CN117438548A - Negative electrode active material for inhibiting zinc dendrite, preparation method thereof, zinc-nickel battery negative electrode material and negative electrode - Google Patents

Negative electrode active material for inhibiting zinc dendrite, preparation method thereof, zinc-nickel battery negative electrode material and negative electrode Download PDF

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Publication number
CN117438548A
CN117438548A CN202210853768.8A CN202210853768A CN117438548A CN 117438548 A CN117438548 A CN 117438548A CN 202210853768 A CN202210853768 A CN 202210853768A CN 117438548 A CN117438548 A CN 117438548A
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negative electrode
sulfur
zinc
zinc oxide
active material
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王江林
马永泉
刘孝伟
赵磊
朱军平
李伟伟
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Shandong Hetai New Energy Co ltd
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Shandong Hetai New Energy Co ltd
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/244—Zinc electrodes
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to the technical field of batteries, and provides a negative electrode active material for inhibiting zinc dendrite, a preparation method thereof, a zinc-nickel battery negative electrode material and a negative electrode, wherein the negative electrode active material is sulfur-doped carbon-coated zinc oxide, and raw materials of the sulfur-doped carbon-coated zinc oxide comprise zinc oxide, a carbon source, a sulfur-containing organic compound and deionized water. According to the invention, the zinc electrode material is modified, the anode active material is sulfur-doped carbon-coated zinc oxide, which has the effect of inhibiting zinc dendrite growth, and as sulfur and carbon have adsorption capacity on zinc element, the zinc electrode material can play a role of inhibiting dissolution of zinc metazincate ions, thereby reducing the reduction of capacitance in the charging and discharging process of a zinc-nickel battery and improving the cycle performance of the battery; meanwhile, the sulfur-doped carbon can effectively improve the electrolyte wettability of the carbon-coated zinc oxide, is beneficial to improving the conduction of hydroxyl ions in the electrode, and is beneficial to realizing the high-current charge and discharge of the zinc-nickel battery.

Description

Negative electrode active material for inhibiting zinc dendrite, preparation method thereof, zinc-nickel battery negative electrode material and negative electrode
Technical Field
The invention relates to the technical field of batteries, in particular to a negative electrode active material for inhibiting zinc dendrite, a preparation method thereof, a zinc-nickel battery negative electrode material and a negative electrode.
Background
The zinc-nickel battery has the advantages of high safety, no combustion or explosion, environmental protection, economy, high specific energy of mass and the like, and becomes one of the batteries which are popular in the current new energy industry. Compared with the existing secondary alkaline battery, the mass specific energy density of the zinc-nickel battery can reach 80-120Wh/kg, which is far higher than that of lead-acid battery and cadmium-nickel battery. In addition, the zinc-nickel battery is nontoxic and pollution-free, and has great advantages compared with the existing nickel-cadmium battery; compared with the existing lithium ion battery, the lithium ion battery has high safety, does not burn or explode, and can be used in the field with higher safety requirements. And zinc is used as a main material of the battery cathode, so that the cost is low, and the manufacturing cost of the battery is reduced. Finally, the zinc-nickel battery has excellent high-rate performance, can be charged and discharged with large current, has good low-temperature performance, and becomes one of the batteries with the most potential in the field of power batteries.
However, the existing zinc-nickel battery has a serious zinc dendrite problem, namely zinc dendrite grows on the surface of a zinc cathode to penetrate through a diaphragm to reach an anode, so that the battery is short-circuited, and in addition, the zinc electrode is dissolved and deformed. The main reasons for these situations can be ascribed to the defects of the zinc electrode itself, namely, zinc oxide and zinc hydroxide are generated when the zinc electrode discharges, and the electrolyte of the zinc-nickel battery is a strong alkaline electrolyte, so that zinc oxide and zinc hydroxide are dissolved in the electrolyte. Along with the circulation of the battery, zinc dendrite growth is more serious, even a short circuit phenomenon occurs, the charge and discharge capacity of the battery is rapidly reduced, and the circulation performance is seriously reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the technical problem of how to inhibit the growth of zinc dendrite and the dissolution of an electrode so as to improve the cycle performance of a battery.
In order to solve the technical problem, the first aspect of the present invention provides a negative electrode active material for inhibiting zinc dendrites, wherein the negative electrode active material is sulfur-doped carbon-coated zinc oxide, and the raw materials of the sulfur-doped carbon-coated zinc oxide comprise zinc oxide, a carbon source, a sulfur-containing organic compound and deionized water.
Further, the sulfur-doped carbon-coated zinc oxide comprises the following raw materials in percentage by mass: carbon source: sulfur-containing organic compounds: deionized water = 1: (0.1-0.5): (0.05-0.5): (0.5-2). The mass ratio of the materials is within the range of the ratio, so that the sulfur-doped carbon coating layer can be effectively formed on the surface of the zinc oxide.
Further, the carbon source is selected from one or more of the following: glucose, sucrose, fructose and starch. The carbon source is an aldehyde compound which is easy to dissolve in water, provides carbon elements and forms a carbon coating structure on the surface of zinc oxide.
Further, the sulfur-containing organic compound material is selected from one or more of the following: thiourea, L-cysteine, L-histidine, thioglycolic acid and methionine. The sulfur-containing organic compound is a soluble sulfide that can be effectively dispersed in an aqueous solution and is used to provide the sulfur element required for doping.
The second aspect of the present invention provides a method for preparing the negative electrode active material for inhibiting zinc dendrites, comprising the steps of:
s1, adding grinding media into a ball mill, weighing a carbon source, sulfur-containing organic matters and deionized water, and adding the carbon source, the sulfur-containing organic matters and the deionized water into the ball mill for ball milling and mixing to form a water-soluble prepolymer;
s2, weighing zinc oxide, adding the zinc oxide into the water-soluble prepolymer, and continuing ball milling to form slurry;
s3, placing the slurry into a spray dryer for spray drying to obtain dried raw material powder;
and S4, placing the raw material powder into a calciner, heating to a set temperature under the protection of inert gas, carrying out heat preservation roasting, and cooling to room temperature to obtain the sulfur-doped carbon-coated zinc oxide.
Further, the roasting temperature in the step S4 is 700-1000 ℃, and the heat preservation time is 2-6h.
Further, the grinding medium in the step S1 includes five sizes of zirconia balls, and the mass ratio of the zirconia balls is that of zirconia balls with a diameter of 10 mm: zirconia balls with the diameter of 5 mm: zirconia balls with diameter of 2 mm: zirconia balls with diameter of 1 mm: diameter 0.5mm zirconia balls = 1: (1-2): (1-3): (3-7): (0.5-10). The zirconia balls have the advantages of high strength, high toughness, good wear resistance, high temperature resistance and corrosion resistance, and small dispersed pollution to grinding materials, and the zirconia balls are mixed according to the proportion of a certain diameter and weight for use, so that the particle size of materials can be controlled within a required range.
Further, the rotational speed of the ball mill in the step S1 and the step S2 is 5-50rad/min, the ball milling time is 15-60min, the feeding temperature of the slurry in the step S3 into the spray dryer is 160-300 ℃, the discharging temperature is 60-150 ℃, the feeding speed is 1-5L/h, and the rotational speed of the centrifugal disc of the spray dryer is 3000-5000rad/min. The spray dryer is a device capable of simultaneously completing drying and granulating, all products are spherical particles, the drying speed is high, the surface area of feed liquid is greatly increased after atomization, and raw material powder with uniform granularity, good fluidity, good solubility, high product purity and good quality can be obtained by controlling the feeding temperature, the discharging temperature and the feeding speed of slurry into the spray dryer.
A third aspect of the present invention provides a negative electrode material for a zinc-nickel battery, comprising the negative electrode active material for inhibiting zinc dendrites described above.
The fourth aspect of the invention provides a zinc-nickel battery anode, which comprises a current collector and the anode material, wherein the anode material is coated on the current collector.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the zinc electrode material is modified, the anode active material is sulfur-doped carbon-coated zinc oxide, which has the effect of inhibiting zinc dendrite growth, and as sulfur and carbon have adsorption capacity on zinc element, the zinc electrode material can play a role of inhibiting dissolution of zinc metazincate ions, thereby reducing the reduction of capacitance in the charging and discharging process of a zinc-nickel battery and improving the cycle performance of the battery; meanwhile, the sulfur-doped carbon can effectively improve the electrolyte wettability of the carbon-coated zinc oxide, is beneficial to improving the conduction of hydroxyl ions in the electrode, and is beneficial to realizing the high-current charge and discharge of the zinc-nickel battery.
(2) The sulfur doped in the anode active material can be coordinated with sulfur-philic anode active material elements such as Sn, sb, bi and the like in the electrolyte to form a metal coordination polymer, so that the composition, structure and thickness of the carbon coating layer are optimized, the specific capacity of the anode material is improved, the hydrogen evolution potential of the anode material is improved, and the charge and discharge efficiency of the zinc-nickel battery is further improved.
(3) According to the preparation method of the negative electrode active material, the ball mill is adopted to ball mill the raw materials, so that the raw materials can be fully mixed, the material viscosity can be regulated and controlled by controlling the rotation speed and time of the ball mill, the ball mill is more suitable for feeding treatment of a spray dryer, five zirconia balls with different sizes are added into the ball mill to serve as grinding media, the ball mill treated materials are high in uniformity, uniform in granularity and large in specific surface area, and the sulfur-doped carbon coating layer can be uniformly coated on the surfaces of zinc oxide particles in the spray drying process.
(4) The preparation method of the negative electrode active material comprises the steps of firstly dissolving and prepolymerizing a sulfur-containing organic compound and a carbon source in water, prepolymerizing the sulfur-containing compound and an aldehyde-based compound (such as monosaccharide, polysaccharide and the like) to obtain a water-soluble thiourea aldehyde prepolymer, uniformly dispersing sulfur urea-formaldehyde resin and zinc oxide due to the affinity of sulfur in the sulfur urea-formaldehyde resin, and uniformly spraying and drying to obtain a uniform resin modified layer which covers the surfaces of nano zinc oxide particles, and carrying out deep polymerization and carbonization on the urea-formaldehyde prepolymer in the subsequent calcination process to obtain a functionalized carbon coated layer, wherein the hydrogen escape overpotential is increased by sulfur doping in the carbon layer, and the charge and discharge efficiency of the battery is improved.
Drawings
Fig. 1 is a flowchart of a preparation process of a negative electrode active material according to an embodiment of the present invention;
fig. 2 is an XRD diffractogram of the negative electrode active material prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of zinc oxide;
FIG. 4 is a scanning electron microscope image of the sulfur-doped carbon-coated zinc oxide prepared in example 1 of the present invention;
FIG. 5 is a scanning electron microscope image of the sulfur-doped carbon-coated zinc oxide prepared in example 1 of the present invention;
FIG. 6 is a scanning electron microscope image of sulfur-doped carbon-coated zinc oxide prepared in example 2 of the present invention.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. It should be noted that the following examples are only for illustrating the implementation method and typical parameters of the present invention, and are not intended to limit the scope of the parameters described in the present invention, so that reasonable variations are introduced and still fall within the scope of the claims of the present invention.
It should be noted that endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and that such range or value should be understood to include values approaching such range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The embodiment of the invention provides a zinc-nickel battery anode, which comprises a current collector and an anode material coated on the current collector. The negative electrode material includes a negative electrode active material that suppresses zinc dendrites, and may further include an additive, a conductive agent, a binder, a dispersant, and the like. The negative electrode active material is sulfur-doped carbon-coated zinc oxide and is prepared by reacting zinc oxide, a carbon source, a sulfur-containing organic compound and deionized water.
In a specific embodiment, the raw material mass ratio of the anode active material is zinc oxide: carbon source: sulfur-containing organic compounds: deionized water = 1: (0.1-0.5): (0.05-0.5): (0.5-2). The carbon source is an aldehyde compound which is easy to dissolve in water, such as glucose, sucrose, fructose, starch and the like; the sulfur-containing compound is thiourea, L-cysteine, L-histidine, thioglycollic acid, methionine, etc. which are easily dissolved in water.
The preparation method of the negative electrode active material is shown in fig. 1, and comprises the following steps:
s1, adding grinding media into a ball mill, weighing a carbon source, sulfur-containing organic matters and deionized water, and adding the materials into the ball mill for ball milling and mixing to form a water-soluble prepolymer. The sulfur-containing organic compound and the carbon source are dissolved and prepolymerized in water, the sulfur-containing compound and the aldehyde-based compound are prepolymerized to obtain a water-soluble thiourea aldehyde prepolymer, and the affinity of sulfur in the sulfur urea-formaldehyde resin and zinc oxide is favorable for uniformly dispersing the sulfur urea-formaldehyde resin and the zinc oxide.
S2, weighing zinc oxide, adding the zinc oxide into the water-soluble prepolymer obtained in the step S1, and continuing ball milling to form slurry. The rotating speed of the ball mill in the steps S1 and S1 is 5-50rad/min, the ball milling time is 15-60min, and the slurry viscosity can be regulated and controlled by controlling the rotating speed and time of the ball mill, so that the ball mill is more suitable for feeding treatment of a spray dryer. Five zirconia balls with different sizes are added into a ball mill to serve as grinding media, and the mass ratio of the zirconia balls with different sizes is that the zirconia balls with the diameters of 10 mm: zirconia balls with the diameter of 5 mm: zirconia balls with diameter of 2 mm: zirconia balls with diameter of 1 mm: diameter 0.5mm zirconia balls = 1: (1-2): (1-3): (3-7): (0.5-10). The ball-milled material has high uniformity, uniform granularity and large specific surface area.
S3, placing the slurry obtained in the step S2 into a spray dryer for spray drying, wherein the feeding temperature is 160-300 ℃, the discharging temperature is 60-150 ℃, the feeding speed is 1-5L/h, and the rotating speed of a centrifugal disc of the spray dryer is 3000-5000rad/min, so that the dried raw material powder is obtained. The sulfur-doped carbon coating layer uniformly covers the surface of the zinc oxide particles in the spray drying process. The feeding speed is matched with the rotating speed of the centrifugal disc, the discharging speed and the particle size of the materials are controlled, and the spray dryer is prevented from being blocked.
S4, placing the raw material powder obtained in the step S3 into a calciner, introducing inert gas at the temperature lower than 100 ℃, detecting that the oxygen content in the calciner is less than or equal to 100ppm, starting heating, heating the inert gas to a set temperature under the protection of the inert gas by adopting one or two mixed gases of nitrogen and argon, preserving heat and roasting, wherein the roasting temperature is 700-1000 ℃, the preserving heat time is 2-6h, and cooling to room temperature to obtain the sulfur-doped carbon-coated zinc oxide. In the calcination process, deep polymerization and carbonization of the urea formaldehyde prepolymer occur to obtain a functionalized carbon coating layer, and sulfur doping in the carbon layer also increases the hydrogen escaping overpotential and improves the charge and discharge efficiency.
The sulfur-doped carbon-coated zinc oxide has the effect of inhibiting zinc dendrite growth, and as sulfur and carbon have adsorption capacity on zinc element, the dissolution of metazincate ions can be inhibited, so that the reduction of capacitance in the charging and discharging process of the zinc-nickel battery can be reduced, and the cycle performance of the battery can be improved. The sulfur-doped carbon can effectively improve the electrolyte infiltration of the carbon-coated zinc oxide, is beneficial to improving the conduction of hydroxide ions in the electrode, and is beneficial to realizing the high-current charge and discharge of the zinc-nickel battery. The doped sulfur can be coordinated with sulfur-philic anode active material elements such as Sn, sb, bi and the like in the electrolyte to form a metal coordination polymer, and the composition, structure and thickness of the carbon coating layer are optimized, so that the specific capacity of the anode material is improved, the hydrogen evolution potential of the anode material is improved, and the charge and discharge efficiency of the zinc-nickel battery is further improved.
The present invention will be described in detail by way of specific examples.
Example 1
Preparing sulfur-doped carbon-coated zinc oxide as a negative electrode active material, comprising the steps of:
adding grinding medium zirconia balls into a ball mill, wherein the mass ratio of the zirconia balls with the sizes is that the zirconia balls with the diameters of 10 mm: zirconia balls with the diameter of 5 mm: zirconia balls with diameter of 2 mm: zirconia balls with diameter of 1 mm: diameter 0.5mm zirconia balls = 1:2:2:4.5:0.5 kg of glucose, 0.1kg of thiourea and 1kg of deionized water are weighed, added into a ball mill, the rotation speed of the ball mill is set to 25rad/min, the ball milling time is set to 30min, and the water-soluble prepolymer is formed after ball milling and mixing.
Zinc oxide 1kg is added into the water-soluble prepolymer, the rotating speed of a ball mill is set to be 50rad/min, and the ball milling time is set to be 45min, so that slurry is formed.
And (3) putting the obtained slurry into a spray dryer for spray drying, setting the feeding speed of spray drying to be 1L/h, setting the feeding temperature of spray drying to be 150 ℃, setting the discharging temperature to be 90 ℃, setting the rotating speed of a centrifugal disc of spray drying to be 3000rad/min, and spray drying to obtain dried raw material powder.
And (3) placing the obtained dry raw material powder into a calciner, heating to 800 ℃ under the protection of nitrogen, preserving heat and roasting for 4 hours, and taking out the material after the temperature in the calciner is cooled to room temperature to obtain the sulfur-doped carbon-coated zinc oxide.
XRD diffraction analysis was performed on the sulfur-doped carbon-coated zinc oxide obtained in this example, and the result is shown in FIG. 2, in which it can be seen that the doped carbon-coated zinc oxide has a crystal structure consistent with that of zinc oxide before the treatment, indicating that the crystal structure of zinc oxide is not damaged by the above-mentioned preparation method; the XRD diffractograms also showed no diffraction peaks for carbon and sulfur, indicating that the carbon layer and doped sulfur are present in the amorphous or microcrystalline thin layer structure.
As shown in FIG. 4, compared with the zinc oxide which is not doped and coated in FIG. 3, the scanning electron microscope image of the sulfur-doped carbon-coated zinc oxide obtained in the embodiment can obviously show that the interface becomes fuzzy after the surface of the zinc oxide particles is coated, the zinc oxide particles are connected together through the coating layer, and the sulfur-doped carbon coating layer plays a role in effectively improving the wettability of zinc oxide electrolyte, is beneficial to improving the conduction of hydroxide ions in the electrode and is beneficial to the high-current charge and discharge of the zinc-nickel battery. According to the transmission electron microscope picture shown in fig. 5, a transparent doping layer is coated on the surface of the black zinc oxide particles in a more visual reaction mode.
Example 2
Preparing sulfur-doped carbon-coated zinc oxide as a negative electrode active material, comprising the steps of:
adding grinding medium zirconia balls into a ball mill, wherein the mass ratio of the zirconia balls with the sizes is that the zirconia balls with the diameters of 10 mm: zirconia balls with the diameter of 5 mm: zirconia balls with diameter of 2 mm: zirconia balls with diameter of 1 mm: diameter 0.5mm zirconia balls = 1:2:2:3:2, weighing 0.4kg of glucose, 0.08kg of thiourea and 0.8kg of deionized water, adding into a ball mill, setting the rotating speed of the ball mill to be 50rad/min, and the ball milling time to be 60min, and performing ball milling and mixing to form the water-soluble prepolymer.
Zinc oxide 1kg is added into the water-soluble prepolymer, the rotating speed of a ball mill is set to be 30rad/min, and the ball milling time is set to be 30min, so that slurry is formed.
And (3) putting the obtained slurry into a spray dryer for spray drying, setting the feeding speed of spray drying to be 1L/h, setting the feeding temperature of spray drying to be 180 ℃, setting the discharging temperature to be 100 ℃, setting the rotating speed of a centrifugal disc of spray drying to be 3500rad/min, and spray drying to obtain dried raw material powder.
And (3) placing the obtained dry raw material powder into a calciner, heating to 1000 ℃ under the protection of argon, preserving heat and roasting for 3 hours, and taking out the material after the temperature in the calciner is cooled to room temperature to obtain the sulfur-doped carbon-coated zinc oxide.
The sem image of the sulfur-doped carbon-coated zinc oxide obtained in this example is shown in fig. 6, and compared with the zinc oxide which is not doped and coated in fig. 3, it is obvious that the interface becomes blurred after the surface of the zinc oxide particles is coated, and the zinc oxide particles are connected together by the coating layer.
Example 3
Preparing sulfur-doped carbon-coated zinc oxide as a negative electrode active material, comprising the steps of:
adding grinding medium zirconia balls into a ball mill, wherein the mass ratio of the zirconia balls with the sizes is that the zirconia balls with the diameters of 10 mm: zirconia balls with the diameter of 5 mm: zirconia balls with diameter of 2 mm: zirconia balls with diameter of 1 mm: diameter 0.5mm zirconia balls = 1:2:3:4:6, weighing 0.1kg of sucrose, 0.1kg of L-cysteine and 0.6kg of deionized water, adding into a ball mill, setting the rotation speed of the ball mill to be 10rad/min, and the ball milling time to be 40min, and performing ball milling and mixing to form a water-soluble prepolymer.
Zinc oxide 1kg is added into the water-soluble prepolymer, the rotating speed of a ball mill is set to be 20rad/min, and the ball milling time is set to be 50min, so that slurry is formed.
And (3) placing the obtained slurry into a spray dryer for spray drying, setting the feeding speed of spray drying to be 3L/h, setting the feeding temperature of spray drying to be 300 ℃, setting the discharging temperature to be 150 ℃, setting the rotating speed of a centrifugal disc of spray drying to be 4000rad/min, and spray drying to obtain dried raw material powder.
And (3) placing the obtained dry raw material powder into a calciner, heating to 700 ℃ under the protection of nitrogen, preserving heat and roasting for 6 hours, and taking out the material after the temperature in the calciner is cooled to room temperature to obtain the sulfur-doped carbon-coated zinc oxide.
Example 4
Preparing sulfur-doped carbon-coated zinc oxide as a negative electrode active material, comprising the steps of:
adding grinding medium zirconia balls into a ball mill, wherein the mass ratio of the zirconia balls with the sizes is that the zirconia balls with the diameters of 10 mm: zirconia balls with the diameter of 5 mm: zirconia balls with diameter of 2 mm: zirconia balls with diameter of 1 mm: diameter 0.5mm zirconia balls = 1:1.5:2:5:10, weighing 0.4kg of fructose, 0.05kg of L-histidine and 0.5kg of deionized water, adding into a ball mill, setting the rotating speed of the ball mill to be 5rad/min, and performing ball milling for 60min to form a water-soluble prepolymer after ball milling and mixing.
Zinc oxide 1kg is added into the water-soluble prepolymer, the rotating speed of a ball mill is set to be 30rad/min, and the ball milling time is set to be 20min, so that slurry is formed.
And (3) putting the obtained slurry into a spray dryer for spray drying, setting the feeding speed of spray drying to be 4L/h, setting the feeding temperature of spray drying to be 250 ℃, setting the discharging temperature to be 120 ℃, setting the rotating speed of a centrifugal disc of spray drying to be 4500rad/min, and spray drying to obtain dried raw material powder.
And (3) placing the obtained dry raw material powder into a calciner, heating to 900 ℃ under the protection of argon, preserving heat and roasting for 3 hours, and taking out the material after the temperature in the calciner is cooled to room temperature to obtain the sulfur-doped carbon-coated zinc oxide.
Example 5
Preparing sulfur-doped carbon-coated zinc oxide as a negative electrode active material, comprising the steps of:
adding grinding medium zirconia balls into a ball mill, wherein the mass ratio of the zirconia balls with the sizes is that the zirconia balls with the diameters of 10 mm: zirconia balls with the diameter of 5 mm: zirconia balls with diameter of 2 mm: zirconia balls with diameter of 1 mm: diameter 0.5mm zirconia balls = 1:1.6:2.5:5.5:8, weighing 0.35kg of starch, 0.35kg of thioglycollic acid and 1.6kg of deionized water, adding into a ball mill, setting the rotating speed of the ball mill to be 45rad/min, and performing ball milling for 25min to form a water-soluble prepolymer after ball milling and mixing.
Zinc oxide 1kg is added into the water-soluble prepolymer, the rotating speed of a ball mill is set to be 35rad/min, and the ball milling time is set to be 35min, so that slurry is formed.
And (3) placing the obtained slurry into a spray dryer for spray drying, setting the feeding speed of spray drying to be 3.5L/h, setting the feeding temperature of spray drying to be 260 ℃, setting the discharging temperature to be 80 ℃, setting the rotating speed of a centrifugal disc of spray drying to be 3300rad/min, and spray drying to obtain dried raw material powder.
And (3) placing the obtained dry raw material powder into a calciner, heating to 750 ℃ under the protection of nitrogen, preserving heat, roasting for 2.5h, and taking out the material after the temperature in the calciner is cooled to room temperature to obtain the sulfur-doped carbon-coated zinc oxide.
Example 6
Preparing sulfur-doped carbon-coated zinc oxide as a negative electrode active material, comprising the steps of:
adding grinding medium zirconia balls into a ball mill, wherein the mass ratio of the zirconia balls with the sizes is that the zirconia balls with the diameters of 10 mm: zirconia balls with the diameter of 5 mm: zirconia balls with diameter of 2 mm: zirconia balls with diameter of 1 mm: diameter 0.5mm zirconia balls = 1:1:1:4:7, weighing 0.5kg of fructose, 0.5kg of methionine and 2kg of deionized water, adding into a ball mill, setting the rotating speed of the ball mill to be 50rad/min, and the ball milling time to be 60min, and performing ball milling and mixing to form the water-soluble prepolymer.
Zinc oxide 1kg is added into the water-soluble prepolymer, the rotating speed of a ball mill is set to be 50rad/min, and the ball milling time is set to be 60min, so that slurry is formed.
And (3) putting the obtained slurry into a spray dryer for spray drying, setting the feeding speed of spray drying to be 5L/h, setting the feeding temperature of spray drying to be 280 ℃, setting the discharging temperature to be 75 ℃, setting the rotating speed of a centrifugal disc of spray drying to be 5000rad/min, and spray drying to obtain dried raw material powder.
And (3) placing the obtained dry raw material powder into a calciner, heating to 950 ℃ under the protection of nitrogen, preserving heat, roasting for 5.5h, and taking out the material after the temperature in the calciner is cooled to room temperature to obtain the sulfur-doped carbon-coated zinc oxide.
Comparative example
Zinc oxide, carbon-coated zinc oxide, and sulfur-doped carbon-coated zinc oxide of example 1 were used as negative electrode active materials, respectively. 600g of negative electrode active material, 200g of additive calcium carbonate, 30g of conductive agent graphite, 100g of adhesive 60% PTFE emulsion and 200g of dispersing agent deionized water are weighed, uniformly mixed to prepare negative electrode slurry, and the negative electrode slurry is coated on the surface of a current collector to prepare a 1.6V/8Ah single cell. The three batteries were subjected to battery capacity testing.
The zinc oxide is used as a negative electrode active material to prepare a single cell battery, the discharge capacity of the single cell battery rapidly decays in the battery capacity test process, and the discharge capacity of the single cell battery is close to 0 after 50 times of circulation. The carbon-coated zinc oxide and the sulfur-doped carbon-coated zinc oxide are used as negative electrode active materials to prepare single-cell batteries, and in the previous 400 cycle tests, the discharge capacities of the two are basically kept unchanged, so that the consistency of the batteries is good; along with the continuous proceeding of the cycle test, when the cycle times reach 800 times, the discharge capacity of the carbon-coated zinc oxide single cell battery is attenuated from 8Ah to 5Ah, and the discharge capacity is 62.5% of the original discharge capacity; when the cycle number reaches 800, the discharge capacity of the sulfur-doped carbon-coated zinc oxide single cell is reduced from 8Ah to 6.4Ah, and the discharge capacity is still 80%, so that the discharge capacity reduction speed of the carbon-coated zinc oxide single cell is obviously faster than that of a single cell made of sulfur-doped carbon-coated zinc oxide.
The result shows that the sulfur-doped carbon-coated zinc oxide serving as the anode active material can effectively inhibit the growth of zinc dendrites, and the cycle life of a single cell prepared by taking the sulfur-doped carbon-coated zinc oxide serving as the anode active material is greatly prolonged.
Although the present invention is disclosed above, the present invention is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention, and the scope of the invention should be assessed accordingly to that of the appended claims.

Claims (10)

1. The negative electrode active material for inhibiting zinc dendrites is characterized in that the negative electrode active material is sulfur-doped carbon-coated zinc oxide, and the raw materials of the sulfur-doped carbon-coated zinc oxide comprise zinc oxide, a carbon source, a sulfur-containing organic compound and deionized water.
2. The negative electrode active material for inhibiting zinc dendrites according to claim 1, wherein the sulfur-doped carbon-coated zinc oxide has a raw material mass ratio of zinc oxide: carbon source: sulfur-containing organic compounds: deionized water = 1: (0.1-0.5): (0.05-0.5): (0.5-2).
3. The negative electrode active material for inhibiting zinc dendrites according to claim 2, wherein the carbon source is selected from one or more of the following: glucose, sucrose, fructose and starch.
4. The negative electrode active material for inhibiting zinc dendrites according to claim 2, wherein the sulfur-containing organic compound material is selected from one or more of the following: thiourea, L-cysteine, L-histidine, thioglycolic acid and methionine.
5. A method for producing the negative electrode active material for inhibiting zinc dendrites according to any one of claims 1 to 4, comprising the steps of:
s1, adding grinding media into a ball mill, weighing a carbon source, sulfur-containing organic matters and deionized water, and adding the carbon source, the sulfur-containing organic matters and the deionized water into the ball mill for ball milling and mixing to form a water-soluble prepolymer;
s2, weighing zinc oxide, adding the zinc oxide into the water-soluble prepolymer, and continuing ball milling to form slurry;
s3, placing the slurry into a spray dryer for spray drying to obtain dried raw material powder;
and S4, placing the raw material powder into a calciner, heating to a set temperature under the protection of inert gas, carrying out heat preservation roasting, and cooling to room temperature to obtain the sulfur-doped carbon-coated zinc oxide.
6. The method for producing a negative electrode active material for inhibiting zinc dendrites according to claim 5, wherein the baking temperature in step S4 is 700 to 1000 ℃ and the holding time is 2 to 6 hours.
7. The method for producing a negative electrode active material for inhibiting zinc dendrites according to claim 5, wherein the grinding medium in step S1 comprises five-sized zirconia balls each having a mass ratio of 10 mm-diameter zirconia balls: zirconia balls with the diameter of 5 mm: zirconia balls with diameter of 2 mm: zirconia balls with diameter of 1 mm: diameter 0.5mm zirconia balls = 1: (1-2): (1-3): (3-7): (0.5-10).
8. The method for preparing a negative electrode active material for inhibiting zinc dendrites according to claim 5, wherein the rotational speed of the ball mill in step S1 and step S2 is 5-50rad/min, the ball milling time is 15-60min, the feeding temperature of the slurry in step S3 into the spray dryer is 160-300 ℃, the discharging temperature is 60-150 ℃, the feeding speed is 1-5L/h, and the rotational speed of the centrifugal disc of the spray dryer is 3000-5000rad/min.
9. A negative electrode material for a zinc-nickel battery, comprising the negative electrode active material for inhibiting zinc dendrites according to any one of claims 1 to 4.
10. A negative electrode for a zinc-nickel battery, comprising a current collector and the negative electrode material of claim 9, wherein the negative electrode material is coated on the current collector.
CN202210853768.8A 2022-07-12 2022-07-12 Negative electrode active material for inhibiting zinc dendrite, preparation method thereof, zinc-nickel battery negative electrode material and negative electrode Pending CN117438548A (en)

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