CN117985697A - A lithium manganate/nitrogen-doped carbon nanotube composite material and its preparation method and use - Google Patents
A lithium manganate/nitrogen-doped carbon nanotube composite material and its preparation method and use Download PDFInfo
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Abstract
The invention provides a lithium manganate/nitrogen-doped carbon nanotube composite material, a preparation method and application thereof, wherein the preparation method is characterized in that Mn 2+ is coordinated with folic acid and hydrazine hydrate, hydrogen bonding among folic acid molecules and bridging of hydrazine hydrate molecules are utilized to enable the three to self-assemble into a nano tubular structure Mn-FA/NTs, organic matters are carbonized to form nitrogen-doped carbon nanotubes, free C generated by carbonization is utilized to perform oxidation-reduction reaction with Mn 2+ and potassium permanganate, manganese is converted into Mn 3+～Mn4+, a small amount of Mn-Nx is generated, and then lithium manganate material with spinel structure is generated through mixing solid phase reaction with a lithium source and is in-situ embedded between the nitrogen-doped carbon nanotubes, so that the lithium manganate/nitrogen-doped carbon nanotube composite material is obtained.
Description
Technical Field
The invention belongs to the technical field of lithium resource extraction, and relates to a lithium manganate/nitrogen doped carbon nano tube composite material, and a preparation method and application thereof.
Background
With the increasing prominence of resource and environmental issues, lithium ion batteries are becoming one of the most important electrical energy storage devices in daily life, with the rapid increase in lithium demand. Solid-phase lithium resources are gradually approaching exhaustion, and technologies for extracting lithium by utilizing liquid-phase lithium resources, such as salt lake brine, which occupy 80% of global lithium resources are attracting more and more attention. The traditional liquid phase lithium extraction technology mainly comprises a precipitation method, a solvent extraction method, an ion exchange method, a calcination leaching method and the like. Among them, the ion exchange method based on inorganic ion sieve is attracting attention due to high extraction efficiency. However, the ion exchange method of the inorganic ion sieve needs to use a large amount of strong acid for washing in the desorption process, and serious corrosion and pollution are caused to equipment and environment. Based on the above, researchers propose to use an electrochemical method for adsorbing and desorbing lithium ions, and one of the key points of the electrochemical method is to select a lithium extraction electrode material, so that lithium manganate becomes one of the most promising electrode materials in the electrochemical lithium extraction field in consideration of the biosafety and the lithium extraction efficiency of the electrode material.
How to make lithium manganate have abundant electroactive sites, have high selectivity to Li ions, and simultaneously shorten the lithium ion transmission path so as to optimize the lithium extraction capacity and the lithium extraction rate is an important target for the development of the lithium manganate electrode material performance.
Carbon nanotubes are special carbon materials composed of five-, six-or seven-membered rings of carbon atoms linked together, which can be understood as hollow tubes of one or more layers rolled up in a flat shape like paper, with tube diameters generally in the nanometer range. Because the carbon nano tube has a layered structure similar to graphene, the carbon nano tube has high strength, electrical conductivity, thermal conductivity and chemical stability, and is often used as an electrical conduction agent and a functional additive to prepare a composite electrode material so as to improve the comprehensive performance of the electrode material.
In the field of lithium extraction in electrochemical salt lakes, adding graphene materials (such as graphene, graphite, acetylene black, carbon nanotubes and the like) has been proved to improve the lithium extraction capacity and the Li ion selectivity of an electrode, but because the binding force between the graphene materials and the electrode materials is poor, in order to avoid falling, the electrode materials and the graphene materials are mixed with a binder to prepare a composite electrode material, and the mixing mode ensures that the dispersion degree of the conductive agent and the electrode active material is poor, agglomeration is easy to cause, the binder is a non-electrochemical active substance, and the composite electrode material is easy to cover an active adsorption site by the binder, so that the overall performance is reduced.
Disclosure of Invention
In view of the problems existing in the prior art, the invention aims to provide a lithium manganate/nitrogen-doped carbon nanotube composite material, a preparation method and application thereof, wherein the preparation method is characterized in that the three materials are self-assembled into a nano tubular structure Mn-FA/NTs by utilizing the coordination effect of Mn 2+ and folic acid and hydrazine hydrate, the hydrogen bonding effect among folic acid molecules and the bridging effect of hydrazine hydrate molecules, then organic matters are carbonized to form nitrogen-doped carbon nanotubes, free C generated by carbonization is utilized to perform oxidation-reduction reaction with Mn 2+ and potassium permanganate, manganese element is converted into Mn 3+～Mn4+, a small amount of Mn-Nx is generated, and then a lithium manganate material with a spinel structure is generated by mixing solid phase reaction with a lithium source and is embedded between the nitrogen-doped carbon nanotubes in situ, so that the lithium manganate/nitrogen-doped carbon nanotube composite material is obtained.
To achieve the purpose, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a method for preparing a lithium manganate/nitrogen doped carbon nanotube composite material, the method comprising:
Mixing manganese salt, folic acid and hydrazine hydrate to form a mixed solution, and carrying out hydrothermal reaction to obtain Mn-FA/NTs;
Mixing Mn-FA/NTs with potassium permanganate, and carbonizing to obtain Mn-NC/NTs;
Mixing Mn-NC/NTs with lithium salt, and performing high-temperature treatment to obtain the lithium manganate/nitrogen-doped carbon nano tube composite material LMO-NC/NTs.
Among Mn-FA/NTs, mn-NC/NTs and LMO-NC/NTs, the "/" represents that composite materials are formed, FA represents folic acid, NTs represents nanotubes, NC represents nitrogen doped carbon, and LMO represents lithium manganate. Mn-Nx refers to a substance formed by nitrogen and manganese.
The lithium manganate/nitrogen doped carbon nanotube composite material is a nanotube precursor synthesized by Mn 2+ provided by manganese salt, folic Acid (FA) and hydrazine hydrate through hydrothermal reaction, and is prepared by a solid-phase synthesis method with a lithium source after carbonization and oxidation reduction reaction. Specifically, the coordination effect of Mn 2+, folic acid and hydrazine hydrate, the hydrogen bonding effect among folic acid molecules and the bridging effect of hydrazine hydrate molecules enable the three to be self-assembled into a precursor Mn-FA/NTs of a nano tubular structure through hydrothermal reaction, and Mn elements are distributed inside and outside the nano tubular structure of the precursor. Carbonizing Mn-FA/NTs in an inert atmosphere to carbonize organic matters in the precursor to form nitrogen-doped carbon nanotubes, and carrying out oxidation-reduction reaction on free C generated in the carbonization process, mn 2+ and potassium permanganate to convert Mn 2+ and MnO 4- into Mn 3+～Mn4+, and generating Mn-Nx to be loaded between the nitrogen-doped carbon nanotubes to obtain Mn-NC/NTs; further, mn-NC/NTs and a lithium source are mixed for solid phase synthesis, so that the lithium manganate material with a spinel structure is prepared, and lithium manganate crystals are inlaid between the nitrogen-doped carbon nanotubes.
In the lithium manganate/nitrogen-doped carbon nanotube composite material obtained by the preparation method, on one hand, the nitrogen-doped carbon nanotube has better hydrophilicity than a common carbon nanotube, and nitrogen-doped atoms can change the local charge density of the carbon nanotube, improve the electron transmissibility of the carbon nanotube, reduce the resistance coefficient, thereby improving the lithium diffusion speed and the lithium extraction capacity; on the other hand, the specific in-situ synthesis mode ensures that the dispersibility and the binding force of the lithium manganate crystal and the nitrogen-doped carbon nano tube are better, the mesoporous structure in the composite material is more, the pore diameter dispersibility is smaller, the resistivity of the electrode is further reduced, and the lithium extraction rate and the lithium extraction capacity are improved; in addition, the existence of Mn-Nx in the intermediate product Mn-FA/NTs enables manganese element to be more easily converted into Mn 4+ in the subsequent solid-phase reaction with a Li source, so that the Mn 4+/Mn3+ proportion in the material is improved, the problem of manganese dissolution loss of lithium manganate is favorably inhibited, and the cycling stability of the material is improved.
The following technical scheme is a preferred technical scheme of the invention, but is not a limitation of the technical scheme provided by the invention, and the technical purpose and beneficial effects of the invention can be better achieved and realized through the following technical scheme.
According to the preferable technical scheme, the preparation method comprises the steps of preparing manganese salt and folic acid into suspension, and then dropwise adding hydrazine hydrate solution to obtain mixed solution.
Preferably, the solvent in the suspension comprises ethanol and water in a volume ratio of (0.8-1.5): 1, such as 0.8:1, 0.9:1, 1:1, 1.2:1, 1.3:1, 1.4:1 or 1.5:1, etc., but not limited to the recited values, other non-recited values within the above ranges are equally applicable.
Preferably, the mass concentration of the hydrazine hydrate solution is 60% to 70%, for example, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69% or 70%, etc., but is not limited to the recited values, and other non-recited values within the above-mentioned range are equally applicable.
In the preparation method of the invention, folic acid is also used as a main carbon source, and the absence of folic acid can also lead to the failure of nanotube formation, while hydrazine hydrate is used as a main nitrogen source.
As a preferable technical scheme of the invention, the molar ratio is 1 (0.5-1): (120-140), the dosage of the manganese salt, folic acid and hydrazine hydrate is controlled, for example 1:0.5:120、1:0.6:120、1:0.7:120、1:0.8:120、1:0.9:120、1:1:120、1:0.5:125、1:0.6:125、1:0.7:125、1:0.8:125、1:0.9:125、1:1:125、1:0.5:130、1:0.6:130、1:0.7:130、1:0.8:130、1:0.9:130、1:1:130、1:0.5:135、1:0.6:135、1:0.7:135、1:0.8:135、1:0.9:135、1:1:135、1:0.5:140、1:0.6:140、1:0.7:140、1:0.8:140、1:0.9:140 or 1:1:140, but the invention is not limited to the listed values, and other non-listed values in the above-mentioned numerical range are applicable.
Preferably, the manganese salt comprises a soluble divalent manganese salt comprising manganese chloride and/or manganese nitrate.
In a preferred embodiment of the present invention, the temperature of the hydrothermal reaction is 150 to 170 ℃, for example 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃ or the like, and the time is 1 to 3 hours, for example 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value ranges are equally applicable.
As a preferable technical scheme of the invention, the mass ratio of Mn-FA/NTs to potassium permanganate is controlled to be 1 (0.2-0.5), for example, 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45 or 1:0.5, etc., but the invention is not limited to the listed values, and other non-listed values in the above-mentioned numerical ranges are applicable.
Preferably, the carbonization treatment is performed under a protective atmosphere comprising argon.
Preferably, the carbonization treatment is performed at a temperature of 550 to 650 ℃, such as 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃ or the like for a time of 1 to 3 hours, such as1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours or the like, and a heating rate of 1 to 5 ℃/min, such as1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min or the like, but the carbonization treatment is not limited to the recited values, and other non-recited values within the above-recited range are equally applicable.
As a preferable technical scheme of the invention, the preparation method comprises the steps of dispersing Mn-NC/NTs in a solvent, adding lithium salt for mixing, heating for evaporating the solvent, drying, grinding and then carrying out the high-temperature treatment.
Preferably, the solvent comprises ethanol.
The temperature of the heating evaporation is preferably 40 to 60 ℃, for example 40 ℃, 450 ℃, 50 ℃, 55 ℃, 60 ℃, or the like, but is not limited to the values listed, and other values not listed in the above-mentioned value ranges are equally applicable.
Preferably, the temperature of the drying is 60 to 80 ℃, for example 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or the like, but is not limited to the recited values, and other values not recited in the above-mentioned numerical ranges are equally applicable.
Preferably, the amount of the lithium salt to Mn-NC/NTs is controlled in terms of molar ratio of Li to Mn (1.05-1.2): 1, for example, 1.05:1, 1.08:1, 1.1:1, 1.12:1, 1.14:1, 1.16:1, 1.18:1, or 1.2:1, etc., but not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
Preferably, the lithium salt comprises at least one of lithium chloride, lithium nitrate, or lithium acetate, such as typical but non-limiting combinations comprising lithium chloride in combination with lithium nitrate, lithium chloride in combination with lithium acetate, or lithium acetate in combination with lithium nitrate, and the like.
As a preferable technical scheme of the invention, the high-temperature treatment comprises the steps of carrying out heat treatment in an autoclave, and then heating up for calcination.
The heat treatment is preferably performed at a temperature of 100 to 200 ℃, for example, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃,200 ℃, or the like, for a time of 24 to 60 hours, for example, 24 hours, 28 hours, 32 hours, 36 hours, 40 hours, 44 hours, 48 hours, 52 hours, 56 hours, 60 hours, or the like, but is not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
The calcination temperature is preferably 400 to 600 ℃, for example 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃, 600 ℃ or the like, and the time is 2 to 6 hours, for example 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, or 6 hours or the like, but not limited to the recited values, and other non-recited values within the above-recited value ranges are equally applicable.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
Dispersing soluble divalent manganese salt and folic acid in ethanol water solution, wherein the volume ratio of ethanol to water is (0.8-1.5): 1, carrying out intense stirring, carrying out ultrasonic treatment until the solution is a uniform brown suspension, then dropwise adding hydrazine hydrate solution with the mass concentration of 60-70%, controlling the molar ratio of manganese salt to folic acid to hydrazine hydrate to be 1 (0.5-1): 120-140), carrying out ultrasonic treatment on the obtained mixed solution, transferring the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 2 hours at 150-170 ℃, carrying out repeated suction filtration and washing for multiple times by using deionized water and ethanol, and drying to obtain brown powder Mn-FA/NTs;
according to the mass ratio of 1 (0.2-0.5), uniformly paving the powder obtained by mixing and grinding Mn-FA/NTs and potassium permanganate in a porcelain boat, heating to 550-650 ℃ at 1-5 ℃/min under Ar gas condition, and preserving heat for 1-3 hours to carry out carbonization treatment to obtain Mn-NC/NTs;
Dispersing Mn-NC/NTs in ethanol by ultrasonic, adding lithium salt, controlling the dosage of the lithium salt and Mn-NC/NTs according to the molar ratio of Li to Mn of (1.05-1.2), heating to 40-60 ℃, continuously stirring until the solvent is completely volatilized, drying the mixture at 60-80 ℃, grinding until no obvious granular sensation is generated, transferring the mixture into an autoclave, heat-treating the mixture at 100-200 ℃ for 24-60 h, and calcining the mixture at 400-600 ℃ for 2-6 h to obtain the lithium manganate/nitrogen-doped carbon nano tube composite material LMO-NC/NTs.
In a second aspect, the present invention provides a lithium manganate/nitrogen doped carbon nanotube composite material, obtained according to the preparation method of the first aspect.
In a third aspect, the present invention provides a use of a lithium manganate/nitrogen doped carbon nanotube composite material, the use comprising use in salt lake lithium extraction.
Compared with the prior art, the invention has at least the following beneficial effects:
The invention provides a new preparation method for synthesizing a lithium manganate/nitrogen-doped carbon nano tube composite material, which utilizes Mn 2+, folic acid and hydrazine hydrate to form a nano tube precursor, and generates nitrogen-doped carbon nano tubes through carbonization and generates Mn 3+～Mn4+ through oxidation-reduction reaction, and then generates spinel lithium manganate inlaid between the nitrogen-doped carbon nano tubes in situ through solid-phase reaction with lithium salt; the preparation method can obtain the composite material with better dispersibility and binding force without using a binder, is simple and convenient, and is easy for large-scale production;
The lithium manganate/nitrogen doped carbon nano tube composite material has more mesoporous structure and smaller aperture dispersibility, is beneficial to further reducing the resistivity of an electrode and improving the lithium extraction rate and the lithium extraction capacity; in addition, the existence of Mn-Nx in the intermediate product Mn-FA/NTs enables manganese element to be more easily converted into Mn 4+ in the subsequent solid-phase reaction with a Li source, so that the Mn 4+/Mn3+ proportion in the material is improved, the problem of manganese dissolution loss of lithium manganate is favorably inhibited, and the cycling stability of the material is improved.
Drawings
FIG. 1 is an XRD pattern of LMO-NC/NTs obtained in example 1.
FIG. 2 is an SEM image of LMO-NC/NTs obtained in example 1.
FIG. 3 is an SEM image of LMO-NC/NTs obtained in comparative example 1.
FIG. 4 is a TEM image of LMO-NC/NTs obtained in example 1.
FIG. 5 is a XPS full scan spectrum of Mn-FA/NTs, mn-NC/NTs and LMO-NC/NTs obtained in example 1.
FIG. 6 is a narrow spectrum of XPS oxygen for Mn-FA/NTs obtained in example 1.
FIG. 7 is a narrow spectrum of XPS nitrogen element of Mn-FA/NTs obtained in example 1.
FIG. 8 is a narrow spectrum of XPS manganese element of Mn-NC/NTs and LMO-NC/NTs obtained in example 1.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments.
It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a preparation method of a lithium manganate/nitrogen doped carbon nano tube composite material, which comprises the following steps:
(1) Dispersing manganese chloride serving as a soluble divalent manganese salt and folic acid in an ethanol water solution (the volume ratio of ethanol to water is 0.8:1), controlling the concentration of folic acid in the ethanol water solution to be 1g/40mL, vigorously stirring, performing ultrasonic treatment until the solution is a uniform brown suspension, then dropwise adding a hydrazine hydrate solution with the mass concentration of 65%, controlling the molar ratio of manganese salt to folic acid to hydrazine hydrate to be 1:0.5:120, ultrasonically transferring the obtained mixed solution into a hydrothermal reaction kettle, performing hydrothermal reaction for 2h at 170 ℃, repeatedly performing suction filtration and washing with deionized water and ethanol for multiple times, and drying to obtain brown powder Mn-FA/NTs;
(2) Uniformly paving the powder obtained by mixing and grinding Mn-FA/NTs and potassium permanganate in a porcelain boat according to the mass ratio of 1:0.2, heating to 600 ℃ at 2 ℃/min under Ar gas condition, and preserving heat for 2 hours for carbonization treatment to obtain Mn-NC/NTs;
(3) Dispersing Mn-NC/NTs in ethanol by ultrasonic, controlling the solid-liquid ratio to be 1g:50mL, adding lithium chloride as lithium salt, controlling the dosage of the lithium salt and Mn-NC/NTs according to the molar ratio of Li to Mn to be 1.05:1, heating to 50 ℃, continuously stirring until the solvent is completely volatilized, drying the mixture at 70 ℃, grinding until no obvious granular sensation exists, transferring the mixture into an autoclave, heat-treating the mixture at 100 ℃ for 48h, and calcining the mixture at 500 ℃ for 4h to obtain the lithium manganate/nitrogen-doped carbon nano tube composite material LMO-NC/NTs.
Example 2
The embodiment provides a preparation method of a lithium manganate/nitrogen doped carbon nano tube composite material, which comprises the following steps:
(1) Dispersing manganese nitrate serving as a soluble divalent manganese salt and folic acid in an ethanol water solution (the volume ratio of ethanol to water is 1.5:1), controlling the concentration of folic acid in the ethanol water solution to be 1g/50mL, vigorously stirring, performing ultrasonic treatment until the solution is a uniform brown suspension, then dropwise adding a hydrazine hydrate solution with the mass concentration of 65%, controlling the molar ratio of manganese salt to folic acid to hydrazine hydrate to be 1:1:140, ultrasonically transferring the obtained mixed solution into a hydrothermal reaction kettle, performing hydrothermal reaction for 2h at 150 ℃, repeatedly performing suction filtration and washing with deionized water and ethanol for multiple times, and drying to obtain brown powder Mn-FA/NTs;
(2) Uniformly paving the powder obtained by mixing and grinding Mn-FA/NTs and potassium permanganate in a porcelain boat according to the mass ratio of 1:0.5, heating to 600 ℃ at 2 ℃/min under the Ar gas condition, and preserving heat for 2 hours for carbonization treatment to obtain Mn-NC/NTs;
(3) Dispersing Mn-NC/NTs in ethanol by ultrasonic, controlling the solid-liquid ratio to be 1g:50mL, adding lithium chloride as lithium salt, controlling the dosage of the lithium salt and Mn-NC/NTs according to the molar ratio of Li to Mn to be 1.1:1, heating to 50 ℃, continuously stirring until the solvent is completely volatilized, drying the mixture at 70 ℃, grinding until no obvious granular sensation exists, transferring the mixture into an autoclave, heat-treating the mixture at 200 ℃ for 48h, and calcining the mixture at 400 ℃ for 4h to obtain the lithium manganate/nitrogen-doped carbon nano tube composite material LMO-NC/NTs.
Example 3
The embodiment provides a preparation method of a lithium manganate/nitrogen doped carbon nano tube composite material, which comprises the following steps:
(1) Dispersing manganese nitrate serving as a soluble divalent manganese salt and folic acid in an ethanol water solution (the volume ratio of ethanol to water is 1:1), controlling the concentration of folic acid in the ethanol water solution to be 1g/40mL, vigorously stirring, performing ultrasonic treatment until the solution is a uniform brown suspension, then dropwise adding a hydrazine hydrate solution with the mass concentration of 65%, controlling the molar ratio of manganese salt, folic acid to hydrazine hydrate to be 1:0.8:130, ultrasonically transferring the obtained mixed solution into a hydrothermal reaction kettle, performing hydrothermal reaction for 2h at 160 ℃, repeatedly performing suction filtration and washing with deionized water and ethanol for multiple times, and drying to obtain brown powder Mn-FA/NTs;
(2) Uniformly paving the powder obtained by mixing and grinding Mn-FA/NTs and potassium permanganate in a porcelain boat according to the mass ratio of 1:0.3, heating to 600 ℃ at 2 ℃/min under the Ar gas condition, and preserving heat for 2 hours for carbonization treatment to obtain Mn-NC/NTs;
(3) Dispersing Mn-NC/NTs in ethanol by ultrasonic, controlling the solid-liquid ratio to be 1g:50mL, adding lithium chloride as lithium salt, controlling the dosage of the lithium salt and Mn-NC/NTs according to the molar ratio of Li to Mn to be 1.2:1, heating to 50 ℃, continuously stirring until the solvent is completely volatilized, drying the mixture at 70 ℃, grinding until no obvious granular sensation exists, transferring the mixture into an autoclave, heat-treating the mixture at 200 ℃ for 48h, and calcining the mixture at 600 ℃ for 4h to obtain the lithium manganate/nitrogen-doped carbon nano tube composite material LMO-NC/NTs.
Comparative example 1
This comparative example provides a method for preparing a lithium manganate/nitrogen doped carbon nanotube composite material, which does not use hydrazine hydrate, except that the other conditions are exactly the same as example 3.
Comparative example 2
This comparative example provides a method for preparing a lithium manganate/nitrogen doped carbon nanotube composite material, which does not use potassium permanganate, except that the other conditions are exactly the same as in example 3.
Comparative example 3
The comparative example provides a composite material of nitrogen doped nanotubes and LiMn 2O4, the preparation method of which comprises:
(1) Solid phase synthesis of LiMn 2O4: weighing MnO 2 and LiOH as raw materials according to the molar ratio of Li/Mn of 1:2, fully grinding and mixing, and preparing LiMn 2O4 with a spinel structure through a high-temperature solid phase reaction at 700 ℃;
(2) Composite material: and mixing and grinding the LiMn 2O4 and the nitrogen-doped nano tube according to the mass ratio of 1:0.5 to obtain the composite material.
Characterization and testing:
and I, observing the microscopic morphology of the material by adopting a JEOL JSM-6490LV type scanning electron microscope.
The crystal phase and crystal structure of the material were studied by X-ray powder diffractometer (XRD, rigaku D/max-2600PC, japan), and the test was conducted by using K.alpha.rays of Cu, the wavelength lambda being 0.154056nm, the voltage 40kV, the current 40mA, and the scanning range 2. Theta. Being 10 to 80 ℃. XRD test results were analyzed using the jack 6 software.
And III, testing the morphology of the sample by using a transmission electron microscope model Talos F200S G.
And IV, determining the components, valence and other information of the surface of the material by adopting an ESCALAB 250Xi type X-ray photoelectron spectrometer.
And V, measuring nitrogen adsorption-desorption curves of the composite materials obtained in the examples and the comparative examples by using a high-performance specific surface and a micropore analyzer BSD-PM1 to obtain internal micropore structure information.
FIG. 1 is an XRD pattern of LMO-NC/NTs obtained in example 1. As can be seen from the figure, diffraction peaks at 26.2 DEG and 42.2 DEG correspond to (002) and (100) crystal planes of a carbon material (PDF: 89-8487), respectively, and the derivative peaks are relatively sharp, indicating that LMO-NC/NTs have good crystallinity. Other diffraction peaks were consistent with LiMn 2O4 (JCPDS.35-0782). The results show that the material obtained in example 1 is a composite of LiMn 2O4 and carbon nanotubes. XRD testing of the composite material obtained in comparative example 2 shows that the product does not conform to LiMn 2O4.
Fig. 2 and 3 are SEM images of the composite materials obtained in example 1 and comparative example 1, respectively. It can be seen from the figure that a composite material of tubular structure could not be obtained without the addition of hydrazine hydrate.
FIG. 4 is a TEM image of LMO-NC/NTs obtained in example 1. As can be seen from the figure, spinel lithium manganate particles are embedded in the nanotubes.
FIG. 5 is a XPS full scan spectrum of Mn-FA/NTs, mn-NC/NTs and LMO-NC/NTs obtained in example 1. As can be seen from the figure, the Mn-FA/NTs show C1s, N1s, O1s, mn 2p3/2 and Mn 2p1/2; mn-NC/NTs show C1s, N1s, mn 2p3/2 and Mn 2p1/2; the LMO-NC/NTs show C1s, N1s, mn 2p3/2, mn 2p1/2 and Li 1s.
FIGS. 6 and 7 show the XPS oxygen element narrow spectrum and the XPS nitrogen element narrow spectrum of Mn-FA/NTs obtained in example 1, respectively. The narrow spectrum of Mn-FA/NTs O shows that the difference between the binding energies of C=O (binding energy 532. Lev) and C-O (binding energy 532.5 eV) of the carboxylic acid group is 0.4eV, which is much smaller than the difference of 1.5eV between the two in the free carboxylic acid, indicating that the electron delocalization effect in the carboxyl group in Mn-FA/NTs is increased, confirming that both O of the carboxylic acid group in folic acid are involved in coordination with Mn, and the other oxygen element in the map comes from coordination water (binding energy 533.2 eV). The narrow N-element spectrum of Mn-FA/NTs shows that the N1s spectrum can be split into 399.6eV (NH 2-)、400.6eV(N2H4 -Mn), 401.1eV and 401.6eV (pteroic acid N). Therefore, it is shown that Mn 2+ coordinates with folic acid and hydrazine hydrate.
FIG. 8 shows XPS manganese element narrow spectra of Mn-NC/NTs and LMO-NC/NTs obtained in example 1. The narrow spectrum of Mn element of Mn-NC/NTs shows that binding energies 653.8eV and 642.5eV, 652.6 and 641.3eV, 651.1eV and 640eV correspond to Mn 4+、Mn3+ and Mn-Nx respectively, which indicates that Mn 2+ and MnO 4- undergo oxidation-reduction reaction and Mn-Nx is generated in carbonization process.
The narrow spectrum of Mn element of LMO-NC/NTs shows that the peak intensity corresponding to Mn 3+、Mn4+ and Mn-Nx is changed, the larger the peak intensity is, the more the content is indicated, the content of Mn 4+ is improved after the curing reaction with Li source, the quantity of Mn-Nx is reduced, and the conversion of part of Mn-Nx into Mn 4+ is illustrated, so that the preparation method provided by the invention is beneficial to improving the content of Mn 4+/Mn3+, thereby inhibiting the dissolution loss of Mn element.
VI, preparation and test of lithium extraction electrode:
The composites obtained in examples and comparative examples, carbon black, polyvinylidene fluoride were mixed with N-methylpyrrolidone (NMP) in a weight ratio of 7:2:1 to prepare a slurry for working electrode. And then loading the slurry on carbon fiber cloth at a concentration of 6mg/cm < 2 >, and drying for 10 hours at 80 ℃ to obtain the lithium-rich electrode. Further, the prepared lithium-rich electrode is taken as an anode, the Ag/AgCl electrode is taken as a cathode, and the two electrodes are placed in 0.05M KCl solution to be subjected to electrochemical treatment for 2 hours under the constant potential condition of 1.0V, so that the lithium-poor electrode is obtained.
The lithium extraction performance of a sample is inspected by adopting a lithium-rich electrode|lean lithium electrode system (electrochemical deintercalation method), specifically, a lithium-rich electrode is taken as an anode, a lean lithium electrode is taken as a cathode, an anion exchange membrane is used for separating an anode chamber from a cathode chamber, wherein electrolyte (recovery liquid) of the anode chamber is 0.05M KCl solution, electrolyte (extraction liquid) of the cathode chamber is 0.05M mixed solution of LiCl and MgCl 2 of 1M, the electrode spacing is 4.5cm, and the voltage is constant at 1V. Taking Ag as a counter electrode, extracting Li from a lithium-poor electrode obtained after lithium removal as a cathode, converting the lithium-poor electrode into an anode, removing lithium in a body system, sampling in a recovery tank for a plurality of times, analyzing the concentration of Li +、Mg2+ and Mn ions by utilizing ICP-OES, calculating indexes such as lithium extraction capacity E Li (mg/g), lithium extraction rate r E(mg·g-1·min-1), separation coefficient alpha Li/Mg, manganese dissolution loss rate E Mn (mg/g) and the like, and the calculation formula is shown as follows:
In the method, in the process of the invention, AndThe final mass concentration and volume of Li ions in the recovered liquid are respectively; /(I)AndRespectively sampling the mass concentration and the volume of Li ions at a certain time; t (min) is the sampling time,AndThe molar concentration of Li +、Mg2+ in the recovery liquid at the time t is respectively; /(I)AndThe molar concentration of Li +、Mg2+ in the recovery liquid at the moment 0 respectively; /(I)AndThe final mass concentration and volume of Mn ions in the recovered liquid; /(I)AndRespectively sampling mass concentration and volume of Mn ions at a certain time; m (g) is the mass of the lithium ion sieve precursor.
The results are reported in Table 1.
TABLE 1
From the above, it can be seen that:
According to the preparation method, mn 2+, folic acid and hydrazine hydrate are coordinated, hydrogen bonding among folic acid molecules and bridging of hydrazine hydrate molecules are utilized to enable the three to be self-assembled into a nano-tube-shaped structure Mn-FA/NTs, then organic matters are carbonized to form nitrogen-doped carbon nano tubes, free C generated by carbonization is utilized to carry out oxidation-reduction reaction with Mn 2+ and potassium permanganate, manganese element is converted into Mn 3+～Mn4+, a small amount of Mn-Nx is generated, and then lithium manganate material with spinel structure is generated through mixing solid phase reaction with a lithium source and is embedded between the nitrogen-doped carbon nano tubes in situ, so that the lithium manganate/nitrogen-doped carbon nano tube composite material is obtained. In the comparative example 1, hydrazine hydrate is not used, the lithium extraction rate of the obtained product is obviously reduced, and in the comparative example 2, lithium manganate cannot be synthesized and lithium extraction cannot be performed because potassium permanganate is not used; in addition, the potassium permanganate needs to be used separately from the manganese salt, and if the manganese salt and the potassium permanganate are mixed simultaneously in the step (1) to carry out hydrothermal reaction, divalent manganese coordination is affected to form the nanotube. The lithium extraction performance of the product obtained by the invention is more excellent than that of the composite material of the nitrogen doped nanotube and LiMn 2O4 in comparative example 3.
The detailed structural features of the present invention are described in the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. The preparation method of the lithium manganate/nitrogen doped carbon nano tube composite material is characterized by comprising the following steps of:
Mixing manganese salt, folic acid and hydrazine hydrate to form a mixed solution, and carrying out hydrothermal reaction to obtain Mn-FA/NTs;
Mixing Mn-FA/NTs with potassium permanganate, and carbonizing to obtain Mn-NC/NTs;
Mixing Mn-NC/NTs with lithium salt, and performing high-temperature treatment to obtain the lithium manganate/nitrogen-doped carbon nano tube composite material LMO-NC/NTs.
2. The preparation method according to claim 1, wherein the preparation method comprises preparing manganese salt and folic acid into suspension, and then dripping hydrazine hydrate solution to obtain mixed solution;
preferably, the solvent in the suspension comprises ethanol and water in a volume ratio of (0.8-1.5): 1;
Preferably, the mass concentration of the hydrazine hydrate solution is 60% -70%.
3. The preparation method according to claim 1 or 2, wherein the molar ratio is 1 (0.5-1): (120-140) controlling the amounts of manganese salt, folic acid and hydrazine hydrate;
Preferably, the manganese salt comprises a soluble divalent manganese salt comprising manganese chloride and/or manganese nitrate.
4. A method according to any one of claims 1 to 3, wherein the hydrothermal reaction is carried out at a temperature of 150 to 170 ℃ for a period of 1 to 3 hours.
5. The preparation method according to any one of claims 1 to 4, wherein the mass ratio is 1 (0.2 to 0.5) by controlling the amounts of Mn-FA/NTs and potassium permanganate;
preferably, the carbonization treatment is performed under a protective atmosphere, the protective atmosphere comprising argon;
preferably, the carbonization treatment is carried out at 550-650 ℃ for 1-3 hours at a heating rate of 1-5 ℃/min.
6. The preparation method according to any one of claims 1 to 5, wherein the preparation method comprises dispersing Mn-NC/NTs in a solvent, adding a lithium salt to mix, heating to evaporate the solvent, drying, grinding, and then performing the high temperature treatment;
Preferably, the amount of the lithium salt and Mn-NC/NTs is controlled according to the mole ratio of Li to Mn of (1.05-1.2) 1;
Preferably, the lithium salt includes at least one of lithium chloride, lithium nitrate, or lithium acetate.
7. The production method according to any one of claims 1 to 6, wherein the high-temperature treatment comprises heat treatment in an autoclave and then calcination at an elevated temperature;
preferably, the temperature of the heat treatment is 100-200 ℃ and the time is 24-60 h;
Preferably, the calcination temperature is 400-600 ℃ and the time is 2-6 h.
8. The method according to any one of claims 1 to 7, characterized in that the method comprises:
Dispersing soluble divalent manganese salt and folic acid in ethanol water solution, wherein the volume ratio of ethanol to water is (0.8-1.5): 1, carrying out intense stirring, carrying out ultrasonic treatment until the solution is a uniform brown suspension, then dropwise adding hydrazine hydrate solution with the mass concentration of 60-70%, controlling the molar ratio of manganese salt to folic acid to hydrazine hydrate to be 1 (0.5-1): 120-140), carrying out ultrasonic treatment on the obtained mixed solution, transferring the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 2 hours at 150-170 ℃, carrying out repeated suction filtration and washing for multiple times by using deionized water and ethanol, and drying to obtain brown powder Mn-FA/NTs;
according to the mass ratio of 1 (0.2-0.5), uniformly paving the powder obtained by mixing and grinding Mn-FA/NTs and potassium permanganate in a porcelain boat, heating to 550-650 ℃ at 1-5 ℃/min under Ar gas condition, and preserving heat for 1-3 hours to carry out carbonization treatment to obtain Mn-NC/NTs;
Dispersing Mn-NC/NTs in ethanol by ultrasonic, adding lithium salt, controlling the dosage of the lithium salt and Mn-NC/NTs according to the molar ratio of Li to Mn of (1.05-1.2), heating to 40-60 ℃, continuously stirring until the solvent is completely volatilized, drying the mixture at 60-80 ℃, grinding until no obvious granular sensation is generated, transferring the mixture into an autoclave, heat-treating the mixture at 100-200 ℃ for 24-60 h, and calcining the mixture at 400-600 ℃ for 2-6 h to obtain the lithium manganate/nitrogen-doped carbon nano tube composite material LMO-NC/NTs.
9. A lithium manganate/nitrogen doped carbon nanotube composite material, characterized in that it is obtained according to the preparation method of any one of claims 1-8.
10. Use of the lithium manganate/nitrogen doped carbon nanotube composite material according to claim 9, wherein the use comprises use in salt lake lithium extraction.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679625A (en) * | 2007-05-29 | 2010-03-24 | 栗村化学株式会社 | Chain-end functionalized methoxy poly(ethylene glycol)and metal nano-particles using the same |
| CN103588820A (en) * | 2013-09-11 | 2014-02-19 | 南京大学 | Folic acid-nickel coordination polymer nanotube as well as preparation method and application thereof |
| CN105576256A (en) * | 2015-12-19 | 2016-05-11 | 华南理工大学 | Nano lithium manganite loaded carbon material cathode catalyst used for oxygen reduction of air electrode as well as preparation method and application of nano lithium manganite loaded carbon material cathode catalyst |
| CN108892176A (en) * | 2018-07-10 | 2018-11-27 | 青岛华冠恒远锂电科技有限公司 | A kind of high magnification lithium manganate composite anode material production method |
| CN114368787A (en) * | 2022-01-10 | 2022-04-19 | 东华大学 | High-conductivity and high-stability lithium manganate material and application thereof |
| US20230256116A1 (en) * | 2023-04-27 | 2023-08-17 | King Saud University | Nanocomposites of nitrogen-doped graphene oxide and manganese oxide for photodynamic therapy and magnetic resonance imaging |
-
2024
- 2024-01-31 CN CN202410136433.3A patent/CN117985697B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679625A (en) * | 2007-05-29 | 2010-03-24 | 栗村化学株式会社 | Chain-end functionalized methoxy poly(ethylene glycol)and metal nano-particles using the same |
| CN103588820A (en) * | 2013-09-11 | 2014-02-19 | 南京大学 | Folic acid-nickel coordination polymer nanotube as well as preparation method and application thereof |
| CN105576256A (en) * | 2015-12-19 | 2016-05-11 | 华南理工大学 | Nano lithium manganite loaded carbon material cathode catalyst used for oxygen reduction of air electrode as well as preparation method and application of nano lithium manganite loaded carbon material cathode catalyst |
| CN108892176A (en) * | 2018-07-10 | 2018-11-27 | 青岛华冠恒远锂电科技有限公司 | A kind of high magnification lithium manganate composite anode material production method |
| CN114368787A (en) * | 2022-01-10 | 2022-04-19 | 东华大学 | High-conductivity and high-stability lithium manganate material and application thereof |
| US20230256116A1 (en) * | 2023-04-27 | 2023-08-17 | King Saud University | Nanocomposites of nitrogen-doped graphene oxide and manganese oxide for photodynamic therapy and magnetic resonance imaging |
Non-Patent Citations (1)
| Title |
|---|
| DADHICH.BK ET.AL: "Folate-Directed Shape-Transformative Synthesis of Hollow Silver Nanocubes:plasmom tunability, growth kinetics, and catalytic applications", 《ACS APPLIED NANO MATERIALS》, vol. 1, no. 8, 31 August 2018 (2018-08-31), pages 4294 - 4305 * |
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