CN105140041A - Liquid solar cell and preparation method thereof - Google Patents

Liquid solar cell and preparation method thereof Download PDF

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CN105140041A
CN105140041A CN201510518861.3A CN201510518861A CN105140041A CN 105140041 A CN105140041 A CN 105140041A CN 201510518861 A CN201510518861 A CN 201510518861A CN 105140041 A CN105140041 A CN 105140041A
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liquid
container
shell structure
solar energy
energy battery
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CN105140041B (en
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高荣礼
符春林
蔡苇
陈刚
邓小玲
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Jiaxing Dingshan Information Technology Co.,Ltd.
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Chongqing University of Science and Technology
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Abstract

The invention discloses a liquid solar cell with variable structure and adjustable photovoltaic effect and a preparation method of the liquid solar cell. The liquid solar cell comprises a container, wherein the container comprises a substrate and a surrounding wall; the surrounding wall is composed of a side wall and a top wall; the surrounding wall is fixed on the substrate to form the container; an upper electrode is arranged on the lower surface of the top wall; a lower electrode is arranged on the upper surface of the substrate; the container is filled with magnetoelectric liquid; the magnetoelectric liquid is prepared by mixing core-shell structure nanoparticles, a hydrophilic surfactant and oily base liquid; the cores of the core-shell structure nanoparticles are magnetic particles; and the claddings are ferroelectric particles. The preparation method of the liquid solar cell comprises the following steps: (1) preparing the upper electrode and the lower electrode; (2) preparing the container; and (3) adding the magnetoelectric liquid to the container to obtain the liquid solar cell.

Description

Liquid solar energy battery and preparation method thereof
Technical field
The present invention relates to technical field of solar batteries, particularly relate to a kind of liquid solar energy battery and preparation method thereof.
Background technology
Energy crisis is the great difficult problem that our times various countries face, and exploitation regenerative resource is the effective way alleviating this problem.In numerous regenerative resource, solar energy has aboundresources, widely distributed, the clean advantage such as clean and enjoy favor because of it.Photovoltaic generation is a kind of principal mode of exploitation solar energy, and its principle utilizes photovoltaic effect to make photovoltaic cell, and the transform light energy of the sun is become electric energy.Photovoltaic cell is mainly divided into silicon, copper indium diselenide, GaAs, cadmium telluride and polymer photovoltaic cell etc.There is the shortcomings such as conversion efficiency is low, poor stability, production cost are higher in existing industrial thin-film solar cells.Wanting to change above shortcoming, by improving preparation technology and the technical parameter of film, or the utilization ratio of light can be improved.First method faces the problems such as R&D cycle long, cost is high, technical difficulty, and therefore, the utilization ratio improving light improves the important means of conversion efficiency, seems very necessary.Want the utilance improving sunlight, can pass through to improve film to the absorptivity of sunlight, and the thickness increasing film can accomplish this point.But film thickness is thicker, the stability of solar cell will certainly be reduced, also can increase the recombination rate of photo-generated carrier simultaneously, reduce conversion efficiency.Because nano wire (nano chain) has the character not available for a series of film, such as it has absorptivity, the low recombination rate high to light, one end of this external nano wire (nano chain) has stronger electric field (being similar to the electric field near needle point), therefore has higher collection efficiency to photo-generated carrier.Therefore prepare high-quality, possess specific texture, lower defect, higher purity (high principal phase ratio) nano wire (nano chain) be the effective means improving solar cell photoelectric conversion efficiency.Therefore, how to prepare there is specific texture, highly purified solar cell nanometer line (nano chain) just seems very necessary.
The weak point of current nano wire and preparation method thereof:
Prepare the method mainly bag hydro thermal method of nano wire at present, electrochemical process, sol-gel process, direct precipitation method, vapour deposition process.Regardless of which kind of method, be all difficult to obtain the nano wire with specific orientation, and preparation process more complicated.
In addition, nano wire is made solar cell and there are some defects, such as, because nano wire is thinner, how electrode and nano wire are coupled together that to transmit photo-generated carrier be cumbersome thing; Its two, if nano wire has broken for some reason, whole solar cell has just been scrapped, and again must make a sample, waste time and energy; Three, nanowire solar cells is once carry out, and shape, structure are all unmodifiable, and photovoltaic effect also just can not regulate and control.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of structurally variable, photovoltaic effect regulatable liquid solar energy battery and preparation method thereof is provided.
The object of the present invention is achieved like this:
A preparation method for liquid solar energy battery, the method is carried out according to the following steps:
Step 1) prepare electrode
Get substrate, and for the leg of covering substrate, described leg comprises sidewall, roof, prepares top electrode at the lower surface of roof;
Step 2) prepare container
Leg is fixed on substrate, obtains the container of hermetically-sealed construction;
Step 3) prepare liquid solar energy battery
Get nuclear shell structure nano particulate, lipophilic surfactant, oiliness base fluid, the core of described nuclear shell structure nano particulate is magnetic particle, the involucrum of nuclear shell structure nano particulate is ferroelectricity particulate, by nuclear shell structure nano particulate, lipophilic surfactant, oiliness base fluid Homogeneous phase mixing, obtain magnetoelectricity liquid, magnetoelectricity liquid is added in container, obtains liquid solar energy battery.
In order to obtain larger photoelectric current when illumination, preferably, the thickness of described container had both been less than 1/5 of container length, was less than 1/5 of container width again, formed the container of laminated structure.
In order to alleviate weight, the thickness of leg, and ensure its insulation property, preferably, the material of described leg adopts plastics.
Conveniently leg is fixed on substrate, preferably, step 2) in, described leg is adhesively fixed on substrate.
In order to ensure that base fluid can not burn when toasting, preferably, step 3) in, described oiliness base fluid is at least one in silicone oil, detergent alkylate, Polybutene oil.
In order to ensure the oleophylic performance of surfactant, preferably, step 3) in, described lipophilic surfactant is oleic acid.
In order to by nuclear shell structure nano particulate, lipophilic surfactant, oiliness base fluid Homogeneous phase mixing, preferably, step 3) in, nuclear shell structure nano particulate, lipophilic surfactant, the mixed method of oiliness base fluid is: first, by nuclear shell structure nano particulate and lipophilic surfactant Homogeneous phase mixing, then, by nuclear shell structure nano particulate, the mixture of lipophilic surfactant adds in oiliness base fluid, then, by nuclear shell structure nano particulate, lipophilic surfactant, the mixture of oiliness base fluid is put in air-tight bottle, finally, air-tight bottle is placed on shaking table and shakes, make being distributed in oiliness base fluid of nuclear shell structure nano particulate homogenous.
In order to magnetoelectricity liquid is added in container, preferably, step 3) in, described magnetoelectricity liquid syringe injects container.
Preferably, described magnetic particle is CFO nanoparticle, and described ferroelectricity particulate is BTO nanoparticle.
A kind of liquid solar energy battery, comprise container, this container comprises substrate, leg, described leg is made up of sidewall, roof, described leg is fixed on container substrate being formed hermetically-sealed construction, the lower surface of described roof is provided with top electrode, the upper surface of described substrate is provided with bottom electrode, the full magnetoelectricity liquid of described container content, described magnetoelectricity liquid is mixed formed by nuclear shell structure nano particulate, lipophilic surfactant, oiliness base fluid, the core of described nuclear shell structure nano particulate is magnetic particle, and the involucrum of nuclear shell structure nano particulate is ferroelectricity particulate.
The ferroelectric solar cell of current research is all solid-state, and liquid ferroelectric solar cell have not been reported.This is because when ferroelectric material is in liquefaction time, temperature is generally all higher than its ferroelectrie Curie temperature, and now ferroelectric material loses ferroelectricity.Therefore, we propose " liquid solar energy battery " this concept in the world first, and give its preparation method.
But, here so-called liquid solar energy battery, not refer to that (material is in liquid temperature all higher than its Curie temperature to proper " liquid state " solar cell, so also there is no liquid ferroelectric substance at present), and refer to and be dispersed in (fluidcarrier) in base fluid by particle diameter at the ferroelectric particulate homogenous that has of about 10nm, by adion (Charge repulsion) or on surface band long-chain molecule (virial repulsion) reach anti-agglomeration and form stable colloidal dispersion, afterwards magnetic field is applied to particulate, particulate is made to become chain, be connected with nano wire with electrode, just constitute solar cell.
Owing to have employed technique scheme, the present invention has following beneficial effect:
1, ferromagnetic fine particles has flowable, and its form is unbodied, and therefore, liquid solar energy battery structure is variable, photovoltaic effect controllable, and the scope of application is extensive.
2, under magnetic fields, having ferroelectric particulate can rotate, and due in a liquid, so its coercive field can be smaller, due to Brownian movement, turning under magnetic field is easier.Need to apply relatively large electric field in solids and could allow change polarised direction, electric field easily causes sample breakdown too greatly.
3, under electric field action, in solid iron electric material, the orientation of electricdomain can only along some orientation close to direction of an electric field, might not along direction of an electric field, and for ferroelectricity liquid, because ferromagnetic fine particles can freely rotate in a liquid, therefore the orientation of its electricdomain can completely along magnetic direction.
Accompanying drawing explanation
Fig. 1 is the structural representation of container;
Fig. 2 is under normal state, the structural representation of liquid solar energy battery;
When Fig. 3 is for applying vertical direction magnetic field, the structural representation of liquid solar energy battery;
Fig. 4 is the TEM figure of CFO-BFO nucleocapsid structure;
Fig. 5 is the I-V curve of battery structure under illumination-not illumination.
In accompanying drawing, 1 is bottom electrode, and 2 is leg, and 3 is nuclear shell structure nano particulate, and 4 is base fluid, and 5 is ferroelectric nano chain, and 6 is top electrode.
Embodiment
Because ferroelectric solar cell is generally by bottom electrode, ferroelectric thin film, top electrode, the sandwich structure of three part compositions.Therefore, replace traditional ferroelectric thin film layer with having ferroelectric liquid here.Change the status architecture of particulate in ferroelectric liquid by applying outfield, thus regulate and control the structure of ferroelectric solar cell.
Relative to electric field, drive with magnetic field and there is certain advantage: magnetic field is a kind of noncontact field.Miniaturization, Long-distance Control can be realized, do not need contact just not to need wire, in addition, drive with magnetic field and there is not the breakdown possibility of sample.With the magnetic field that magnet is such, relative to magnetic field, save electric energy.
But general ferromagnetic fine particles does not have magnetic, be obviously uncontrollable particle movement situation with magnetic field.Therefore, we are by wrapping up one deck ferroelectricity layer on the surface of magnetic particle, and so just obtaining magnetic is core, and ferroelectricity is the composite material of shell.
See Fig. 2, Fig. 3, a kind of preferred embodiment of liquid solar energy battery, comprise container, this container comprises substrate, leg, described leg is by sidewall, roof forms, described leg is fixed on container substrate being formed hermetically-sealed construction, the lower surface of described roof is provided with top electrode, the upper surface of described substrate is provided with bottom electrode, the full magnetoelectricity liquid of described container content, described magnetoelectricity liquid is by nuclear shell structure nano particulate, lipophilic surfactant, oiliness base fluid mixing composition, the core of described nuclear shell structure nano particulate is magnetic particle, the involucrum of nuclear shell structure nano particulate is ferroelectricity particulate.
Top electrode in this patent, bottom electrode inserting needle, for the orientation in accompanying drawing, can be front and back electrode or left and right electrode etc. in the middle of actual.Be dispersed in base fluid form so-called ferroelectricity liquid because we will have ferroelectric nanoparticle, therefore, in order to characterize the ferroelectricity of ferroelectricity liquid, just need to apply magnetic field to ferroelectricity liquid, make the ferroelectricity particulate in liquid polarized.Therefore, the liquid that base fluid just should select conductivity very poor, such as close to the grease class of insulation, should have some other performance in addition: breakdown strength is high, dielectric loss angle tangent is little, and insulation resistivity is high, and relative dielectric constant is little; Next has excellent process based prediction model.As vapourizing temperature is high, flash-point is high, and difficulty is fired or do not fired as far as possible; Solidifying point is low, suitable viscosity and viscosity-temperature profile; Thermal conductivity is large, and specific heat capacity is large; Heat stability is good, resistance to oxidation; Inspiratory little under magnetic fields; Compatibility between it and the solid material contacted with it will be got well; Toxicity is low, easily biological-degradable.Also require that source is wide, price is low.As for the silicone oil under high temperature and detergent alkylate, polybutene wet goods).Then, in base fluid, add a certain amount of surfactant, afterwards ferromagnetic fine particles is put into base fluid, shake, or ultrasonic vibration makes it even.Finally apply magnetic field along two corresponding electrode direction, make particulate form nano chain, and be connected with two electrodes.Just define solar cell.By size, the direction of controlling magnetic field, just obtain different structures.
See Fig. 1 to Fig. 3, a kind of preferred embodiment of the preparation method of liquid solar energy battery:
Step 1) prepare electrode
For pulsed laser deposition, also can be other method, such as magnetron sputtering, sol-gel process etc.With La 0.7sr 0.3mnO 3be example as bottom electrode, also can adopt other material, such as conductive oxide ITO, La 0.5sr 0.5coO 3deng or metal, Au, Pt, Ag etc.First at SrTiO 3substrate (can certainly be the substrate of other type, silicon chip, glass etc.) cleans with ultrasonic wave respectively in acetone, alcohol, dries; With sand paper, chip bench is polished, and clean up, the substrate heat conduction elargol dried is bonded on chip bench, then block substrate according to the shape of required electrode, size, the corresponding mask plate of number.Put into after drying on cavity heating station, start to vacuumize.Treat that air pressure is extracted into 10 -4during Pa, start heated substrate platform.Attention should slowly be heated, and is generally heated to 700 DEG C of needs about 90 minutes.After reaching target temperature, with baffle plate, substrate is blocked, and pass into desired gas to certain pressure intensity.The energy of setting laser and frequency parameter, carry out pre-sputtering to remove La 0.7sr 0.3mnO 3film is (here with La 0.7sr 0.3mnO 3: being abbreviated as LSMO is example as the bottom electrode measuring photovoltaic effect, also can select other conductive films) dirt on surface, make film expose fresh surface, the pre-sputtering time is generally 2 ~ 5 minutes; In pre-sputtering process, the adjustment parameter such as laser optical path, range, with make plumage brightness end and chip bench tangent.Rotate chip bench and film, and make laser at X, Y-direction particles; After treating temperature, stable gas pressure, remove baffle plate, deposit.Select suitable sedimentation time according to required film thickness, after deposition terminates, be filled with certain gas as required and slow cooling.
Take the leg in covering substrate, described leg comprises sidewall, roof, the film that the material employing organic substance thin slice of leg or other material do, and in the present embodiment, leg adopts plastic sheet to make, and prepares top electrode at the lower surface of roof.Top electrode can by metals such as metal spraying on the roof of surfacing, spray silver, or with preparation of metals such as gold, silver in sol evenning machine spin coating, or it is also passable to prepare top electrode by other method.In actual fabrication process, the top electrode of arbitrary shape, arbitrary dimension, any number can be prepared as required.
Step 2) prepare container
As shown in Figure 1, by leg by AB glue, 502 glue etc., cover from surrounding and top and bond to substrate, obtain laminar container, the length of container and wide all much larger than thick.Its objective is to form " flake ".Because too thick, the Carrier recombination that illumination produces just many, the photoelectric current obtained is just smaller.Such as long and wide is all 1cm, and thickness is 1mm.Also other method process vessel can be passed through.
Step 3) prepare liquid solar energy battery
1st step: the preparation of CFO-BTO magnetic-electric core-shell structure magnetic particulate:
Preparation has ferromagnetic Conjugate ferrite (CFO) nanoparticle:
Such as, by FeCl 36H 2o (0.04mol, 100mL) and Co (NO 3) 26H 2o (0.02mol, 100mL) mixes, and adds NaOH (0.35mol, 500mL), then mixed solution is heated to boiling, the rapid stirring of companion. and boiling takes off natural sedimentation after continuing 1min. the fully HNO of the rear 1mol/L of precipitation 3solution cleans sediment until pH value is 7. then cleaning products therefrom is obtained after acetone dehydration, the operation such as dry required having ferromagnetic CFO nanoparticle.
Ferroelectric barium titanate (BTO) particulate is prepared with sol-gel process:
1) preparation of barium precursor liquid: join in barium acetate by appropriate glacial acetic acid, is placed in 80 DEG C of thermostat water bath heating for dissolving, is transferred in volumetric flask after cooling, adopts buret to drip ethylene glycol ethyl ether constant volume and namely obtains Ba precursor liquid.2) preparation of titanium precursor liquid: join in butyl titanate as mixed solvent using glacial acetic acid and ethylene glycol ethyl ether, transfers in volumetric flask after dissolving, and adopts buret instillation ethylene glycol ethyl ether constant volume namely to obtain Ti precursor liquid.Ti precursor liquid is added drop-wise in Ba precursor liquid, adds appropriate acetylacetone,2,4-pentanedione after dropping to adjust dissolved adhesiveness, after mixing, namely obtained the colloidal sol of pure barium titanate through 24 hours.If the colloidal sol of barium titanate doping need be prepared, only need add appropriate La precursor liquid, Nd precursor liquid or Co precursor liquid simultaneously, after hours aging through 24, namely obtain the colloidal sol of barium titanate doping.If be necessary, ethanol in proper amount amine also can be added to control the viscosity of colloidal sol.Then joining in colloidal sol by CFO magnetic nanometer particles, finally toasted on heating station by the mixture of the colloidal sol obtained and particulate, put into box type furnace and sinter after drying, is 900 DEG C in sintering temperature, and the time is 2h.After fully being ground by products therefrom, obtain the required CFO-BTO nanoparticle with magnetic-electric nucleocapsid structure.
2nd step: the preparation of CFO-BTO magnetic-electric nucleocapsid structure magnetoelectricity liquid:
According to the demand of oneself, certain mass had being dispersed in certain density silicone oil of CFO-BTO magnetic-electric nuclear shell structure nano particulate homogenous.The features such as silicone oil has high-low temperature resistant, chemical stability is good, steam forces down, viscosity temperature influence is little are the desirable carrier fluids of magnetoelectricity liquid.But the characteristic of silicone oil water and oil repellence makes must have oleophylic performance by having the surfactant that CFO-BTO magnetic-electric nuclear shell structure nano particulate homogenous is scattered in wherein, and energy coated magnetic particulate, otherwise easily there is the phenomenons such as reunion, sedimentation.Use oleic acid as surfactant.
Be specially: as requested, such as, need configuration particulate volume fraction to be 5%, cumulative volume be 100ml there is CFO-BTO magnetic-electric nucleocapsid structure magnetoelectricity liquid, so, required particulate volume is 5ml, and its density is about 6g/cm 3, then the quality of particulate is needed to be 30g; The concentration of oleic acid is 2%, then need the oleic acid measuring 2ml; The volume of silicone oil is 100-5-2=93ml; Therefore,
First, what weigh 30g has that CFO-BTO magnetic-(volume is about 5cm to electric nucleocapsid structure 3), add in the oleic acid of 2ml, shake, be then dispersed in uniformly in 93ml silicone oil, in the vial putting good seal into or other container, shaking table carries out shake about 1 hour.Then just obtaining microsome integration number is 5%, cumulative volume be 100ml there is CFO-BTO magnetic-magnetic magnetoelectricity liquid of electric nucleocapsid structure tool.
3rd step: CFO-BTO magnetoelectricity liquid syringe will be obtained in previous step or other method is injected in container, just obtain the liquid solar energy battery in Fig. 2.
Liquid solar energy battery in use can apply magnetic field as required, just obtains the ferroelectricity nano chain in required direction along magnetic direction.In the present embodiment, there is ferroelectric nanoparticle under magnetic fields and just can move, form nano chain, just obtain the ferroelectric nano chain of vertical direction shown in Fig. 3.Change the size in magnetic field, direction, the size of magnetic field gradient, just can obtain different chain spacing, the ferroelectric nano chain of chain thickness.Top electrode and bottom electrode wire couple together, and access loop, encapsulates, test.
Detect obtained solar cell, result is as follows:
As can be known from Fig. 4, the BTO powder prepared by us is spherical substantially, is on average directly about 20nm.As can be known from Fig. 5, surface by the quantity regulating and controlling particle chains, thus can regulate and control its electric conductivity by the size changing magnetic field
In addition, can find that the solar cell that we obtain has obvious photovoltaic effect, namely under illumination and not illumination, depress in same electrical the electric current obtained and there is obvious difference.Our sample of surface has obvious photovoltaic performance.
What finally illustrate is, above preferred embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although by above preferred embodiment to invention has been detailed description, but those skilled in the art are to be understood that, various change can be made to it in the form and details, and not depart from claims of the present invention limited range.

Claims (10)

1. a preparation method for liquid solar energy battery, is characterized in that, the method is carried out according to the following steps:
Step 1) prepare electrode
Get substrate, and for the leg of covering substrate, described leg comprises sidewall, roof, prepares top electrode at the lower surface of roof;
Step 2) prepare container
Leg is fixed on substrate, obtains the container of hermetically-sealed construction;
Step 3) prepare liquid solar energy battery
Get nuclear shell structure nano particulate, lipophilic surfactant, oiliness base fluid, the core of described nuclear shell structure nano particulate is magnetic particle, the involucrum of nuclear shell structure nano particulate is ferroelectricity particulate, by nuclear shell structure nano particulate, lipophilic surfactant, oiliness base fluid Homogeneous phase mixing, obtain magnetoelectricity liquid, magnetoelectricity liquid is added in container, obtains liquid solar energy battery.
2. the preparation method of liquid solar energy battery according to claim 1, is characterized in that, the thickness of described container had both been less than 1/5 of container length, was less than 1/5 of container width again, forms the container of laminated structure.
3. the preparation method of liquid solar energy battery according to claim 1, is characterized in that, the material of described leg adopts plastics.
4. the preparation method of liquid solar energy battery according to claim 1, is characterized in that, step 2) in, described leg is adhesively fixed on substrate.
5. the preparation method of liquid solar energy battery according to claim 1, is characterized in that, step 3) in, described oiliness base fluid is at least one in silicone oil, detergent alkylate, Polybutene oil.
6. the preparation method of liquid solar energy battery according to claim 1, is characterized in that, step 3) in, described lipophilic surfactant is oleic acid.
7. the preparation method of liquid solar energy battery according to claim 1, it is characterized in that, step 3) in, nuclear shell structure nano particulate, lipophilic surfactant, the mixed method of oiliness base fluid is: first, by nuclear shell structure nano particulate and lipophilic surfactant Homogeneous phase mixing, then, by nuclear shell structure nano particulate, the mixture of lipophilic surfactant adds in oiliness base fluid, then, by nuclear shell structure nano particulate, lipophilic surfactant, the mixture of oiliness base fluid is put in air-tight bottle, finally, air-tight bottle is placed on shaking table and shakes, make being distributed in oiliness base fluid of nuclear shell structure nano particulate homogenous.
8. the preparation method of liquid solar energy battery according to claim 1, is characterized in that, step 3) in, described magnetoelectricity liquid syringe injects container.
9. liquid solar energy battery according to claim 1, it is characterized in that: described magnetic particle is CFO nanoparticle, described ferroelectricity particulate is BTO nanoparticle.
10. the liquid solar energy battery prepared of the arbitrary described method of claim 1 to 9, it is characterized in that: comprise container, this container comprises substrate, leg, described leg is by sidewall, roof forms, described leg is fixed on container substrate being formed hermetically-sealed construction, the lower surface of described roof is provided with top electrode, the upper surface of described substrate is provided with bottom electrode, the full magnetoelectricity liquid of described container content, described magnetoelectricity liquid is by nuclear shell structure nano particulate, lipophilic surfactant, oiliness base fluid mixing composition, the core of described nuclear shell structure nano particulate is magnetic particle, the involucrum of nuclear shell structure nano particulate is ferroelectricity particulate.
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CN108267483A (en) * 2018-01-29 2018-07-10 重庆科技学院 A kind of device and method for testing multiferroic liquid properties
CN108445058A (en) * 2018-03-07 2018-08-24 重庆科技学院 Multiferroic liquid physics characteristic test device

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108267483A (en) * 2018-01-29 2018-07-10 重庆科技学院 A kind of device and method for testing multiferroic liquid properties
CN108267483B (en) * 2018-01-29 2023-10-27 重庆科技学院 Device and method for testing multiferroic liquid performance
CN108445058A (en) * 2018-03-07 2018-08-24 重庆科技学院 Multiferroic liquid physics characteristic test device
CN108445058B (en) * 2018-03-07 2023-06-06 重庆科技学院 Multiferroic liquid physical property testing device

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