CN104869676A - Low-voltage transparent electrothermal film and preparation process thereof - Google Patents
Low-voltage transparent electrothermal film and preparation process thereof Download PDFInfo
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- CN104869676A CN104869676A CN201510203373.3A CN201510203373A CN104869676A CN 104869676 A CN104869676 A CN 104869676A CN 201510203373 A CN201510203373 A CN 201510203373A CN 104869676 A CN104869676 A CN 104869676A
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/84—Heating arrangements specially adapted for transparent or reflecting areas, e.g. for demisting or de-icing windows, mirrors or vehicle windshields
- H05B3/86—Heating arrangements specially adapted for transparent or reflecting areas, e.g. for demisting or de-icing windows, mirrors or vehicle windshields the heating conductors being embedded in the transparent or reflecting material
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Abstract
The invention discloses a low-voltage transparent electrothermal film which comprises a transparent base material, a transparent conductive layer and electrodes. The transparent conductive layer is formed on at least one side of the transparent base material; the electrodes are formed by bus bars and a plurality of inner electrodes, wherein the inner electrodes extend oppositely from the bus bars to form interdigital electrodes; and the electrodes are arranged on the transparent conductive layer and are in electrical contact with the transparent conductive layer. Through the arrangement of the bus bars and the inner electrodes, distance between two electrodes is reduced and resistance of the transparent conductive layer between the two electrodes is reduced, so that low-voltage power supply can be used, and the voltage of a daily lithium battery can be used normally, and a temperature of 90-180 DEG C can be reached quickly by heating. The two surfaces of graphene can be provided with two sets of electrodes respectively, and the inner electrodes of the two sets of electrodes are staggered for a certain distance, so that heating uniformity can be further ensured, and heating temperature is improved under the same low voltage.
Description
Technical field
The present invention relates to a kind of transparent electric heating film and preparation technology thereof, especially a kind of low-voltage transparent electric heating film and preparation method thereof.
Background technology
Transparent heating film is typically employed in film material plated surface transparent conducting coating, then conductive electrode is made on conductive coating surface, electrode is generally two parallel bonding jumpers, two bonding jumpers connect positive source and negative pole respectively, electric current flows through transparent conducting coating and produces heat, as shown in Figure 1 (be the patent of CN103828482A see publication number).The square resistance when thickness is thinner such as electrically conducting transparent layer graphene conventional at present, carbon nano-tube, ITO, FTO, AZO etc. is comparatively large, and this makes to use higher supply power voltage to meet heating requirements, is unfavorable for safety and the portability instructions for use of Electric radiant Heating Film; And, though thickness increases can reduce use voltage, add material cost, reduce production efficiency and light transmittance simultaneously.
Publication number is CN102883486A, name is called in the patent of " a kind of transparent electrical-heating film based on Graphene and preparation method thereof ", transparent electrical-heating film comprises transparent flexible substrate, transparent flexible substrate arranges graphene film, graphene film is provided with conduction and connects nethike embrane, conduction connects nethike embrane and is provided with electrode, and electrode is connected nethike embrane with conduction and graphene film is electrically connected; Electrode arranges overcoat, and overcoat covers on electrode, and covers on graphene film and conduction connection nethike embrane.This patent proposes to adopt Graphene to be connected the transparent heating material of nethike embrane as Electric radiant Heating Film with conduction, and the method can connect by conduction the sheet resistance that nethike embrane reduces whole clearing electric conducting material, but there is following shortcoming:
1) conduction connects the sheet resistance of nethike embrane usually much smaller than Graphene sheet resistance, and the two is and connects relation, plays mainly conduction connection nethike embrane instead of the Graphene of heat effect like this.
2) conduction connects the wire diameter <5 μm of nethike embrane, is very easily burnt Electric radiant Heating Film was lost efficacy when adopting conventional metal material to be energized.
A kind of Graphene flexible and transparent heating element and preparation method thereof was also once proposed, for the uniformity strengthening heating uses patterned transparent electrode, receiving electrode in the middle part of transparency electrode in prior art.But patterned electrodes also uses transparent conductive material, because transparent conductive material conductivity is poor, also be difficult to after introducing patterned electrodes obtain the effect reducing and use voltage, multilayer (5-6 layer) Graphene therefore must be used to reduce resistance and use voltage to reduce.In addition, if use two parallel poles instead of patterned electrodes, then the heating uniformity obtained is poor, thermal self-restraint stress and more than minimum point difference 60K, is difficult to realize practical requirement.
Summary of the invention
In order to solve problems of the prior art, the invention provides a kind of low-voltage transparent electric heating film, this transparent electric heating film can work under low-voltage (≤12V), reaches the temperature of expection.
Further, this transparent electric heating film heating uniformity is good.
Further, this transparent electric heating film uses thinner transparency conducting layer heating, use Graphene can use single-layer graphene as during transparency conducting layer, this Electric radiant Heating Film uses very low voltage (as≤1.5V) can obtain the heating effect identical with conventional transparent Electric radiant Heating Film simultaneously, and what play heating functioin is transparency conducting layer.
Another object of the present invention is to provide the preparation technology of above-mentioned low-voltage transparent electric heating film.
In order to solve aforementioned technical problem, reaching above-mentioned technique effect, the invention provides following technical scheme:
A kind of low-voltage transparent electric heating film, comprises transparent base, transparency conducting layer, electrode; Transparency conducting layer is formed at least side of transparent base; Electrode is made up of busbar and some interior electrodes, and interior electrode extends to form interdigital electrode in opposite directions by busbar; Electrode to be positioned on transparency conducting layer and with transparency conducting layer electrical contact.
Preferably, electrode by thick busbar and some carefully in electrode form, busbar connects the negative or positive electrode of power supply, and make two adjacent interior polarities of electrode contrary, the electric current that during energising, positive bus bar provides flows into electrode in corresponding negative pole by electrode in each positive pole and finally all imports negative bus bar.
Preferably, the negative or positive electrode of busbar one termination power.
Further preferably, positive and negative two cover electrodes can be set respectively on transparency conducting layer two sides, interior electrode of this two covers electrode staggers certain distance, namely positive and negative interdigital electrode is placed in transparency conducting layer both sides respectively, form the interdigital electrode separated by transparency conducting layer, ensure that uniform current is by transparency conducting layer, can ensure the uniformity heated so further.
Preferably, the material of transparency conducting layer is including but not limited to Graphene, carbon nano-tube, ITO, FTO, AZO etc.
Preferably, electrode can be made up of transparent conductive material, and wherein, preferred transparent electrode material is Graphene.
Preferably, electrode to be positioned on graphene layer and to be integrally formed with graphene layer.
Preferably, electrode material is including but not limited to silver, material that electric conductivity such as silver slurry, copper, copper slurry, aluminium, ITO etc. is good.Electrode material is best with Copper Foil.
Preferably, electrode can be formed between transparent base and transparency conducting layer.
Preferably, transparent base can be glass or polymer, and transparent base is including but not limited to films such as PET, PVC, PE, PC.More preferably, polymer can be: PET, PMMA, PVDF, PANI, or its composition.
Preferably, described transparency conducting layer is single or multiple lift Graphene.The best is single-layer graphene.
The application of electrode of special construction of the present invention, on single-layer graphene, can make this transparent electric heating film work under low-voltage (≤12V), can use more low-voltage on multi-layer graphene.
Preferably, graphene layer can use dopant; More preferably, dopant can be inorganic/organic blended dose.
Preferably, can on electrode and graphene layer protective mulch; More preferably, protective layer can adopt flexible clear materials.
Preferably, the material of transparent covering layer is including but not limited to films such as PET, PVC, PE, PC.
Preferably, can by electrode serial or parallel connection of the present invention.
Preferably, can by transparent electric heating film serial or parallel connection of the present invention.
Further, described interior electrode is linear, waveform or zigzag, described busbar is according to the shape of Electric radiant Heating Film and application demand, can linearly shape, shaped form, the pattern form of busbar and interior electrode composition, according to the shape of Electric radiant Heating Film and application demand, also can surround square, circular, oval or arbitrary shape.
Preferred, described busbar is positioned at the edge of transparency conducting layer, and contacts well with transparency conducting layer, and described interior electrode is extended to another busbar by a busbar, and adjacent inner electrodes, from different busbar, extends in opposite directions.
Further, the present inventor finds, for obtaining good temperature homogeneity at lower voltages, for the electrode of special construction of the present invention, in final warming temperature, initial temperature, supply power voltage, two, the square resistance of electrode spacing and transparency conducting layer meets following formula:
T=kU
2/d
2R+t (1)
Wherein: in two electrode spacing laminated according to electrically conducting transparent in electrode spacing calculate,
T---initial temperature, unit is DEG C;
T---Electric radiant Heating Film heats up institute to final warming temperature, and unit is DEG C;
U---supply power voltage, unit is V, U≤12V;
D---interior electrode spacing, unit is cm;
R---transparency conducting layer square resistance, unit is Ω/;
K---constant, span is that 10-200, k span has different according to the coefficient of conductivity between Electric radiant Heating Film from air, and the coefficient of conductivity between Electric radiant Heating Film and air is inversely proportional to.
Adopting the electrode of special construction of the present invention, made by spacing interelectrode in reduction two resistance of two interelectrode transparency conducting layers reduce, is a kind of optimization approach, makes to use low voltage power supply to become possibility.Normally can adopt daily lithium battery voltage, rapid heat temperature raising can be reached.
Preferably, the busbar of Electric radiant Heating Film and interior electrode can be same material, and also can be different materials, its length is according to the size design of Electric radiant Heating Film.For ensureing temperature homogeneity, the width of busbar and thickness need consider current carrying capacity and the resistivity of material therefor, resistivity is enough little, to reduce the voltage drop on busbar, in ensureing, electrode is arranged on the diverse location ceiling voltage of busbar and minimum voltage difference is no more than 10%, and current carrying capacity determines busbar sectional area and must be greater than a certain numerical value guarantee busbar and do not burnt.The present inventor finds to there is following formula (2):
n(n+1)lρ
l/WHR<1/5 (2)
Wherein:
N interval is created altogether in n---the area that interior electrode makes busbar surround;
ρ
1---bus bar materials resistivity, unit is Ω m;
L---the every root length of interior electrode, by wherein the longest interior electrode calculating when length does not wait, unit is m;
W---busbar width, unit is m;
H---busbar thickness, unit is m;
R---transparency conducting layer square resistance, unit is Ω/.
Preferably, interior electrode ensures current carrying capacity and considers that on same interior electrode, maximum voltage difference is no more than 10%.The present inventor finds to there is following formula (3):
nl
2ρ
2/whLR<1/5 (3)
Wherein:
N interval is created altogether in n---the area that interior electrode makes busbar surround;
L---the every root length of interior electrode, by wherein the longest interior electrode calculating when length does not wait, unit is m;
ρ
2---inner electrode resistivity, unit is Ω m;
W---interior electrode width, unit is m;
H---interior thickness of electrode, unit is m;
L---every root busbar plays electrode in last root by first interior electrode and stops the raw length of common property, unit m;
R---transparency conducting layer square resistance, unit is Ω/.
The present invention makes the resistance of two interelectrode transparency conducting layers reduce by adopting interelectrode spacing in the electrode of special construction, reduction two, thus can low voltage power supply be used, normally can adopt daily lithium battery voltage, can reach and be heated to 90-180 DEG C rapidly.Positive and negative two cover electrodes can be arranged at Graphene two sides respectively, form the interdigital electrode separated by Graphene, the uniformity heated can be ensured so further, under same low-voltage, improve the temperature of heating.
For the transparent conductive material be grown in metal foil substrate, the metal foil substrate pattern-making polarizing electrode of the good transparent conductive film of superficial growth can be adopted, preparation process can be simplified like this, save time and material cost, the conductivity of metal forming is good simultaneously, be conducive to the control of Electric radiant Heating Film temperature homogeneity, detailed process is as follows:
1, the transparent conductive material be grown in metal foil substrate is prepared;
2, transparent base and metal forming are grown there is the one side of transparent conductive material to be bonded together;
3, in metal foil surfaces, make mask by the method for photoetching or printing, mask pattern designs on request;
4, the transparent base/transparency conducting layer/metal forming making mask is placed in etching liquid, etches away not by the metal of mask protection;
5, remove the mask of surface of metal electrode, form patterned electrodes.
Further preferably, can cover protective clear layer on transparency conducting layer and patterned electrodes, concrete steps are as follows:
6, will the protective clear layer perforate of band glue, to expose the electrode that will go between when itself and lower electrode and transparency conducting layer are fitted;
7, fit behind the hole of protective clear layer and the good position of electrode pair;
8, lead-in wire is made at the electrode place that aperture exposes.
Preferably, transparent conductive material can be Graphene.
Preferably, using transparent adhesive tape transparent base and metal forming to be grown has the one side of transparent conductive material to bond.More preferably, described transparent adhesive tape is including but not limited to various UV light-cured resin, PUR, silica gel etc.
Preferably, described metal forming can be selected from but be not limited to Copper Foil, nickel foil, corronil paper tinsel etc.
Preferably, described etching liquid is selected according to metal forming, can add the material improving transparent conductive material conductivity in etching liquid.
Preferably, the method removing surface of metal electrode mask described in can select the method for hand stripping or solution removal according to mask material.
Preferably, the preparation method of a kind of low-voltage transparent electric heating film of the present invention also can adopt following steps:
1, transparent base and transparency conducting layer are bonded together;
2, make electrode over transparent conductive layer, the method for directly printing electrocondution slurry or evaporation electric conducting material can be adopted to carry out, and electrode pattern designs according to demand for heat.
Further preferably, can on transparency conducting layer and electrode protective mulch, concrete steps are as follows:
3, will the protective clear layer perforate of band glue, to expose the electrode that will go between when itself and lower electrode and transparency conducting layer are fitted;
4, fit behind the hole of protective clear layer and the good position of electrode pair;
5, lead-in wire is made at the electrode place that aperture exposes.
Beneficial effect of the present invention:
(1) because the introducing of busbar and interior electrode reduces the electrode spacing of transparency conducting layer well, compared with the electrode design scheme of existing transparent electric heating film, lower power voltage supply can be used, the compact powers such as lithium battery so just can be used to power.
(2) electrode design of the thin interior electrode of thick busbar under the condition that heating voltage is identical, can use the transparent conductive material that conductivity is poor, obtains the heating effect identical with the material of good conductivity by changing interior electrode spacing.
(3) under the fixing condition of supply voltage and transparent conductive material, different heating powers can be realized by control busbar area and interior electrode spacing, thus meet different heating-up temperature demands.
(4) pattern metal paper tinsel makes the process simplification of electrode electrode fabrication, improves the conductive capability of electrode, saves Production Time, reduce the material cost needed for making.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification, together with embodiments of the present invention for explaining the present invention, is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is that in background technology, transparent heating film electrode arranges figure;
Fig. 2 is the distribution of electrodes figure of the Electric radiant Heating Film of the embodiment of the present invention 1;
Fig. 3 is the profile of a preferred embodiment of the invention;
Fig. 4 is the distribution of electrodes figure of the Electric radiant Heating Film of the embodiment of the present invention 2;
Fig. 5 is the distribution of electrodes figure of the Electric radiant Heating Film of the embodiment of the present invention 3;
Fig. 6 is the distribution of electrodes figure of the Electric radiant Heating Film of the embodiment of the present invention 4;
Fig. 7 is the Temperature Distribution photo of Electric radiant Heating Film (not preferred scheme) the thermal infrared imager shooting of the embodiment of the present invention 1;
Fig. 8 is the Temperature Distribution photo of Electric radiant Heating Film (preferred version) the thermal infrared imager shooting of the embodiment of the present invention 1;
Fig. 9 is Electric radiant Heating Film (preferred version) the straight line temperature profile of the embodiment of the present invention 1, and horizontal is Electric radiant Heating Film positional representation from left to right as mark, and vertical is temperature as mark;
Figure 10 is the Temperature Distribution photo of Electric radiant Heating Film (not preferred scheme) the thermal infrared imager shooting of the embodiment of the present invention 2;
Figure 11 is the Temperature Distribution photo of Electric radiant Heating Film (preferred version) the thermal infrared imager shooting of the embodiment of the present invention 2;
Figure 12 is Electric radiant Heating Film (preferred version) the straight line temperature profile of the embodiment of the present invention 2, and horizontal is Electric radiant Heating Film positional representation from left to right as mark, and vertical is temperature as mark;
Figure 13 is the Electric radiant Heating Film straight line temperature profile of the embodiment of the present invention 3;
Figure 14 is the Electric radiant Heating Film straight line temperature profile of the embodiment of the present invention 4;
Figure 15 is the Electric radiant Heating Film straight line temperature profile of the embodiment of the present invention 5;
Figure 16 is the Electric radiant Heating Film straight line temperature profile of the embodiment of the present invention 6;
Figure 17 is the Electric radiant Heating Film straight line temperature profile of the embodiment of the present invention 7;
Figure 18 is the Electric radiant Heating Film straight line temperature profile of the embodiment of the present invention 8;
Figure 19 is the Electric radiant Heating Film straight line temperature profile of the embodiment of the present invention 9;
Figure 20 is the Electric radiant Heating Film straight line temperature profile of the embodiment of the present invention 10;
Figure 21 is the Electric radiant Heating Film straight line temperature profile of the embodiment of the present invention 11.
In figure, 1--transparency conducting layer, 2--electrode, 21--busbar, electrode in 22-, 3--transparent base, 4--transparent covering layer.
Embodiment:
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein is only for instruction and explanation of the present invention, is not intended to limit the present invention.
In the examples below, although numerical value meets three formula all simultaneously, but the pattern electrode of electrode in thin for thick busbar, as long as parameter meets at least any one formula all can realize goal of the invention of the present invention, solves the technical problem to be solved in the present invention.Just give the execution mode simultaneously meeting three formula in embodiment, but any restriction can not be formed to technical solution of the present invention.
The resistivity relating to material in following examples is all well known in the art, and such as, the resistivity of copper is 1.75 × 10
-8Ω m, the resistivity of silver slurry is 8 × 10
-8Ω m, Graphene (individual layer) 1 × 10
-8Ω m.
Embodiment 1:
Shown in Fig. 2,3, single-layer graphene is as the low-voltage transparent electric heating film of heater, and electrode adopts the printing of silver slurry.
Preparation technology is as follows:
1, at upper transfer one layer graphene of the PET (transparent base) of area 150mm × 150mm thickness 125 μm, Graphene is overdoping, and sheet resistance is 250 Ω/;
2, use screen printing apparatus to print ag paste electrode pattern on the Graphene shifted, as shown in Figure 2, interior electrode spacing is 6mm to pattern form, wide 1mm, silver slurry thickness 25 μm;
3, the electrode pattern printed is placed in baking oven to toast, make the solidification of silver slurry, baking temperature is 130 DEG C, and the time is 40min.
Initial temperature is room temperature (22 DEG C), in such cases, lead-in wire is connected respectively the both positive and negative polarity of 5V power supply, after tested, within 60 seconds, stable state can be reached, Figure 7 shows that the Temperature Distribution photo using thermal infrared imager shooting, now the mean temperature of Electric radiant Heating Film can reach about 77.5 DEG C, (room temperature is 22 DEG C).Coincidence formula T=kU
2/ d
2r+t (K=200).
Test result shows, the electrode design scheme using us to invent, and the average heating power using heating film during 3.7V power voltage supply is 1500w/m
2left and right, and when voltage is 3.7V, use traditional Electric radiant Heating Film average heating power without interior electrode to be 5.4w/m
2left and right, reach the identical heating effect of Electric radiant Heating Film newly-designed with us and use voltage to be increased to about 612V, this is considerably beyond human safety voltage.
Preferably, following steps are carried out further:
4, the OCA glue of area 150mm × 150mm thickness 50 μm and PET of the same area are fit together;
5, use PET/OCA that laser cutting device is posting to open square opening, hole size is 5mm × 5mm, and after the position of perforate will ensure that this PET/OCA and electrode pattern are fitted, bus bar termination exposes the electrode of 5mm × 5mm;
6, to behind good position, PET/OCA and electrode pattern are fitted;
7, the electrode exposed at aperture goes out to make lead-in wire;
In such cases, recording Electric radiant Heating Film resistance is 2.7 Ω, lead-in wire is connected respectively the both positive and negative polarity of 5V power supply, after tested, within 60 seconds, can stable state be reached, Figure 8 shows that the Temperature Distribution photo using thermal infrared imager shooting, Figure 9 shows that straight line temperature profile, now the mean temperature of Electric radiant Heating Film can reach about 66 DEG C (room temperature is 22 DEG C), coincidence formula T=kU
2/ d
2if voltage is 3.7V, stable rear mean temperature is 42 DEG C to R+t (k=158), if voltage is 7.4V, stable rear mean temperature is 103 DEG C, coincidence formula T=kU
2/ d
2r+t (k=133).
Test result shows, the electrode design scheme using us to invent, and the average heating power using heating film during 3.7V power voltage supply is 1300w/m
2left and right, and when voltage is 3.7V, use traditional Electric radiant Heating Film average heating power without interior electrode to be 5w/m
2left and right, reach the identical heating effect of Electric radiant Heating Film newly-designed with us and use voltage to be increased to about 60V, this is considerably beyond human safety voltage.
Embodiment 2:
The present embodiment adopts two layer graphenes as the low-voltage transparent electric heating film of heater, and electrode adopts the printing of silver slurry.
1, at upper transfer two layer graphene of the PET (transparent base) of area 120mm × 120mm thickness 125 μm, Graphene is overdoping, and sheet resistance is 120 Ω/;
2, screen printing apparatus is used to print ag paste electrode pattern on the Graphene shifted, pattern form as shown in Figure 4, busbar outside diameter 96mm, the longest interior electrode is 73mm, and interior electrode spacing is 6mm, raw 17 intervals of common property, wide 1mm, the wide 8mm of busbar, it is 130mm that busbar plays by first interior electrode the length that in last root, electrode stops, silver slurry thickness 25 μm;
3, the electrode pattern printed is placed in baking oven to toast, make the solidification of silver slurry, baking temperature is 130 DEG C, and the time is 40min.
In such cases, lead-in wire is connected respectively the both positive and negative polarity of 5V power supply, after tested, 60S can reach stable state, Figure 10 shows that the Temperature Distribution photo using thermal infrared imager shooting, now the mean temperature of Electric radiant Heating Film can reach about 137.7 DEG C (initial temperature is room temperature 22 DEG C), coincidence formula T=kU
2/ d
2r+t (K=200).
Test result shows, the electrode design scheme using us to invent, and the average heating power using heating film during 3.7V power voltage supply is 3168w/m
2left and right, and when voltage is 3.7V, use traditional Electric radiant Heating Film average heating power without interior electrode to be 11.4w/m
2left and right, reach the identical heating effect of Electric radiant Heating Film newly-designed with us and use voltage to be increased to about 616.6V, this is considerably beyond human safety voltage.
Preferably, following steps are carried out further:
4, the OCA glue of area 120mm × 120mm thickness 50 μm and PET of the same area are fit together;
5, use PET/OCA that laser cutting device is posting to open square opening, hole size is 5mm × 5mm, and after the position of perforate will ensure that this PET/OCA and electrode pattern are fitted, bus bar termination exposes the electrode of 5mm × 5mm;
6, to behind good position, PET/OCA and electrode pattern are fitted;
7, the electrode exposed at aperture goes out to make lead-in wire;
In such cases, recording Electric radiant Heating Film resistance is 2 Ω, lead-in wire is connected respectively the both positive and negative polarity of 5V power supply, after tested, 40S clock can reach stable state, and shown in Figure 11,12, now the mean temperature of Electric radiant Heating Film can reach about 90.9 DEG C (room temperature is 22 DEG C).Coincidence formula T=kU
2/ d
2r+t (k=119.1)
Test result shows, the electrode design scheme using us to invent, and the average heating power using heating film during 3.7V power voltage supply is 1300w/m
2left and right, and when voltage is 3.7V, use traditional Electric radiant Heating Film average heating power without interior electrode to be 5w/m
2left and right, reach the identical heating effect of Electric radiant Heating Film newly-designed with us and use voltage to be increased to about 60V, this is considerably beyond human safety voltage.
After tested, the diverse location ceiling voltage of busbar and minimum voltage difference 0.2%, on interior electrode, maximum voltage difference is no more than 0.004%.
Embodiment 3:
Shown in Figure 5, single-layer graphene is as the low-voltage transparent electric heating film of heater, and preparation technology is as follows:
1, to be 150mm × 300mm thickness by the Copper Foil having grown Graphene (through overdoping, sheet resistance is 250 Ω/ to Graphene) and size the be PET of 125 μm is by together with UV glue laminating, and Copper Foil size is 140mm × 280mm, and thickness is 25 μm;
2, by UV adhesive curing, wavelength is 365nm, and energy is 1000mJ/cm
2;
3, use screen printing apparatus on the Copper Foil posted, print peelable glue mask, pattern form as shown in Figure 5, now, be equivalent to Electric radiant Heating Film be divided into two, form the effect of the two pieces of Electric radiant Heating Film series connection in left and right, the actual voltage that utilizes reduces by half, interior electrode spacing is 3mm, long 108mm, wide 1mm, totally 32, raw 30 intervals of common property, the wide 8mm of busbar, it is 100mm that busbar plays by first interior electrode the length that in last root, electrode stops, copper thickness 25 μm;
4, the electrode pattern printed is placed in baking oven to toast, peelable glue is solidified, baking temperature is 135 DEG C, and the time is 40min;
5, the sample after baking is placed in the FeCl of 30%
3etch in etching liquid, etching terminates after washing and dries up, and takes the peelable glue of electrode surface off.
In such cases, recording Electric radiant Heating Film resistance is 1.7 Ω, lead-in wire is connected respectively the both positive and negative polarity (be 1.85V relative to the Electric radiant Heating Film of half) of 3.7V lithium ion battery, after tested, the temperature that 30S stablizes rear Electric radiant Heating Film can reach about 46 DEG C, shown in Figure 13, (room temperature is 22 DEG C), coincidence formula T=kU
2/ d
2r+t (K=160).
Test result shows, and uses electrode design scheme of the present invention, and when using 3.7V voltage (voltage being applied to two electrodes is 1.85V) to power, the average heating power of heating film is 1521w/m
2left and right, and when voltage is 3.7V, use traditional Electric radiant Heating Film without interior electrode, reach the identical heating effect of Electric radiant Heating Film newly-designed with us uses voltage need be increased to about 616V, and this is considerably beyond human safety voltage.
Preferably, following steps are carried out further:
6, the OCA glue of area 150mm × 300mm thickness 50 μm and PET of the same area are fit together;
7, use PET/OCA that laser cutting device is posting to open square opening, hole size is 5mm × 5mm, and after the position of perforate will ensure that this PET/OCA and electrode pattern are fitted, bus bar termination exposes the electrode of 5mm × 5mm;
8, to behind good position, PET/OCA and electrode pattern are fitted;
9, the electrode exposed at aperture goes out to make lead-in wire;
Recording Electric radiant Heating Film resistance is 2.5 Ω, lead-in wire is connected respectively the both positive and negative polarity of 3.7V (the actual voltage that utilizes is equivalent to 1.85V) lithium ion battery, after tested, the temperature that 70S stablizes rear Electric radiant Heating Film can reach about 45 DEG C (room temperature is 22 DEG C), coincidence formula T=kU
2/ d
2r+t (K=151).
After tested, the diverse location ceiling voltage of busbar and minimum voltage difference 0.2%, on interior electrode, maximum voltage difference is no more than 0.004%.
Embodiment 4:
The present embodiment adopts ito thin film as the low-voltage transparent electric heating film of heater, and silver slurry is as electrode, and design is with reference to Fig. 2, and preparation technology is as follows:
1, screen printing apparatus is used in sheet resistance for being of a size of 150mm × 150mm, sheet resistance is ito thin film (sheet resistance is 400 Ω/) the upper printing ag paste electrode pattern of 150 Ω, pattern form as shown in Figure 2, interior electrode spacing is 6mm, long 108mm, wide 1mm, totally 15, raw 15 intervals of common property, the wide 8mm of busbar, silver slurry thickness 25 μm;
2, the electrode pattern printed is placed in baking oven to toast, make the solidification of silver slurry, baking temperature is 130 DEG C, and the time is 40min.
3, the OCA glue of area 150mm × 150mm thickness 50 μm and PET of the same area are fit together;
4, use PET/OCA that laser cutting device is posting to open square opening, hole size is 5mm × 5mm, and after the position of perforate will ensure that this PET/OCA and electrode pattern are fitted, bus bar termination exposes the electrode of 5mm × 5mm;
5, to behind good position, PET/OCA and electrode pattern are fitted;
6, the electrode exposed at aperture goes out to make lead-in wire;
In such cases, recording Electric radiant Heating Film resistance is 5 Ω, lead-in wire is connected respectively the both positive and negative polarity of 12V power supply, after tested, 55S can reach stable state, see Figure 14, now the mean temperature of Electric radiant Heating Film can reach about 92 DEG C (room temperature is 22 DEG C), coincidence formula T=kU
2/ d
2r+t (K=70).
After tested, the diverse location ceiling voltage of busbar and minimum voltage difference 0.05%, on interior electrode, maximum voltage difference is no more than 0.01%.
Embodiment 5:
The present embodiment transparency conducting layer adopts single-layer graphene (250 Ω/), electrode adopts 10 layer graphenes, during preparation, with reference to the optimal way of embodiment 1, difference is: adopt the mode continuing transfer Graphene on graphene film, be transferred to 11th layer, stop transfer, then 10 layer graphenes are above etched into patterned electrodes, or adopt direct growth multi-layer graphene, make patterned electrodes again, the design of the present embodiment electrode is see accompanying drawing 2, interior electrode spacing is 3mm, long 108mm, wide 1mm, totally 15, raw 15 intervals of common property, the wide 8mm of busbar, it is 60mm that busbar plays by first interior electrode the length that in last root, electrode stops, electrode (10 layer graphene) thick 35nm.
In such cases, recording Electric radiant Heating Film resistance is 2 Ω, lead-in wire is connected respectively the both positive and negative polarity of 1.5V power supply, after tested, 85S can reach stable state, see Figure 15, now the mean temperature of Electric radiant Heating Film can reach about 34 DEG C (room temperature is 22 DEG C), coincidence formula T=kU
2/ d
2r+t (K=120).
After tested, the diverse location ceiling voltage of busbar and minimum voltage difference 0.1%, on interior electrode, maximum voltage difference is no more than 0.02%.
Embodiment 6:
The present embodiment adopts 4 layer graphenes (62.5 Ω/) as transparency conducting layer, electrode adopts ITO, during preparation, according to the optimal way of embodiment 1, difference is: to adopt when being printed in by ITO on conductive layer, electrode patterning design is see Fig. 4, and interior electrode spacing is 4mm, wide 1mm, totally 16, raw 17 intervals of common property, the wide 8mm of busbar, silver slurry thickness 25 μm.
In such cases, recording Electric radiant Heating Film resistance is 0.4 Ω, lead-in wire is connected respectively the both positive and negative polarity of 3.7V power supply, after tested, 100S can reach stable state, see Figure 16, now the mean temperature of Electric radiant Heating Film can reach about 103 DEG C (room temperature is 22 DEG C), coincidence formula T=kU
2/ d
2r+t (K=110.9).
After tested, the diverse location ceiling voltage of busbar and minimum voltage difference 3%, on interior electrode, maximum voltage difference is no more than 1.2%.
Embodiment 7:
The present embodiment is substantially with the preferred version of embodiment 3, and difference is: electrode patterning design is see accompanying drawing 2, and interior electrode spacing is 3mm, long 108mm, wide 1mm, totally 15, raw 15 intervals of common property, the wide 8mm of busbar, copper thickness 25 μm.
In such cases, recording Electric radiant Heating Film resistance is 1.7 Ω, lead-in wire is connected respectively the both positive and negative polarity of 12V power supply, after tested, 100S can reach stable state, see Figure 17, now the mean temperature of Electric radiant Heating Film can reach about 226 DEG C (room temperature is 22 DEG C), coincidence formula T=kU
2/ d
2r+t (K=32).
After tested, the diverse location ceiling voltage of busbar and minimum voltage difference 0.9%, on interior electrode, maximum voltage difference is no more than 0.1%.
Embodiment 8:
The present embodiment is substantially with the not preferred scheme of embodiment 1, difference is, electrode is formed between transparency conducting layer and transparent base, and electrode adopts Copper Foil, graphing design is see accompanying drawing 4, interior electrode spacing is 2mm, long 108mm, wide 1mm, totally 16, raw 17 intervals of common property, the wide 8mm of busbar, copper thickness 25 μm.Using single-layer graphene as the sheet resistance of the transparency conducting layer of material be 250 Ω/.
In such cases, recording Electric radiant Heating Film resistance is 2 Ω, lead-in wire is connected respectively the both positive and negative polarity of 3.7V power supply, after tested, 30S can reach stable state, see Figure 18, now the mean temperature of Electric radiant Heating Film can reach about 143.8 DEG C (room temperature is 22 DEG C), coincidence formula T=kU
2/ d
2r+t (K=89).
After tested, the diverse location ceiling voltage of busbar and minimum voltage difference 0.04%, on interior electrode, maximum voltage difference is no more than 3%.
Embodiment 9:
The positive pole of patterned electrodes and negative pole are provided separately the two sides in transparency conducting layer by the present embodiment employing, form the interdigital electrode separated by transparency conducting layer, patterning schemes is visually with accompanying drawing 2, the material of transparency conducting layer adopts single-layer graphene (sheet resistance is 250 Ω/), the Graphene of electrode employing 5-10 layer or thickness are the Copper Foil of 10-30 μm, the present embodiment preferably have employed the Graphene of 5-10 layer as electrode material, wherein, positive and negative adjacent inner electrodes spacing is 4mm, long 108mm, wide 1mm, totally 15, raw 15 intervals of common property, the wide 8mm of busbar.
In such cases, recording Electric radiant Heating Film resistance is 2.1 Ω, lead-in wire is connected respectively the both positive and negative polarity of 7.5V power supply, after tested, 30S can reach stable state, see Figure 19, now the mean temperature of Electric radiant Heating Film can reach about 210 DEG C (room temperature is 22 DEG C), coincidence formula T=kU
2/ d
2r+t (K=134).
After tested, the diverse location ceiling voltage of busbar and minimum voltage difference 7%, on interior electrode, maximum voltage difference is no more than 4%.
Embodiment 10:
The present embodiment is substantially with embodiment 3, and difference is, patterning schemes adopts accompanying drawing 6, and transparency conducting layer adopts 6 layer graphenes (sheet resistance is 41.6 Ω/), and electrode is Copper Foil.Interior electrode spacing is 10mm, wide 1mm, totally 9, raw 9 intervals of common property, the wide 8mm of busbar, copper thickness 25 μm.
In such cases, recording Electric radiant Heating Film resistance is 0.32 Ω, lead-in wire is connected respectively the both positive and negative polarity of 7.5V power supply, after tested, 30S can reach stable state, see Figure 20, now the mean temperature of Electric radiant Heating Film can reach about 86.3 DEG C (room temperature is 22 DEG C), coincidence formula T=kU
2/ d
2r+t (K=47.6).
After tested, the diverse location ceiling voltage of busbar and minimum voltage difference 2.4%, on interior electrode, maximum voltage difference is no more than 0.3%.
Embodiment 11:
The present embodiment is substantially with embodiment 1, and difference is, interior electrode and busbar adopt different materials.Can be electrode in transparent conductive material is done, busbar be made by metal material; Also can be that different metal material is respectively as interior electrode and busbar; Can also be that transparent conductive material makes busbar, interior electrode be made by metal material.The present embodiment preferable alloy Copper Foil or silver slurry are as the material of busbar, and the Graphene of at least 5 layers is as the material of interior electrode.The present embodiment more preferably using metal platinum as the Graphene of the material of busbar and 10 layers as the material of interior electrode.Single-layer graphene is as the material (sheet resistance is 250 Ω/) of transparency conducting layer.Patterning schemes is see accompanying drawing 2, and in Graphene, electrode spacing is 5mm, long 108mm, wide 1mm, totally 32, the wide 8mm of busbar, thickness 25 μm.
In such cases, recording Electric radiant Heating Film resistance is 1.9 Ω, lead-in wire is connected respectively the both positive and negative polarity of 12V power supply, after tested, 30S can reach stable state, see Figure 21, now the mean temperature of Electric radiant Heating Film can reach about 243 DEG C (room temperature is 22 DEG C), coincidence formula T=kU
2/ d
2r+t (K=96).
After tested, the diverse location ceiling voltage of busbar and minimum voltage difference 1.5%, on interior electrode, maximum voltage difference is no more than 2.3%.
Embodiment 12:
The present embodiment technique is with embodiment 1, and difference is the specific design of electrode.
In order to ensure that interior electrode is arranged on the diverse location ceiling voltage of busbar and minimum voltage difference is no more than 10%, the present embodiment is when making, space-number n, interior electrode extreme length l that inner electrode produces, the width W of busbar, the thickness H of busbar accurately process after carrying out measuring and calculating, make it meet above-mentioned formula (2).
The present embodiment requires being set to of electrode: the long 108mm of interior electrode, raw 15 intervals of common property, the wide 8mm of busbar, thick 25 μm.After tested, the diverse location ceiling voltage of busbar and minimum voltage difference 0.2%.
Lead-in wire is connected respectively the both positive and negative polarity of 1.5V power supply, after tested, 75S clock can reach stable state, and now the mean temperature of Electric radiant Heating Film can reach about 51 DEG C (room temperature is 22 DEG C).
Embodiment 13:
The present embodiment technique is with embodiment 1, and difference is the specific design of electrode.
In order to ensure that on interior electrode, maximum voltage difference is no more than 10%, the present embodiment is when making, the space-number n that inner electrode produces, interior electrode extreme length l, interior electrode width w, interior electrode width h, busbar play by first interior electrode the length L that in last root, electrode stops and carries out the rear accurately process of measuring and calculating, make it meet above-mentioned formula (3).
The present embodiment requires being set to of electrode: the long 108mm of interior electrode, totally 15 interior electrodes, in every root the width of electrode be 1mm, thick 25 μm, raw 15 intervals of common property, the wide 8mm of busbar, it is 99mm that busbar plays by first interior electrode the length that in last root, electrode stops.After tested, on interior electrode, maximum voltage difference is no more than 0.05%.
Lead-in wire is connected respectively the both positive and negative polarity of 7.5V power supply, after tested, 60S clock can reach stable state, and now the mean temperature of Electric radiant Heating Film can reach about 77.4 DEG C (room temperature is 22 DEG C).
Interior electrode in above embodiment all can be made into other shapes such as the wavy or zigzag be parallel to each other.The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment to invention has been detailed description, for a person skilled in the art, it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a low-voltage transparent electric heating film, comprises transparent base, transparency conducting layer, electrode; Transparency conducting layer is formed at least side of transparent base; It is characterized in that: electrode is made up of busbar and some interior electrodes, and interior electrode extends to form interdigital electrode in opposite directions by busbar; Electrode to be positioned on transparency conducting layer and with transparency conducting layer electrical contact.
2. a kind of low-voltage transparent electric heating film according to claim 1, it is characterized in that: electrode by thick busbar and some carefully in electrode form, busbar connects the negative or positive electrode of power supply, make two adjacent interior polarities of electrode contrary, the electric current that during energising, positive bus bar provides flows into electrode in corresponding negative pole by electrode in each positive pole and finally all imports negative bus bar; Preferably, the negative or positive electrode of busbar one termination power; Further preferably, positive and negative two cover electrodes can be set respectively on transparency conducting layer two sides, interior electrode of this two covers electrode staggers certain distance, namely positive and negative interdigital electrode is placed in transparency conducting layer both sides respectively, form the interdigital electrode separated by transparency conducting layer, ensure that uniform current is by transparency conducting layer, can ensure the uniformity heated so further.
3. a kind of low-voltage transparent electric heating film according to claim 1 and 2, is characterized in that: the material of transparency conducting layer is including but not limited to Graphene, carbon nano-tube, ITO, FTO, AZO etc.; Preferably, electrode material is including but not limited to silver, material that electric conductivity such as silver slurry, copper, copper slurry, aluminium, ITO, Graphene etc. is good; Preferably, electrode can be made up of transparent conductive material, and wherein, preferred electrode material is Graphene; Optimum electrode material is Copper Foil; Preferably, electrode is formed on transparency conducting layer; Preferably, electrode to be positioned on graphene layer and to be integrally formed with graphene layer; Preferably, electrode can be formed between transparent base and transparency conducting layer; Preferably, transparent base can be glass or polymer, and transparent base is including but not limited to films such as PET, PVC, PE, PC; More preferably, polymer can be: PET, PMMA, PVDF, PANI, or its composition; Preferably, described transparency conducting layer is single or multiple lift Graphene, best preferred single layer Graphene.
4. a kind of low-voltage transparent electric heating film according to above arbitrary claim, it is characterized in that: preferably, graphene layer can use dopant; More preferably, dopant can be inorganic/organic blended dose; Preferably, can on electrode and graphene layer protective mulch; More preferably, protective layer can adopt flexible clear materials; Preferably, the material of transparent covering layer is including but not limited to films such as PET, PVC, PE, PC.
5. a kind of low-voltage transparent electric heating film according to above arbitrary claim, is characterized in that: can by electrode serial or parallel connection of the present invention; Preferably, can by transparent electric heating film serial or parallel connection of the present invention.
6. a kind of low-voltage transparent electric heating film according to above arbitrary claim, it is characterized in that: described interior electrode is linear, waveform or zigzag, the pattern form of described busbar and interior electrode composition is according to the shape of Electric radiant Heating Film and application demand, can linearly shape, shaped form, also can surround circle, ellipse or arbitrary shape.
7. a kind of low-voltage transparent electric heating film according to above arbitrary claim, is characterized in that: in final warming temperature, initial temperature, supply power voltage, two, the square resistance of electrode spacing and transparency conducting layer meets following formula:
T=kU
2/d
2R+t (1)
Wherein:
T---initial temperature, unit is DEG C;
T---Electric radiant Heating Film heats up institute to final warming temperature, and unit is DEG C;
U---supply power voltage, unit is V, U≤12V;
D---interior electrode spacing, unit is cm;
R---transparency conducting layer square resistance, unit is Ω/;
K---constant, span is that 10-200, k span has different according to the coefficient of conductivity between Electric radiant Heating Film from air, and the coefficient of conductivity between Electric radiant Heating Film and air is inversely proportional to.
8. a kind of low-voltage transparent electric heating film according to above arbitrary claim, it is characterized in that: the setting of busbar should ensure that interior electrode is arranged on the diverse location ceiling voltage of busbar and minimum voltage difference is no more than 10%, meets following formula (2):
n(n+1)lρ
1/WHR<1/5 (2)
Wherein:
N interval is created altogether in n---the area that interior electrode makes busbar surround;
ρ
1---bus bar materials resistivity, unit is Ω m;
L---the every root length of interior electrode, by wherein the longest interior electrode calculating when length does not wait, unit is m;
W---busbar width, unit is m;
H---busbar thickness, unit is m;
R---transparency conducting layer square resistance, unit is Ω/.
9. a kind of low-voltage transparent electric heating film according to above arbitrary claim, is characterized in that: on same interior electrode, maximum voltage difference is no more than 10%, need meet following formula (3):
nl
2ρ
2/whLR<1/5 (3)
Wherein:
N---interior electrode creates n interval;
L---the every root length of interior electrode, by wherein the longest interior electrode calculating when length does not wait, unit is m;
ρ
2---inner electrode resistivity, unit is Ω m;
W---interior electrode width, unit is m;
H---interior thickness of electrode, unit is m;
L---every root busbar plays electrode in last root by first interior electrode and stops the raw length of common property, unit is m;
R---transparency conducting layer square resistance, unit is Ω/.
10. the preparation technology of the low-voltage transparent electric heating film according to above arbitrary claim, is characterized in that: comprise the steps:
1) transparent conductive material be grown in metal foil substrate is prepared;
2) transparent base and metal forming are grown there is the one side of transparent conductive material to be bonded together;
3) in metal foil surfaces, make mask by the method for photoetching or printing, mask pattern designs on request;
4) transparent base/transparency conducting layer/metal forming making mask is placed in etching liquid, etches away not by the metal of mask protection;
5) remove the mask of surface of metal electrode, form patterned electrodes,
Or, the method for directly printing electrocondution slurry or evaporation electric conducting material over transparent conductive layer can be adopted to make electrode.
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CN201510203373.3A CN104869676A (en) | 2015-04-24 | 2015-04-24 | Low-voltage transparent electrothermal film and preparation process thereof |
CN201520956801.5U CN205430649U (en) | 2015-04-24 | 2015-11-26 | Transparent electric heat membrane of low -voltage, high temperature electric heat piece |
CN201510837576.8A CN105517215B (en) | 2015-04-24 | 2015-11-26 | Low-voltage transparent electrothermal film and preparation process thereof, high-temperature electrothermal sheet and preparation process thereof |
US15/014,224 US10631372B2 (en) | 2015-04-24 | 2016-02-03 | Low-power electro-thermal film devices and methods for making the same |
PCT/CN2016/079763 WO2016169481A1 (en) | 2015-04-24 | 2016-04-20 | Electric heating film device and preparation method therefor, and electric heating apparatus |
JP2018506470A JP6802835B2 (en) | 2015-04-24 | 2016-04-20 | Methods and devices for manufacturing electric film devices and electric film devices |
KR1020177033959A KR102041029B1 (en) | 2015-04-24 | 2016-04-20 | Heat Transfer Device and Heat Transfer Device Manufacturing Method and Heat Transfer Device |
EP16782628.8A EP3288337B1 (en) | 2015-04-24 | 2016-04-20 | Electric heating film device and preparation method therefor, and electric heating apparatus |
ES16782628T ES2908327T3 (en) | 2015-04-24 | 2016-04-20 | Electric heating film device and preparation method thereof, and electric heating apparatus |
US16/820,410 US12004272B2 (en) | 2015-04-24 | 2020-03-16 | Low-power electro-thermal film devices and methods for making the same |
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