The utility model content
The technical problem that will solve of the present utility model is to overcome the defective that existing hybrid generator can not be given full play to the effect of electric conduction of carbon fiber material, provides a kind of the biology enzyme generator directly is coated in mixing nano generator on the carbon fiber.
In order to solve the problems of the technologies described above, the utility model is achieved through the following technical solutions:
A kind of mixing nano generator, this mixing nano generator comprise carbon fiber electrode (1), biology enzyme generator (9) and Zinc oxide nanowire electric generator (10); Wherein biology enzyme generator (9) and Zinc oxide nanowire electric generator (10) are set directly on the carbon fiber electrode (1) successively, described biology enzyme generator (9) comprises glucose oxidase anode layer (5), laccase cathode layer (4), conductive electrode (3) and insulating barrier (2), glucose oxidase anode layer (5) and laccase cathode layer (4) are spaced and are arranged on the carbon fiber electrode (1), one is arranged on the conductive electrode (3) among glucose oxidase anode layer (5) and the laccase cathode layer (4), be arranged on the carbon fiber electrode (1) by insulating barrier (2) insulation, wherein conductive electrode (3) is layered on the insulating barrier (2); Another is set directly on the carbon fiber electrode (1) among glucose oxidase anode layer (5) and the laccase cathode layer (4).
Wherein, described carbon fiber electrode (1) is to be used for output electrical signals as the common electrode of biology enzyme generator (9) and Zinc oxide nanowire electric generator (10).
Wherein, described laccase cathode layer (4) is arranged on the conductive electrode (3), is arranged on the carbon fiber electrode on (1) by insulating barrier (2) insulation, and glucose oxidase anode layer (5) is set directly on the carbon fiber electrode (1).
Wherein, described glucose oxidase anode layer (5) is arranged on the conductive electrode (3), is arranged on the carbon fiber electrode on (1) by insulating barrier (2) insulation, and laccase cathode layer (4) is set directly on the carbon fiber electrode (1).
Wherein, described glucose oxidase anode and laccase negative electrode are sequentially arranged on the carbon fiber electrode (1) with the order of glucose oxidase anode/laccase negative electrode or laccase negative electrode/glucose oxidase anode.
Wherein, described Zinc oxide nanowire electric generator (10) comprises the zinc oxide nano-wire array layer 6 that is grown on the carbon fiber electrode (1), is coated in the polymeric dielectric layer (7) on the zinc oxide nano-wire array layer (6), and the electrode layer (8) that joins with polymeric dielectric layer (7).
Wherein, described conductive electrode (3) and electrode layer (8) material therefor independently are selected from respectively a kind of in indium tin metal oxide, Graphene or the nano silver wire membrane coat, or in the gold, silver, platinum, aluminium, nickel, titanium, chromium, tin any one.
Wherein, described polymeric dielectric layer (7) material therefor is polymethyl methacrylate or dimethyl silicone polymer.
Wherein, described insulating barrier (2) material therefor is the PDMS(dimethyl silicone polymer), the PAN(polyacrylonitrile), the PMA(polymethacrylates), the PVC(polyvinyl chloride), the PVP(polyvinylpyrrolidone), phenolic resin glue, natural resin, epoxy polymer be or/and one or more in the synthetic resin.
Wherein, the zinc oxide nanowire vertical-growth of described zinc oxide nano-wire array layer (6) is on carbon fiber electrode (1).
Useful technique effect of the present utility model is: the utility model adopts and directly is coated in the biology enzyme generator on the carbon fiber, simplified the manufacturing process of mixing nano generator, realize simultaneously or independently collection machinery energy or biochemical energy, and then reach and mix the overall performance that nano generator is measured blood pressure and blood sugar.
Embodiment
For fully understanding purpose, feature and the effect of the utility model, by following concrete execution mode, the utility model is elaborated.
The utility model adopts the biology enzyme generator directly is coated on the carbon fiber, has simplified the manufacturing process of mixing nano generator, simultaneously can synchronous acquisition mechanical energy and biological energy source, thus Monitoring Blood Glucose changes.
The employed various materials of the utility model are medical rank, comprise in described conductive electrode 3 and electrode layer 8 material therefor indium tin metal oxides, Graphene or the nano silver wire membrane coat, gold, silver, platinum, aluminium, nickel, titanium, chromium or tin, polymeric dielectric layer 7 material therefor polymethyl methacrylate or dimethyl silicone polymers, insulating barrier 2 material therefor PDMS, PAN, PMA, PVC, PVP, phenolic resin glue, natural resin, epoxy polymer are or/and synthetic resin all is can satisfy will mix nano generator and import to hygienic requirements in the human body fluid.
Shown in the 1-4 the better embodiment of the utility model is described by reference to the accompanying drawings.
Wherein Fig. 1 is that glucose oxidase anode layer 5 directly is connected with carbon fiber electrode 1, and laccase cathode layer 4 is connected with carbon fiber electrode 1 insulation by insulating barrier 2.
Fig. 2 is the outside drawing of the described structure of Fig. 1.
Fig. 3 is the structural representation after the utility model structure and radio frequency component is integrated.
Fig. 4 is another kind of embodiment of the present utility model, and for laccase cathode layer 4 directly is connected with carbon fiber electrode 1, glucose oxidase anode 5 is connected with carbon fiber electrode 1 by insulating barrier 2.
Specifically, a kind of mixing nano generator, this mixing nano generator comprises carbon fiber electrode 1, biology enzyme generator 9 and Zinc oxide nanowire electric generator 10; Wherein biology enzyme generator 9 and Zinc oxide nanowire electric generator 10 are set directly on the carbon fiber electrode 1 successively.Described biology enzyme generator (9) comprises glucose oxidase anode layer 5, laccase cathode layer 4, conductive electrode 3 and insulating barrier 2, glucose oxidase anode layer 5 and laccase cathode layer 4 are spaced and are arranged on the carbon fiber electrode 1, among glucose oxidase anode layer 5 and the laccase cathode layer 4 only one be arranged on the conductive electrode 3, be arranged on the carbon fiber electrode 1 by insulating barrier 2 insulation, wherein conductive electrode 3 is layered on the insulating barrier 2; Another is set directly on the carbon fiber electrode 1 among glucose oxidase anode layer 5 and the laccase cathode layer 4.
Described glucose oxidase anode layer 5 and laccase cathode layer 4 are spaced and are arranged on the carbon fiber electrode 1, refer to that glucose oxidase anode layer 5 and laccase cathode layer 4 are arranged on the carbon fiber electrode 1 by direct or indirect mode.
Wherein, when in body fluid, producing the signal of telecommunication, the anode of biology enzyme generator 9 and anode are to realize by following dual mode respectively: laccase cathode layer 4 is arranged on the conductive electrode 3, then be arranged on the carbon fiber electrode on 1 by insulating barrier 2 insulation, thereby laccase cathode layer 4, conductive electrode 3 and the stacked structure of insulating barrier 2 threes play the effect of negative electrode; On the other hand, glucose oxidase anode layer 5 directly applies and is arranged on the carbon fiber electrode 1, thereby glucose oxidase anode layer 5 and carbon fiber electrode 1 play the effect of anode jointly; Perhaps, glucose oxidase anode layer 5 is arranged on the conductive electrode 3, then be arranged on the carbon fiber electrode on 1 by insulating barrier 2 insulation, thereby glucose oxidase anode layer 5, conductive electrode 3 and the stacked structure of insulating barrier 2 threes plays the effect of anode; On the other hand, laccase cathode layer 4 directly applies and is arranged on the carbon fiber electrode 1, thereby laccase cathode layer 4 and carbon fiber electrode 1 play the effect of negative electrode.Structure (the structure that is only formed by glucose oxidase anode layer 5 that in order to express easily, also will contain in this application glucose oxidase anode layer 5; Perhaps glucose oxidase anode layer 5/ conductive electrode 3/ insulating barrier 2 stepped constructions) be called the glucose oxidase anode, contain the structure (structure that is only formed by laccase cathode layer 4 of laccase cathode layer 4; Perhaps laccase cathode layer 4/ conductive electrode 3/ insulating barrier 2 stepped constructions) be called the laccase negative electrode.
In a kind of embodiment, as shown in Figure 1, mixing nano generator structure of the present utility model is as follows: comprise the laccase negative electrode, glucose oxidase anode and the Zinc oxide nanowire electric generator 10 that are successively set on the carbon fiber electrode 1; Wherein the laccase negative electrode comprises insulating barrier 2, conductive electrode 3 and laccase cathode layer 4, wherein insulating barrier 2 is coated on the carbon fiber electrode 1 and (also can directly the insulating cement that is purchased be bonded on the carbon fiber), bond successively conductive electrode 3 and laccase cathode layer 4 of from-inner-to-outer on insulating barrier 2; Described Zinc oxide nanowire electric generator 10 comprises the zinc oxide nano-wire array layer 6 that is grown on the carbon fiber electrode 1, the electrode layer 8 that is coated in the polymeric dielectric layer 7 on the zinc oxide nano-wire array layer 6 and joins with polymeric dielectric layer 7.
Described conductive electrode 3 and electrode layer 8 material therefors do not have particular provisions, conventional nano generator all can be applicable to the utility model with electrode material, for example any one in indium tin metal oxide, Graphene, nano silver wire membrane coat, gold, silver, platinum, aluminium, nickel, titanium, chromium, tin or its alloy.Electrode layer 8 preferred aluminium foils wherein, tinfoil.
The conventional macromolecular material that can play insulating effect all can be applicable to polymeric dielectric layer 7, for example polymethyl methacrylate or dimethyl silicone polymer.
In Zinc oxide nanowire electric generator, owing to having adopted polymeric dielectric layer, the existence of insulating barrier that the potential barrier of an infinite height is provided, stop the induction electronics in the electrode to pass through zinc oxide/Metal Contact face inner " leakage ".
Described insulating barrier is made by glue class insulating material, preferred PDMS, PAN, PMA, PVC, PVP, phenolic resin glue, epoxy polymer/and synthetic resin in one or more; The preferred epoxy polymer of insulating barrier material therefor.
Described zinc oxide nanowire is grown directly upon on the carbon fiber electrode 1
The operation principle of the utility model mixing nano generator is as follows:
When the mixing nano generator is dipped in the biological fluids that contains glucose, the glucose oxidase of glucose oxidase anode carries out oxidation with glucose, the laccase negative electrode is water with hydrogen reduction, and the glucose oxidase anode directly links to each other with carbon fiber electrode, finally makes the biology enzyme generator produce direct current obtains the biology enzyme generator by its conductive electrode and carbon fiber electrode (common electrode) output the signal of telecommunication.In having the biological fluids of glucose, when pressure cycle is applied to biological fluids, nano wire on the Zinc oxide nanowire electric generator drives at impressed pressure and issues lively attitude stretching, generate the piezoelectricity electromotive force in the nano wire, corresponding transient current obtains the signal of telecommunication of Zinc oxide nanowire electric generator from its electrode layer and carbon fiber electrode (common electrode) output.
In the utility model, Zinc oxide nanowire electric generator and biology enzyme generator are carried out conducting by carbon fiber electrode, both can produce synergy, when Zinc oxide nanowire electric generator and biology enzyme generator series connection formation loop, at stable periodic pressure-acting during in Zinc oxide nanowire electric generator, can be by voltage or the electric current of measuring respectively both, Monitoring Blood Glucose and blood pressure, also can be by the effect of biology enzyme generator to the amplification of Zinc oxide nanowire electric generator signal, measure more exactly voltage or electric current, and then Monitoring Blood Glucose and blood pressure.
Compare with disclosed methods such as Caofeng Pan, mixing nano generator of the present utility model is when realizing that simultaneously mechanical energy and chemical energy be converted into electric energy, both carbon fiber electrodes (common electrode) are derived the signal of telecommunication that obtains separately, give full play to the electric action of carbon fiber electrode, saved cost.
Embodiment
The below describes the manufacture method of mixing nano generator in detail.
The preparation method of Zinc oxide nanowire electric generator 10 is: with zinc oxide seed layer radio frequency sputter to the carbon fiber electrode 1 that cleaned in advance.On zinc oxide seed layer, adopt wet chemistry method growth of zinc oxide nano linear array layer 6.Wet chemistry method growth of zinc oxide nano linear array adopts known technology to realize, for example the method for disclosed a kind of hydro thermal method synthesizing zinc oxide nanometer stick array in the patent application 201110253998.2.Concrete, adopt 0.1mol/L concentration by equimolar urotropine (HMTA) and zinc nitrate hexahydrate (ZnNO
36 (H
2O)) nutrient solution that forms, the generation of carbon fiber electrode 1 there be facing down of zinc oxide seed layer, be placed on the nutrient solution top, growth is 3 hours in the water-bath environment, and the length of nano wire is 300nm, after finishing the zinc oxide nano-wire array growth, it is carried out heating anneal (preferred 145-155 ℃), preferred, after ultrasonic cleaning, dry up with nitrogen gun, place 80 ℃ of vacuumize close annealings 1.5 hours, finally form zinc oxide nano-wire array layer 6; Make insulating polymeric material (preferred polymethyl methacrylate) capping oxidation zinc nano-wire array layer 6 by spin coating afterwards, generate polymeric dielectric layer 7, bonding electrode layer 8 on polymeric dielectric layer 7 subsequently, wherein the thickness of electrode layer is 0.8mm.
About glucose oxidase anode layer 5, laccase cathode layer 4 respectively with the method for the bonding of carbon fiber electrode 1, can use method conventional in the prior art, also can be by following method realization.After the position of preparing to be coated with glucose oxidase on the carbon fiber electrode 1 being placed the potassium nitrate solution oxidation number minute of 0.1mol/L, take out, with adding again 5mg/cm after the intermediate water flushing
3The PBS of glucose oxidase in keep 3h, rear taking-up electrode, wherein the thickness of glucose oxidase is about 45 μ m, the area of electrode is about 15mm
2, use 4mol/cm
3Sodium chloride solution flushing, under 4 ℃, be kept in the PBS afterwards, stand-by.Be coated with a layer insulating 2(phenolic resins at carbon fiber electrode 1), then place conductive electrode 3(gold electrode in the above), by conventional method laccase is fixed on conductive electrode 3(gold electrode subsequently) on, forming the laccase negative electrode, area is about 15mm
2, the laccase layer thickness is 45 μ m.Finished the making of utility model mixing nano generator by above-mentioned steps, adopt conventional wireless radio-frequency, conductive electrode 3(gold electrode with the mixing nano generator made) with the blood sugar signal detector of carbon fiber electrode (common electrode) 1 with the second radio-frequency transmissions assembly 12 integrated formation biology enzyme generators 9, is used for transmitting the electrical signal data of biology enzyme generator 9; With electrode layer 8 and carbon fiber electrode (common electrode) 1 and the first radio-frequency transmissions assembly 11 integrated formation blood pressure signal detectors, be used for the piezoelectric signal of transmission Zinc oxide nanowire electric generator; In addition, adopt conventional wireless radio-frequency to make and the radio frequency reception assembly that mixes nano generator and separate, be used for receiving the signal of telecommunication of blood sugar or blood pressure signal detector, thereby can provide respectively the generating signal of biology enzyme generator 9 and the piezoelectric signal of Zinc oxide nanowire electric generator 10 by mixing nano generator of the present utility model, be used for characterizing blood pressure and the blood sugar concentration of body fluid.
When being placed on the above-mentioned mixing nano generator for preparing in the simulated body fluid (concentration of glucose is 4mmol/l), by connecting conductive electrode 3(gold electrode) and carbon fiber electrode (common electrode) 1 between radio-frequency unit can observe electric current and voltage signal, wherein electric current is about 100nA, and voltage is about 90nV; Afterwards it is applied periodic pressure, this pressure is that the pressure of 1.35 standard atmospheric pressures was periodically used in 1.9 seconds, the retention time of pressure is 0.7 second, find that the alternating voltage that can export Zinc oxide nanowire electric generator by the radio-frequency unit between connecting electrode layer 8 and the carbon fiber electrode (common electrode) 1 on average is about between the 0.1V-0.5V, corresponding current density is about 0.06mA/cm
2
Above-mentioned experiment can prove that mixing nano generator of the present utility model can carry out the mensuration of blood pressure and blood sugar, has given full play to the electric action of carbon fiber, can be applied to diabetic and measure blood sugar.