CN112635738B - Preparation method of FeNiP/C @ MXene composite anode material for lithium ion battery - Google Patents
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Abstract
The invention discloses a preparation method of a FeNiP/C @ MXene composite negative electrode material for a lithium ion battery, which comprises the steps of dissolving nickel acetylacetonate and ammonium ferrous sulfate in ethanol, adding the solution into a solution of N, N-dimethylformamide in which a surfactant and an organic ligand are dissolved, stirring by strong magnetic force, transferring the solution into a high-pressure reaction kettle for reaction, carrying out centrifugal separation, and carrying out vacuum drying to obtain a mixed metal organic framework template; mixing and stirring the template and the pretreated MXene material, and centrifuging to obtain a Fe/Ni-MOF @ MXene precursor; and carrying out phosphorization and calcination on the precursor in a protective atmosphere to obtain the FeNiP/C @ MXene composite material. In the invention, phosphide is crystallized and nucleated in the MOF, the hollow carbon shell provides sufficient space for the volume change of the phosphide in the MOF, and MXene on the outermost layer can limit the side reaction of electrolyte and phosphide, thereby improving the first coulombic efficiency.
Description
Technical Field
The invention belongs to the technical field of material synthesis and energy, and particularly relates to a preparation method of a FeNiP/C @ MXene composite material for a lithium ion battery.
Background
The lithium ion battery has the advantages of high energy density, high working voltage, long cycle life, no memory and the like, is widely applied to the fields of digital codes, energy storage, electric automobiles and the like, and becomes a high-energy battery system with the most bright application prospect.
At present, a commercial lithium ion battery is mainly made of a graphite negative electrode material, but the graphite material has the defect of low specific capacity, and the theoretical capacity of the graphite material is only 372 mAh/g. Therefore, the development of new high-performance negative electrode materials is the key to the development of next-generation high-energy density lithium ion batteries. The metal phosphide has the advantages of ultrahigh reversible capacity, good electron transfer rate and rate capability and the like, and is a novel lithium ion battery cathode material worthy of deep research. However, the energy storage process of such materials has obvious volume expansion and low coulombic efficiency for the first time, and the problem limits the application of metal phosphide as a negative electrode material.
Disclosure of Invention
The invention mainly aims to overcome the defects of the prior art and provides a preparation method of a FeNiP/C @ MXene composite material for a lithium ion battery.
In order to achieve the purpose, the preparation method of the FeNiP/C @ MXene composite anode material for the lithium ion battery provided by the invention comprises the following steps:
(1) dissolving nickel acetylacetonate and ferrous ammonium sulfate in an ethanol solution, magnetically stirring for 0.5-3h, adding the solution into a solution of N, N-dimethylformamide in which a surfactant and an organic ligand are dissolved, strongly magnetically stirring for 0.5-3h, putting the solution into a high-pressure reaction kettle, reacting at 70-180 ℃, and keeping the temperature for 10-36 h;
(2) washing the product obtained in the step (1) with ethanol, then performing centrifugal separation, and performing vacuum drying at 70-120 ℃ for 6-24 hours to obtain a mixed metal organic framework template Fe/Ni-MOF;
(3) mixing and stirring the template Fe/Ni-MOF and the pretreated MXene, aging for 0.5-5 h, and performing centrifugal separation and freeze drying to obtain a hydrogen bond self-assembled Fe/Ni-MOF @ MXene precursor;
(4) and mixing and calcining the Fe/Ni-MOF @ MXene precursor and sodium hypophosphite at the temperature of 200-400 ℃ in a nitrogen atmosphere to obtain the FeNiP/C @ MXene composite negative electrode material for the lithium ion battery.
Preferably, the organic ligand in step (1) comprises-OH and-O groups, which are capable of forming hydrogen bonds with the functional groups of MXene.
Preferably, the organic ligand comprises one or more of terephthalic acid, trimesic acid, cyclohexanedicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, 2, 6-pyridinedicarboxylic acid, 2-pyridinecarboxylic acid.
Preferably, the surfactant in step (1) comprises one or more of polyvinylpyrrolidone, N-ethyl perfluorooctylsulfonamide, sodium polystyrene sulfonate and sodium dodecyl sulfonate.
Preferably, the mass ratio of the ammonium ferrous sulfate to the nickel acetylacetonate in the step (1) is 1 (0.5-5), the mass ratio of the nickel acetylacetonate to the organic ligand is 1 (0.1-6), and the mass ratio of the nickel acetylacetonate to the surfactant is 1 (1-6).
Preferably, the volume ratio of the N, N-dimethylformamide to the ethanol in the step (1) is 1 (0.1-4).
Preferably, the MXene material used in step (3) comprises Ti3C2、Ti2C、Nb2C、V2C、Mo2C, the mass ratio of the template Fe/Ni-MOF to the MXene material is 1 (0.01-0.1).
Preferably, the mass ratio of the precursor to the sodium hypophosphite in the step (4) is 1: (5-20), and calcining conditions are as follows: the heating rate is 1-10 ℃/min, and the calcining time is 1-5 h.
Preferably, the mixed metal organic framework template Fe/Ni-MOF obtained in the step (2) is of a porous structure, and the specific surface area is 100-400 m2/g。
Preferably, the particle size of the FeNiP/C @ MXene composite negative electrode material is 100 nm-10 microns, the carbon content is 0.5-10 wt.%, the thickness of the MXene layer is 5-300 nm, and the specific surface area is 50-700 m2The pores have a diameter of 5 to 40 nm.
The invention concept of the invention is as follows:
the first coulombic efficiency can be effectively improved by compounding the metal phosphide and the two-dimensional material with high coulombic efficiency, for example, the two-dimensional layered metal carbide or nitride, namely MXene material, which is formed in the rise of the years, is typically Ti3C2、Ti2C、Nb2C、V2C、Mo2C and the like. The MXene material is obtained by etching and stripping MAX phase material by HF (or mixed solution of LiF and concentrated HCl) and the like, the etched MXene material has surface functional groups of-OH, -O, -F and the like, a small layer of MXene material can be obtained by the upper layer liquid after etching, and a plurality of layers of MXene materials are arranged at the bottom layer.
Aiming at the defect of lithium storage of metal phosphide, the invention firstly synthesizes a porous hollow metal-organic framework template Fe/Ni-MOF, then utilizes a ligand to form a hydrogen bond with an MXene functional group to realize the self-assembly of the MOF template and the MXene, and finally obtains the FeNiP/C MXene composite material through phosphorization heat treatment. In the material, metal phosphide is crystallized and nucleated in the MOF, the hollow carbon shell provides sufficient space for the volume change of the internal phosphide, the structural integrity of the particle circulation process is guaranteed, MXene at the outermost layer plays a role in protecting and bridging the particles, the side reaction of electrolyte and phosphide is limited, the first coulombic efficiency is improved, and the electrochemical performance of the metal phosphide is enhanced.
Compared with the prior art, the technical scheme adopted by the invention has the following advantages:
1. the invention uses the hollow structure in the carbon shell to relieve the volume expansion of the phosphide in the lithium storage process, thereby prolonging the service life of the battery.
2. The MXene material on the surface of the electrode material can play a role in stabilizing a particle structure, reducing side reactions between phosphide and electrolyte, enhancing the transmission speed of electrons, improving the rate capability of the material and improving the lithium storage stability of the material.
3. The FeNiP/C @ MXene composite negative electrode material prepared by the method has stronger cycle performance, and the reversible capacity of 50 cycles can reach more than 700mAh/g under the high current density of 400 mA/g.
Drawings
FIG. 1 is an SEM image of the FeNiP/C @ MXene composite anode material in example 1.
FIG. 2 is a graph of the cycle performance of the FeNiP/C @ MXene composite anode material in example 1 at a current density of 400 mA/g.
Detailed Description
In order that the invention may be better understood, the invention will now be further described by way of specific embodiments, which are not intended to limit the scope of the invention.
Example 1
A preparation method of a FeNiP/C @ MXene composite anode material for a lithium ion battery comprises the following specific steps:
(1) weighing 10mg of ferrous ammonium sulfate and 42mg of nickel acetylacetonate, dissolving the ferrous ammonium sulfate and the nickel acetylacetonate in 50ml of ethanol solution, stirring the mixture for 1 hour by strong magnetic force, adding the mixed solution into a solution of 25ml of N, N-dimethylformamide in which 90mg of sodium polystyrene sulfonate and 100mg of trimesic acid are dissolved, stirring the mixture for 2 hours by strong magnetic force, putting the solution into a high-pressure reaction kettle, reacting the solution at 120 ℃, and keeping the temperature for 24 hours.
(2) Using ethanol to treatWashing the product in the step (1) for three times, then centrifugally separating, and drying in vacuum at 70 ℃ for 12 hours to obtain a mixed metal organic frame template Fe/Ni-MOF, wherein the template is a porous hollow structure and has a specific surface area of 270.1m2/g。
(3) 50mg of Fe/Ni-MOF and 1mg of a small layer of Ti3C2Mixing and stirring, aging for 1h, and obtaining the hydrogen bond self-assembled Fe/Ni-MOF @ Ti through centrifugal separation and freeze drying3C2And (3) precursor.
(4) And mixing and calcining 30mg of the precursor and 101mg of sodium hypophosphite, wherein the heating rate is 5 ℃/min, the calcining temperature is 350 ℃, the calcining time is 3h, and the calcining atmosphere is nitrogen. Cooling to room temperature in the furnace to obtain the FeNiP/C @ MXene material with the particle size of 200nm, the carbon content of 3 percent, the thickness of the MXene layer of 15nm and the BET specific surface area of 320.4m2(g), the pore distribution is 5-20 nm.
The SEM image of the FeNiP/C @ MXene material prepared in this example is shown in FIG. 1.
And (3) electrochemical performance testing: the prepared electrode material is uniformly mixed with acetylene black and PVDF according to the mass ratio of 8:1:1, a proper amount of N-methyl pyrrolidone is added for dissolution, and the slurry is coated on a copper foil to prepare the electrode. The test electrode was dried in a vacuum oven at 110 ℃ for 24 hours and in a glove box under high-purity argon atmosphere with 1:1:1 (vol/vol) LiPF and EC/DEC/DMC6The 2016 button cell is assembled by taking glass fiber filter paper as a liquid absorption film, taking a PP film as a diaphragm and taking metal lithium as a cell cathode as an electrolyte. Discharging and charging conditions: discharged to 0.02V at the same current density and then recharged to 2V, the current density selected was 400 mA/g. The above cell was tested to obtain fig. 2. As can be seen from FIG. 2, the electrode material prepared by the method of example 1 is charged and discharged at a current density of 400mA/g, and the reversible capacity is maintained at 710.8mAh/g after 50 weeks of circulation, which indicates that the FeNiP/C @ MXene material has better capacity retention rate and circulation stability.
Example 2
A preparation method of a FeNiP/C @ MXene composite anode material for a lithium ion battery comprises the following specific steps:
(1) weighing 35mg of ferrous ammonium sulfate and 81mg of nickel acetylacetonate, dissolving the ferrous ammonium sulfate and the nickel acetylacetonate in 50ml of ethanol solution, stirring the mixture for 2 hours by strong magnetic force, adding the mixed solution into a solution of 121mg of sodium polystyrene sulfonate and 48mg of cyclohexane dicarboxylic acid in 50ml of N, N-dimethylformamide, stirring the mixture for 1.2 hours by strong magnetic force, putting the solution into a high-pressure reaction kettle, reacting the solution at 150 ℃, and keeping the temperature for 36 hours.
(2) Washing the product obtained in the step (1) with ethanol for three times, then carrying out centrifugal separation, and then carrying out vacuum drying for 12 hours at 70 ℃ to obtain a mixed metal organic frame template Fe/Ni-MOF, wherein the template is in a porous hollow structure and has a specific surface area of 220.1m2/g。
(3) 50mg of Fe/Ni-MOF and 2mg of few-layer V2C, mixing and stirring, aging for 2h, and obtaining the hydrogen bond self-assembled Fe/Ni-MOF @ V by centrifugal separation and freeze drying2And C, precursor.
(4) And mixing and calcining 30mg of the precursor and 150mg of sodium hypophosphite, wherein the heating rate is 4 ℃/min, the calcining temperature is 300 ℃, the calcining time is 5h, and the calcining atmosphere is nitrogen. Cooling the furnace to room temperature to obtain FeNiP/C @ V2Material C with particle size of 500nm, carbon content of 5%, MXene layer thickness of 60nm, BET specific surface area of 260.4m2(g), the pore distribution is 10-30 nm.
And (3) electrochemical performance testing: the electrochemical test of this example was the same as example 1, with a reversible capacity of 680.2mAh/g, indicating FeNiP/C @ V2The C material has better capacity retention rate and cycling stability.
Example 3
A preparation method of a FeNiP/C @ MXene composite anode material for a lithium ion battery comprises the following specific steps:
(1) weighing 40mg of ferrous ammonium sulfate and 20mg of nickel acetylacetonate, dissolving the ferrous ammonium sulfate and the nickel acetylacetonate in 50ml of ethanol solution, stirring the mixture for 2.5 hours by strong magnetic force, adding the mixed solution into a solution of 80mg of sodium dodecyl sulfate and 30mg of terephthalic acid dissolved in 200ml of N, N-dimethylformamide, stirring the mixture for 3 hours by strong magnetic force, putting the solution into a high-pressure reaction kettle, reacting the solution at 170 ℃, and keeping the temperature for 20 hours.
(2) Washing the product obtained in the step (1) with ethanol for three times, then performing centrifugal separation, and performing vacuum drying for 8 hours at 100 ℃ to obtain a mixed metal organic frame template Fe/Ni-MOF, wherein the template is a porous hollow junctionStructure, specific surface area 151.6m2/g。
(3) 50mg of Fe/Ni-MOF and 5mg of few-layer Mo2C, mixing and stirring, aging for 2h, and obtaining hydrogen bond self-assembled Fe/Ni-MOF @ Mo through centrifugal separation and freeze drying2And C, precursor.
(4) And mixing and calcining 30mg of the precursor and 300mg of sodium hypophosphite, wherein the heating rate is 4 ℃/min, the calcining temperature is 400 ℃, the calcining time is 5h, and the calcining atmosphere is nitrogen. Cooling the furnace to room temperature to obtain a FeNiP/C @ Mo2C material, wherein the carbon content is 10%, the particle size is 10 mu m, the thickness of the MXene layer is 300nm, and the BET specific surface area is 198.4m2(g), the pore distribution is 10-30 nm.
And (3) electrochemical performance testing: the electrochemical test of this example was the same as example 1, with reversible capacity maintained at 650mAh/g, indicating FeNiP/C @ Mo2The C material has better capacity retention rate and cycling stability.
Example 4
A preparation method of a FeNiP/C @ MXene composite anode material for a lithium ion battery comprises the following specific steps:
(1) weighing 20mg of ferrous ammonium sulfate and 20mg of nickel acetylacetonate, dissolving the ferrous ammonium sulfate and the nickel acetylacetonate in 50ml of ethanol solution, stirring the mixture for 1.5 hours by strong magnetic force, adding the mixed solution into a solution of 280ml of N, N-dimethylformamide in which 110mg of polyvinylpyrrolidone and 90mg of cyclohexanedicarboxylic acid are dissolved, stirring the mixture for 3 hours by strong magnetic force, putting the solution into a high-pressure reaction kettle, reacting the mixture at 90 ℃, and keeping the temperature for 14 hours.
(2) Washing the product obtained in the step (1) with ethanol for three times, then carrying out centrifugal separation, and then carrying out vacuum drying for 13h at 110 ℃ to obtain a mixed metal organic frame template Fe/Ni-MOF, wherein the template is in a porous hollow structure and has a specific surface area of 166m2/g。
(3) 50mg of Fe/Ni-MOF and 2.5mg of a small layer of Ti3C2Mixing and stirring, aging for 2.2h, and obtaining the hydrogen bond self-assembled Fe/Ni-MOF @ Ti through centrifugal separation and freeze drying3C2And (3) precursor.
(4) Mixing and calcining 30mg of precursor and 300mg of sodium hypophosphite at the temperature rise rate of 4 ℃/min and the calcining temperature of 400 ℃ for 5h in the calcining atmosphereIs nitrogen. Cooling the furnace to room temperature to obtain FeNiP/C @ Ti3C2Material with a particle size of 5 μm, 8% carbon, 180nm MXene layer thickness, BET specific surface area of 205.4m2(g), the pore distribution is 10-40 nm.
And (3) electrochemical performance testing: the electrochemical test of this example was the same as example 1, with reversible capacity maintained at 612.2mAh/g, indicating FeNiP/C @ Ti3C2The material has better capacity retention rate and cycling stability.
Comparative examples
The smelting method for preparing the FeNiP material for the lithium ion battery comprises the following specific steps:
(1) weighing 3g of iron powder, 2.5g of nickel powder and 8g of red phosphorus, mixing and pouring into a crucible.
(2) And (3) calcining the crucible in the step (1). The calcination atmosphere is nitrogen, the calcination temperature is 700 ℃, the time is 8 hours, the furnace is cooled to obtain the FeNiP material, and the FeNiP material is ground and sieved by a 400-mesh sieve.
And (3) electrochemical performance testing: electrochemical performance testing of this comparative example was the same as example 1, with the FeNiP material having a reversible capacity of 180.3mAh/g at a current density of 400mA/g for 50 cycles.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a FeNiP/C @ MXene composite anode material for a lithium ion battery is characterized by comprising the following steps of:
(1) dissolving nickel acetylacetonate and ferrous ammonium sulfate in an ethanol solution, magnetically stirring for 0.5-3h, adding the solution into a solution of N, N-dimethylformamide in which a surfactant and an organic ligand are dissolved, strongly magnetically stirring for 0.5-3h, putting the solution into a high-pressure reaction kettle, reacting at 70-180 ℃, and keeping the temperature for 10-36 h;
(2) washing the product obtained in the step (1) with ethanol, then performing centrifugal separation, and performing vacuum drying at 70-120 ℃ for 6-24 hours to obtain a mixed metal organic framework template Fe/Ni-MOF;
(3) mixing and stirring the template Fe/Ni-MOF and the pretreated MXene, aging for 0.5-5 h, and performing centrifugal separation and freeze drying to obtain a hydrogen bond self-assembled Fe/Ni-MOF @ MXene precursor;
(4) and mixing and calcining the Fe/Ni-MOF @ MXene precursor and sodium hypophosphite at the temperature of 200-400 ℃ in a nitrogen atmosphere to obtain the FeNiP/C @ MXene composite negative electrode material for the lithium ion battery.
2. The method of claim 1, wherein the organic ligand in step (1) comprises-OH and-O groups capable of forming hydrogen bonds with the functional groups of MXene.
3. The method of claim 2, wherein the organic ligand comprises one or more of terephthalic acid, trimesic acid, cyclohexanedicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, 2, 6-pyridinedicarboxylic acid, and 2-pyridinecarboxylic acid.
4. The method of claim 1, wherein the surfactant in step (1) comprises one or more of polyvinylpyrrolidone, N-ethyl perfluorooctylsulfonamide, sodium polystyrene sulfonate, and sodium dodecylsulfonate.
5. The preparation method according to claim 1, wherein the mass ratio of the ammonium ferrous sulfate to the nickel acetylacetonate in step (1) is 1 (0.5-5), the mass ratio of the nickel acetylacetonate to the organic ligand is 1 (0.1-6), and the mass ratio of the nickel acetylacetonate to the surfactant is 1 (1-6).
6. The preparation method according to claim 1, wherein the volume ratio of the N, N-dimethylformamide to the ethanol in the step (1) is 1 (0.1-4).
7. As in claimThe production method according to claim 1, wherein the MXene material used in the step (3) comprises Ti3C2、Ti2C、Nb2C、V2C、Mo2C, the mass ratio of the template Fe/Ni-MOF to the MXene material is 1 (0.01-0.1).
8. The preparation method according to claim 1, wherein the mass ratio of the precursor to the sodium hypophosphite in the step (4) is 1: (5-20), and calcining conditions are as follows: the heating rate is 1-10 ℃/min, and the calcining time is 1-5 h.
9. The preparation method of claim 1, wherein the mixed metal organic framework template Fe/Ni-MOF obtained in the step (2) is a porous structure and has a specific surface area of 100-400 m2/g。
10. The preparation method of claim 1, wherein the FeNiP/C @ MXene composite anode material has a particle size of 100nm to 10 μm, a carbon content of 0.5 to 10 wt.%, an MXene layer thickness of 5 to 300nm, and a specific surface area of 50 to 700m2The pores have a diameter of 5 to 40 nm.
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