CN111244584A - Light charging polymer secondary battery and manufacturing method thereof - Google Patents
Light charging polymer secondary battery and manufacturing method thereof Download PDFInfo
- Publication number
- CN111244584A CN111244584A CN202010027064.6A CN202010027064A CN111244584A CN 111244584 A CN111244584 A CN 111244584A CN 202010027064 A CN202010027064 A CN 202010027064A CN 111244584 A CN111244584 A CN 111244584A
- Authority
- CN
- China
- Prior art keywords
- energy storage
- storage layer
- substrate
- counter electrode
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
- H01M14/005—Photoelectrochemical storage cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses a light charging polymer secondary battery and a manufacturing method thereof, relating to the field of solar batteries and comprising a light anode, a first energy storage layer, an electrolyte layer and a second energy storage layer, wherein the first energy storage layer contains an active substance A, the second energy storage layer contains an active substance B, and the oxidation-reduction potential of the active substance A is higher than that of the active substance B; the photo-anode is connected with the first energy storage layer and the second energy storage layer, the photo-anode can transmit generated electrons and holes to the second energy storage layer and the first energy storage layer respectively, and the connection between the photo-anode and the first energy storage layer and/or the connection between the photo-anode and the second energy storage layer can be disconnected; the second energy storage layer and the first energy storage layer can be connected by an external power line, and the second energy storage layer can transfer generated electrons to the first energy storage layer. The solar energy storage system has the advantages that the solar battery is combined with the secondary battery, direct conversion and storage from solar energy to chemical energy are realized, and the integration level of the energy storage system is improved.
Description
Technical Field
The invention relates to the field of solar cells, in particular to a light charging polymer secondary cell and a manufacturing method thereof.
Background
Energy problems are a significant problem facing today's society. Fossil energy accounts for more than 90% of the proportion of the current energy structure, and on one hand, the utilization of fossil energy generates a large amount of polluting gas, which causes great damage to the environment; on the other hand, as the scale of human exploitation and utilization is gradually increased, shortage and exhaustion of fossil energy is becoming reality. Therefore, it is necessary to find a safe, green alternative energy source. Solar energy is an inexhaustible renewable energy source, has the advantages of wide distribution, environmental protection, no pollution and the like, and is generally recognized as the most appropriate alternative energy source. In recent years, the photovoltaic industry has been vigorously developed. The silicon solar cell has high efficiency and good stability, but is expensive; although dye-sensitized solar cells (DSSCs) have the advantages of low cost, simple manufacturing process, suitability for large-scale production, etc., they also have the problem of poor long-term stability. In general, the current photovoltaic conversion technology of solar energy has been developed, but since solar energy is an intermittent and dispersive energy source, it is difficult to store it directly, so it has limited its wider application.
Electrochemical secondary batteries are a simple and efficient electrical energy storage technology and are widely used in the field of electricity storage. However, the battery can only store and utilize energy through the interconversion between electric energy and chemical energy, and cannot directly store solar energy. It is common practice to convert solar energy into electrical energy and then convert the electrical energy into chemical energy for storage, specifically, to connect a photovoltaic cell with an additional electrochemical secondary cell: when the solar energy storage device is illuminated, the photocell is excited by light to generate voltage and photocurrent, and a secondary battery of an external circuit is charged to store energy. The model has the advantages of complex structure, large volume and high cost, and the energy loss of each step of reaction is considered due to multiple times of energy conversion, so that the overall energy efficiency is not too high.
Disclosure of Invention
The present invention is directed to solve at least one of the problems of the prior art, and provides a rechargeable polymer battery with low energy loss and a method for manufacturing the same.
The technical solution of the first aspect of the invention is as follows:
a light charging polymer secondary battery comprises a first energy storage layer, an electrolyte layer, a second energy storage layer and a light anode which can convert absorbed solar energy into electron-hole pairs and can transmit the electron-hole pairs, wherein the first energy storage layer contains an active substance A, the second energy storage layer contains an active substance B, the electrolyte layer contains an electrolyte, the oxidation-reduction potential of the active substance A is higher than that of the active substance B, and the first energy storage layer, the electrolyte layer and the second energy storage layer are in contact in sequence;
the photoanode is connected with the first energy storage layer and the second energy storage layer, and can transfer generated electrons to the second energy storage layer to enable the active substance B to perform positive and negative reactions of a second reversible reaction; meanwhile, the photoanode can transfer the generated holes to the first energy storage layer to enable the active substance A to generate positive and negative reactions of a first reversible reaction, and the connection between the photoanode and the first energy storage layer and/or the connection between the photoanode and the second energy storage layer can be disconnected;
the second energy storage layer and the first energy storage layer can be connected through an external power line, so that the active material B can perform reverse reaction of the second reversible reaction to generate electrons, the generated electrons can be transmitted to the second energy storage layer through the power line, and the active material A can perform reverse reaction of the first reversible reaction after the first energy storage layer obtains the electrons.
Preferably, the photo-anode includes a substance C having redox properties, the redox potential of the substance C is higher than the redox potential of the active substance a, both the first reversible reaction and the second reversible reaction are redox reactions, the forward reaction of the first reversible reaction is an oxidation reaction, the reverse reaction of the first reversible reaction is a reduction reaction, the forward reaction of the second reversible reaction is a reduction reaction, and the reverse reaction of the second reversible reaction is an oxidation reaction.
As a preferred technical solution, the energy storage device further comprises a first substrate which has a pore structure and can conduct electricity, and the electrolyte can contact with the first energy storage layer through the pore structure on the first substrate; the first energy storage layer is connectable to the second energy storage layer through the first substrate.
As a preferable technical solution, the counter electrode further includes a counter electrode substrate, and further includes a counter electrode substrate, the second energy storage layer is modified on the surface of the counter electrode substrate, the first energy storage layer is modified on the surface of the photo-anode, the first energy storage layer, the first substrate, the electrolyte layer, the second energy storage layer, and the counter electrode substrate are sequentially stacked, the second energy storage layer is connected to the photo-anode and the first substrate through the counter electrode substrate, the counter electrode substrate is connected to the photo-anode through an external circuit capable of controlling on-off, and the counter electrode substrate is connected to the first substrate through the power utilization circuit capable of controlling on-off.
As a preferred technical scheme, the active substance A comprises one or more of polyaniline and derivatives thereof, polythiophene and polythiophene derivatives; the active substance B comprises one or more of polypyrrole and polypyrrole derivatives.
Preferably, the electrolyte layer is a solid electrolyte layer.
The technical solution of the second aspect of the invention is as follows:
a method for manufacturing a light charging polymer secondary battery is characterized by comprising the following steps:
s1, modifying the first energy storage layer on the surface of the photo-anode;
s2, modifying the second energy storage layer on the surface of the counter electrode substrate;
s3, closely attaching a first substrate to the upper surface of the first energy storage layer;
s4, placing absorbent paper on the upper surface of the first substrate, placing the counter electrode processed in the step S2 on the upper surface of the absorbent paper, clamping the photo-anode and the counter electrode, and injecting liquid electrolyte into the absorbent paper; alternatively, a solid electrolyte is placed on the upper surface of the first substrate, the counter electrode processed in step S2 is placed on the upper surface of the solid electrolyte, and then the photo-anode and the counter electrode are clamped.
Preferably, the modification method in step S1 includes: immersing a photoanode into electroplating solution containing an active substance A monomer, taking the photoanode as a working electrode, an inert material as a counter electrode, and Ag/Ag + as a reference electrode at a concentration of 60-00 mW/cm2Under light intensity, at 5-5 muA/cm2The current photoelectrochemistry in situ polymerization is carried out for 5-60 min.
Preferably, the modification method in step S2 includes: immersing the counter electrode in an electroplating solution containing active material B monomer, using the counter electrode as working electrode, Ag/Ag+And polymerizing for 90-50 min at a constant voltage of 0.2-0.6V relative to the reference electrode.
As a preferred technical solution, the method for preparing the solid electrolyte in step S4 includes: LiClO is added4Dissolving in acrylic acid, adding white carbon black, fully stirring, and adding an initiator to obtain a solid electrolyte; wherein 0.02-0.025 g LiClO is added into each milliliter of acrylic acid4，LiClO4The concentration of the white carbon black is 0.05-0.2mol/L, and the adding amount of the white carbon black is LiClO445-50% of the mass, and the addition amount of the initiator is LiClO40.9 to 1.2% by mass.
The invention has the beneficial effects that: the solar cell only capable of energy conversion is combined with the secondary cell only capable of energy storage and release, and in the process of light charging, the solar cell only capable of energy conversion is stored in the second energy storage layer by taking the photo-anode as the anode and the second energy storage layer as the cathode through converting solar energy into chemical energy; when no light is discharged, the second energy storage layer serves as a cathode, the first energy storage layer serves as an anode, so that chemical energy is converted into electric energy to be used by an electric device, direct conversion and storage from solar energy to chemical energy can be realized, the integration level of an energy storage system is improved, direct utilization of solar energy can be realized, and storage of solar energy can also be realized; and the consumption of the active substance A in the first energy storage layer, the active substance B in the second energy storage layer and the electrolyte is very small through a light charging and non-light discharging process, and the battery can return to the most initial state, so that infinite charge-discharge cycles of the battery can be realized theoretically.
Drawings
FIG. 1 is a schematic structural view of example 1;
FIG. 2 is a schematic structural view of example 2;
FIG. 3 is a schematic view of the charging principle of the batteries in examples 1 and 2;
FIG. 4 is a schematic view showing the principle of discharge of the batteries in examples 1 and 2;
reference numerals: 1. a photo-anode; 11. a conductive substrate; 12. a dye-sensitized nanoporous semiconductor film; 2. a first electrode; 21. a first substrate 22, a first energy storage layer; 3. a counter electrode; 31. a counter electrode substrate; 32. a second energy storage layer; 4. an electrolyte layer; 41. absorbent paper.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
As shown in fig. 1, a photo-chargeable polymer secondary battery includes a photo-anode 1, a first energy storage layer 22, a first substrate 21, an electrolyte layer 4, and a counter electrode 3.
The photo-anode 1 includes a substance C having oxidation-reduction property, and in this embodiment, the photo-anode 1 includes a conductive substrate 11 and a dye-sensitized nanoporous semiconductor thin film formed on the surface of the conductive substrate 11, and the substance C is a dye. In this embodiment, the conductive substrate 11 is a conductive glass, a nanoporous semiconductorThe film being TiO2The coating and the dye are carboxylic acid polypyridine ruthenium dye. In practical application, the conductive substrate 11 may also be made of other conductive materials, and the nanoporous semiconductor film may also be SnO2And the dye may also be a phosphonic acid polypyridine ruthenium dye, a polynuclear bipyridine ruthenium dye, or the like, and may be flexibly selected by a person skilled in the art according to the actual situation, and the structure and the preparation method of the photoanode 1 are well known by a person skilled in the art, and are not described in detail in this embodiment.
The first energy storage layer 22 contains an active material a, and the oxidation-reduction potential of the dye is higher than that of the active material a. The active material a can perform a first reversible reaction with the electrolyte in the electrolyte layer 4, where the first reversible reaction includes a forward reaction and a reverse reaction, in this embodiment, the active material a is a polymer, specifically, the active material a is polyaniline, in practical applications, the active material a may also be one or more of polyaniline derivatives, polythiophene, and derivatives thereof, and the first reversible reaction is a redox reaction. In this embodiment, the first energy storage layer 22 is modified on the surface of the photo-anode 1.
The first substrate 21 is a conductive material having a pore structure so that an electrolyte can contact the first energy storage layer 22 through the pore structure on the first substrate 21, and the first energy storage layer 22 can be connected to the second energy storage layer 32 through the first substrate 21, thereby facilitating the connection of the first energy storage layer 22 to the photo-anode 1 and the second energy storage layer 22 through the first substrate 21. In this embodiment, the first substrate 21 is a carbon felt, and in practical applications, the first substrate 21 may also be a porous fiber conductive material, and the like, and those skilled in the art may select the substrate flexibly according to actual situations. In this embodiment, the first substrate 21 and the first energy storage layer 22 constitute a first electrode.
The electrolyte layer 4 includes a water-absorbent paper 41 and an electrolyte solution adsorbed on the water-absorbent paper 41, in this embodiment, the electrolyte solution is a liquid electrolyte, the liquid electrolyte is adsorbed on the water-absorbent paper 41 to form the electrolyte layer 4, and the liquid electrolyte is a liquid electrolyte containing LiClO4An organic solution of a lithium salt.
The counter electrode 3 includes a counter electrode substrate 31 and a second energy storage layer 32; in this embodiment, the counter electrode substrate 31 includes a base material and a conductive layer formed on the surface of the base material, the base material is conductive glass, the conductive layer is platinum, in practical application, the base material may also be other substances, and the conductive layer may also be carbon, which can be flexibly selected by a person skilled in the art according to practical situations. The structure and the preparation method of the electrode substrate 31 are well known to those skilled in the art, and are not described in detail in this embodiment. The second energy storage layer 32 contains an active material B, and the oxidation-reduction potential of the active material a is higher than that of the active material B. The active material B is capable of undergoing a second reversible reaction with the electrolyte in the electrolyte layer 4, which in this embodiment is a redox reaction. In this embodiment, the active substances B are all polymers, specifically, the active substance B is polypyrrole, and in practical application, the active substance B may also be one or more of polypyrrole derivatives. In this embodiment, the second energy storage layer 32 is modified on the electrode substrate 31, so that the second energy storage layer 32 is connected to the photo-anode 1 and the first energy storage layer 22.
The photo-anode 1, the first energy storage layer 22, the first substrate 21, the electrolyte layer 4, the second energy storage layer 32 and the counter electrode substrate 31 are sequentially laminated together, the counter electrode substrate 31 is connected with the photo-anode 1 through a first external circuit capable of controlling on-off, and the counter electrode substrate 31 is connected with the first substrate 21 through an external power utilization circuit capable of on-off, wherein the external power utilization circuit is an external power utilization appliance in the embodiment; when sunlight irradiates on the photoanode 1, a first external circuit is connected, and the dye molecules absorb photons to transition from a ground state to an excited state; the excited dye molecule splits into electron-hole pairs (D + h +, e-) which transfer electrons into TiO2The Conduction Band (CB) itself becomes a hole (D +), so that the photo-anode 1 transfers the generated electron to the counter electrode substrate 31 through the first external circuit, and then transfers the electron from the counter electrode substrate 31 to the second energy storage layer 32 to cause the doped polypyrrole to undergo a reduction reaction to generate polypyrrole, and at the same time, the photo-anode 1 transfers the generated hole to the first energy storage layer 22 to cause the polyaniline and the electrolyte to undergo an oxidation reaction, which is the charging process of the battery. When the polypyrrole is communicated with the electrolyte through the external circuit, the polypyrrole can generate oxidation reaction with the electrolyte to generate electrons, and the generated electrons are transferred to the electrolyte through the external circuitThe first substrate 21 is transferred from the first substrate 21 to the first energy storage layer 22, so that polyaniline obtains electrons to undergo a reduction reaction and is reduced, thereby completing the discharge process of the battery.
The battery in the present embodiment combines a solar cell capable of only energy conversion with a secondary cell capable of only energy storage and release, thereby enabling not only direct conversion and storage of solar energy to chemical energy; in addition, the active substances A and B and the electrolyte are very little consumed in a light charging and non-light discharging process, and the battery can return to the most initial state, so that infinite charge-discharge cycles of the battery can be realized theoretically. Meanwhile, the battery in the embodiment has the advantages of compact structure, small volume and portability.
Example 2
Example 2 provides a photo-chargeable polymer secondary battery, and example 2 is different from example 1 in that: the electrolyte layer 4 in example 2 is a solid electrolyte layer, and thus the battery has a structure in which the photo-anode 1, the first energy storage layer 22, the first substrate 21, the solid electrolyte layer 4, the second energy storage layer 32, and the counter electrode substrate 31 are sequentially laminated, and the other structures are the same as in example 1. The solid electrolyte has the characteristics of stable performance and structure and can avoid the short circuit of the positive electrode and the negative electrode, and the solid electrolyte can reduce or avoid the problems of quick battery attenuation and poor cycle life caused by the volatile characteristic of the liquid electrolyte, so that the service life of the battery is prolonged.
The charge and discharge principle of the batteries in the embodiment 1 and the embodiment 2 is shown in fig. 3 and fig. 4, and in the photo-charging process, the battery is regarded as an electrolytic cell, the photo-anode is an anode, the counter electrode is a cathode, and the first electrode 2 is in an idle state; in the absence of light discharge, the counter electrode 3 is defined as the negative electrode and the first electrode 2 as the positive electrode, and the photo-anode 1 is idle.
As shown in fig. 3, the photo anode 1 and the counter electrode 3 are connected and the counter electrode 3 and the first electrode 2 are disconnected during the photo charging process. When sunlight irradiates on the photoanode 1, dye molecules in the photoanode 1 absorb photons to transition from a ground state to an excited state; the excited dye molecule splits into electron-hole pairs (D x (h +,e-)) to transfer electrons into the TiO2The Conduction Band (CB) of (a), itself becomes a hole (D +); the electrons reach the counter electrode 3 via a first external circuit, and the doped state of the [ polymer B ] is formed on the surface of the counter electrode 3+ClO4 -]Reduction to Polymer B with ClO4 -Returning to the electrolyte to charge (remove impurities) the active material B of the electrode 3; the holes are transferred to the polymer A to form the polymer A+Of polymer A+Then with ClO in the electrolyte4 -Formation by electrostatic interaction [ Polymer A+ClO4 -]Charging (doping) of the active material a is completed.
As shown in fig. 4, the discharging process in the absence of light is just opposite to the charging process, the photo anode 1 and the counter electrode 3 are disconnected, the counter electrode 3 and the first electrode 2 are connected, and after photo-charging, electrons can spontaneously flow from the polymer B to the first electrode 2 through an external power line, so that work is applied to an external circuit electric appliance to realize discharging, [ polymer a ] the polymer B is charged by light, and then the electric appliance is charged by light to realize+ClO4 -]Is reduced and dedoped to obtain polymer A, ClO4 -Returning to the electrolyte; the polymer B on the counter electrode 3 is oxidized to the polymer B+And with ClO in the electrolyte4 -Combined to complete doping to obtain [ B+ClO4 -]And the regeneration of active substances is realized.
The discharge reaction equation under the condition of light charge and no light is shown as follows:
reaction of the photo-anode 1 during photo-charging:
Dye+hγ→Dye*(h+,e-) (1)
Dye*(h+,e-)+TiO2→e-(TiO2)+Dye*+(2)
Dye*++ Polymer A + xClO4 -→ Polymer Ax+·xClO4 -+Dye (3)
Reaction to electrode 3 during photo-charging:
polymer Bx+·xClO4 -+e-(TiO2) → Polymer B + xClO4 -(4)
The general reaction equation in the process of photo-charging:
polymer A + Polymer Bx+·xClO4 -→ Polymer Ax+·xClO4 -+ Polymer B (5)
Reaction on electrode 3 during discharge in the absence of light:
polymer B + xClO4 -→ Polymer Bx+·xClO4 -+xe-(6)
Reaction of the first electrode during discharge:
polymer Ax+·xClO4 -+xe-→ Polymer A + xClO4 -(7)
The general chemical reaction equation in the discharge process is as follows:
polymer B + Polymer Ax+·xClO4 -→ Polymer A + Polymer Bx+·xClO4 -(8)
Example 3
This embodiment is a method for manufacturing the battery of embodiment 1, and includes the following steps:
s1, modifying the first energy storage layer 22 on the surface of the photo-anode 1, wherein the specific modification method comprises the following steps: the photoanode 1 was immersed in a plating solution containing a monomer of active material A, which contained 0.01mol/L of the monomer of active material A and 0.1mol/L of LiClO4The acetonitrile solution takes the photo anode 1 as a working electrode, an inert material as a counter electrode and Ag/Ag + as a reference electrode at 80mW/cm2Under light intensity, at 10 μ A/cm2The current photoelectrochemistry in-situ polymerization is carried out for 30 min;
s2, modifying the second energy storage layer 32 on the surface of the counter electrode substrate 31, the specific modification method is as follows: the method for modifying the surface of the counter electrode 3 with the active material B comprises the following steps: the counter electrode 3 was immersed in a plating solution containing a monomer of active material B, the plating solution containing 0.01mol/L of the monomer of active material B and 0.1mol/L of LiClO4With the counter electrode 3 as the working electrode, Ag/Ag+As a reference electrode, polymerization was carried out at a constant pressure of 0.4V relative to the reference electrodeAnd (4) performing treatment for 120 min.
S3, the first substrate 21 is closely attached to the upper surface of the first energy storage layer 22 and led out towards the left end and the right end of the first energy storage layer 22, the first substrate 21 and the conductive substrate 11 of the photoanode 1 are separated by transparent adhesive, and the first substrate 21 is only contacted with the first energy storage layer 22;
s4, placing the water absorbing paper 41 on the upper surface of the first substrate 21, placing the counter electrode 3 processed in the step S2 on the upper surface of the water absorbing paper 41, clamping the photo anode 1 and the counter electrode 3, and injecting liquid electrolyte into the water absorbing paper 41 by using an injector to obtain the battery.
Example 4
This embodiment is a method for manufacturing a battery in embodiment 2, and the difference between this embodiment and embodiment 3 is:
s4, placing a solid electrolyte on the upper surface of the first substrate 21, placing the counter electrode 3 processed in the step S2 on the upper surface of the solid electrolyte, and clamping the photo-anode 1 and the counter electrode 3 to obtain the battery. The preparation method of the solid electrolyte comprises the following steps: 1.06g of LiClO4Dissolving in 50mL of acrylic acid, adding 0.5g of fumed silica, fully stirring, and adding 0.01g of initiator azobisisobutyronitrile to obtain the solid electrolyte.
The above are merely characteristic embodiments of the present invention, and do not limit the scope of the present invention in any way. All technical solutions formed by equivalent exchanges or equivalent substitutions fall within the protection scope of the present invention.
Claims (10)
1. A rechargeable polymer battery, comprising a first energy storage layer (22), an electrolyte layer (4), a second energy storage layer (32) and a photoanode (1) capable of converting absorbed solar energy into electron-hole pairs and transferring the electron-hole pairs, wherein the first energy storage layer (22) contains an active material A, the second energy storage layer (32) contains an active material B, the electrolyte layer (4) comprises an electrolyte, the oxidation-reduction potential of the active material A is higher than that of the active material B, and the first energy storage layer (22), the electrolyte layer (4) and the second energy storage layer (32) are in contact in sequence;
the photoanode (1) is connected with the first energy storage layer (22) and the second energy storage layer (32), and the photoanode (1) can transfer generated electrons to the second energy storage layer (32) to enable positive reaction of a second reversible reaction of the active substance B; meanwhile, the photoanode (1) can transfer the generated holes to the first energy storage layer (22) to enable positive and negative reactions of the first reversible reaction of the active substance A to occur, and the connection between the photoanode (1) and the first energy storage layer (22) and/or the connection between the photoanode and the second energy storage layer (32) can be disconnected;
the second energy storage layer (32) and the first energy storage layer (22) can be connected by an external electric line, and can cause the active material B to undergo a reverse reaction of the second reversible reaction to generate electrons and can transmit the generated electrons to the first energy storage layer (22) through the electric line, and the first energy storage layer (22) can cause the active material A to undergo a reverse reaction of the first reversible reaction after obtaining the electrons.
2. A rechargeable polymer secondary battery as claimed in claim 1, characterized in that the photoanode (1) contains a substance C having redox properties, the redox potential of which is higher than that of the active substance a; the first reversible reaction and the second reversible reaction are both redox reactions, the forward reaction of the first reversible reaction is an oxidation reaction, the reverse reaction of the first reversible reaction is a reduction reaction, the forward reaction of the second reversible reaction is a reduction reaction, and the reverse reaction of the second reversible reaction is an oxidation reaction.
3. A rechargeable polymer secondary battery as claimed in claim 1, characterized by further comprising a first substrate (21) having a pore structure and being capable of conducting electricity, said electrolyte being capable of contacting said first energy storage layer (22) through the pore structure on said first substrate (21); the first energy storage layer (22) can be connected to the second energy storage layer (32) via the first substrate (21).
4. A rechargeable polymer battery as claimed in claim 3, characterized by further comprising a counter electrode substrate (31), the second energy storage layer (32) is modified on the surface of the counter electrode substrate (31), the first energy storage layer (22) is modified on the surface of the photo-anode (1), the first energy storage layer (22), the first substrate (21), the electrolyte layer (4), the second energy storage layer (32) and the counter electrode substrate (31) are sequentially stacked, the second energy storage layer (32) is connected with the photo-anode (1) and the first substrate (21) through the counter electrode substrate (31), the counter electrode substrate (31) is connected with the photo-anode (1) through an external circuit capable of controlling the on-off, the counter electrode substrate (31) and the first substrate (21) are connected by the power line which can be controlled to be on and off.
5. A rechargeable polymer secondary battery as claimed in claim 1, wherein said active material a comprises one or more of polyaniline and its derivatives and polythiophene and its derivatives; the active substance B comprises one or more of polypyrrole and polypyrrole derivatives.
6. A rechargeable polymer secondary battery as claimed in claim 1, characterized in that the electrolyte layer (4) is a solid electrolyte layer.
7. A method for manufacturing a light charging polymer secondary battery is characterized by comprising the following steps:
s1, modifying the first energy storage layer (22) on the surface of the photo-anode (1);
s2, modifying the second energy storage layer (32) on the surface of the counter electrode substrate (31);
s3, closely attaching a first substrate (21) to the upper surface of the first energy storage layer (22);
s4, placing absorbent paper (41) on the upper surface of the first substrate (21), placing the counter electrode (3) processed in the step S2 on the upper surface of the absorbent paper (41), clamping the photo-anode (1) and the counter electrode (3), and injecting liquid electrolyte into the absorbent paper (41); alternatively, a solid electrolyte is placed on the upper surface of the first substrate (21), the counter electrode (3) processed in step S2 is placed on the upper surface of the solid electrolyte, and then the photo-anode (1) and the counter electrode (3) are clamped.
8. The method as claimed in claim 7, wherein the modification of step S1 includes: immersing the photo-anode (1) into an electroplating solution containing an active substance A monomer, taking the photo-anode (1) as a working electrode, an inert material as a counter electrode, Ag/Ag + as a reference electrode, and controlling the concentration of the Ag/Ag + in the electroplating solution at 60-100 mW/cm2Under the light intensity, the light intensity is 5-15 muA/cm2The current photoelectrochemistry in situ polymerization is carried out for 15-60 min.
9. The method as claimed in claim 7, wherein the modification of step S2 includes: immersing the counter electrode (3) in an electroplating solution containing an active material B monomer, using the counter electrode (3) as a working electrode, Ag/Ag+And polymerizing for 90-150 min at a constant voltage of 0.2-0.6V relative to the reference electrode.
10. A rechargeable polymer secondary battery as claimed in claim 7, wherein the method of preparing the solid electrolyte in step S4 includes: LiClO is added4Dissolving in acrylic acid, adding white carbon black, fully stirring, and adding an initiator to obtain a solid electrolyte; wherein 0.02-0.025 g LiClO is added into each milliliter of acrylic acid4，LiClO4The concentration of the white carbon black is 0.05-0.2mol/L, and the adding amount of the white carbon black is LiClO445-50% of the mass, and the addition amount of the initiator is LiClO40.9 to 1.2% by mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010027064.6A CN111244584A (en) | 2020-01-10 | 2020-01-10 | Light charging polymer secondary battery and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010027064.6A CN111244584A (en) | 2020-01-10 | 2020-01-10 | Light charging polymer secondary battery and manufacturing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111244584A true CN111244584A (en) | 2020-06-05 |
Family
ID=70870820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010027064.6A Pending CN111244584A (en) | 2020-01-10 | 2020-01-10 | Light charging polymer secondary battery and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111244584A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19926318A1 (en) * | 1999-06-09 | 2000-12-14 | Horst Ahlers | Electrical energy storage device for autonomous current supply for electrical device uses storage battery in combination with solar cell device for topping-up battery charge |
| US20070051403A1 (en) * | 2005-09-02 | 2007-03-08 | Konica Minolta Business Technologies, Inc. | Photoelectric Converter and Dye Sensitized Solar Cell |
| CN101567273A (en) * | 2009-06-04 | 2009-10-28 | 福州大学 | Energy storage type dye-sensitized solar cell with tripolar structure and preparation method thereof |
| CN102768908A (en) * | 2012-07-20 | 2012-11-07 | 合肥工业大学 | Energy storage dye sensitization solar battery and preparation method thereof |
| CN104321844A (en) * | 2013-03-22 | 2015-01-28 | 松下电器产业株式会社 | Photoelectric conversion element |
| CN106785243A (en) * | 2017-02-28 | 2017-05-31 | 南开大学 | Light fills secondary cell |
| CN206412412U (en) * | 2016-10-21 | 2017-08-15 | 苏州今道创业投资有限公司 | A kind of light charging secondary battery construction |
| CN107256926A (en) * | 2017-05-12 | 2017-10-17 | 哈尔滨工业大学深圳研究生院 | Solar energy and the dual-purpose battery device of ion energy storage and preparation method thereof |
-
2020
- 2020-01-10 CN CN202010027064.6A patent/CN111244584A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19926318A1 (en) * | 1999-06-09 | 2000-12-14 | Horst Ahlers | Electrical energy storage device for autonomous current supply for electrical device uses storage battery in combination with solar cell device for topping-up battery charge |
| US20070051403A1 (en) * | 2005-09-02 | 2007-03-08 | Konica Minolta Business Technologies, Inc. | Photoelectric Converter and Dye Sensitized Solar Cell |
| CN101567273A (en) * | 2009-06-04 | 2009-10-28 | 福州大学 | Energy storage type dye-sensitized solar cell with tripolar structure and preparation method thereof |
| CN102768908A (en) * | 2012-07-20 | 2012-11-07 | 合肥工业大学 | Energy storage dye sensitization solar battery and preparation method thereof |
| CN104321844A (en) * | 2013-03-22 | 2015-01-28 | 松下电器产业株式会社 | Photoelectric conversion element |
| CN206412412U (en) * | 2016-10-21 | 2017-08-15 | 苏州今道创业投资有限公司 | A kind of light charging secondary battery construction |
| CN106785243A (en) * | 2017-02-28 | 2017-05-31 | 南开大学 | Light fills secondary cell |
| CN107256926A (en) * | 2017-05-12 | 2017-10-17 | 哈尔滨工业大学深圳研究生院 | Solar energy and the dual-purpose battery device of ion energy storage and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lv et al. | Photoelectrochemical energy storage materials: design principles and functional devices towards direct solar to electrochemical energy storage | |
| Saito et al. | Application of poly (3, 4-ethylenedioxythiophene) to counter electrode in dye-sensitized solar cells | |
| Zhang et al. | An organic electroactive material for flow batteries | |
| McKone et al. | Solar energy conversion, storage, and release using an integrated solar-driven redox flow battery | |
| Yan et al. | Solar rechargeable redox flow battery based on Li 2 WO 4/LiI couples in dual-phase electrolytes | |
| Ikeda et al. | Conductive polymer–carbon–imidazolium composite: a simple means for constructing solid-state dye-sensitized solar cells | |
| WO2012162390A1 (en) | Flow battery and mn/v electrolyte system | |
| CN103247816A (en) | Semi-solid flow cell | |
| Nagai et al. | Energy-storable dye-sensitized solar cell with a polypyrrole electrode | |
| CN102867978B (en) | Flow energy storage battery structure | |
| Lei et al. | A solar rechargeable battery based on hydrogen storage mechanism in dual-phase electrolyte | |
| Lei et al. | A quasi-solid-state solar rechargeable battery with polyethylene oxide gel electrolyte | |
| CN103633330B (en) | A kind of flow battery combination electrode and liquid flow energy storage battery | |
| CN112490477B (en) | Aqueous all-organic mixed liquid flow battery based on conjugated microporous polymer negative electrode containing redox active side group unit | |
| CN101630594B (en) | Preparation method of composite membrane counter electrode used for dye-sensitized solar cells | |
| CN104916884A (en) | Photo-electrochemical redox flow energy storage battery with vanadium compound as active substance | |
| Jin et al. | Graphene tailored gel electrolytes for quasi-solid-state quantum dot-sensitized solar cells | |
| CN107275095B (en) | A kind of compound lithium ion secondary battery that can be charged with dye sensitization of solar | |
| Di et al. | Available photo-charging integrated device constructed with dye-sensitized solar cells and lithium-ion battery | |
| CN108364792A (en) | A kind of preparation method and applications of nickel cobalt selenium hollow ball-shape multilevel structure material | |
| CN107946624A (en) | A kind of water system full stress-strain flow battery and its construction method and application based on indigo derivative | |
| CN110676073A (en) | Electrolyte, enhanced all-solid-state flexible supercapacitor based on electrolyte and preparation method of enhanced all-solid-state flexible supercapacitor | |
| US20130244123A1 (en) | Biocathode-photoanode device and method of manufacture and use | |
| CN112952212A (en) | Aqueous manganese dioxide-metal secondary battery | |
| Zhao et al. | Recent progress in device designs and dual‐functional photoactive materials for direct solar to electrochemical energy storage |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200605 |