CN109786709B - Ferroferric oxide/carbon composite negative electrode material and preparation method and application thereof - Google Patents
Ferroferric oxide/carbon composite negative electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a ferroferric oxide/carbon composite negative electrode material and a preparation method and application thereof. The anode material provided by the invention comprises Fe3O4Fine particles and a carbon layer coating Fe3O4Fine particles and connecting them together into a whole, the Fe3O4the/C composite negative electrode material is a porous material. The preparation method comprises the following steps: 1) mixing a carbonaceous reducing agent solution with an iron source to obtain a reaction mixed solution; 2) soaking template microspheres in the reaction mixed solution obtained in the step (1), and carrying out solid-liquid separation to obtain solids so as to obtain a reaction precursor; 3) calcining the reaction precursor in the step (2) under protective atmosphere to obtain the Fe3O4the/C composite negative electrode material. The negative electrode material has high charge-discharge specific capacity, high cycling stability and high conductivity, and is suitable for sodium/potassium ion batteries. The preparation method has the advantages of simple process, relatively mild synthesis conditions, high repeatability and low cost.
Description
Technical Field
The invention belongs to the technical field of batteries, relates to an electrode material, and particularly relates to a ferroferric oxide/carbon composite anode material as well as a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, high discharge voltage, environmental friendliness, no memory effect and the like, and is widely applied to electronic products, electric automobiles and smart power grids. However, the scarcity of lithium resources limits the large-scale application of lithium ion batteries. On the other hand, sodium and potassium have abundant reserves, low prices, and physical and chemical properties similar to those of lithium, so that sodium/potassium ion batteries have attracted much attention as a novel secondary energy system for replacing lithium ion batteries.
The conventional graphite cathode material for the secondary battery is used for a sodium-ion battery, and the capacity of the graphite cathode material is about 20 mAh/g. While the research on the negative electrode material of the potassium ion battery is mainly focused on graphite, the theoretical capacity of the potassium ion battery is only 279 mAh/g. Metal oxides have been extensively studied relative to graphite due to their higher gravimetric and volumetric specific capacities than carbon materials. However, metal oxides tend to cause large volume changes and low electron conductivity during ion intercalation and deintercalation, resulting in severe capacity fade. Therefore, the search for a high-performance sodium/potassium ion battery anode material is urgent.
CN107507978A discloses a sodium ion battery FeS2/Fe3O4the/C negative electrode material and the preparation method thereof comprise the following steps: mixing an iron source solution and a sodium lignosulfonate solution according to the molar ratio of Fe to S of 1: 1-5 to obtain a solution A; carrying out hydrothermal treatment on the solution A to obtain a brownish black precipitate; drying and fully grinding the precipitate to obtain a composite material precursor; calcining the composite material precursor in the protective gas atmosphere to obtain FeS2/Fe3O4a/C composite material. However, the preparation process of the scheme is complicated, the raw materials are complex, the cost is high, and the specific capacity of the preparation is still to be improved.
CN102208641A discloses a one-step method for synthesizing hollow sphere structure Fe3O4A method for preparing a negative electrode material of a lithium ion battery. The method mainly comprises the following steps: step 1, uniformly mixing iron salt, a mineralizer, a solvent, a surfactant and an additive, wherein the iron salt: the molar ratio of the mineralizer is 1:5 to 1: 15; step 2, stirring the mixture obtained in the step 1 for 0.5 to 5 hours in a constant-temperature water bath at the temperature of between 30 and 50 ℃ to form a uniform solution; step 3, transferring the solution obtained in the step 2 to a 50mL polytetrafluoroethylene reaction kettle, and reacting at the temperature of 180-220 ℃ for 6-96 hours; step 4, centrifugally separating the product obtained in the step 3, washing the product with distilled water and absolute ethyl alcohol for 2 to 5 times respectively, and drying the product in vacuum at the temperature of between 80 and 110 ℃ for 9 to 12 hours to obtain a product Fe3O4C; and 5, respectively characterizing the obtained Fe 3O 4/C product by XRD, SEM and TEM (HTEM), and carrying out electrochemical performance analysis on a sample subjected to solvothermal reaction for 48 hours at 200 ℃. However, the cathode material prepared by the method is a lithium ion battery cathode material, and is not suitable for a sodium/potassium ion battery. And the method has complicated steps and is not beneficial to industrial production.
CN103208625B discloses a preparation method of an iron oxide-based high-performance negative electrode material of a lithium ion battery, which comprises the following steps: (1) preparing a solution: selecting iron salt as an iron source, weighing a certain mass of the iron salt, dissolving the iron salt in a certain amount of solvent, and uniformly stirring to form a clear solution, wherein the concentration of the iron salt is controlled to be 0.02-1 mol/100ml, and the solution is marked as solution A; selecting sodium salt as a precipitator, weighing the required mass, dissolving the sodium salt in a certain amount of solvent, adding a certain amount of dispersant, and magnetically stirring to form a uniform and transparent solution, wherein the concentration of the sodium salt is controlled to be 0.02-1 mol/100ml, and the solution is marked as solution B; (2) dropwise adding the solution B into the solution A, and continuously stirring until the mixed solution is a yellow brown uniform solution; (3) weighing a certain amount of carbonaceous matrix material, adding the carbonaceous matrix material into the mixed solution obtained in the step (2), continuously stirring for a period of time, and performing ultrasonic dispersion on the suspension for 0.5-2 hours; (4) pouring a proper amount of turbid liquid formed in the step (3) into a hydrothermal kettle with a polytetrafluoroethylene lining, and reacting for 12-72 hours at a certain temperature in a constant temperature box to obtain powder particles, wherein the certain temperature refers to the temperature of the constant temperature box being 120-220 ℃; (5) separating the powder particles obtained in the step (4), washing the powder particles with deionized water and ethanol, and drying the powder in a vacuum drying oven at a certain temperature for 5-12 h to obtain loose porous Fe3O4a/C composite material. However, the method has complex process and long flow, and the prepared cathode material is a lithium ion battery cathode material and is not suitable for a sodium/potassium ion battery.
Therefore, the development of a sodium/potassium ion battery anode material which has high theoretical capacity, high conductivity, low cost, abundant natural resources and no toxicity has important significance in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a ferroferric oxide/carbon composite negative electrode material, and a preparation method and application thereof. The invention provides ferroferric oxide/carbon (Fe)3O4the/C) composite negative electrode material has the advantages of large specific capacity, high cycling stability, good conductivity and low resistivity.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides Fe3O4a/C composite anode material, the Fe3O4the/C composite negative electrode material comprises Fe3O4Particles and a carbon layer, the carbon layerCoated with Fe3O4Fine particles and connecting them together into a whole, the Fe3O4the/C composite negative electrode material is a porous material.
The invention provides Fe3O4the/C composite anode material has a porous structure, and Fe in the porous structure3O4The particles are coated with a carbon layer, the carbon layer functions as a connecting agent, and Fe3O4The particles are connected together as a whole. Such a unique structure allows the present invention to provide Fe3O4the/C composite cathode material is particularly suitable for sodium/potassium ion batteries.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
As a preferable embodiment of the present invention, said Fe3O4the/C composite negative electrode material is a three-dimensional ordered porous material. The three-dimensional ordered structure can enable charges and ions to rapidly migrate, relieve the problem of volume expansion caused in the circulation process to a certain extent, and enable the Fe provided by the invention3O4the/C composite negative electrode material has better electrochemical performance and is more suitable for sodium/potassium ion batteries.
Preferably, the Fe3O4the/C composite anode material comprises macropores and mesopores, the pore diameter of the macropores is 50-100nm, such as 50nm, 60nm, 70nm, 80nm, 90nm or 100nm, and the like, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable, and the pore diameter of the mesopores is 5-15nm, such as 5nm, 8nm, 10nm, 12nm or 15nm, and the like, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the Fe3O4The porosity of the/C composite anode material is 20% to 70%, for example, 20%, 30%, 40%, 50%, 60%, or 70%, etc., but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the Fe3O4In the/C composite negative electrode material, the ratio of the pore volume of the macropores to the pore volume of the mesopores is 2:1-4: 1. In the present invention, if the ratio of the pore volume of the macropores to the pore volume of the mesopores is too large, the specific surface area is too large, and an irreversible side reaction between the electrode material and the electrolyte occurs; if the ratio of the pore volume of the macropores to the pore volume of the mesopores is too small, the specific surface area is too small, which is not favorable for rapid diffusion of ions.
Preferably, the Fe3O4The specific surface area of the/C composite negative electrode material is 80-120m2g-1E.g. 80m2g-1、90m2g-1、100m2g-1、110m2g-1Or 120m2g-1And the like, but are not limited to the recited values, and other values not recited within the numerical range are also applicable.
In a second aspect, the present invention provides Fe as described in the first aspect3O4A preparation method of/C composite anode material comprises the following steps:
(1) mixing a carbonaceous reducing agent solution with an iron source to obtain a reaction mixed solution;
(2) soaking template microspheres in the reaction mixed solution obtained in the step (1), and carrying out solid-liquid separation to obtain solids so as to obtain a reaction precursor;
(3) calcining the reaction precursor in the step (2) under protective atmosphere to obtain the Fe3O4the/C composite negative electrode material.
In the preparation method provided by the invention, a carbonaceous reducing agent is used as both a carbon source and a reducing agent, a precursor is obtained by soaking the template microspheres, and then the precursor is subjected to heat treatment to finally obtain the Fe with the three-dimensional ordered porous structure3O4the/C composite negative electrode material contains micropores and macropores, has uniform pore size distribution, and is favorable for transmission of ions and electrons. In the preparation method provided by the invention, the carbonaceous reducing agent is calcined to generate gas, so that the negative electrode material product forms a porous structure.
The preparation method provided by the invention has the advantages of simple process, relatively mild synthesis conditions, high repeatability and low cost.
In a preferable embodiment of the present invention, in the solution of the carbonaceous reducing agent in step (1), the carbonaceous reducing agent is ascorbic acid.
Preferably, the solvent in the carbonaceous reducing agent solution in the step (1) is a mixed solvent of ethylene glycol and methanol. The mixed solvent is used for more effectively solving the problem of agglomeration of metal particles.
Preferably, the volume ratio of the ethylene glycol to the methanol in the mixed solvent of ethylene glycol and methanol is 3:1.5 to 3:2.5, for example, 3:1.5, 3:1.7, 3:2, 3:2.3 or 3:2.5, but not limited to the enumerated values, and other non-enumerated values within the range are also applicable, preferably 3:2.
In a preferred embodiment of the present invention, in the step (1), the iron source includes iron nitrate. In the present invention, the iron nitrate includes not only pure iron nitrate but also hydrate of iron nitrate (Fe (NO)3)3·9H2O)。
Preferably, in the step (1), the mixing method is stirring mixing.
Preferably, in step (1), the mixing time is 1 to 3 hours, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, or 3 hours, but not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the concentration of the iron source in the reaction mixture in step (1) is 0.5 to 3mol/L, for example, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, or 3mol/L, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the molar ratio of the iron source to the carbonaceous reducing agent in the reaction mixture of step (1) is from 2:1 to 13:1, for example, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1 or 13:1, but is not limited to the recited values, and other values not recited within this range of values are equally applicable.
In a preferred embodiment of the present invention, in step (2), the soaking time is 8-15h, such as 8h, 9h, 10h, 11h, 12h, 13h, 14h or 15h, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, in step (2), the template microspheres are Polystyrene (PS) microspheres. The polystyrene microspheres are used as templates and can be removed during calcination to form macropores on a negative electrode material product, but the negative electrode material shrinks to a certain extent during calcination, and the actually observed macropore diameter is smaller than the diameter of the template microspheres due to the limitation of a characterization method (scanning electron microscope observation).
In the present invention, the polystyrene microspheres are preferably self-assembled monodisperse polystyrene microspheres.
Preferably, in step (2), the particle size of the template microsphere is 250-325nm, such as 250nm, 260nm, 270nm, 280nm, 290nm, 300nm, 310nm, 320nm or 325nm, but not limited to the values listed, and other values not listed in the range of the values are also applicable. If the particle size of the template microsphere is too large, the specific surface area is too large, and irreversible side reactions between the electrode material and the electrolyte occur; if the particle size of the template microsphere is too small, the specific surface area is too small, and the rapid diffusion of ions is not facilitated.
Preferably, in step (2), the mass ratio of the template microspheres to the iron source is 1:1 to 1:6, such as 1:1, 1:2, 1:3, 1:4, 1:5, or 1:6, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, in the step (2), the solid-liquid separation method comprises vacuum filtration.
Preferably, the step (2) further comprises drying the solid obtained by solid-liquid separation. The specific conditions of the drying can be selected according to actual conditions, and can be carried out in a forced air drying oven at 50 ℃.
As a preferred technical scheme of the invention, the protective atmosphere in the step (3) comprises a nitrogen atmosphere and/or an argon atmosphere.
Preferably, step (3) further comprises: after calcination, the product obtained is cooled to 20-30 ℃, i.e. to room temperature.
As a preferable technical scheme of the invention, the calcination in the step (3) is two-step calcination, and the temperature of the second-step calcination is higher than that of the first-step calcination. In the invention, two-step calcination is preferably adopted to ensure that the reaction is more complete and the template microspheres are removed more cleanly. If only one step of calcination is performed, the reaction is insufficient and the removal of the template microspheres is incomplete.
Preferably, the temperature of the first step calcination is 250-350 ℃, such as 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃ or 350 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable, preferably 300 ℃.
Preferably, the time for the first calcination step is 3-5h, such as 3h, 3.5h, 4h, 4.5h or 5h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the first calcination step is carried out at a temperature increase rate of 0.5-2 deg.C/min, such as 0.5 deg.C/min, 1 deg.C/min, 1.5 deg.C/min, or 2 deg.C/min, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature of the second step calcination is 450-550 ℃, such as 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃ or 550 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable, preferably 500 ℃.
Preferably, the second calcination step is carried out for a time period of 3 to 5 hours, such as 3 hours, 3.5 hours, 4 hours, 4.5 hours, or 5 hours, but not limited to the recited values, and other values not recited within the range are also applicable.
Preferably, the second calcination step is carried out at a temperature increase rate of 0.5-2 deg.C/min, such as 0.5 deg.C/min, 1 deg.C/min, 1.5 deg.C/min, or 2 deg.C/min, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
As a further preferable technical scheme of the preparation method, the method comprises the following steps:
(1) stirring and mixing an ascorbic acid solution and ferric nitrate for 1-3 hours to obtain a reaction mixed solution;
wherein the concentration of the iron source is 0.5-3mol/L, the molar ratio of the iron source to the carbonaceous reducing agent is 2:1-13:1, and the solvent in the ascorbic acid solution is a mixed solvent consisting of ethylene glycol and methanol in a volume ratio of 3: 2;
(2) soaking polystyrene microspheres in the reaction mixed solution obtained in the step (1) for 8-15h, vacuum-filtering to obtain a solid, and drying the solid to obtain a reaction precursor;
wherein the particle size of the polystyrene microsphere is 250-325nm, and the mass ratio of the polystyrene microsphere to the iron source is 1:1-1: 6;
(3) and (3) calcining the reaction precursor in the step (2) in a protective atmosphere in two steps, wherein in the first step, the temperature is increased to 300 ℃ at the heating rate of 0.5-2 ℃/min, then the calcination is carried out for 3-5h in a heat preservation way, in the second step, the temperature is increased to 500 ℃ at the heating rate of 0.5-2 ℃/min, then the calcination is carried out for 3-5h in a heat preservation way, and then the calcination is cooled to 20-30 ℃ to obtain the Fe3O4the/C composite negative electrode material.
In a third aspect, the present invention provides Fe as described in the first aspect3O4Use of/C composite anode material, Fe3O4the/C composite negative electrode material is used for a sodium ion battery or a potassium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides Fe3O4the/C composite negative electrode material has a unique structure, shows high charge-discharge specific capacity, high cycling stability and good conductivity, and is particularly suitable for sodium ion batteries or potassium ion batteries. The invention provides Fe3O4The first charging specific capacity of the/C composite negative electrode material used for the sodium ion battery can reach 361.1mAh/g, and the conductivity can reach 5.0 multiplied by 10-4S/m, the capacity retention rate after 50 times of charge-discharge cycles with the current density of 50mA/g can reach 88%; the invention provides Fe3O4The first charging specific capacity of the/C composite negative electrode material used for the potassium ion battery can reach 294.9mAh/g, and the conductance of the material can be adjustedThe rate can reach 4.0 multiplied by 10-4S/m, the capacity retention rate after 50 times of charge-discharge cycles with the current density of 50mA/g can reach 84%;
(2) the preparation method provided by the invention is simple to operate, low in cost, high in yield, high in repeatability and easy to control the product structure.
Drawings
FIG. 1 shows Fe prepared in example 13O4SEM scanning of the/C composite negative electrode material;
FIG. 2 shows Fe in example 13O4Composite negative electrode material/C and preparation of Fe in comparative example 13O4XRD diffraction pattern of the cathode material;
FIG. 3 is Fe prepared in example 13O4Composite negative electrode material/C and preparation of Fe in comparative example 13O4The negative electrode material is used as a cycle performance diagram of the negative electrode material of the sodium battery at the current density of 50 mA/g.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1
This example used the following method to prepare Fe3O4the/C composite negative electrode material:
(1) weighing 0.33 g of ascorbic acid, adding the ascorbic acid into a mixed solution consisting of 3ml of ethylene glycol and 2ml of methanol, and stirring the ascorbic acid and the mixed solution until a clear ascorbic acid solution is obtained; 3.03 g of Fe (NO)3)3·9H2Adding O into the ascorbic acid solution, and continuously stirring for 1.5h to obtain a reaction mixed solution;
in the reaction mixture, the concentration of ferric nitrate was 1.5mol/L, and the molar ratio of ferric nitrate to ascorbic acid was 4: 1.
(2) 1 g of self-assembled monodisperse PS microspheres (with the particle size of 250-325nm) are soaked in the solution for 10h, then the precursor is obtained by vacuum filtration, and the precursor is placed in a forced air drying oven at 50 ℃ for drying for 24 h;
wherein, PS microspheres and Fe (NO)3)3·9H2The mass ratio of O is about 1:3.
(3) Placing the dried precursor in a tube furnace, carrying out two-step calcination in argon atmosphere, firstly heating to 300 ℃ at the heating rate of 1 ℃/min, carrying out heat preservation calcination for 3h, then heating to 500 ℃ at the heating rate of 1 ℃/min, carrying out heat preservation calcination for 5h, cooling to 25 ℃, and obtaining the Fe3O4the/C composite material is a negative electrode material of a sodium/potassium ion battery.
For the sample of this example, the appearance structure characterization was performed by using a Scanning Electron Microscope (SEM), and the pore structure characterization was performed by using a fully automatic multifunctional gas adsorption apparatus, and the results are as follows.
Fe prepared in this example3O4the/C composite negative electrode material comprises Fe3O4Fine particles and a carbon layer coating Fe3O4Fine particles and connecting them together into a whole, the Fe3O4the/C composite negative electrode material is a three-dimensional ordered porous material and comprises macropores and mesopores, wherein the pore diameter of the macropores is 50-80nm, and the pore diameter of the mesopores is 5-12 nm; said Fe3O4The porosity of the/C composite negative electrode material is 60 percent; said Fe3O4In the/C composite negative electrode material, the ratio of the pore volume of macropores to the pore volume of mesopores is 4:1, and the Fe3O4The specific surface area of the/C composite negative electrode material is 120m2g-1。
Other embodiments also perform structural characterization according to the structural testing methods described above.
Fe prepared in this example3O4The electrochemical performance test results of the/C composite negative electrode material are shown in the table 1 and the table 2.
FIG. 1 shows Fe obtained in this example3O4Scanning Electron Microscope (SEM) scanning image of the/C composite material sodium/potassium ion battery negative electrode material. As can be seen from the figure, Fe is formed by thermal decomposition3O4C is a distinct porous structure containing mesopores andlarge pores and a three-dimensional ordered porous structure is presented as a whole.
Example 2
This example used the following method to prepare Fe3O4the/C composite negative electrode material:
(1) weighing 0.1887 g of ascorbic acid, adding the ascorbic acid into a mixed solution consisting of 3ml of ethylene glycol and 2ml of methanol, and stirring the mixture until a clear ascorbic acid solution is obtained; (2) 3.03 g of Fe (NO)3)3·9H2Adding O into the ascorbic acid solution, and continuously stirring for 2 hours to obtain a reaction mixed solution;
in the reaction mixture, the concentration of ferric nitrate was 1.5mol/L, and the molar ratio of ferric nitrate to ascorbic acid was 7: 1.
(2) 1 g of self-assembled monodisperse PS microspheres (with the particle size of 250-325nm) are soaked in the solution for 12h, then the precursor is obtained by vacuum filtration, and the precursor is placed in a forced air drying oven at 50 ℃ for drying for 30 h;
wherein, PS microspheres and Fe (NO)3)3·9H2The mass ratio of O is about 1:3.
(3) Placing the dried precursor in a tubular furnace, and calcining in a nitrogen atmosphere for two steps, namely heating to 300 ℃ at a heating rate of 0.5 ℃/min, carrying out heat preservation calcination for 3h, heating to 500 ℃ at a heating rate of 0.5 ℃/min, carrying out heat preservation calcination for 3h, cooling to 20 ℃ to obtain the Fe3O4the/C composite material is a negative electrode material of a sodium/potassium ion battery.
Fe prepared in this example3O4the/C composite negative electrode material comprises Fe3O4Fine particles and a carbon layer coating Fe3O4Fine particles and connecting them together into a whole, the Fe3O4the/C composite negative electrode material is a three-dimensional ordered porous material and comprises macropores and mesopores, wherein the pore diameter of the macropores is 50-70nm, and the pore diameter of the mesopores is 5-8 nm; said Fe3O4The porosity of the/C composite negative electrode material is 50%; said Fe3O4In the/C composite negative electrode material, the ratio of the pore volume of macropores to the pore volume of mesopores is 2:1, and the Fe3O4/C composite negative electrode materialThe specific surface area of the material is 98m2g-1。
Fe prepared in this example3O4The electrochemical performance test results of the/C composite negative electrode material are shown in the table 1 and the table 2.
Example 3
This example used the following method to prepare Fe3O4the/C composite negative electrode material:
(1) weighing 0.132 g of ascorbic acid, adding the ascorbic acid into a mixed solution consisting of 3ml of ethylene glycol and 2ml of methanol, and stirring the ascorbic acid and the mixed solution until a clear ascorbic acid solution is obtained; 3.03 g of Fe (NO)3)3·9H2Adding O into the ascorbic acid solution, and continuously stirring for 3 hours to obtain a reaction mixed solution;
in the reaction mixture, the concentration of ferric nitrate is 1.5mol/L, and the molar ratio of ferric nitrate to ascorbic acid is 10: 1.
(2) Soaking 0.5 g of self-assembled monodisperse PS microspheres (with the particle size of 250-325nm) in the solution for 15h, then carrying out vacuum filtration to obtain a precursor, and placing the precursor in a forced air drying oven at 50 ℃ for drying for 20 h;
wherein, PS microspheres and Fe (NO)3)3·9H2The mass ratio of O is about 1: 6.
(3) Placing the dried precursor in a tubular furnace, and calcining in a nitrogen atmosphere for two steps, namely heating to 300 ℃ at the heating rate of 1.5 ℃/min, keeping the temperature, calcining for 4 hours, heating to 500 ℃ at the heating rate of 1.5 ℃/min, keeping the temperature, calcining for 5 hours, cooling to 30 ℃ to obtain the Fe3O4the/C composite material is a negative electrode material of a sodium/potassium ion battery.
Fe prepared in this example3O4the/C composite negative electrode material comprises Fe3O4Fine particles and a carbon layer coating Fe3O4Fine particles and connecting them together into a whole, the Fe3O4the/C composite negative electrode material is a three-dimensional ordered porous material and comprises macropores and mesopores, wherein the pore diameter of the macropores is 70-100nm, and the pore diameter of the mesopores is 6-11 nm; said Fe3O4The porosity of the/C composite negative electrode material is 20%; said Fe3O4In the/C composite negative electrode material, the ratio of the pore volume of macropores to the pore volume of mesopores is 3:1, and the Fe3O4The specific surface area of the/C composite negative electrode material is 89m2g-1。
Fe prepared in this example3O4The electrochemical performance test results of the/C composite negative electrode material are shown in the table 1 and the table 2.
Example 4
This example used the following method to prepare Fe3O4the/C composite negative electrode material:
(1) weighing 0.1016 g of ascorbic acid, adding the ascorbic acid into a mixed solution consisting of 3ml of ethylene glycol and 2ml of methanol, and stirring the mixture until a clear ascorbic acid solution is obtained; 3.03 g of Fe (NO)3)3·9H2Adding O into the ascorbic acid solution, and continuously stirring for 1h to obtain a reaction mixed solution;
in the reaction mixture, the concentration of ferric nitrate was 1.5mol/L, and the molar ratio of ferric nitrate to ascorbic acid was 13: 1.
(2) Soaking 0.8 g of self-assembled monodisperse PS microspheres (with the particle size of 250-325nm) in the solution for 8h, then performing vacuum filtration to obtain a precursor, and placing the precursor in a forced air drying oven at 50 ℃ for drying for 36 h;
wherein, PS microspheres and Fe (NO)3)3·9H2The mass ratio of O is about 1: 3.8.
(3) Placing the dried precursor in a tube furnace, and calcining in argon atmosphere in two steps, namely heating to 300 ℃ at the heating rate of 0.5 ℃/min, keeping the temperature, calcining for 3 hours, heating to 500 ℃ at the heating rate of 0.5 ℃/min, keeping the temperature, calcining for 5 hours, cooling to 25 ℃ to obtain the Fe3O4the/C composite material is a negative electrode material of a sodium/potassium ion battery.
Fe prepared in this example3O4the/C composite negative electrode material comprises Fe3O4Fine particles and a carbon layer coating Fe3O4Fine particles and connecting them together into a whole, the Fe3O4the/C composite negative electrode material is a three-dimensional ordered porous material and comprises macropores and mesopores, wherein the macroporesThe aperture of (A) is 60-90nm, and the aperture of the mesopores is 8-12 nm; said Fe3O4The porosity of the/C composite negative electrode material is 30 percent; said Fe3O4In the/C composite negative electrode material, the ratio of the pore volume of macropores to the pore volume of mesopores is 3.5:1, and the Fe3O4The specific surface area of the/C composite negative electrode material is 87m2g-1。
Fe prepared in this example3O4The electrochemical performance test results of the/C composite negative electrode material are shown in the table 1 and the table 2.
Example 5
This example used the following method to prepare Fe3O4the/C composite negative electrode material:
(1) weighing 0.66 g of ascorbic acid, adding the ascorbic acid into a mixed solution consisting of 3ml of ethylene glycol and 2ml of methanol, and stirring the ascorbic acid and the mixed solution until a clear ascorbic acid solution is obtained; 6.06 g of Fe (NO)3)3·9H2Adding O into the ascorbic acid solution, and continuously stirring for 1h to obtain a reaction mixed solution;
in the reaction mixture, the concentration of ferric nitrate is 3mol/L, and the molar ratio of ferric nitrate to ascorbic acid is 4: 1.
(2) 1.5 g of self-assembled monodisperse PS microspheres (with the particle size of 250-325nm) are soaked in the solution for 10h, then the precursor is obtained by vacuum filtration and is placed in a forced air drying box at 50 ℃ for drying for 25 h;
wherein, PS microspheres and Fe (NO)3)3·9H2The mass ratio of O is about 1: 4.
(3) Placing the dried precursor in a tube furnace, carrying out two-step calcination in argon atmosphere, firstly heating to 300 ℃ at the heating rate of 1 ℃/min, carrying out heat preservation calcination for 3h, then heating to 500 ℃ at the heating rate of 1 ℃/min, carrying out heat preservation calcination for 3h, cooling to 25 ℃, and obtaining the Fe3O4the/C composite material is a negative electrode material of a sodium/potassium ion battery.
Fe prepared in this example3O4the/C composite negative electrode material comprises Fe3O4Fine particles and a carbon layer coating Fe3O4Microparticles and connecting them togetherTo become a whole, the Fe3O4the/C composite negative electrode material is a three-dimensional ordered porous material and comprises macropores and mesopores, wherein the pore diameter of the macropores is 70-100nm, and the pore diameter of the mesopores is 7-12 nm; said Fe3O4The porosity of the/C composite negative electrode material is 70%; said Fe3O4In the/C composite negative electrode material, the ratio of the pore volume of macropores to the pore volume of mesopores is 2.1:1, and the Fe3O4The specific surface area of the/C composite negative electrode material is 80m2g-1。
Fe prepared in this example3O4The electrochemical performance test results of the/C composite negative electrode material are shown in the table 1 and the table 2.
Example 6
This example used the following method to prepare Fe3O4the/C composite negative electrode material:
(1) weighing 0.22 g of ascorbic acid, adding the ascorbic acid into a mixed solution consisting of 3ml of ethylene glycol and 2ml of methanol, and stirring to obtain an ascorbic acid solution; 1.01 g of Fe (NO)3)3·9H2Adding O into the ascorbic acid solution, and continuously stirring for 1.5h to obtain a reaction mixed solution;
in the reaction mixture, the concentration of ferric nitrate is 0.5mol/L, and the molar ratio of ferric nitrate to ascorbic acid is 2: 1.
(3) 1 g of self-assembled monodisperse PS microspheres (with the particle size of 250-325nm) are soaked in the solution for 11h, then the precursor is obtained by vacuum filtration and is placed in a forced air drying box at 50 ℃ for drying for 24 h;
wherein, PS microspheres and Fe (NO)3)3·9H2The mass ratio of O is about 1: 1.
(4) Placing the dried precursor in a tubular furnace, performing two-step calcination in a mixed atmosphere of nitrogen and argon, firstly heating to 300 ℃ at a heating rate of 1.5 ℃/min, performing heat preservation calcination for 4h, then heating to 500 ℃ at a heating rate of 1.5 ℃/min, performing heat preservation calcination for 5h, cooling to 25 ℃, and obtaining the Fe3O4the/C composite material is a negative electrode material of a sodium/potassium ion battery.
Fe prepared in this example3O4the/C composite negative electrode material comprises Fe3O4Fine particles and a carbon layer coating Fe3O4Fine particles and connecting them together into a whole, the Fe3O4the/C composite negative electrode material is a three-dimensional ordered porous material and comprises macropores and mesopores, wherein the pore diameter of the macropores is 50-90nm, and the pore diameter of the mesopores is 5-9 nm; said Fe3O4The porosity of the/C composite negative electrode material is 40%; said Fe3O4In the/C composite negative electrode material, the ratio of the pore volume of macropores to the pore volume of mesopores is 3.2:1, and the Fe3O4The specific surface area of the/C composite negative electrode material is 90m2g-1。
Fe prepared in this example3O4The electrochemical performance test results of the/C composite negative electrode material are shown in the table 1 and the table 2.
Example 7
This example used the following method to prepare Fe3O4the/C composite negative electrode material:
(1) weighing 0.22 g of ascorbic acid, adding the ascorbic acid into a mixed solution consisting of 3ml of ethylene glycol and 2ml of methanol, and stirring the ascorbic acid and the mixed solution to obtain a clear ascorbic acid solution; 2.02 g of Fe (NO)3)3·9H2Adding O into the ascorbic acid solution, and continuously stirring for 2.5h to obtain a reaction mixed solution;
in the reaction mixture, the concentration of ferric nitrate is 1mol/L, and the molar ratio of ferric nitrate to ascorbic acid is 4: 1.
(2) 1.5 g of self-assembled monodisperse PS microspheres (with the particle size of 250-325nm) are soaked in the solution for 10h, then the precursor is obtained by vacuum filtration and is placed in a forced air drying box at 50 ℃ for drying for 28 h;
wherein, PS microspheres and Fe (NO)3)3·9H2The mass ratio of O is about 1: 35.
(3) Placing the dried precursor in a tubular furnace, performing two-step calcination in a mixed atmosphere of nitrogen and argon, firstly heating to 300 ℃ at a heating rate of 0.5 ℃/min, performing heat preservation calcination for 3h, then heating to 500 ℃ at a heating rate of 0.5 ℃/min, performing heat preservation calcination for 4h, cooling to 25 ℃, and then performing heat preservation calcinationTo obtain said Fe3O4the/C composite material is a negative electrode material of a sodium/potassium ion battery.
Fe prepared in this example3O4the/C composite negative electrode material comprises Fe3O4Fine particles and a carbon layer coating Fe3O4Fine particles and connecting them together into a whole, the Fe3O4the/C composite negative electrode material is a three-dimensional ordered porous material and comprises macropores and mesopores, wherein the pore diameter of the macropores is 60-85nm, and the pore diameter of the mesopores is 11-15 nm; said Fe3O4The porosity of the/C composite negative electrode material is 60 percent; said Fe3O4In the/C composite negative electrode material, the ratio of the pore volume of macropores to the pore volume of mesopores is 3.5:1, and the Fe3O4The specific surface area of the/C composite negative electrode material is 97m2g-1。
Fe prepared in this example3O4The electrochemical performance test results of the/C composite negative electrode material are shown in the table 1 and the table 2.
Example 8
Fe of the present example3O4The preparation method of the/C composite anode material is as in example 1, except that:
in the step (1), ascorbic acid was added to a mixed solution of 3ml of ethylene glycol and 1.5ml of methanol.
In the step (2), the soaking time is 15 h.
In the step (3), firstly, the temperature is raised to 250 ℃ at the heating rate of 2 ℃/min, and the heat preservation and calcination are carried out for 5h, and then the temperature is raised to 450 ℃ at the heating rate of 2 ℃/min, and the heat preservation and calcination are carried out for 5 h.
Fe prepared in this example3O4the/C composite negative electrode material comprises Fe3O4Fine particles and a carbon layer coating Fe3O4Fine particles and connecting them together into a whole, the Fe3O4the/C composite negative electrode material is a three-dimensional ordered porous material and comprises macropores and mesopores, wherein the pore diameter of the macropores is 70-100nm, and the pore diameter of the mesopores is 8-11 nm; said Fe3O4The porosity of the/C composite negative electrode material is 60 percent; said Fe3O4In the/C composite negative electrode material, the ratio of the pore volume of macropores to the pore volume of mesopores is 3.7:1, and the Fe3O4The specific surface area of the/C composite negative electrode material is 98m2g-1。
Fe prepared in this example3O4The electrochemical performance test results of the/C composite negative electrode material are shown in the table 1 and the table 2.
Example 9
Fe of the present example3O4The preparation method of the/C composite anode material is as in example 1, except that:
in the step (1), ascorbic acid was added to a mixed solution of 3ml of ethylene glycol and 2.5ml of methanol.
In the step (3), firstly, the temperature is raised to 350 ℃ for heat preservation and calcination, and then the temperature is raised to 550 ℃ for heat preservation and calcination
Fe prepared in this example3O4the/C composite negative electrode material comprises Fe3O4Fine particles and a carbon layer coating Fe3O4Fine particles and connecting them together into a whole, the Fe3O4the/C composite negative electrode material is a three-dimensional ordered porous material and comprises macropores and mesopores, wherein the pore diameter of the macropores is 80-100nm, and the pore diameter of the mesopores is 10 nm; said Fe3O4The porosity of the/C composite negative electrode material is 50%; said Fe3O4In the/C composite negative electrode material, the ratio of the pore volume of macropores to the pore volume of mesopores is 4:1, and the Fe3O4The specific surface area of the/C composite negative electrode material is 100m2g-1。
Fe prepared in this example3O4The electrochemical performance test results of the/C composite negative electrode material are shown in the table 1 and the table 2.
Comparative example 1
This comparative example prepared Fe as follows3O4And (3) anode material:
(1) 3.03 g Fe (NO) are weighed out3)3·9H2Adding O into a mixed solution consisting of 3ml of ethylene glycol and 2ml of methanol, and stirring for 1.5 hours to obtain a reaction mixed solution;
in the reaction mixture, the concentration of ferric nitrate was 1.5 mol/L.
(2) 1 g of self-assembled monodisperse PS microspheres (the particle size is the same as that of the PS microspheres in the embodiment 1) are soaked in the solution for 10h, then the precursor is obtained by vacuum filtration, and the precursor is placed in a forced air drying oven at 50 ℃ for drying for 24 h;
(3) placing the dried precursor in a tubular furnace, carrying out two-step calcination in argon atmosphere, firstly heating to 300 ℃ at the heating rate of 1 ℃/min, carrying out heat preservation calcination for 3h, then heating to 500 ℃ at the heating rate of 1 ℃/min, carrying out heat preservation calcination for 5h, cooling to 25 ℃, and obtaining Fe3O4And (3) powder.
Fe prepared in this comparative example3O4The results of the electrochemical performance tests of the negative electrode are shown in tables 1 and 2.
FIG. 2 shows Fe in example 13O4the/C composite negative electrode material (marked as Fe in the figure)3O4Preparation of Fe from/C) and comparative example 13O4Negative electrode material (denoted as Fe in the figure)3O4) XRD diffractogram of (a). As shown, Fe prepared in example 13O4C and Fe prepared in comparative example 13O4Each diffraction peak of the material is equal to Fe3O4The diffraction peaks of the standard card (JCPDS No.88-0315) are all corresponding, and no impurity peak appears, indicating that the purity is higher. On the other hand, due to Fe in the product of example 13O4The surface-coated carbon layer is amorphous carbon, so that no obvious XRD diffraction peak exists in the product.
FIG. 3 is Fe prepared in example 13O4Composite negative electrode material/C and preparation of Fe in comparative example 13O4The negative electrode material is used as a cycle performance diagram of the negative electrode material of the sodium battery at the current density of 50mA/g (the specific method for preparing the sodium ion battery refers to the part of an electrochemical performance test method). As can be seen from the figure, Fe prepared in example 13O4the/C composite negative electrode material has good circulation stability with the current density of 50mA/g, the charge-discharge specific capacity of the material is still kept about 300mAh/g after continuous charge-discharge for 50 times, and the Fe prepared in the comparative example 13O4GranulesThe discharge specific capacity of the lithium ion battery is only about 80mAh/g after continuous charging and discharging for 50 times.
The electrochemical performance test method comprises the following steps:
and testing the conductivity by adopting a four-probe resistivity tester.
The negative electrode materials prepared in the embodiments and the comparative examples are made into sodium ion batteries or potassium ion batteries for specific capacity and cycle performance tests.
The method for manufacturing the sodium and potassium ion battery comprises the following steps: 0.24g of the obtained three-dimensional porous Fe was weighed3O4The preparation method comprises the following steps of adding 0.03g of acetylene black conductive agent into an agate mortar, grinding for 20 minutes, adding 0.6g of 5% N-methyl pyrrolidone solution dissolved with PVDF binder, continuously grinding for 10 minutes, and coating the mixture on copper foil to prepare Fe3O4a/C electrode plate. Drying the prepared electrode slice in a vacuum drying oven at 120 ℃ for 8 hours, and then assembling a sodium/potassium battery and Fe in an argon glove box3O4the/C electrode plate is a working electrode, and for a sodium battery, metal sodium is a counter electrode, and glass fiber is a diaphragm. The electrolyte solute used in the sodium battery is NaClO4The solvent was (EC/DEC1:1(W/W), 5% FEC), and the solution concentration was 1 mol/L. For potassium batteries, potassium metal is the counter electrode and glass fiber is the separator. The electrolyte solute for potassium battery is KPF6The solvent was (EC/DEC1:1(W/W)), and the solution concentration was 0.8 mol/L.
A Wuhan blue battery test system is adopted to carry out charge-discharge circulation at 25 ℃ and with the current density of 50mA/g between 0.01V and 3.0V, and the specific capacity and the circulation performance are tested. The results of the electrochemical performance tests are shown in tables 1 and 2.
Table 1 test results of sodium ion battery prepared
Table 2 test results of potassium ion battery prepared
As can be seen from the above examples and comparative examples, the present invention provides Fe3O4the/C composite negative electrode material has unique structure, large specific surface area, high charge-discharge specific capacity, high cycling stability and good conductivity, and is particularly suitable for sodium ion batteries or potassium ion batteries. Comparative example the solution according to the invention was not used, since no carbonaceous reducing agent, Fe, was added during the preparation3O4The carbon layer is not coated on the surface of the carbon layer, and the product is not a three-dimensional ordered porous material, so the product performance is inferior to that of the example 1.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (33)
1. Fe3O4the/C composite negative electrode material is characterized in that the Fe3O4the/C composite negative electrode material comprises Fe3O4Fine particles and a carbon layer coating Fe3O4Fine particles and connecting them together into a whole, the Fe3O4the/C composite negative electrode material is a porous material, and the Fe3O4In the/C composite negative electrode material, the ratio of the pore volume of macropores to the pore volume of mesopores is 2:1-4:1, and the Fe3O4the/C composite negative electrode material is a three-dimensional ordered porous material.
2. Fe according to claim 13O4the/C composite negative electrode material is characterized in that the Fe3O4the/C composite negative electrode material comprises macropores and mesopores, wherein the pore diameter of the macropores is 50-100nm, and the pore diameter of the mesopores is 5-15 nm.
3. Fe according to claim 13O4the/C composite negative electrode material is characterized in that the Fe3O4The porosity of the/C composite negative electrode material is 20-70%.
4. Fe according to claim 13O4the/C composite negative electrode material is characterized in that the Fe3O4The specific surface area of the/C composite negative electrode material is 80-120m2g-1。
5. Fe as defined in any one of claims 1 to 43O4The preparation method of the/C composite negative electrode material is characterized by comprising the following steps of:
(1) mixing a carbonaceous reducing agent solution with an iron source to obtain a reaction mixed solution;
(2) soaking template microspheres in the reaction mixed solution obtained in the step (1), and carrying out solid-liquid separation to obtain solids so as to obtain a reaction precursor;
(3) calcining the reaction precursor in the step (2) under protective atmosphere to obtain the Fe3O4the/C composite negative electrode material.
6. The method according to claim 5, wherein in the solution of the carbonaceous reductant in step (1), the carbonaceous reductant is ascorbic acid.
7. The method according to claim 5, wherein the solvent in the carbonaceous reducing agent solution of step (1) is a mixed solvent of ethylene glycol and methanol.
8. The method according to claim 7, wherein the volume ratio of the ethylene glycol to the methanol is 3:1.5 to 3: 2.5.
9. The production method according to claim 8, wherein the mixed solvent of ethylene glycol and methanol is added in a volume ratio of 3:2.
10. The method according to claim 5, wherein in the step (1), the iron source comprises iron nitrate.
11. The method according to claim 5, wherein in the step (1), the mixing is performed by stirring.
12. The method according to claim 5, wherein the mixing time in step (1) is 1 to 3 hours.
13. The method according to claim 5, wherein the concentration of the iron source in the reaction mixture of step (1) is 0.5 to 3 mol/L.
14. The method according to claim 5, wherein the molar ratio of the iron source to the carbonaceous reducing agent in the reaction mixture of step (1) is 2:1 to 13: 1.
15. The method according to claim 5, wherein the soaking time in the step (2) is 8-15 h.
16. The method according to claim 5, wherein in the step (2), the template microspheres are polystyrene microspheres.
17. The method according to claim 5, wherein in the step (2), the particle size of the template microsphere is 250-325 nm.
18. The preparation method according to claim 5, wherein in the step (2), the mass ratio of the template microspheres to the iron source is 1:1-1: 6.
19. The production method according to claim 5, wherein in the step (2), the solid-liquid separation method comprises vacuum filtration.
20. The method according to claim 5, wherein the step (2) further comprises drying the solid obtained by the solid-liquid separation.
21. The method of claim 5, wherein the protective atmosphere of step (3) comprises a nitrogen atmosphere and/or an argon atmosphere.
22. The method of claim 5, wherein step (3) further comprises: after calcination, the product obtained is cooled to 20-30 ℃.
23. The method according to claim 5, wherein the calcination in the step (3) is a two-step calcination, and the temperature of the second step calcination is higher than that of the first step calcination.
24. The method as claimed in claim 23, wherein the temperature of the first step calcination is 250-350 ℃.
25. The method of claim 24, wherein the first calcination is carried out at a temperature of 300 ℃.
26. The method of claim 23, wherein the first step calcination is carried out for a time period of 3 to 5 hours.
27. The method of claim 23, wherein the first calcination step is carried out at a temperature increase rate of 0.5 to 2 ℃/min.
28. The method as claimed in claim 23, wherein the temperature of the second-step calcination is 450-550 ℃.
29. The method of claim 28, wherein the second calcination step is carried out at a temperature of 500 ℃.
30. The method of claim 23, wherein the second calcination step is carried out for a time period of 3 to 5 hours.
31. The method of claim 23, wherein the second calcination step is carried out at a temperature increase rate of 0.5 to 2 ℃/min.
32. The method for preparing according to claim 5, characterized in that it comprises the following steps:
(1) stirring and mixing an ascorbic acid solution and ferric nitrate for 1-3 hours to obtain a reaction mixed solution;
wherein the concentration of the iron source is 0.5-3mol/L, the molar ratio of the iron source to the carbonaceous reducing agent is 2:1-13:1, and the solvent in the ascorbic acid solution is a mixed solvent consisting of ethylene glycol and methanol in a volume ratio of 3: 2;
(2) soaking polystyrene microspheres in the reaction mixed solution obtained in the step (1) for 8-15h, vacuum-filtering to obtain a solid, and drying the solid to obtain a reaction precursor;
wherein the particle size of the polystyrene microsphere is 250-325nm, and the mass ratio of the polystyrene microsphere to the iron source is 1:1-1: 6;
(3) and (3) calcining the reaction precursor in the step (2) in a protective atmosphere in two steps, wherein in the first step, the temperature is increased to 300 ℃ at the heating rate of 0.5-2 ℃/min, then the calcination is carried out for 3-5h in a heat preservation way, in the second step, the temperature is increased to 500 ℃ at the heating rate of 0.5-2 ℃/min, then the calcination is carried out for 3-5h in a heat preservation way, and then the calcination is cooled to 20-30 ℃ to obtain the Fe3O4the/C composite negative electrode material.
33. Fe as defined in any one of claims 1 to 43O4Use of a/C composite anode material, characterized in that the Fe3O4the/C composite negative electrode material is used for a sodium ion battery or a potassium ion battery.
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