CN109400905B - Metal organic framework Mn-BTC and preparation method and application thereof - Google Patents
Metal organic framework Mn-BTC and preparation method and application thereof Download PDFInfo
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Abstract
A process for preparing Mn-BTC with metal-organic skeleton includes such steps as preparing Mn (CH)3COO)2·4H2O, PVP-30, a mixed solution of ethanol and water, and trimesic acid as raw materials, and the preparation of the solution A, the preparation of the solution B, the mixing and aging, the centrifugal washing, the vacuum drying and the like. The MOFs prepared by the method is complete in sphere, has a spherical shape, is good in product dispersibility, has high crystallinity without adhesion, and the micro-spherical manganese selenide/carbon composite material prepared by the method has high specific surface area and porosity, shows excellent lithium storage performance, is high in product purity, can reach the purity of 99.2%, is high in yield, can reach more than 70%, is large in electricity storage capacity, is long in cycle life, is simple and feasible in process flow, and is worthy of market popularization.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a metal organic framework and a preparation method of a microspherical manganese selenide/carbon composite material thereof.
Background
With the increasing exhaustion of fossil energy represented by petroleum and the increasing environmental pollution caused by the combustion of fossil energy, people urgently need a sustainable and renewable clean energy. The lithium ion battery has the advantages of high energy density, long cycle life, environmental friendliness and the like, is distinguished from a plurality of new energy sources, and has wide application in the fields of mobile electronic equipment, new energy automobiles and the like. However, the negative electrode material of the current commercial lithium ion battery is graphite, the theoretical capacity of the graphite is only 372mAh/g, the capacity requirement of large electronic equipment such as an electric automobile cannot be met, and the application and development of the lithium ion battery are limited. Scientists have developed a variety of negative electrode materials to improve the capacity of lithium ion batteries, such as carbon materials, transition metal oxides, transition metal sulfides, transition metal selenides, and the like.
Compared with transition metal oxides and transition metal sulfides, the transition metal selenide not only has high volume specific capacity and mass specific capacity, but also has low voltage platform, small polarization and better conductivity, and is a potential lithium ion battery cathode material. However, similar to the transition metal oxide, the transition metal selenide may undergo a large volume change due to intercalation and deintercalation of lithium ions during charging and discharging, thereby crushing and pulverizing the active material, causing the active material to be separated from the current collector, losing electrical contact, causing capacity fading and cycle performance degradation. In addition, the transition metal phosphide has poor electronic conductivity, hinders the rapid transfer of electrons in the active material, and limits the electrochemical response of the active material, so that the rapid charge-discharge capacity and the rate capability of the active material are poor.
At present, research for improving the lithium storage performance of the transition metal selenide mainly focuses on two aspects, one is to compound the transition metal selenide with carbon materials such as graphene and carbon nanotubes, and the like, and by utilizing the excellent conductivity and mechanical property of the carbon materials, the conductivity of the transition metal selenide is improved and the stress generated by volume expansion in the circulation process is absorbed; the other method is to prepare the transition metal selenide with the nano-scale and porous structure, enlarge the specific surface area of the material, increase the contact area of the electrode material and the electrolyte, shorten the diffusion path of electrons and lithium ions and buffer the stress generated by volume expansion.
The metal organic framework compounds, called MOFs for short, are organic-inorganic hybrid materials with molecular pores formed by self-assembly of organic ligands and metal ions through coordination bonds. The MOFs have the advantages of porosity, large specific surface area, component adjustability and the like, so that the MOFs have wide application prospects in the fields of gas collection and storage, gas separation, catalysis, sensors, energy storage and the like, and have attracted wide attention since the birth of the last ninety years. Meanwhile, due to the porous structure and the organic framework of the MOFs and the abundant adjustability of metal ions, the MOFs can be used as a precursor for preparing porous materials, such as carbon materials, metal oxides, metal sulfides, metal selenides and the like. The porous material derived from the MOFs can retain the porous structure and the large specific surface area of the MOFs, meanwhile, the organic framework can be converted into porous carbon under high-temperature inert atmosphere, and the porous carbon/metal compound composite material can be prepared under the condition that no external carbon source is introduced.
In view of the prior art, the preparation of MOFs still has the technical problems that the spherical shape is incomplete, is hemispheric or other incomplete spheres, even is broken into fine particles, the spherical shape cannot be seen, the product dispersibility is poor, adhesion is easy to occur and the like; the manganese selenide/carbon composite material also has the technical problems of low product purity, low yield, small electric storage capacity, short cycle life, poor stability in the using process, easy occurrence of the condition of large and small current and the like, and needs to be solved urgently.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a metal organic framework Mn-BTC with excellent performance.
The second purpose of the invention is to provide a preparation method of the microspherical manganese selenide/carbon composite material.
The purpose of the invention is realized by the following technical scheme:
a process for preparing Mn-BTC with organic metal skeleton includes such steps as preparing Mn (CH)3COO)2·4H2O, PVP-30, a mixed solution of ethanol and water, and trimesic acid as raw materials, which are respectively subjected to the steps of preparation of the solution A, preparation of the solution B, mixing and aging, centrifugal washing, vacuum drying and the like in sequence.
Further, the solution A is prepared by taking Mn (CH)3COO)2·4H2Dissolving O and PVP-K30 in a mixed solution composed of ethanol and deionized water, and stirring and dissolving at a rotating speed of 300-400 r/min to obtain a mixed solution A; wherein Mn (CH)3COO)2·4H2The mass ratio of O to PVP-K30 is 0.2449-0.4898: 1-3, and the unit is g/g; the PVP-K30 and the mixture of ethanol and deionized waterThe mass-to-volume ratio of the solution is 1-3: 100, and the unit is g/ml.
Further, the preparation of the solution B is to dissolve trimesic acid in a mixed solution consisting of ethanol and deionized water, and to stir the solution to obtain the solution B; the mass-volume ratio of the mixed solution of the trimesic acid, the ethanol and the deionized water is 0.6304-0.8994: 100, and the unit is g/ml.
Further, the mixing and aging step is that the prepared solution A is dropwise added into the solution B under the stirring condition, the rotating speed is 300-400 r/min during dropwise adding, stirring is continued for 10-20 min, stirring is stopped, and the mixture is placed at room temperature for aging for 20-24 h; wherein the volume ratio of the solution A to the solution B is 1: 100.
Further, the centrifugal washing is to carry out centrifugal separation on the aged product, collect centrifugal precipitate, wash the precipitate for 3 times by using a mixed solution of ethanol and deionized water, and collect the precipitate for later use; the dosage is 1: 100-1: 150 in volume ratio.
Further, the vacuum drying is to place the prepared precipitate at 55-65 ℃ in air for drying for 12-15 h, and the obtained product is the microspherical metal organic framework compound Mn-BTC, and the product is white and spherical.
Further, the mixed solution of the ethanol and the deionized water is prepared by mixing the ethanol and the deionized water according to the volume ratio of 1: 1.
A preparation method of a microspherical manganese selenide/carbon composite material is characterized in that the prepared microspherical metal organic framework compound Mn-BTC and selenium powder are respectively placed at two ends of a porcelain boat, then the porcelain boat is placed in a tube furnace, the Mn-BTC is placed at the downstream, the selenium powder is placed at the upstream, the temperature is increased to 400-600 ℃ from room temperature at the heating rate of 2-5 ℃/min under the argon atmosphere, and the temperature is kept at 400-600 ℃ for 2-4 hours, so that the microspherical manganese selenide/carbon composite material is obtained.
Further, the mass ratio of the Mn-BTC to the Se powder is 1:1 to 10.
The invention has the following beneficial effects:
the metal organic framework prepared by the invention has a spherical shape, and the spherical shape is complete,Uniform, good product dispersibility, and high crystallinity without adhesion. The microsphere manganese selenide/carbon composite material prepared by the method has regular shape, uniform shape, good dispersibility, higher specific surface area and porosity; simultaneously, the lithium storage performance is excellent, the purity of the product is high and can reach 99.2 percent, the yield is high and can reach more than 70 percent, the storage capacity is large, the cycle life is long, and the lithium storage capacity is 100mA g-1After 100 charge-discharge cycles at the current density of (1), the discharge capacity of the material is 784mAh g-1The power storage capacity is large, the cycle life is long, the cycle frequency can reach 100 times at least and can reach 200 times at most, the stability in the use process is good, the condition that the current is suddenly large or small can not occur, the process flow is simple and feasible, and the power storage device is worthy of market popularization.
Drawings
FIG. 1 is an SEM photograph of a microspherical metal organic framework compound Mn-BTC in example 1 of the present invention.
Fig. 2 is an SEM image of the microspherical manganese selenide/carbon composite material of example 1 of the present invention.
Fig. 3 is an XRD pattern of the microspherical manganese selenide/carbon composite in example 1 of the present invention.
Fig. 4 is a cycle curve diagram of the microspherical manganese selenide/carbon composite material as a lithium battery cathode material in example 1 of the invention at a current density of 100 mA/g.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention based on the above-described disclosure.
Example 1:
preparation of microspherical metal organic framework compound Mn-BTC: weighing 2mmol of Mn (CH)3COO)2·4H2O and 3g PVP (K30) were dissolved in a mixed solution of 100ml ethanol and deionized water (v: v =1: 1) with stirring at 350 rpm, and 4.28mmol of trimesic acid was weighed and dissolved in a mixed solution of 100ml ethanol and deionized waterIn the solution (v: v =1: 1), the stirring speed was 350 rpm, and after the solution was completely dissolved by stirring, Mn (CH) was transferred using a 1ml pipette3COO)2·4H2Dripping the O solution into a trimesic acid solution, stirring at the rotation speed of 350 r/min for 10min, aging at room temperature for 24h after stopping stirring, centrifugally separating the product, washing for 3 times by using a mixed solution of ethanol and deionized water (v: v =1: 1), wherein the volume ratio of the mixed solution of ethanol and deionized water is 1:120, and then placing at 60 ℃ for vacuum drying for 12h to obtain the product, namely the microspherical metal organic framework compound Mn-BTC.
Example 2:
the microspherical metal organic framework compound Mn-BTC prepared in example 1 was mixed with Se powder in the following ratio of 1:10, then placing the porcelain boats in a tube furnace with Mn-BTC at the downstream and Se powder at the upstream, heating the porcelain boats from room temperature to 450 ℃ at the heating rate of 3 ℃/min under the argon atmosphere, and preserving the heat at 450 ℃ for 3 hours to obtain the microspheric manganese selenide/carbon composite material.
The prepared microspherical manganese selenide/carbon composite material well keeps the microspherical morphology of a metal organic framework compound, has high crystallinity, higher specific surface area and porosity, shows excellent lithium storage performance, and has high product purity which can reach 99.2 percent.
The experimental results show that: the microspherical manganese selenide/carbon composite material prepared by the method has excellent lithium storage performance, and the lithium storage performance is 100mA g-1After 100 charge-discharge cycles at the current density of (1), the discharge capacity of the material is 784mAh g-1After experiment, the cycle can be cycled for 200 times without attenuation. The high specific surface area and porosity provided by the microspherical manganese selenide/carbon composite material are beneficial to increasing the reaction area and promoting the transfer of electrons and ions, and meanwhile, the existence of carbon can relieve the stress generated in the charging and discharging process, thereby effectively improving the lithium storage performance.
Example 3:
a preparation method of a microspherical manganese selenide/carbon composite material comprises the following steps:
1. preparation of microspherical metal organic framework compound Mn-BTC: weighing 2mmol of Mn (CH)3COO)2·4H2Dissolving O and 3g PVP (K30) in a mixed solution of 100ml ethanol and deionized water (v: v =1: 1) under stirring at the rotation speed of 400 r/min, weighing 4.28mmol of trimesic acid, dissolving in a mixed solution of 100ml ethanol and deionized water (v: v =1: 1) at the stirring rotation speed of 400 r/min, and after completely dissolving through stirring, using a 1ml pipette to remove Mn (CH) with a CH (CH) gun3COO)2·4H2Dripping the O solution into a trimesic acid solution, stirring at the rotation speed of 400 r/min for 10min, aging at room temperature for 24h after stopping stirring, centrifugally separating a product, washing for 3 times by using a mixed solution of ethanol and deionized water (v: v =1: 1), wherein the volume ratio of the mixed solution of ethanol and deionized water is 1:150, and then placing at 60 ℃ for vacuum drying for 12h to obtain a microspherical metal organic framework compound Mn-BTC, wherein the product is white and spherical;
2. the preparation of the microspherical manganese selenide/carbon composite material based on the framework comprises the following steps: mixing the microspherical metal organic framework compound Mn-BTC prepared in the step 1) with Se powder according to the weight ratio of 1: and 6, respectively placing the porcelain boats at two ends of the porcelain boat, then placing the porcelain boats in a tube furnace, enabling Mn-BTC to be downstream and Se powder to be upstream, heating the porcelain boats to 500 ℃ from room temperature at a heating rate of 2 ℃/min under the argon atmosphere, and keeping the temperature at 500 ℃ for 2 hours to obtain the microspheric manganese selenide/carbon composite material.
The prepared microspherical manganese selenide/carbon composite material well keeps the microspherical appearance of a metal organic framework compound, has high crystallinity, higher specific surface area and porosity, shows excellent lithium storage performance, has high product purity which can reach 99.1 percent, large electricity storage capacity, long cycle life, can be cycled for at least 100 times, can be recycled for at most 200 times without attenuation, has good stability in the using process and can not generate the condition of sudden and sudden small current.
Example 4:
a preparation method of a microspherical manganese selenide/carbon composite material comprises the following steps:
1. micro-ball goldPreparation of organic framework compound Mn-BTC: weighing 2mmol of Mn (CH)3COO)2·4H2Dissolving O and 3g PVP (K30) in a mixed solution of 100ml ethanol and deionized water (v: v =1: 1) under stirring at the rotation speed of 300 r/min, weighing 4.28mmol of trimesic acid, dissolving in a mixed solution of 100ml ethanol and deionized water (v: v =1: 1) at the stirring rotation speed of 300 r/min, and after completely dissolving through stirring, using a 1ml pipette to remove Mn (CH) from the mixed solution3COO)2·4H2Dripping the O solution into a trimesic acid solution, stirring at the rotation speed of 300 r/min for 10min, aging at room temperature for 24h after stopping stirring, centrifugally separating a product, washing for 3 times by using a mixed solution of ethanol and deionized water (v: v =1: 1), wherein the volume ratio of the mixed solution of ethanol and deionized water is 1:100, and then placing at 60 ℃ for vacuum drying for 12h to obtain a microspherical metal organic framework compound Mn-BTC, wherein the product is white and spherical;
2. the preparation of the microspherical manganese selenide/carbon composite material based on the organic framework comprises the following steps: mixing the microspherical metal organic framework compound Mn-BTC prepared in the step 1) with Se powder according to the weight ratio of 1: and 8, respectively placing the porcelain boats at two ends of the porcelain boat, then placing the porcelain boats in a tube furnace, enabling Mn-BTC to be downstream and Se powder to be upstream, heating the porcelain boats to 550 ℃ from room temperature at a heating rate of 5 ℃/min under an argon atmosphere, and keeping the temperature at 450 ℃ for 2 hours to obtain the microspheric manganese selenide/carbon composite material.
The prepared microspherical manganese selenide/carbon composite material well keeps the microspherical appearance of a metal organic framework compound, has high crystallinity, higher specific surface area and porosity, shows excellent lithium storage performance, has high product purity which can reach 99.1 percent, large electricity storage capacity, long cycle life, can be cycled for at least 100 times, can be recycled for at most 200 times without attenuation, has good stability in the using process and can not generate the condition of sudden and sudden small current.
Claims (3)
1. A preparation method of a microspherical manganese selenide/carbon composite material based on a metal organic framework Mn-BTC is characterized by comprising the following steps: it is Mn (CH)3COO)2·4H2O、PVP-30、Respectively preparing a solution A, a solution B, mixing, aging, centrifuging, washing, vacuum drying and the like to prepare a microspherical metal organic framework Mn-BTC by using a mixed solution of ethanol and water and trimesic acid as raw materials, and mixing the prepared microspherical metal organic framework compound Mn-BTC with Se powder according to the ratio of 1:10, then placing the porcelain boats in a tube furnace, enabling Mn-BTC to be downstream and Se powder to be upstream, heating the temperature from room temperature to 450 ℃ at the heating rate of 3 ℃/min under the argon atmosphere, and preserving the heat at 450 ℃ for 3 hours to obtain the microspheric manganese selenide/carbon composite material; the solution A is prepared by taking Mn (CH)3COO)2·4H2Dissolving O and PVP-K30 in a mixed solution composed of ethanol and deionized water, and stirring and dissolving at a rotating speed of 300-400 r/min to obtain a mixed solution A; the Mn (CH)3COO)2·4H2The mass ratio of O to PVP-K30 is 0.2449-0.4898: 1-3, and the unit is g/g; the mass-volume ratio of the mixed solution composed of the PVP-K30, ethanol and deionized water is 1-3: 100, and the unit is g/ml; the preparation of the solution B is to dissolve trimesic acid in a mixed solution consisting of ethanol and deionized water, and stir the mixed solution to obtain the solution B; the mass-volume ratio of the mixed solution of the trimesic acid, the ethanol and the deionized water is 0.6304-0.8994: 100, and the unit is g/ml; the mixed aging is to drop the prepared solution A into the solution B under the stirring condition, the rotating speed is 300-400 r/min during dropping, the stirring is continued for 10-20 min, the stirring is stopped, and the solution A is placed at room temperature for aging for 20-24 h; wherein the volume ratio of the solution A to the solution B is 1: 100; the centrifugal washing is to carry out centrifugal separation on the aged product, collect centrifugal precipitate, wash the precipitate for 3 times by using a mixed solution of ethanol and deionized water, and collect the precipitate for later use; the volume ratio of the dosage of the ethanol to the dosage of the deionized water is 1: 100-1: 150.
2. The preparation method of claim 1, wherein the vacuum drying is carried out by drying the prepared precipitate in air at 55-65 ℃ for 12-15 h.
3. The method according to claim 2, wherein the mixed solution of ethanol and deionized water is prepared by mixing ethanol and deionized water in a volume ratio of 1: 1.
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| CN113444257A (en) * | 2021-06-21 | 2021-09-28 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Preparation method and application of unsaturated coordination manganese-based metal organic framework composite material |
| CN113571674B (en) * | 2021-09-22 | 2021-12-24 | 河南师范大学 | Preparation method and application of in-situ carbon-coated binary transition metal oxide heterojunction bowl-shaped nano composite material |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962037A (en) * | 2012-11-01 | 2013-03-13 | 中国科学院大连化学物理研究所 | Metal-organic framework material for methane adsorption separation and preparation method thereof |
| CN106076418A (en) * | 2016-03-14 | 2016-11-09 | 郑州航空工业管理学院 | A kind of metallic organic framework composite and preparation method |
Family Cites Families (1)
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962037A (en) * | 2012-11-01 | 2013-03-13 | 中国科学院大连化学物理研究所 | Metal-organic framework material for methane adsorption separation and preparation method thereof |
| CN106076418A (en) * | 2016-03-14 | 2016-11-09 | 郑州航空工业管理学院 | A kind of metallic organic framework composite and preparation method |
Non-Patent Citations (3)
| Title |
|---|
| "A new strategy to effectively alleviate volume expansionand enhance the conductivity of hierarchical MnO@C nanocomposites for lithium ion batteries";Zhe Cui etal;《Journal of Materials Chemistry A》;20171107;第5卷(第41期);第21699-21708页 * |
| "钠离子电池中碳负极及碳材料提升负极复合物储钠性能的研究";吕红艳;《中国博士学位论文全文数据库工程科技II辑》;20180115(第01期);第C042-149页 * |
| Zhe Cui etal."A new strategy to effectively alleviate volume expansionand enhance the conductivity of hierarchical MnO@C nanocomposites for lithium ion batteries".《Journal of Materials Chemistry A》.2017,第5卷(第41期),第21699-21708页. * |
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