CN116741949A - Organic-inorganic hybrid perovskite material and preparation method and application thereof - Google Patents

Organic-inorganic hybrid perovskite material and preparation method and application thereof Download PDF

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CN116741949A
CN116741949A CN202210194515.4A CN202210194515A CN116741949A CN 116741949 A CN116741949 A CN 116741949A CN 202210194515 A CN202210194515 A CN 202210194515A CN 116741949 A CN116741949 A CN 116741949A
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organic
perovskite material
inorganic hybrid
hybrid perovskite
solution
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王要兵
陈宇
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Mindu Innovation Laboratory
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Mindu Innovation Laboratory
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses an organic-inorganic hybrid perovskite material, a preparation method and application thereof, wherein the perovskite material has the characteristics of AM n X 3n+1 (formula 1) a structure containing a large-sized organic cation of a redox active site, the perovskite material having excellent optical absorption characteristics, reversible redox active sites, and being capable of rapid intramolecular charge transfer under photon excitation; in addition, the preparation method of the perovskite material has simple process, and the structure morphology of the perovskite material can be adjusted by changing the structure of the organic cations, so that the application field of the perovskite material is expanded.

Description

Organic-inorganic hybrid perovskite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to an organic-inorganic hybrid perovskite material, a preparation method thereof and application of the organic-inorganic hybrid perovskite material serving as an anode material in a light-assisted lithium battery device.
Background
Currently, various new energy policies are issued worldwide to achieve carbon balance, and efficient use of solar energy in electrochemical energy storage systems has attracted considerable attention from researchers. However, in the existing research, the solar cell and the energy storage device are usually connected through an external long wire, which causes ohmic transmission loss and reduces energy storage efficiency. Integrating lithium ion battery and solar battery into one device can directly integrate solar energyConverts the electrochemical energy into the electrochemical energy, and improves the energy utilization and conversion efficiency. In order to realize the integrated device, a dual-function photoelectric electrode material is required to be designed, which can generate separated holes and electrons to capture solar energy and can be used as Li supply + An active site of a redox reaction that performs reversible intercalation and deintercalation.
Organic-inorganic hybrid perovskite (Organic-inorganic Hybrid Perovskite) materials have been attracting attention in applications of devices such as solar cells, photodetectors, light emitting diodes, and lasers because of their advantages of energy band adjustability, high carrier mobility, large light absorption coefficient, high photoelectric conversion efficiency, and the like. The expression of the two-dimensional organic-inorganic hybrid perovskite is AM n X 3n+1 Wherein A represents a divalent cation and M represents Pb 2+ ，Sn 2+ An isodivalent cation, X represents I - ，Br - And (3) plasma halogen ions. Based on the structural adjustability of the perovskite A-site organic cation, cations with functional groups (such as carbonyl C=O, C=N groups and the like) with the function of storing lithium ions can be introduced, so that reversible redox reactions are realized to charge and discharge the battery.
At present, organic-inorganic hybrid perovskite materials are reported as negative electrode materials of lithium ion batteries in China, but perovskite materials are used as positive electrode materials of lithium ion batteries, and applications for light-assisted lithium ion batteries are reported freshly. Therefore, the lithium ion battery with better performance can be still realized in the field, and based on the structural adjustability of organic cations in the organic-inorganic hybrid perovskite material, the perovskite positive electrode material with high-efficiency difunctional activity can be designed, so that the lithium ion battery has excellent photoelectric characteristics, also shows satisfactory battery performance under illumination, and achieves the aim of directly storing solar energy to electrochemical energy.
Disclosure of Invention
Aiming at the problems, the invention provides an organic-inorganic hybrid perovskite material, a preparation method thereof and application of the organic-inorganic hybrid perovskite material as a positive electrode material in a light-assisted lithium ion battery, wherein the organic-inorganic hybrid perovskite material is used as the positive electrode material of the lithium ion battery, so that the light-assisted charging/discharging function is realized for the first time, and the higher direct conversion of solar energy into electrochemical energy storage is realized.
The technical scheme of the invention is as follows:
an organic-inorganic hybrid perovskite material having a structure represented by the following formula 1:
AM n X 3n+1 1 (1)
Wherein A represents an organic cation containing a carbonyl group; m represents Pb and/or Sn plasma; x represents a halogen ion, and n is 1.
According to an embodiment of the present invention, the organic cation containing a carbonyl group may be provided by a compound having the following formula 2;
wherein B is two oxo (=o) -substituted phenyl, naphthyl, anthracenyl groups; more preferably, 2 oxo are in para-position;
r is one, two or more amino groups, preferably 2 amino groups, more preferably 2 amino groups at symmetrical ends of B.
According to an embodiment of the present invention, the compound of formula 2 is 2, 6-diaminoanthraquinone or 2, 5-diaminop-benzoquinone.
According to an embodiment of the invention, X is an F ion, a Cl ion, a Br ion or an I ion, preferably an I ion.
According to an embodiment of the invention, M is Pb ion.
According to an exemplary embodiment of the invention, the perovskite material is DAPbI 4 Or DAsnI 4 DA is an organic cation containing a carbonyl group, provided by 2, 6-diaminoanthraquinone.
According to an embodiment of the invention, the organic-inorganic hybrid perovskite material is rod-shaped.
According to an embodiment of the present invention, the carbonyl-containing organic cation is intercalated as an organic layer into an inorganic layer PbX 2 Is a kind of medium.
According to an embodiment of the present invention, the organic-inorganic hybrid perovskite material has a structure substantially as shown in (a) of fig. 1.
According to an embodiment of the invention, the organic-inorganic hybrid perovskite material has an X-ray diffraction pattern substantially as shown in fig. 1 (b).
According to an embodiment of the invention, the organic-inorganic hybrid perovskite material has an electron microscopy image substantially as shown in fig. 2.
According to an embodiment of the present invention, in the organic-inorganic hybrid perovskite material, the ground state cation a and the inorganic layer PbX 2 And the charge transfer can be realized under the illumination. Preferably, the organic-inorganic hybrid perovskite material has an absorption in the ultraviolet visible region, for example a strong absorption in the range of 410-650 nm.
The invention also provides a preparation method of the organic-inorganic hybrid perovskite material, which comprises the following steps: and mixing and reacting the M-containing compound, hydrogen halide and a compound providing organic cations to prepare the organic-inorganic hybrid perovskite material.
Wherein the organic cation-providing compound has a structure as shown in formula 2 above.
According to an embodiment of the invention, the M-containing compound is Pb (CH) 3 COO) 2 ·3H 2 O and/or stannous oxide (SnO).
According to an embodiment of the invention, the hydrogen halide is HI and/or HBr.
According to an embodiment of the invention, the method further comprises adding a stabilizer, wherein the stabilizer is H 3 PO 2 。
Preferably, the stabilizer is added in solution.
Preferably, the volume ratio of stabilizer to hydrogen halide solution is (20-50) μL to 1mL.
According to an embodiment of the invention, the molar ratio of the M-containing compound to the organic cation providing compound is (15-60): 1, illustratively 17:1, 21:1, 30:1, 42:1, 60:1.
According to an embodiment of the invention, the hydrogen halide is added as a hydrogen halide solution, the mass to volume ratio of the M-containing compound to the hydrogen halide solution being 1g (4-10 mL), exemplary 1g:10mL. Wherein the hydrogen halide solution is an aqueous solution of hydrogen halide.
According to an embodiment of the invention, the mass fraction of the hydrogen halide solution is 45.0% to 58.0%, preferably 46.0% to 55.0%.
According to an embodiment of the invention, the method comprises mixing the M-containing compound, the hydrogen halide solution and the stabilizer solution, and adding the organic cation-providing compound after a clear yellow solution has been formed.
According to an embodiment of the present invention, the reaction temperature is 70-120 ℃, illustratively 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃, and the reaction time is 5-60min, illustratively 5min, 10min, 20min, 30min, 40min, 50min, 60min. In a preferred embodiment, the reaction temperature is 80℃and the reaction time is 30 minutes.
According to an embodiment of the present invention, the preparation method of the organic-inorganic hybrid perovskite comprises the following steps:
(1) Mixing an M-containing compound, a hydrogen halide solution, and a stabilizer;
(2) And (3) adding a compound providing organic cations after the mixed solution in the step (1) is clear yellow, and heating for reaction to prepare the organic-inorganic hybrid perovskite material.
According to an embodiment of the invention, the method further comprises a post-treatment step, filtering and washing the prepared product to obtain the purified organic-inorganic hybrid perovskite material.
As an exemplary embodiment of the present invention, the preparation method of the organic-inorganic hybrid perovskite material includes the steps of:
1) Weighing Pb (CH) 3 COO) 2 ·3H 2 O is put into a liquid phase bottle;
2) Add HI solution and H to liquid phase bottle 3 PO 2 The solution starts to stir;
3) After a clear yellow solution appears in the liquid phase bottle, adding 2, 6-diaminoanthraquinone, and heating for reaction;
4) And cooling after the reaction is finished, filtering and cleaning the obtained product to obtain the organic-inorganic hybrid perovskite material.
Preferably, the organic-inorganic hybrid perovskite material has the meaning as indicated above.
The invention also provides a positive electrode material of the lithium ion battery, which comprises the organic-inorganic hybrid perovskite material.
According to an embodiment of the present invention, the positive electrode material further includes a conductive agent and a binder; preferably, the mass ratio of the organic-inorganic hybrid perovskite material to the conductive agent to the binder is (45-70): (45-20): 10, preferably 60:30:10.
According to an embodiment of the present invention, the binder is one of polyvinylidene fluoride, polyvinyl alcohol, sodium carboxymethyl cellulose, preferably polyvinylidene fluoride; the conductive agent is at least one of conductive graphite, acetylene black, super P, carbon nano tubes and graphene; preferably multiwall carbon nanotubes.
The invention also provides a preparation method of the positive electrode material of the lithium ion battery, which comprises the following steps: dispersing the organic-inorganic hybrid perovskite material, the conductive agent and the binder in a dispersing agent solution to form slurry; and coating the slurry on a current collector, and drying and rolling to prepare the lithium ion battery anode material.
According to an embodiment of the invention, the dispersant solution is an N-methylpyrrolidone solution or an acetone solution; n-methylpyrrolidone solution is preferred.
According to an embodiment of the invention, the temperature of the drying is 40-90 ℃, preferably 45 ℃, for a time of 3-14 hours, preferably 4 hours or 12 hours.
As an exemplary embodiment of the present invention, the method for preparing a positive electrode material of a lithium ion battery includes the steps of:
(S1) weighing the organic-inorganic hybrid perovskite material, a conductive agent and a binder;
(S2) weighing a dispersing agent solution, and dispersing the solid weighed in the step (S1) in the solution to form uniform slurry;
(S3) dripping the slurry on a 304-mesh stainless steel net with the diameter of 14mm, and drying;
and (S4) uniformly rolling the electrode dried in the step (S3), and drying in vacuum overnight to obtain the lithium ion battery anode material.
The invention also provides a lithium ion battery, which comprises the positive electrode material.
The invention also provides a preparation method of the lithium ion battery, which comprises the following steps: and assembling the positive electrode material, the lithium sheet, the diaphragm and the electrolyte in an inert atmosphere to obtain the lithium ion battery.
According to an embodiment of the present invention, the electrolyte is a solution obtained by dissolving an inorganic salt containing lithium in an organic solvent; the concentration of the electrolyte can be 0.1-2.0mol/L; wherein the lithium-containing inorganic salt is at least one selected from lithium perchlorate, lithium hexafluorophosphate and lithium bistrifluoro methanesulfonimide (LiTFSI); the organic solvent is at least one selected from propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, sulfolane, 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME). Illustratively, the electrolyte is a 1.0mol/L LiTFSI organic solution, and the organic solvent employed is a 1:1 volume ratio of DOL to DME mixed solvent.
According to an embodiment of the invention, the separator is exemplified by a Celgard2400 microporous membrane.
As an exemplary embodiment of the present invention, the method for preparing a lithium ion battery includes: using a CR2032 type button cell case with a positive electrode case having a diameter of 1.2mm and 19 holes, the assembly process was performed in an argon-protected glove box; and taking the positive electrode material as a working electrode, taking a lithium sheet as a counter electrode, taking a Celgard2400 microporous membrane as a diaphragm, dripping electrolyte, and packaging to obtain the lithium ion battery.
Description of the terminology:
the DAPbI in the invention is DAPbI 4 Is the same substance.
The beneficial effects of the invention are that
(1) The invention synthesizes an organic-inorganic perovskite material containing large-size organic cations of redox active centers, has excellent optical absorption characteristics, reversible redox active sites and can carry out rapid intramolecular charge transfer under photon excitation; in addition, the preparation method of the perovskite material has simple process, and the structure morphology of the perovskite material can be adjusted by changing the structure of the organic cations, so that the application field of the perovskite material is expanded.
(2) The organic-inorganic hybrid perovskite material is successfully applied to the lithium ion battery as the positive electrode material, so that the conversion from solar energy to electrochemical energy under the light-assisted condition is efficiently realized. When the material is used as a lithium ion battery anode material, the current and the voltage change are obvious under illumination, and the material can be rapidly charged and discharged. And when the light-assisted charging is performed, the charging power is saved by more than 10%; in the light-assisted discharge, the discharge power is increased by about 10%. Under illumination, reversible electrochemical reaction and intramolecular charge transfer have synergistic effect, and provide conditions for direct conversion of solar energy into electrochemical energy.
(3) The battery technology used for assembling the light-assisted lithium organic battery is obviously different from that of a perovskite solar battery, and the battery is simple in assembly technology, low in cost and beneficial to industrialization.
Drawings
Fig. 1 is a schematic structural diagram of an organic-inorganic hybrid perovskite material DAPbI prepared in example 1 of the present invention and an X-ray diffraction pattern, wherein (a) is a topography of a product, and (b) is an X-ray diffraction pattern.
FIG. 2 is an electron micrograph (scale 500 nm) of the organic-inorganic hybrid perovskite material DAPBI prepared according to example 1 of the present invention.
Fig. 3 is EDS data for the organic-inorganic hybrid perovskite material DAPbI prepared in example 1 of the present invention.
Fig. 4 is an XPS diagram of perovskite material DAPbI prepared in example 1 of the present invention.
FIG. 5 is a graph of solid UV absorption and Tauc of perovskite material DABI and cationic 2, 6-diaminoanthraquinone DAAQ thereof prepared in example 1 of the present invention.
FIG. 6 is a solid state fluorescence emission spectrum of perovskite material DAPBI and cationic 2, 6-diaminoanthraquinone DAAQ thereof prepared in example 1 of the present invention.
FIG. 7 is a graph of fluorescence lifetime of perovskite material DAPBI and cationic 2, 6-diaminoanthraquinone DAAQ thereof prepared in example 1 of the present invention.
FIG. 8 is a graph showing that the button type lithium ion battery assembled in example 9 of the present invention has a sweep rate of 0.3mV s at 3.0-1.6V in the absence of illumination -1 Is a cyclic voltammogram of (c).
Fig. 9 is an electrochemical impedance spectrum of the assembled button lithium ion battery of example 9 of the present invention in the absence of illumination.
Fig. 10 is a charge and discharge curve of the button lithium ion battery assembled in example 9 of the present invention in the absence of illumination.
Fig. 11 is a photo-response test chart of the assembled button lithium ion battery in example 9 of the present invention in the absence of illumination.
Fig. 12 is an I-P and I-V test chart of the button lithium ion battery assembled in example 9 of the present invention in the absence of illumination.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Experimental medicine and equipment: lead acetate trihydrate (Pb (CH) 3 COO) 2 ·3H 2 O) or other lead salts, hydroiodic acid, hypophosphorous acid, 2, 6-diaminoanthraquinone, 25mL liquid phase bottle, stirring magneton, forced air drying oven.
Example 1
1. 1g of lead acetate trihydrate (Pb (CH) 3 COO) 2 ·3H 2 O), placing the mixture into a liquid phase bottle;
2. continuously adding 10mL of HI solution with the mass fraction of 47% and 200 mu L of hypophosphorous acid solution into a liquid phase bottle, and stirring until a clear yellow solution appears;
3. continuing to add 30mg of 2, 6-Diaminoanthraquinone (DAAQ) to the liquid phase bottle;
4. gradually heating to 80 ℃, reacting for 30min, and naturally cooling to prepare the organic-inorganic hybrid perovskite material DAPBI 4 。
Example 2
1.2 g of lead acetate trihydrate (Pb (CH) 3 COO) 2 ·3H 2 O), placing the mixture into a liquid phase bottle;
2. continuously adding 10mL of HI solution with the mass fraction of 47% and 200 mu L of hypophosphorous acid solution into a liquid phase bottle, and stirring until a clear yellow solution appears;
3. continuously adding 30mg of 2, 6-diaminoanthraquinone into the liquid phase bottle;
4. gradually heating to 80 ℃, reacting for 30min, and naturally cooling to prepare the organic-inorganic hybrid perovskite material DAPBI 4 。
Example 3
1. 1g of lead acetate trihydrate (Pb (CH) 3 COO) 2 ·3H 2 O), placing the mixture into a liquid phase bottle;
2. continuously adding 10mL of HI solution with the mass fraction of 47% and 200 mu L of hypophosphorous acid solution into a liquid phase bottle, and stirring until a clear yellow solution appears;
3. continuously adding 30mg of 2, 6-diaminoanthraquinone into the liquid phase bottle;
4. gradually heating to 100 ℃, reacting for 30min, and naturally cooling to prepare the organic-inorganic hybrid perovskite material DAPBI 4 。
Example 4
1. 1g of lead acetate trihydrate (Pb (CH) 3 COO) 2 ·3H 2 O), placing the mixture into a liquid phase bottle;
2. continuously adding 10mL of HI solution with the mass fraction of 47% and 200 mu L of hypophosphorous acid solution into a liquid phase bottle, and stirring until a clear yellow solution appears;
3. continuously adding 30mg of 2, 6-diaminoanthraquinone into the liquid phase bottle;
4. gradually heating to 80 ℃, and naturally cooling after reacting for 60minPreparing the organic-inorganic hybrid perovskite material DAPBI 4 。
The products of examples 1-4 were structurally characterized using X-ray diffraction techniques. The results show that the perovskite materials are obtained in examples 1-4.
The perovskite material obtained in example 1 was good in crystal form and high in yield, and approximately 500mg of perovskite material DAPBI was obtained 4 . As can be seen from the schematic structural diagram of the perovskite of FIG. 1 (a), the organic cation 2, 6-diaminoanthraquinone is intercalated as an organic layer into an inorganic layer PbI 2 Forming a perovskite structure; in fig. 1, (b) is the XRD diffraction result of the organic-inorganic hybrid perovskite material DAPbI; the scanning electron microscope of fig. 2 shows that the perovskite material is rod-shaped; whereas the EDS shown in FIG. 3 shows a Pb to I ratio of 1:4, illustrating that it is a two-dimensional perovskite material; and as can be seen from XPS of fig. 4, 284.7eV,286.1eV and 287.1eV are respectively assigned to C-C, C-N and c=o bonds in the C1S spectrum; N1S and O1S of the perovskite material are respectively 401.7eV and 533.3eV, which further proves that NH in the perovskite 3 + And c=o. The spectra of Pb 4f and I3 d are substantially in accordance with the literature.
Example 5
1. Weighing 1g of stannous oxide SnO, and placing into a liquid phase bottle;
2. continuously adding 10mL of HI solution with the mass fraction of 47% and 200 mu L of hypophosphorous acid solution into a liquid phase bottle, and stirring until a clear yellow solution appears;
3. continuing to add 30mg of 2, 6-Diaminoanthraquinone (DAAQ) to the liquid phase bottle;
4. gradually heating to 80 ℃, reacting for 30min, and naturally cooling to prepare the organic-inorganic hybrid perovskite material DAsnI 4 。
Example 6
1. Weighing 1g of stannous oxide SnO, and placing into a liquid phase bottle;
2. continuously adding 10mL of HI solution with the mass fraction of 47% and 200 mu L of hypophosphorous acid solution into a liquid phase bottle, and stirring until a clear yellow solution appears;
3. continuing to add 60mg of 2, 6-Diaminoanthraquinone (DAAQ) to the liquid phase bottle;
4. gradually heating toAfter reacting for 30min at 80 ℃, naturally cooling to prepare the organic-inorganic hybrid perovskite material DAsnI 4 。
Example 7
1. Weighing 1g of stannous oxide SnO, and placing into a liquid phase bottle;
2. continuously adding 10mL of HI solution with the mass fraction of 47% and 200 mu L of hypophosphorous acid solution into a liquid phase bottle, and stirring until a clear yellow solution appears;
3. continuing to add 30mg of 2, 6-Diaminoanthraquinone (DAAQ) to the liquid phase bottle;
4. gradually heating to 100 ℃, reacting for 30min, and naturally cooling to prepare the organic-inorganic hybrid perovskite material DAsnI 4 。
Example 8
Optical Properties of organic-inorganic hybrid perovskite materials
The ultraviolet visible diffuse reflectance spectrum (UV-Vis-NIR) is shown in FIG. 5 (a), and a clear difference between perovskite DAPBI and cationic DAAQ prepared in example 1 can be seen. DABI absorbs in the whole ultraviolet visible region, has strong absorption in the range of 410-650nm, and is a ground state cation DAAQ and an inorganic layer PbI 2 Charge transfer between them. As can be seen from fig. 5 (b), the optical bandgaps of DAPbI and DAAQ are 2.3 and 1.9eV, respectively. The solid state fluorescence emission spectrum (as in fig. 6) further demonstrates intramolecular charge transfer of DAPbI. Compared to the strong peak of DAAQ around 675nm, DAPbI fluorescence emission spectrum shows a negligible peak around 575nm, due to the apparent quenching fluorescence, revealing accelerated charge transfer.
In addition, fluorescence lifetime (as in fig. 7) was used to evaluate charge separation and charge recombination of perovskite materials. DAPbI has a longer lifetime (τ= 1308.8 ps) than DAAQ (τ= 578.7 ps). The lifetime of DAPbI is significantly extended because of the excellent crystallinity with rod-like morphology and the more favorable intramolecular charge transfer kinetics, thus suppressing non-radiative recombination.
Example 9
Lithium ion battery performance of organic-inorganic hybrid perovskite material serving as lithium ion battery anode material under light assistance
The specific test method comprises the following steps:
grinding the organic-inorganic hybrid perovskite material prepared in the embodiment 1 in a mortar, drying, taking polyvinylidene fluoride as a binder, taking N-methyl pyrrolidone as a dispersing agent solution, taking multi-wall carbon nano tubes as a conductive agent, and according to the organic-inorganic hybrid perovskite material: multiwall carbon nanotubes: polyvinylidene fluoride=6:3:1, and is mixed and stirred into uniform slurry, the uniform slurry is dripped on a 304-mesh stainless steel net with the diameter of a tablet of 14mm, the uniform slurry is rolled after being dried for 4 hours at 45 ℃, and finally the positive electrode material is prepared after being dried overnight at 45 ℃ in vacuum and is reserved for standby. The assembled button cell takes a positive electrode material as a working electrode, a lithium sheet as a counter electrode, a diaphragm as a Celgard2400 microporous membrane, an electrolyte as a 1.0mol/L LiTFSI organic solution, and a solvent as a mixed solvent system of DOL and DME in a volume ratio of 1:1.
In order to enable the light source to irradiate the electrode material, the battery assembly was performed in an argon-protected glove box using a CR2032 type button battery case with a positive electrode case having a diameter of 1.2mm and 19 holes. The assembled CR2032 button cell takes a positive electrode material as a working electrode, a lithium sheet as a counter electrode, a diaphragm as a Celgard2400 microporous membrane, a proper amount of electrolyte is dripped, and the lithium ion cell is obtained after packaging. The prepared lithium ion battery was subjected to photoelectrochemical test using a xenon lamp (PLSSXE 300, beijing pofiry technology limited, china) with an unfiltered light source, and the test results are shown in fig. 8-12.
FIG. 8 shows that the button type lithium ion battery has a sweep rate of 0.3mV s at 3.0-1.6V in the absence of illumination -1 Is a cyclic voltammogram of (c). As can be seen from the cyclic voltammogram of FIG. 8, in the dark field, a stable redox peak (1.92/2.24V Vs Li/Li + ) Indicating that the perovskite material has a reversible redox reaction. The reduction peak at 1.92V refers to the transfer of two electrons to the carbonyl group with formation of the lithium enoate, while the oxidation peak at about 2.24V refers to reoxidation of the lithium enoate to form the carbonyl group. After the addition of light, in addition to the significantly enhanced current, a certain shift in redox peaks occurred, indicating that the redox process of perovskite DAPbI after illumination was enhanced and the possibility of solar energy utilization under illumination. Fig. 9 shows an assembled button lithium ion batteryElectrochemical impedance spectroscopy in the absence of illumination. As can be seen from fig. 9, the impedance of DAPbI after the addition of light is about half that of DAPbI without light, indicating that the resistance to interfacial charge transfer after the addition of light is reduced, the intrinsic conductivity is enhanced, again demonstrating the effective charge transport and rapid reaction kinetics of DAPbI.
Fig. 10 is a charge and discharge curve of a button lithium ion battery with no illumination. As can be seen from FIG. 10, the perovskite material DABI is compared with the cationic DAAQ after the addition of light 4 The voltage at the discharge plateau rises significantly and the voltage at the charge plateau drops faster.
The invention also explores the light response of the battery in the charging and discharging process, as shown in fig. 11, and is the light response test of the assembled button type lithium ion battery in the absence of illumination, and the voltage of the platform is reduced by 150mV (a) after light is added in the charging process; and the voltage of the platform rises by 100mV (b) after light is added in the discharging process, so that the high-voltage solar energy storage device has excellent stability and solar energy storage performance.
In addition, current-voltage (I-V) curves were used to evaluate the photo-response of operating voltages at different current densities during discharge and charge, FIG. 12 is an I-P and I-V test of an assembled button lithium ion battery with and without illumination, where FIGS. 12 (a) - (b), 12 (c) - (d) represent the I-V and I-P curves of DAPBI during charge and discharge, respectively. In the charging process, when no light (i.e. dark field) is added, the perovskite DAPBI is formed by the method of initially adding 0.01mA cm -2 The operating voltage of 2.21V rises to 3mA cm -2 Is 2.94V; after addition of light (i.e. bright field), the perovskite DAPBI was at 3mA cm -2 The operating voltage of (a) was reduced by 0.28V (fig. 12 a). While DAPBI was at 3mA cm -2 With and without light, the corresponding input powers were 7.99 and 9.01mW cm -2 (b) Indicating 11.3% input power savings and 0.5% solar-electrochemical energy storage efficiency (200 mW cm -2 Is better than the prior art).
The discharge voltage of DAPBI under each current density is higher than that under the condition of no light, and the discharge voltage is 3mA cm -2 There is a voltage difference of 0.31V, and the output power is increased by 18.3% (as in FIG. 12 (d), without and under the addition of light)The power of (C) is 5.29 and 6.26mW cm -2 ) The solar-electrochemical energy storage efficiency was improved by 0.49% (fig. 12 (c) and (d)). In contrast, the voltage difference between charge and discharge of perovskite DAPbI is much higher than that of cationic DAAQ.
From the photoelectric data, it is shown that the perovskite material containing carbonyl organic cations can realize rapid charge transfer, improved redox activity and enhanced charge/discharge process under illumination, thereby realizing efficient direct solar energy-to-electrochemical energy storage conversion.
The embodiments of the present invention have been described above by way of example. However, the scope of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art, which fall within the spirit and principles of the present invention, are intended to be included within the scope of the present invention.

Claims (10)

1. An organic-inorganic hybrid perovskite material characterized by having a structure represented by the following formula 1:
AM n X 3n+1 1 (1)
Wherein A represents an organic cation containing a carbonyl group; m represents Pb or Sn ions; x represents a halogen ion, and n is 1.
2. The material of claim 1, wherein the carbonyl-containing organic cation is provided by a compound having formula 2 below;
wherein B is two oxo (=o) -substituted phenyl, naphthyl, anthracenyl groups; more preferably, 2 oxo are in para-position;
r is one, two or more amino groups, preferably 2 amino groups, more preferably 2 amino groups at symmetrical ends of B.
Preferably, the compound of formula 2 is 2, 6-diaminoanthraquinone or 2, 5-diaminop-benzoquinone.
Preferably, X is F ion, cl ion, br ion or I ion, preferably I ion.
Preferably, M is Pb ions.
3. A material according to claim 1 or 2, wherein the perovskite material is DAPbI 4 Or DAsnI 4 DA is an organic cation containing a carbonyl group, provided by 2, 6-diaminoanthraquinone. Preferably, the organic-inorganic hybrid perovskite material is rod-shaped.
Preferably, the carbonyl-containing organic cation is intercalated as an organic layer into an inorganic layer PbX 2 Is a kind of medium.
Preferably, in the organic-inorganic hybrid perovskite material, the ground state cations A and the inorganic layer PbX 2 And the charge transfer can be realized under the illumination. Preferably, the organic-inorganic hybrid perovskite material has an absorption in the ultraviolet visible region, for example a strong absorption in the range of 410-650 nm.
4. A method for preparing an organic-inorganic hybrid perovskite material according to any one of claims 1 to 3, wherein the method comprises: and mixing and reacting the M-containing compound, hydrogen halide and a compound providing organic cations to prepare the organic-inorganic hybrid perovskite material.
5. The method of claim 4, wherein the M-containing compound is Pb (CH) 3 COO) 2 ·3H 2 O and/or SnO.
Preferably, the method further comprises adding a stabilizer, wherein the stabilizer is H 3 PO 2 。
Preferably, the volume ratio of stabilizer to hydrogen halide solution is (20-50) μL to 1mL.
Preferably, the molar ratio of the M-containing compound to the organic cation-providing compound is (15-60): 1.
The hydrogen halide is added in the form of a hydrogen halide solution, and the mass volume ratio of the M-containing compound to the hydrogen halide solution is 1 (g): 4-10 (mL).
6. The process according to claim 4 or 5, wherein the reaction temperature is 70-120 ℃.
Preferably, the M-containing compound, the hydrogen halide solution and the stabilizer solution are mixed first, and after a clear yellow solution has been developed, the organic cation-providing compound is added.
7. A positive electrode material for a lithium ion battery, characterized in that the positive electrode material comprises the organic-inorganic hybrid perovskite material according to any one of claims 1 to 3.
8. The positive electrode material according to claim 7, further comprising a conductive agent and a binder; preferably, the mass ratio of the organic-inorganic hybrid perovskite material to the conductive agent to the binder is (45-70): 45-20): 10.
9. The method for producing a positive electrode material according to claim 7 or 8, characterized in that the method comprises: dispersing the organic-inorganic hybrid perovskite material, the conductive agent and the binder in a dispersing agent solution to form slurry; and coating the slurry on a current collector, and drying and rolling to prepare the anode material.
10. A lithium ion battery, characterized in that the battery comprises the positive electrode material according to claim 7 or 8.
Preferably, a method for preparing a lithium ion battery, the method comprising: assembling the positive electrode material, the lithium sheet, the diaphragm and the electrolyte according to claim 7 or 8 in an inert atmosphere to obtain the lithium ion battery.
CN202210194515.4A 2022-03-01 2022-03-01 Organic-inorganic hybrid perovskite material and preparation method and application thereof Pending CN116741949A (en)

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