CN111509566A - 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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- CN111509566A CN111509566A CN201910095602.2A CN201910095602A CN111509566A CN 111509566 A CN111509566 A CN 111509566A CN 201910095602 A CN201910095602 A CN 201910095602A CN 111509566 A CN111509566 A CN 111509566A
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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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a composite material negative ion release head and a preparation method thereof. The composite material negative ion release head comprises a conductive metal wire and a composite material layer, wherein the composite material layer is formed on the surface of the conductive metal wire and is formed by a composite material of a carbon nano material and a metal. The method comprises the following steps: carrying out plasma surface modification on the carbon nano-material by adopting a precursor containing metal ions to obtain a composite material of the carbon nano-material and metal; dissolving a composite material of a carbon nano material and a metal in water to obtain a composite material aqueous solution of the carbon nano material and the metal; and putting the conductive metal wire into the composite material aqueous solution, and depositing and growing a composite material layer on the surface of the conductive metal wire to obtain the composite material negative ion release head. An anion generating electrode is also disclosed. The negative ion release head made of the composite material can generate ecological-grade small-particle-size negative oxygen ions with high concentration, has high negative ion purity, and also has the functions of bacteriostasis, disinfection and the like.
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 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 negative ions have high purity and hardly generate derivatives such as ozone, positive ions and the like.
However, the carbon fiber anion release heads on the market generally work under the negative pressure of more than 8000V to ensure the release concentration of anions. Such a high negative pressure is not only costly and high in risk factor, but also has a high possibility of generating ozone, nitrogen oxides, electromagnetic waves and electrostatic pollution. In addition, the current carbon fiber anion releasing heads have single function, and if other materials are introduced into the anion releasing heads, the functionality of the anion releasing heads can be increased. However, the carbon nanomaterial is very easy to agglomerate in the dispersion process, the difficulty of doping other materials is great, and the preparation process is complex.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a composite material negative ion release head, a preparation method thereof and a negative ion generating electrode. The method of the invention can introduce functional metal into the anion releasing head and release anions with higher concentration.
In order to achieve the above object, the present invention provides, in a first aspect, a composite negative ion emitting head comprising a conductive wire and a composite layer formed on a surface of the conductive wire, the composite layer being formed of a composite material of a carbon nanomaterial and a metal.
In embodiments of the invention, the metal may be selected from any one or more of platinum, silver, titanium, copper and iron.
In an embodiment of the present invention, the carbon nanomaterial may be selected from any one or more of carbon nanotubes, carbon nanowires, fullerenes, fullerols, and graphenes.
In an embodiment of the invention, the mass ratio of the carbon nanomaterial to the metal may be 250-1250: 1, optionally 500-1000: 1.
In the embodiment of the invention, the thickness of the composite material layer can be 2-10 nm.
In a second aspect, the present invention provides a method of making a composite negative ion-releasing head, the method comprising:
carrying out plasma surface modification on the carbon nano-material by adopting a precursor containing metal ions to obtain a composite material of the carbon nano-material and metal;
dissolving the composite material of the carbon nano material and the metal in water to obtain a composite material aqueous solution of the carbon nano material and the metal; and
and putting a conductive metal wire into the composite material aqueous solution, and depositing and growing a 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 plasma surface modification of the carbon nanomaterial with a precursor containing metal ions may include:
oxidizing the carbon nanomaterial with oxidizing plasma;
dissolving the oxidized carbon nanomaterial in an aqueous solution of a precursor containing metal ions, and mixing to obtain a metal-loaded carbon nanomaterial; and
and reducing the carbon nano material loaded with the metal by adopting reducing plasma.
In an embodiment of the present invention, the metal ions may be selected from any one or more of platinum ions, silver ions, titanium ions, copper ions, and iron ions.
The precursor containing metal ions is selected from any one or more of metal salts and chloroplatinic acid.
In an embodiment of the present invention, the oxidation conditions may include: the oxidizing plasma is oxygen plasma, the pressure is 10-35 Pa, optionally 20-25 Pa, and the reaction time is 5-35 min, optionally 15-30 min.
In an embodiment of the present invention, the dissolving and mixing the oxidized carbon nanomaterial in an aqueous solution of a precursor containing metal ions to obtain the metal-loaded carbon nanomaterial may include:
mixing the oxidized carbon nano material with an aqueous solution of a precursor containing metal ions, and carrying out ultrasonic treatment; and
and carrying out suction filtration, cleaning, drying and grinding on the solution subjected to ultrasonic treatment.
In an embodiment of the present invention, the mass ratio of the carbon nanomaterial before oxidation to the metal ion in the aqueous solution of the precursor containing the metal ion may be 50 to 250:1, and optionally 100 to 200: 1.
In an embodiment of the present invention, the concentration of the aqueous solution of the metal ion-containing precursor may be 0.1 to 0.6 mol/L.
In the embodiment of the invention, the ultrasonic treatment time is 3-8 h.
In an embodiment of the present invention, the reducing conditions may include: the reductive plasma is hydrogen plasma and/or ammonia plasma, the pressure is 10-35 Pa, and optionally 20-25 Pa; the reaction time is 5-35 min, optionally 15-30 min.
In the embodiment of the invention, the method adopted when the composite material layer is deposited and grown on the surface of the conductive metal wire is 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, optionally 16 to 30 hours.
In a third aspect, the invention provides the composite material negative ion release head prepared by the method.
In a fourth aspect, the present invention provides an anion generating electrode, which comprises 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 with the metal rod, and the anion releasing head is the composite material anion releasing head as described above or the composite material anion releasing head prepared by the method as described above.
The composite material negative ion release head can generate ecological-grade small-particle-size negative oxygen ions with high concentration, small particle size, high activity and long migration distance, and the negative ions have high purity and hardly generate byproducts such as ozone, nitrogen oxide and the like; besides, the composite material anion releasing head can release anions and also have other functions, such as bacteriostasis, disinfection, decontamination and the like; meanwhile, the composite material negative ion release head has higher hardness and long service life.
The method for preparing the negative ion release head of the composite material has the advantages of short time consumption, less introduced impurities, higher product activity and low cost.
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.
The pressures mentioned herein are gauge pressures.
In a first aspect, embodiments of the present invention provide a composite negative ion release head, which includes a conductive metal wire and a composite material layer formed on a surface of the conductive metal wire, where the composite material layer is formed of a composite material of a carbon nanomaterial and a metal.
The composite material negative ion release head provided by the embodiment of the invention is formed by the conductive metal wire and the composite material layer deposited on the conductive metal wire, the conductive metal wire and the composite material layer are both beneficial to forming negative ions, the introduction of metal does not bring adverse effects on the performance of the negative ion release head, ecological-grade small-particle-size negative oxygen ions with high concentration, small particle size, high activity and long migration distance can be generated, the purity of the negative ions is high, and by-products such as ozone, nitrogen oxide and the like are hardly generated. Moreover, the composite material layer comprises metal, so that the composite material negative ion release head is endowed with more functions, for example, when the metal is platinum with high conductivity, the conductivity of the composite material negative ion release head can be improved, and the release concentration of negative ions is further improved; when the metal is silver with the functions of bacteriostasis and disinfection, the negative ion release head made of the composite material has the functions of bacteriostasis and disinfection; when the metal is titanium with the functions of decontamination and sterilization, the released negative ions have the functions of decontamination and sterilization.
In addition, the composite material negative ion release head of the embodiment of the invention introduces the conductive metal wire which has conductivity, is convenient for the transmission and release of current carriers, and can improve the hardness of the negative ion release head, thereby prolonging the service life of the negative ion release head under high negative pressure.
In embodiments of the present invention, the metal may be selected from any one or more of platinum, silver, titanium, copper and iron.
In the embodiment of the present invention, the carbon nanomaterial may be selected from any one or more of carbon nanotubes, carbon nanowires, fullerenes, fullerols, and graphenes.
In the embodiment of the invention, the mass ratio of the carbon nano material to the metal can be 250-1250: 1, for example, 500-1000: 1.
In the embodiment of the invention, the thickness of the composite material layer can be 2-10 nm. The composite material layer with the thickness can release negative ions with higher concentration, has better adhesive property on the conductive metal wire and is not easy to fall off.
In the embodiment of the present invention, the conductive metal wire may be a titanium wire, a molybdenum wire, a tungsten wire, or an iron wire. In the gas embodiment of the present invention, stainless steel wire may be used instead of conductive wire.
In the embodiment of the invention, 20-40 conductive metal wires can be arranged on 1 negative ion release head.
In a second aspect, embodiments of the present invention provide a method of making a composite negative ion release head, the method comprising:
carrying out plasma surface modification on the carbon nano-material by adopting a precursor containing metal ions to obtain a composite material of the carbon nano-material and metal;
dissolving the composite material of the carbon nano material and the metal in water to obtain a composite material aqueous solution of the carbon nano material and the metal; and
and putting a conductive metal wire into the composite material aqueous solution, and depositing and growing a composite material layer on the surface of the conductive metal wire to obtain the composite material negative ion release head.
According to the preparation method provided by the embodiment of the invention, by adopting the plasma surface modification technology, not only can harmful groups on the surface of the carbon nano material be removed, but also beneficial chemical groups are introduced on the surface of the carbon nano material, so that the water solubility and the adsorption performance of the carbon nano material are greatly improved; meanwhile, metal can be introduced on the surface of the carbon nano material.
In addition, the preparation method of the embodiment of the invention also has the characteristics of plasma surface modification:
(1) the dry process does not need to treat waste liquid and waste gas, thereby saving energy and reducing cost;
(2) short action time (several seconds to several minutes) and high efficiency;
(3) modification occurs only in the surface layer (a few angstroms to microns) and thus does not affect the intrinsic properties of the matrix;
(4) less introduction of impurities and higher product activity;
(5) simple process, convenient operation and little pollution, and is suitable for the requirement of environmental protection.
In an embodiment of the present invention, the performing plasma surface modification on the carbon nanomaterial by using the precursor containing the metal ion may include:
oxidizing the carbon nanomaterial with oxidizing plasma;
dissolving the oxidized carbon nanomaterial in an aqueous solution of a precursor containing metal ions, and mixing to obtain a metal-loaded carbon nanomaterial; and
and reducing the carbon nano material loaded with the metal by adopting reducing plasma.
In the embodiment of the present invention, the metal ions may be selected from any one or more of platinum ions, silver ions, titanium ions, copper ions, and iron ions.
In an embodiment of the present invention, the precursor containing metal ions may include chloroplatinic acid and/or a metal salt, for example, at least any one of silver nitrate, chloroplatinic acid, titanium tetrachloride, ferric nitrate, ferric chloride, and the like.
The oxidation conditions may include: the oxidant is oxygen (corresponding to the obtained oxygen plasma), and the reaction time is 5-35 min, for example, 10-30 min; the pressure is 10 to 35Pa, for example, 20 to 25 Pa. Before the oxidation reaction, a plasma generator for the oxidation reaction can be vacuumized to 3-5 Pa, oxygen is introduced into the plasma generator for air replacement, oxygen is continuously introduced after the air replacement is completed, and the pressure in the plasma generator is controlled to be 10-35 Pa.
The C-C bond of the carbon nano material can be broken through oxidation to form C-OH or C-O-C groups, and the groups are favorable for subsequent loading of metal ions.
In the embodiment of the invention, the particle size of the carbon nano material can be less than or equal to 1 μm, for example, can be 100-500 nm.
In an embodiment of the present invention, the dissolving and mixing the oxidized carbon nanomaterial in an aqueous solution of a precursor containing metal ions to obtain the metal-loaded carbon nanomaterial may include:
mixing the oxidized carbon nano material with an aqueous solution of a precursor containing metal ions, and carrying out ultrasonic treatment; and
and carrying out suction filtration, cleaning, drying and grinding on the solution subjected to ultrasonic treatment.
In the embodiment of the present invention, the mass ratio of the carbon nanomaterial before oxidation to the metal ion in the aqueous solution of the precursor containing the metal ion may be 50 to 250:1, for example, 100 to 200: 1. The mass ratio can ensure that the metal loaded on the carbon nano material has better functions of bacteriostasis, disinfection, decontamination and the like.
In the embodiment of the invention, the concentration of the aqueous solution of the precursor of the metal ions can be 0.1-0.6 mol/L, for example, 0.2-0.5 mol/L.
In an embodiment of the present invention, the ultrasonic treatment conditions may include: the power is 200-600W, and the time is 3-8 h, for example, 5-6 h.
And (3) filtering the solution after the ultrasonic treatment, washing a filter cake by using flowing water, and drying at 60-80 ℃. Drying and grinding to obtain nano-grade particles.
The conditions for the reduction may include: the reducing agent is hydrogen and/or ammonia gas (correspondingly obtaining hydrogen plasma and/or ammonia plasma); the pressure is 10 to 35Pa, for example, 20 to 25 Pa; the reaction time is 5 to 35min, for example, 10 to 30 min. Before the reduction reaction, a plasma generator for carrying out the reduction reaction can be vacuumized to 3-5 Pa, and then hydrogen and/or ammonia gas is introduced into the plasma generator for carrying out air replacement.
In the embodiment of the invention, in the composite material aqueous solution of the carbon nano material and the metal, the volume fraction of the composite material can be 5-30%. The aqueous solution of the volume fraction composite material is beneficial to forming a composite material layer with a uniform film layer on the conductive metal wire in a short time.
In the embodiment of the invention, the method used for depositing and growing the composite material layer on the surface of the conductive metal wire can 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 with a desired thickness. The thickness of the 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 carbon nano material and the metal, 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 third aspect, the embodiment of the invention provides the composite material negative ion release head prepared by the method.
In a fourth 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 the composite material ion releasing head as described above or the composite material anion releasing head prepared by the method as described above.
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.
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 carbon nano tubes with the particle size of 100-500 nm into an inductively coupled plasma generator, vacuumizing to 3Pa, introducing oxygen into the inductively coupled plasma generator until the pressure in the plasma generator is stabilized at 20Pa, setting the power of the plasma generator to be 80W, and maintaining for 20min to obtain oxidized carbon nano tube particles;
s2, adding the oxidized carbon nanotube particles into a silver nitrate aqueous solution with the concentration of 0.1 mol/L, performing ultrasonic treatment for 5 hours at the power of 600W, performing suction filtration, cleaning a filter cake with deionized water, drying at 60 ℃, and grinding to obtain particles with the particle size of 100-500 nm, wherein the mass ratio of the carbon nanotube before oxidation added in the step S1 to silver ions in the silver nitrate aqueous solution is 100: 1;
s3: putting the particles obtained in the step S2 into an inductively coupled plasma generator again, vacuumizing to 3Pa, introducing hydrogen into the inductively coupled plasma generator until the pressure in the plasma generator is stabilized at 20Pa, setting the power of the plasma generator to 80W, and maintaining for 20min to obtain a composite material;
s4: adding deionized water into the composite material obtained in the step S3 to prepare a composite material aqueous solution with the volume fraction of 10 percent of the composite material;
s5: bundling 25 titanium wires on a titanium rod through copper wires, putting the titanium wires into the composite material aqueous solution, 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 composite material layer with the thickness of 2nm on the titanium wires by adopting a vertical deposition method (through testing, the mass ratio of carbon nanotubes to silver in the composite material layer is 500:1), thereby obtaining the composite material anion release head;
s6: and taking the composite material negative ion release head out of the composite material aqueous 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 with the particle size of 100-500 nm into an inductively coupled plasma generator, vacuumizing to 4Pa, introducing oxygen into the inductively coupled plasma generator until the pressure in the plasma generator is stabilized at 25Pa, setting the power of the plasma generator to be 100W, and maintaining for 15min to obtain oxidized graphene particles;
s2, adding the oxidized graphene particles into a chloroplatinic acid aqueous solution with the concentration of 0.3 mol/L, performing ultrasonic treatment for 5.5 hours at the power of 400W, performing suction filtration, cleaning a filter cake with deionized water, drying at 70 ℃, and grinding to obtain particles with the particle size of 100-500 nm, wherein the mass ratio of the graphene before oxidation to platinum ions in the chloroplatinic acid aqueous solution added in the step S1 is 150: 1;
s3: putting the particles obtained in the step S2 into an inductively coupled plasma generator again, vacuumizing to 4Pa, introducing hydrogen into the inductively coupled plasma generator until the pressure in the plasma generator is stabilized at 25Pa, setting the power of the plasma generator to be 100W, and maintaining for 15min to obtain a composite material;
s4: adding deionized water into the composite material obtained in the step S3 to prepare a composite material aqueous solution with the volume fraction of 15 percent of the composite material;
s5: 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 S4, then putting the molybdenum wires into a thermostat, setting the temperature of the thermostat to be 80 ℃, and growing a composite material layer with the thickness of 7nm on the molybdenum wires by adopting a vertical deposition method (through testing, the mass ratio of graphene to platinum in the composite material layer is 750:1), thereby obtaining the composite material negative ion release head;
s6: and taking the composite material negative ion release head out of the composite material aqueous solution, and drying at the constant temperature of 70 ℃ for 50 minutes.
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: putting fullerol with the particle size of 100-500 nm into an inductively coupled plasma generator, vacuumizing to 5Pa, introducing oxygen into the inductively coupled plasma generator until the pressure in the plasma generator is stabilized at 35Pa, setting the power of the plasma generator to be 110W, and maintaining for 30min to obtain oxidized fullerol particles;
s2, adding the oxidized fullerol particles into a titanium tetrachloride aqueous solution with the concentration of 0.6 mol/L, performing ultrasonic treatment for 5 hours at the power of 600W, performing suction filtration, cleaning a filter cake with deionized water, drying at the temperature of 60 ℃, and grinding to obtain particles with the particle size of 100-500 nm, wherein the mass ratio of the fullerol added in the step S1 before oxidation to titanium ions in the titanium tetrachloride aqueous solution is 200: 1;
s3: putting the particles obtained in the step S2 into an inductively coupled plasma generator again, vacuumizing to 5Pa, introducing hydrogen into the inductively coupled plasma generator until the pressure in the plasma generator is stabilized at 35Pa, setting the power of the plasma generator to be 110W, and maintaining for 30min to obtain a composite material;
s4: adding deionized water into the composite material obtained in the step S3 to prepare a composite material aqueous solution with the volume fraction of the composite material being 30%;
s5: bundling 35 tungsten filaments on a tungsten rod through copper wires, putting the tungsten filaments into the composite material aqueous solution, then putting the tungsten filaments into a thermostat, setting the temperature of the thermostat to be 100 ℃, and growing a composite material layer with the thickness of 10nm on the tungsten filaments by adopting a vertical deposition method (through testing, the mass ratio of the fullerol to the titanium in the composite material layer is 1000:1), thereby obtaining the composite material anion release head;
s6: and taking the composite material negative ion release head out of the composite material aqueous solution, and drying at the constant temperature of 80 ℃ for 30 minutes.
Example 4
This embodiment differs from embodiment 2 only in that: the mass ratio of the graphene before oxidation to the platinum ions in the chloroplatinic acid aqueous solution in step S2 is 50: 1. Through testing, the mass ratio of graphene to platinum in the composite material layer is 250: 1.
Example 5
This embodiment differs from embodiment 2 only in that: in step S1, the pressure in the plasma generator was stabilized at 10Pa for a 5min period.
Example 6
This embodiment differs from embodiment 2 only in that: in step S3, the pressure in the plasma generator was stabilized at 10Pa for a 5min period.
Example 7
This example differs from example 2 only in that: the temperature of the oven in step S5 was 120 ℃.
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 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
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. 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
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, compared with the fullerene anion release head of the comparative example, the anion release amount of the composite anion release head of the embodiment of the present invention is increased, which indicates that the layered carbon nanomaterial of the embodiment of the present invention is favorable for releasing more anions, and the introduction of the metal does not adversely affect the performance of the anion release head, so that the composite anion release head of the embodiment of the present invention can generate ecological small-particle-size negative oxygen ions with more small particle sizes, high activity and long migration distance, and the diversity of functions is increased. 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
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. 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 2 m 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
Ozone and nitrogen oxide release amounts (NO and NO) of anion releasing heads of examples and comparative examples2Total amount released) the test results are shown in table 2.
TABLE 2
As can be seen from table 2, the composite material anion releasing heads of the examples of the present invention did not release nitrogen oxide and the amount of ozone released was reduced relative to the anion releasing heads of the comparative examples, as compared to the fullerene anion releasing heads of the comparative examples, indicating that the introduction of metal and conductive wire did not adversely affect the purity of anions.
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 (10)
1. A composite material negative ion release head is characterized by comprising a conductive metal wire and a composite material layer, wherein the composite material layer is formed on the surface of the conductive metal wire, and the composite material layer is formed by a composite material of a carbon nano material and a metal.
2. The composite negative ion releasing head of claim 1, wherein the metal is selected from any one or more of platinum, silver, titanium, copper and iron; and/or
The carbon nano material is selected from any one or more of carbon nano tube, carbon nano wire, fullerene alcohol and graphene; and/or
The mass ratio of the carbon nanomaterial to the metal is 250-1250: 1, optionally 500-1000: 1; and/or
The thickness of the composite material layer is 2-10 nm.
3. A method of making a composite negative ion release head, the method comprising:
carrying out plasma surface modification on the carbon nano-material by adopting a precursor containing metal ions to obtain a composite material of the carbon nano-material and metal;
dissolving the composite material of the carbon nano material and the metal in water to obtain a composite material aqueous solution of the carbon nano material and the metal; and
and putting a conductive metal wire into the composite material aqueous solution, and depositing and growing a composite material layer on the surface of the conductive metal wire to obtain the composite material negative ion release head.
4. The method of claim 3, wherein the plasma surface modification of the carbon nanomaterial with a precursor containing metal ions comprises:
oxidizing the carbon nanomaterial with oxidizing plasma;
dissolving the oxidized carbon nanomaterial in an aqueous solution of a precursor containing metal ions, and mixing to obtain a metal-loaded carbon nanomaterial; and
reducing the carbon nanomaterial loaded with the metal by adopting reducing plasma;
optionally, the metal ions are selected from any one or more of platinum ions, silver ions, titanium ions, copper ions and iron ions; and/or
The precursor containing metal ions is selected from any one or more of metal salts and chloroplatinic acid.
5. The method of claim 4, wherein the oxidizing conditions comprise: the oxidizing plasma is oxygen plasma, the pressure is 10-35 Pa, optionally 20-25 Pa, and the reaction time is 5-35 min, optionally 15-30 min.
6. The method of claim 4, wherein dissolving the oxidized carbon nanomaterial in an aqueous solution of a precursor containing metal ions and mixing to obtain the metal-loaded carbon nanomaterial comprises:
mixing the oxidized carbon nano material with an aqueous solution of a precursor containing metal ions, and carrying out ultrasonic treatment; and
and carrying out suction filtration, cleaning, drying and grinding on the solution subjected to ultrasonic treatment.
7. The method of claim 6, wherein the mass ratio of the carbon nanomaterial before oxidation to the metal ions in the aqueous solution of the metal ion-containing precursor is 50-250: 1, optionally 100-200: 1; and/or
The concentration of the aqueous solution of the precursor containing the metal ions is 0.1-0.6 mol/L, and/or
The ultrasonic treatment time is 3-8 h.
8. The method of claim 4, wherein the reducing conditions comprise: the reductive plasma is hydrogen plasma and/or ammonia plasma, the pressure is 10-35 Pa, and optionally 20-25 Pa; the reaction time is 5-35 min, optionally 15-30 min.
9. The method of claim 3, wherein the method adopted when the composite material layer is deposited and grown on the surface of the conductive metal wire is a vertical deposition method, and the conditions of the vertical deposition method comprise: the temperature is 50-120 ℃, and optionally, the temperature is 60-100 ℃; the time is 15 to 31 hours, optionally 16 to 30 hours.
10. 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 material anion releasing head of claim 1 or 2 or the composite material anion releasing head prepared by the method of any one of claims 3 to 9.
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