Available light or electricity are realized storage batteries
Technical field
The present invention relates to a kind of accumulation energy type battery, particularly a kind ofly both can also can electricity consumption carry out storage batteries with sunlight.
Background technology
Along with the development of World Economics, the raising of living standards of the people, limited natural resources such as coal, oil, natural gas can not satisfy the needs of human development.Solar energy has incomparable advantage: cleaning, never exhausted, all can obtain all over the world.Therefore the exploitation of solar energy, utilization increase year by year.Solar battery technology is the device that directly changes into luminous energy electric energy through photoelectric effect or Photochemical effects.Silicon such as present monocrystalline silicon and polysilicon are that the application of solar cell has got into extensive developing stage.But conventional solar cell can not be got up the electrical power storage that produces, and silicon is that solar cell costs an arm and a leg, and is unfavorable for the popularization and application of solar battery technology.
Traditional storage battery such as lead-acid battery, Ni-MH battery, lithium battery can only charge to it in electricity consumption, wait under the situation that does not have power supply in the open air and can't charge, thereby limited the scope of application of storage battery.
TiO
2Be a kind of N type oxide semiconductor, its Detitanium-ore-type has higher activity, and its valence band is about 3.2eV to the energy gap of conduction band.As UV-irradiation TiO
2The time, the electronics (e on its valence band
-) will be stimulated transits to conduction band, on valence band, produces corresponding hole (h simultaneously
+), formed electron-hole pair.Electronics, the hole that produces separated under the internal electric field effect and moved to particle surface.The hole has very strong oxidizability, can cobalt hydroxide be oxidized to hydroxy cobalt oxide,
Co(OH)
2+OH
-+h
+→CoOOH+H
2O
Palladium is a kind of high activity that has, and under the effect of electronics, can proton is reduced into hydrogen atom and be stored into to form PdH in the dot matrix.By PdH is negative pole, and hydroxy cobalt oxide is that positive pole can constitute battery, when load links to each other with positive and negative electrode respectively with lead, electrochemical reaction takes place respectively in alkaline solution:
Negative pole: PdH+OH
-→ Pd+H
2O+e
-
Anodal: CoOOH+H
2O+e
-→ Co (OH)
2+ OH
-
Its cell reaction is: PdH+CoOOH → Pd+Co (OH)
2
This battery can store electrical energy, in needs, will be stored in chemical energy in the positive and negative electrode and be transformed into electric energy and discharge.After discharging electric energy, the back reaction of above-mentioned reaction takes place respectively at both positive and negative polarity in available charged with direct current, realizes the function of store electrical energy.
In the storage battery development process, make full use of TiO
2Photoelectric converting function combine with the storage hydrogen function of palladium or palldium alloy, realize that light and electricity can both carry out storage batteries, still do not have successful precedent.
Summary of the invention
The technical problem that the present invention will solve is, provides a kind of and can realize the light charging, can realize the novel storage battery of electricity charging again.
For the technical solution problem, technical scheme provided by the invention is: storage battery is a positive electrode with cobalt hydroxide and composite titania material, and palladium or palladium-copper alloy are negative material; It is catholyte that side of the positive electrode is added with aqueous slkali; It is anolyte that negative side is added with acid solution, and cation exchange resin is a barrier film, isolates positive and negative polarities and aqueous slkali and acid solution; Aqueous slkali is potassium hydroxide or sodium hydrate aqueous solution, and acid solution is hydrochloric acid or aqueous sulfuric acid.
In the storage battery among the present invention, storage battery just have the multilayer structure that forms of compacting, be followed successively by from outside to inside: electro-conductive glass, be coated on the TiO of conductive glass surface with adhesive
2Layer, load on the cobalt hydroxide-TiO of nickel foam
2Mixture layer, nickel foam; Storage battery is to load on carbon on the foam copper and carry palladium or palldium alloy is a negative pole; The carbon that loads on anodal nickel foam, the negative pole carries palladium or palldium alloy is settled with barrier film respectively relatively, and form sandwich structure: being aqueous slkali between positive pole and the barrier film, is acid solution between negative pole and the barrier film.
Aqueous slkali is potassium hydroxide or sodium hydrate aqueous solution among the present invention, and concentration is 1~6mol L
-1Said acid solution is hydrochloric acid or aqueous sulfuric acid, and concentration is 1~6mol L
-1
Among the present invention, said palldium alloy is palladium-copper alloy: PdCu
x, the scope of x is 0~1.
Among the present invention, said electro-conductive glass is the quartz glass that applies indium tin oxide layer.
Among the present invention, said electro-conductive glass is the part of battery case wall.
Among the present invention, said adhesive is the POLYPROPYLENE GLYCOL aqueous solution, and concentration is 5wt.%.
Among the present invention, said TiO
2Be Detitanium-ore-type TiO
2
Among the present invention, said positive pole makes through following manner: get less than 200 purpose Co (OH)
2Powder, less than 400 purpose Detitanium-ore-type TiO
2Powder, and as the 5wt.% POLYPROPYLENE GLYCOL aqueous solution of adhesive, ground and mixed, Co (OH)
2, TiO
2, POLYPROPYLENE GLYCOL mass ratio be 1: 0.1~0.3: 0.1~0.3; Mixture is coated on the nickel foam, after drying quartz glass is scribbled indium tin oxide layer and the cobalt hydroxide-TiO that loads on nickel foam
2Mixture layer is relative, at 100Kg cm
-2The moulding of pressure pressed, 300~500 ℃ of heat treatment 10~60 minutes under inert gas shielding then, cooling.
Among the present invention, said anodal negative pole makes through following manner:
Get that to contain the palladium amount be that the carbon of 5~60wt.% carries palladium or palldium alloy and as the POLYPROPYLENE GLYCOL aqueous solution ground and mixed of the 5wt.% of adhesive, wherein the mass ratio of palladium and POLYPROPYLENE GLYCOL is 1: 0.1~0.2; After mixing, mixture is applied on the foam copper, dry the back at 100Kg cm
-2The moulding of pressure pressed; 300~500 ℃ of heat treatment 10~60 minutes under inert gas shielding then, cooling.
Among the present invention, in the said positive pole, be coated on the TiO of conductive glass surface with adhesive
2Layer, load on the Co (OH) of nickel foam
2-TiO
2Mixture layer is drawn binding post respectively.
Among the present invention, using nickel foam is to consider that Ni has corrosion resistance preferably in alkaline solution as the carrier of positive pole, and the micropore in the nickel foam can store anolyte; Using foam copper is to consider that Cu has corrosion resistance preferably in acid solution as the carrier of negative pole, and the micropore in the foam copper can store catholyte.
The electrochemical principle that the present invention realizes according to this:
As solar light irradiation TiO
2The time, the electronics (e on its valence band
-) will be stimulated transits to conduction band, on valence band, produces corresponding hole (h simultaneously
+), formed electron-hole pair.Electronics, the hole that produces separated under the internal electric field effect and moved to particle surface.The hole has very strong oxidizability, can cobalt hydroxide be oxidized to hydroxy cobalt oxide,
Co(OH)
2+OH
-+h
+→CoOOH+H
2O
TiO
2Electronics on the conduction band then is transferred to negative pole through the lead that is connected in palladium or palldium alloy, and the catalytic action through Pd on negative pole is with the proton (H in the anolyte
+) being reduced into hydrogen atom, hydrogen atom forms metal hydride (PdH or PdCu from palladium or palldium alloy diffusion into the surface to palladium or palldium alloy alloy dot matrix
xH).The energy that its effect is equivalent to use sunlight is with Co (OH)
2Electronics pass through TiO
2And the lead that is connected in negative pole is transferred to negative pole, under the effect of electronics, proton is reduced into hydrogen atom, realizes the light charging process.Along with the carrying out of light charging, anodal Co (OH)
2Constantly be oxidized to CoOOH, constantly form PdH at negative pole, voltage also increases thereupon between the two poles of the earth, realizes the process (as shown in Figure 1) of light charging:
After battery is full of, all Co (OH)
2All be oxidized to CoOOH, Pd has also changed PdH into, breaks off connecting anodal and negative pole TiO
2The lead of film side, with the metal hydride side of negative pole with CoOOH is anodal links to each other with load with lead, electrochemical reaction takes place respectively in both positive and negative polarity, produces electric current, the external acting:
Negative pole: PdH → Pd+H
++ e
-
Anodal: CoOOH+H
2O+e
-→ Co (OH)
2+ OH
-
At this moment, the hydrogen in the metal hydride is changed into proton by electrochemistry oxygen, and anodal CoOOH is obtained Co (OH) by electrochemical reduction
2When discharge finished, both positive and negative polarity is got back to the state before the light charging again, and was as shown in Figure 2.
If, also can realize the back reaction of above-mentioned both positive and negative polarity reaction, and realize the charging of battery with the positive and negative polarities of battery 2 volts voltage in addition.
The beneficial effect that the present invention has:
The present invention has not only realized the opto-electronic conversion of solar energy, carries out the real-time storage of electric energy, also can realize the electricity charging simultaneously, thereby has widened the charging modes of storage battery.Both can use traditional mode to utilize direct current to charge in batteries, and can use sunlight that storage battery is charged again, this is the revolution of battery technology.We can say that the present invention is a kind of solar cell of accumulation energy type, is again a kind of traditional storage battery simultaneously.
When the present invention utilizes solar energy storage, pollution-free, no CO2 emission, environmental friendliness; The intensification of electricity generate function and energy storage function makes the solar cell power generation device be easy to miniaturization; Can be widely used in fields such as illumination, household electrical appliance, meteorology, geology, oil, railway, aviation, traffic signals, farming and animal husbandry special light sources, have high social and economic benefit.
Description of drawings
The migration of electronics and material when Fig. 1 charges for light, the electrochemical reaction of generation.
Fig. 2 is for after the light charging, the migration of electronics and material during discharge, the electrochemical reaction of generation.
Fig. 3 is the structure of storage battery in the instance of the present invention.
After Fig. 4 is instance medium ultraviolet linear light charging of the present invention, the discharge performance of battery.
Fig. 5 is the constant current charge-discharge curve of battery under the room temperature in the instance of the present invention.
Reference numeral among Fig. 3 is: 1-is coated on the TiO on the conduction quartz glass as nickel foam, the 2-of anodal carrier
2Layer, 3-load on the TiO on nickel foam surface
2Particle, 4-load on the Co (OH) of nickel foam upper surface
2, 5-conduction quartz glass, 6-sealing ring, the 7-carbon that loads on the nickel foam surface as glass, the 9-of chamber wall as the foam copper of negative pole carrier, 8-carries palladium or palldium alloy, 10-perfluoro sulfonic acid membrane.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail:
Embodiment one: the anodal making
Get anatase titanium dioxide powder 0.1 gram (<400 order) and put into mortar and adhesive: POLYPROPYLENE GLYCOL (PVA) aqueous solution (concentration is 5wt.%) grinds, and the mass ratio of titanium dioxide and PVA is 1: 0.1.Be coated to area after mixing lentamente and be the film forming of drying in the shade on the indium tin oxide layer of quartzy electro-conductive glass of 2x2 square centimeter.Get Co (OH)
2(<200 order) 1 gram and anatase titanium dioxide powder (<400 order) are put into mortar and adhesive: POLYPROPYLENE GLYCOL (PVA) aqueous solution (concentration is 5wt.%) carries out ground and mixed, is coated on the nickel foam that area is the 1.5x1.5 square centimeter Co (OH)
2, TiO
2With the mass ratio of PVA be 1: 0.1: 0.1.After drying, scribble Co (OH) to nickel foam
2And TiO
2The face of mixture and tin indium oxide conduction quartz glass scribble TiO
2Towards right, place on the electro-conductive glass, 0.5 centimetre surplus limit is reserved on each limit of glass, at 0.1kg cm
-2The moulding of pressure pressed.Under nitrogen protection, 500 ℃ of heat treatment 10 minutes, cooling then makes the positive pole of solar cell.
Embodiment two: negative pole is made
Get carbon and carry palladium (palladium content 5wt.%) 1 gram and adhesive: POLYPROPYLENE GLYCOL (PVA) aqueous solution (concentration is 5wt.%) carries out ground and mixed, is coated on the foam copper that area is the 1.5x1.5 square centimeter, and the mass ratio that carbon carries palladium and PVA is 1: 0.1.After drying, at 100kg cm
-2The moulding of pressure pressed.Under nitrogen protection, 500 ℃ of heat treatment 15 minutes, cooling then makes the negative pole of battery.
Embodiment three: the battery assembling
Get anatase titanium dioxide powder 0.1 gram (<400 order) and put into mortar and adhesive: POLYPROPYLENE GLYCOL (PVA) aqueous solution (concentration is 5wt.%) grinds, and the mass ratio of titanium dioxide and PVA is 1: 0.15.Be coated to area after mixing lentamente and be the film forming of drying in the shade on the indium tin oxide layer of quartzy electro-conductive glass of 2x2 square centimeter.Get Co (OH)
2Carry out ground and mixed with the anatase titanium dioxide and POLYPROPYLENE GLYCOL (PVA) aqueous solution (concentration is 5wt.%), be coated on the nickel foam that area is the 1.5x1.5 square centimeter Co (OH)
2, TiO
2With the mass ratio of PVA be 1: 0.2: 0.2.After drying, scribble Co (OH) to nickel foam
2And TiO
2Face and tin indium oxide conduction quartz glass scribble TiO
2Towards right, place on the electro-conductive glass, 0.5 centimetre surplus limit is reserved on each limit of glass, at 0.1kg cm
-2The moulding of pressure pressed.Under nitrogen protection, 500 ℃ of heat treatment 15 minutes, cooling then makes the positive pole of battery.
Respectively at TiO
2Film side and nickel foam side are drawn binding post, draw binding post to the negative pole that embodiment two obtains.The carbon of negative pole is carried relative with barrier film and the anodal assembling of palladium side, form sandwich structure, the material of barrier film is a perfluorinated sulfonic resin.Negative pole-film-anodal assembly and another sheet glass and sealing ring are assembled into battery by Fig. 3, inject 2mol L at side of the positive electrode
-12 milliliters of KOH solution, inject 2mol L in negative side
-1H
2SO
42 milliliters of solution.
After anodal 1 hour, take out positive pole and negative pole with 300 watts of ultra-violet lamp irradiations.Detect through X-ray diffraction, contain CoOOH in the positive pole, contain PdH in the negative pole.
Embodiment four: be the battery of negative material with the palladium-copper alloy
Get anatase titanium dioxide powder 0.1 gram (<400 order) and put into mortar and adhesive: POLYPROPYLENE GLYCOL (PVA) aqueous solution (concentration is 5wt.%) grinds, and the mass ratio of titanium dioxide and PVA is 1: 0.2.Be coated to area after mixing lentamente and be the film forming of drying in the shade on the indium tin oxide layer of conduction quartz glass of 2x2 square centimeter.Get Co (OH)
2(<200 order) 0.5 gram and anatase titanium dioxide powder (<400 order) are put into mortar and adhesive: POLYPROPYLENE GLYCOL (PVA) aqueous solution (concentration is 5wt.%) carries out ground and mixed, is coated on the nickel foam that area is the 1.5x1.5 square centimeter Co (OH)
2, TiO
2With the mass ratio of PVA be 1: 0.3: 0.2.After drying, scribble Co (OH) to nickel foam
2And TiO
2Face and tin indium oxide conduction quartz glass scribble TiO
2Towards right, place on the electro-conductive glass, 0.5 centimetre surplus limit is reserved on each limit of glass, at 0.1kgcm
-2The moulding of pressure pressed.Under nitrogen protection, 500 ℃ of heat treatment 15 minutes, cooling then makes the positive pole of battery.
Getting carbon carries palladium-copper alloy PdCu/C (palladium content 25wt.%) 2 gram and put into mortar and adhesive: POLYPROPYLENE GLYCOL (PVA) aqueous solution (concentration is 5wt.%) carries out ground and mixed; Be coated on the foam copper that area is the 1.5x1.5 square centimeter, PdCu/C, with the mass ratio of PVA be 1: 0.3.After drying, at 100kg cm
-2The moulding of pressure pressed.Under nitrogen protection, 500 ℃ of heat treatment 15 minutes, cooling then makes the negative pole of battery.
The carbon of negative pole is carried relative with perfluoro sulfonic acid membrane and the anodal assembling of palladium-copper alloy side, form sandwich structure.Negative pole-film-anodal assembly and another sheet glass and sealing ring are assembled into battery by Fig. 3, inject 6mol L at side of the positive electrode
-12 milliliters of NaOH solution, inject 6mol L in negative side
-12 milliliters of HCl solution.
Embodiment five: the light charging of battery
Get anatase titanium dioxide powder 0.1 gram (<400 order) and put into mortar and adhesive: POLYPROPYLENE GLYCOL (PVA) aqueous solution (concentration is 5wt.%) grinds, and the mass ratio of titanium dioxide and PVA is 1: 0.2.Be coated to area after mixing lentamente and be the film forming of drying in the shade on the indium tin oxide layer of conduction quartz glass of 2x2 square centimeter.Get 1 gram Co (OH)
2(<200 order) and anatase titanium dioxide powder (<400 order) are put into mortar and adhesive: POLYPROPYLENE GLYCOL (PVA) aqueous solution (concentration is 5wt%) carries out ground and mixed, is coated on the nickel foam that area is the 1.5x1.5 square centimeter Co (OH)
2, TiO
2With the mass ratio of PVA be 1: 0.2: 0.15.After drying, scribble Co (OH) to nickel foam
2And TiO
2Face and tin indium oxide conduction quartz glass scribble TiO
2Towards right, place on the electro-conductive glass, 0.5 centimetre surplus limit is reserved on each limit of glass, at 100kg cm
-2The moulding of pressure pressed.Under argon shield, 500 ℃ of heat treatment 12 minutes, cooling then makes the positive pole of battery.
Get carbon and carry palladium-copper alloy PdCu
0.1/ C (palladium content 50 wt%) 0.7 gram is put into mortar and adhesive: POLYPROPYLENE GLYCOL (PVA) aqueous solution (concentration is 5wt.%) carries out ground and mixed, is coated on the foam copper that area is the 1.5x1.5 square centimeter PdCu
0.5/ C, with the mass ratio of PVA be 1: 0.15.After drying, at 100kg cm
-2The moulding of pressure pressed.Under argon shield, 500 ℃ of heat treatment 12 minutes, cooling then makes the negative pole of battery.
The PdCu that scribbles with negative pole
0.1Relative with perfluoro sulfonic acid membrane and the anodal assembling of the side of/C forms sandwich structure.Negative pole-film-anodal assembly and another sheet glass and sealing ring are assembled into battery by Fig. 3, inject 1mol L at side of the positive electrode
-12 milliliters of NaOH solution, inject 1mol L in negative side
-1H
2SO
42 milliliters of solution.
Close switch K is with the anodal TiO of battery
2The terminal of film side links to each other with lead with negative terminal, and is anodal with ultraviolet irradiation, when treating that bubble appears in negative pole or positive pole, opens K switch, breaks off connecting negative pole TiO
2Film side and the anodal lead that is connected are taken out positive pole and negative pole.Detect through X-ray diffraction, contain CoOOH in the positive pole, contain PdCu in the negative pole
0.1H.
Embodiment six: the light charging back discharge of battery
Get anatase titanium dioxide powder 0.1 gram (<400 order) and put into mortar and adhesive: POLYPROPYLENE GLYCOL (PVA) aqueous solution (concentration is 5wt.%) grinds, and the mass ratio of titanium dioxide and PVA is 1: 0.2.Be coated to area after mixing lentamente and be the film forming of drying in the shade on the indium tin oxide layer of conduction quartz glass of 2x2 square centimeter.Get 1 gram Co (OH)
2(<200 order) and anatase titanium dioxide powder (<400 order) are put into mortar and adhesive: POLYPROPYLENE GLYCOL (PVA) aqueous solution (concentration is 5wt.%) carries out ground and mixed, is coated on the nickel foam that area is the 1.5x1.5 square centimeter Co (OH)
2, TiO
2With the mass ratio of PVA be 1: 0.2: 0.15.After drying, scribble Co (OH) to nickel foam
2And TiO
2Face and tin indium oxide conduction quartz glass scribble TiO
2Towards right, place on the electro-conductive glass, 0.5 centimetre surplus limit is reserved on each limit of glass, at 100kg cm
-2The moulding of pressure pressed.Under argon shield, 400 ℃ of heat treatment 30 minutes, cooling then makes the positive pole of battery.
Get carbon and carry palladium-copper alloy PdCu
0.5/ C (palladium content 60wt%) 0.7 gram is put into mortar and adhesive: POLYPROPYLENE GLYCOL (PVA) aqueous solution (concentration is 5wt.%) carries out ground and mixed, is coated on the foam copper that area is the 1.5x1.5 square centimeter PdCu
0.5/ C, with the mass ratio of PVA be 1: 0.15.After drying, at 100kg cm
-2The moulding of pressure pressed.Under argon shield, 400 ℃ of heat treatment 30 minutes, cooling then makes the negative pole of battery.
The PdCu that scribbles with negative pole
0.5Relative with perfluoro sulfonic acid membrane and the anodal assembling of the side of/C forms sandwich structure.Negative pole-film-anodal assembly and another sheet glass and sealing ring are assembled into battery by Fig. 3, inject 3mol L at side of the positive electrode
-12 milliliters of KOH solution, inject 3mol L in negative side
-1H
2SO
42 milliliters of solution.
Close switch K is with the anodal TiO of battery
2The terminal of film side links to each other with lead with negative terminal, and is anodal with ultraviolet irradiation, when treating that bubble appears in negative pole or positive pole, opens K switch, breaks off connecting negative pole TiO
2Film side and the anodal lead that is connected connect both positive and negative polarity with load respectively with lead and discharge.Fig. 4 be the irradiation of 300 watts of ultra-violet lamps after anodal 1 hour battery carry out the discharge curve of 30mA constant current discharge.
Embodiment seven: the routine of battery discharges and recharges
Get anatase titanium dioxide powder 0.1 gram (<400 order) and put into mortar and adhesive: POLYPROPYLENE GLYCOL (PVA) aqueous solution (concentration is 5wt.%) grinds, and the mass ratio of titanium dioxide and PVA is 1: 0.2.Be coated to area after mixing lentamente and be the film forming of drying in the shade on the indium tin oxide layer of conduction quartz glass of 2x2 square centimeter.Get 1 gram Co (OH)
2(<200 order) and anatase titanium dioxide powder (<400 order) are put into mortar and adhesive: POLYPROPYLENE GLYCOL (PVA) aqueous solution (concentration is 5wt.%) carries out ground and mixed, is coated on the nickel foam that area is the 1.5x1.5 square centimeter Co (OH)
2, TiO
2With the mass ratio of PVA be 1: 0.2: 0.15.After drying, scribble Co (OH) to nickel foam
2And TiO
2Face and tin indium oxide conduction quartz glass scribble TiO
2Towards right, place on the electro-conductive glass, 0.5 centimetre surplus limit is reserved on each limit of glass, at 100kg cm
-2The moulding of pressure pressed.Under nitrogen protection, 300 ℃ of heat treatment 60 minutes, cooling then makes the positive pole of battery.
Getting carbon carries palladium-copper alloy Pd/C (palladium content 40wt.%) 0.7 gram and put into mortar and adhesive: POLYPROPYLENE GLYCOL (PVA) aqueous solution (concentration is 5wt.%) carries out ground and mixed; Be coated on the foam copper that area is the 1.5x1.5 square centimeter, Pd/C, with the mass ratio of PVA be 1: 0.15.After drying, at 100kg cm
-2The moulding of pressure pressed.Under nitrogen protection, 300 ℃ of heat treatment 60 minutes, cooling then makes the negative pole of battery.
With relative with perfluoro sulfonic acid membrane and the anodal assembling of a side that scribbles PdCu/C of negative pole, form sandwich structure.Negative pole-film-anodal assembly and another sheet glass and sealing ring are assembled into battery by Fig. 3, inject 3mol L at side of the positive electrode
-12 milliliters of KOH solution, inject 3mol L in negative side
-12 milliliters of HCl solution.
Storage battery is through behind the constant current charge of 50mA, and the constant current with 50mA discharges again.Fig. 5 is the charging and discharging curve of battery under the room temperature.
What more than announce at last, only is specific embodiment of the present invention.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.