CN108682791B - Method for preparing inorganic perovskite negative electrode material with layered structure by vapor phase method - Google Patents
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Abstract
The invention discloses a method for preparing an inorganic perovskite negative electrode material with a layered structure by a vapor phase method, which relates to the technical field of preparation of lithium ion battery negative electrode materials. According to the principles of physical vapor deposition and chemical vapor deposition, inorganic lead bromide and cesium bromide are used as raw materials, are deposited on the surface of a copper foil substrate through heating and evaporation, are subjected to subsequent annealing treatment by regulating and controlling evaporation rate, deposition thickness and thickness proportion, and prepare a compact and uniform pure inorganic perovskite material which is used as a lithium ion battery cathode material, shows good thermodynamic stability and excellent physicochemical properties, and is simple in process.
Description
Technical Field
The invention relates to the technical field of preparation of lithium ion battery cathode materials, in particular to a method for preparing an inorganic perovskite cathode material with a layered structure by a vapor phase method.
Background
With the continuous development and progress of human society, the dependence on fossil energy is more and more serious. The depletion of fossil energy such as coal and petroleum and the environmental pollution caused by the development and utilization of fossil energy are becoming more and more serious. Therefore, the development of new renewable clean energy is imminent, and new renewable energy represented by solar energy and wind energy is fully developed and utilized in recent years. However, how to efficiently realize energy conversion and storage is always a focus of attention. Lithium ion batteries are widely used in electronic products, power batteries and energy storage systems due to the advantages of high working voltage, high energy storage density, long cycle life and the like, and especially under the dual pressure of energy and environment, energy-saving and environment-friendly new energy automobiles gradually enter the market and are rapidly developed. However, how to reduce the cost, improve the energy density and the cycle performance is always the key point of the domestic and foreign research.
The common negative electrode material for the lithium ion battery mainly comprises a graphite negative electrode, and has good cycle performance, easy acquisition of materials and large storage capacity, so that the material is widely applied to the fields of electronic consumer products and power batteries. However, the low theoretical specific capacity, the poor high-rate discharge performance and the lithium dendrite formed by easy precipitation of lithium at the lithium deintercalation potential close to the lithium potential, so that the short circuit and other defects restrict the application of the lithium dendrite in low cost and high energy density. Currently, negative electrode materials that have been commercialized mainly include graphite particles, carbon-coated graphite particle negative electrodes, silicon-carbon composite materials, and the like. The negative electrode materials such as graphite need to be graphitized under a high temperature condition and subsequent coating and other processes, so that the preparation and production process is complex and the cost is high.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a method for preparing an inorganic perovskite negative electrode material with a layered structure by a vapor phase method, the process is simple, and the prepared material has good thermodynamic stability and excellent physical and chemical properties.
The invention provides a method for preparing an inorganic perovskite negative electrode material with a layered structure by a vapor phase method, which comprises the steps of sequentially or simultaneously depositing lead bromide and cesium bromide on a copper foil substrate by the vapor phase method under the vacuum condition, and then heating and annealing in the air to obtain the inorganic perovskite negative electrode material.
Preferably, the method comprises the following steps:
s1, respectively placing lead bromide powder and cesium bromide powder on two heating boats of an evaporation system, and adhering copper foil to a tray right above;
s2, vacuumizing the evaporation system, sequentially or simultaneously heating a burning boat containing lead bromide and cesium bromide, performing vapor deposition, and monitoring the film thickness by using a film thickness gauge in the deposition process;
s3, after the reaction is finished, closing the evaporation system, taking out the copper foil, placing the copper foil on a heating table, and annealing the copper foil for 20-40min at the temperature of 140 ℃ in the air to obtain the uniform and compact perovskite negative electrode material.
Preferably, in the step S1, vacuum is applied until the vacuum degree is 10-3Pa。
Preferably, in the step S2, the deposition rate is
The total deposition time is 3-5h, and the deposition thickness ratio of the lead bromide to the cesium bromide is 1.8-2.2: 1.
preferably, in S2, the thicknesses of the sequentially deposited lead bromide and cesium bromide are 10 μm and 5 μm, respectively.
Preferably, in S3, the annealing temperature is 130 ℃ and the annealing time is 30 min.
Preferably, in S3, the obtained perovskite negative electrode material is CsPb2Br5Or CsPb2Br5-CsPbBr3Mixed phases of (1).
Has the advantages that: according to the principles of physical vapor deposition and chemical vapor deposition, inorganic lead bromide and cesium bromide are used as raw materials, are deposited on the surface of a copper foil substrate through heating and evaporation, are subjected to subsequent annealing treatment by regulating and controlling evaporation rate, deposition thickness and thickness proportion, and are prepared into a compact and uniform pure inorganic perovskite material.
Drawings
FIG. 1 is an SEM image of an inorganic perovskite material prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of an inorganic perovskite material prepared in example 2 of the present invention;
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
The invention provides a method for preparing an inorganic perovskite negative electrode material with a layered structure by a vapor phase method, which comprises the following steps:
s1, weighing a certain amount of lead bromide powder and cesium bromide powder, respectively placing the lead bromide powder and the cesium bromide powder on two heating boats of an evaporation system, and adhering copper foil to a tray right above the heating boats;
s2, pumping the vacuum degree of the system to be evaporated to 10-3Pa, vapor deposition is started. Firstly, opening a film thickness meter, heating a burning boat (heating source) containing lead bromide, starting to monitor the film thickness, after reacting for 2.5 hours, closing the lead bromide heating source, starting a cesium bromide heating source, simultaneously converting parameters of the film thickness meter, starting to monitor the film thickness of the cesium bromide, and after heating and evaporating for 2.5 hours, closing the cesium bromide heating source. Wherein cesium bromide is about 5 μm thick and lead bromide is about 10 μm thick;
and S3, after the reaction is finished, closing the evaporation system, taking out the sample, putting the sample on a heating table, and heating and annealing the sample in the air at 130 ℃ for 30min to obtain the uniform and compact perovskite negative electrode material.
SEM representation is carried out on the morphology of the prepared perovskite negative electrode material, and as can be seen from figure 1, the perovskite negative electrode material obtained by the method in the embodiment has a uniform and compact structure.
Example 2
The invention provides a method for preparing an inorganic perovskite negative electrode material with a layered structure by a vapor phase method, which comprises the following steps:
s1, weighing a certain amount of lead bromide powder and cesium bromide powder, respectively placing the lead bromide powder and the cesium bromide powder on two heating boats of an evaporation system, and adhering copper foil to a tray right above the heating boats;
s2, pumping the vacuum degree of the system to be evaporated to 10-3Pa, starting the vapor deposition, firstOpening the film thickness meter, simultaneously heating a burning boat (heating source) containing cesium bromide and lead bromide, starting to monitor the film thickness of the cesium bromide and the lead bromide, and after reacting for 5 hours, closing the cesium bromide and lead bromide heating source; wherein the thickness of the evaporated cesium bromide is about 5 μm and the thickness of the lead bromide is about 10 μm;
and S3, after the reaction is finished, closing the evaporation system, taking out the sample, putting the sample on a heating table, and heating and annealing the sample in the air at 130 ℃ for 30min to obtain the uniform and compact perovskite negative electrode material.
XRD characterization is carried out on the prepared perovskite negative electrode material, lead bromide and cesium bromide are deposited on an FTO glass substrate according to the method in the embodiment, then XRD characterization is carried out, the result is a curve shown in figure 2-a, and CsPbBr is added3Deposition of standards onto FTO glass for CsPbBr3XRD characterization is carried out on the standard substance and the FTO glass substrate, the results are respectively 2-b curves and 2-c curves, and as can be seen from figure 2, the component CsPb of the perovskite negative electrode material prepared in the embodiment is CsPb2Br5-CsPbBr3The phase standard of the mixed phase is consistent with that of the PDF card.
Example 3
The invention provides a method for preparing an inorganic perovskite negative electrode material with a layered structure by a vapor phase method, which comprises the following steps:
s1, weighing a certain amount of lead bromide powder and cesium bromide powder, respectively placing the lead bromide powder and the cesium bromide powder on two heating boats of an evaporation system, and adhering copper foil to a tray right above the heating boats;
s2, pumping the vacuum degree of the system to be evaporated to 10-3When Pa, starting vapor deposition, firstly opening a film thickness instrument, simultaneously heating a burning boat (a heating source) containing cesium bromide and lead bromide, starting monitoring the film thickness of the cesium bromide and the lead bromide, and after reacting for 3 hours, closing the heating source of the cesium bromide and the lead bromide; wherein the film thickness ratio of evaporated lead bromide to cesium bromide is 1.8: 1, the thickness of the cesium bromide is 5 μm;
and S3, after the reaction is finished, closing the evaporation system, taking out the sample, putting the sample on a heating table, and heating and annealing at 135 ℃ in the air for 20min to obtain the uniform and compact perovskite negative electrode material.
Example 4
The invention provides a method for preparing an inorganic perovskite negative electrode material with a layered structure by a vapor phase method, which comprises the following steps:
s1, weighing a certain amount of lead bromide powder and cesium bromide powder, respectively placing the lead bromide powder and the cesium bromide powder on two heating boats of an evaporation system, and adhering copper foil to a tray right above the heating boats;
s2, pumping the vacuum degree of the system to be evaporated to 10-3When Pa, starting vapor deposition, firstly opening a film thickness meter, heating a burning boat (heating source) containing lead bromide, starting to monitor the film thickness, after reacting for 3 hours, closing the lead bromide heating source, starting a cesium bromide heating source, simultaneously converting parameters of the film thickness meter, starting to monitor the film thickness of the cesium bromide, and after heating and evaporating for 2 hours, closing the cesium bromide heating source; wherein the film thickness ratio of evaporated lead bromide to cesium bromide is 2.2: 1, the thickness of the cesium bromide is 5 μm;
and S3, after the reaction is finished, closing the evaporation system, taking out the sample, putting the sample on a heating table, and heating and annealing at 140 ℃ for 40min in the air to obtain the uniform and compact perovskite negative electrode material.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (6)
1. A method for preparing inorganic perovskite negative electrode material of lamellar structure by vapor phase method, characterized by, under the vacuum condition, deposit lead bromide, cesium bromide on the copper foil substrate sequentially or at the same time through the vapor phase method, heat anneal in the air, get; the method for preparing the inorganic perovskite anode material with the layered structure by the vapor phase method comprises the following steps:
s1, respectively placing lead bromide powder and cesium bromide powder on two heating boats of an evaporation system, and adhering copper foil to a tray right above;
s2, vacuumizing the evaporation system, sequentially or simultaneously heating a burning boat containing lead bromide and cesium bromide, performing vapor deposition, and monitoring the film thickness by using a film thickness gauge in the deposition process;
s3, after the reaction is finished, closing the evaporation system, taking out the copper foil, placing the copper foil on a heating table, and annealing the copper foil for 20-40min at the temperature of 140 ℃ in the air to obtain the uniform and compact perovskite negative electrode material.
2. The vapor phase method for preparing an inorganic perovskite anode material with a layered structure according to claim 1, wherein in S1, vacuum is applied until the vacuum degree is 10-3Pa。
3. The vapor-phase method for preparing an inorganic perovskite anode material with a layered structure according to claim 1, wherein in S2, the deposition rate is
The total deposition time is 3-5h, and the deposition thickness ratio of the lead bromide to the cesium bromide is 1.8-2.2: 1.
4. the vapor-phase method for producing an inorganic perovskite anode material with a layered structure according to claim 3, wherein the thicknesses of the sequentially deposited lead bromide and cesium bromide in S2 are 10 μm and 5 μm, respectively.
5. The vapor phase method for preparing the inorganic perovskite anode material with the layered structure according to claim 1, wherein in the step S3, the annealing temperature is 130 ℃ and the annealing time is 30 min.
6. The method for preparing the inorganic perovskite negative electrode material with the layered structure by the gas phase method according to claim 1, wherein in the step S3, the obtained perovskite negative electrode material is CsPb2Br5Or CsPb2Br5-CsPbBr3Mixed phases of (1).
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| CN109065834B (en) * | 2018-07-12 | 2021-07-09 | 合肥国轩高科动力能源有限公司 | Preparation method of inorganic perovskite derivative phase used as negative electrode material for lithium ions |
| CN109713100B (en) * | 2018-12-21 | 2020-10-16 | 华中科技大学 | Method for preparing active layer of all-inorganic perovskite light-emitting diode |
| CN111384361B (en) * | 2018-12-29 | 2021-08-20 | 北京大学 | Two-dimensional organic perovskite lithium ion battery electrode and preparation method thereof |
| CN111326657B (en) * | 2020-03-09 | 2021-03-16 | 成都信息工程大学 | CsPbBr3/CsPb2Br5Composite film and preparation method thereof |
| CN112234190B (en) * | 2020-10-14 | 2022-02-01 | 中国计量大学 | Lead-based negative electrode material |
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| CN106876533A (en) * | 2017-01-22 | 2017-06-20 | 郑州大学 | One kind is based on MgO CsPbBr3Luminescent device of structure and preparation method thereof |
| CN107381624A (en) * | 2017-06-21 | 2017-11-24 | 浙江大学 | A kind of preparation method of the ultra-thin inorganic lead halogen perovskite nanocluster based on chemical vapor deposition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106876533A (en) * | 2017-01-22 | 2017-06-20 | 郑州大学 | One kind is based on MgO CsPbBr3Luminescent device of structure and preparation method thereof |
| CN107381624A (en) * | 2017-06-21 | 2017-11-24 | 浙江大学 | A kind of preparation method of the ultra-thin inorganic lead halogen perovskite nanocluster based on chemical vapor deposition |
Non-Patent Citations (1)
| Title |
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| Composite Perovskites of Cesium Lead Bromide for Optimized Photoluminescence;Yichuan Ling等;《J. Phys. Chem. Lett.》;20170705;附件S2铯铅溴化物的制备 * |
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