CN111355135A - Composite material negative ion release head, preparation method thereof and negative ion generating electrode - Google Patents
Composite material negative ion release head, preparation method thereof and negative ion generating electrode Download PDFInfo
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- CN111355135A CN111355135A CN201811573797.9A CN201811573797A CN111355135A CN 111355135 A CN111355135 A CN 111355135A CN 201811573797 A CN201811573797 A CN 201811573797A CN 111355135 A CN111355135 A CN 111355135A
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01T—SPARK GAPS; OVERVOLTAGE ARRESTERS USING SPARK GAPS; SPARKING PLUGS; CORONA DEVICES; GENERATING IONS TO BE INTRODUCED INTO NON-ENCLOSED GASES
- H01T23/00—Apparatus for generating ions to be introduced into non-enclosed gases, e.g. into the atmosphere
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01T—SPARK GAPS; OVERVOLTAGE ARRESTERS USING SPARK GAPS; SPARKING PLUGS; CORONA DEVICES; GENERATING IONS TO BE INTRODUCED INTO NON-ENCLOSED GASES
- H01T19/00—Devices providing for corona discharge
- H01T19/04—Devices providing for corona discharge having pointed electrodes
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for preparing a composite material negative ion release head. The method comprises the following steps: thinning the graphene; carrying out surface modification on fullerene; preparing a graphene and fullerene composite material aqueous solution by adopting the graphene subjected to thinning treatment and the fullerene subjected to surface modification; and (3) putting the conductive metal wire into the graphene and fullerene composite material aqueous solution, and depositing and growing a graphene and fullerene composite material layer on the surface of the conductive metal wire to obtain the composite material negative ion release head. The invention also discloses the composite material anion release head prepared by the method and an anion generating electrode. The method can improve the solubility of the graphene and the fullerene in water, and the prepared composite material negative ion release head can generate ecological-grade small-particle-size negative oxygen ions with small particle size, high activity and long migration distance, and has high negative ion purity and long service life.
Description
Technical Field
The invention relates to a negative ion generating technology, in particular to a composite material negative ion release head, a preparation method thereof and a negative ion generating electrode.
Background
At present, the most advanced anion generation technology at home and abroad basically adopts a negative high voltage source to make carbon fibers into a discharge electrode, namely an anion release head. The negative ion releasing head is fixed on the metal rod to form a negative ion generating electrode. When the negative ion generating electrode is applied, the negative ion generating electrode is connected with a high-voltage power supply, the negative ion releasing head sprays carriers to the surrounding space at a high speed, the carriers are quickly captured by air ions to form air negative ions, and meanwhile, the positive ions are neutralized and reduced by utilizing the potential induction of a negative electric field to obtain a relatively purified negative ion field. The carbon fiber material adopted by the relatively advanced anion release head on the market at present is mainly fullerene (C60). The fullerene is a superconducting material with the resistance close to zero, is beneficial to the free precipitation of electric ions, can generate ecological-grade small-particle-size negative oxygen ions with small particle size, high activity and long migration distance, has high negative ion purity, and hardly generates derivatives such as ozone, positive ions and the like.
However, the fullerene anion generator on the market has the problem of slow response speed of the device, and the concentration of anions can rise after the device is started for a certain time.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a negative ion release head made of a graphene and fullerene composite material, a preparation method thereof and a negative ion generating electrode. The method for preparing the negative ion release head made of the composite material improves the response speed of the negative ion release head on the basis of guaranteeing high negative ion concentration and purity.
In order to achieve the above object, in a first aspect, the present invention provides a method of preparing a composite negative ion emitting head, the method comprising:
thinning the graphene;
carrying out surface modification on fullerene;
preparing a graphene and fullerene composite material aqueous solution by adopting the graphene subjected to thinning treatment and the fullerene subjected to surface modification; and
and putting a conductive metal wire into the graphene and fullerene composite material aqueous solution, and depositing and growing a graphene and fullerene composite material layer on the surface of the conductive metal wire to obtain the composite material negative ion release head.
In an embodiment of the present invention, the thinning processing on the graphene may include: ball-milling graphene until the particle size is less than 1 mu m; optionally, the ball milling is by plasma assisted ball milling.
In an embodiment of the present invention, the conditions of the plasma-assisted ball milling may include: the pressure is 0.01-1 MPa, and the ball milling environment is inert atmosphere.
In an embodiment of the present invention, the surface modification of fullerene may include:
dissolving fullerene in an organic solvent to obtain a first mixed solution;
dissolving a surfactant in a dispersing agent to obtain a second mixed solution;
mixing the first mixed solution with the second mixed solution so as to modify the surface of fullerene; and
and (5) removing impurities from the system.
In an embodiment of the invention, the surfactant may be an N-vinyl amide surfactant, optionally polyvinylpyrrolidone.
In the embodiment of the present invention, the dispersant may be selected from any one or more of aromatic hydrocarbons, halogenated aromatic hydrocarbons, alcohol solvents, and halogenated alkanes.
In an embodiment of the invention, the mass ratio of the fullerene to the surfactant may be 1:80 to 200, optionally 1:100 to 150.
In an embodiment of the present invention, the dissolving of the fullerene in the organic solvent may include: mixing fullerene with an organic solvent in a container, and ultrasonically dispersing until no fullerene is attached to the inner wall of the container and the solution in the container is not layered.
In an embodiment of the present invention, the performing impurity removal processing on the system may include: and (4) carrying out rotary evaporation on the system until the solution in the system is completely evaporated to dryness.
In the embodiment of the invention, the temperature of the rotary evaporation can be 50-100 ℃, and optionally 60-80 ℃.
In an embodiment of the present invention, the preparing of the graphene and fullerene composite aqueous solution using the graphene after the refinement treatment and the fullerene after the surface modification may include:
dissolving the graphene subjected to thinning treatment and the fullerene subjected to surface modification in water, and performing impurity removal treatment to obtain a primary aqueous solution of the graphene and fullerene composite material;
concentrating the primary aqueous solution to obtain a concentrated solution; and
and activating the concentrated solution to obtain the graphene and fullerene composite material aqueous solution.
In an embodiment of the present invention, the dissolving the graphene after the refinement treatment and the fullerene after the surface modification in water, and performing the impurity removal treatment may include: mixing the graphene subjected to thinning treatment and the fullerene subjected to surface modification with water, and performing ultrasonic dispersion; and centrifuging the solution subjected to ultrasonic dispersion until the pH value of the lower-layer precipitate is 6.5-7.5, and dissolving the lower-layer precipitate in water to obtain the primary aqueous solution of the graphene and fullerene composite material.
In an embodiment of the present invention, a mass ratio of the graphene after the thinning treatment to the fullerene after the surface modification may be 0.1 to 1:1, optionally 0.1 to 0.5: 1.
In an embodiment of the present invention, the concentration process may include: and drying the primary aqueous solution at the temperature of 20-30 ℃ for 3-5 hours.
In an embodiment of the present invention, the activation treatment may include: and sintering the concentrated solution in an inert atmosphere at 90-120 ℃ for 0.5-1.5 hours, and controlling the concentrated solution in the composite material aqueous solution of graphene and fullerene, wherein the volume fraction of the graphene and fullerene composite material is 5-30%.
In the embodiment of the present invention, the method used for depositing and growing the graphene and fullerene composite layer on the surface of the conductive metal wire may be a vertical deposition method.
In an embodiment of the present invention, the conditions of the vertical deposition method may include: the temperature is 50-120 ℃, and optionally, the temperature is 60-100 ℃; the time is 15 to 31 hours.
In the embodiment of the invention, the thickness of the graphene and fullerene composite material layer can be 2-10 nm.
In a second aspect, the invention provides the composite material negative ion release head prepared by the method.
In a third aspect, the present invention provides an anion generating electrode, which includes a metal rod, a conductive fixing device, and an anion releasing head, wherein the anion releasing head is fixed on the metal rod through the conductive fixing device, and is electrically connected to the metal rod, and the anion releasing head is the composite anion releasing head as described above.
The method for preparing the negative ion release head of the composite material can improve the solubility of graphene and fullerene in water. The prepared composite material negative ion release head can generate ecological-grade small-particle-size negative oxygen ions with small particle size, high activity and long migration distance, and the purity of the negative ions is high, and almost no by-products such as ozone, nitrogen oxide and the like are generated; and the response speed is obviously higher, and the service life is longer.
Drawings
Fig. 1 is a schematic structural view of a negative ion generating electrode according to an embodiment of the present invention.
Fig. 2 is a process flow chart of the preparation of the composite material negative ion release head according to the embodiment of the invention.
Reference numerals in the drawings denote:
1-metal rod 2-conductive fixing device 3-negative ion release head
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, embodiments of the present invention provide a method for preparing a composite material negative ion release head, the method comprising:
thinning the graphene;
carrying out surface modification on fullerene;
preparing a graphene and fullerene composite material aqueous solution by adopting the graphene subjected to thinning treatment and the fullerene subjected to surface modification; and
and putting a conductive metal wire into the graphene and fullerene composite material aqueous solution, and depositing and growing a graphene and fullerene composite material layer on the surface of the conductive metal wire to obtain the composite material negative ion release head.
In an embodiment of the present invention, the thinning processing on the graphene may include: ball milling the graphene until the particle size is less than 1 mu m.
In embodiments of the present invention, the ball milling may be plasma assisted ball milling.
The plasma auxiliary ball milling is to introduce cold field discharge plasma into mechanical ball milling, so that the powder is subjected to mechanical impact in the ball milling process and also subjected to thermal impact effect and activation effect of the plasma, wherein the process comprises the following steps: 1) the higher electron temperature of the plasma can lead to a "thermal explosion" phenomenon of the material; 2) the high-speed high-temperature pulse electrons of the plasma bombard the surface of the material, so that the thermal stress and strain of the micro-area of the powder are increased; 3) the material particles in the plasma have high activity, and the material surface can be activated by high energy after the material particles are adsorbed and deposited on the surface of the powder. The factors act together to accelerate the processes of refining, activating and alloying of the powder, improve the preparation efficiency of the powder and realize energy conservation and environmental protection.
In an embodiment of the present invention, the conditions of the plasma-assisted ball milling may include: the pressure is 0.01-1 MPa, for example, 0.1-0.2 MPa, and the thermal shock effect and the activation effect of the plasma generated under the pressure are good, so that the ball milling efficiency can be obviously improved; the ball milling environment is inert atmosphere.
In the present invention, the term "pressure" refers to gauge pressure.
Before ball-milling, carry out 3 ~ 4 times atmosphere washing to the spherical ink jar with the inert gas who forms the ball-milling environment earlier to the air in the clean discharge spheroidal graphite jar, graphene is by the oxidation when preventing the ball-milling process. And introducing inert gas into the nodular graphite tank after cleaning, and controlling the pressure in the nodular graphite tank to be 0.01-1 MPa. The particle size of the graphene before ball milling can be 100-200 meshes, and the particle size of the graphene after ball milling is less than 1 μm, for example, can be 100-500 nm. The mass ratio of the graphene to the grinding balls can be 0.5-5: 40, for example, 1: 40; the ball milling time may be 2 to 6 hours, for example, 3 hours. The ball milling apparatus may include: the power supply has a discharge voltage of 15-18 kv, a discharge frequency of 10-20 kHz, and an input current of 1.5-3A.
In an embodiment of the present invention, the surface modification of fullerene may include:
dissolving fullerene in an organic solvent to obtain a first mixed solution;
dissolving a surfactant in a dispersing agent to obtain a second mixed solution;
mixing the first mixed solution with the second mixed solution so as to modify the surface of fullerene; and
and (5) removing impurities from the system.
In an embodiment of the present invention, the dissolving of the fullerene in the organic solvent may include: mixing fullerene with an organic solvent in a container, and ultrasonically dispersing until no fullerene is attached to the inner wall of the container and the solution in the container is not layered.
The organic solvent may be selected from commonly used nonpolar organic solvents for dissolving fullerene, for example, toluene, cyclohexane, chloroform, etc. The amount of the organic solvent is only required to ensure that the fullerene is completely immersed, and for example, the mass ratio of the fullerene to the organic solvent can be 0.5-1: 1. The frequency of the ultrasonic dispersion can be 100-150 times/min.
In an embodiment of the invention, the surfactant may be an N-vinyl amide surfactant, for example, polyvinylpyrrolidone (PVP). The dispersant is used for dispersing PVP and can be selected from any one or more of aromatic hydrocarbon, halogenated aromatic hydrocarbon, alcohol solvent and halogenated alkane, for example, the dispersant can be selected from any one or more of chlorotoluene, chloroform, toluene, methanol and ethanol, and optionally the dispersant is chloroform. In the second mixed solution, the mass fraction of PVP may be 5% to 15%.
In an embodiment of the present invention, a mass ratio of the fullerene to the surfactant may be 1:80 to 200, for example, 1:100 to 150. The mass ratio of the fullerene to the surfactant can obtain a good dispersing effect, and the problem of overlong subsequent impurity removal treatment time caused by the excessive amount of the surfactant can be avoided.
In an embodiment of the present invention, the performing impurity removal processing on the system may include: and (4) carrying out rotary evaporation on the system until the solution in the system is completely evaporated to dryness.
Most of impurities such as organic solvents, surfactants, dispersants and the like in the system can be removed through rotary evaporation. In the embodiment of the invention, the temperature of the rotary evaporation can be 50-100 ℃, for example, 60-80 ℃, and the temperature can not only ensure the efficiency of the rotary evaporation, but also can not change the performance of the fullerene. The rotation speed can be 100-200 r/min.
In an embodiment of the present invention, the preparing of the graphene and fullerene composite aqueous solution using the graphene after the refinement treatment and the fullerene after the surface modification may include:
dissolving the graphene subjected to thinning treatment and the fullerene subjected to surface modification in water, and performing impurity removal treatment to obtain a primary aqueous solution of the graphene and fullerene composite material;
concentrating the primary aqueous solution to obtain a concentrated solution; and
and activating the concentrated solution to obtain the graphene and fullerene composite material aqueous solution.
In an embodiment of the present invention, the dissolving the graphene after the refinement treatment and the fullerene after the surface modification in water, and performing the impurity removal treatment may include:
mixing the graphene subjected to thinning treatment and the fullerene subjected to surface modification with water, and performing ultrasonic dispersion; and
and centrifuging the solution subjected to ultrasonic dispersion until the pH value of the lower-layer precipitate is 6.5-7.5, and dissolving the lower-layer precipitate in water to obtain the primary aqueous solution of the graphene and fullerene composite material.
During impurity removal treatment, a small amount of organic solvent, surfactant and dispersant which are remained in fullerene are dispersed in water, and then the remained small amount of organic solvent, surfactant and dispersant are thoroughly separated from the system through subsequent centrifugation.
In an embodiment of the present invention, the conditions of the ultrasonic dispersion may include: the frequency can be 100-150 times/min, and the time can be 10-30 minutes.
In an embodiment of the present invention, a mass ratio of the graphene after the thinning treatment to the fullerene after the surface modification may be 0.1 to 1:1, and optionally, may be 0.1 to 0.5: 1.
The centrifugation can separate the solid particles in the turbid liquid from the liquid dissolved with the organic solvent, the surfactant and the dispersant by using the action of gravity, so that the graphene and the fullerene form a precipitate in the lower layer, and the organic solvent, the surfactant and the dispersant are dispersed in the solution in the upper layer. After each centrifugation, the upper layer solution is poured off, the lower layer precipitate is taken out and dissolved in water, and the pH of the lower layer precipitate is measured, for example, 0.1 to 0.5mg of the lower layer precipitate is taken out and dissolved in 1 to 5mg of water, and the pH of the solution is measured by dipping the solution with a pH test paper, and the pH is taken as the pH of the lower layer precipitate. And when the pH value of the lower-layer precipitate is 6.5-7.5 (a small amount of precipitate is dissolved in a small amount of water, and the pH value of the precipitate is measured), the organic solvent, the surfactant and the dispersant in the system are basically removed completely. The centrifugation times can be 2-4 times, the centrifugation speed can be 6000-7500 rpm, the time of each centrifugation can be 5-10 min, the volume ratio of the water added in each centrifugation to the dispersion solution before the centrifugation can be 1/3-1/2: 1, the solution on the upper layer is poured out after each centrifugation is finished, and the next centrifugation is carried out after the water is added again.
And after the centrifugation is finished, pouring the upper layer solution, and uniformly dissolving the lower layer precipitate in water to obtain the primary aqueous solution of the graphene and fullerene composite material.
In the embodiment of the present invention, the concentration process may be performed in a dry manner. The conditions for drying may include: the temperature is 20-30 ℃ and the time is 3-5 hours. For example, the temperature is 22-25 ℃; the time is 4-5 hours.
The purpose of the concentration treatment includes: evaporating part of water in the solution to avoid the subsequent activation treatment in an environment with more water vapor, which is easy to generate impurities; and secondly, the concentration of the solution is improved to a certain extent, and the subsequent deposition is facilitated to grow a graphene and fullerene composite material layer with proper thickness and uniform particles. Because the water content in the system is less, the purpose of concentration treatment can be realized after drying for 3-5 hours at the temperature of 20-30 ℃.
In the embodiment of the present invention, the activation treatment may be performed by sintering under an inert atmosphere. The conditions for sintering may include: the temperature is 90-120 ℃, the time is 0.5-1.5 hours, and the temperature is controlled in the graphene and fullerene composite material aqueous solution, wherein the volume fraction of the graphene and fullerene composite material is 5-30%; for example, the temperature may be 100 to 110 ℃, the time may be 1 to 1.2 hours, and the volume fraction of the graphene and fullerene composite material may be 10 to 20%.
In the graphene and fullerene composite material aqueous solution, the volume fraction of the graphene and fullerene composite material is controlled to be 5-30%, so that a composite material layer with proper thickness (for example, 2-10 nm) and good uniformity can be obtained in the subsequent deposition growth process.
On one hand, the graphene and the fullerene can be excited through activation treatment, so that the graphene and the fullerene can be better combined and a synergistic effect can be generated; on the other hand, the residual organic solvent and dispersant may be further volatilized and removed.
If the concentration treatment step is omitted and the activation is directly carried out, at the activation temperature, water in the system is converted into water vapor and is sealed in a closed activation device, so that the activation environment is changed, and impurities are easily generated.
In an embodiment of the present invention, the inert atmosphere may be selected from any one or more of helium (He), neon (Ne), and argon (Ar). Activation in an inert atmosphere can prevent the fullerene from being oxidized.
In the embodiment of the present invention, the method used for depositing and growing the graphene and fullerene composite layer on the surface of the conductive metal wire may be a vertical deposition method. The vertical deposition method has the advantages of simple process, low growth temperature, low viscosity of the growth solution, good integrity of the grown composite material layer and more uniform surface.
In the embodiment of the invention, the temperature for depositing and growing the composite material layer by adopting the vertical deposition method can be 50-120 ℃, for example, 60-100 ℃. The deposition temperature of 50-120 ℃ is favorable for forming a composite material layer with good compactness, and the speed of forming the composite material layer is high. The deposition time may be 15 to 31 hours, for example, 16 to 30 hours. The deposition time of 15-31 hours is beneficial to forming a composite material layer of graphene and fullerene with a desired thickness.
In the embodiment of the invention, the thickness of the graphene and fullerene composite material layer can be 2-10 nm.
In an embodiment of the invention, the method further comprises: and after the growth of the composite material layer is finished, taking the composite material negative ion release head out of the composite material aqueous solution of the graphene and the fullerene, and drying. The drying can be realized by a constant-temperature drying mode, the drying temperature can be 60-80 ℃, and the drying time can be 30-60 minutes.
In a second aspect, the embodiment of the invention provides a composite material negative ion release head prepared by the method.
In a third aspect, an embodiment of the present invention provides an anion generating electrode, as shown in fig. 1, the anion generating electrode includes a metal rod 1, a conductive fixing device 2, and an anion releasing head 3, the anion releasing head 3 is fixed on the metal rod 1 through the conductive fixing device 2, the anion releasing head 3 is electrically connected to the metal rod 1, and the anion releasing head 3 is a composite anion releasing head prepared by the above method.
Examples
The present invention will be described in detail below by way of examples, but the present invention is not limited thereto. In the following examples, unless otherwise specified, all methods used are conventional in the art, and all reagents used are commercially available.
The particle size of the raw material graphene adopted in the following embodiments is 100-200 meshes.
Example 1
As shown in fig. 2, the method for preparing the negative ion discharging head and the negative ion generating electrode of the present embodiment includes:
s1: placing graphene and grinding balls into a plasma-assisted vibration ball milling device, firstly, carrying out atmosphere cleaning on a ball milling tank for 3 times by adopting argon, introducing argon after cleaning, controlling the pressure in the nodular graphite tank to be 0.1MPa, and carrying out plasma-assisted ball milling for 6 hours to obtain graphene with the particle size of 100-500 nm; the mass ratio of the graphene to the grinding ball is 0.5:40, the discharge voltage of a power supply is 15kv, the discharge frequency is 10kHz, and the input current is 1.5A;
s2: adding toluene into a container containing fullerene, controlling the mass ratio of the fullerene to the toluene to be 1:1, and ultrasonically dispersing at the frequency of 100 times/min until no fullerene is attached to the inner wall of the container and the solution in the container is not layered to obtain a first mixed solution;
s3: mixing polyvinylpyrrolidone with chloroform to obtain a second mixed solution, controlling the mass fraction of polyvinylpyrrolidone in the second mixed solution to be 15%, adding the first mixed solution obtained in the step S2 into the second mixed solution, controlling the mass ratio of fullerene to polyvinylpyrrolidone to be 1:100, and stirring by magnetic force to fully mix the fullerene and the polyvinylpyrrolidone;
s4: rotationally evaporating the solution obtained in the step S3 at 60 ℃, wherein the rotational speed is 100r/min until the solution in the system is completely evaporated to dryness;
s5: mixing the graphene obtained in the step S1 with the fullerene obtained in the step S4, adding deionized water into the mixture, and then ultrasonically dispersing for 20min at the frequency of 100 times/min to form a uniformly mixed dispersion solution; wherein the mass ratio of graphene to fullerene to water is 0.1:1: 10;
s6: adding deionized water into the dispersed solution obtained in the step S5, centrifuging at 6000rpm for 10min, repeatedly centrifuging for 2 times, wherein the volume ratio of the deionized water added in each centrifugation to the dispersed solution obtained in the step S5 is 1/2:1, centrifuging for 2 times, pouring out the upper-layer solution, dissolving 0.1mg of lower-layer precipitate in 1mg of deionized water, measuring the pH value to be 6.7, and dissolving the obtained lower-layer precipitate in the deionized water to obtain a primary aqueous solution of graphene and fullerene;
s7: drying the primary aqueous solution at 20 ℃ for 5 hours to obtain a concentrated solution;
s8: sintering the concentrated solution for 1.5 hours at 90 ℃ in an argon atmosphere to obtain a graphene and fullerene composite material aqueous solution; wherein, in the graphene and fullerene composite material aqueous solution, the volume fraction of the graphene and fullerene composite material is 10%;
s9: bundling 25 titanium wires on a titanium rod through copper wires, putting the titanium wires into the composite material aqueous solution obtained in the step S8, then putting the titanium wires into a thermostat, setting the temperature of the thermostat to be 60 ℃ and the time to be 30 hours, and growing a graphene and fullerene composite material layer with the thickness of 2nm on the titanium wires by adopting a vertical deposition method, thereby obtaining a composite material negative ion release head;
s10: and taking the composite material negative ion release head out of the composite material water solution, and drying at the constant temperature of 60 ℃ for 60 minutes.
Example 2
As shown in fig. 2, the method for preparing the negative ion discharging head and the negative ion generating electrode of the present embodiment includes:
s1: placing graphene and grinding balls into a plasma-assisted vibration ball milling device, firstly, carrying out atmosphere cleaning on a ball milling tank for 4 times by adopting argon, introducing argon after cleaning, controlling the pressure in the nodular graphite tank to be 0.2MPa, and carrying out plasma-assisted ball milling for 3 hours to obtain graphene with the particle size of 100-500 nm; the mass ratio of the graphene to the grinding ball is 1:40, the discharge voltage of a power supply is 17kv, the discharge frequency is 15kHz, and the input current is 2.5A;
s2: adding toluene into a container containing fullerene, controlling the mass ratio of the fullerene to the toluene to be 0.5:1, and ultrasonically dispersing at the frequency of 150 times/min until no fullerene is attached to the inner wall of the container and the solution in the container is not layered to obtain a first mixed solution;
s3: mixing polyvinylpyrrolidone with chloroform to obtain a second mixed solution, controlling the mass fraction of polyvinylpyrrolidone in the second mixed solution to be 10%, adding the first mixed solution obtained in the step S2 into the second mixed solution, controlling the mass ratio of fullerene to polyvinylpyrrolidone to be 1:130, and stirring by magnetic force to fully mix the fullerene and the polyvinylpyrrolidone;
s4: rotationally evaporating the solution obtained in the step S3 at 70 ℃, wherein the rotational speed is 150r/min until the solution in the system is completely evaporated to dryness;
s5: mixing the graphene obtained in the step S1 with the fullerene obtained in the step S4, adding deionized water into the mixture, and then ultrasonically dispersing for 15min at the frequency of 130 times/min to form a uniformly mixed dispersion solution; wherein the mass ratio of graphene to fullerene to water is 0.3:1: 10;
s6: adding deionized water into the dispersed solution obtained in the step S5, centrifuging at 7000rpm for 8min, repeatedly centrifuging for 3 times, wherein the volume ratio of the deionized water added in each centrifugation to the dispersed solution obtained in the step S5 is 1/3:1, centrifuging for 3 times, pouring out the upper-layer solution, dissolving 0.3mg of lower-layer precipitate in 3mg of deionized water, measuring the pH value to be 6.9, and dissolving the obtained lower-layer precipitate in deionized water to obtain a primary aqueous solution of graphene and fullerene;
s7: drying the primary aqueous solution at 25 ℃ for 4 hours to obtain a concentrated solution;
s8: sintering the concentrated solution for 1 hour at 105 ℃ in an argon atmosphere to obtain a graphene and fullerene composite material aqueous solution; wherein, in the graphene and fullerene composite material aqueous solution, the volume fraction of the graphene and fullerene composite material is 20%;
s9: bundling 30 molybdenum wires on a molybdenum rod through copper wires, putting the molybdenum wires into the composite material aqueous solution obtained in the step S8, then putting the molybdenum wires into a thermostat, setting the temperature of the thermostat to be 80 ℃, and growing a composite material layer of graphene and fullerene with the thickness of 7nm on the molybdenum wires by adopting a vertical deposition method for 24 hours, thereby obtaining a composite material anion release head;
s10: and taking the composite material negative ion release head out of the composite material water solution, and drying for 50 minutes at a constant temperature of 70 ℃.
Example 3
As shown in fig. 2, the method for preparing the negative ion discharging head and the negative ion generating electrode of the present embodiment includes:
s1: placing graphene and grinding balls into a plasma-assisted vibration ball milling device, firstly, carrying out atmosphere cleaning on a ball milling tank for 4 times by using neon, introducing the neon after the cleaning is finished, controlling the pressure in the ball milling tank to be 0.8MPa, and carrying out plasma-assisted ball milling for 2 hours to obtain the graphene with the particle size of 100-500 nm; the mass ratio of the graphene to the grinding ball is 5:40, the discharge voltage of a power supply is 18kv, the discharge frequency is 20kHz, and the input current is 3A;
s2: adding toluene into a container containing fullerene, controlling the mass ratio of the fullerene to the toluene to be 0.5:1, and ultrasonically dispersing at the frequency of 150 times/min until no fullerene is attached to the inner wall of the container and the solution in the container is not layered to obtain a first mixed solution;
s3: mixing polyvinylpyrrolidone with chloroform to obtain a second mixed solution, controlling the mass fraction of polyvinylpyrrolidone in the second mixed solution to be 5%, adding the first mixed solution obtained in the step S2 into the second mixed solution, controlling the mass ratio of fullerene to polyvinylpyrrolidone to be 1:150, and stirring by magnetic force to fully mix the fullerene and the polyvinylpyrrolidone;
s4: rotationally evaporating the solution obtained in the step S3 at 80 ℃, wherein the rotational speed is 200r/min until the solution in the system is completely evaporated to dryness;
s5: mixing the graphene obtained in the step S1 with the fullerene obtained in the step S4, adding deionized water into the mixture, and then ultrasonically dispersing for 10min at the frequency of 150 times/min to form a uniformly mixed dispersion solution; wherein the mass ratio of graphene to fullerene to water is 0.5:1: 10;
s6: adding deionized water into the dispersed solution obtained in the step S5, centrifuging at 7500rpm for 5min, repeatedly centrifuging for 4 times, wherein the volume ratio of the deionized water added in each centrifugation to the dispersed solution obtained in the step S5 is 1/3:1, centrifuging for 4 times, pouring out the upper layer solution, dissolving 0.5mg of lower layer precipitate in 5mg of deionized water, measuring the pH value to be 7.3, and dissolving the obtained lower layer precipitate in deionized water to obtain a primary aqueous solution of graphene and fullerene;
s7: drying the primary aqueous solution at 30 ℃ for 3 hours to obtain a concentrated solution;
s8: sintering the concentrated solution for 1 hour at 105 ℃ in a neon atmosphere to obtain a graphene and fullerene composite material aqueous solution; wherein, in the graphene and fullerene composite material aqueous solution, the volume fraction of the graphene and fullerene composite material is 25%;
s9: binding 35 tungsten filaments on a tungsten rod through copper wires, putting the tungsten filaments into the composite material aqueous solution obtained in the step S8, then putting the tungsten filaments into a thermostat, setting the temperature of the thermostat to be 100 ℃, and growing a composite material layer of graphene and fullerene with the thickness of 10nm on the tungsten filaments by adopting a vertical deposition method for 15 hours, thereby obtaining a composite material anion release head;
s10: and taking the composite material negative ion release head out of the composite material water solution, and drying for 30 minutes at a constant temperature of 80 ℃.
Example 4
This example differs from example 2 only in that: in step S3, the mass ratio of fullerene to polyvinylpyrrolidone is 1: 80.
Example 5
This example differs from example 2 only in that: in step S5, the mass ratio of graphene to fullerene is 1: 1.
Example 6
This example differs from example 2 only in that: the temperature of the oven in step S9 was 120 ℃.
Example 7
This example differs from example 2 only in that: the temperature of the rotary evaporation in step S4 was 100 ℃.
Comparative example 1
The negative ion emitting head of this comparative example comprises fullerene and the same molybdenum rod as in example 2 of the present invention, and fibers of the fullerene are bundled on the molybdenum rod.
Performance testing
1. Anion release Performance test
1) Testing instrument
Hand-held atmospheric negative ion tester-manufacturer: hua Si Tong; the instrument model is as follows: WST-3200 Pro.
2) Test conditions
Temperature: 18 deg.C
Relative humidity: 18 percent of
PM2.5：30μg/m2
Output voltage connected to one end of the metal rod: 40 kV.
3) Test procedure
A tester holds the atmosphere negative ion tester, respectively stands in the positive front, the left side of the negative ion release head to be tested in the direction of 22.5 degrees, and the right side of the negative ion release head to be tested in the direction of 22.5 degrees, and respectively stands at the positions 2 and 4m away from the negative ion release head to be tested, and the quantity of negative ions released by the negative ion release head to be tested is tested.
4) Test results
After the anion releasing heads of each example and comparative example were prepared, the use was continued for 10 hours, and then the test was performed. The test results of the negative ion emitting heads of examples and comparative examples are shown in Table 1 (note: the left, middle and right in Table 1 indicate the 22.5 degree left direction, the right direction and the front direction of the negative ion emitting head, respectively).
TABLE 1
As can be seen from table 1, the negative ion release amount of the composite negative ion release head according to the example of the present invention was not reduced or even more compared to the fullerene negative ion release head according to the comparative example. The introduction of the graphene and the conductive metal wire does not bring adverse effects on the release amount of negative ions, and the negative ion release head made of the composite material provided by the embodiment of the invention can generate ecological-grade small-particle-size negative oxygen ions with small particle size, high activity and long migration distance.
However, it was found during the test that the negative ion release amount of the composite negative ion release head of each example of the present invention was stable within a time of <10 seconds, thereby reading the data in table 1, whereas the fullerene negative ion release head of the comparative example required a time of >1 minute to read the data in table 1. The phenomenon shows that the response speed of the negative ion release head is remarkably improved by introducing the graphene, and more negative ions can be released in a short time.
In addition, the introduction of the conductive metal wire improves the hardness of the anion release head, thereby prolonging the service life of the anion release head.
2. Ozone and nitrogen oxides (NO and NO)2) Release amount test
1) Testing instrument
Nitrogen oxide tester-manufacturer: polyclone; the instrument model is as follows: WSQ-NOX;
ozone tester-manufacturer: polyclone; the instrument model is as follows: WSQ-O3.
2) Test conditions
Temperature: 18 deg.C
Relative humidity: 18 percent of
PM2.5：30μg/m2
Output voltage connected to one end of the metal rod: 40 kV.
3) Test procedure
A tester holds a nitrogen oxide tester or an ozone tester by hands, respectively stands in the positions which are respectively in the positive front, the left side and the right side of the negative ion release head to be tested and are respectively 2m and 4m away from the negative ion release head in the direction of 22.5 degrees, and tests the concentration of ozone and nitrogen oxide released by the negative ion release head to be tested.
4) Test results
After the anion releasing heads of each example and comparative example were prepared, the use was continued for 10 hours, and then the test was performed. Ozone and nitrogen oxides (NO and NO) of anion releasing heads of examples2Total release) test results are shown in table 2.
TABLE 2
As can be seen from table 2, compared with the fullerene anion release head of the comparative example, the composite anion release head of the embodiment of the present invention does not release nitrogen oxide, and the amount of ozone released is also reduced relative to the anion release head of the comparative example, indicating that the purity of anions is not adversely affected by the introduction of graphene and conductive wires.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A method of making a composite negative ion release head, the method comprising:
thinning the graphene;
carrying out surface modification on fullerene;
preparing a graphene and fullerene composite material aqueous solution by adopting the graphene subjected to thinning treatment and the fullerene subjected to surface modification; and
and putting a conductive metal wire into the graphene and fullerene composite material aqueous solution, and depositing and growing a graphene and fullerene composite material layer on the surface of the conductive metal wire to obtain the composite material negative ion release head.
2. The method according to claim 1, wherein the thinning of the graphene comprises: ball-milling graphene until the particle size is less than 1 mu m;
optionally, the ball milling is performed by plasma-assisted ball milling;
further optionally, the conditions of the plasma assisted ball milling comprise: the pressure is 0.01-1 MPa, and the ball milling environment is inert atmosphere.
3. The method of claim 1, wherein said surface modifying fullerenes comprises:
dissolving fullerene in an organic solvent to obtain a first mixed solution;
dissolving a surfactant in a dispersing agent to obtain a second mixed solution;
mixing the first mixed solution with the second mixed solution so as to modify the surface of fullerene; and
and (5) removing impurities from the system.
4. A process according to claim 3, wherein the surfactant is an N-vinyl amide surfactant, optionally polyvinylpyrrolidone; and/or
The dispersing agent is selected from any one or more of aromatic hydrocarbon, halogenated aromatic hydrocarbon, alcohol solvent and halogenated alkane; and/or
The mass ratio of the fullerene to the surfactant is 1: 80-200, and optionally 1: 100-150; and/or
The dissolving of the fullerene in the organic solvent comprises: mixing fullerene with an organic solvent in a container, and ultrasonically dispersing until no fullerene is attached to the inner wall of the container and the solution in the container is not layered.
5. The method of claim 3, wherein the dedoping of the system comprises: performing rotary evaporation on the system until the solution in the system is completely evaporated to dryness;
optionally, the temperature of the rotary evaporation is 50-100 ℃, and further optionally 60-80 ℃.
6. The method of claim 1, wherein the preparing of the graphene and fullerene composite aqueous solution from the refined graphene and the surface-modified fullerene comprises:
dissolving the graphene subjected to thinning treatment and the fullerene subjected to surface modification in water, and performing impurity removal treatment to obtain a primary aqueous solution of the graphene and fullerene composite material;
concentrating the primary aqueous solution to obtain a concentrated solution; and
and activating the concentrated solution to obtain the graphene and fullerene composite material aqueous solution.
7. The method according to claim 6, wherein the dissolving of the graphene after the refining treatment and the fullerene after the surface modification in water, and the impurity removal treatment comprises: mixing the graphene subjected to thinning treatment and the fullerene subjected to surface modification with water, and performing ultrasonic dispersion; centrifuging the solution subjected to ultrasonic dispersion until the pH of the lower-layer precipitate is 6.5-7.5, and dissolving the lower-layer precipitate in water to obtain a primary aqueous solution of the graphene and fullerene composite material; and/or
The mass ratio of the graphene subjected to thinning treatment to the fullerene subjected to surface modification is 0.1-1: 1, and optionally 0.1-0.5: 1.
8. The method of claim 6, wherein the concentration process comprises: drying the primary aqueous solution at 20-30 ℃ for 3-5 hours; and/or
The activation treatment comprises: and sintering the concentrated solution in an inert atmosphere at 90-120 ℃ for 0.5-1.5 hours, and controlling the concentrated solution in the composite material aqueous solution of graphene and fullerene, wherein the volume fraction of the graphene and fullerene composite material is 5-30%.
9. The method according to any one of claims 1 to 8, wherein the method used for depositing the composite layer of graphene and fullerene on the surface of the conductive wire is a vertical deposition method;
the conditions of the vertical deposition method include: the temperature is 50-120 ℃, and optionally, the temperature is 60-100 ℃; the time is 15-31 hours; and/or
The thickness of the composite material layer of the graphene and the fullerene is 2-10 nm.
10. A composite negative ion releasing head prepared according to the method of any one of claims 1 to 9.
11. An anion generating electrode, characterized in that, the anion generating electrode comprises a metal rod, a conductive fixing device and an anion releasing head, the anion releasing head is fixed on the metal rod through the conductive fixing device, and the anion releasing head is electrically connected with the metal rod, the anion releasing head is the composite anion releasing head of claim 10.
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