CN102148267B - Tungstic oxide semiconductor battery and preparation method therefor - Google Patents
Tungstic oxide semiconductor battery and preparation method therefor Download PDFInfo
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- CN102148267B CN102148267B CN201010616885XA CN201010616885A CN102148267B CN 102148267 B CN102148267 B CN 102148267B CN 201010616885X A CN201010616885X A CN 201010616885XA CN 201010616885 A CN201010616885 A CN 201010616885A CN 102148267 B CN102148267 B CN 102148267B
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Abstract
The invention relates to a tungstic oxide semiconductor battery and a preparation method therefor. The preparation method comprises the following steps: taking tungstic oxide as a raw material, adding a conductive agent, an activating agent, an addition agent and an organic polymer film-forming agent to the raw material so as to prepare tungstic oxide semiconductor battery sizing, taking two metal foils with different work functions as a positive electrode and a negative electrode, pasting the positive electrode and the negative electrode in the same horizontal plane of a plastic substrate, then pouring the tungstic oxide semiconductor battery sizing into the surface of the electrodes, and drying and packaging the electrodes. The tungstic oxide semiconductor battery has the effects of (1) semiconductor chemical effect, electron transportation is carried out between the two metal electrodes with different work functions; (2) photoelectric effect, the electric current of the battery obviously increases when the battery is irradiated under the sun; and (3) thermoelectric effect, the electric current increases along with the rising of temperature when the battery is in a certain temperature range (5-100 DEG C).
Description
Technical field
The present invention relates to a kind of tungsten oxide semi-conductor cell and preparation method thereof.
Background technology
Tungsten oxide (WO
3) be a kind of N-N-type semiconductor N metal oxide, WO
3Always have anaerobic condition in various degree, promptly comprise a certain amount of oxygen room, so be typically expressed as WO
3-x, its corresponding spectral absorption performance is following:
WO
3Yellow 675nm
W
18O
49(WO
2.72) purple 620nm
W
20O
58(WO
2.9) blue 550nm
Because tungsten oxide has very excellent optical property, electrical properties and stable semiconducting behavior, a lot of fields such as photocatalytic degradation water hydrogen, photochemical catalyst, energy-accumulation material, absorbing material, photochromic, electrochromism, gas-discoloration and gas sensor have been widely used at present.Patent 200510111479 " nano titanium oxide photocatalyst of Wolfram oxide modified visible light activity and method thereof " for example, this patent is a raw material with ammonium tungstate and butyl titanate, with the precipitation method and the synthetic WO of hydro thermal method
3The nano titanium dioxide photocatalyst of modifying has high visible light photocatalysis active under wavelength shines greater than the 400nm visible light.Patent 02107410 " synthetic method of tungstic acid predecessor and the these hydrogen sulfide gas sensor of processing thereof "; This patent is a certain amount of soluble tungsten compound of dissolving; Add tackifier; Regulate the viscosity that is fit to, be rotated coating or silk screen printing and be coated on the substrate, through high-temperature process the organic substance decomposition is obtained uniform WO again
3Film is processed these hydrogen sulfide gas sensor.Patent 200810019529 " a kind of purposes of light degradation catalyst tungstic oxide nano-powder ", this patent utilization hydrothermal reaction at low temperature and chemical precipitation method prepare WO
3Powder has good effect to the methylene blue photocatalytic degradation.Patent 200810088485 " tungsten oxide photcatalyst ", this patent utilization is with WO
3Powder is a carrier, and the diameter that supports 0.03-5% on its surface is the platinum particulate photochemical catalyst of 3nm-20nm.Patent 200810116299 and 200810116300; This two patent dripping hydrochloric acid in certain density sodium tungstate solution forms yellow latex solution; After centrifugation, product is distributed to processes nano wire in the potassium sulfate solution, then tungsten oxide nano and frit-sintered are worn out; Process gas sensor, this element is to the H of 1-100ppm
2, CO and NH
3Good sensitivity characteristic is arranged.This patent of patent 200710030222 " based on nanometer tungsten oxide integrated all-solid-state pH electrochemical sensor and preparation method thereof " is work electrode with the nanometer tungsten oxide, is that reference electrode is integrated on the same substrate and processes all-solid-state pH electrochemical sensor with all solid state Ag/AgCl.In sum, do not see the report that utilizes tungsten oxide semi-conducting material manufacturing battery at present as yet.
Summary of the invention
The object of the present invention is to provide a kind of tungsten oxide semi-conductor cell and preparation method thereof.
The invention belongs to a kind of brand-new oxide semiconductor battery, it has characteristic of semiconductor according to tungsten oxide and puts forward.The present invention is raw material with the tungsten oxide; Add conductive agent, activator, additive and organic polymer film forming agent and process tungsten oxide semi-conductor cell slurry; And be positive and negative electrode with two kinds of metal formings of different work functions, positive and negative electrode sticks on the same horizontal plane of plastics egative film, then with tungsten oxide semi-conductor cell slurry injecting electrode surface; Through drying, encapsulating, process the tungsten oxide semi-conductor cell.
The manufacture method of tungsten oxide semi-conductor cell of the present invention can adopt following two kinds of technical schemes.
One of technical scheme: take by weighing a certain amount of tungsten oxide powder, add 20-30 deionized water doubly, stir fast; Fully disperse, drip an amount of additive, activator, conductive agent, fully stir; Adding percent concentration again is the organic polymer film forming agent of 5-15%; Fully stir, concentrate 40-80 ℃ of condition stirring then, process tungsten oxide semi-conductor cell slurry; Cell size is injected into plane electrode, plane interdigitation electrode surface, perhaps be injected into stereo electrod to, tandem stereo electrod between, dry at leisure under the room temperature, encapsulate, process the tungsten oxide semi-conductor cell, measure its open circuit voltage and short circuit current.
Two of technical scheme: take by weighing a certain amount of tungsten oxide powder in agate mortar; Add an amount of additive, activator, conductive agent; Fully grind evenly, tungsten oxide semi-conductor cell slurry is processed in an organic polymer film forming agent number grinding that drips percent concentration again and be 5-15%, and slurry is injected into plane electrode, plane interdigitation electrode surface; Perhaps be injected into stereo electrod to, tandem stereo electrod between; Dry at leisure under the room temperature, encapsulate, process the tungsten oxide semi-conductor cell, measure its open circuit voltage and short circuit current.
The additive of preparation tungsten oxide semi-conductor cell of the present invention is small molecule alcohols such as ethylene glycol, glycerine, isopropyl alcohol and n-butanol.
The activator of preparation tungsten oxide semi-conductor cell of the present invention is Li
+, K
+, Na
+, NH
4 +, Ag
+Deng the monovalent ion compound.The concentration of activator is every liter of 0.1-0.5 mole.
The conductive agent of preparation tungsten oxide semi-conductor cell of the present invention is CNT, C
60Or Graphene, be medium with the absolute ethyl alcohol, be mixed with the suspension that concentration is 0.1-1%.
The conductive agent of preparation tungsten oxide semi-conductor cell of the present invention also can be organic conductive polymer, for example polyaniline liquid.
The organic polymer film forming agent of preparation tungsten oxide semi-conductor cell of the present invention is that polyvinyl alcohol, the degree of polymerization are 10
5-10
7PEO (PEO), methylcellulose, ethyl cellulose, polyacrylamide and shitosan etc., its percent concentration of organic polymer film forming agent is 5-15%.
Tungsten oxide raw material of the present invention can be commercially available tungsten oxide raw material, also can adopt the tungsten oxide raw material of following technical scheme preparation.The tungsten oxide raw material of the preferred following technical scheme preparation of the present invention.
The preparation of tungsten oxide raw material of the present invention can be adopted following three kinds of technical schemes.
One of technical scheme: the tungstates that with concentration is every liter of 0.1-3 mole is a raw material, presses tungstates: stabilizer=1: the concentration ratio preparation tungstates reaction solution of 0.05-0.5 mole under agitation is added drop-wise to the tungstates reaction solution in the precipitant solution of every liter of 0.5-16 mole; Up to pH value 2-4; Obtain faint yellow deposition, through suction filtration, wash neutrality, drench 1-3 time with absolute ethyl alcohol; 100-120 ℃ was dried by the fire 1-3 hour, and obtained powder.Obtained faint yellow tungsten oxide in 1-4 hour through 400-600 ℃ of calcining again, after comminution by gas stream or ball milling obtain ultra-fine faint yellow tungsten oxide powder.
The tungstates of preparation tungsten oxide raw material is sodium tungstate or ammonium tungstate in one of technical scheme of the present invention.
The stabilizer of preparation tungsten oxide raw material is acetic acid, citric acid, oxalic acid, tartaric acid, maleic acid or malic acid in one of technical scheme of the present invention, and the concentration of stabilizer is every liter of 0.05-0.5 mole.
The precipitation reagent of preparation tungsten oxide raw material is hydrochloric acid, nitric acid or sulfuric acid in one of technical scheme of the present invention, and the concentration of precipitation reagent is every liter of 0.5-16 mole.
Two of technical scheme: be placed in crucible or the ceramic evaporation ware high temperature 500-600 ℃ of calcining 1-4 hour through 300 purpose metal tungsten powders with 99.9%, obtain faint yellow tungsten oxide, obtain ultra-fine faint yellow tungsten oxide powder through comminution by gas stream or ball milling again.
Three of technical scheme: pass through 300 purpose metal tungsten powders with 99.9%; Add hydrogen peroxide solution and an amount of acid and under 40-80 ℃ of stirring condition, react and obtained faint yellow deposition in 1-3 hour, through suction filtration, wash neutrality, drench 1-3 time with absolute ethyl alcohol; 100-120 ℃ was dried by the fire 1-3 hour, and obtained powder.Obtained faint yellow tungsten oxide in 1-4 hour through 400-600 ℃ of calcining again, after comminution by gas stream or ball milling obtain ultra-fine faint yellow tungsten oxide powder.
The method for making its electrode that the present invention relates to is:
(1) making of plane electrode.The metal forming of two kinds of different work functions is cut into wide 1-2mm; Long 1-5cm's is rectangular; Sticking with glue agent is attached on the surperficial same horizontal plane of plastic sheet; The about 1-3mm of two interelectrode distances, electrode end picks out lead-in wire, and the plastic strip with thick about 1-2mm around electrode has enclosed the plane electrode that formation is about the wide about 5-15mm of 1-5cm.See Fig. 1;
(2) making of plane interdigitation electrode.The metal forming of two kinds of different work functions is cut into the comb type positive and negative electrode piece of wide 2mm, long 1.5-5cm, spacing 6-8mm.Carefully, careful with on the parallel surperficial same horizontal plane that relatively sticks on the plastics egative film of two comb type positive and negative electrodes; Process the interdigitation electrode of finger beam 2mm, spacing 1-2mm; And pick out lead-in wire respectively at the end of two electrodes, around electrode, surround the plane interdigitation electrode of certain area then with the ambroin sheet of thick 1-2mm.See Fig. 2;
(3) the right making of stereo electrod.The metal forming of two kinds of different work functions is cut into the strip that is about the wide about 1-2mm of 1-5cm; Stick on the insulating trip surface of two thick about 2-3mm respectively; On then that it is the relative thirty years of age same horizontal plane that sticks on the plastics egative film; The about 1-3mm of two interelectrode distances, electrode end picks out lead-in wire, and it is right to process stereo electrod.See Fig. 3;
(4) the right making of tandem stereo electrod.At first the metal forming of two kinds of different work functions is sticked on the two sides of the plastic strip of thick about 2-3mm respectively; And two metal formings are coupled together with lead-in wire; Confirm the number of series-connected cell as required, it sticked on the same horizontal plane of plastics egative film that the positive and negative electrode that makes by the right manufacture method of stereo electrod then sticks on the both sides of series connection electrode; It is right to process the tandem stereo electrod, sees Fig. 4.
The metal forming of preparation tungsten oxide semi-conductor cell of the present invention is meant goldleaf, silver foil, Copper Foil, zinc paper tinsel, nickel foil and aluminium foil etc.
The light-emitting diode (LED) of tungsten oxide semi-conductor cell of the present invention three series connection can startup 1.8-2.5V.See Fig. 5.
Tungsten oxide semi-conductor cell of the present invention has: (1) Semiconductor Chemistry effect.Promptly between two electrodes of different work functions metal, produce electron transport; (2) photoelectric effect.Battery is under solar irradiation, and the electric current of battery has apparent in view increase; (3) thermoelectric effect.Battery (5-100 ℃) electric current in certain temperature range raises with temperature and increases.
Description of drawings
Fig. 1 plane electrode sketch map.
Fig. 2 plane interdigitation electrode sketch map.
Fig. 3 stereo electrod is to sketch map.
Fig. 4 tandem stereo electrod is to sketch map.
The plane electrode tungsten oxide semi-conductor cell of 3 series connection of Fig. 5 and 1.5V dry cell work contrast shooting.
Embodiment
The making of embodiment 1 tungsten oxide semi-conductor cell.
(1) making of plane electrode.Copper Foil and zinc paper tinsel are cut into wide 2mm respectively; The bonding jumper of long 2cm; Stick with glue agent or double faced adhesive tape and stick on the same horizontal plane of plastics backsheet surface, the spacing of two electrodes is 2mm, and picks out lead-in wire respectively at the end of two electrodes; Around electrode, surround one with the ambroin sheet of thick about 2mm then and be about the wide about 0.7mm of 1.5cm, effective area is 1.05cm
2Slurry chamber.
(2) preparation of tungsten oxide raw material.Press sodium tungstate: the concentration ratio preparation 100ml sodium tungstate reactant liquor of acetic acid=1: 0.2 mole; Under the magnetic agitation condition, the sodium tungstate reactant liquor being added drop-wise to 30ml concentration lentamente is in 2 moles every liter the hydrochloric acid solution, progressively generates faint yellow deposition, when pH value 3; Continue to stir after 30 minutes; Through suction filtration, wash neutrality, drench 2 times 100 ℃ of dryings 2 hours then with absolute ethyl alcohol; Obtained faint yellow tungsten oxide particulate in 3 hours through 450 ℃ of calcinings again, after ball milling obtains faint yellow loose tungsten oxide powder.
(3) making of tungsten oxide semi-conductor cell.Take by weighing after the faint yellow tungsten oxide powder of 0.5 gram adds 5 ethylene glycol and 1 0.2 mole of every liter of concentration in agate mortar lithium carbonate grinds evenly, drip 10% 5 of polyvinyl alcohol again and fully grind evenly, obtain thicker slurry.This slurry is injected in the slurry chamber of above-mentioned plane electrode, dries at leisure under the room temperature, encapsulate, process the tungsten oxide semi-conductor cell.Measuring open circuit voltage is 0.98V and short circuit current 0.92mA.
The making of embodiment 2 tungsten oxide semi-conductor cells.
(1) the right making of stereo electrod.Silver foil and zinc paper tinsel are sheared the bonding jumper of the wide 2mm of growth 4cm respectively; End at two bonding jumpers picks out lead-in wire respectively; Stick with glue agent and respectively two bonding jumpers are sticked on the insulating trip surface of two thick 3mm, on then that it is the relative thirty years of age same horizontal plane that sticks on the plastics egative film, two interelectrode distances are 3mm; And between two electrodes, add the insulating trip of long 4mm, wide 3mm, be 0.96cm so that between two electrodes, form wide 3mm, a long 3.2cm effective area
2Slurry chamber.
(2) preparation of tungsten oxide raw material.Press sodium tungstate: the concentration ratio preparation 200ml sodium tungstate reactant liquor of citric acid=1: 0.3 mole; Under the magnetic agitation condition, the sodium tungstate reactant liquor being added drop-wise to 20ml concentration lentamente is in 3 moles every liter the salpeter solution, progressively generates faint yellow deposition, when pH value 2; Continue to stir after 30 minutes; Through suction filtration, wash neutrality, drench 3 times 120 ℃ of dryings 1.5 hours then with absolute ethyl alcohol; Obtained faint yellow tungsten oxide particulate in 2 hours through 550 ℃ of calcinings again, after ball milling obtains faint yellow loose tungsten oxide powder.
(3) making of tungsten oxide semi-conductor cell.Take by weighing the flaxen tungsten oxide powder of 1 gram in beaker; Add deionized water 20ml; Magnetic agitation 30 minutes ultrasonic 10 minutes, under agitation adds 3 of isopropyl alcohols, adds 0.1 mole every liter 1 in ammonium hydroxide, adds 1 0.1% Graphene ethanol liquid again; Add 8% polyacrylamide 2ml, under 60 ℃ of magnetic agitation, be condensed into the paste slurry.This slurry is injected in the right slurry chamber of stereo electrod, dry at leisure under the room temperature, encapsulate, process the tungsten oxide semi-conductor cell, measuring open circuit voltage is that 1.0V and short circuit current are 1.1mA.
The making of embodiment 3 tungsten oxide semi-conductor cells.
(1) making of plane electrode.Copper Foil and zinc paper tinsel are cut into wide 2mm respectively; The bonding jumper of long 3cm; Stick with glue agent or double faced adhesive tape and stick on the same horizontal plane of plastics egative film, the spacing of two electrodes is 2mm, and picks out lead-in wire respectively at the end of two electrodes; Around electrode, surround one with the ambroin sheet of thick about 2mm then and be about the wide about 0.6mm of 2.5cm, effective area is 1.5cm
2Slurry chamber.
(2) preparation of tungsten oxide raw material.Take by weighing 2 grams 99.9% through 300 purpose metal tungsten powders, it is layered in the magnetic evaporating dish, calcined 2 hours for 600 ℃, natural cooling obtains the tungsten oxide particulate, obtains faint yellow tungsten oxide powder through ball milling.
(3) making of tungsten oxide semi-conductor cell.Take by weighing 2 gram tungsten oxide powders in beaker, be dissolved in the 30ml deionized water magnetic agitation 30 minutes; Ultrasonic 10 minutes, add 5 isopropyl alcohols, 2 0.1 mole of every liter of Klorvess Liquids; Fully stirred 30 minutes; Add 2 electrically conductive polyanilines, add the 5ml8% ethyl cellulose, be condensed into the paste slurry 70 ℃ of magnetic agitation.In the slurry chamber with this slurry injecting electrode surface, dry at leisure under the room temperature, encapsulate, process the tungsten oxide semi-conductor cell, measuring its open circuit voltage is that 895mV and short circuit current are 0.9mA.
The making of embodiment 4 tungsten oxide semi-conductor cells.
(1) making of plane interdigitation electrode.Copper Foil and zinc paper tinsel are cut into the comb type positive and negative electrode of wide 2mm, long 3cm, spacing 6mm respectively.Careful about on the parallel same horizontal plane that relatively sticks on the plastics egative film of two comb type positive and negative electrodes; Process the interdigitation electrode; And picking out lead-in wire respectively at the end of two electrodes, the ambroin sheet with thick 2mm surrounds the long 5cm effective area of a wide about 2cm 10cm around electrode then
2Slurry chamber.
(2) preparation of tungsten oxide raw material.Take by weighing 1 gram 99.9% through 300 purpose metal tungsten powders, add deionized water 20ml, magnetic agitation 10 minutes; Add the 10ml hydrogen peroxide solution and 2 concentration are in the hydrochloric acid solution of 1M, 40 ℃ of stirring reactions 1 hour progressively generate faint yellow deposition; Through suction filtration, wash neutrality; Drench 2 times with absolute ethyl alcohol then,, obtain yellow loose tungsten oxide powder through ball milling behind the natural cooling again through 500 ℃ of calcinings 2 hours.
(3) making of tungsten oxide semi-conductor cell.Take by weighing 3 gram tungsten oxides and add deionized water 50ml, stirred 30 minutes, ultrasonic 20 minutes, add 5 of ethylene glycol, add 3 0.1 mole of every liter of silver nitrates, under magnetic agitation, add 2 0.2 mole of every liter of C
60Alcohol suspension adds the methylcellulose of 5ml10%, is condensed into the paste slurry 60 ℃ of magnetic agitation.This slurry equably in the slurry chamber on injection plane interdigital electrode surface, is dried at leisure under the room temperature, encapsulates, process the tungsten oxide semi-conductor cell, measuring its open circuit voltage is that 1.15V and short circuit current are 2.5mA.
The making of embodiment 5 tungsten oxide semi-conductor cells.
(1) the right making of tandem stereo electrod.Cut the plastic strip of 3 thick 2mm of the wide 3mm of long 4cm; Stick Copper Foil and the zinc paper tinsel of the wide 2mm of long 4cm respectively in the both sides of each plastic strip; And with lead-in wire Copper Foil and zinc paper tinsel are coupled together endways; Then it is sticked on the mid portion of the surperficial same horizontal plane of plastic sheet, each plastic strip spacing 2mm.Cut the plastic strip of 2 thick 2mm of the wide 3mm of long 4cm in addition again; Stick Copper Foil and the zinc paper tinsel of the wide 2mm of long 4cm respectively in a side of each plastic strip; And pick out lead-in wire endways; By the outside of anodal and negative pole (copper is anodal, and zinc is negative pole) above-mentioned 3 plastic sheets of corresponding stickup, it is right to process 4 tandem stereo electrods then.
(2) preparation of tungsten oxide raw material.Press sodium tungstate: the concentration ratio preparation 150ml sodium tungstate reactant liquor of malic acid=1: 0.1 mole; Under the magnetic agitation condition, the sodium tungstate reactant liquor being added drop-wise to 40ml concentration lentamente is in 3 moles every liter the sulfuric acid solution, progressively generates faint yellow deposition, when pH value 2; Continue to stir after 30 minutes; Through suction filtration, wash neutrality, drench 3 times 120 ℃ of dryings 1.5 hours then with absolute ethyl alcohol; Obtained faint yellow tungsten oxide particulate in 2 hours through 550 ℃ of calcinings again, after ball milling obtains faint yellow loose tungsten oxide powder.
(3) making of tungsten oxide semi-conductor cell.Take by weighing the above-mentioned flaxen tungsten oxide powder of 1.5 grams in beaker, add deionized water 40ml, magnetic agitation 30 minutes ultrasonic 20 minutes, under agitation adds 2 of glycerine, addition polymerization is right is 1 * 10
5Concentration is 8% PEO (PEO) 5ml, and magnetic agitation 30 minutes is condensed into slurry again under 50 ℃ of magnetic agitation.This slurry is injected in the right slurry chamber of 4 stereo electrods, dries at leisure under the room temperature, encapsulate, process 4 tandem stereo electrods to the tungsten oxide semi-conductor cell, measuring open circuit voltage is that 3.2V and short circuit current are 2.1mA.
Should be noted that at last: above embodiment only is illustrative rather than definitive thereof technical scheme of the present invention; The enforcement personnel can carry out corresponding modification or some replacement to the present invention; And do not break away from spirit of the present invention; Any modification or local replacement all should be encompassed in the middle of the claim scope of the present invention.
Claims (1)
1. tungsten oxide semi-conductor cell; It is characterized in that with the tungsten oxide being raw material; Add conductive agent, activator, additive and organic polymer film forming agent and process tungsten oxide semi-conductor cell slurry, and be positive and negative electrode with two kinds of metal formings of different work functions, positive and negative electrode sticks on the same horizontal plane of plastics egative film; Then with tungsten oxide semi-conductor cell slurry injecting electrode surface, through drying, encapsulating.
2. the preparation method of the described tungsten oxide semi-conductor cell of claim 1 is characterized in that taking by weighing a certain amount of tungsten oxide powder, adds 20-30 deionized water doubly; Stir fast, fully disperse, drip an amount of additive, activator, conductive agent; Fully stir, adding percent concentration again is the organic polymer film forming agent of 5-15%, fully stirs; Concentrate 40-80 ℃ of condition stirring then, process tungsten oxide semi-conductor cell slurry; Cell size is injected into plane electrode, plane interdigitation electrode surface, perhaps be injected into stereo electrod to, tandem stereo electrod between, dry at leisure under the room temperature, encapsulate, process the tungsten oxide semi-conductor cell, measure its open circuit voltage and short circuit current.
3. the preparation method of the described tungsten oxide semi-conductor cell of claim 1; It is characterized in that taking by weighing a certain amount of tungsten oxide powder in agate mortar, add an amount of additive, activator, conductive agent, fully grind evenly; Tungsten oxide semi-conductor cell slurry is processed in an organic polymer film forming agent number grinding that drips percent concentration again and be 5-15%; Slurry is injected into plane electrode, plane interdigitation electrode surface, perhaps be injected into stereo electrod to, tandem stereo electrod between, dry at leisure under the room temperature, encapsulate; Process the tungsten oxide semi-conductor cell, measure its open circuit voltage and short circuit current.
4. according to the preparation method of claim 2 or 3 described tungsten oxide semi-conductor cells, it is characterized in that described additive is ethylene glycol, glycerine, isopropyl alcohol or n-butanol.
5. according to the preparation method of claim 2 or 3 described tungsten oxide semi-conductor cells, it is characterized in that described activator is Li
+, K
+, Na
+, NH
4 +, or Ag
+, the concentration of activator is every liter of 0.1-0.5 mole.
6. according to the preparation method of claim 2 or 3 described tungsten oxide semi-conductor cells, it is characterized in that described conductive agent is CNT, C
60Or Graphene, be medium with the absolute ethyl alcohol, be mixed with the suspension that concentration is 0.1-1%.
7. according to the preparation method of claim 2 or 3 described tungsten oxide semi-conductor cells, it is characterized in that described conductive agent is a polyaniline liquid.
8. according to the preparation method of claim 2 or 3 described tungsten oxide semi-conductor cells, it is characterized in that described organic polymer film forming agent is that polyvinyl alcohol, the degree of polymerization are 10
5-10
7PEO, methylcellulose, ethyl cellulose, polyacrylamide or shitosan, its percent concentration of organic polymer film forming agent is 5-15%.
9. according to the preparation method of claim 2 or 3 described tungsten oxide semi-conductor cells; It is characterized in that described tungsten oxide powder prepares by following method: the tungstates that with concentration is every liter of 0.1-3 mole is a raw material, presses tungstates: stabilizer=1: the concentration ratio preparation tungstates reaction solution of 0.05-0.5 mole under agitation is added drop-wise to the tungstates reaction solution in the precipitant solution of every liter of 0.5-16 mole; Up to pH value 2-4; Obtain faint yellow deposition, through suction filtration, wash neutrality, drench 1-3 time with absolute ethyl alcohol; 100-120 ℃ was dried by the fire 1-3 hour, and obtained powder; Obtained faint yellow tungsten oxide in 1-4 hour through 400-600 ℃ of calcining again, after comminution by gas stream or ball milling obtain ultra-fine faint yellow tungsten oxide powder.
10. the preparation method of tungsten oxide semi-conductor cell according to claim 9 is characterized in that described tungstates is sodium tungstate or ammonium tungstate.
11. the preparation method of tungsten oxide semi-conductor cell according to claim 9 is characterized in that described stabilizer is acetic acid, citric acid, oxalic acid, tartaric acid, maleic acid or malic acid, the concentration of stabilizer is every liter of 0.05-0.5 mole.
12. the preparation method of tungsten oxide semi-conductor cell according to claim 9 is characterized in that described precipitation reagent is hydrochloric acid, nitric acid or sulfuric acid, the concentration of precipitation reagent is every liter of 0.5-16 mole.
13. preparation method according to claim 2 or 3 described tungsten oxide semi-conductor cells; It is characterized in that described tungsten oxide powder prepares by following method: be placed in crucible or the ceramic evaporation ware high temperature 500-600 ℃ of calcining 1-4 hour through 300 purpose metal tungsten powders with 99.9%; Obtain faint yellow tungsten oxide, obtain ultra-fine faint yellow tungsten oxide powder through comminution by gas stream or ball milling again.
14. preparation method according to claim 2 or 3 described tungsten oxide semi-conductor cells; It is characterized in that described tungsten oxide powder prepares by following method: pass through 300 purpose metal tungsten powders with 99.9%; Add hydrogen peroxide solution and an amount of acid and under 40-80 ℃ of stirring condition, react and obtained faint yellow deposition in 1-3 hour, through suction filtration, wash neutrality, drench 1-3 time with absolute ethyl alcohol; 100-120 ℃ was dried by the fire 1-3 hour, and obtained powder; Obtained faint yellow tungsten oxide in 1-4 hour through 400-600 ℃ of calcining again, after comminution by gas stream or ball milling obtain ultra-fine faint yellow tungsten oxide powder.
15. tungsten oxide semi-conductor cell according to claim 1; It is characterized in that described method for making its electrode is: the metal forming of two kinds of different work functions is cut into wide 1-2mm; Long 1-5cm's is rectangular, sticks with glue agent and is attached on the surperficial same horizontal plane of plastic sheet, the about 1-3mm of two interelectrode distances; Electrode end picks out lead-in wire, and the plastic strip with thick about 1-2mm around electrode has enclosed the plane electrode that formation is about the wide about 5-15mm of 1-5cm.
16. tungsten oxide semi-conductor cell according to claim 1; It is characterized in that described method for making its electrode is: the comb type positive and negative electrode piece that the metal forming of two kinds of different work functions is cut into wide 2mm, long 1.5-5cm, spacing 6-8mm; Carefully, careful with on the parallel surperficial same horizontal plane that relatively sticks on the plastics egative film of two comb type positive and negative electrodes; Process the interdigitation electrode of finger beam 2mm, spacing 1-2mm; And pick out lead-in wire respectively at the end of two electrodes, around electrode, surround the plane interdigitation electrode of certain area then with the ambroin sheet of thick 1-2mm.
17. tungsten oxide semi-conductor cell according to claim 1; It is characterized in that described method for making its electrode is: the metal forming of two kinds of different work functions is cut into the strip that is about the wide about 1-2mm of 1-5cm; Stick on the insulating trip surface of two thick about 2-3mm respectively, on then that it is the relative thirty years of age same horizontal plane that sticks on the plastics egative film, the about 1-3mm of two interelectrode distances; Electrode end picks out lead-in wire, and it is right to process stereo electrod.
18. tungsten oxide semi-conductor cell according to claim 1; It is characterized in that described method for making its electrode is: the two sides that at first metal forming of two kinds of different work functions sticked on the plastic strip of thick about 2-3mm respectively; And two metal formings are coupled together with lead-in wire; Confirm the number of series-connected cell as required; It is sticked on the same horizontal plane of plastics egative film, and the positive and negative electrode that makes by the right manufacture method of stereo electrod then sticks on the both sides of series connection electrode, and it is right to process the tandem stereo electrod.
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|---|---|---|---|
| CN201010616885XA CN102148267B (en) | 2010-12-31 | 2010-12-31 | Tungstic oxide semiconductor battery and preparation method therefor |
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| CN102148267B true CN102148267B (en) | 2012-11-07 |
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| CN104091958B (en) * | 2014-07-09 | 2016-03-09 | 哈尔滨工程大学 | Graphene attaches the preparation method of plastics load AuCo sodium borohydride electro-oxidizing-catalyzing agent |
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| CN109225201B (en) * | 2018-08-21 | 2021-07-30 | 北京工业大学 | Preparation method and application of micro-nano tungsten oxide |
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| CN116354399B (en) * | 2023-06-02 | 2023-08-04 | 崇义章源钨业股份有限公司 | Method for preparing loose nano tungsten oxide |
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