CN113104824A - Se doped Fe2Preparation method of P self-supporting sodium ion battery cathode material - Google Patents

Se doped Fe2Preparation method of P self-supporting sodium ion battery cathode material Download PDF

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CN113104824A
CN113104824A CN202110224556.9A CN202110224556A CN113104824A CN 113104824 A CN113104824 A CN 113104824A CN 202110224556 A CN202110224556 A CN 202110224556A CN 113104824 A CN113104824 A CN 113104824A
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sodium ion
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CN113104824B (en
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高林
刘洋
杨学林
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China Three Gorges University CTGU
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Abstract

The invention provides Se-doped Fe2The preparation method of the P self-supporting sodium ion battery cathode material comprises the specific operation of sequentially ultrasonically cleaning the foamed nickel by deionized water and absolute ethyl alcohol. Using foamed nickel as current collector and nitric acidUsing iron as Fe source, preparing FeOOH precursor by one-step hydrothermal method, then using sodium hypophosphite as P source and selenium powder as Se source, converting the prepared precursor into Se-doped Fe by chemical vapor deposition method2And P. The material prepared by the method is used as a negative electrode material of a sodium ion battery, and has the characteristics of excellent cycling stability and high specific capacity. Se-doped Fe2The P array material still has the specific capacity of 541.2 mA h g < -1 > after 1000 cycles under the current density of 100 mA g < -1 > in the voltage range of 0.01-3V. And the reversible specific capacity of the material still has 451.9 mA h g < -1 > after 100 cycles at 500 mA g < -1 >. The Se-doped Fe2P material is used as a cathode material of a sodium ion battery, and has excellent cycling stability, rate capability and wide application prospect.

Description

Se doped Fe2Preparation method of P self-supporting sodium ion battery cathode material
Technical Field
The invention belongs to the field of sodium ion battery cathode materials, and particularly relates to selenium-doped Fe2A preparation method and application of a P self-supporting sodium ion battery cathode material are provided.
Technical Field
Lithium ion batteries are widely used in daily life due to their advantages of high energy density, excellent cycle performance, low pollution, etc. Currently, lithium ion batteries still face the problems of small lithium resource reserves, large development difficulty, high battery cost and the like. Sodium ion batteries have electrochemical properties similar to those of lithium ion batteries, and sodium salt resources are abundant, so that the sodium ion batteries are attracted by researchers in recent years. The role of the electrode negative electrode material is particularly important in the overall battery, which determines the performance of the overall battery. The problems of volume effect and the like generally exist in the circulation process of the negative electrode material, so that the nano particles can be agglomerated, pulverized or fall off from a current collector, and further the electrochemical performance is attenuated. The iron-based electrode material has rich raw material resources, low price, safety and no pollution, and is expected to become an ideal electrode material. However, the electrochemical performance of the iron-based electrode material still needs to be further improved.
Disclosure of Invention
The invention aims to provide Se-doped Fe with simple preparation process, no binder, low energy consumption and low cost aiming at the existing synthesis process2P material and a preparation method thereof. Se-doped Fe prepared by the method2The P self-supporting material is used as a negative electrode material of the sodium ion battery and has the characteristics of excellent cycle stability and high capacity.
Se doped Fe2The P self-supporting sodium ion battery negative electrode material is in a sheet-ball shape and is uniformly distributed on the Ni net, and the shape of the P self-supporting sodium ion battery negative electrode material is in the sheet-ball shape, so that the volume expansion of the electrode material in the charging and discharging processes is favorably inhibited, the mechanical stress is buffered, the pulverization is reduced, and the cycle performance and the rate capability of the battery are improved.
Said Se-doped Fe2The preparation method of the P (wherein, x is more than 0 and less than 0.3) material comprises the following steps:
(1) the specific operation is to mix foamed nickel (thickness 0.2 mm, purity 99.9%, 3X 3 cm)2) Sequentially de-ionized
Ultrasonically cleaning with water and absolute ethyl alcohol.
(2) Weighing urea, ferric nitrate and ammonium fluoride, adding into deionized water, and stirring for 10-30 min; the molar ratio of the urea to the ferric nitrate to the ammonium fluoride is 1-2:10-20:2-8, and preferably the molar ratio of the urea to the ferric nitrate to the ammonium fluoride is 1:10: 8.
(3) Transferring the uniformly stirred solution into a hydrothermal reaction kettle, and putting the cleaned nickel foam into the uniformly stirred solution at the temperature of 100-oAnd C, carrying out hydrothermal treatment for 6-10h to prepare a hydroxide precursor. Placing the precursor in a temperature range of 50-80 deg.C oAnd C, drying in a constant-temperature drying oven for 5-24 h.
(4) Placing the mixture of the prepared hydroxide precursor, selenium powder and sodium hypophosphite in two material boats respectively, placing the material boat containing the mixture of the sodium hypophosphite and the selenium powder on one side close to the air inlet of the tube furnace, placing the material boat containing the hydroxide precursor on one side of the air outlet, wherein the distance between the two material boats is 3-5cm, and obtaining Se-doped Fe at high temperature2P self-supporting sodium ion battery cathode material
In the calcining step, nitrogen is filled in the tubular furnace, and the temperature in the furnace is controlled at 2-5 ℃ for min under the nitrogen atmosphere-1Temperature up to 250-450 DEGoAnd C, calcining for 1-2 h at the temperature, and naturally cooling to room temperature. Preferably, this step is carried out at N2In the atmosphere, dry hydroxide precursor is arranged at the central position of the tubular furnace, sodium hypophosphite is arranged at the position of an air inlet, 250-oCalcining C for 2-10h to prepare Fe2P, then placing selenium powder at the position of an air inlet to prepare Fe2P is arranged at the central position of the tubular furnace at 300-450 DEGoCalcining C for 1-5h to obtain Se-doped Fe with different concentrations2And P material.
Compared with the prior synthesis technology, the invention has the beneficial effects that:
the invention provides Se-doped Fe2Preparation method of P self-supporting sodium ion battery cathode materialThe method specifically comprises the step of ultrasonically cleaning the foamed nickel by using deionized water and absolute ethyl alcohol in sequence. Preparing FeOOH precursor by using foamed nickel as a current collector and ferric nitrate as a Fe source through a one-step hydrothermal method, and then converting the prepared precursor into Se-doped Fe through a chemical vapor deposition method by using sodium hypophosphite as a P source and selenium powder as a Se source2And P. The material prepared by the method is used as a negative electrode material of a sodium ion battery, and has the characteristics of excellent cycling stability and high specific capacity. Se-doped Fe2The P array material still has the specific capacity of 541.2 mA h g < -1 > after 1000 cycles under the current density of 100 mA g < -1 > in the voltage range of 0.01-3V. And the reversible specific capacity of the material still has 451.9 mA h g < -1 > after 100 cycles at 500 mA g < -1 >. Se-doped Fe2The P material is used as a sodium ion battery cathode material, and has excellent cycle stability, rate capability and wide application prospect.
The invention takes ferric nitrate as an iron source, sodium hypophosphite as a phosphorus source and selenium powder as a selenium source, and the selected raw materials have rich sources and low cost; the material obtained by the invention is Se-doped Fe2P material with spherical shape is doped with Se, which is favorable for improving the first coulombic efficiency and conductivity of the material, and the Se is doped with Fe2The P material takes the foamed nickel as a current collector, the structure of the foamed nickel and FeP sheet spherical nano particles can buffer volume expansion, the electrochemical stability is improved, meanwhile, the use of a binder is omitted, and the material performance is improved under the condition of reducing the cost.
Drawings
FIG. 1 shows Fe prepared in example 12XRD pattern of P.
FIG. 2 shows Fe prepared in example 12SEM images of P at different magnifications, a 3000 times and B10000 times.
FIG. 3 Se-doped Fe prepared in example 22SEM images of P material with different magnifications, wherein A is 3000 times, and B is 10000 times.
FIG. 4 Se-doped Fe prepared in example 22P material element mapping graph.
FIG. 5 Se-doped Fe prepared in examples 1 and 22P and Fe2Graph comparing the rate capability of P material.
FIG. 6 Se-doped Fe prepared in examples 1 and 22P and Fe2P material at a current density of 100 mA g-1Cyclic performance versus time plot.
FIG. 7 shows Fe prepared in example 12P material at a current density of 100 mA g-1The first three cycles of charge and discharge curves.
FIG. 8 Se-doped Fe prepared in example 22P material at a current density of 100 mA g-1The first three cycles of charge and discharge curves.
Detailed description of the preferred embodiments
Example 1
Weighing urea, ferric nitrate and ammonium fluoride according to a molar ratio of 1:10:8, adding the mixture into 30ml of deionized water, stirring for 30 min, uniformly mixing, transferring the mixture into a 50ml hydrothermal reaction kettle, adding cleaned nickel foam, and carrying out hydrothermal reaction for 10h at 120 ℃. And after the reaction is completed, taking out the foamed nickel, and drying in a 50 ℃ oven for 12h to obtain the ferric hydroxide precursor. The precursor is placed at the central position of a tube furnace, 0.5g of sodium hypophosphite is placed at the air inlet position, the distance between two material boats is 4cm, and the distance between the two material boats is N2Under the protection, the precursor is added with 2 oC min-1Heating the mixture from room temperature to 350 ℃, calcining the mixture for 2 hours, and cooling the mixture to room temperature to obtain Fe2P-array material.
It can be seen from FIG. 1 that the diffraction peak of the prepared material coincides with Fe2P standard card (JCPDS number 074-2And P material. As can be seen from FIG. 2, Fe2The P material is in the shape of a sheet sphere. Electrochemical performance tests were performed on the material prepared in example 1: the method comprises the steps of putting an active substance, acetylene black and polyvinylidene fluoride (PVDF) into a mortar according to the mass ratio of 8:1:1, mixing and grinding uniformly, then dropping N-methylpyrrolidone solvent (NMP) and grinding into a slurry state, uniformly coating the slurry on copper foil, drying and cutting into circular electrode plates (the diameter is 14 mm), and then putting the circular electrode plates into a vacuum drying oven at 120 ℃ for drying for 12 hours. Taking the dried electrode slice as a working electrode, taking metal sodium as a counter electrode and taking NaPF as electrolyte6V. (EC + DMC) (volume ratio 1:1), septum (Celgard 2400), after fillingA CR2025 button cell was assembled in an argon-filled glove box. As can be seen from FIG. 5, it is 100 mA g-1Has 400 mAh g at current density-1The specific capacity of (A). As can be seen from FIG. 6, at 500 mA g-1The specific capacity is kept at 350 mA h g after 1000 cycles-1. As can be seen from FIG. 7, Fe was produced2The P material has a significant charge-discharge plateau that phosphide materials possess.
Example 2
Fe prepared in example 12The P-array material is arranged at the central position of the tube furnace, and then 0.2 g of selenium powder is arranged at the position of an air inlet to prepare Fe2P is arranged at the central position of the tube furnace at N2Will be protected by 2 oC min-1Raising the temperature from room temperature to 350 DEG C oCalcining C for 2h, wherein the distance between the two material boats is 4cm, and cooling to room temperature to obtain Se-doped Fe2And P material.
FIG. 3 is a schematic diagram of Se-doped Fe prepared2SEM image of P material, Se-doped Fe2The shape of the P self-supporting composite material is a sheet ball shape, and Se is uniformly distributed on the sheet ball (figure 4). By synthesizing special morphology, pulverization of the electrode material in the charging and discharging process is reduced, material agglomeration is inhibited, volume deformation is relieved, and rate capability and cycling stability of the battery are improved. Electrochemical performance tests were performed on the material prepared in example 2: the method comprises the steps of putting an active substance, acetylene black and polyvinylidene fluoride (PVDF) into a mortar according to the mass ratio of 8:1:1, mixing and grinding uniformly, then dropping N-methylpyrrolidone solvent (NMP) and grinding into a slurry state, uniformly coating the slurry on copper foil, drying and cutting into circular electrode plates (the diameter is 14 mm), and then putting the circular electrode plates into a vacuum drying oven at 120 ℃ for drying for 12 hours. Taking the dried electrode slice as a working electrode, taking metal sodium as a counter electrode and taking NaPF as electrolyte6V. (EC + DMC) (volume ratio 1:1), separator (Celgard 2400), CR2025 button cell assembled in a glove box filled with argon. As can be seen from FIG. 5, it is 100 mA g-1Has 541.2 mAh g at current density-1Specific capacity. As can be seen from FIG. 6, at 500 mA g-1The time is kept at 451.9 mA h g after 1000 cycles-1By reaction with Fe2P is compared, and the cycling stability of the battery is obviously improvedAnd rate capability. As can be seen from FIG. 8, Se was doped with Fe2P does not change its original charge-discharge properties.
Example 3
In the same manner as in example 2, Fe alone2The distance between P and selenium powder in a tube furnace is 3cm, and Se-doped Fe is prepared2And P material. It is at 100 mA g-1Has 500.2 mAh g at current density-1Specific capacity of 500 mA g-1The capacity of the product is still maintained at 302.5 mA h g after 1000 cycles-1。
Example 4
In the same manner as in example 2, Se-doped Fe was prepared only in an amount of 0.1 g2And P material. It is at 100 mA g-1Has 511.3 mAh g at current density-1Specific capacity of 500 mA g-1The capacity of the product is still maintained at 302.3 mA h g after 1000 cycles-1。
Example 5
In the same manner as in example 2, Se-doped Fe was prepared only in an amount of 0.5g2And P material. It is at 100 mA g-1Has 420.5 mAh g at current density-1Specific capacity of 500 mA g-1The capacity of the product is still maintained at 207.5 mA hr g after 1000 cycles-1。
Example 6
EXAMPLES like example 2, only Fe was prepared2P is arranged at the central position of the tube furnace at N2Will be protected by 2 oC min-1Heating from room temperature to 400 deg.C oCalcining C for 2h to obtain Se-doped Fe2And P material. It is at 100 mA g-1Has 400.3 mAh g at current density-1Specific capacity of 500 mA g-1The capacity of the product is still maintained at 217.8 mA h g after 1000 cycles-1。
Example 7
In the same manner as in example 5, only Fe was prepared2P is arranged at the central position of the tube furnace at N2Will be protected by 2 oC min-1Heating from room temperature to 400 deg.C oCalcining C for 2h to obtain Se-doped Fe2And P material. It is at 100 mA g-1300.3 mAh g at current density-1Specific capacity of 500 mA g-1The capacity of the product is kept at 200.5 mA h g after 1000 cycles-1。
Example 8
In the same manner as in example 5, only Fe was prepared2P is arranged at the central position of the tube furnace at N2Will be protected by 2 oC min-1Heating from room temperature to 450 deg.C oCalcining C for 2h to obtain Se-doped Fe2And P material. Cooling to room temperature to obtain Se-doped Fe2And P material. It is at 100 mA g-1300.3 mAh g at current density-1Specific capacity of 500 mA g-1The capacity of the product is still kept at 210.5 mA h g after 1000 cycles-1。
Example 9
In the same embodiment as example 2, only the hydroxide precursor was scraped off from the Ni mesh and mixed with sodium hypophosphite and then calcined, the resulting product was mixed with selenium powder again and then calcined, and the resulting Se-doped Fe was obtained2P material at 100 mA g-1300.2mAh g at current density-1Specific capacity of 500 mA g-1The capacity of the glass is kept at 150.3mA h g after 1000 cycles of time circulation-1。
Example 10
Example 2, only Fe scraped from Ni mesh2P and selenium powder are mixed and then calcined to obtain Se-doped Fe2P material at 100 mA g-1Has a current density of 310.2mAh g-1Specific capacity of 500 mA g-1The capacity of the glass is kept at 200.3mA h g after 1000 cycles of time circulation-1。

Claims (6)

  1. Se doping of Fe2The preparation method of the P self-supporting sodium ion battery cathode material is characterized by comprising the following steps:
    (1) mixing and uniformly stirring urea, ferric nitrate and ammonium fluoride, transferring the mixture to a hydrothermal reaction kettle, and putting the cleaned nickel foam into a uniformly stirred solution for hydrothermal preparation to obtain a hydroxide precursor;
    （2）placing the mixture of the prepared hydroxide precursor, selenium powder and sodium hypophosphite in two material boats respectively, placing the material boat containing the mixture of the sodium hypophosphite and the selenium powder on one side close to the air inlet of the tube furnace, placing the material boat containing the hydroxide precursor on one side of the air outlet, wherein the distance between the two material boats is 3-5cm, and obtaining Se-doped Fe at high temperature2P is self-supporting sodium ion battery cathode material.
  2. 2. Se-doped Fe of claim 12The preparation method of the P self-supporting sodium ion battery cathode material is characterized in that the molar ratio of urea to ferric nitrate to ammonium fluoride is 1-2:10-20: 2-8.
  3. 3. Se-doped Fe of claim 12The preparation method of the P self-supporting sodium ion battery cathode material is characterized in that the hydrothermal reaction temperature is 100-150-oC, reacting for 6-10h to obtain a hydroxide precursor, and placing the precursor in a temperature range of 50-80 DEG C oCDrying in a constant temperature drying oven for 5-24 h.
  4. 4. Se-doped Fe of claim 12The preparation method of the P self-supporting sodium ion battery cathode material is characterized in that the mass ratio of the selenium powder to the sodium hypophosphite is 1:1-1: 5.
  5. 5. Se-doped Fe of claim 12The preparation method of the P self-supporting sodium ion battery cathode material is characterized in that nitrogen is filled in a tubular furnace, and the temperature in the furnace is controlled at 2-5 ℃ for min under the nitrogen atmosphere-1Temperature up to 250-450 DEGoAnd C, calcining for 1-2 h at the temperature, and naturally cooling to room temperature.
  6. 6. Se-doped Fe of claim 52The preparation method of the P self-supporting sodium ion battery cathode material is characterized in that N is2In the atmosphere, dry hydroxide precursor is arranged at the central position of the tubular furnace, sodium hypophosphite is arranged at the position of an air inlet, 250-oC calcination 2-Fe is prepared after 3h2P, then placing selenium powder at the position of an air inlet to prepare Fe2P is arranged at the central position of the tubular furnace at 300-450 DEGoCalcining C for 1-5h to obtain Se-doped Fe2And P material.
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CN114150341A (en) * 2021-10-13 2022-03-08 武汉工程大学 Transition metal selenide electrocatalytic material and preparation method and application thereof
CN114477101A (en) * 2022-01-18 2022-05-13 三峡大学 Preparation method of self-supporting selenium-titanium-oxygen sodium array
CN114804045A (en) * 2022-05-19 2022-07-29 武汉科技大学 Preparation method and application of iron-nickel phosphide nanosheet forming capacitor material
CN115321503A (en) * 2022-09-09 2022-11-11 北京化工大学 Carbon-free Fe 7 Se 8 Preparation method and application of sodium-based storage electrode material
CN115321503B (en) * 2022-09-09 2023-05-16 北京化工大学 Carbon-free Fe 7 Se 8 Preparation method and application of sodium-based electrode material

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