CN109904426B - MXene induced growth nano iron oxide composite material, preparation method and application thereof - Google Patents
MXene induced growth nano iron oxide composite material, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a nano iron oxide composite material for MXene induced growth, which comprises the following steps: A) mixing Ti3AlC2Adding the mixture into HF solution for etching to obtain an etching product; B) mixing the etching product with a tetramethyl ammonium hydroxide solution, intercalating, then adding LiOH, and reacting to obtain an intermediate product; the mass ratio of the LiOH to the etching product is (0.04-0.09): 1; C) dispersing the intermediate product in water, performing ultrasonic treatment for 1-1.5 hours, and centrifuging to obtain a supernatant which is an MXene solution; D) sequentially adding an iron salt solution and an alkali liquor into the MXene solution, and carrying out in-situ growth to obtain a nano ferric oxide composite material; the ferric salt solution comprises ferric salt and a dispersing agent. The invention also provides the MXene induced growth nano iron oxide composite material and application thereof.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a nano iron oxide composite material for MXene induced growth, a preparation method and application thereof.
Background
The lithium ion battery has the characteristics of low cost, environmental friendliness, high energy density, no memory effect, light weight and the like, and is widely applied to many fields such as mobile phones, computers, electric vehicles and the like. At present, graphite is generally adopted as a traditional negative electrode material, but the specific capacity of the material is low, and with the demand of social development, new negative electrode materials with higher specific capacity are paid more and more attention. Iron oxide is one of them, and it has the following advantages for the negative pole of lithium ion battery: (1) higher specific mass capacity (1007 mAh/g); (2) abundant natural reserves; (3) is non-toxic and harmless. However, it also has its own drawbacks: (1) poor conductivity; (2) volume expansion occurs during the process of lithium deintercalation, which affects the cycle performance of the battery.
MXene is a new class of two-dimensional materials with near-metallic conductivity (conductivity about 10)5S/m) can be used for improving the conductivity of the iron oxide, and meanwhile, the unique two-dimensional nanostructure can also be used for buffering the volume expansion of the iron oxide in the lithium intercalation and deintercalation process, so that the electrochemical performance of the iron oxide is improved. At present, the method for modifying iron oxide with MXene mainly focuses on physical modification, for example, patent CN 108630920A and patent CN 107221428A both prepare the composite material of iron oxide and MXene by mechanical ultrasound and mixed membrane extraction, thereby improving the electrochemical performance of the iron oxide.
However, the physical modification method has some inevitable disadvantages, firstly, because the mechanical ultrasound is difficult to ensure good uniformity, the particle size of iron oxide particles is different, so that aggregation occurs among particles in the subsequent mixed film-drawing process, and secondly, the problem that MXene with a lamellar structure is stacked also occurs, so that part of MXene loses the effect of the buffer template, the excellent conductivity of MXene cannot be exerted, the volume expansion effect of the buffer iron oxide in the lithium desorption and insertion process is reduced, and the electrochemical performance of the composite material is influenced. In view of this, it is critical to explore a more uniform and more effective composite modification method.
Disclosure of Invention
The invention aims to provide MXene-induced growth nano iron oxide, a preparation method and application thereof.
The invention provides a preparation method of a nano iron oxide composite material for MXene induced growth, which comprises the following steps:
A) mixing Ti3AlC2Adding the mixture into HF solution for etching to obtain an etching product;
B) mixing the etching product with a tetramethyl ammonium hydroxide solution, intercalating, then adding LiOH, and reacting to obtain an intermediate product;
the mass ratio of the LiOH to the etching product is (0.04-0.09): 1;
C) dispersing the intermediate product in water, performing ultrasonic treatment for 1-1.5 hours, and centrifuging to obtain a supernatant which is an MXene solution;
D) sequentially adding an iron salt solution and an alkali liquor into the MXene solution, carrying out in-situ growth, and annealing the obtained product to obtain a nano ferric oxide composite material;
the ferric salt solution comprises ferric salt and a dispersing agent.
Preferably, the etching temperature is 50-70 ℃;
the etching time is 12-36 hours.
Preferably, the mass concentration of the tetramethylammonium hydroxide solution is 15-40%.
Preferably, the iron salt is FeCl3、Fe2(SO4)3And Fe (NO)3)3One or more of the above;
fe in the iron salt solution3The concentration of + is 0.005-0.02 mol/L.
Preferably, the dispersing agent is one or more of polyvinylpyrrolidone, cetyl trimethyl ammonium bromide and polydiallyl dimethyl ammonium chloride;
the mass concentration of the dispersing agent in the ferric salt solution is 0.1-0.5 g/L.
Preferably, the content of-OH functional groups in the MXene solution is 30-60%.
Preferably, the molar ratio of the iron ions in the MXene solution and the iron salt solution to the alkali in the alkali liquor is (0.5-2):1: 3.
Preferably, the temperature of the in-situ compounding is 40-60 ℃;
the in-situ compounding time is 3-5 hours.
The invention provides a nano iron oxide composite material for MXene induced growth, which is prepared according to the preparation method.
The invention provides an application of the nano iron oxide composite material induced by MXene as a negative electrode material in a lithium ion battery.
The invention provides a preparation method of a nano iron oxide composite material for MXene induced growth, which comprises the following steps: A) mixing Ti3AlC2Adding the mixture into HF solution for etching to obtain an etching product; B) mixing the etching product with a tetramethyl ammonium hydroxide solution, intercalating, then adding LiOH, and reacting to obtain an intermediate product; the mass ratio of the LiOH to the etching product is (0.04-0.09): 1; C) dispersing the intermediate product in water, performing ultrasonic treatment for 1-1.5 hours, and centrifuging to obtain a supernatant which is an MXene solution; D) sequentially adding an iron salt solution and an alkali liquor into the MXene solution, and carrying out in-situ growth to obtain a nano ferric oxide composite material; the ferric salt solution comprises ferric salt and a dispersing agent. The MXene with small lamella and a specific-OH content range is prepared by a specific method, and not only can the problem of easy stacking be avoided, but also nano iron oxide with smaller grain size and more uniform distribution can be induced to grow on the surface of the MXene, so that the problem of volume expansion of the iron oxide in the lithium intercalation and deintercalation process is solved, the conductivity is improved, and the electrochemical performance is improved. Experimental results show that the capacity retention rate of the lithium ion battery assembled by using the nano iron oxide composite material prepared by the preparation method as a negative electrode material under the condition of high current density of 4A/g is 29.6%, and the lithium ion battery can still maintain the higher capacity of 264.3mAh/g after 1000 times of circulation.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows MXene and Fe in example 1 of the present invention2O3@ MXene's Raman spectrum;
FIG. 2 shows MXene and Fe in example 1 of the present invention2O3XPS-O1s fine Spectrum @ MXene;
FIG. 3 is a product morphology chart of example 1 of the present invention and comparative example 1;
FIG. 4 is a graph of rate capability for example 1 of the present invention and comparative example 1;
FIG. 5 is a graph of cycle performance of example 1 of the present invention and comparative example 1;
FIG. 6 is a product morphology chart of example 2 of the present invention and comparative example 2;
FIG. 7 is a product morphology chart of example 3 of the present invention and comparative example 3.
Detailed Description
The invention provides a preparation method of a nano iron oxide composite material for MXene induced growth, which comprises the following steps:
A) mixing Ti3AlC2Adding the mixture into HF solution for etching to obtain an etching product;
B) mixing the etching product with a tetramethyl ammonium hydroxide solution, intercalating, then adding LiOH, and reacting to obtain an intermediate product;
the mass ratio of the LiOH to the etching product is (0.04-0.09): 1;
C) dispersing the intermediate product in water, performing ultrasonic treatment for 1-1.5 hours, and centrifuging to obtain a supernatant which is an MXene solution;
D) sequentially adding an iron salt solution and an alkali liquor into the MXene solution, and carrying out in-situ growth to obtain a nano ferric oxide composite material;
the ferric salt solution comprises ferric salt and a dispersing agent.
According to the invention, the solution is preferably stirred for full etching, and then the obtained etched solid product is washed for 3-5 times by deionized water and then is dried in vacuum to obtain a powdery etching product.
In the present invention, theTi3AlC2The mass ratio of (3) to the volume of HF is preferably 1g:10mL, and the mass concentration of the HF solution is preferably 30-50%, more preferably 40%; the etching temperature is preferably 50-70 ℃, and more preferably 60-65 ℃; the etching time is preferably 12-36 hours, and more preferably 24 hours; the temperature of the vacuum drying is preferably 60-80 ℃, more preferably 65-75 ℃, and most preferably 70 ℃; the time for vacuum drying is preferably 8-24 hours, and more preferably 12-18 hours.
After the etching is finished, the etching product is preferably added into a tetramethylammonium hydroxide solution for stirring, and the step is used for intercalation to increase the interlayer distance, so that the interlayer stripping is facilitated, and MXene with smaller interlayer is obtained.
In the invention, the mass concentration of the tetramethylammonium hydroxide solution is preferably 15-40%, more preferably 20-35%, and most preferably 25-30%; the stirring temperature is preferably room temperature; the stirring time is preferably 24 to 36 hours.
After intercalation is finished, LiOH is continuously added into a reaction system for stirring, the aim of the step is to convert partial-F functional groups in MXene into-OH functional groups, so that the-OH functional groups account for 30-60% of the total functional groups, and the researches of pen workers find that the-OH functional groups in MXene are beneficial to heterogeneous nucleation reaction, can provide nucleation sites for iron oxide crystals, and are beneficial to inducing the growth of small-particle-size iron oxide crystals when the-OH functional groups account for 30-60% of the total functional groups.
In the invention, the mass ratio of the LiOH to the etching product is (0.04-0.09): 1, more preferably (0.05 to 0.08): 1, specifically, in embodiments of the present invention, may be 0.07:1, 0.09:1, or 0.04: 1; the temperature of stirring in this step is preferably room temperature; the stirring time is preferably 24 to 36 hours.
After the conversion of the functional groups, adding the obtained solid product into deionized water for redispersion, and carrying out ultrasonic treatment, wherein the step aims to strip the lamella and obtain MXene of the small lamella, and the growth of iron oxide crystals by taking the MXene of the small lamella (1-2 mu m) as a substrate is also beneficial to the growth of iron oxide grains with small grain size.
In the invention, the frequency of the ultrasonic wave is preferably 40-60 KHz; the time of the ultrasonic treatment is preferably 1-1.5 hours. Under the ultrasonic conditions, a small flake layer MXene with a specific size can be obtained.
After a specific MXenen solution is obtained, adding an iron salt solution into the MXenen solution, stirring, dropwise adding an alkali liquor, stirring to obtain a solid product, and performing freeze drying and annealing on the solid product to obtain the nano iron oxide composite material.
In the invention, the alkali liquor is preferably NaOH and/or KOH, and the concentration of the alkali liquor is preferably 0.01-0.05 mol/L, more preferably 0.02-0.04 mol/L, and most preferably 0.03 mol/L.
The iron salt solution preferably comprises an iron salt and a dispersant, and the iron salt is preferably a soluble iron salt such as FeCl3、Fe2(SO4)3And Fe (NO)3)3One or more of the above; fe in the iron salt solution3The concentration of the + is preferably 0.005-0.02 mol/L, more preferably 0.01-0.015 mol/L; the dispersing agent is preferably one or more of polyvinylpyrrolidone, cetyl trimethyl ammonium bromide and polydiallyl dimethyl ammonium chloride; the mass concentration of the dispersing agent in the ferric salt solution is 0.1-0.5 g/L, more preferably 0.2-0.4 g/L, and most preferably 0.3 g/L.
According to the invention, the dispersing agent is added into the ferric salt solution, so that Fe can be effectively dispersed3+Let the subsequent Fe2O3The crystal is uniformly nucleated.
In the invention, the molar ratio of MXene in the MXene solution to iron ions in the iron salt solution and alkali in the alkali liquor is preferably (0.5-2) to 1:3, more preferably (1-2) to 1:3, and most preferably 1:1: 3; the stirring temperature after the iron salt solution is added is preferably room temperature; the stirring time after the ferric salt solution is added is preferably 30-60 min; the stirring temperature after the alkali liquor is added is preferably 40-60 ℃, more preferably 45-55 ℃, and most preferably 50 ℃; the stirring time after the alkali liquor is added is preferably 3-5 hours, and more preferably 4 hours.
According to the invention, the annealing is preferably carried out in an argon atmosphere, and the annealing temperature is preferably 200-400 ℃; more preferably 250-350 ℃, and most preferably 300 ℃; the annealing time is preferably 0.5 to 2 hours, and more preferably 2 to 1.5 hours.
The invention also provides a nano iron oxide composite material for MXene induced growth, which is prepared according to the preparation method.
In the invention, in the nano iron oxide composite material, the size of an MXene sheet layer is 1-2 μm; the particle size of the nano iron oxide particles growing on the MXene surface in situ is about 50nm, and the nano iron oxide particles are uniformly dispersed without agglomeration.
The invention also provides application of the nano iron oxide composite material as a cathode material in a lithium ion battery.
The invention has no special limitation to the types of the lithium ion batteries, and the lithium ion batteries which are commonly used by the technicians in the field and take the nano ferric oxide as the cathode can be adopted. In embodiments of the invention, the carbon black may: polyvinylidene fluoride (PVDF) is mixed in a ratio of 80:10:10 to prepare an electrode plate serving as a working electrode, a lithium plate serving as a counter electrode, a porous polypropylene film (Celgard 2300) for a diaphragm and 1MLiPF for an electrolyte6A mixed solution of Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (w/w ═ 1:1) was assembled into a button cell, and rate performance and cycle performance tests were performed.
The invention provides a preparation method of a nano iron oxide composite material for MXene induced growth, which comprises the following steps: A) mixing Ti3AlC2Adding the mixture into HF solution for etching to obtain an etching product; B) mixing the etching product with a tetramethyl ammonium hydroxide solution, intercalating, then adding LiOH, and reacting to obtain an intermediate product; the mass ratio of the LiOH to the etching product is (0.04-0.09): 1; C) dispersing the intermediate product in water, performing ultrasonic treatment for 1-1.5 hours, and centrifuging to obtain a supernatant which is an MXene solution; D) sequentially adding an iron salt solution and an alkali liquor into the MXene solution for in-situ growth to obtain the nano ferric oxide composite material(ii) a The ferric salt solution comprises ferric salt and a dispersing agent. The MXene with small lamella and a specific-OH content range is prepared by a specific method, and not only can the problem of easy stacking be avoided, but also nano iron oxide with smaller grain size and more uniform distribution can be induced to grow on the surface of the MXene, so that the problem of volume expansion of the iron oxide in the lithium intercalation and deintercalation process is solved, the conductivity is improved, and the electrochemical performance is improved. Experimental results show that the capacity retention rate of the lithium ion battery assembled by using the nano iron oxide composite material prepared by the preparation method as a negative electrode material under the condition of high current density of 4A/g is 29.6%, and the lithium ion battery can still maintain the higher capacity of 264.3mAh/g after 1000 times of circulation.
In order to further illustrate the present invention, the MXene-induced growth nano iron oxide, the preparation method and the application thereof provided by the present invention are described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
(1) Preparation of a platelet-layer MXene solution with a content of-OH functional groups of 50%
10g of Ti were weighed3AlC2(MAX) powder, which was slowly added to 100mL of 40% by mass HF solution, stirring was continued at 50 ℃ for 24 h. And then, washing the fully etched solid product with deionized water for 3-5 times, and then putting the washed solid product into an oven for vacuum drying for 12 hours at the temperature of 60 ℃ to obtain a powder product.
Weighing 1g of the powder, adding 25mL of a tetramethylammonium hydroxide (TMAOH) solution with the mass fraction of 25%, stirring at room temperature for 36h, adding 0.07g of LiOH solid powder, stirring at room temperature for 24h, centrifuging, adding the solid isolate into 500mL of deionized water for redispersion, performing ultrasonic treatment for 1h, and centrifuging the solution at the rotation speed of 3500rpm for 1h to obtain a supernatant, namely an MXene solution with the content of the-OH functional groups of 50%.
(2) Preparation of dispersant modified Fe3+Dispersion liquid
100mL of Fe was prepared3+FeCl with concentration of 0.01mol/L3Adding 10mg polyvinylpyrrolidone into the solution, and stirring at room temperatureStirring for 1h to obtain dispersant modified Fe3+And (3) dispersing the mixture.
(3) The small lamella MXene with the content of-OH functional group of 50 percent is used for inducing the growth of the nano ferric oxide
Taking 100mL of the small slice layer MXene solution with the content of-OH functional group being 50%, slowly adding 25mL of dispersing agent modified Fe3+The dispersion was stirred at room temperature for 30min, 25mL of 0.03mol/L NaOH solution was added dropwise, and the mixture was stirred at 40 ℃ for 3 h. Then, washing the obtained solid product with deionized water for 3-5 times, freeze-drying, and finally annealing at 200 ℃ for 1h in an argon atmosphere to obtain a final product, namely Fe2O3@MXene。
For comparison, comparative example 1 (iron oxide) was synthesized as follows: take 100mLFe3+FeCl with concentration of 0.1mol/L3The solution was added slowly to 100mL of 0.3mol/L NaOH solution and stirred at 40 ℃ for 3 h. And then washing the obtained solid product with deionized water for 3-5 times, freeze-drying, and finally annealing for 1h at 200 ℃ in an argon atmosphere.
Both example 1 and comparative example 1 were run as active: carbon black: polyvinylidene fluoride (PVDF) is mixed in a ratio of 80:10:10 to prepare an electrode plate serving as a working electrode, a lithium plate serving as a counter electrode, a porous polypropylene film (Celgard 2300) for a diaphragm and 1MLiPF for an electrolyte6A mixed solution of Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (w/w ═ 1:1) was assembled into a button cell, and rate performance and cycle performance tests were performed.
FIG. 1 shows MXene and Fe2O3Raman diagram of @ MXene, FIG. 2 MXene and Fe2O3XPS-O1s Fine Spectrum of @ MXene, it was found by comparison that part of the Ti-O-H group of MXene was converted into a Ti-O-Fe group, demonstrating that the-OH function of MXene was Fe2O3The crystal provides a nucleation site.
FIG. 3 is a graph showing the morphology of example 1 and comparative example 1, wherein (a) is Fe2O3(b) is Fe2O3Scanning Electron microscopy of @ MXene, (c) is Fe2O3(d) is Fe2O3Transmission electron microscopy of @ MXene, comparative findings show that MXene induces growth of Fe2O3The particle size of the nano particles is about 50nm, and Fe prepared by not adding MXene2O3The grain diameter of the nano-particles is about 100nm, the size of MXene lamella is 1-2 μm, and the MXene with the lamella content and the content of-OH functional groups of 50 percent can induce the growth of Fe with smaller grain diameter size2O3And (3) nanoparticles. Also, Fe prepared without addition of MXene2O3The nanoparticles obviously show serious particle aggregation phenomenon, while Fe grows through MXene induction2O3The nano particles are uniformly distributed on the surface of the MXene lamella and have uniform size, and the addition of the dispersing agent is proved to play a key role.
FIG. 4 is a graph of rate performance for example 1 and comparative example 2, with the capacity retention for example at high current density (4A/g) being 29.6%, much higher than for comparative example (2.8%). FIG. 5 is a graph of cycle performance for the examples and the control, with the examples maintaining a higher capacity (264.3mAh/g) after 1000 cycles, much higher than the control (92.4 mAh/g).
Example 2
(1) Preparation of a platelet-layer MXene solution with a content of-OH functional groups of 30%
10g of Ti were weighed3AlC2(MAX) powder, which was slowly added to 100mL of 40% by mass HF solution, stirring was continued at 70 ℃ for 24 h. And then, washing the fully etched solid product with deionized water for 3-5 times, and then putting the washed solid product into an oven for vacuum drying for 12 hours at the temperature of 80 ℃ to obtain a powder product.
Weighing 2g of the powder, adding 50mL of a tetramethylammonium hydroxide (TMAOH) solution with the mass fraction of 25%, stirring at room temperature for 48h, adding 0.08g of LiOH solid powder, stirring at room temperature for 36h, centrifuging, adding the solid isolate into 500mL of deionized water for redispersion, performing ultrasonic treatment for 1.5h, and centrifuging the solution at the rotation speed of 3500rpm for 1h to obtain a supernatant, namely an MXene solution with the platelet content and the content of-OH functional groups of 30%.
(2) Preparation of dispersant modified Fe3+Dispersion liquid
Preparing 200mL of Fe with a certain volume3+Fe (NO) at a concentration of 0.01mol/L3)3Adding 30mg of polydiallyldimethylammonium chloride into the solution, and stirring for 1h at room temperature to obtain dispersing agent modified Fe3+And (3) dispersing the mixture.
(3) The small lamella MXene with the content of-OH functional group of 30 percent is used for inducing the growth of the nano ferric oxide
100mL of MXene solution containing 30% of-OH functional group in the above small piece layer was added slowly 30mL of dispersant-modified Fe3+The dispersion was stirred at room temperature for 30min, then 30mL of 0.03mol/L KOH solution was added dropwise and stirred at 60 ℃ for 5 h. Then, washing the obtained solid product with deionized water for 3-5 times, freeze-drying, and finally annealing at 400 ℃ for 1h in an argon atmosphere to obtain a final product, namely Fe2O3@MXene。
For comparison, comparative example 2 (iron oxide) was synthesized as follows: 100mL of Fe was taken3+Fe (NO) at a concentration of 0.1mol/L3)3The solution was added slowly with 100mL of 0.3mol/L KOH solution and stirred at 60 ℃ for 5 h. And then washing the obtained solid product with deionized water for 3-5 times, freeze-drying, and finally annealing for 1h at 400 ℃ in an argon atmosphere.
FIG. 6 is a graph showing the morphology of example 2 and comparative example 2, wherein (a) is Fe2O3(b) is Fe2O3Scanning electron microscope picture of @ MXene, comparative finding that MXene induces growth of Fe2O3The nano particles are uniformly distributed on the surface of the MXene lamella, the size is uniform, the particle diameter is about 50nm, the size of the MXene lamella is 1-2 mu m, and Fe prepared by adding no MXene is added2O3The nanoparticles have serious aggregation phenomenon, the particle size is about 100nm, and the fact that MXene with the small lamella content and the content of-OH functional groups of 30 percent can induce the growth of Fe with smaller particle size2O3And (3) nanoparticles.
Both example 2 and comparative example 2 were run according to active substance: carbon black: polyvinylidene fluoride (PVDF) is mixed according to the proportion of 80:10:10 to prepare an electrode plate serving as a working electrode, a lithium plate serving as a counter electrode and a porous polypropylene film (Celgard 2300) for a diaphragm) 1M LiPF for electrolyte6A mixed solution of Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (w/w ═ 1:1) was assembled into a button cell, and rate performance and cycle performance tests were performed. The capacity retention rate of the example at a large current density (4A/g) is 28.2%, which is much higher than that of the comparative example (2.1%). Moreover, the example can still maintain higher capacity (252.4mAh/g) after 1000 cycles, which is much higher than the control example (89.1 mAh/g).
Example 3
(1) Preparation of a platelet-layer MXene solution with a-OH functionality content of 60%
10g of Ti were weighed3AlC2(MAX) powder, which was slowly added to 100mL of 40% by mass HF solution, stirring was continued at 60 ℃ for 24 h. And then, washing the fully etched solid product with deionized water for 3-5 times, and then putting the washed solid product into an oven to be dried in vacuum for 12 hours at the temperature of 70 ℃ to obtain a powder product.
Weighing 1g of the powder, adding 25mL of a tetramethylammonium hydroxide (TMAOH) solution with the mass fraction of 25%, stirring at room temperature for 48h, adding 0.09g of LiOH solid powder, stirring at room temperature for 24h, centrifuging, adding the solid isolate into 500mL of deionized water for redispersion, performing ultrasonic treatment for 1.5h, and centrifuging the solution at the rotation speed of 3500rpm for 1h to obtain a supernatant, namely an MXene solution with the platelet and-OH functional group content of 60%.
(2) Preparation of dispersant modified Fe3+Dispersion liquid
100mL of Fe was prepared3+Fe at a concentration of 0.01mol/L2(SO4)3Adding 15mg of hexadecyl trimethyl ammonium bromide into the solution, and stirring the solution for 1 hour at room temperature to obtain dispersing agent modified Fe3+And (3) dispersing the mixture.
(3) MXene with small lamella and-OH functional group content of 60% is used for inducing growth of nano iron oxide
100mL of MXene solution containing 60% of-OH functional group in the above small piece layer was added slowly 20mL of dispersant-modified Fe3+The dispersion was stirred at room temperature for 30min, then 20mL of 0.03mol/L NaOH solution was added dropwise, and the mixture was stirred at 50 ℃ for 4 h. Then, the obtained solid product was washed with deionized water3-5 times, freeze-drying, and finally annealing at 300 ℃ for 1h in an argon atmosphere to obtain a final product, namely Fe2O3@MXene。
For comparison, comparative example 3 (iron oxide) was synthesized as follows: 100mL of Fe was taken3+Fe at a concentration of 0.1mol/L2(SO4)3The solution was added slowly with 100ml NaOH solution of 0.3mol/L concentration and stirred at 50 ℃ for 4 h. And then washing the obtained solid product with deionized water for 3-5 times, freeze-drying, and finally annealing for 1h at 300 ℃ in an argon atmosphere.
FIG. 7 is a graph showing the morphology of example 3 and comparative example 3, wherein (a) is Fe2O3(b) is Fe2O3Scanning electron microscope picture of @ MXene, comparative finding that MXene induces growth of Fe2O3The nano particles are uniformly distributed on the surface of the MXene lamella, the size is uniform, the particle diameter is about 50nm, the size of the MXene lamella is 1-2 mu m, and Fe prepared by adding no MXene is added2O3The nanoparticles have serious aggregation phenomenon, the particle size is about 100nm, and the fact that MXene with the small lamella content and the content of-OH functional groups of 60 percent can induce the growth of Fe with smaller particle size2O3And (3) nanoparticles.
The examples and the control were carried out according to the active substance: carbon black: polyvinylidene fluoride (PVDF) is mixed according to the proportion of 80:10:10 to prepare an electrode plate serving as a working electrode, a lithium plate serving as a counter electrode, a porous polypropylene film (Celgard 2300) for a diaphragm, and 1M LiPF for electrolyte6A mixed solution of Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (w/w ═ 1:1) was assembled into a button cell, and rate performance and cycle performance tests were performed. The capacity retention rate of the example at a large current density (4A/g) was 27.4%, which is much higher than that of the comparative example (1.7%). Furthermore, the example can still maintain a higher capacity (239.4mAh/g) after 1000 cycles, which is much higher than the control (81.5 mAh/g).
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of MXene induced growth nano iron oxide composite material comprises the following steps:
A) mixing Ti3AlC2Adding the mixture into HF solution for etching to obtain an etching product;
B) mixing the etching product with a tetramethyl ammonium hydroxide solution, intercalating, then adding LiOH, and reacting to obtain an intermediate product;
the mass ratio of the LiOH to the etching product is (0.04-0.09): 1;
C) dispersing the intermediate product in water, performing ultrasonic treatment for 1-1.5 hours, and centrifuging to obtain a supernatant which is an MXene solution;
the content of-OH functional groups in the MXene solution is 30-60%;
D) sequentially adding an iron salt solution and an alkali liquor into the MXene solution, carrying out in-situ growth, and annealing the obtained product to obtain a nano ferric oxide composite material;
the ferric salt solution comprises ferric salt and a dispersing agent.
2. The preparation method according to claim 1, wherein the etching temperature is 50-70 ℃;
the etching time is 12-36 hours.
3. The method according to claim 1, wherein the tetramethylammonium hydroxide solution has a mass concentration of 15 to 40%.
4. The method according to claim 1, wherein the iron salt is FeCl3、Fe2(SO4)3And Fe (NO)3)3One or more of the above;
fe in the iron salt solution3+The concentration of (b) is 0.005-0.02 mol/L.
5. The preparation method according to claim 1, wherein the dispersant is one or more of polyvinylpyrrolidone, cetyltrimethylammonium bromide and polydiallyldimethylammonium chloride;
the mass concentration of the dispersing agent in the ferric salt solution is 0.1-0.5 g/L.
6. The preparation method of claim 1, wherein the molar ratio of MXene in the MXene solution to iron ions in the iron salt solution to alkali in the alkali liquor is (0.5-2):1: 3.
7. The preparation method according to claim 1, wherein the temperature of the in-situ growth is 40-60 ℃;
the in-situ growth time is 3-5 hours.
8. An MXene induced growth nano iron oxide composite material prepared by the preparation method of any one of claims 1 to 7.
9. The use of the MXene-induced growth nano-iron oxide composite material of claim 8 as a negative electrode material in a lithium ion battery.
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