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CN101719571B - Battery capable of using light or electricity for charging - Google Patents

Battery capable of using light or electricity for charging Download PDF

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Publication number
CN101719571B
CN101719571B CN2009101549049A CN200910154904A CN101719571B CN 101719571 B CN101719571 B CN 101719571B CN 2009101549049 A CN2009101549049 A CN 2009101549049A CN 200910154904 A CN200910154904 A CN 200910154904A CN 101719571 B CN101719571 B CN 101719571B
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palladium
solution
tio
battery
storage battery
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CN101719571A (en
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李洲鹏
刘宾虹
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • Y02E60/10Energy storage using batteries

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Abstract

本发明涉及储能型电池,旨在提供一种既可以用太阳光也可以用电进行充电的蓄电池。该蓄电池以氢氧化钴和二氧化钛复合材料为正极材料,钯或钯铜合金为负极材料,正极侧加有碱溶液为阴极液,负极侧加有酸溶液为阳极液,阳离子交换树脂为隔膜,隔离正负两极以及碱溶液和酸溶液,碱溶液为氢氧化钾或氢氧化钠水溶液,酸溶液为盐酸或硫酸水溶液。本发明拓宽了蓄电池的充电方式。既可使用传统的方式利用直流电对蓄电池充电,又可以使用太阳光对蓄电池进行充电;无污染、无二氧化碳排放,环境友好;发电功能和储电功能的集约化使太阳能电池发电装置易于小型化;可广泛用于照明、家用电器、气象、地质、石油、铁路、航空、交通信号、农牧业特殊光源等领域。

Figure 200910154904

The invention relates to an energy storage battery, aiming to provide a storage battery that can be charged by both sunlight and electricity. The storage battery uses cobalt hydroxide and titanium dioxide composite materials as the positive electrode material, palladium or palladium copper alloy as the negative electrode material, an alkaline solution is added to the positive electrode side as the catholyte, an acid solution is added to the negative electrode side as the anolyte, and the cation exchange resin is used as the diaphragm. Positive and negative poles, alkali solution and acid solution, the alkali solution is potassium hydroxide or sodium hydroxide aqueous solution, and the acid solution is hydrochloric acid or sulfuric acid aqueous solution. The invention broadens the charging mode of the accumulator. The traditional method can be used to charge the battery with direct current, and the battery can be charged with sunlight; it has no pollution, no carbon dioxide emissions, and is environmentally friendly; the intensification of power generation and storage functions makes it easy to miniaturize the solar cell power generation device; Can be widely used in lighting, household appliances, meteorology, geology, petroleum, railways, aviation, traffic signals, special light sources for agriculture and animal husbandry and other fields.

Figure 200910154904

Description

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:
Figure G2009101549049D00031
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.

Claims (5)

1.一种可用光或电实现充电的蓄电池,以阳离子交换膜为隔膜,其特征在于,隔膜将正极侧的碱溶液和负极侧的酸溶液隔开;蓄电池的正极具有压制而成的复层结构,由外至内依次为:导电玻璃、涂覆于导电玻璃表面的TiO2层、加载于泡沫镍的氢氧化钴-TiO2混合物层、泡沫镍;蓄电池以加载于泡沫铜上的碳载钯或钯合金为负极;正极的泡沫镍、负极上加载的碳载钯或钯合金分别与隔膜相对安置,形成夹心结构:正极与隔膜之间为碱溶液,负极与隔膜之间为酸溶液;1. A storage battery that can be charged by light or electricity, with a cation exchange membrane as a diaphragm, is characterized in that the diaphragm separates the alkaline solution on the positive side from the acid solution on the negative side; the positive electrode of the storage battery has a pressed layer The structure, from outside to inside, is as follows: conductive glass, TiO2 layer coated on the surface of conductive glass, cobalt hydroxide- TiO2 mixture layer loaded on nickel foam, nickel foam; the storage battery is loaded on the carbon-loaded copper foam Palladium or palladium alloy is the negative electrode; nickel foam on the positive electrode and carbon-supported palladium or palladium alloy loaded on the negative electrode are respectively placed opposite to the diaphragm to form a sandwich structure: there is an alkaline solution between the positive electrode and the diaphragm, and an acid solution between the negative electrode and the diaphragm; 所述碱溶液为氢氧化钾或氢氧化钠水溶液,浓度为1~6mol L-1;所述酸溶液为盐酸或硫酸水溶液,浓度为1~6mol L-1The alkali solution is an aqueous potassium hydroxide or sodium hydroxide solution with a concentration of 1 to 6 mol L -1 ; the acid solution is an aqueous hydrochloric acid or sulfuric acid solution with a concentration of 1 to 6 mol L -1 ; 所述导电玻璃是涂覆氧化铟锡层的石英玻璃;The conductive glass is quartz glass coated with an indium tin oxide layer; 所述粘合剂为聚丙烯醇水溶液,浓度为5wt.%;The binder is an aqueous solution of polypropylene alcohol, and the concentration is 5wt.%. 所述正极通过下述方式制得:The positive electrode is prepared in the following manner: 取小于400目的锐钛矿型二氧化钛粉末放入研钵中,与作为粘合剂的浓度为5wt.%的聚丙烯醇水溶液进行研磨,二氧化钛与粘合剂的质量比为1∶0.1、或者1∶0.15、或者1∶0.2;混合均匀后涂敷到石英导电玻璃的氧化铟锡层上进行阴干成膜;取小于200目的Co(OH)2粉末、小于400目的锐钛矿型TiO2粉末,以及作为粘合剂的5wt.%聚丙烯醇水溶液,研磨混合,Co(OH)2、TiO2、聚丙烯醇的质量比为1∶0.1~0.3∶0.1~0.3;将混合物涂敷到泡沫镍上,晾干后将氧化铟锡导电玻璃涂有TiO2的面与加载于泡沫镍的氢氧化钴-TiO2混合物层相对,在100Kg cm-2的压力下压制成型,然后在惰性气体保护下300~500℃热处理10~60分钟,冷却;Take the anatase titanium dioxide powder of less than 400 meshes and put it into a mortar, and grind it with an aqueous solution of poly(propylene alcohol) with a concentration of 5wt.% as a binder, and the mass ratio of titanium dioxide to the binder is 1:0.1, or 1 : 0.15, or 1: 0.2; after mixing evenly, apply it on the indium tin oxide layer of quartz conductive glass to dry in the shade; take Co(OH) 2 powder less than 200 mesh, anatase TiO 2 powder less than 400 mesh, And 5wt.% polypropylene alcohol aqueous solution as binder, grinding and mixing, the mass ratio of Co(OH) 2 , TiO 2 , polypropylene alcohol is 1: 0.1~0.3: 0.1~0.3; the mixture is applied to foamed nickel After drying, the surface of the indium tin oxide conductive glass coated with TiO 2 is opposed to the cobalt hydroxide-TiO 2 mixture layer loaded on nickel foam, and it is pressed under a pressure of 100Kg cm -2 , and then under the protection of an inert gas Heat treatment at 300-500°C for 10-60 minutes, then cool; 所述负极通过下述方式制得:取含钯量为5~60wt.%的碳载钯或钯合金与作为粘合剂的5wt.%的聚丙烯醇水溶液研磨混合,其中钯与聚丙烯醇的质量比为1∶0.1~0.2;混合均匀后,将混合物涂敷泡沫铜上,晾干后在100Kg cm-2的压力下压制成型;然后在惰性气体保护下300~500℃热处理10~60分钟,冷却。The negative electrode is prepared by grinding and mixing carbon-supported palladium or palladium alloy containing 5-60wt.% palladium with 5wt.% polypropylene alcohol aqueous solution as a binder, wherein palladium and polypropylene alcohol The mass ratio is 1:0.1~0.2; after mixing evenly, the mixture is coated on the foamed copper, and after drying, press molding under the pressure of 100Kg cm -2 ; then heat treatment at 300~500℃ for 10~60 minutes, to cool. 2.根据权利要求1所述的蓄电池,其特征在于,所述TiO2为锐钛矿型TiO22 . The storage battery according to claim 1 , wherein the TiO 2 is anatase TiO 2 . 3.根据权利要求1所述的蓄电池,其特征在于,所述钯合金为钯铜合金:PdCux,x的范围为0<x≤1。3 . The storage battery according to claim 1 , wherein the palladium alloy is a palladium-copper alloy: PdCux , and the range of x is 0<x≤1. 4.根据权利要求1所述的蓄电池,其特征在于,所述导电玻璃是电池容器壁的组成部分。4. The battery of claim 1, wherein the conductive glass is an integral part of the wall of the battery container. 5.根据权利要求1所述的蓄电池,其特征在于,所述正极中,以粘合剂涂覆于导电玻璃表面的TiO2层、加载于泡沫镍的Co(OH)2-TiO2混合物层分别引出接线端子。5. accumulator according to claim 1 is characterized in that, in described positive pole, is coated on the TiO2 layer of conducting glass surface with binder, is loaded on the Co(OH) 2 - TiO2 mixture layer of nickel foam Lead out the terminals separately.
CN2009101549049A 2009-11-26 2009-11-26 Battery capable of using light or electricity for charging Expired - Fee Related CN101719571B (en)

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CN1411077A (en) * 2001-09-26 2003-04-16 北京科技大学 Nano titanium dioxide film and its manufacturing method
CN1571168A (en) * 2003-07-25 2005-01-26 鸿富锦精密工业(深圳)有限公司 Solar cell and electrodes thereof

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