Preparation for the Graphene/sulfur/conducting polymer composite material of lithium-sulphur cell positive electrode
Method
Technical field
The present invention relates to lithium sulphur battery electrode field of material preparation technology, refer in particular to a kind of for lithium-sulphur cell positive electrode
The preparation method of Graphene/sulfur/conducting polymer composite material.
Background technology
Lithium ion battery is widely used in the various mobile electron such as notebook computer, photographing unit, mobile phone, panel computer
Equipment.Due to the fast development of mobile electronic device, the specific capacity to battery and specific energy require more and more higher.Commercialization at present
Lithium ion battery can not be met due to the restriction of itself theoretical capacity, so in the urgent need to developing height ratio capacity high-energy-density
Secondary cell, and lithium-sulfur cell (theoretical specific capacity be 1675.0 mAh/g, specific energy be 2500 Wh/kg, 2800 Wh/L)
It is considered as one of high-energy battery the most promising.It is entirely different with traditional lithium ion battery, for example LiCoO2,
The theoretical capacity of LiFePO4 and ternary material only has 149.0,170.0,270.0 mAh/g, the theoretical capacity of these materials
It is limited to the deintercalation quantity of lithium ion, in the lattice of these materials of Lithium-ion embeding in electric discharge, deviate from during charging, deintercalation again
Quantity can not be too many, otherwise can lead to these metal oxide materials structures that irreversible change occurs, ultimately result in battery complete
Total loss is bad.And lithium-sulfur cell is fracture by sulfur sulfide linkage and is formed and discharge to complete and charge it is possible to realize more Gao Rong
Amount charge and discharge.Lithium-sulfur cell problem main at present or many sulphions dissolving cycle performance of leading to of migration are poor.Future solves this
Individual problem mainly passes through both positive and negative polarity and electrolyte is all constantly improved.Wherein made with conductive carbon material and sulfur and be just combined
Pole material, carbon-based material serves as conducting bridge, builds conductive network between particles, improves electronic conductivity;Carbon-based material is to sulfur
Granule is coated, and the change of suppression shuttle effect and electrode material volume in charge and discharge process is thus improve following of battery
The ring life-span.
Chinese patent ZL 201210485646.4 discloses a kind of carbon sulfur composite for lithium-sulphur cell positive electrode, is
The elemental sulfur of injection porous hollow carbon ball, wherein porous hollow carbon ball pass through simple Template synthesis, and using melting diffusion
Method elemental sulfur is injected in porous hollow carbon ball.This positive electrode has that preparation method is simple, specific capacity is larger, coulomb
Efficiency high, good cycle, but, because employing hollow carbon sphere, virtually greatly reduce volume energy density.
Chinese patent ZL201410229448.0 discloses a kind of composite modified material of sulfur for lithium sulfur battery anode material
The preparation method of material, by high-energy ball milling-microwave-assisted, the means such as gas-phase polymerization cladding, is just preparing high-performance lithium-sulfur cell
The method of pole material.Preparation process is simple, short preparation period, and product property is excellent.But, Graphene is porous material, greatly
Hole is a lot, and the main precedence partition of elemental sulfur is in macropore so that the utilization rate of elemental sulfur reduces.Capacity is not played well.
Content of the invention
In view of this, the present invention is directed to the disappearance of prior art presence, and its main purpose is to provide one kind for lithium sulfur electricity
The preparation method of the Graphene/sulfur/conducting polymer composite material of pond positive pole, described composite contain sulfur/graphene particles/
Conducting polymer, the method is simple to operation, is especially suitable for large-scale production.
For achieving the above object, the present invention is using as purgation technical scheme:
A kind of preparation method of the Graphene/sulfur/conducting polymer composite material for lithium-sulphur cell positive electrode, including following
Step:
(1)Mechanical mixture
Elemental sulfur and Graphene are added in homogenizer according to mass ratio, using rotating speed 500~5000 r/
Min carries out disperseing 1~4h, and elemental sulfur is dispersed in graphene sheet layer;
(2)Isostatic pressed merges
Elemental sulfur and Graphene mixture press-powder are filled in the rubber mold of iso-static pressure shaping machine, by high-frequency electromagnetic
Vibration, so that press-powder obtains closely knit, carries out evacuation, discharges the air between powder particle after sealing, put into equipped with water or oil
In high-pressure bottle, it is pressurized to 100~200 MPa, be heated to 150~200 DEG C, pressure-maintaining and heat-preservation 10~20h, after being cooled to room temperature
It is pressed into block;
(3)Polymerization cladding
After block is used Universalpulverizer to crush, it is added in the HCl solution that concentration is 0.5-1M, ultrasonic disperse 10
~50 minutes, and be aided with ice-water bath and form suspension, take polymer monomer to be added in above-mentioned suspension, then ultrasonic disperse 10~
50 minutes, and it is aided with ice-water bath;Initiator ammonium persulfate is dissolved in the HCl solution that concentration is 0.5~1M, and is slowly added dropwise
To in reaction system, polymer monomer is 1 with the mol ratio of Ammonium persulfate.:1, time for adding controlled at 10~50 minutes, dried
After can be prepared by Graphene/sulfur/conducting polymer composite material.
As a kind of preferred version, step(1)Described in elemental sulfur be 99% purity, the granularity of elemental sulfur is 1~5 μ
m.
As a kind of preferred version, step(1)Described in Graphene be single or multiple lift Graphene, it is using oxidation also
Former method, mechanical stripping method, epitaxial growth method or chemical vapor deposition obtain.
As a kind of preferred version, step(3)Described in polymer monomer be selected from aniline, pyrroles, in thiophene at least one
Kind.
The present invention compared with prior art has clear advantage and beneficial effect, specifically, by technique scheme
Understand:
1st, the present invention adopts simple and easy to do mechanical mixture, and isostatic pressed merges, and elemental sulfur is wrapped up by the means such as polymerization cladding
Graphene constitute three-dimensional conductive network in, the good electrical contact between elemental sulfur and Graphene can be maintained, shorten lithium from
The evolving path of son is it is ensured that the electronics conduction of electrode material will not be lost;Simultaneously conducting polymer elemental sulfur is carried out completely equal
Even cladding, prevents the directly contact of the polysulfide ion in reaction and electrolyte, effectively thus improve material first
Efficiency for charge-discharge and cycle performance.
2nd, introduce isostatic pressed to merge, so that elemental sulfur and the integration engineering of Graphene is occurred mainly in mesopore and aperture, have
Avoid the capacity that elemental sulfur leads in the reunion of graphenic surface can not bring into play to effect, and volume energy can be improved
Density and high rate performance.
3rd, present invention process is simple, and easy to operate, production equipment is few, thus further reduces cost, easy to utilize,
It is suitable to large-scale production.
For more clearly illustrating architectural feature and effect of the present invention, come to this with specific embodiment below in conjunction with the accompanying drawings
Bright it is described in detail.
Brief description
Fig. 1 is the preparation flow schematic diagram of the preferred embodiments of the invention.
Specific embodiment
Refer to shown in Fig. 1, it is multiple that the present invention discloses a kind of Graphene/sulfur/conducting polymer for lithium-sulphur cell positive electrode
The preparation method of condensation material, comprises the following steps:
(1)Mechanical mixture
Elemental sulfur and Graphene are added in homogenizer according to mass ratio, using rotating speed 500~5000 r/
Min carries out disperseing 1~4h, and elemental sulfur is dispersed in graphene sheet layer;Described elemental sulfur is 99% purity, simple substance
The granularity of sulfur be 1~5 μm, described Graphene be single or multiple lift Graphene, its be using oxidation-reduction method, mechanical stripping method,
Epitaxial growth method or chemical vapor deposition obtain.
(2)Isostatic pressed merges
Elemental sulfur and Graphene mixture press-powder are filled in the rubber mold of iso-static pressure shaping machine, by high-frequency electromagnetic
Vibration, so that press-powder obtains closely knit, carries out evacuation, discharges the air between powder particle after sealing, put into equipped with water or oil
In high-pressure bottle, it is pressurized to 100~200 MPa, be heated to 150~200 DEG C, pressure-maintaining and heat-preservation 10~20h, after being cooled to room temperature
It is pressed into block;
(3)Polymerization cladding
After block is used Universalpulverizer to crush, it is added in the HCl solution that concentration is 0.5-1M, ultrasonic disperse 10
~50 minutes, and be aided with ice-water bath and form suspension, take polymer monomer to be added in above-mentioned suspension, then ultrasonic disperse 10~
50 minutes, and it is aided with ice-water bath;Initiator ammonium persulfate is dissolved in the HCl solution that concentration is 0.5~1M, and is slowly added dropwise
To in reaction system, polymer monomer is 1 with the mol ratio of Ammonium persulfate.:1, time for adding controlled at 10~50 minutes, dried
After can be prepared by Graphene/sulfur/conducting polymer composite material, this step(3)Described polymer monomer be selected from aniline, pyrroles,
At least one in thiophene.
The present invention will be described to use specific embodiment below.
Embodiment 1
(1)Mechanical mixture
Elemental sulfur and Graphene are added in homogenizer according to mass ratio, are carried out point using rotating speed 500r/min
Scattered 4h, elemental sulfur is dispersed in graphene sheet layer;In the present embodiment, described elemental sulfur is 99% purity, simple substance
The granularity of sulfur is 1 μm, and described Graphene is single-layer graphene, and it is to be obtained using oxidation-reduction method.
(2)Isostatic pressed merges
Elemental sulfur and Graphene mixture press-powder are filled in the rubber mold of iso-static pressure shaping machine, by high-frequency electromagnetic
Vibration, so that press-powder obtains closely knit, carries out evacuation, discharges the air between powder particle after sealing, put into equipped with water or oil
In high-pressure bottle, it is pressurized to 100 MPa, be heated to 180 DEG C, pressure-maintaining and heat-preservation 10h, it is pressed into block after being cooled to room temperature;
(3)Polymerization cladding
After block is used Universalpulverizer to crush, it is added in the HCl solution that concentration is 0.5M, 30 points of ultrasonic disperse
Clock, and be aided with ice-water bath and form suspension, take polymer monomer to be added in above-mentioned suspension, then ultrasonic disperse 20 minutes, and
It is aided with ice-water bath;Initiator ammonium persulfate is dissolved in the HCl solution that concentration is 0.8M, and is slowly dropped to reaction system
In, polymer monomer is 1 with the mol ratio of Ammonium persulfate.:1, time for adding controlled at 20 minutes, can be prepared by graphite after drying
Alkene/sulfur/conducting polymer composite material, in the present embodiment, described polymer monomer is selected from aniline.
Embodiment 2
(1)Mechanical mixture
Elemental sulfur and Graphene are added in homogenizer according to mass ratio, are carried out using rotating speed 1000 r/min
Dispersion 3h, elemental sulfur is dispersed in graphene sheet layer;In the present embodiment, described elemental sulfur is 99% purity, single
The granularity of matter sulfur is 2 μm, and described Graphene is multi-layer graphene, and it is to be obtained using mechanical stripping method.
(2)Isostatic pressed merges
Elemental sulfur and Graphene mixture press-powder are filled in the rubber mold of iso-static pressure shaping machine, by high-frequency electromagnetic
Vibration, so that press-powder obtains closely knit, carries out evacuation, discharges the air between powder particle after sealing, put into equipped with water or oil
In high-pressure bottle, it is pressurized to 120 MPa, be heated to 160 DEG C, pressure-maintaining and heat-preservation 12h, it is pressed into block after being cooled to room temperature;
(3)Polymerization cladding
After block is used Universalpulverizer to crush, it is added in the HCl solution that concentration is 0.8M, 20 points of ultrasonic disperse
Clock, and be aided with ice-water bath and form suspension, take polymer monomer to be added in above-mentioned suspension, then ultrasonic disperse 30 minutes, and
It is aided with ice-water bath;Initiator ammonium persulfate is dissolved in the HCl solution that concentration is 0.5M, and is slowly dropped to reaction system
In, polymer monomer is 1 with the mol ratio of Ammonium persulfate.:1, time for adding controlled at 30 minutes, can be prepared by graphite after drying
Alkene/sulfur/conducting polymer composite material, in the present embodiment, described polymer monomer is selected from pyrroles.
Embodiment 3
(1)Mechanical mixture
Elemental sulfur and Graphene are added in homogenizer according to mass ratio, are carried out using rotating speed 1500 r/min
Dispersion 1.6h, elemental sulfur is dispersed in graphene sheet layer;In the present embodiment, described elemental sulfur is 99% purity,
The granularity of elemental sulfur is 3 μm, and described Graphene is single-layer graphene, and it is to be obtained using epitaxial growth method.
(2)Isostatic pressed merges
Elemental sulfur and Graphene mixture press-powder are filled in the rubber mold of iso-static pressure shaping machine, by high-frequency electromagnetic
Vibration, so that press-powder obtains closely knit, carries out evacuation, discharges the air between powder particle after sealing, put into equipped with water or oil
In high-pressure bottle, it is pressurized to 130 MPa, be heated to 170 DEG C, pressure-maintaining and heat-preservation 15h, it is pressed into block after being cooled to room temperature;
(3)Polymerization cladding
After block is used Universalpulverizer to crush, it is added in the HCl solution that concentration is 0.6M, 40 points of ultrasonic disperse
Clock, and be aided with ice-water bath and form suspension, take polymer monomer to be added in above-mentioned suspension, then ultrasonic disperse 10 minutes, and
It is aided with ice-water bath;Initiator ammonium persulfate is dissolved in the HCl solution that concentration is 0.7M, and is slowly dropped to reaction system
In, polymer monomer is 1 with the mol ratio of Ammonium persulfate.:1, time for adding controlled at 40 minutes, can be prepared by graphite after drying
Alkene/sulfur/conducting polymer composite material, in the present embodiment, described polymer monomer is selected from thiophene.
Embodiment 4
(1)Mechanical mixture
Elemental sulfur and Graphene are added in homogenizer according to mass ratio, are carried out using rotating speed 2000 r/min
Dispersion 2h, elemental sulfur is dispersed in graphene sheet layer;In the present embodiment, described elemental sulfur is 99% purity, single
The granularity of matter sulfur is 4 μm, and described Graphene is multi-layer graphene, and it is to be obtained using chemical vapor deposition.
(2)Isostatic pressed merges
Elemental sulfur and Graphene mixture press-powder are filled in the rubber mold of iso-static pressure shaping machine, by high-frequency electromagnetic
Vibration, so that press-powder obtains closely knit, carries out evacuation, discharges the air between powder particle after sealing, put into equipped with water or oil
In high-pressure bottle, it is pressurized to 140 MPa, be heated to 150 DEG C, pressure-maintaining and heat-preservation 11h, it is pressed into block after being cooled to room temperature;
(3)Polymerization cladding
After block is used Universalpulverizer to crush, it is added in the HCl solution that concentration is 0.7M, 10 points of ultrasonic disperse
Clock, and be aided with ice-water bath and form suspension, take polymer monomer to be added in above-mentioned suspension, then ultrasonic disperse 40 minutes, and
It is aided with ice-water bath;Initiator ammonium persulfate is dissolved in the HCl solution that concentration is 0.6M, and is slowly dropped to reaction system
In, polymer monomer is 1 with the mol ratio of Ammonium persulfate.:1, time for adding controlled at 25 minutes, can be prepared by graphite after drying
Alkene/sulfur/conducting polymer composite material, in the present embodiment, described polymer monomer is selected from aniline and pyrroles.
Embodiment 5
(1)Mechanical mixture
Elemental sulfur and Graphene are added in homogenizer according to mass ratio, are carried out using rotating speed 3000 r/min
Dispersion 2.5h, elemental sulfur is dispersed in graphene sheet layer;In the present embodiment, described elemental sulfur is 99% purity,
The granularity of elemental sulfur is 5 μm, and described Graphene is multi-layer graphene, and it is to be obtained using oxidation-reduction method.
(2)Isostatic pressed merges
Elemental sulfur and Graphene mixture press-powder are filled in the rubber mold of iso-static pressure shaping machine, by high-frequency electromagnetic
Vibration, so that press-powder obtains closely knit, carries out evacuation, discharges the air between powder particle after sealing, put into equipped with water or oil
In high-pressure bottle, it is pressurized to 150 MPa, be heated to 200 DEG C, pressure-maintaining and heat-preservation 14h, it is pressed into block after being cooled to room temperature;
(3)Polymerization cladding
After block is used Universalpulverizer to crush, it is added in the HCl solution that concentration is 0.9M, 50 points of ultrasonic disperse
Clock, and be aided with ice-water bath and form suspension, take polymer monomer to be added in above-mentioned suspension, then ultrasonic disperse 45 minutes, and
It is aided with ice-water bath;Initiator ammonium persulfate is dissolved in the HCl solution that concentration is 1M, and is slowly dropped in reaction system,
Polymer monomer is 1 with the mol ratio of Ammonium persulfate.:1, time for adding controlled at 50 minutes, can be prepared by after drying Graphene/
Sulfur/conducting polymer composite material, in the present embodiment, described polymer monomer is selected from aniline.
Embodiment 6
(1)Mechanical mixture
Elemental sulfur and Graphene are added in homogenizer according to mass ratio, are carried out using rotating speed 4000 r/min
Dispersion 1h, elemental sulfur is dispersed in graphene sheet layer;In the present embodiment, described elemental sulfur is 99% purity, single
The granularity of matter sulfur is 2 μm, and described Graphene is single-layer graphene, and it is to be obtained using mechanical stripping method.
(2)Isostatic pressed merges
Elemental sulfur and Graphene mixture press-powder are filled in the rubber mold of iso-static pressure shaping machine, by high-frequency electromagnetic
Vibration, so that press-powder obtains closely knit, carries out evacuation, discharges the air between powder particle after sealing, put into equipped with water or oil
In high-pressure bottle, it is pressurized to 170 MPa, be heated to 190 DEG C, pressure-maintaining and heat-preservation 18h, it is pressed into block after being cooled to room temperature;
(3)Polymerization cladding
After block is used Universalpulverizer to crush, it is added in the HCl solution that concentration is 1M, 50 points of ultrasonic disperse
Clock, and be aided with ice-water bath and form suspension, take polymer monomer to be added in above-mentioned suspension, then ultrasonic disperse 30 minutes, and
It is aided with ice-water bath;Initiator ammonium persulfate is dissolved in the HCl solution that concentration is 0.9M, and is slowly dropped to reaction system
In, polymer monomer is 1 with the mol ratio of Ammonium persulfate.:1, time for adding controlled at 10 minutes, can be prepared by graphite after drying
Alkene/sulfur/conducting polymer composite material, in the present embodiment, described polymer monomer is selected from aniline, pyrroles and thiophene.
Embodiment 7
(1)Mechanical mixture
Elemental sulfur and Graphene are added in homogenizer according to mass ratio, are carried out using rotating speed 4500 r/min
Dispersion 2h, elemental sulfur is dispersed in graphene sheet layer;In the present embodiment, described elemental sulfur is 99% purity, single
The granularity of matter sulfur is 3 μm, and described Graphene is multi-layer graphene, and it is to be obtained using mechanical stripping method.
(2)Isostatic pressed merges
Elemental sulfur and Graphene mixture press-powder are filled in the rubber mold of iso-static pressure shaping machine, by high-frequency electromagnetic
Vibration, so that press-powder obtains closely knit, carries out evacuation, discharges the air between powder particle after sealing, put into equipped with water or oil
In high-pressure bottle, it is pressurized to 190 MPa, be heated to 190 DEG C, pressure-maintaining and heat-preservation 18h, it is pressed into block after being cooled to room temperature;
(3)Polymerization cladding
After block is used Universalpulverizer to crush, it is added in the HCl solution that concentration is 0.8M, 30 points of ultrasonic disperse
Clock, and be aided with ice-water bath and form suspension, take polymer monomer to be added in above-mentioned suspension, then ultrasonic disperse 40 minutes, and
It is aided with ice-water bath;Initiator ammonium persulfate is dissolved in the HCl solution that concentration is 0.6M, and is slowly dropped to reaction system
In, polymer monomer is 1 with the mol ratio of Ammonium persulfate.:1, time for adding controlled at 40 minutes, can be prepared by graphite after drying
Alkene/sulfur/conducting polymer composite material, in the present embodiment, described polymer monomer is selected from pyrroles and thiophene.
Embodiment 8
(1)Mechanical mixture
Elemental sulfur and Graphene are added in homogenizer according to mass ratio, are carried out using rotating speed 5000 r/min
Dispersion 1h, elemental sulfur is dispersed in graphene sheet layer;In the present embodiment, described elemental sulfur is 99% purity, single
The granularity of matter sulfur is 1 μm, and described Graphene is single-layer graphene, and it is to be obtained using chemical vapor deposition.
(2)Isostatic pressed merges
Elemental sulfur and Graphene mixture press-powder are filled in the rubber mold of iso-static pressure shaping machine, by high-frequency electromagnetic
Vibration, so that press-powder obtains closely knit, carries out evacuation, discharges the air between powder particle after sealing, put into equipped with water or oil
In high-pressure bottle, it is pressurized to 200 MPa, be heated to 150 DEG C, pressure-maintaining and heat-preservation 20h, it is pressed into block after being cooled to room temperature;
(3)Polymerization cladding
After block is used Universalpulverizer to crush, it is added in the HCl solution that concentration is 0.6M, 20 points of ultrasonic disperse
Clock, and be aided with ice-water bath and form suspension, take polymer monomer to be added in above-mentioned suspension, then ultrasonic disperse 30 minutes, and
It is aided with ice-water bath;Initiator ammonium persulfate is dissolved in the HCl solution that concentration is 1M, and is slowly dropped in reaction system,
Polymer monomer is 1 with the mol ratio of Ammonium persulfate.:1, time for adding controlled at 30 minutes, can be prepared by after drying Graphene/
Sulfur/conducting polymer composite material, in the present embodiment, described polymer monomer is selected from aniline, pyrroles and thiophene.
Comparative example 1
Using elemental sulfur directly as positive electrode.
Comparative example 2
Carry out polymerization cladding and composite is obtained after mechanical mixture, its preparation process does not carry out isostatic pressed.
For detecting the chemical property of Graphene/sulfur/conducting polymer composite material of the present invention, use half-cell method of testing
Test, with the composite of above example and comparative example: PVDF: Super-p=80: 5: 15(Weight ratio), plus in right amount:Formylmerphalan
Base ketopyrrolidine mediation pulp, coats on aluminium foil and is dried in vacuum drying oven and make lithium-sulphur cell positive electrode in 12 hours
Piece, does negative pole with 130 microns of lithium paper tinsel, and 20 microns of PE perforated membrane is barrier film, and 1, the 3- dioxolanes of 1M LiSO3CF3/
Diethylene glycol dimethyl ether/sulfolane/dimethoxy-ethane(Volume ratio 50/20/10/20)Solution as electrolyte, to electrode
For lithium piece, the glove box full of argon is assembled into button cell.Carry out constant current charge-discharge in LAND battery test system real
Test, charging/discharging voltage is limited in 1.5-3.0 V, charging and discharging currents are 100mA/g, the discharge and recharge cabinet computerizeing control enters line number
According to collection and control.The data obtaining is as shown in table 1 below:
The composite of the preparation of embodiment 1~8 and the chemical property of comparative example 1,2 composites that table 1 represents
As can be known from Table 1, compared with the comparative example 1 of elemental sulfur, the introducing of Graphene and conducting polymer is all to battery
Capacity, high rate performance, cycle performance are significantly improved.Compared with the comparative example 2 not carrying out isostatic pressed operation, isostatic pressed operation
Introducing the high rate performance of composite can be made to be greatly improved.These results show synthesized Graphene/sulfur/conduction
Polymer composites are effectively improved electrical conductivity it is suppressed that volumetric expansion, decrease shuttle loss.So, the present invention carries
The anode composite material of lithium sulfur battery going out has a good application prospect.
The design focal point of the present invention is:The present invention passes through using simple and easy to do mechanical mixture, and isostatic pressed merges, polymerization
Elemental sulfur is wrapped in the three-dimensional conductive network of Graphene composition the means such as cladding, can maintain between elemental sulfur and Graphene
Good electrical contact, shortens the evolving path of lithium ion it is ensured that the electronics conduction of electrode material will not be lost;Conducting polymer simultaneously
Thing is uniformly coated completely to elemental sulfur, effectively prevents the directly contact of the polysulfide ion in reaction and electrolyte,
Thus improve first charge-discharge efficiency and the cycle performance of material.And, introduce isostatic pressed to merge, make elemental sulfur and Graphene
Integration engineering occur mainly in mesopore and aperture, be effectively prevented from the appearance that elemental sulfur leads in the reunion of graphenic surface
Amount can not be brought into play, and can improve volume energy density and high rate performance.Present invention process is simple, easy to operate, raw
Product equipment is few, thus further reduces cost, easy to utilize, is suitable to large-scale production.
The above, be only presently preferred embodiments of the present invention, not the technical scope of the present invention imposed any restrictions,
Therefore any trickle amendment, equivalent variations and modification that every technical spirit according to the present invention is made to above example, all still
Belong in the range of technical solution of the present invention.