CN115000370A - Molybdenum dioxide confinement growth and modification three-dimensional porous carbon composite electrode material and preparation method thereof - Google Patents
Molybdenum dioxide confinement growth and modification three-dimensional porous carbon composite electrode material and preparation method thereof Download PDFInfo
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- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 title claims abstract description 165
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 18
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- 239000011733 molybdenum Substances 0.000 claims abstract description 15
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- 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
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- 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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract
A molybdenum dioxide limited-area growth and modification three-dimensional porous carbon composite electrode material and a preparation method thereof comprise (1) preparing a precursor solution containing molybdenum groups and carbon by a template method; preparing a precursor solution containing molybdenum base and carbon according to a certain molar ratio, mixing and stirring until the precursor solution is completely dissolved to obtain a precursor solution; (2) drying the precursor solution obtained in the step (1) by adopting a freeze drying process; (3) carbonizing the precursor powder obtained in the step (2) under a protective atmosphere to obtain MoO 2 And (3) carrying out limited-domain growth and modifying the three-dimensional porous carbon composite electrode material. The invention has the characteristics of low preparation cost, simple and convenient process, mass production, stable cycle performance and excellent rate performance.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a molybdenum dioxide confinement growth and modification three-dimensional porous carbon composite electrode material and a preparation method thereof.
Background
Transition metal oxides in a plurality of lithium ion battery negative electrode materials are prepared by the advantages of high theoretical capacity, low cost, abundant resources, environmental friendliness, easiness in preparation and the like, and are widely researched. Under the large background that science and technology are rapidly developed and the demand of people for energy storage is sharply increased, the lithium ion battery cathode material with high specific capacity and power density is promoted to enter the commercial market, and the development prospect and research significance of the transition metal oxide are further widened. Among the various transition metal oxides, molybdenum dioxide (MoO) 2 ) Due to its higher theoretical capacity (838mAh g) -1 ) Good electronic conductivity and reliable ion transport characteristics are of great interest as potential negative electrode materials for lithium ion batteries. However, molybdenum dioxide, as a conventional transition metal oxide, still has some limitations. That is, there is a great volume change during the lithium ion intercalation/deintercalation process to cause pulverization or agglomeration of particles, thereby affecting the cycle performance. The conductivity and ion diffusion kinetics of molybdenum dioxide still need to be further improved in order to optimize its rate capability. The above-mentioned disadvantages will prevent the commercial application of molybdenum dioxide as a negative electrode material for lithium ion batteries.
A large number of studies have shown that MoO 2 The MoO can be obviously improved by the nanocrystallization of particles, the compounding with conductive materials such as graphene, carbon nanotube biomass carbon and the like or the combination of the two methods 2 The electrochemical performance of the material is used as the negative electrode material of the lithium ion battery. For example, Zhang et al (p.l.zhang, s.z.guo, j.z.liu, c.c.zhou, s.li, y.yang, j.wu, d.yu, l.y.chen, Highly university nitrogen-coped carbon purified MoO, of the science and technology university in china (p.l.zhang, s.z.guo, j.z.liu, c.c.zhou, s.li, y.yang, j.wu, d.yu, l.y.chen, hi hly. university nitrogen-coped carbon purified MoO) 2 nanopopcorns as anode for high-performance lithium/sodium-ion storage[J]Journal of colloid and Interface Science 2020,563, 318-327) a novel double annealing process was designed to synthesize a nitrogen-doped carbon-modified nano popcorn structure (MoO) 2 /NC) at 0.5Ag -1 The capacity can be kept at 1073mAh g after 200 times of circulation -1 (ii) a Yao et al, university of wuhan (y.Chen,R.H.Yu,Q.Chen,J.X.Zhu,X.F.Hong,L.Zhou,J.S.Wu,L.Q.Mai,Confining ultrafine MoO 2 in a carbon matrix enables hybrid Li ion and Li metal storage[J]Applied materials and interfaces 2020,12,40648- 2 Composite material (MoO) 2 /C) at 200mAg -1 Can maintain 810mAh g under the current density -1 Has a specific capacity and simultaneously has an ultra-long cycle performance, namely 1.0Ag -1 The capacity retention rate can be about 75% after 1000 cycles of current density. Although a series of researches on molybdenum dioxide as a negative electrode material of a lithium battery are relatively extensive and have made great progress, most of the researches including the above-mentioned documents and patents still have the problems of relatively complex preparation process, relatively high material preparation cost, relatively great difficulty in mass production and the like, and meanwhile, transition metal oxides have a common problem that the capacity change is relatively large in the circulating process, and a lithium ion battery positive electrode material matched with the transition metal oxides is difficult to find, so that further application of molybdenum dioxide in commercialization is limited.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a molybdenum dioxide confinement growth and modification three-dimensional porous carbon composite electrode material and a preparation method thereof, and the material has the characteristics of low preparation cost, simple and convenient process, mass production, stable cycle performance and excellent rate performance.
In order to achieve the purpose, the invention adopts the technical scheme that:
a molybdenum dioxide limited-area growth and modification three-dimensional porous carbon composite electrode material and a preparation method thereof are provided, the composite electrode material is molybdenum dioxide limited-area growth and modification three-dimensional porous carbon, the three-dimensional porous structure is composed of a carbon matrix, and MoO is limited-area growth in the three-dimensional network-shaped porous carbon matrix 2 The composite material has a honeycomb-like three-dimensional porous structure, and the three-dimensional porous structure formed by the carbon matrix can be used as an effective buffer matrix to relieve MoO in multiple charging and discharging processes 2 The volume change caused by lithium intercalation and lithium removal of the nano particles improves the cycling stability of the material; carbon (C)The surface activity of the matrix can be regulated and controlled by doping nitrogen in the matrix, so that the alkalinity and the hydrophilicity of the material are improved, and the conductivity of the material is improved; meanwhile, oxygen vacancies introduced into the surface of the sample are used as an intrinsic defect, are used as an electronic charge carrier to obviously improve the conductivity, and are also used as an additional active center of the redox reaction to increase the specific capacity of the electrode material.
The current density of the composite electrode material is 0.1Ag -1 Circulating for 130 circles, and the specific capacity reaches 918.2mAh g -1 Coulombic efficiency remained at 99%; and/or a current density of 1.0Ag -1 Next, the specific capacity reaches 607.0mAh g at the maximum after 900 cycles of circulation -1 The coulombic efficiency is kept above 99%.
A molybdenum dioxide limited-area growth and modification three-dimensional porous carbon composite electrode material and a preparation method thereof comprise the following steps;
(1) preparing a precursor solution containing molybdenum base and carbon by a template method; preparing a precursor solution containing molybdenum base and carbon according to a certain molar ratio, mixing and stirring until the precursor solution is completely dissolved to obtain a precursor solution;
(2) drying the precursor solution obtained in the step (1) by adopting a freeze drying process;
(3) carbonizing the precursor powder obtained in the step (2) under a protective atmosphere to obtain MoO 2 And (3) carrying out limited-domain growth and modifying the three-dimensional porous carbon composite electrode material.
Furthermore, the hard template method in the step (1) adopts NaCl as a template, but the method is not limited to NaCl, and CaCO can also be used 3 The NaCl template, the molybdenum base precursor solution and the carbon-containing precursor solution are coated on the surface of NaCl particles when the NaCl template, the molybdenum base precursor solution and the carbon-containing precursor solution are dissolved in water, and then the molybdenum base precursor is dispersed in the carbon precursor and is converted into MoO through freeze drying and heat treatment processes 2 The nano particles grow in a limited domain mode, modify the three-dimensional porous carbon, coat the three-dimensional porous carbon on the surface of NaCl particles, and remove a NaCl template after being washed by ethanol to obtain MoO 2 And (3) carrying out domain-limited growth and modifying the three-dimensional porous carbon composite material.
Further, when the solution is prepared in the step (1), the solvent is high-purity water or deionized water, the molybdenum-containing precursor is ammonium molybdate but is not limited to ammonium molybdate, and other molybdenum salts can be used for preparing the precursor, and the carbon-containing precursor is glucose but is not limited to glucose, and carbon-containing precursors such as agar-agar powder, fish gelatin powder, bacterial cellulose and the like can also be used.
Further, the mass ratio of ammonium molybdate providing molybdenum element and glucose providing carbon source in the step (1) is added according to the ratio of 1: 1.
Further, in the step (1), the magnetic stirring speed is 200-600 rpm, and the stirring time is 1-2 hours.
Further, a freeze dryer is adopted in the step (2), the cooling speed is 2-8 ℃/min, the freeze-drying temperature is-40 to-60 ℃, and the time is 36-72 hours.
Further, the protective atmosphere in the step (3) is inert gas: inert gases such as argon, nitrogen, and the like, but not limited thereto; reducing gases such as hydrogen, alkene/alkyne gases, but not limited thereto.
Further, in the carbonization process in the step (3), the heating rate is 5-10 ℃/min, the heat preservation temperature is 400-900 ℃, and the heat preservation time is 2-8 hours.
Further, in the carbonization process in the step (3), melamine is added into the precursor powder for nitrogen doping, and urea or other nitrogen-containing medicines can be adopted for nitrogen doping.
Further, the MoO 2 The three-dimensional porous carbon composite electrode material is grown in a limited area and modified for preparing the lithium ion battery.
The invention has the beneficial effects.
The invention utilizes a hard template method combined with freeze drying and subsequent carbonization processes to prepare the molybdenum dioxide confinement growth and modified three-dimensional porous carbon composite electrode material. Compared with the traditional material, the three-dimensional porous structure of the composite material can provide more ion transmission channels, and MoO in the charge and discharge process is relieved 2 The volume is changed, and the cycling stability of the material is improved. Due to the unique design structure, the introduction of nitrogen element and oxygen vacancy, the limited domain growth of the synthesized molybdenum dioxide and the modification of the three-dimensional porous carbon composite electrodeThe electrode material shows excellent electrochemical performance. Compared with the existing research, the composite electrode material prepared by the template method, freeze drying and carbonization has the advantages that:
(1) the preparation method is simple, mass production can be realized, controllability is strong, and multiple tests prove that the electrode material prepared by the method has good repeatability in morphology and electrochemical performance, and excellent electrochemical performance such as cycle performance, rate performance and the like.
(2) MoO with nitrogen-doped carbon three-dimensional porous composite structure is prepared by simple regulation and control 2 And (3) a base anode material.
(3) The molybdenum dioxide prepared by the method grows in a limited domain and modifies the three-dimensional porous carbon composite electrode material, and the material is cheap in the process of preparing the finished battery, so that the industrialization cost is saved, the process flow is simplified, and the method is suitable for large-scale production.
Description of the drawings:
FIG. 1 is a MoO synthesized by the method of the present invention 2 SEM images of the three-dimensional porous carbon composite material grown and modified in a limited area.
FIG. 2 is a MoO prepared by the method of the present invention 2 And (3) XRD test results of the three-dimensional porous carbon composite material subjected to limited-area growth and modification.
FIG. 3 is a MoO prepared at different temperatures according to the method of the present invention 2 Electron paramagnetic resonance testing of the three-dimensional porous carbon composite material grown and modified in a limited domain.
FIG. 4 is a MoO prepared by the method of the present invention 2 And carrying out limited-area growth and modifying the rate capability of the three-dimensional porous carbon composite material.
FIG. 5 is a low current density versus high current density cycle chart of the composite electrode material of the present invention.
FIG. 6 is a low current density and high current density cycle chart of the composite electrode material of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
MoO 2 The preparation method of the three-dimensional porous carbon composite material with limited-area growth and modification comprises the following steps:
(1) adding 0.6g of ammonium molybdate, 0.6g of glucose and 10g of sodium chloride into 30ml of deionized water to prepare a solution, and stirring the solution on a magnetic stirrer for 1 hour until the solution is completely dissolved;
(2) freeze drying the prepared precursor solution in a freeze dryer at-50 deg.C for 48h to obtain white powdery precursor
(3) Weighing 0.6g of urea, grinding and mixing the freeze-dried precursor and the urea, keeping the temperature at 600 ℃ for 4 hours at the heating rate of 10 ℃/min in a nitrogen atmosphere tube furnace, cooling to room temperature, cleaning with deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 12 hours to obtain a black sample, namely MoO 2 And (3) carrying out domain-limited growth and modifying the three-dimensional porous carbon composite material. FIG. 1 shows MoO 2 SEM picture of three-dimensional porous carbon composite material grown and modified in limited domain, and the fact that the material synthesized by the method has a three-dimensional porous structure, MoO, is found by figure 1 2 The particles are grown in a three-dimensional porous carbon matrix in a limited domain; FIG. 2 shows MoO 2 The XRD spectrogram of the three-dimensional porous carbon composite material is grown and modified in a limited area, and the comparison with a standard card shows that the phase of the obtained product is MoO 2 (ii) a FIG. 3 MoO prepared by the method of the invention 2 Electron paramagnetic resonance tests of the three-dimensional porous carbon composite material subjected to limited-domain growth and modification prove that the concentration of oxygen vacancies in the composite material can be effectively changed by changing the heat treatment temperature;
MoO obtained in example 1 2 The three-dimensional porous carbon composite material with limited domain growth and modification is prepared into an electrode by the following method:
MoO is weighed according to the mass ratio of 8:1:1 2 Carrying out limited-area growth and modification on a three-dimensional porous carbon composite material, SuperP and tetrafluoroethylene, uniformly mixing, adding 10-15 drops of N-methylpyrrolidone, continuously grinding for 1-2 hours, uniformly coating a copper foil with a scraper to prepare an electrode, drying, adopting a metal lithium sheet as a positive electrode, and carrying out electric dischargeThe amount of the hydrolyzed solution is 1mol L -1 LiPF of 6 the/EC-DMC, the diaphragm chooses the polypropylene millipore diaphragm, assemble 2032 half-cell. FIG. 4 is the rate performance of a half cell; FIGS. 5 and 6 show the half-cells at a current density of 0.1Ag, respectively -1 ，1.0Ag -1 The cycle performance of (c). MoO of the invention 2 The three-dimensional porous carbon composite electrode material is grown and modified in a limited area and is 0.1-20Ag -1 The current density range shows excellent rate performance; at 0.1Ag -1 Under the current density, after circulating for 130 circles, the actual specific capacity reaches 918.2mAh g -1 The coulomb efficiency is kept above 99%; the electrode material of the invention is 1.0Ag -1 Charging and discharging under high current density, and after 900 cycles, the actual specific capacity reaches 607.0mAh g -1 The coulombic efficiency is kept above 99%.
Example 2
MoO 2 The preparation method of the three-dimensional porous carbon composite material with limited-area growth and modification comprises the following steps:
(1) 0.6g of ammonium molybdate, 0.6g of glucose and 10g of sodium chloride were added to 30ml of deionized water to prepare a solution, and the solution was stirred on a magnetic stirrer for 1 hour until complete dissolution.
(2) Putting the prepared precursor solution into a freeze dryer, and freeze-drying for 48 hours at-50 ℃ to obtain white powder;
(3) weighing 0.6g of urea, grinding and mixing the freeze-dried precursor and the urea, heating up at a heating rate of 10 ℃/min in a nitrogen atmosphere tube furnace, keeping the temperature at 400 ℃ for 4 hours, cooling to room temperature, cleaning with deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 12 hours to obtain a black sample, namely MoO 2 And (3) carrying out limited-domain growth and modifying the three-dimensional porous carbon composite material.
Example 3
MoO 2 The preparation method of the three-dimensional porous carbon composite material with limited-area growth and modification comprises the following steps:
(1) 0.6g of ammonium molybdate, 0.6g of glucose and 10g of sodium chloride were added to 30ml of deionized water to prepare a solution, and the solution was stirred on a magnetic stirrer for 1 hour until complete dissolution.
(2) Putting the prepared precursor solution into a freeze dryer, and freeze-drying for 48 hours at-50 ℃ to obtain white powder;
(3) weighing 0.6g of urea, grinding and mixing the freeze-dried precursor and the urea, heating up at a heating rate of 10 ℃/min in a nitrogen atmosphere tube furnace at 500 ℃ for 4 hours, cooling to room temperature, cleaning with deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 12 hours to obtain a black sample, namely MoO 2 And (3) carrying out domain-limited growth and modifying the three-dimensional porous carbon composite material.
Example 4
MoO 2 The preparation method of the three-dimensional porous carbon composite material with limited-area growth and modification comprises the following steps:
(1) 0.6g of ammonium molybdate, 0.6g of glucose and 10g of sodium chloride were added to 30ml of deionized water to prepare a solution, and the solution was stirred on a magnetic stirrer for 1 hour until complete dissolution.
(2) Putting the prepared precursor solution into a freeze dryer, and freeze-drying for 48 hours at-50 ℃ to obtain white powder;
(3) weighing 0.6g of urea, grinding and mixing the freeze-dried precursor and the urea, heating up at a rate of 10 ℃/min in a nitrogen atmosphere tube furnace, keeping the temperature at 700 ℃ for 4 hours, cooling to room temperature, cleaning with deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 12 hours to obtain a black sample, namely MoO 2 And (3) carrying out domain-limited growth and modifying the three-dimensional porous carbon composite material.
Example 5
MoO 2 The preparation method of the three-dimensional porous carbon composite material with limited-area growth and modification comprises the following steps:
(1) 0.6g of ammonium molybdate, 0.6g of glucose and 10g of sodium chloride were added to 30ml of deionized water to prepare a solution, and the solution was stirred on a magnetic stirrer for 1 hour until complete dissolution.
(2) Putting the prepared precursor solution into a freeze dryer, and freeze-drying for 48 hours at-50 ℃ to obtain white powder;
(3) weighing 0.6g of urea, grinding and mixing the freeze-dried precursor and the urea, keeping the temperature at 800 ℃ for 4 hours at a heating rate of 10 ℃/min in a nitrogen atmosphere tube furnace, cooling to room temperature, cleaning with deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 12 hours to obtain a black sample.
Example 6
MoO 2 The preparation method of the three-dimensional porous carbon composite material with limited-area growth and modification comprises the following steps:
(1) 0.6g of ammonium molybdate, 0.6g of glucose and 10g of sodium chloride were added to 30ml of deionized water to prepare a solution, and the solution was stirred on a magnetic stirrer for 1 hour until complete dissolution.
(2) Putting the prepared precursor solution into a freeze dryer, and freeze-drying for 48 hours at-50 ℃ to obtain white powder;
(3) weighing 0.6g of melamine, grinding and mixing the freeze-dried precursor and the melamine, keeping the temperature at 400 ℃ for 4 hours in a nitrogen atmosphere tube furnace at the heating rate of 10 ℃/min, cooling to room temperature, cleaning with deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 12 hours to obtain a black sample, namely MoO 2 And (3) carrying out domain-limited growth and modifying the three-dimensional porous carbon composite material.
Example 7
MoO 2 The preparation method of the three-dimensional porous carbon composite material with limited-area growth and modification comprises the following steps:
(1) 0.6g of ammonium molybdate, 0.6g of glucose and 10g of calcium carbonate were added to 30ml of deionized water to prepare a solution, and the solution was stirred on a magnetic stirrer for 1 hour until completely dissolved.
(2) Putting the prepared precursor solution into a freeze dryer, and freeze-drying for 48 hours at-50 ℃ to obtain white powder;
(3) weighing 0.6g of urea, grinding and mixing the freeze-dried precursor and the urea, heating up at a heating rate of 10 ℃/min in a nitrogen atmosphere tube furnace, keeping the temperature at 400 ℃ for 4 hours, cooling to room temperature, cleaning with deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 12 hours to obtain a black sample, namely MoO 2 And (3) carrying out domain-limited growth and modifying the three-dimensional porous carbon composite material.
Example 8
MoO 2 The preparation method of the three-dimensional porous carbon composite material with limited-area growth and modification comprises the following steps:
(1) 0.6g of ammonium molybdate, 0.6g of agar powder and 10g of sodium chloride are added into 30ml of deionized water to prepare a solution, and the solution is stirred on a magnetic stirrer for 1 hour until the solution is completely dissolved.
(2) Putting the prepared precursor solution into a freeze dryer, and freeze-drying for 48 hours at-50 ℃ to obtain white powder;
(3) weighing 0.6g of urea, grinding and mixing the freeze-dried precursor and the urea, heating up at a heating rate of 10 ℃/min in a nitrogen atmosphere tube furnace, keeping the temperature at 400 ℃ for 4 hours, cooling to room temperature, cleaning with deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 12 hours to obtain a black sample, namely MoO 2 And (3) carrying out limited-domain growth and modifying the three-dimensional porous carbon composite material.
Example 9
MoO 2 The preparation method of the three-dimensional porous carbon composite material with limited-area growth and modification comprises the following steps:
(1) 0.6g of ammonium molybdate, 0.6g of agar powder and 10g of sodium chloride are added into 30ml of deionized water to prepare a solution, and the solution is stirred on a magnetic stirrer for 1 hour until the solution is completely dissolved.
(2) Putting the prepared precursor solution into a freeze dryer, and freeze-drying for 48 hours at-50 ℃ to obtain white powder;
(3) weighing 0.6g of urea, grinding and mixing the freeze-dried precursor and the urea, heating up at a rate of 5 ℃/min in a nitrogen atmosphere tube furnace, keeping the temperature at 400 ℃ for 4 hours, cooling to room temperature, cleaning with deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 12 hours to obtain a black sample, namely MoO 2 And (3) carrying out domain-limited growth and modifying the three-dimensional porous carbon composite material.
Example 10
MoO 2 The preparation method of the three-dimensional porous carbon composite material with limited-area growth and modification comprises the following steps:
(1) 0.6g of ammonium molybdate, 0.6g of Japan agar and 10g of sodium chloride are added into 30ml of deionized water to prepare a solution, and the solution is stirred on a magnetic stirrer for 1 hour until the solution is completely dissolved.
(2) Putting the prepared precursor solution into a freeze dryer, and freeze-drying for 48 hours at-50 ℃ to obtain white powder;
(3) weighing 0.6g of urea, grinding and mixing the freeze-dried precursor and the urea, heating up at a rate of 10 ℃/min in a nitrogen atmosphere tube furnace, keeping the temperature at 700 ℃ for 8 hours, cooling to room temperature, cleaning with deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 12 hours to obtain a black sample, namely MoO 2 And (3) carrying out limited-domain growth and modifying the three-dimensional porous carbon composite material.
The invention provides a preparation method of molybdenum dioxide limited-domain growth and modified three-dimensional porous carbon composite electrode material, which synthesizes oxygen vacancy defect-rich three-dimensional porous nitrogen-doped carbon-modified MoO by combining a simple controllable hard template method with freeze drying and subsequent heat treatment process 2 A composite material. The introduced oxygen vacancy is used as an intrinsic defect, can be used as an electronic charge carrier to obviously improve the conductivity, and can also be used as an additional active center of redox reaction to increase the specific capacity of an electrode material; materials containing oxygen vacancies exhibit significant charge transfer phenomena and charge distribution imbalances compared to the original lattice, resulting in the creation of a positive charge at the center of the oxygen vacancy and a region of equivalent negative charge around the oxygen vacancy. During discharge, the electric field is directed from the defect-free region to the negative charge region due to the coulomb force, which accelerates Li + So that the lithium ion battery is gathered around the oxygen vacancy area, and after lithiation, the negative charge area tends to be neutral; during charging, the secondary electric field directs the positively charged region at the oxygen vacancy center to the electrically neutral lithiated layer, accelerating Li + The intercalation and deintercalation in the electrochemical process improve the rate capability. The oxygen vacancy concentration is introduced and regulated, so that MoO can be effectively relieved 2 Slow reaction kinetics and volume expansion of active substances, and excellent comprehensive electrochemical properties are obtained. The preparation method is low in cost and simple in process, batch production can be realized, and the prepared electrode material has stable cycle performance and rate capability while improving the capacity.
The molybdenum dioxide grows in a limited domain and modifies a three-dimensional porous carbon composite electrode material, the porous carbon promotes the conductivity, and the molybdenum dioxide nano particles are limited in a conductive carbon matrix, so that MoO in the circulation process is effectively relieved 2 Is expanded in volume; the nitrogen-doped carbon material can regulate and control the surface activity of the nitrogen-doped carbon material, improve the alkalinity and the hydrophilicity of the material, improve the conductivity of the material and show excellent electrochemical performance; a three-dimensional porous structure with a complete structure is obtained by regulating and controlling the carbonization temperature, and the capacitance contribution of the electrode material is also increased so as to improve the capacity performance of the electrode material; in particular, oxygen vacancy defects introduced by heat treatment act as electron charge carriersThe conductivity is remarkably improved, and simultaneously, the specific capacity of the electrode material is increased as an additional active center of oxidation-reduction reaction, which promotes Li + The rate capability of the embedded and separated process is obviously improved.
The invention obtains a strategy for regulating and controlling the local built-in electric field energy by utilizing the oxygen vacancy defect concentration so as to optimize the electrochemical performance. Quantitative control of the oxygen vacancy concentration in the molybdenum dioxide confinement growth and modified three-dimensional porous carbon composite electrode material is realized through variable parameters such as accurate temperature control and reaction duration control; and testing the cycle performance, rate capability, capacity performance and impedance performance of the material to obtain the rule of the influence of oxygen vacancy defects on the electrochemical performance.
The invention provides a molybdenum dioxide limited-area growth and modification three-dimensional porous carbon composite electrode material product which has low preparation cost, simple and convenient process, mass production and excellent comprehensive electrochemical properties such as stable cycle performance, excellent rate performance and the like.
Claims (10)
1. The molybdenum dioxide confinement-growth and modification three-dimensional porous carbon composite electrode material is characterized in that the composite electrode material is molybdenum dioxide confinement-growth and modification three-dimensional porous carbon, the three-dimensional porous structure is composed of a carbon matrix, and MoO is confined-grown in the three-dimensional network-shaped porous carbon matrix 2 And (3) nanoparticles.
2. The molybdenum dioxide limited-area growth and modification three-dimensional porous carbon composite electrode material and the preparation method thereof according to claim 1, wherein the composite electrode material has a current density of 0.1A g -1 Circulating for 130 circles, and the specific capacity reaches 918.2mAh g -1 Coulombic efficiency remained at 99%; and/or a current density of 1.0A g -1 Then, the circulation is carried out for 900 circles, and the specific capacity reaches 607.0mAh g to the maximum -1 The coulombic efficiency is kept above 99%.
3. The preparation method of the molybdenum dioxide limited-domain growth and modification three-dimensional porous carbon composite electrode material and the preparation method thereof according to claim 1 or 2 is characterized by comprising the following steps;
(1) preparing a precursor solution containing molybdenum base and carbon by a template method; preparing a precursor solution containing molybdenum base and carbon according to a certain molar ratio, mixing and stirring until the precursor solution is completely dissolved to obtain a precursor solution;
(2) drying the precursor solution obtained in the step (1) by adopting a freeze drying process;
(3) carbonizing the precursor powder obtained in the step (2) under a protective atmosphere to obtain MoO 2 And (3) carrying out limited-domain growth and modifying the three-dimensional porous carbon composite electrode material.
4. The preparation method of the molybdenum dioxide confinement-growth and modification three-dimensional porous carbon composite electrode material and the preparation method thereof according to claim 3, characterized in that when the solution is prepared in the step (1), the solvent is high-purity water or deionized water, the molybdenum-containing precursor is ammonium molybdate, but not only ammonium molybdate, but also other molybdenum salts can be used for preparing the precursor, and the carbon-containing precursor is glucose, but also carbon-containing precursors such as agar-agar powder, fish gelatin powder, bacterial cellulose and the like.
5. The preparation method of the molybdenum dioxide limited-domain growth and modification three-dimensional porous carbon composite electrode material and the preparation method thereof according to claim 3, wherein the mass ratio of ammonium molybdate providing molybdenum element to glucose providing carbon source in the step (1) is 1: 1.
6. The preparation method of the molybdenum dioxide limited-domain growth and modification three-dimensional porous carbon composite electrode material and the preparation method thereof according to claim 3, wherein in the step (1), the magnetic stirring speed is 200-600 r/min, and the stirring time is 1-2 hours.
7. The preparation method of the molybdenum dioxide limited-domain growth and modification three-dimensional porous carbon composite electrode material and the preparation method thereof according to claim 3, characterized in that a freeze dryer is adopted in the step (2), the cooling speed is 2-8 ℃/min, the freeze-drying temperature is-40 to-60 ℃, and the time is 36-72 hours.
8. The preparation method of the molybdenum dioxide confinement-growth and modification three-dimensional porous carbon composite electrode material and the preparation method thereof according to claim 3, wherein the protective atmosphere in the step (3) is inert gas: inert gases such as argon, nitrogen, and the like, but not limited thereto; reducing gases such as hydrogen, alkene/alkyne gases, but not limited thereto;
in the carbonization process of the step (3), the heating rate is 5-10 ℃/min, the heat preservation temperature is 400-900 ℃, and the heat preservation time is 2-8 hours;
in the carbonization process in the step (3), melamine is added into the precursor powder for nitrogen doping, and urea or other nitrogen-containing medicines can also be adopted for nitrogen doping.
9. The molybdenum dioxide limited-area growth and modification three-dimensional porous carbon composite electrode material and the preparation method thereof according to claim 3, wherein NaCl is used as a template in the hard template method in the step (1), but the NaCl is not limited to the NaCl, and CaCO can also be used as the CaCO 3 When the NaCl template, the molybdenum-based precursor solution and the carbon-containing precursor solution are dissolved in water together, the molecules of the molybdenum-based precursor solution and the carbon-containing precursor solution wrap the surface of NaCl particles, and then the NaCl template, the molybdenum-based precursor solution and the carbon-containing precursor solution are subjected to freeze drying and heat treatment to disperse the molybdenum-based precursor in the carbon precursor and convert the molybdenum-based precursor into MoO 2 The nano particles grow in a limited domain mode, modify the three-dimensional porous carbon, coat the three-dimensional porous carbon on the surface of NaCl particles, and remove a NaCl template after being washed by ethanol to obtain MoO 2 And (3) carrying out domain-limited growth and modifying the three-dimensional porous carbon composite material.
10. The molybdenum dioxide confinement grown and modified three-dimensional porous carbon composite electrode material according to any one of claims 1-9, wherein the MoO is 2 The three-dimensional porous carbon composite electrode material is grown in a limited area and modified for preparing the lithium ion battery.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102623677A (en) * | 2012-04-09 | 2012-08-01 | 华中科技大学 | Process for producing high capacity molybdenum dioxide/carbon cathode materials |
| CN104966817A (en) * | 2014-12-01 | 2015-10-07 | 天津大学 | Molybdenum disulfide-carbon three-dimensional porous network composite and preparation method thereof |
| CN105390672A (en) * | 2015-10-21 | 2016-03-09 | 天津大学 | Preparation method for three-dimensional nitrogen-doped mesoporous carbon ultra-thin nanosheet material |
| CN109399722A (en) * | 2018-12-27 | 2019-03-01 | 陕西科技大学 | A kind of preparation method of porous rodlike molybdenum dioxide/carbon composite |
| CN109449411A (en) * | 2018-10-30 | 2019-03-08 | 陕西科技大学 | A kind of method of confinement synthesis tungsten disulfide@C combination electrode material |
| CN110364366A (en) * | 2019-06-30 | 2019-10-22 | 华南理工大学 | A kind of high-performance electric chemistry capacitor anode material molybdenum dioxide and nitrogen-doped carbon composite material and preparation method and application |
| CN110544773A (en) * | 2019-08-23 | 2019-12-06 | 天津大学 | Preparation method of three-dimensional porous carbon confinement MOFs current collector for lithium metal negative electrode |
| CN110571436A (en) * | 2019-08-23 | 2019-12-13 | 天津大学 | Preparation method of three-dimensional porous carbon loaded flaky molybdenum disulfide current collector for lithium metal cathode |
| CN110767904A (en) * | 2019-11-08 | 2020-02-07 | 中南大学 | Preparation method of battery cathode material with nitrogen-doped porous carbon embedded with cuprous phosphide and product thereof |
| CN111106335A (en) * | 2019-12-20 | 2020-05-05 | 三峡大学 | Preparation method of lithium ion battery composite negative electrode material |
| CN114743807A (en) * | 2022-05-19 | 2022-07-12 | 江苏大学 | Inside and outside raw MoO2Preparation method of/three-dimensional carbon composite material |
-
2022
- 2022-06-02 CN CN202210625598.8A patent/CN115000370A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102623677A (en) * | 2012-04-09 | 2012-08-01 | 华中科技大学 | Process for producing high capacity molybdenum dioxide/carbon cathode materials |
| CN104966817A (en) * | 2014-12-01 | 2015-10-07 | 天津大学 | Molybdenum disulfide-carbon three-dimensional porous network composite and preparation method thereof |
| CN105390672A (en) * | 2015-10-21 | 2016-03-09 | 天津大学 | Preparation method for three-dimensional nitrogen-doped mesoporous carbon ultra-thin nanosheet material |
| CN109449411A (en) * | 2018-10-30 | 2019-03-08 | 陕西科技大学 | A kind of method of confinement synthesis tungsten disulfide@C combination electrode material |
| CN109399722A (en) * | 2018-12-27 | 2019-03-01 | 陕西科技大学 | A kind of preparation method of porous rodlike molybdenum dioxide/carbon composite |
| CN110364366A (en) * | 2019-06-30 | 2019-10-22 | 华南理工大学 | A kind of high-performance electric chemistry capacitor anode material molybdenum dioxide and nitrogen-doped carbon composite material and preparation method and application |
| CN110544773A (en) * | 2019-08-23 | 2019-12-06 | 天津大学 | Preparation method of three-dimensional porous carbon confinement MOFs current collector for lithium metal negative electrode |
| CN110571436A (en) * | 2019-08-23 | 2019-12-13 | 天津大学 | Preparation method of three-dimensional porous carbon loaded flaky molybdenum disulfide current collector for lithium metal cathode |
| CN110767904A (en) * | 2019-11-08 | 2020-02-07 | 中南大学 | Preparation method of battery cathode material with nitrogen-doped porous carbon embedded with cuprous phosphide and product thereof |
| CN111106335A (en) * | 2019-12-20 | 2020-05-05 | 三峡大学 | Preparation method of lithium ion battery composite negative electrode material |
| CN114743807A (en) * | 2022-05-19 | 2022-07-12 | 江苏大学 | Inside and outside raw MoO2Preparation method of/three-dimensional carbon composite material |
Non-Patent Citations (2)
| Title |
|---|
| ZHIFENG DAI: "High capacity MoO2-based anode enabled by 3D carbon in-situ embedment through a green template strategy", SYNTHETIC METALS, 3 September 2021 (2021-09-03) * |
| 王常耀: "原位限域生长策略制备有序介孔碳负载的超小MoO3纳米颗粒", 高等学校化学学报, 31 May 2021 (2021-05-31), pages 1589 - 1597 * |
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