CN102637896A - Photo-assisted chargeable lithium ion secondary battery - Google Patents
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- CN102637896A CN102637896A CN2012101163810A CN201210116381A CN102637896A CN 102637896 A CN102637896 A CN 102637896A CN 2012101163810 A CN2012101163810 A CN 2012101163810A CN 201210116381 A CN201210116381 A CN 201210116381A CN 102637896 A CN102637896 A CN 102637896A
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Abstract
The invention relates to a photo-assisted chargeable lithium ion secondary battery, belonging to a cross domain of a photo-electro-chemical solar battery and a lithium ion secondary battery. The battery consists of an anode, a diaphragm, a cathode, an electrolyte solution and a lead wire. The diaphragm is located between the anode and the cathode; an external circuit between the anode and the cathode is communicated by using the lead wire; and an internal circuit is communicated by using the electrolyte solution to form a closing loop; the anode is a photo-permeability anode used by the photo-electro-chemical solar battery; the cathode is a cathode used by the lithium ion secondary battery; the diaphragm is an oxidation-resistant diaphragm capable of transmitting lithium ions and iodide ions and not transmitting iodide molecules, and the diaphragm is used by the lithium ion secondary battery; and the electrolyte solution is an organic electrolyte solution used by a lithium ion secondary battery containing Lil and/or LiBr. The battery has great stored energy capacity and solves a self-discharging phenomenon. The stored chemical energy can stably exit. Meanwhile, the charging electric energy consumption can be saved by using low voltage to charge under illumination. The photo-assisted chargeable lithium ion secondary battery provided by the invention has the advantages of low cost, simple equipment and good repeatability.
Description
Technical field
The present invention relates to a kind of smooth auxiliary charging lithium rechargeable battery; Specifically; Be particularly related to a kind of new type light auxiliary charging lithium rechargeable battery that combines and form with photoelectricity conversion and secondary battery material, belong to the crossing domain of Optical Electro-Chemistry solar cell and lithium rechargeable battery.
Background technology
Optical Electro-Chemistry solar cell and the lithium rechargeable battery a very long time of large-scale commercial applications application, the developmental research of current material is also ripe all the more.In today,, all be unable to do without the application of battery no matter in where; In the natural deposit energy such as coal, oil day by day exhausted futures, electric energy will become the maximum source of supply of the energy.Since but the battery of first commercial application occurring in the research department from 18 beginnings of the century, the assembling form of the performance of battery material and battery is just always in constantly improving.At first, from the consideration to the macro environment protection, pollutant sources metals such as cadmium, mercury are replaced by green material gradually; Then, scientist begins to be devoted to improve the performance of battery, like opto-electronic conversion quantum efficiency, fill factor, curve factor, power density, energy density and security feature etc.; At last; Reach certain level in the battery material performance; Especially after can large-scale commercial applications using; Scientist and manufacturer begin to be devoted to the improvement of battery assembling form and outward appearance, make in the hope of reaching that battery realization volume is little when guaranteeing battery performance, light weight and characteristics such as elegant in appearance.
Although battery is already through there being development history for a long time, but still exist some that problem to be solved is arranged.Wherein, There are following shortcoming respectively in existing Optical Electro-Chemistry solar cell and lithium rechargeable battery: on the one hand, though the energy source solar energy of Optical Electro-Chemistry solar cell is natural, nexhaustible with free of contamination, be a very desirable energy source; But the photoelectric conversion efficiency of existing Optical Electro-Chemistry solar cell material is low; Be difficult to realize the photoelectric conversion efficiency more than 10%, in addition, its quantum efficiency and fill factor, curve factor are also unsatisfactory; Lithium rechargeable battery does not all reach perfect condition on energy density, power density and security performance, all in perfecting process progressively; On the other hand, the Optical Electro-Chemistry solar cell can only be used to the energy from the sun when fine day, and its electrode material and Optical Electro-Chemistry solar battery apparatus itself all do not have the energy storage effect; Lithium rechargeable battery can only merely rely on electric energy to be converted into chemical energy; Sole mode through the external charging facility charges; The user site does not have suitable electrically-charging equipment if the electric energy of lithium rechargeable battery exhausts, and then lithium rechargeable battery will can not use owing to charging; In addition, also there is the problem that the electric energy for low tension can't effectively utilize in lithium rechargeable battery.
For addressing the above problem, need a kind of can convergent light electrochemistry solar cell and the lithium rechargeable battery advantage in one, and the battery of environmental protection.Therefore, produced a kind of new ideas battery---light auxiliary charging lithium rechargeable battery.Light charging electrode material for using in the said smooth auxiliary charging lithium rechargeable battery begins that from 1880s correlative study is arranged.1980, Tributsch proposed the notion of light charging electrode material, thought that semiconductor combines lamellar compound can realize the double action of opto-electronic conversion and energy storage.Human CuFeTe such as T.Nomiyama subsequently
2Do light charging electrode material, use CuFeTe
2| LiClO
4| the Pt system is tested said material property, found the light charge effects at xenon lamp during as light source, but voltage has only tens millivolts, and is very low and unstable, and people such as T.Nomiyama have analyzed the influence of the structure of the compound that said material uses to the charging behavior.At the beginning of 21 century; People such as Xinjing Zou, Hiroyuki Usui study titanium dioxide and coated carbon nanotube material thereof in Japan; This research with the pulse laser method with the electro-deposition of titanium dioxide and coated carbon nanotube material thereof on electro-conductive glass; Same doing at xenon lamp found stable light charge effects under the light source condition, under illumination and the discharging current under the non-illumination reach as high as 0.8 μ A/cm
2, and contrasted in different atmosphere, under the different pressures and the electrode performance during different-grain diameter, analyzed the reason that makes a difference.The achievement in research of nearest relevant smooth charging electrode material is the Chien-Tsung Wang proposition by Taiwan; This research has prepared the electrode material of coated by titanium dioxide vanadic oxide with sol-gal process and supercritical drying, has studied the discharge and recharge behavior of said electrode material under ultraviolet lighting.Because the advantage that makes light charging electrode material have Optical Electro-Chemistry solar cell and lithium rechargeable battery concurrently is very difficult; Therefore; The performance index that existing smooth charging electrode material is less and relevant are also undesirable; So far do not occur as yet being applicable to that simultaneously photoelectricity transforms and electrical power storage, and the electrochemical appliance of well behaved smooth auxiliary charging.
Mainly there is following defective in the light charging electrode material of above-mentioned existing research: on the one hand; Oxidation or reduction reaction storage power take place in the semiconductor active material self that in charging process, only relies on the light charging electrode; Because the semiconductor active material on the light charging electrode exists with coating form; Active matter quality is few, so energy stored is very limited; On the other hand; Said smooth charging electrode material is arranged in same electrolytic cell as anodal and negative pole in light auxiliary charging lithium rechargeable battery; Do not adopt barrier film that positive pole and negative pole are separated, therefore anodal charged matter can be fallen by the ortho states material consumption of going back in the electrolyte solution very soon, and the chemical energy that causes said smooth auxiliary charging lithium rechargeable battery to store can't steady in a long-termly exist; Show weak point discharge time, the self-discharge phenomenon that the charging interval is long.
Summary of the invention
, the chemical energy that store limited to light auxiliary charging lithium rechargeable battery storage power in the prior art can't the defective that exist steady in a long-term; The object of the present invention is to provide a kind of smooth auxiliary charging lithium rechargeable battery, said battery can increase the storage power of said battery through transform the formation that combines of semiconductor positive electrode and lithium ion secondary battery negative pole lithium storage materials with the photoelectricity of Optical Electro-Chemistry solar cell; Solve self-discharge phenomenon; Make the chemical energy stable existence of storage, simultaneously, low voltage capable of using is charged to save rechargeable electrical energy consumption under illumination; With low cost, the simple and good reproducibility of equipment.
The objective of the invention is to realize through following technical scheme.
A kind of smooth auxiliary charging lithium rechargeable battery, said battery is made up of positive pole, barrier film, negative pole, electrolyte solution and lead; Wherein, barrier film makes positive pole and negative pole spatially have the structure of cellular-type between positive pole and negative pole, and external circuit is communicated with lead between positive pole and the negative pole, and interior circuit is communicated with electrolyte solution, constitutes the closed-loop path.
The said electrode that just very has light transmission mainly is made up of positive active material and plus plate current-collecting body, is the common employed positive pole of this area Optical Electro-Chemistry solar cell.Specifically, said positive active material comprises titanium dioxide (TiO
2), one or more the compound in zinc oxide, tin oxide, strontium titanates, tungsten oxide or the iron oxide, be solid or hollow microballoon, microtubule, little rod or the microfilament of nanometer to micro-meter scale.
Said plus plate current-collecting body is the common employed plus plate current-collecting body light transmissive material of this area Optical Electro-Chemistry solar cell, and specifically, said light transmissive material is the conducting high polymers thing film that has the electro-conductive glass of light transmission or have light transmission.Wherein, said electro-conductive glass is preferably the electro-conductive glass of tin indium oxide (ITO) electro-conductive glass, doped tin indium oxide or the zinc oxide transparent conducting glass (FTO electro-conductive glass) of doped with fluorine.Said conducting high polymers thing film need carry out surface conductance and modify; The method that said surface conductance is modified is the common employed surface conductance method of modifying of conducting high polymers thing film in the Optical Electro-Chemistry solar cell of this area; Specifically, said surface conductance method of modifying comprises chemical plating, electrochemistry plating, chemical bonding, vacuum evaporating, vacuum plating, hot pressing is compound and/or the macromolecule self assembly.
Said positive active material and anode collection bluk recombination are obtained positive pole; Said complex method is positive active material and the common employed method of anode collection bluk recombination in the Optical Electro-Chemistry solar cell of this area, and specifically, said complex method comprises sintering, vapor deposition, chemisorbed, physical absorption and/or chemical doping.Said anodal conduction one side contacts with electrolyte solution.
Said negative pole mainly is made up of negative electrode active material, conductive agent, adhesive and negative current collector, is the common employed negative pole of this area lithium rechargeable battery.Said negative pole conduction one side contacts with electrolyte solution.
Said barrier film is the common employed resistance to oxidation of this area lithium rechargeable battery, can sees through lithium ion and iodide ion, does not see through the barrier film of iodine molecule; Said barrier film is preferably Kynoar (PVDF) material barrier film.
Said electrolyte solution is the common employed organic electrolyte solution of this area lithium rechargeable battery, also contains LiI and/or LiBr as solute, takes on electrolyte and storage compound.
Beneficial effect
1. a kind of smooth auxiliary charging lithium rechargeable battery of the present invention; Support salt in the electrolyte solution is the salt that contains lithium ion; Because just very the Optical Electro-Chemistry solar cell uses the semi-conducting electrode material, the overpotential of the photo-electro chemical oxidation reaction of the anion of said support salt on said positive pole is very low under illumination condition, therefore; The charging voltage of battery according to the invention under illumination condition can reduce greatly; Reach 0.9 volt than the reduction of the charging voltage under the non-illumination condition, as auxiliary energy battery is charged owing to said battery can effectively utilize luminous energy, so; Reduced in the charging process the consumption of electric energy, more more superior than conventional lithium rechargeable battery;
2. a kind of smooth auxiliary charging lithium rechargeable battery of the present invention; Active solute LiI in the electrolyte solution and LiBr are liquid or solid (the electrode material form with embedding lithium state exist) by the product of electrolysis; The chemically stable degree of product is very high, can be stored in said inside battery safely; In addition, barrier film can effectively be avoided the interaction of both positive and negative polarity material and the mixing of Optical Electro-Chemistry product (charging product), so improved the fail safe of battery, has reduced the self discharge degree of battery; Said battery mainly carries out energy storage by the active solute LiI and the LiBr that contain in the organic electrolyte solution as storage compound, when the amount of said active solute increases, can significantly improve the energy of said battery storage;
3. a kind of smooth auxiliary charging lithium rechargeable battery of the present invention; Material with the chemical energy stores can discharge through the form of electrochemical reaction with electric energy; Realized under illumination condition, storing luminous energy, under non-illumination condition, used the purpose of electric energy, avoided the defective of Optical Electro-Chemistry solar cell " just can have when light is arranged; just do not have when having light ", and solved self-discharge phenomenon;
4. a kind of smooth auxiliary charging lithium rechargeable battery of the present invention, with low cost, equipment is simple, and good reproducibility has very strong market application foreground.
Description of drawings
Fig. 1 is the structural principle sketch map of a kind of smooth auxiliary charging lithium rechargeable battery among the embodiment.
Fig. 2 is X-ray diffraction (XRD) figure of titania powder among the embodiment.
Fig. 3 is scanning electron microscopy (SEM) figure of titania powder among the embodiment.
Fig. 4 is the linear volt-ampere curve figure of the positive pole of light auxiliary charging lithium rechargeable battery, control cell A and control cell B among the embodiment.
Fig. 5 is under illumination condition, among the embodiment light auxiliary charging lithium rechargeable battery in charging process, iodine molecule (I in the anodal side electrolyte solution of barrier film
2) the ultraviolet-visible spectrogram of concentration change.
Fig. 6 is the charging voltage variation diagram of light auxiliary charging lithium rechargeable battery under the filaments of sun and optical condition among the embodiment.
Among the figure: 1-plus plate current-collecting body, 2-positive active material, 3-barrier film, 4-negative current collector, 5-negative electrode active material, 6-lead.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is described further.
Embodiment
A kind of smooth auxiliary charging lithium rechargeable battery, as shown in Figure 1, said battery is made up of positive pole, barrier film 3, negative pole, electrolyte solution and lead 6; Wherein, barrier film 3 makes positive pole and negative pole spatially have the structure of cellular-type between positive pole and negative pole, is communicated with lead 6 between positive pole and the negative pole.
Said positive pole mainly is made up of positive active material 2 titania powders and plus plate current-collecting body 1FTO electro-conductive glass; Through titania powder is coated in above the FTO electro-conductive glass of 1cm * 1cm with coating method, to put into 500 ℃ of sintering 1h of Muffle furnace then and obtain said positive pole, the thickness of titania powder is 50 μ m.Wherein, said titania powder is the anatase titanium dioxide powder, and diffraction maximum is sharp-pointed, and crystalline form is better, and is as shown in Figure 2; Said titania powder is a micron particles, and particle is fine and smooth and be evenly distributed, and the particle diameter of primary particle is a submicron-scale, and certain reunion is arranged, and the particle diameter of offspring is micro-meter scale, and is as shown in Figure 3.
Said negative pole is mainly by negative electrode active material 5Li
4Ti
5O
12, conductive agent commodity super P by name, adhesive PVDF and negative current collector 4 Copper Foils form.With Li
4Ti
5O
12, super P and PVDF compressing tablet on the Copper Foil of 1cm * 1cm as the negative pole with embedding/lithium ionic insertion/deinsertion function, wherein Li
4Ti
5O
12Thickness be 100 μ m, the thickness of Copper Foil is 50 μ m.
Said electrolyte solution passes through LiI and LiClO
4Be dissolved in to dispose in propene carbonate (PC) solvent and obtain, consumption is 3cm
3, wherein, the concentration of LiI is 0.02mol/L, LiClO
4Concentration be 0.5mol/L.
It is following that the light auxiliary charging lithium rechargeable battery that present embodiment is prepared carries out performance test:
1. linear volt-ampere curve figure
The positive and negative electrode of the light auxiliary charging lithium rechargeable battery that present embodiment is made uses the positive and negative electrode of lead and CHI work station (CHI-660A, Shanghai occasion China) to be connected respectively; With silver (Ag) electrode is reference electrode, is connected through the reference electrode of lead with said CHI work station, with the sweep speed of 1mV/s; Under illumination and dark condition, test respectively, obtain the linear volt- ampere curve 1 and 3 among Fig. 4, wherein; Curve 1 is the linear volt-ampere curve of said anode under dark condition; Can know that from this curve said anode does not show tangible photoelectric effect under the dark condition of illumination not having, electric current is almost 0A; Curve 3 is the linear volt-ampere curve figure of said anode under illumination condition; Can know from this curve; When under illumination condition, receiving positive electrode potential that illumination excites and being 0.1V; Photoelectric current can reach 500 μ A, shows that positive active material 2 titanium dioxide have obviously been received to excite, and electron-hole pair occurs and separates.In addition; Also make positive active material 2 and be acetylene black; All the other control cell A and positive active materials 2 with present embodiment light auxiliary charging lithium rechargeable battery are Pt, and all the other are with the control cell B of present embodiment light auxiliary charging lithium rechargeable battery; Wherein, positive pole among control cell A and the B and present embodiment light auxiliary charging lithium rechargeable battery just has an equal light-receiving area.Under dark condition; Said control cell A and B to test with identical condition and the method for the said smooth auxiliary charging lithium rechargeable battery of present embodiment, are obtained the anodal linear volt-ampere curve 2 and the anodal linear volt-ampere curve 4 of control cell B of control cell A among Fig. 4; Fig. 4 below abscissa is English: the implication of Potential/V vs Ag-QRE is the electromotive force of Ag during as reference electrode.
2. under illumination condition, light auxiliary charging lithium rechargeable battery in charging process, the concentration change of iodine molecule in the barrier film 3 anodal side electrolyte solutions
Measure under illumination condition with the Hitachi-2800 spectrophotometer, under the different time, the concentration change of charging product obtains Fig. 5 to battery in the barrier film 3 anodal side electrolyte solutions in charging process.As shown in Figure 5, constantly carry out (t along with the charging interval
1, t
2And t
3), the iodine molecule concentration in the said electrolyte solution constantly increases, and these iodine molecules all come from iodide ion (I oxidized in the electrolyte solution
-); The increase of iodine molecule concentration has explained that oxidation product is retained in the space that is constituted between barrier film 3 and the positive pole; Explain that the said battery of present embodiment changes into electric energy and successfully storage through the photoelectricity conversion with luminous energy; Thereby realize effectively utilizing luminous energy, reduced in the charging process the consumption of electric energy and reduce self-discharge of battery as auxiliary energy.
Light auxiliary charging lithium rechargeable battery under dark condition with optical condition under charging behavior figure
Discharge and recharge appearance (Land) with commercialization present embodiment light auxiliary charging lithium rechargeable battery is carried out the charge-discharge performance test, obtain Fig. 6.Fig. 6 result shows that when charging reached 1h, under the dark condition of non-illumination, the charging voltage of said battery was near 2.9V, and charging voltage is near 2V under optical condition, and both compare, and the charging voltage under the optical condition approximately reduces 0.9V than the charging voltage under the dark condition.
The present invention includes but be not limited to above embodiment, every any replacement or local improvement of being equal to of under spirit of the present invention and principle, carrying out all will be regarded as within protection scope of the present invention.
Claims (9)
1. light auxiliary charging lithium rechargeable battery, it is characterized in that: said battery is made up of positive pole, barrier film (3), negative pole, electrolyte solution and lead (6); Wherein, barrier film (3) is between positive pole and negative pole, and external circuit is communicated with lead (6) between positive pole and the negative pole, and interior circuit is communicated with electrolyte solution, constitutes the closed-loop path; The used printing opacity of said just very Optical Electro-Chemistry solar cell is anodal; Negative pole is the used negative pole of lithium rechargeable battery; Barrier film (3) is the used resistance to oxidation of lithium rechargeable battery, can sees through lithium ion and iodide ion; Do not see through the barrier film (3) of iodine molecule, electrolyte solution is the used organic electrolyte solution of lithium rechargeable battery that contains LiI and/or LiBr.
2. a kind of smooth auxiliary charging lithium rechargeable battery according to claim 1; It is characterized in that: said positive pole is mainly by positive active material (2) and plus plate current-collecting body (1) compound composition; Positive active material (2) is one or more the compound in titanium dioxide, zinc oxide, tin oxide, strontium titanates, tungsten oxide or the iron oxide, is solid or hollow microballoon, microtubule, little rod or the microfilament of nanometer to micro-meter scale.
3. a kind of smooth auxiliary charging lithium rechargeable battery according to claim 2 is characterized in that: electro-conductive glass or the conducting high polymers thing film of plus plate current-collecting body (1) for having light transmission.
4. a kind of smooth auxiliary charging lithium rechargeable battery according to claim 3 is characterized in that: said electro-conductive glass is the electro-conductive glass of tin indium oxide electro-conductive glass, doped tin indium oxide or the zinc oxide transparent conducting glass of doped with fluorine.
5. a kind of smooth auxiliary charging lithium rechargeable battery according to claim 3 is characterized in that: said conducting high polymers thing film is carried out surface conductance modify.
6. a kind of smooth auxiliary charging lithium rechargeable battery according to claim 5 is characterized in that: said surface conductance method of modifying is chemical plating, electrochemistry plating, chemical bonding, vacuum evaporating, vacuum plating, hot pressing is compound and/or the macromolecule self assembly.
7. a kind of smooth auxiliary charging lithium rechargeable battery according to claim 2 is characterized in that: said positive active material (2) is sintering, vapor deposition, chemisorbed, physical absorption and/or chemical doping with the complex method of plus plate current-collecting body (1).
8. a kind of smooth auxiliary charging lithium rechargeable battery according to claim 1 is characterized in that: said negative pole mainly is made up of negative electrode active material (5), conductive agent, adhesive and negative current collector (4).
9. a kind of smooth auxiliary charging lithium rechargeable battery according to claim 1 is characterized in that: said barrier film (3) material is a Kynoar.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104409217A (en) * | 2014-11-24 | 2015-03-11 | 常州大学 | Photocathode and solar cell with same |
| CN106856152A (en) * | 2015-12-09 | 2017-06-16 | 中国科学院上海高等研究院 | Light strengthens electrochemical energy storing device structure and method |
| CN108183242A (en) * | 2017-11-20 | 2018-06-19 | 南京航空航天大学 | A kind of preparation method of novel lithium-air battery and its anode |
| CN109698378A (en) * | 2018-12-21 | 2019-04-30 | 华中科技大学 | A kind of light regulation lithium ion battery and preparation method thereof |
| CN115360358A (en) * | 2022-08-24 | 2022-11-18 | 哈尔滨工业大学 | An all-solid-state lithium battery based on light excitation and its application |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104409217A (en) * | 2014-11-24 | 2015-03-11 | 常州大学 | Photocathode and solar cell with same |
| CN106856152A (en) * | 2015-12-09 | 2017-06-16 | 中国科学院上海高等研究院 | Light strengthens electrochemical energy storing device structure and method |
| CN108183242A (en) * | 2017-11-20 | 2018-06-19 | 南京航空航天大学 | A kind of preparation method of novel lithium-air battery and its anode |
| CN108183242B (en) * | 2017-11-20 | 2021-01-08 | 南京航空航天大学 | A kind of lithium-air battery and preparation method of positive electrode thereof |
| CN109698378A (en) * | 2018-12-21 | 2019-04-30 | 华中科技大学 | A kind of light regulation lithium ion battery and preparation method thereof |
| CN115360358A (en) * | 2022-08-24 | 2022-11-18 | 哈尔滨工业大学 | An all-solid-state lithium battery based on light excitation and its application |
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Application publication date: 20120815 |