CN113381008B - Preparation method and application of surface fluorinated nano ferroferric oxide lithium ion battery cathode material - Google Patents
Preparation method and application of surface fluorinated nano ferroferric oxide lithium ion battery cathode material Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a surface fluorinated nano ferroferric oxide lithium ion battery cathode material3O4The precursor, then the material synthesized by surface modification with ammonium fluoride has a better nano spherical structure, the particle size of the material is between 200 and 250nm, the material has excellent electrochemical performance, and after the material is assembled into a battery, the capacity after the material is cycled for 300 times is 1382mAh/g under the current density of 0.5A/g; in addition, the material has excellent high-rate performance and extraordinary long cycle performance, and still has reversible capacity of 796mAh/g after 2000 cycles at the current density of 10A/g; under the high current density of 20A/g, after the circulation for 2000 times, 352mAh/g of reversible specific capacity still exists.
Description
The technical field is as follows:
the invention relates to the technical field of new energy materials, in particular to a preparation method and application of a surface fluorinated nano ferroferric oxide lithium ion battery cathode material.
The background art comprises the following steps:
under the influence of the large use of fossil fuels, global climate change and environmental pollution are becoming more serious, and new energy automobiles driven by lithium ion batteries are developed vigorously. Although manufacturers have introduced electric vehicles with a variety of range, consumer acceptance of pure electric vehicles is still limited. Anxiety of driving mileage, long charging waiting time and the number of charging stations are main factors restricting the popularization of the electric automobile, wherein the quick charging capacity of the battery becomes an important performance index of the electric automobile. However, the capacity and rate performance of many anode materials tend to be either poor or not compatible. Graphite has been widely used in commercial lithium ion battery cathode materials, but the capacity and rate capability of graphite are difficult to meet the requirements of power batteries. The transition metal compound shows excellent capacity performance when being used as a lithium ion battery cathode material, and becomes a potential substitute material of commercial graphite. The main problems of the transition metal compound as the negative electrode are a large volume change during charge and discharge and poor electrical conductivity, and thus the cycle life of the battery is poor. To alleviate these problems, the material is typically reduced to nanometer size and carbon coated to increase the conductivity and buffer the volume change of the material. However, how to achieve the stability of the material under high-rate charge and discharge conditions is a great challenge.
Ferroferric oxide (Fe)3O4) Is a metal oxide with low cost, abundant reserves and no harm to the environment. The main advantages of the ferroferric oxide used as the lithium ion battery cathode material are that the ferroferric oxide has higher theoretical specific capacity (926 mAh/g) and relatively high safe lithium intercalation potential (0.8V). Therefore, research and preparation of novel Fe with high performance, easy preparation and low cost3O4The lithium ion battery cathode material not only meets the requirements of the current social development, but also has obvious economic benefit and strategic significance. To increase Fe3O4The electrochemical properties of the metal and the nonmetal are modified by a plurality of methods, such as metal and nonmetal doping, carbon coating, and shape and size adjustment, and further research is needed.
The invention content is as follows:
the invention aims to provide a preparation method and application of a surface fluorinated nano ferroferric oxide lithium ion battery cathode material3O4Surface fluorination modification is carried out, so that the electrochemical performance is improved, and the obtained material has high performanceThe specific capacity, the high rate performance and the long-circulating stable electrochemical activity are realized, the specific capacity is still up to 352mAh/g after the circulation for 2000 times under the current density of 20A/g, under the condition, the full charge only needs several minutes, the preparation cost is low, the method is suitable for industrial production and is easy to scale.
The invention is realized by the following technical scheme:
a preparation method of a surface fluorinated nano ferroferric oxide lithium ion battery cathode material comprises the following steps:
a. completely dissolving soluble ferric salt in a solvent, adding a precipitator, uniformly stirring, carrying out solvothermal reaction on the mixed solution at the temperature of 160 ℃ for 8-24h, carrying out centrifugal separation, cleaning and drying after the reaction, and collecting a ferroferric oxide precursor powder sample, wherein the molar ratio of iron in the soluble ferric salt to the precipitator is 1: 1-6;
b. b, adding the ferroferric oxide precursor powder sample obtained in the step a into NH4In the aqueous solution of F, a ferroferric oxide precursor powder sample and NH4The molar ratio of F is 1:3-15, stirring and reacting for 4-36h at room temperature, centrifugally separating after reacting, cleaning, drying and collecting a powdery sample;
c. and c, calcining the sample obtained in the step b for 2-6h at the temperature of 400-600 ℃ under the protective atmosphere to obtain the black nano ferroferric oxide composite material with the surface fluorinated and modified.
Preferably, the soluble iron salt is one or a mixture of ferric chloride, ferric acetylacetonate, ferric nitrate or crystalline hydrates thereof.
Preferably, the precipitant is one or more of urea, sodium hydroxide, and potassium hydroxide.
Preferably, the solvent of step a is one or a mixture of ethylene glycol, isopropanol and glycerol.
And c, the protective atmosphere in the step c is nitrogen or argon.
The method comprises the following steps of (a) centrifugally separating, cleaning, drying and collecting a ferroferric oxide precursor powder sample: washing the centrifugal separation sample powder with ethanol for 2-4 times, then putting the sample powder into a vacuum drying oven, drying the sample powder for 4-24 hours at the temperature of 40-100 ℃, and collecting the powder sample.
The steps of the centrifugal separation, the cleaning, the drying and the collection of the powdery sample in the step b are as follows: and washing the centrifugal separation sample powder with deionized water for 2-4 times, then washing with ethanol for 1-4 times, then putting into a vacuum drying oven, drying for 4-24h at 40-100 ℃, and then collecting the powdery sample.
The invention also protects the application of the surface fluorinated nano ferroferric oxide lithium ion battery cathode material obtained by the preparation method in a lithium ion battery cathode.
The invention has the following beneficial effects:
the invention adds precipitator into ferric salt solution to synthesize subminiature nano Fe3O4And performing surface modification on the precursor by using ammonium fluoride, and carbonizing the precursor in an inert atmosphere to form the microporous carbon layer. The material synthesized by the invention has a good nano spherical structure, the particle size of the material is between 200 and 250nm, so the material has excellent electrochemical performance, high specific capacity, high rate performance and long-cycle stable electrochemical activity, and after the material is assembled into a battery, the capacity of the battery is 1382mAh/g after 300 cycles under the current density of 0.5A/g; in addition, the material has excellent high-rate performance and extraordinary long cycle performance, and still has reversible capacity of 796mAh/g after 2000 cycles at the current density of 10A/g; under the condition of large current density of 20A/g, after 2000 times of circulation, the reversible specific capacity of 352mAh/g can still be obtained. Under the condition, the full charge only needs a few minutes, the preparation cost is low, and the method is suitable for industrial production and easy for scale production.
Description of the drawings:
FIG. 1 is an XRD pattern of a fluorine-modified nano ferroferric oxide composite material prepared in example 1.
FIG. 2 is a TEM image of the fluorine-modified nano ferroferric oxide composite material prepared in example 1.
FIG. 3 is a graph of the cycle performance of the fluorine-modified nano ferroferric oxide composite material prepared in example 1 under different current densities.
FIG. 4 is a long cycle performance graph of the fluorine-modified nano ferroferric oxide composite material prepared in example 1 at a current density of 20A/g.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1: fluorine modified nano ferroferric oxide composite material for preparing lithium ion battery cathode
1.0811g of ferric chloride hexahydrate was added to 90mL of ethylene glycol at room temperature, and the mixture was stirred and dissolved at a medium-high speed of a magnetic stirrer for 0.5 hour. After complete dissolution, 1.8g of urea was added to the above solution and stirred well. Adding the obtained uniform solution into a 150mL stainless steel autoclave, reacting for 16 hours at 200 ℃, centrifugally separating the sample after reaction, washing for 4 times by using ethanol to obtain a precipitate, putting the precipitate into a vacuum drying oven, drying for 8 hours at 60 ℃, and collecting a powdery nano ferroferric oxide sample. 0.57620g of NH were weighed4And F, adding the mixture into 100mL of aqueous solution, stirring for half an hour, adding 0.2g of dried powdered ferroferric oxide sample, magnetically stirring for 24 hours at room temperature, and respectively centrifugally washing for 3 times by using deionized water and absolute ethyl alcohol to obtain black precipitate. Drying the obtained precipitate in a vacuum drying oven at 60 deg.C for 8 hr to obtain final product, N at 500 deg.C2Calcining for 3 hours in an inert atmosphere at the heating rate of 1 ℃/min to obtain the fluorine modified nano ferroferric oxide powder. The XRD characterization results are shown in FIG. 1, and the TEM image of the internal structure is shown in FIG. 2.
Mixing the prepared fluorine-modified nano ferroferric oxide composite material with a binder PVDF and a conductive agent Super-P according to the weight ratio of 7: 1.5: 1.5, adding a proper amount of N-methyl pyrrolidone as a solvent to prepare slurry, coating the slurry on a copper foil, performing vacuum drying and rolling punching to obtain a negative plate with the diameter of 12mm, and taking the negative plate as a research electrode. And adding a proper amount of lithium ion electrolyte, and assembling the button cell by taking the lithium sheet as a counter electrode.
And (3) measuring the performance of the electrode:
and testing the prepared experimental button cell by using a cell testing system at normal temperature to test the cycling stability performance of the cell. The cycle performance is that constant current charge and discharge tests are carried out under the heavy current density of 0.5A/g, 2A/g, 5A/g, 10A/g and 20A/g, and the charge and discharge voltage interval is 0.01-3.00V. During first charge and discharge, the prepared negative electrode material has very high lithium storage capacity (1235.6mAh/g), the specific discharge capacity is 871.0mAh/g, and the coulombic efficiency is about 100%.
Rate capability and long-term stability determination:
the test results are shown in fig. 3 and 4: the capacity of the material after circulating for 300 times is 1382mAh/g under the current density of 0.5A/g; under the current density of 10A/g, the reversible capacity of 796mAh/g is still remained after the circulation for 2000 times; under the high current density of 20A/g, after 2000 times of circulation, 352mAh/g reversible capacity still exists. This shows that the material has excellent cycle reversibility at different current densities, has higher reversible capacity at lower current densities, and has good long cycle stability at higher current densities.
Example 2
1.0811g of ferric chloride hexahydrate was added to 90mL of ethylene glycol at room temperature, and the mixture was stirred at a medium-high speed of a magnetic stirrer for 0.5 hour to dissolve the compound. After complete dissolution, 1.8g of urea was added to the above solution and stirred well. Adding the obtained uniform solution into a 150mL stainless steel autoclave, reacting for 16 hours at 200 ℃, centrifugally separating the sample after reaction, washing for 4 times by using ethanol to obtain a precipitate, putting the precipitate into a vacuum drying oven, drying for 8 hours at 60 ℃, and collecting a powdery nano ferroferric oxide sample. 0.2880g of NH were weighed4And F, adding the mixture into 100mL of aqueous solution, stirring for half an hour, adding 0.2g of dried powdery ferroferric oxide sample, magnetically stirring for 24 hours at room temperature, and respectively centrifugally washing for 3 times by using deionized water and absolute ethyl alcohol to obtain black precipitates. Drying the obtained precipitate in a vacuum drying oven at 60 deg.C for 8 hr to obtain final product, N at 500 deg.C2Calcining for 3 hours in an inert atmosphere at the heating rate of 1 ℃/min to obtain the fluorine modified nano ferroferric oxide powder.
Mixing the prepared fluorine-modified nano ferroferric oxide powder with a binder PVDF and a conductive agent Super-P according to the weight ratio of 7: 1.5: 1.5, adding 1.5mL of N-methyl pyrrolidone as a solvent to prepare slurry (the slurry has a flow-like and non-flow state), coating the slurry on a copper foil, performing vacuum drying and roll punching to obtain a negative plate with the diameter of 12mm, and taking the negative plate as a research plate. And adding a proper amount of lithium ion electrolyte, and assembling the button cell by taking the lithium sheet as a counter electrode. The determination method is as described in example 1, and the capacity of the material after circulation for 200 times is 1379mAh/g under the current density of 0.5A/g; under the current density of 10A/g, after circulating for 2000 times, the reversible capacity of 615mAh/g still exists; under the high current density of 20A/g, after 2000 times of circulation, the reversible capacity of 172mAh/g still exists.
Example 3
1.0811g of ferric chloride hexahydrate was added to 90mL of ethylene glycol at room temperature, and the mixture was stirred and dissolved at a medium-high speed of a magnetic stirrer for 0.5 hour. After complete dissolution, 1.8g of urea was added to the above solution and stirred well. Adding the obtained uniform solution into a 150mL stainless steel autoclave, reacting for 16 hours at 200 ℃, centrifugally separating the sample after reaction, washing for 4 times by using ethanol to obtain a precipitate, putting the precipitate into a vacuum drying oven, drying for 8 hours at 60 ℃, and collecting a powdery nano ferroferric oxide sample. 0.8640g of NH were weighed4And F, adding the mixture into 100mL of aqueous solution, stirring for half an hour, adding 0.2g of dried powdery ferroferric oxide sample, magnetically stirring for 24 hours at room temperature, and respectively centrifugally washing for 3 times by using deionized water and absolute ethyl alcohol to obtain black precipitates. Drying the obtained precipitate in a vacuum drying oven at 60 deg.C for 8 hr to obtain final product, N at 500 deg.C2Calcining for 3 hours in an inert atmosphere at the heating rate of 1 ℃/min to obtain the fluorine modified nano ferroferric oxide powder.
Mixing the prepared fluorine-modified nano ferroferric oxide powder with a binder PVDF and a conductive agent Super-P according to the weight ratio of 7: 1.5: 1.5, adding 1.5mL of N-methyl pyrrolidone as a solvent to prepare slurry (the slurry has a flow-like and non-flow state), coating the slurry on a copper foil, performing vacuum drying and roll punching to obtain a negative plate with the diameter of 12mm, and taking the negative plate as a research plate. And adding a proper amount of lithium ion electrolyte, and assembling the button cell by taking the lithium sheet as a counter electrode. The measurement method is as described in example 1, and the capacity of the material after circulation for 200 times is 981mAh/g under the current density of 0.5A/g; under the current density of 10A/g, after circulating for 2000 times, 659mAh/g reversible capacity still exists; under the high current density of 20A/g, the reversible capacity of 295mAh/g still exists after 2000 times of circulation.
Claims (5)
1. A preparation method of a surface fluorinated nano ferroferric oxide lithium ion battery cathode material is characterized by comprising the following steps:
a. completely dissolving soluble ferric salt in a solvent, wherein the solvent is one or a mixture of ethylene glycol, isopropanol and glycerol, adding a precipitator, the precipitator is one or more of urea, sodium hydroxide and potassium hydroxide, the molar ratio of iron in the soluble ferric salt to the precipitator is 1:1-6, uniformly stirring, carrying out solvothermal reaction on the mixed solution, reacting at 160-220 ℃ for 8-24h, centrifugally separating sample powder after the reaction, washing the sample powder with ethanol for 2-4 times, then putting the sample powder into a vacuum drying box, drying at 40-100 ℃ for 4-24h, and collecting a powdery sample;
b. b, adding the ferroferric oxide precursor powder sample obtained in the step a into NH4In the aqueous solution of F, a ferroferric oxide precursor powder sample and NH4The molar ratio of F is 1:3-15, stirring and reacting for 4-36h at room temperature, centrifugally separating after reacting, cleaning, drying and collecting a powdery sample;
c. and c, calcining the sample obtained in the step b for 2-6h at the temperature of 400-600 ℃ under the protective atmosphere to obtain the black nano ferroferric oxide composite material with the surface fluorinated and modified.
2. The preparation method of the surface-fluorinated nano ferroferric oxide lithium ion battery anode material according to claim 1, wherein the soluble ferric salt is one or a mixture of ferric chloride, ferric acetylacetonate, ferric nitrate or a crystalline hydrate thereof.
3. The preparation method of the surface-fluorinated nano ferroferric oxide lithium ion battery anode material according to claim 1, wherein the protective atmosphere in the step c is nitrogen or argon.
4. The preparation method of the surface-fluorinated nano ferroferric oxide lithium ion battery anode material according to claim 1, wherein the steps of centrifuging, cleaning, drying and collecting the powdery sample in the step b are as follows: and washing the centrifugal separation sample powder with deionized water for 2-4 times, then washing with ethanol for 1-4 times, then putting into a vacuum drying oven, drying for 4-24h at 40-100 ℃, and then collecting the powdery sample.
5. The application of the surface fluorinated nano ferroferric oxide lithium ion battery cathode material obtained by the preparation method of any of claims 1-4 in a lithium ion battery cathode.
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