CN112018346A - Phosphorus-doped CoSe2Mxene composite material and preparation method thereof - Google Patents
Phosphorus-doped CoSe2Mxene composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses phosphorus-doped CoSe2The method for preparing/MXene composite material comprises the step of synthesizing CoSe by using MXene material as a framework2Loaded on MXene and doped with CoSe through phosphorus2the/MXene composite material is prepared into the high-performance potassium ion battery negative electrode material. CoSe2The metal property of (2) and MXene with good conductivity accelerate ion transfer and improve the rate performance. MXene has the functions of inhibiting agglomeration, increasing active sites and specific surface area and stabilizing skeleton of the whole structure, and the special self-repairing layered space can adapt to the situation that potassium ions are repeatedly intercalatedThe volume expands, thereby improving the cycle stability. Doping with small amounts of heteroatom phosphorus to make CoSe2the/MXene composite material has increased electronegativity and increased adsorption capacity, thereby improving the charge and discharge capacity. The result shows that the unique material structure is used as the negative electrode of the potassium ion battery, the structural stability is improved, the excellent potassium storage performance, the high specific capacity and the good cycling stability are shown, and the preparation is simple and rapid.
Description
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to phosphorus-doped CoSe2a/MXene composite material and a preparation method thereof.
Background
With the rapid growth of large-scale commercial application, the wide application of lithium ion batteries in electronic devices and electric vehicles makes lithium resources scarce, and the cost thereof continuously rises, thus becoming a concern of people. In addition, lithium dendrites are not highly safe and are another significant problem facing lithium ion batteries. Therefore, new energy storage devices with low cost and high safety are needed to be searched as substitutes for lithium ion batteries. Compared with the natural abundance of lithium in the crust, the potassium resource is rich and the cost is low. Potassium ion batteries are a promising alternative to lithium ion batteries, and research into them is being carried out. However, the large size of potassium ions and the slow reaction kinetics lead to poor cell performance.
CoSe2Is a transition metal phosphorus compound, is an important alkali ion intercalation material, has the characteristics of large capacity, high conversion rate, high safety and the like, and has good application prospect. But the defects are also obvious, such as poor conductivity, easy agglomeration, poor rate performance caused by large volume expansion in the charging and discharging process and rapid capacity attenuation.
MXene has a unique accordion-shaped multilayer structure and good conductivity, and is considered to be an electrode material with development potential. The MXene accordion-shaped multilayer structure is beneficial to increasing the contact area during ion diffusion; good conductivity can accelerate ion diffusion kinetics; surface functional groups may enhance adsorption capacity. However, the interlayer spacing is small and the surface functional group has a certain adsorbability, so that the single use cannot achieve the ideal effectAnd (4) fast ion migration effect. To solve the above problems, CoSe is added2The active site and the interlayer spacing are increased by phosphorus doping, and the potassium storage performance of the conductive material is hopeful to be improved. MXene has a unique layered structure and good conductivity, and is a good load frame material.
Disclosure of Invention
In view of the problems of the prior art, it is an object of the present invention to provide a phosphorus-doped CoSe2the/MXene composite material. Another object of the present invention is to provide the above phosphorus-doped CoSe2A preparation method of/MXene composite material. Further, the invention provides phosphorus-doped CoSe2Application of/MXene composite material, and phosphorus-doped CoSe2the/MXene composite material is used for the negative electrode of the potassium ion battery.
The invention adopts the following technical scheme:
the invention designs and constructs phosphorus-doped CoSe for high-performance potassium storage2the/MXene negative electrode material utilizes the MXene material as a frame to synthesize CoSe2Loaded on MXene and doped with CoSe by a small amount of phosphorus2the/MXene composite material. The specific scheme is as follows:
phosphorus-doped CoSe2The preparation method belongs to a solvothermal method and specifically comprises the following steps:
(1) weighing appropriate amount of CoSe2Nanoparticles of CoSe2Adding the nano particles into a proper amount of solvent, and fully stirring to obtain a suspension liquid which is uniformly distributed;
(2) mixing MXene nanosheets, the suspension, a phosphorus source and water to prepare a mixed solution with the concentration of 1-100mg/ml, and then stirring for 6-12 h;
(3) pouring the stirred mixed solution into a lining of a reaction kettle, sealing the reaction kettle, putting the reaction kettle into an oven, heating to the temperature of 120-220 ℃, continuously reacting for 12-18h, naturally cooling, centrifuging, washing, and drying in a vacuum drying oven at the temperature of 50-80 ℃ to obtain a crude product;
(4) grinding the crude product obtained in the step (3) by using a mortar to obtain uniformly distributed solidPutting the bulk powder into a corundum ark, gradually heating to 200-350 ℃ in a tubular furnace filled with protective atmosphere, calcining for 2-4h, collecting the calcined product after the furnace temperature is lower than 40 ℃ to obtain phosphorus-doped CoSe2the/MXene composite material.
Further, the solvent is at least one of N, N-dimethylformamide, ethanol and acetone, and preferably N, N-dimethylformamide; the detergent is at least one of deionized water and ethanol, and preferably, the deionized water is used for cleaning for 3-9 times, and then the absolute ethanol is used for cleaning for 3-9 times.
Further, MXene is Ti3C2Tx、V3C2Tx、V2CTx、Nb4C3Tx、Ti3CNTxOne or more of (a). Such as Ti2CTx，V2CTxPreferably, the mass ratio is 1:1 to 5 of Ti3C2TxAnd V3C2Tx。
Further, the phosphorus source is one or more of triphenylphosphine, sodium dihydrogen phosphate and potassium dihydrogen phosphate.
Further, CoSe2The particle size of the nano particles is 15nm-120nm, and the size of the MXene nano sheets is 100nm-1500 nm.
Further, the phosphorus doping amount in the phosphorus-doped CoSe2/MXene composite material is 0.1-20 wt%, such as 0.1-4 wt%, 6-10 wt%, and 7-13 wt%.
Further, in the step (3), the reaction kettle is heated in an oven to 120-.
Further, MXene nanosheets and CoSe2The mole ratio of the nanoparticles to the phosphorus source is 1: 1: 0.01-0.8.
Further, the rotation speed of the centrifugation in the step (3) is 5500-; the vacuum drying temperature is 50-80 deg.C, preferably 60 deg.C, and drying time is 12-16h, such as 12h, 14h, and 16 h.
Further, the protective gas in step (4) is one or more of argon, helium and nitrogen, preferably argon.
Phosphorus-doped CoSe2Phosphorus-doped CoSe2/MXene composite material prepared by the preparation method of/MXene.
A potassium ion battery anode comprising the phosphorus doped CoSe2a/Mxene composite material.
The invention has the beneficial effects that:
(1) MXene can be used as a framework, so that a layered structure is supported, and the transfer and ion adsorption areas are larger; CoSe2The nanoparticles of (a) may be mainly concentrated at the edges of the lamellae, CoSe2The nano material grows and nucleates on the MXene lamella, can effectively improve the interlayer spacing, increase the specific surface area, increase the area between the electrode material and the electrolyte, reduce the electron transmission and ion diffusion resistance, and has the layered structure of MXene and the nano material CoSe2Interaction prevents agglomeration; meanwhile, phosphorus doping provides new electrochemical active sites and vacancies, which is beneficial to increasing the transmission channel of ions and leading CoSe2The components of the/MXene composite material are tightly combined, the synergistic effect of the components is enhanced, the conductivity and the interlayer spacing of the composite material are increased, and the volume expansion is inhibited to a certain extent, so that the electrochemical performance of the composite material is improved. See MXene, CoSe2Has synergistic effect with phosphorus atom.
(2) Phosphorus doped CoSe2the/MXene composite material greatly expands the distance between the sheets while keeping an accordion-shaped layered structure, effectively prevents the stacking of the material sheets, and has the advantages of obvious reversible capacity and cycle performance.
(3) The material of the invention has simple preparation, low cost, safety and controllability, controllable doping amount and convenient realization of phosphorus doped CoSe2The application of the/MXene composite material as the negative electrode material of the potassium ion battery.
Drawings
Fig. 1 is a scanning electron micrograph of the MXene material alone in comparative example 1;
FIG. 2 is a phosphorus-doped C in example 1oSe2Scanning electron microscope images of the/MXene composite material;
FIG. 3 phosphorus-doped CoSe in example 12And the cycle performance of the/MXene composite material assembled potassium ion battery is measured at the current density of 100 mA/g.
FIG. 4 is a graph of the cycle performance of the MXene anode material alone assembled potassium ion battery of comparative example 1 at a current density of 100 mA/g;
FIG. 5 CoSe alone in comparative example 22And (3) a cycle performance graph of the assembled potassium ion battery with the negative electrode material under the current density of 100 mA/g.
FIG. 6 is CoSe of comparative example 32The cycle performance of the/MXene material assembled potassium ion battery is measured under the current density of 100 mA/g.
FIG. 7 is a comparative schematic diagram of the impedance of potassium ion battery assembled by MXene material alone, CoSe2/MXene material and phosphorus doped CoSe2/MXene composite material.
Detailed Description
For better explanation of the present invention, the following specific examples are further illustrated, but the present invention is not limited to the specific examples. Wherein the materials are commercially available unless otherwise specified.
Wherein the materials are commercially available unless otherwise specified;
the CoSe2Nanoparticles were purchased from maona new energy limited, thaizhou, brand 2D Semiconductors, model: 7579.65, purity: 99.999%, species: electron, optical material, optical band gap of 0.5 eV;
the Ti3C2TxNanoparticles were purchased from beijing beike science and technology ltd, code BK2020011814, size: 1-5 μm, purity: 99%, product application field: energy storage, catalysis, analytical chemistry, and the like.
The method is a conventional method unless otherwise specified.
Example 1
Phosphorus-doped CoSe2The preparation method of the/MXene composite material comprises the following steps:
(1) 21.6mg of CoSe were weighed out2Adding nanoparticles into 10ml N, N-Dimethylformamide (DMF), stirring to obtain uniformly distributed suspension, and adding 16.7mg MXene (Ti)3C2Tx) Mixing the nanosheets, the suspension, 0.6mg of sodium dihydrogen phosphate and 15ml of deionized water, and then magnetically stirring for 7 hours;
(2) pouring the stirred mixed solution into a reaction kettle lining with the capacity of 60ml, sealing the reaction kettle, putting the reaction kettle into an oven, heating to 180 ℃, continuously reacting for 14 hours, naturally cooling, centrifuging for 5 minutes under the condition of 7500r/min, cleaning the filter residue with deionized water for 5 times, cleaning the filter residue with absolute ethyl alcohol for 5 times, setting the drying temperature in a vacuum drying oven to be 60 ℃, and drying for 12 hours to obtain a crude product;
(3) grinding the crude product obtained in the step (2) by using a mortar to obtain uniformly distributed solid powder, putting the solid powder into a corundum ark, gradually heating to 300 ℃ in a tubular furnace filled with argon atmosphere, calcining for 4 hours, collecting the calcined product after the furnace temperature is lower than 40 ℃ to obtain phosphorus-doped CoSe2the/MXene composite material.
Doping CoSe with phosphorus2The preparation method comprises the following steps of taking/MXene composite material as an active ingredient, uniformly mixing the active ingredient with conductive agent super P carbon and polyvinylidene fluoride binder in a mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, uniformly stirring, coating the mixture on a copper foil, drying and cutting the mixture into pieces to be used as working electrodes, taking 1M KFSI EC (ethylene carbonate) and PC (propylene carbonate) (1:1) as electrolyte, cutting metal potassium pieces into proper sizes to be used as counter electrodes, cutting glass fibers into sizes smaller than a battery shell and larger than a battery pole piece to be used as diaphragms, and assembling into 2032 type button half batteries; all assembly was performed in an inert atmosphere glove box.
Phosphorus doped CoSe of this example2Under the current density of 100mA/g, the specific capacity of the potassium ion battery assembled by the MXene composite negative electrode material is stabilized at 327.8mA h/g after the electrode is charged and discharged for 100 times, the specific capacity is 1.17 times of that of a CoSe2/MXene (278.1mA h/g) material, 2.97 times of that of a pure CoSe2(110.2mA h/g) material and 5.3 times of that of a pure MXene (61.1mA h/g) material, the coulombic efficiency reaches 97.8%, and the phosphorus-doped CoSe obtained in the embodiment is doped with phosphorus2the/MXene composite material has good potassium storage performance and charge-discharge cycle stability.
Example 2
A preparation method of a phosphorus-doped CoSe2/MXene composite material comprises the following steps:
(1) 21.6mg of CoSe were weighed out2Adding nanoparticles into 10ml N, N-Dimethylformamide (DMF), stirring to obtain uniformly distributed suspension, and adding 16.7mg MXene (Ti)3C2Tx) Mixing the nanosheets, the suspension, 0.4mg of sodium dihydrogen phosphate and 20ml of deionized water, and then magnetically stirring for 7 hours;
(2) pouring the stirred mixed solution into a reaction kettle lining with the capacity of 60ml, sealing the reaction kettle, putting the reaction kettle into an oven, heating to 180 ℃, continuously reacting for 12 hours, naturally cooling, centrifuging for 5 minutes under the condition of 7500r/min, cleaning the filter residue with deionized water for 5 times, cleaning the filter residue with absolute ethyl alcohol for 5 times, setting the drying temperature in a vacuum drying oven to be 60 ℃, and drying for 14 hours to obtain a crude product;
(3) and (3) grinding the crude product obtained in the step (2) by using a mortar to obtain uniformly distributed solid powder, putting the solid powder into a corundum ark, gradually heating to 300 ℃ in a tubular furnace filled with argon atmosphere, calcining for 4 hours, and collecting a calcined product after the furnace temperature is lower than 40 ℃ to obtain the phosphorus-doped CoSe2/MXene composite material.
Doping CoSe with phosphorus2The preparation method comprises the following steps of taking/MXene composite material as an active ingredient, uniformly mixing the active ingredient with conductive agent super P carbon and polyvinylidene fluoride binder in a mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, uniformly stirring, coating the mixture on a copper foil, drying and cutting the mixture into pieces to be used as working electrodes, taking 1M KFSI EC (ethylene carbonate) and PC (propylene carbonate) (1:1) as electrolyte, cutting metal potassium pieces into proper sizes to be used as counter electrodes, cutting glass fibers into sizes smaller than a battery shell and larger than a battery pole piece to be used as diaphragms, and assembling into 2032 type button half batteries; all assembly was performed in an inert atmosphere glove box.
Phosphorus doped CoSe of this example2Under the current density of 100mA/g, the electrode is charged and discharged for 100 timesThe specific capacity is stabilized at 333.5mAh/g, the coulombic efficiency reaches 99.7 percent, and the phosphorus-doped CoSe obtained by the embodiment2the/MXene composite material has good potassium storage performance and charge-discharge cycle stability.
Example 3
Phosphorus-doped CoSe2The preparation method of the/MXene composite material comprises the following steps:
(1) 43.2mg of CoSe were weighed out2Adding nanoparticles into 12ml N, N-Dimethylformamide (DMF), stirring to obtain uniformly distributed suspension, and adding 32mg MXene (Ti)3C2Tx) Mixing the nanosheets, the suspension, 1mg of sodium dihydrogen phosphate and 25ml of deionized water, and then magnetically stirring for 9 hours;
(2) pouring the stirred mixed solution into a reaction kettle lining with the capacity of 60ml, sealing the reaction kettle, putting the reaction kettle into an oven, heating to 180 ℃, continuously reacting for 14 hours, naturally cooling, centrifuging for 5 minutes under the condition of 7500r/min, cleaning the filter residue with deionized water for 5 times, cleaning the filter residue with absolute ethyl alcohol for 5 times, setting the drying temperature in a vacuum drying oven to be 60 ℃, and drying for 12 hours to obtain a crude product;
(3) grinding the crude product obtained in the step (2) by using a mortar to obtain solid powder so as to enable the solid powder to be uniformly distributed, putting the powder into a corundum ark, gradually heating the powder to 300 ℃ in a tubular furnace filled with argon atmosphere, calcining the powder for 4 hours, collecting the calcined product after the furnace temperature is lower than 40 ℃ to obtain phosphorus-doped CoSe2the/MXene composite material.
Doping CoSe with phosphorus2The preparation method comprises the following steps of taking/MXene composite material as an active ingredient, uniformly mixing the active ingredient with conductive agent super P carbon and polyvinylidene fluoride binder in a mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, uniformly stirring, coating the mixture on a copper foil, drying and cutting the mixture into pieces to be used as working electrodes, taking 1M KFSI EC (ethylene carbonate) and PC (propylene carbonate) (1:1) as electrolyte, cutting metal potassium pieces into proper sizes to be used as counter electrodes, cutting glass fibers into sizes smaller than a battery shell and larger than a battery pole piece to be used as diaphragms, and assembling into 2032 type button half batteries; all assembly was performed in an inert atmosphere glove box.
Phosphorus of this exampleDoped CoSe2Under the current density of 100mA/g, the specific capacity of the potassium ion battery assembled by the/MXene composite negative electrode material is stabilized at 319.3mAh/g after the electrode is charged and discharged for 100 times, the coulombic efficiency reaches 99.7%, and the phosphorus-doped CoSe2/MXene composite material obtained in the embodiment has good potassium storage performance and charge-discharge cycle stability.
Example 4
Phosphorus-doped CoSe2The preparation method of the/MXene composite material comprises the following steps:
(1) 43.2mg of CoSe were weighed out2Adding nanoparticles into 10ml N, N-Dimethylformamide (DMF), stirring to obtain uniformly distributed suspension, and adding 32mg MXene (Ti)3C2Tx) Mixing the nanosheets, the suspension, 1.8mg of sodium dihydrogen phosphate and 20ml of deionized water, and then magnetically stirring for 7 hours;
(2) pouring the stirred mixed solution into a reaction kettle lining with the capacity of 60ml, sealing the reaction kettle, putting the reaction kettle into an oven, heating to 180 ℃, continuously reacting for 12 hours, naturally cooling, centrifuging for 5 minutes under the condition of 7500r/min, cleaning the filter residue with deionized water for 5 times, cleaning the filter residue with absolute ethyl alcohol for 5 times, setting the drying temperature in a vacuum drying oven to be 60 ℃, and drying for 12 hours to obtain a crude product;
(3) grinding the crude product obtained in the step (2) by using a mortar to obtain solid powder so as to enable the solid powder to be uniformly distributed, putting the powder into a corundum ark, gradually heating the powder to 300 ℃ in a tubular furnace filled with argon atmosphere, calcining the powder for 3 hours, collecting the calcined product after the furnace temperature is lower than 40 ℃ to obtain phosphorus-doped CoSe2the/MXene composite material.
Doping CoSe with phosphorus2The preparation method comprises the following steps of taking/MXene composite material as an active ingredient, uniformly mixing the active ingredient with conductive agent super P carbon and polyvinylidene fluoride binder in a mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, uniformly stirring, coating the mixture on a copper foil, drying and cutting the copper foil to obtain a working electrode, taking 1M KFSI EC (ethylene carbonate) and PC (propylene carbonate) (1:1) as electrolyte, cutting a metal potassium sheet to a proper size to obtain a counter electrode, cutting glass fibers to a size smaller than a battery shell and larger than a battery pole piece to obtain a diaphragm, and assembling the diaphragm into a 2032 type button semi-halfA battery; all assembly was performed in an inert atmosphere glove box.
Phosphorus doped CoSe of this example2Under the current density of 100mA/g, the specific capacity of the potassium ion battery assembled by the/MXene composite negative electrode material is stabilized at 335.2mAh/g after the electrode is charged and discharged for 100 times, the coulombic efficiency reaches 98.6%, and the phosphorus-doped CoSe2/MXene composite material obtained in the embodiment has good potassium storage performance and charge-discharge cycle stability.
Comparative example 1
Weighing 80mg of MXene material, 10mg of super P and 10mg of polyvinylidene fluoride binder, mixing, adding a small amount of N-methylpyrrolidone, stirring, coating on a copper foil, drying at 90 ℃ for 3 hours, cutting the copper foil into a round shape by using a slicing machine to serve as a working electrode, drying, putting the round shape into an inert atmosphere glove box with oxygen and water contents lower than 0.4ppm, and assembling into a 2032 type button battery by using a metal potassium sheet as a counter electrode and glass fiber as a diaphragm.
FIG. 4 is a graph of the cycle performance of MXene material assembled potassium ion batteries measured at a current density of 100 mA/g.
As can be seen from the figure, the MXene material assembled potassium ion battery has good cycling stability in the charging and discharging processes under the current density of 100mA/g, but the specific capacity is smaller and is 61.1mA h/g.
Comparative example 2
80mg of CoSe were weighed2Mixing the materials, 10mg of super P and 10mg of polyvinylidene fluoride binder, adding a small amount of N-methyl pyrrolidone, stirring, coating on a copper foil, drying at 90 ℃ for 3 hours, cutting the copper foil into a round shape by a slicer to be used as a working electrode, drying, putting into an inert atmosphere glove box with oxygen and water contents lower than 0.4ppm, and assembling into a 2032 type button battery by using a metal potassium sheet as a counter electrode and using glass fiber as a diaphragm.
FIG. 5 is CoSe2Material assembly potassium ion battery cycling performance plots measured at a current density of 100 mA/g.
As can be seen, CoSe2The specific capacity of the material assembled potassium ion battery is relatively unstable in the charging and discharging process under the current density of 100mA/g, and is 110.2mA h/g.
Comparative example 3
(1) 21.6mg of CoSe were weighed out2Adding nanoparticles into 10ml N, N-Dimethylformamide (DMF), stirring to obtain uniformly distributed suspension, and adding 16.7mg MXene (Ti)3C2Tx) Mixing the nanosheets, the suspension and 15ml of deionized water, and then magnetically stirring for 7 hours;
(2) pouring the stirred mixed solution into a reaction kettle lining with the capacity of 60ml, sealing the reaction kettle, putting the reaction kettle into an oven, heating to 180 ℃, continuously reacting for 14h, and naturally cooling to obtain a precipitate;
(3) washing the precipitate obtained in the step (2) with deionized water for 5 times, then washing with absolute ethyl alcohol for 5 times, transferring the product to a centrifuge, centrifuging for 5min under the condition of 7500r/min, setting the drying temperature in a vacuum drying oven at 60 ℃, and drying for 12h to obtain a crude product;
(4) grinding the crude product obtained in the step (3) by using a mortar to obtain uniformly distributed solid powder, putting the solid powder into a corundum ark, gradually heating to 300 ℃ in a tubular furnace filled with argon atmosphere, calcining for 4 hours, collecting the calcined product after the furnace temperature is lower than 40 ℃ to obtain CoSe2the/MXene composite material.
By CoSe2The preparation method comprises the following steps of taking/MXene composite material as an active ingredient, uniformly mixing the active ingredient with conductive agent super P carbon and polyvinylidene fluoride binder in a mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, uniformly stirring, coating the mixture on a copper foil, drying and cutting the mixture into pieces to be used as working electrodes, taking 1M KFSI EC (ethylene carbonate) and PC (propylene carbonate) (1:1) as electrolyte, cutting metal potassium pieces into proper sizes to be used as counter electrodes, cutting glass fibers into sizes smaller than a battery shell and larger than a battery pole piece to be used as diaphragms, and assembling into 2032 type button half batteries; all assembly was performed in an inert atmosphere glove box.
FIG. 6 is CoSe2The cycle performance of the/MXene material assembled potassium ion battery is measured under the current density of 100 mA/g.
As can be seen, CoSe2The potassium ion battery assembled by the/MXene material has good cycling stability in the charging and discharging processes under the current density of 100mA/g, and the specific capacity is 278.1mA h/g.
FIG. 1 is a scanning electron micrograph of MXene material alone in comparative example 1, and FIG. 2 is phosphorus-doped CoSe in example 12Scanning electron microscope images of the/MXene composite material. As can be seen from fig. 1-2, the MXene material before doping has an accordion-like layered structure, and the layers are completely separated from each other, the structure is complete, and the phenomenon of layered fracture does not occur. The doped MXene material presents a great deal of fine phosphorus doped CoSe2Nanoparticles are uniformly attached to the surface of MXene material, and phosphorus is doped with CoSe2The introduction of the nano particles enlarges the distance between the sheet layers, and the agglomeration phenomenon does not occur, thereby showing that the phosphorus is doped with CoSe2the/MXene composite material greatly expands the distance between the sheets while keeping an accordion-shaped layered structure, and effectively hinders the stacking of the material sheets.
FIG. 3 phosphorus-doped CoSe in example 12The reversible capacity of the potassium ion battery assembled by the/MXene composite material after 100 circles of circulation is 272.8mA h/g; FIG. 4 is a graph of cycle performance of the MXene negative electrode material alone assembled potassium ion battery in comparative example 1 at a current density of 100mA/g, and the reversible capacity after 100 cycles is 61.1mA h/g; FIG. 5 CoSe alone in comparative example 22According to a cycle performance diagram of the potassium ion battery assembled by the negative electrode material under the current density of 100mA/g, the nanosheets are easy to agglomerate, the structure is unstable, the charge and discharge performance is poor, and the specific capacity is degraded after 30 cycles of circulation; FIG. 6 is CoSe of comparative example 32Cycle performance plot of potassium ion battery assembled with MXene materials at a current density of 100mA/g, CoSe2The potassium ion battery assembled by the MXene material has good potassium storage performance in the charging and discharging process under the current density of 100mA/g, has higher specific capacity and stable charging and discharging performance, is still not ideal in battery performance, and needs to be further improved in electrochemical performance.
3-6, the reversible capacity of the MXene material alone after 100 cycles is very low, only 61.1mA h/g; CoSe alone2The material has the capacity of storing potassium, but is easy to agglomerate and has an unstable structure in the charge and discharge processes; CoSe not doped with phosphorus atom2the/MXene material has higher reversible capacity and better cycle performanceHowever, the phosphorus-doped CoSe2/MXene composite material still has obvious advantages of reversible capacity and cycle performance.
This is because MXene can act as a framework, providing a layered structure support, larger transfer and ion adsorption areas; the nano-particles of CoSe2 can be mainly concentrated at the edges of the sheets, the nano-material of CoSe2 forms nucleation on the growth of MXene sheets, the interlayer spacing can be effectively improved, the specific surface area is increased, the area between the electrode material and the electrolyte is increased, the electron transmission and ion diffusion resistance are reduced, and the agglomeration is prevented by the interaction of the MXene in the layered structure and the CoSe2 in the nano-material; meanwhile, phosphorus doping provides new electrochemical active sites and vacancies, which is favorable for increasing the transmission channel of ions, so that the components of the CoSe2/MXene composite material are tightly combined, the synergistic effect of the components is enhanced, the conductivity and the interlayer spacing of the composite material are simultaneously favorable for increasing, and the volume expansion is inhibited to a certain extent, thereby improving the electrochemical performance of the composite material. MXene, CoSe2 and phosphorus atoms are seen to have synergistic effect.
FIG. 7 is MXene materials alone, CoSe alone2Material, CoSe2/MXene material, phosphorus doped CoSe2Comparative schematic diagram of testing impedance of potassium ion battery assembled by/MXene composite material. The semi-circle diameter of the curve in the intermediate frequency region represents the size of the charge transfer resistance Rct, and as can be seen from fig. 7, the Rct values of phosphorus-doped CoSe2/MXene, CoSe2/MXene material, individual CoSe2 material and individual MXene material become larger in turn, which indicates that the charge transfer resistances thereof become larger in turn. CoSe2The charge transfer resistance Rct of the/MXene composite material is smaller than that of the MXene material due to CoSe2The nano material grows and nucleates on the MXene lamella, the interlayer spacing is improved, the specific surface area is increased, the area between the electrode material and the electrolyte is increased, the transmission channel of ions and electrons is increased, the ion transfer is accelerated together with the MXene with good conductivity, and the electron transmission resistance is reduced. Phosphorus doped CoSe2the/MXene composite material is relative to CoSe not doped with phosphorus2The charge transfer resistance Rct of the/MXene material is further reduced because a small amount of heteroatom phosphorus is doped to ensure that CoSe is added2the/MXene composite material has increased electronegativity and increased adsorption capacity, thereby improving ion transfer capacity. Phosphorus doping to further improve the layer spacing increase ratioThe area, the increase of the transmission channel of the electrons, and the synergistic effect lead to the reduction of the transmission resistance of the electrons and the ions.
The above description is only a preferred specific operation example of the present invention, and is not intended to limit the scope of the application of the present invention, and other related fields are within the protection and coverage of the present invention.
Claims (10)
1. Phosphorus-doped CoSe2The preparation method of the/Mxene composite material is characterized by comprising the following preparation steps:
(1) mixing CoSe2Dispersing the nano particles in a solvent to obtain a suspension;
(2) mixing MXene nanosheets, the suspension, a phosphorus source and water to prepare a mixed solution with the concentration of 1-100mg/ml, and stirring for 6-12 h;
(3) heating the stirred mixed solution to the temperature of 120-220 ℃, reacting for 12-18h, cooling, centrifuging, washing and drying to obtain a crude product;
(4) fully grinding the crude product obtained in the step (3), calcining for 2-4h at the temperature of 200-350 ℃ in protective atmosphere, cooling and collecting to obtain phosphorus-doped CoSe2the/MXene composite material.
2. The phosphorus doped CoSe of claim 12The preparation method of the/Mxene composite material is characterized in that the solvent is at least one of N, N-dimethylformamide, cyclohexane and xylene; the detergent is at least one of water and ethanol.
3. The phosphorus doped CoSe of claim 12The preparation method of the/Mxene composite material is characterized in that MXene is Ti3C2Tx、V3C2Tx、V2CTx、Nb4C3Tx、Ti3CNTxOne or more of (a).
4. The phosphorus doped CoSe of claim 12A method for preparing a/Mxene composite material,the method is characterized in that the phosphorus source is one or more of triphenylphosphine, sodium dihydrogen phosphate and potassium dihydrogen phosphate.
5. The phosphorus doped CoSe of claim 12The preparation method of the/Mxene composite material is characterized in that the phosphorus doping amount in the phosphorus-doped CoSe2/MXene composite material is 0.1-20 wt%.
6. The phosphorus doped CoSe of claim 12The preparation method of the/Mxene composite material is characterized in that the MXene nanosheet and CoSe are prepared2The mole ratio of the nanoparticles to the phosphorus source is 1: 1: 0.01-0.8.
7. The phosphorus doped CoSe of claim 12The preparation method of the/Mxene composite material is characterized in that the rotation speed of the centrifugation in the step (3) is 5500-9000r/min, and the centrifugation time is 3-8 min.
8. The phosphorus doped CoSe of claim 12The preparation method of the/Mxene composite material is characterized in that the protective gas in the step (4) is one or more of argon, helium and nitrogen.
9. A potassium ion battery negative electrode, characterized in that it comprises phosphorus-doped CoSe prepared by the preparation method of any one of claims 1 to 82a/Mxene composite material.
10. A potassium ion battery comprising the battery negative electrode of claim 9.
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| CN113584519A (en) * | 2021-07-09 | 2021-11-02 | 哈尔滨工业大学（深圳） | Electrocatalyst and preparation method and application thereof |
| CN114220972A (en) * | 2021-11-19 | 2022-03-22 | 广东工业大学 | CoSe2/MXene composite material and preparation method and application thereof |
| CN114220961A (en) * | 2022-02-21 | 2022-03-22 | 浙江大学 | Composite nano material for sodium ion battery and preparation method thereof |
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| CN114512653B (en) * | 2022-02-22 | 2023-01-06 | 广东工业大学 | Preparation method of nitrogen-doped MXene-loaded molybdenum disulfide composite material, product and application of product |
| CN114975991A (en) * | 2022-05-13 | 2022-08-30 | 郑州大学 | Titanium-based positive electrode material of chemical pre-embedded sodium/potassium ion battery and preparation method and application thereof |
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