CN114639815A - Preparation method of sodium ion battery negative electrode material, negative electrode sheet and sodium ion battery - Google Patents

Preparation method of sodium ion battery negative electrode material, negative electrode sheet and sodium ion battery Download PDF

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CN114639815A
CN114639815A CN202210366725.7A CN202210366725A CN114639815A CN 114639815 A CN114639815 A CN 114639815A CN 202210366725 A CN202210366725 A CN 202210366725A CN 114639815 A CN114639815 A CN 114639815A
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carbon
negative electrode
ion battery
mixture
sodium
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陈浩峰
陈世勇
梁向龙
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Dongguan Wotaitong New Energy Co ltd
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Dongguan Wotaitong New Energy Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/049—Manufacturing of an active layer by chemical means
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5805—Phosphides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes

Abstract

The invention provides a preparation method of a sodium ion battery negative electrode material, a negative electrode sheet and a sodium ion battery, wherein the method comprises the following steps: adding the carbon nano tube into an ethanol solution, and performing ultrasonic treatment to obtain a first sample; FeCl is added3、CH4N2O and a carbon source are sequentially added into the first sample and uniformly stirredThen putting the mixture into a closed container for synthesis reaction at 180 ℃, and cooling, centrifuging and drying a product after the synthesis reaction is finished to obtain a first mixture; mixing the first mixture with NaH2PO2Putting the mixture into an inert gas atmosphere, and heating the mixture to a preset temperature according to a specified speed so as to ensure that the first mixture and NaH2PO2Carrying out sufficient phosphorization reaction to obtain a sodium ion battery cathode material, namely a carbon nano tube/iron phosphide/carbon composite material; the negative electrode material prepared by the preparation method of the sodium-ion battery negative electrode material provided by the embodiment of the invention has good structural stability, can bear heavy current charge and discharge, and has good long-term cycle characteristics.

Description

Preparation method of sodium ion battery negative electrode material, negative electrode sheet and sodium ion battery
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of batteries, in particular to a preparation method of a negative electrode material of a sodium-ion battery, a negative electrode plate and the sodium-ion battery.
[ background of the invention ]
The lithium battery has the advantages of long cycle life, energy conservation, environmental protection, no pollution, low maintenance cost, complete charge and discharge, light weight and the like, and compared with the lithium element in the lithium battery, the sodium element has richer resources, low cost and wide distribution, and the sodium element and the lithium element belong to the same main group of the periodic table of elements and have similar physical and chemical properties. In view of the current shortage of lithium resources, sodium ion batteries are expected to replace lithium ion batteries.
The working principle of the sodium ion battery is similar to that of the lithium ion battery, sodium ions are separated from one end of a positive electrode and embedded into a negative electrode material in the charging process, and the charging capacity is closely related to the quantity of the embedded sodium ions, namely, the more the embedded sodium ions are, the higher the charging capacity is. During the discharge process, sodium ions embedded in the negative electrode material are extracted and move back to the positive electrode. However, since the radius of sodium ions is larger than that of lithium ions, conventional lithium ion battery negative electrode materials cannot be used as negative electrode materials for sodium ion batteries.
In recent years, research on negative electrode materials for sodium ion batteries has been focused mainly on carbon materials and some non-carbon materials (metal and oxide materials, alloy materials, phosphorus, and the like). Although the non-carbon material has high storage capacity, the non-carbon material has the problems of low conductivity, large volume change, easy pulverization and the like, and cannot meet the long-term use of the sodium ion battery. The existing carbon material has the advantages of rich resources, simple preparation and the like, but has the problems of insufficient cycling stability, low specific capacity and the like, and can not meet the requirement of long-term use of the sodium ion battery.
In view of the above, it is actually necessary to provide a novel method for preparing a negative electrode material of a sodium ion battery, a negative electrode sheet and a sodium ion battery to overcome the above defects.
[ summary of the invention ]
The invention aims to provide a preparation method of a sodium ion battery negative electrode material, a negative electrode piece and a sodium ion battery.
In order to achieve the above object, in a first aspect, the present invention provides a method for preparing a negative electrode material of a sodium ion battery, including the following steps:
adding the carbon nano tube into an ethanol solution, and performing ultrasonic treatment to obtain a first sample;
FeCl is added3、CH4N2Sequentially adding O and a carbon source into the first sample, uniformly stirring, putting into a closed container for synthetic reaction, and cooling, centrifuging and drying a product after the synthetic reaction is finished to obtain a first mixture;
putting the first mixture and a phosphorus source into an inert gas atmosphere, and heating to a preset temperature according to a specified speed to ensure that the first mixture and NaH2PO2And carrying out sufficient phosphating reaction to obtain the carbon nano tube/iron phosphide/carbon composite material, wherein the carbon nano tube/iron phosphide/carbon composite material is a sodium ion battery cathode material.
In a preferred embodiment, before the step of dissolving the carbon nanotubes in an ethanol solution and obtaining the first sample after the ultrasonic treatment, the preparation method further comprises:
and purifying the carbon nano tube.
In a preferred embodiment, before the step of dissolving the carbon nanotubes in an ethanol solution and obtaining the first sample after the ultrasonic treatment, the method further comprises the step of preparing the carbon nanotubes, wherein the preparation process of the carbon nanotubes comprises the following steps:
heating a carbon nanotube growth catalyst and introducing carbon source airflow to generate the carbon nanotube under the catalytic action of the carbon nanotube growth catalyst, wherein the carbon nanotube growth catalyst comprises a carbon carrier, and an active component oxide and an inactive component oxide which are uniformly distributed on the carbon carrier.
In a preferred embodiment, the method further comprises: and carrying out acid treatment on the carbon nano tube.
In a preferred embodiment, when the carbon source is glucose, the carbon nanotubes and FeCl are used3、CH4N2The weight ratio of O to glucose is 1: 20: 10: 10.
in a preferred embodiment, the FeCl is3、CH4N2And O and a carbon source are sequentially added into the first sample, and are stirred uniformly and then are put into a closed container for synthetic reaction, wherein the synthetic reaction comprises the following steps:
FeCl is added3、CH4N2And sequentially adding O and a carbon source into the first sample, uniformly stirring, putting into a polytetrafluoroethylene reaction kettle, and continuing for 12 hours at the temperature of 180 ℃ to perform a synthetic reaction.
In a preferred embodiment, the specified rate is 1-3 ℃/min and the preset temperature is 350-450 ℃.
In a preferred embodiment, the step of placing the first mixture and the phosphorus source into an inert gas atmosphere, and raising the temperature to a preset temperature at a specified rate to allow the first mixture and the phosphorus source to perform sufficient phosphating reaction to obtain the carbon nanotube/iron phosphide/carbon composite material comprises:
and putting the first mixture and a phosphorus source into an inert gas atmosphere, heating to a preset temperature at a specified rate, and keeping the constant temperature for 1-2 hours when the temperature is raised to the preset temperature, so that the first mixture and the phosphorus source are subjected to sufficient phosphating reaction to obtain the carbon nano tube/iron phosphide/carbon composite material.
In a second aspect, the invention further provides a negative electrode sheet, and the negative electrode sheet comprises the sodium-ion battery negative electrode material prepared by the preparation method of the sodium-ion battery negative electrode material.
In a third aspect, the invention further provides a sodium ion battery, which comprises the negative plate.
Compared with the prior art, the preparation method of the sodium ion battery cathode material, the cathode sheet and the sodium ion battery provided by the invention have the advantages that the carbon nano tube is added into the ethanol solution, and a first sample is obtained after ultrasonic treatment; then FeCl is added3、CH4N2Sequentially adding O and a carbon source into the first sample, uniformly stirring, putting the second sample into a closed container for synthetic reaction, and cooling, centrifuging and drying a product after the synthetic reaction is finished to obtain a first mixture; finally, the first mixture and the phosphorus source are placed in an inert gas atmosphere, and the temperature is raised to a preset temperature according to a specified speed, so that the first mixture and the phosphorus source are subjected to sufficient phosphating reaction, and a sodium ion battery cathode material, namely a carbon nano tube/iron phosphide/carbon composite material, is obtained; the negative electrode material prepared by the preparation method of the sodium-ion battery negative electrode material provided by the embodiment of the invention has good structural stability, can bear heavy current charge and discharge, and has good long-term cycle characteristics.
[ description of the drawings ]
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a flow chart of a method for preparing a negative electrode material of a sodium-ion battery provided by the invention;
FIG. 2 is a Raman diagram of the negative electrode material of the sodium-ion battery provided by the invention;
fig. 3 is a rate performance diagram of the negative electrode sheet provided by the invention.
[ detailed description ] embodiments
In order to make the objects, technical solutions and advantageous effects of the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and the detailed description. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
It is also to be understood that the terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the specification of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It should be further understood that the term "and/or" as used in this specification and the appended claims refers to and includes any and all possible combinations of one or more of the associated listed items.
As shown in fig. 1, the present invention provides a method for preparing a sodium ion negative electrode material, which may include the following steps 101-104.
Step 101, adding a carbon nano tube into an ethanol solution, and performing ultrasonic treatment to obtain a first sample;
step 102, FeCl3(iron chloride), CH4N2Adding O (urea) and a carbon source into the first sample in sequence, stirring uniformly, putting into a closed container for synthetic reaction, and cooling, centrifuging and drying a product after the synthetic reaction is finished to obtain a first mixture;
103, putting the first mixture and a phosphorus source into an inert gas atmosphere, and heating to a preset temperature at a specified speed to perform sufficient phosphating reaction on the first mixture and the phosphorus source to obtain a carbon nano tube/iron phosphide/carbon composite material, wherein the carbon nano tube/iron phosphide/carbon composite material is a sodium ion battery cathode material.
According to the preparation method of the sodium ion battery cathode material provided by the embodiment of the invention, the carbon nano tube is added into an ethanol solution, and a first sample is obtained after ultrasonic treatment; FeCl is added3、CH4N2O and a carbon source are sequentially added into the first sample, and the mixture is placed after being uniformly stirredPutting the mixture into a closed container for synthetic reaction, and cooling, centrifuging and drying a product after the synthetic reaction is finished to obtain a first mixture; putting the first mixture and a phosphorus source into an inert gas atmosphere, and heating to a preset temperature at a specified rate to perform sufficient phosphating reaction on the first mixture and the phosphorus source to obtain a sodium ion battery cathode material, namely a carbon nano tube/iron phosphide/carbon composite material; the negative electrode material prepared by the preparation method of the sodium-ion battery negative electrode material provided by the embodiment of the invention has good structural stability, can bear heavy current charge and discharge, and has good long-term cycle characteristics.
The preparation method of the negative electrode material of the sodium-ion battery is further exemplified below.
In step 101, a carbon nanotube is added to an ethanol solution, and a first sample is obtained after ultrasonic treatment.
In the step, the carbon nano tubes can be added into the ethanol solution and dissolved for 30min by ultrasonic, so that the carbon nano tubes are uniformly dispersed in the ethanol solution.
In order to improve the purity of the carbon nanotubes, in some alternative embodiments of the present invention, the carbon nanotubes need to be pretreated before step 101.
Illustratively, the carbon nanotubes can be purified by washing the carbon nanotubes to remove impurities on the surface of the carbon nanotubes. For example, the carbon nanotubes may be washed with an acetone solution and then dried to purify the carbon nanotubes.
Illustratively, the carbon nanotubes may be purified by subjecting the carbon nanotubes to a high temperature heat treatment. For example, the carbon nanotubes may be purified by exposing the carbon nanotubes to a temperature of 3000 ℃ to vaporize the metal catalyst remaining in the carbon nanotubes.
Illustratively, the carbon nanotubes can be purified by the action of magnetic and electric fields. For example, the carbon nanotubes may be purified by placing the carbon nanotubes in an electromagnetic wave device, introducing an inert gas, and electromagnetically acting for a certain time under the conditions of a specific magnetic field strength and an electromagnetic frequency to cause the residual metal impurities in the carbon nanotubes to fall off.
In some optional embodiments of the present invention, before step 101, the carbon nanotubes need to be pretreated, which may also refer to a specific carbon nanotube preparation method, so as to improve the purity of the carbon nanotubes.
Illustratively, the carbon nanotube preparation process includes: the carbon nanotube growth catalyst is heated and simultaneously introduced with carbon source gas flow to generate the carbon nanotubes under the catalytic action of the carbon nanotube growth catalyst, wherein the carbon nanotube growth catalyst comprises a carbon carrier, and an active component oxide and an inactive component oxide which are uniformly distributed on the carbon carrier, and the carbon source gas flow can use ethylene.
In the example, the carbon nanotube is generated by catalyzing the carbon nanotube growth catalyst with the carbon carrier, and compared with the conventional method for generating the carbon nanotube by catalyzing with the metal catalyst, the method can reduce impurities in the carbon nanotube and improve the purity of the carbon nanotube.
It should be noted that, in some alternative embodiments, the carbon nanotubes may be replaced by a hard carbon material prepared from a biomass material and having an interlayer distance of 0.36-0.4 nm. Illustratively, the method comprises the steps of cleaning fallen leaves with deionized water as a raw material, drying, carbonizing in a tubular furnace in a nitrogen atmosphere, heating to a set temperature from room temperature at a heating rate of 3-6 ℃/min, keeping the temperature for more than 2 hours to fully carbonize the fallen leaves, taking out and fully grinding a carbonized product, cleaning with 3mol/L diluted hydrochloric acid, adjusting the pH to be neutral with deionized water, and drying to obtain the hard carbon material for replacing the carbon nano tube. Wherein the set temperature range is 1000-1400 ℃, and the experiment proves that 71 percent of interlayer spacing in the hard carbon material obtained by carbonization in the temperature range of 1000-1400 ℃ is within the range of 0.36-0.4 nm.
The preparation method of the hard carbon material in the example has a simple preparation process, and ensures that the prepared hard carbon material has a large proportion and is suitable for being used as a negative electrode material of a sodium-ion battery; and the hard carbon material prepared from the biomass material is adopted to replace the carbon nano tube, so that the material cost can be reduced.
In some optional embodiments of the present invention, the pretreating the carbon nanotubes further includes: the carbon nano tube is subjected to acid treatment, so that a large number of defects and oxygen-containing surface functional groups are generated on the surface of the carbon nano tube, and the efficiency of subsequent reaction is improved.
For example, the carbon nanotubes may be added to a mixed solution of hydrogen peroxide and nitric acid to react, and then washed and dried. Wherein, the volume ratio of the hydrogen peroxide to the nitric acid in the mixed solution of the hydrogen peroxide and the nitric acid can be 2: 1; the reaction time and temperature may be set empirically, for example, the reaction time may be 2 hours and the reaction temperature may be 60 ℃.
In step 102, FeCl is applied3、CH4N2And sequentially adding O and a carbon source into the first sample, uniformly stirring, putting into a closed container for synthetic reaction, and cooling, centrifuging and drying a product after the synthetic reaction is finished to obtain a first mixture.
Wherein the carbon source can be one of glucose, sucrose and fructose. The synthesis method adopted in the step can grow active particles Fe on the surface of the carbon nano tube3O4(ferroferric oxide), the carbon source can also play the role of a reaction guiding agent in the step so as to ensure that active particles Fe are obtained3O4The dispersion is uniform.
Illustratively, the carbon source is glucose, and the carbon nanotube and FeCl are obtained in the above steps3、CH4N2The weight ratio of O to glucose is 1: 20: 10: 10. for example, 0.05g of carbon nanotubes can be taken and put into ethanol solution, dissolved by ultrasound for 30min, and then 1g of FeCl can be added30.5g of CH4N2O and 0.5g of glucose were sequentially added to the first sample to carry out the treatment of the subsequent steps.
Illustratively, the foregoing will FeCl3、CH4N2O and a carbon source are sequentially added into the first sample, and the mixture is put into a closed container after being uniformly stirredThe synthesis reaction can comprise:
FeCl is added3、CH4N2And sequentially adding O and a carbon source into the first sample, uniformly stirring, then putting into a polytetrafluoroethylene reaction kettle, and continuing for 12 hours at a specific temperature to perform a synthetic reaction.
Wherein, FeCl is added3、CH4N2And in the process of stirring the first sample after the step O and the carbon source, the first sample can be stirred for 30min by magnetic force, so that the stirring is ensured to be uniform. And (3) putting the uniformly stirred sample into a polytetrafluoroethylene reaction kettle, then putting the polytetrafluoroethylene reaction kettle into a heater, controlling the temperature to stably rise to a specific temperature, and keeping the temperature constant for 12 hours. Wherein the specific temperature may be 180 ℃. According to the embodiment of the invention, the active particle Fe can be grown on the surface of the carbon nano tube by heating once3O4Convenient operation and high growth efficiency.
And after the synthesis reaction is finished and the polytetrafluoroethylene reaction kettle is cooled to room temperature, taking out the precipitate in the polytetrafluoroethylene reaction kettle, separating by using a centrifugal machine, washing by using distilled water and ethanol respectively, and then drying in a drying box to obtain a first mixture.
In step 103, the first mixture and the phosphorus source are placed in an inert gas atmosphere, and the temperature is raised to a preset temperature according to a specified rate, so that the first mixture and the phosphorus source perform a sufficient phosphating reaction, and a carbon nanotube/iron phosphide/carbon composite material is obtained, wherein the carbon nanotube/iron phosphide/carbon composite material is a sodium ion battery negative electrode material.
The inert gas may be helium, neon, argon, etc., although in some embodiments, nitrogen may also be used, i.e., the first mixture and the phosphorus source are placed in a nitrogen atmosphere.
And under the protection of nitrogen or inert gas, carrying out heat treatment on the first mixture and the phosphorus source to ensure that the first mixture and the phosphorus source carry out sufficient phosphating reaction to obtain the carbon nano tube/iron phosphide/carbon composite material. The phosphorus source is NaH2PO2(sodium hypophosphite) as an example, NaH with increasing reaction temperature2PO2Can be used forDecompose and release H3P (phosphine) gas, releasing H3P gas and Fe in the first mixture3O4Reaction takes place, Fe3O4Is reduced into FeP (iron phosphide), and simultaneously aromatic compounds generated by the polymerization of the carbon source in the first mixture are continuously carbonized and coated on the surface of the FeP under the action of high temperature to obtain the carbon nano tube/iron phosphide/carbon composite material with carbon-coated nano particles anchored on the carbon nano tube, namely CNT/FeP/C. The contents of FeP, the elastic carbon shell (i.e. the carbon coated on the surface of FeP) and the carbon nano tube in the carbon nano tube/iron phosphide/carbon composite material are respectively 58-60%, 4.8-5.2% and 34.8-37.2%. In a specific example, the contents of the FeP, the elastic carbon shell (i.e., the carbon coated on the surface of the FeP), and the carbon nanotube in the carbon nanotube/iron phosphide/carbon composite material are 59.3%, 5%, and 35.7%, respectively.
To control the degree of phosphating, the Fe in the first mixture is3O4Complete reduction to FeP, the above specified rate can be controlled at 1-3 deg.C/min, such as 2 deg.C/min; the predetermined temperature may be controlled to be 350-450 deg.C, such as 400 deg.C. In addition, the first mixture and NaH can be kept constant for 1-2h when the temperature is raised to the preset temperature2PO2Sufficient phosphating reaction is performed.
Illustratively, in step 103 above, the first mixture may be placed into a tube furnace and NaH may be added2PO2Placed at the upper tuyere of flowing inert gas/nitrogen, NaH as the temperature slowly increases2PO2Decomposed and released H3And P gas flows to the position of the first mixture along with the flowing inert gas/nitrogen to perform a phosphating reaction with the first mixture.
The sodium ion battery cathode material prepared by the preparation method of the sodium ion battery cathode material provided by the embodiment is a carbon nanotube/iron phosphide/carbon composite material, and the carbon nanotube in the sodium ion battery cathode material is used as a framework, so that the monodispersity of an active substance can be maintained, and the stress caused by particle agglomeration can be reduced. Meanwhile, the elastic carbon shell coated on the surface of the FeP can relieve mechanical stress caused by volume expansion/contraction in the process of sodium ion embedding/removing, and can be used as a protective layer to avoid direct contact of active substances and electrolyte, so that corrosion is reduced.
In addition, the prepared sodium ion battery cathode material is subjected to Raman test, and the test result is shown in figure 2 and is positioned at 1350cm-1The sum of the left and right positions of 1580cm-1The left and right positions have two distinct peaks, corresponding to sp2 hybridized disordered carbon of the D band and graphitized carbon of the G band, respectively. The strength ratio of the disordered carbon to the graphitized carbon is about 0.8, which shows that highly-crystallized carbon exists in the prepared negative electrode material of the sodium-ion battery, provides a foundation for the rapid transfer of electrons, is beneficial to the rapid transfer of electrons, and realizes excellent rate capability.
The invention also provides a negative plate which comprises the carbon nano tube/iron phosphide/carbon composite material prepared by the embodiment.
The invention also provides a sodium-ion battery, which comprises the negative electrode sheet in the embodiment.
In addition, a charge-discharge characteristic test is carried out on the negative plate made of the carbon nano tube/iron phosphide/carbon composite material prepared by the preparation method, specifically, a voltage of 0.01-3V and a current density of 0.5Ag are adopted-1And (3) carrying out charge-discharge characteristic test on the negative plate to obtain: the first charging specific capacity is 700mAhg-1And a specific discharge capacity of 425mAhg-1The corresponding initial coulombic efficiency was 60.7%, the large initial capacity loss was due to irreversible Na2O and SEI layer (solid electrolyte interphase) formation, can be understood as a normal phenomenon. After several rounds of activation reaction, the coulomb efficiency corresponding to the charge and discharge of the negative electrode sheet is close to 100% basically from the fifth round, which indicates that the negative electrode sheet has good reversible characteristics.
In addition, the rate performance test of the negative electrode sheet made of the carbon nanotube/iron phosphide/carbon composite material prepared as described above was also conducted to obtain the results shown in FIG. 3, that is, at 0.5 to 8Ag-1Under the current density of (1), in the voltage range of 0.01-3V, along with the gradual increase of the current, the capacity of the negative plate is gradually increasedDecreasing but the overall capacity retention is higher. At a current density of 1Ag-1And 2Ag-1In the case of (1), the negative electrode sheet exhibited 364mAhg-1And 340mAhg-1The corresponding capacity loss is 24mAhg when the current is doubled-1The capacity retention rate was 93%. When the current density is increased to 5Ag-1In this case, the negative plate can still be maintained at 285mAhg-1The reversible capacity of (a). When the current returns to 0.5Ag again-1When the specific capacity is equal to 386mAhg-1And maintain a stable specific capacity over subsequent cycles. The negative plate can bear large current charge and discharge, and is more beneficial to the migration of sodium ions and electrons.
Meanwhile, the cycle performance test is carried out on the negative plate made of the carbon nano tube/iron phosphide/carbon composite material obtained by the preparation method, and the following results are obtained: in 3Ag-1Under the current density of the anode plate, the anode plate has no obvious capacity loss in the whole circulation process, and can still maintain 321mAhg after 1200 cycles-1The reversible specific capacity is high, the coulomb efficiency in the circulation process is close to 100 percent, and the cathode plate has excellent long-term circulation characteristics.
According to the preparation method of the sodium ion battery cathode material provided by the embodiment of the invention, the carbon nano tube is added into an ethanol solution, and a first sample is obtained after ultrasonic treatment; FeCl is added3、CH4N2Sequentially adding O and a carbon source into the first sample, uniformly stirring, putting into a closed container for carrying out synthesis reaction at 180 ℃, and cooling, centrifuging and drying a product after the synthesis reaction is finished to obtain a first mixture; mixing the first mixture with NaH2PO2Putting the mixture into an inert gas atmosphere, and heating the mixture to a preset temperature according to a specified speed so as to ensure that the first mixture and NaH2PO2Carrying out sufficient phosphorization reaction to obtain a sodium ion battery cathode material, namely a carbon nano tube/iron phosphide/carbon composite material; the negative electrode material prepared by the preparation method of the sodium-ion battery negative electrode material provided by the embodiment of the invention has good structural stability, can bear heavy current charge and discharge, and has good long-term cycle characteristics. By usingThe negative plate made of the carbon nanotube/iron phosphide/carbon composite material prepared by the embodiment of the invention has good reversible characteristics, excellent rate capability and excellent long-term cycle characteristics as well as a sodium ion battery.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (10)

1. A preparation method of a sodium-ion battery negative electrode material is characterized by comprising the following steps:
adding the carbon nano tube into an ethanol solution, and performing ultrasonic treatment to obtain a first sample;
FeCl is added3、CH4N2Sequentially adding O and a carbon source into the first sample, uniformly stirring, putting into a closed container for synthetic reaction, and cooling, centrifuging and drying a product after the synthetic reaction is finished to obtain a first mixture;
and putting the first mixture and a phosphorus source into an inert gas atmosphere, and heating to a preset temperature at a specified rate to perform sufficient phosphating reaction on the first mixture and the phosphorus source to obtain the carbon nano tube/iron phosphide/carbon composite material, wherein the carbon nano tube/iron phosphide/carbon composite material is a sodium ion battery cathode material.
2. The method for preparing the negative electrode material of the sodium-ion battery as claimed in claim 1, wherein before the step of dissolving the carbon nanotubes in an ethanol solution and obtaining the first sample after ultrasonic treatment, the method further comprises:
and purifying the carbon nano tube.
3. The method for preparing the negative electrode material of the sodium-ion battery as claimed in claim 1, wherein before the step of dissolving the carbon nanotubes in the ethanol solution and obtaining the first sample after the ultrasonic treatment, the method further comprises the step of preparing the carbon nanotubes, and the preparation process of the carbon nanotubes comprises the following steps:
heating a carbon nanotube growth catalyst and introducing carbon source airflow to generate the carbon nanotube under the catalytic action of the carbon nanotube growth catalyst, wherein the carbon nanotube growth catalyst comprises a carbon carrier, and an active component oxide and an inactive component oxide which are uniformly distributed on the carbon carrier.
4. The method for preparing the negative electrode material for the sodium-ion battery according to any one of claims 1 to 3, further comprising:
and carrying out acid treatment on the carbon nano tube.
5. The method for preparing the negative electrode material of the sodium-ion battery as claimed in claim 1, wherein when the carbon source is glucose, the carbon nanotube and FeCl are used3、CH4N2The weight ratio of O to glucose is 1: 20: 10: 10.
6. the method for preparing the negative electrode material of the sodium-ion battery of claim 5, wherein FeCl is added3、CH4N2And O and a carbon source are sequentially added into the first sample, and are stirred uniformly and then are put into a closed container for synthetic reaction, wherein the synthetic reaction comprises the following steps:
FeCl is added3、CH4N2And sequentially adding O and a carbon source into the first sample, uniformly stirring, putting into a polytetrafluoroethylene reaction kettle, and continuing for 12 hours at the temperature of 180 ℃ to perform a synthetic reaction.
7. The method for preparing the negative electrode material of the sodium-ion battery as claimed in claim 1, wherein the designated rate is 1-3 ℃/min, and the preset temperature is 350-450 ℃.
8. The negative electrode of the sodium-ion battery of claim 1The preparation method of the material is characterized in that the first mixture and the phosphorus source are put into an inert gas atmosphere and heated to a preset temperature according to a specified speed, so that the first mixture and NaH are mixed2PO2Carrying out sufficient phosphating reaction to obtain the carbon nano tube/iron phosphide/carbon composite material, which comprises the following steps:
and putting the first mixture and a phosphorus source into an inert gas atmosphere, heating to a preset temperature at a specified rate, and keeping the constant temperature for 1-2 hours when the temperature is raised to the preset temperature, so that the first mixture and the phosphorus source are subjected to sufficient phosphating reaction to obtain the carbon nano tube/iron phosphide/carbon composite material.
9. A negative electrode sheet, characterized in that the negative electrode sheet comprises the carbon nanotube/iron phosphide/carbon composite material prepared by the method for preparing the sodium-ion battery negative electrode material as recited in any one of claims 1 to 8.
10. A sodium ion battery comprising the negative electrode sheet according to claim 9.
CN202210366725.7A 2022-04-08 2022-04-08 Preparation method of sodium ion battery negative electrode material, negative electrode sheet and sodium ion battery Withdrawn CN114639815A (en)

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