ for 20 minutes, filtered, and dried to obtain a zinc electrode material filled with potassium dodecylbenzenesulfonate.
Grinding the zinc electrode material filled with the potassium dodecylbenzenesulfonate serving as a negative electrode material and PTFE according to the mass ratio of 90: 10, mechanically mixing, repeatedly rolling to obtain an electrode blank, covering the blank on a zinc-plated copper net up and down at a density of 100Kg cm-2Is pressed and molded under the pressure of the pressure to obtain the zinc electrode.
Example eight: preparation of zinc-nickel battery
The ZY-652D dispersing agent is an anionic polycarboxylate ammonium salt surfactant produced by Shanghai catalpi chemical Limited company, and has excellent dispersing capacity for zinc oxide. 10g of the phosphorus-doped carbon-coated zinc oxide obtained in the fourth example was placed in a 80mL hydrothermal kettle containing 20 wt.% ZY-652D dispersant (Shanghai catalpi) aqueous solution, subjected to hydrothermal treatment at 160 ℃ for 20 minutes, filtered, and dried to obtain the zinc electrode material filled with the anionic polycarboxylate.
Taking the zinc electrode material of the anionic polycarboxylate as a negative electrode material, grinding the negative electrode material and PTFE according to the mass ratio of 90: 10, mechanically mixing the negative electrode material and the PTFE, repeatedly rolling the mixture to obtain an electrode blank material, and covering the blank material on a zinc-plated copper net up and down by 100Kg cm-2Is pressed and molded under the pressure of the pressure to obtain the zinc electrode.
Adding deionized water into nickel hydroxide, nickel carbonyl powder and a binder CMC (sodium carboxymethyl cellulose) according to a mass ratio of 8:1:1, grinding into paste, coating the paste on foamed nickel, drying and then 100Kg cm-2Is press-molded under the pressure of (1) to obtain a positive electrode (nickel positive electrode).
And (2) separating the zinc electrode from the nickel positive electrode by using a microporous polypropylene film, respectively arranging the positive electrode material and the negative electrode material on two sides of the diaphragm in opposite directions to form a sandwich structure, and adding 6mol/L KOH electrolyte to obtain the zinc-nickel battery.
Example nine: zinc-nickel battery of zinc electrode material based on compound surfactant
And (3) taking 10g of phosphorus-doped carbon-coated zinc oxide obtained in the fourth embodiment, placing the phosphorus-doped carbon-coated zinc oxide in an 80mL hydrothermal kettle containing 10 wt.% of span-80 and Tween-20 aqueous solution, carrying out hydrothermal treatment at 160 ℃ for 20 minutes, filtering, and drying to obtain the zinc electrode material filled with the compound surfactant.
Grinding the zinc electrode material as a negative electrode material and PTFE at a mass ratio of 90: 10, mechanically mixing, repeatedly rolling to obtain an electrode blank, covering the blank on a zinc-plated copper net at 100Kg cm-2Is pressed and molded under the pressure of the pressure to obtain the zinc electrode.
Adding deionized water into nickel hydroxide, nickel carbonyl powder and a binder CMC (sodium carboxymethyl cellulose) according to a mass ratio of 8:1:1, grinding into paste, coating the paste on foamed nickel, drying and then 100Kg cm-2Is press-molded under the pressure of (1) to obtain a positive electrode (nickel positive electrode).
And (2) separating the zinc electrode from the nickel positive electrode by using a microporous polypropylene film, respectively arranging the positive electrode material and the negative electrode material on two sides of the diaphragm in opposite directions to form a sandwich structure, and adding 9mol/L KOH electrolyte to obtain the zinc-nickel battery.
Example ten: performance of zinc-nickel battery
10g of phosphorus-doped carbon-coated zinc oxide obtained in example four was placed in an 80mL hydrothermal kettle containing 20 wt.% octadecyl propyl hydroxysultaine (emulsion chemical) aqueous solution, subjected to hydrothermal treatment at 160 ℃ for 20 minutes, filtered, and dried to obtain a zinc electrode material filled with octadecyl propyl hydroxysultaine, wherein the weight of the electrode material was increased by 0.5g, which indicates that the content of octadecyl propyl hydroxysultaine reached 5 wt.%.
Grinding the zinc electrode material as a negative electrode material and PTFE at a mass ratio of 90: 10, mechanically mixing, repeatedly rolling to obtain an electrode blank, covering the blank on a zinc-plated copper net at 100Kg cm-2Is pressed and molded under the pressure of the pressure to obtain the zinc electrode.
Adding deionized water into nickel hydroxide, nickel carbonyl powder and a binder CMC (sodium carboxymethyl cellulose) according to a mass ratio of 8:1:1, grinding into paste, coating the paste on foamed nickel, drying and then 100Kg cm-2Is press-molded under the pressure of (1) to obtain a positive electrode (nickel positive electrode).
And (2) separating the zinc electrode from the nickel positive electrode by using a microporous polypropylene film, respectively arranging the positive electrode material and the negative electrode material on two sides of the diaphragm in opposite directions to form a sandwich structure, and adding 12mol/L KOH electrolyte to obtain the zinc-nickel battery.
Tests show that the gram capacity of the zinc electrode of the zinc-nickel battery exceeds 340mAh/g, the charge-discharge efficiency reaches 90 percent, and the 700-time circulation capacity is still kept at 300mAh/g (see a curve 1 in figure 1).
Comparative example 1
Taking 10g of phosphorus-doped carbon-coated zinc oxide obtained in the fourth embodiment as a negative electrode material, grinding the negative electrode material and PTFE at a mass ratio of 90: 10, mechanically mixing the negative electrode material and PTFE, repeatedly rolling the mixture to obtain an electrode blank, covering the blank on a zinc-coated copper mesh from top to bottom, and covering 100Kg cm of the blank with the zinc-coated copper mesh-2Pressing under the pressure of the electrolyte to obtain a zinc electrode, forming a traditional zinc-nickel battery together with the nickel anode and the electrolyte, and adding 0.5g of octadecyl propyl hydroxysulfobetaine to dissolve in the electrolyte.
The test result shows that the performance of the zinc electrode prepared by the traditional method can only maintain the stability of 200 cycles even if the surfactant is added into the electrolyte (see curve 2 in figure 2). Therefore, the zinc electrode prepared by taking phosphorus-doped carbon-coated zinc oxide filled with octadecyl propyl hydroxysulfobetaine as a negative electrode material obviously improves the performance stability of the zinc-nickel battery.
Finally, the foregoing disclosure is directed to only certain embodiments of the invention. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.

Claims (7)

1. A preparation method of a zinc cathode material for inhibiting zinc dendrites is characterized by comprising the following steps:
(1) dissolving 0.1-0.5 g of triphenylphosphine oxide in 50mL of tetrahydropyran at 90 ℃, and performing ultrasonic vibration dispersion for 5 minutes to obtain a triphenylphosphine oxide solution; dissolving 2-5 g of beta-cyclodextrin in 50mL of deionized water at 90 ℃, and dropwise adding the deionized water into a triphenylphosphine oxide solution; after ultrasonic vibration dispersion for 30 minutes, stirring and cooling to ensure that the phenyl group enters a cyclodextrin cavity, thereby obtaining a cyclodextrin inclusion compound solution of the triphenylphosphine oxide;
(2) adding 25g of nano zinc oxide into 100mL of deionized water, and stirring to form zinc oxide suspension; then dropwise adding the solution into a cyclodextrin inclusion compound solution of triphenylphosphine oxide, uniformly stirring, and then carrying out spray drying to obtain a precursor;
(3) the precursor is placed in a tube furnace at N2Heating to 250 ℃ under the atmosphere protection, and pre-carbonizing for 2 h; then heating to 700 ℃, and carbonizing for 4h at constant temperature; then cooling to room temperature to obtain phosphorus-doped carbon-coated zinc oxide;
(4) taking 10g of phosphorus-doped carbon-coated zinc oxide, placing the 10g of phosphorus-doped carbon-coated zinc oxide in 80mL of hydrothermal kettle containing 10-50 wt.% of surfactant aqueous solution, and carrying out hydrothermal treatment at 80-160 ℃ for 20-60 minutes; and filtering and drying to obtain the zinc cathode material filled with the surfactant and used for inhibiting the zinc dendrites.
2. The method as claimed in claim 1, wherein in the step (1), the temperature is reduced by stirring at a cooling rate of 1 ℃/min.
3. The method according to claim 1, wherein in the step (3), the temperature rising speed of the two successive times is 20 ℃/min and 10 ℃/min respectively.
4. The method according to claim 1, wherein the surfactant is at least one of an ionic surfactant, a non-ionic surfactant, and an amphoteric surfactant.
5. A method of making a zinc electrode using the zinc dendrite inhibiting zinc negative electrode material of claim 1 comprising the steps of:
(1) taking a zinc cathode material and a binder PTFE according to the mass ratio of 9: 1, and carrying out mechanical grinding, mixing and repeated rolling to obtain an electrode blank material;
(2) covering the upper and lower surfaces of the galvanized copper mesh with the electrode blank material at 100Kg cm-2Is pressed and molded under the pressure of the pressure to obtain the zinc electrode.
6. A zinc-nickel battery comprises a diaphragm, a positive electrode, a negative electrode and electrolyte, wherein the positive electrode and the negative electrode are respectively arranged on two sides of the diaphragm in opposite directions to form a sandwich structure, and the electrolyte is arranged in the sandwich structure; it is characterized in that the preparation method is characterized in that,
the negative electrode is a zinc electrode prepared by the method of claim 5;
the positive electrode is prepared by the following steps: taking nickel hydroxide, nickel carbonyl powder and binder sodium carboxymethyl cellulose according to the mass ratio of 8:1:1, adding deionized water, grinding and blending into paste, and coating the paste on foamed nickel; drying at 100Kg cm-2Is pressed and molded under the pressure of (3) to obtain the positive electrode.
7. The zinc-nickel battery according to claim 6, wherein the electrolyte is 6-12 mol/L KOH solution, and the separator is a microporous polypropylene film.
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