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CN111747449A - Superfine MoO uniformly bridged inside flaky carbon matrix2Electrode material of nano particles and preparation method and application thereof - Google Patents

Superfine MoO uniformly bridged inside flaky carbon matrix2Electrode material of nano particles and preparation method and application thereof Download PDF

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CN111747449A
CN111747449A CN202010689639.0A CN202010689639A CN111747449A CN 111747449 A CN111747449 A CN 111747449A CN 202010689639 A CN202010689639 A CN 202010689639A CN 111747449 A CN111747449 A CN 111747449A
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moo
electrode material
nano
uniformly
ultrafine
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麦立强
余若瀚
陈子昂
周亮
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Wuhan University of Technology WUT
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Abstract

The invention relates to the technical field of nano materials and electrochemistry, in particular to a flaky carbon matrix internally and uniformly bridged superfine MoO2Electrode material of nano particles and preparation method thereof, and nano particlesThe material can be used as a negative active material of a lithium ion battery with high capacity and long cycle life, and is a three-dimensional flower-shaped structure formed by laminating and interweaving sheet-shaped carbon matrix substructures, wherein the thickness of a sheet layer of the carbon matrix is 10-20nm, the diameter of a single flower-shaped structure formed by the carbon matrix is 2-6um, and the MoO is2The diameter of the nano-particles is 1-3 nm. The nano material can be used as a lithium ion battery cathode material. The material has the characteristics of simple process, mild reaction conditions and excellent electrochemical performance.

Description

Superfine MoO uniformly bridged inside flaky carbon matrix2Electrode material of nano-particles and electrode material thereofPreparation method and application
Technical Field
The invention relates to the technical field of nano materials and electrochemistry, in particular to a flaky carbon matrix internally and uniformly bridged superfine MoO2The material can be used as a negative electrode active material of a lithium ion battery with high capacity and long cycle life.
Background
Energy shortage and environmental pollution have become two major problems facing the world today. The development and utilization of green clean energy has great significance for relieving energy shortage and reducing environmental pollution. At present, a lithium ion battery is taken as one of representatives of clean energy storage systems, and is widely applied to the fields of portable electronic equipment, automobile power batteries, large-scale energy storage and the like. However, the current commercialized graphite anode has low specific capacity (372mAh g)-1) And the safety is poor, and the increasing energy density requirement is difficult to meet. And with the further expansion of energy demand, the shortage of lithium resources will severely restrict the application and development thereof, which also puts higher demands on the full utilization of the existing lithium resources: the capacity and the cycle life of the electrode material are further improved under the existing conditions. Transition Metal Oxides (TMOs) based on a conversion reaction mechanism are lithium battery cathode materials with great development prospects. Over the past decades, a large number of transition metal oxides, such as Fe, have been extensively studied2O3、V2O5、MoO3And the like.
Due to low metal resistivity (8.8 × 10)-5Ω·cm-1) High theoretical capacity (838mAh g)-1) And low cost, molybdenum dioxide (MoO)2) Has been considered one of the most attractive anode materials. However, two key problems with this electrode material are that during charging and discharging, the MoO is present2The intermediates of nanoparticle conversion reactions often suffer from poor lithium intercalation kinetics and severe volume expansion, resulting in undesirable cycle performance and lifetime. In recent years, smaller volume expansion and fast dissociation of composite carbon matrices by constructing elaborate nanostructures has been achievedThe improvement of the electrochemical performance by the electron/electron transmission speed becomes a research hotspot, and the uniform carbon composite structure is constructed on the ultra-small nanometer scale (less than 5nm) to form the ultra-fine MoO2The electrode material with nano particles uniformly bridged inside the flaky carbon matrix, high capacity and cycle life of more than 1000 circles is not reported.
Disclosure of Invention
In view of the above, the present invention provides a method for uniformly bridging ultrafine MoO inside a flaky carbon matrix2The electrode material of the nano particles, the preparation method and the application thereof have the characteristics of high capacity and stable circulation, and the energy density of the lithium ion battery cathode material is greatly improved, and the excellent stability is also shown.
The technical scheme adopted by the invention for solving the problems is as follows: superfine MoO uniformly bridged inside flaky carbon matrix2The electrode material of the nano particles is a three-dimensional flower-shaped structure formed by laminating and interweaving sheet-shaped carbon matrix substructures, wherein the thickness of a sheet layer of the carbon matrix is 10-20nm, the diameter of a single flower-shaped structure formed by the carbon matrix is 2-6um, and the MoO is2The diameter of the nano-particles is 1-3 nm.
The inside of the flaky carbon matrix is uniformly bridged with ultrafine MoO2The preparation method of the electrode material of the nano particles comprises the following steps: adding MoO3Adding the nanobelt solution and dopamine hydrochloride into a deionized water solution of trihydroxymethyl aminomethane, fully and uniformly stirring at room temperature, washing, and drying to obtain a flower-shaped Mo-polydopamine composite (Mo-PDA); sintering the obtained product in an inert atmosphere to obtain the superfine MoO uniformly bridged in the flaky carbon matrix2Electrode material of nanoparticles.
According to the scheme, the MoO3The preparation method of the nanobelt solution comprises the following steps:
1) mixing Mo powder with H2O2And H2Stirring the mixture in the O mixed solution uniformly;
2) transferring the solution obtained in the step 1) into a reaction container for heating, taking out, and naturally cooling to room temperature to obtain MoO3Nanobelt solution.
According to the scheme, the time for fully stirring is 2-8 h.
According to the scheme, the mass of the Mo powder in the step 1) is 0.5-3.5 g; h in the mixed solution2O2And H2O two are 10-80mL each.
According to the scheme, the MoO3The nano-belt solution is 1-10mL, the dopamine hydrochloride is 0.1-1g, the tris (hydroxymethyl) aminomethane is 0.1-1g, and the deionized water is 20-200 mL.
According to the scheme, the heating temperature is 160-200 ℃, and the heating time is 6-48 h;
according to the scheme, the sintering temperature is 600-1000 ℃, and the sintering time is 1-4 h.
The inside of the flaky carbon matrix is uniformly bridged with ultrafine MoO2The nano-particle electrode material is applied as a negative electrode active material of a lithium ion battery with high capacity and long cycle life.
The invention designs a delicate nano microstructure, and the flaky carbon matrix is used as an electron transport network and an electrode active substance (MoO) at the same time2) A carrier providing good conductivity to the electrode material and internal MoO during charging and discharging2The nanoparticles provide good buffering of volume expansion, stabilizing their microstructure, and at the same time, due to the carbon to MoO2Confinement effect of particle size such that MoO2Can maintain its size below 3nm even after high temperature treatment, and greatly reduce MoO2The volume of the nanoparticles expands during charging and discharging. MoO2Compared with the traditional supported point contact, the embedded structure of the nano particles and the carbon matrix greatly improves the contact area of the active material and the conductive network, greatly improves the conduction of electrons/ions in the microstructure and bridged MoO2The nanoparticles are also beneficial to constructing a lithium ion transmission channel, and the structure endows the electrode material with excellent electron/ion conduction capability and structural stability. When the material is used as a negative electrode material and tested, the current density is 200mA g-1The capacity is 810mAh g-1(ii) a When the current density is 1.0A g-1At all, even after 1000 cycles, the capacity is still480mAh g-175% of the capacity is maintained.
In addition, ultrafine MoO is uniformly bridged in the flaky carbon matrix2The electrode material of the nano particles is synthesized by a sol-gel method, the process is simple, the nano microstructure of the electrode material can be controlled by changing the concentration of reactants, the reaction temperature and the reaction time, and the work provides a scheme for the structural design of the next generation of long-circulation and high-energy density materials.
The invention has the beneficial effects that: based on the unique advantages of the structure under the nanometer scale, the superfine MoO is uniformly bridged in the flaky carbon matrix2The nano-particle electrode material shows excellent cycling stability and high capacity when being used as a lithium ion negative electrode material through a simple synthesis method, and is a potential application material of a lithium ion battery with high capacity and long cycle life.
Drawings
FIG. 1 shows the ultrafine MoO uniformly bridged inside the flaky carbon matrix of example 1 of the present invention2XRD pattern of electrode material of nanoparticles;
FIG. 2 shows the ultrafine MoO uniformly bridged inside the flaky carbon matrix of example 1 of the present invention2SEM images of the electrode material of the nanoparticles;
FIG. 3 shows the ultrafine MoO uniformly bridged inside the flaky carbon matrix of example 1 of the present invention2TEM images of the electrode material of the nanoparticles;
FIG. 4 shows the ultrafine MoO uniformly bridged inside the flaky carbon matrix of example 1 of the present invention2A synthesis mechanism diagram of the electrode material of the nano-particles;
FIG. 5 shows the ultrafine MoO uniformly bridged inside the flaky carbon matrix of example 1 of the present invention2HRTEM of the electrode material of the nanoparticles;
FIG. 6 shows the ultrafine MoO uniformly bridged inside the flaky carbon matrix of example 1 of the present invention2STEM map of the electrode material edge region of the nanoparticles;
FIG. 7 shows the ultrafine MoO uniformly bridged inside the flaky carbon matrix of example 1 of the present invention2A low magnification STEM map of the electrode material of the nanoparticles and a partially magnified STEM map thereof;
FIG. 8 is an embodiment of the present inventionUltrafine MoO uniformly bridged inside the flaky carbon matrix of example 12High magnification STEM plot of electrode material of nanoparticles;
FIG. 9 shows the ultrafine MoO uniformly bridged inside the flaky carbon matrix of example 1 of the present invention2High current density cycling profile of nanoparticle electrode material (current density of 1A g)-1)。
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and improvements without departing from the principle of the embodiments of the present invention, and such modifications and improvements are considered to be within the scope of the embodiments of the present invention.
Example 1
The preparation method of the electrode material with the ultrafine MoO2 nano particles uniformly bridged in the flaky carbon matrix comprises the following steps:
1) 0.96g of Mo powder was mixed and added to 20mL of H2O2And 20mL H2Stirring the mixed solution for 12 hours;
2) transferring the solution obtained in the step 1) into a 100mL reaction kettle, heating at 180 ℃ for 24h, taking out the reaction kettle, and naturally cooling to room temperature to obtain MoO3A nanobelt solution;
3) adding 2mL of the product obtained in the step 2) and 0.3g of dopamine hydrochloride into 100mL of deionized water dissolved with 0.1214g of tris (hydroxymethyl) aminomethane, stirring for 4h, washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying in an oven at 80 ℃ to obtain a flower-shaped Mo-polydopamine composite (Mo-PDA);
4) placing the product obtained in the step 3) in a tubular furnace to be sintered for 2 hours at 800 ℃ in Ar atmosphere to obtain the superfine MoO uniformly bridged in the flaky carbon matrix2Electrode material of nanoparticles.
As shown in fig. 4, the synthesis mechanism of the present invention is: based on a synthesis method of a sol-gel method, firstly, MoO is obtained by synthesis3The nanobelt is subjected to dissolution reaction/redeposition with dopamine hydrochloride to obtain a flower-shaped Mo-polydopamine composite material (Mo-PDA), and finally the material is obtained by annealing; such three-dimensional nanostructures can be effectiveThe buffer electrode material can buffer the expansion and contraction in the charging and discharging process and improve MoO2The kinetics of the nano-particle conversion reaction process for releasing and inserting lithium is realized, so that the multiplying power and the cycle performance of the battery are effectively improved.
Superfine MoO uniformly bridged in the prepared flaky carbon matrix2The XRD pattern of the electrode material of the nano-particles is shown in figure 1, and the diffraction peaks of the product are consistent with those of JCPDS card No.65-1273 and belong to a monoclinic system. SEM images (FIG. 2) and TEM images (FIG. 3) show the flower type structure of the material, and the thickness of the nano-flakes can be observed to be about 10-20 nm. High resolution TEM (HRTEM, FIG. 5) nanosheet side image display, MoO2The ultra-fine particles are embedded in the amorphous carbon layer. In the STEM image of the nanosheets (FIG. 6), many small bright spots of uniform white color, i.e., MoO embedded therein, were observed2And (3) nanoparticles. From the STEM image (FIG. 7), it can be seen that the petal part of the three-dimensional flower-like structure is composed of a plurality of thin sheet substructures which are interwoven and overlapped with each other, and the substructures are loaded with the ultrafine MoO2Carbon matrix nanoflakes of particles, enlarged in the area indicated by the red box in FIG. 7, where MoO can be seen2The nanoparticles are 1-3nm in size, and at a further higher magnification MoO can be observed2The nanoparticles are bridged to each other inside the carbon matrix (fig. 8).
This example is an ultrafine MoO2The application of the electrode material with nanoparticles uniformly bridged inside the carbon matrix is as follows: the preparation process of the positive plate adopts superfine MoO2The electrode material with nano particles uniformly bridged in the carbon matrix, acetylene black as a conductive agent, sodium alginate as a binder, and the mass ratio of the active material to the acetylene black to the sodium alginate is 70: 20: 10, dispersing in deionized water, uniformly stirring and ultrasonically treating for 4 hours to obtain electrode slurry. And coating the electrode slurry on the surface of the copper foil, and drying at 85 ℃ to obtain the positive electrode plate. A button lithium ion battery is assembled by taking 1M LiPF dissolved in Ethylene Carbonate (EC) and dimethyl carbonate (DMC) as electrolyte, a lithium sheet as a cathode, Celgard 2400 as a diaphragm and CR 2025 type stainless steel as a battery shell. The remaining steps of the preparation method of the lithium ion battery are the same as those of the ordinary preparation method.
As shown in figure 9 of the drawings,the ultrafine MoO obtained in this example2The electrode material with nanoparticles uniformly bridged inside the carbon matrix is exemplified when the current density is 1.0A g-1Then, even after 1000 cycles, the capacity still remains 480mAh g-175% of the capacity is maintained. The results indicate ultrafine MoO2The electrode material with nano particles uniformly bridged in the carbon matrix has excellent high-capacity performance and is a potential application material of a lithium ion battery with high capacity and long cycle life
Example 2
1) 1.5g of Mo powder was mixed and added to 30mL of H2O2And 30mL of H2Stirring the mixed solution of O for 18 hours;
2) transferring the solution obtained in the step 1) into a 100mL reaction kettle, heating for 24h at 200 ℃, taking out the reaction kettle, and naturally cooling to room temperature to obtain MoO3A nanobelt solution;
3) adding 2mL of the product obtained in the step 2) and 0.6g of dopamine hydrochloride into 100mL of deionized water dissolved with 0.2g of tris (hydroxymethyl) aminomethane, stirring for 4h, washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying in an oven at 80 ℃ to obtain a flower-shaped Mo-polydopamine composite (Mo-PDA);
4) putting the product obtained in the step 3) into a tubular furnace, and sintering for 4 hours at 800 ℃ in Ar atmosphere to obtain the superfine MoO uniformly bridged in the flaky carbon matrix2Electrode material of nanoparticles.
The ultrafine MoO was uniformly bridged in the sheet-like carbon matrix obtained in this example2The electrode material of the nano particles is taken as an example, and the constant current charging and discharging result carried out under 1000mA/g shows that the first discharge specific capacity of the nano particles can reach 550mAh g-1320mAh g after 1000 cycles-1The capacity retention rate reaches 58 percent.
Example 3
1) 0.5g of Mo powder was mixed and added to 20mL of H2O2And 20mL H2Stirring for 6 hours in the O mixed solution;
2) transferring the solution obtained in the step 1) into a 100mL reaction kettle, heating at 170 ℃ for 12h, taking out the reaction kettle, and naturally cooling to room temperature to obtain MoO3A nanobelt solution;
3) adding 2mL of the product obtained in the step 2) and 0.2g of dopamine hydrochloride into a solution of 0.1214g of tris (hydroxymethyl) aminomethane dissolved in 100mL of deionized water, stirring for 4 hours, washing for 4 times by using deionized water and absolute ethyl alcohol respectively, and drying;
4) and (3) placing the product obtained in the step 3) into a tubular furnace, and sintering for 4 hours at 700 ℃ in Ar atmosphere to obtain the electrode material with the inside of the flaky carbon matrix uniformly bridged with the ultrafine MoO2 nano particles.
The ultrafine MoO was uniformly bridged in the sheet-like carbon matrix obtained in this example2The electrode material of the nano particles is taken as an example, and the constant current charging and discharging result carried out under 1000mA/g shows that the first discharge specific capacity of the nano particles can reach 450mAh g-1280mAh g after 1000 cycles-1The capacity retention rate reaches 62.2 percent.
Example 4
1) 0.5g of Mo powder was mixed and 10mL of H was added2O2And 10mL H2Stirring the mixed solution for 3 hours;
2) transferring the solution obtained in the step 1) into a 100mL reaction kettle, heating for 12h at 160 ℃, taking out the reaction kettle, and naturally cooling to room temperature to obtain MoO3A nanobelt solution;
3) adding 2mL of the product obtained in the step 2) and 0.2g of dopamine hydrochloride into 100mL of deionized water dissolved with 0.12g of tris (hydroxymethyl) aminomethane, stirring for 4h, washing with deionized water and absolute ethyl alcohol for 4 times respectively, and drying in an oven at 80 ℃ to obtain a flower-shaped Mo-polydopamine composite (Mo-PDA);
4) putting the product obtained in the step 3) into a tubular furnace, and sintering for 4 hours at 800 ℃ in Ar atmosphere to obtain the superfine MoO uniformly bridged in the flaky carbon matrix2Electrode material of nanoparticles.
The ultrafine MoO was uniformly bridged in the sheet-like carbon matrix obtained in this example2The electrode material of the nano particles is taken as an example, and the constant current charging and discharging result carried out under 1000mA/g shows that the first discharge specific capacity of the nano particles is 350mAh g-1After 200 cycles, 100mAh g-1The capacity retention rate was 28.6%.
Example 5
1) 0.1g of Mo powder was mixed and 15mL of H was added2O2And 15mL H2Stirring the mixed solution for 1 hour;
2) transferring the solution obtained in the step 1) into a 100mL reaction kettle, heating at 180 ℃ for 12h, taking out the reaction kettle, and naturally cooling to room temperature to obtain MoO3A nanobelt solution;
3) adding 2mL of the product obtained in the step 2) and 0.2g of dopamine hydrochloride into 100mL of deionized water dissolved with 0.1214g of tris (hydroxymethyl) aminomethane, stirring for 6h, washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying in an oven at 80 ℃ to obtain a flower-shaped Mo-polydopamine composite (Mo-PDA);
4) placing the product obtained in the step 3) in a tubular furnace to be sintered for 2 hours at 800 ℃ in Ar atmosphere to obtain the superfine MoO uniformly bridged in the flaky carbon matrix2Electrode material of nanoparticles.
The ultrafine MoO was uniformly bridged in the sheet-like carbon matrix obtained in this example2The electrode material of the nano particles is taken as an example, and the constant current charging and discharging result carried out under 1000mA/g shows that the first discharge specific capacity of the nano particles is 220mAh g-183mAh g after 350 post-cycles-1The capacity retention rate was 37.7%.
Example 6
1) 0.4g of Mo powder was mixed and 40mL of H was added2O2And 40mL H2Stirring the mixed solution for 12 hours;
2) transferring the solution obtained in the step 1) into a 100mL reaction kettle, heating at 180 ℃ for 12h, taking out the reaction kettle, and naturally cooling to room temperature to obtain MoO3A nanobelt solution;
3) adding 2mL of the product obtained in the step 2) and 0.5g of dopamine hydrochloride into 100mL of deionized water dissolved with 0.2428g of tris (hydroxymethyl) aminomethane, stirring for 12h, washing for 5 times by using deionized water and absolute ethyl alcohol respectively, and drying in an oven at 80 ℃ to obtain a flower-shaped Mo-polydopamine composite (Mo-PDA);
4) putting the product obtained in the step 3) into a tubular furnace, and sintering for 4 hours at 800 ℃ in Ar atmosphere to obtain the superfine MoO uniformly bridged in the flaky carbon matrix2Electrode material of nanoparticles.
The sheet-like carbon substrate obtained in this exampleInternal uniform bridging of ultrafine MoO2The electrode material of the nano-particles is taken as an example, and the constant current charging and discharging result carried out under 1000mA/g shows that the first discharge specific capacity of the nano-particles is 278mAh g-153mAh g after 350 post-cycles-1The capacity retention rate was 19.1%.

Claims (9)

1. Superfine MoO uniformly bridged inside flaky carbon matrix2The electrode material of the nano particles is a three-dimensional flower-shaped structure formed by laminating and interweaving sheet-shaped carbon matrix substructures, wherein the thickness of a sheet layer of the carbon matrix is 10-20nm, the diameter of a single flower-shaped structure formed by the carbon matrix is 2-6um, and the MoO is2The diameter of the nano-particles is 1-3 nm.
2. The flaky carbon substrate of claim 1 in which ultrafine MoO is uniformly bridged inside2The preparation method of the electrode material of the nano particles comprises the following steps: adding MoO3Adding the nanobelt solution and dopamine hydrochloride into a deionized water solution of trihydroxymethyl aminomethane, fully and uniformly stirring at room temperature, washing, and drying to obtain a flower-shaped Mo-polydopamine composite material; sintering the obtained product in an inert atmosphere to obtain the superfine MoO uniformly bridged in the flaky carbon matrix2Electrode material of nanoparticles.
3. The carbon substrate of claim 2, wherein the ultrafine MoO is uniformly bridged inside the sheet-like carbon substrate2A method for preparing a nanoparticle electrode material, characterized in that said MoO3The preparation method of the nanobelt solution comprises the following steps:
1) mixing Mo powder with H2O2And H2Stirring the mixture in the O mixed solution uniformly;
2) transferring the solution obtained in the step 1) into a reaction container for heating, taking out, and naturally cooling to room temperature to obtain MoO3Nanobelt solution.
4. The carbon substrate of claim 2, wherein the ultrafine MoO is uniformly bridged inside the sheet-like carbon substrate2A method for preparing electrode material of nano particles is characterized in thatThe time for fully stirring is 2-8 h.
5. The flaky carbon substrate of claim 3 in which ultrafine MoO is uniformly bridged inside2The preparation method of the electrode material of the nano particles is characterized in that the mass of the Mo powder in the step 1) is 0.5-3.5 g; h in the mixed solution2O2And H2O two are 10-80mL each.
6. The carbon substrate of claim 2, wherein the ultrafine MoO is uniformly bridged inside the sheet-like carbon substrate2A method for preparing a nanoparticle electrode material, characterized in that said MoO3The nano-belt solution is 1-10mL, the dopamine hydrochloride is 0.1-1g, the tris (hydroxymethyl) aminomethane is 0.1-1g, and the deionized water is 20-200 mL.
7. The sheet-like carbon matrix of claim 3, wherein the inside of the matrix is uniformly bridged with ultrafine MoO2The preparation method of the electrode material of the nano-particles is characterized in that the heating temperature is 160-200 ℃, and the heating time is 6-48 h.
8. The carbon substrate of claim 2, wherein the ultrafine MoO is uniformly bridged inside the sheet-like carbon substrate2The preparation method of the electrode material of the nano-particles is characterized in that the sintering temperature is 600-1000 ℃, and the sintering time is 1-4 h.
9. The flaky carbon substrate of claim 1 in which ultrafine MoO is uniformly bridged inside2The nano-particle electrode material is applied as a negative electrode active material of a lithium ion battery with high capacity and long cycle life.
CN202010689639.0A 2020-07-17 2020-07-17 Superfine MoO uniformly bridged inside flaky carbon matrix2Electrode material of nano particles and preparation method and application thereof Pending CN111747449A (en)

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CN113387385A (en) * 2021-08-16 2021-09-14 河南师范大学 Preparation method and application of two-dimensional amorphous molybdenum-based oxide composite material with oxygen-rich vacancy defects

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CN112310385A (en) * 2020-10-12 2021-02-02 浙江理工大学 Silver-ear-shaped nanosphere material assembled by molybdenum dioxide nanoparticles inlaid with carbon nanosheets and preparation and application thereof
CN113387385A (en) * 2021-08-16 2021-09-14 河南师范大学 Preparation method and application of two-dimensional amorphous molybdenum-based oxide composite material with oxygen-rich vacancy defects

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