CN112397705B - Lithium ion battery cathode material and preparation method and application thereof - Google Patents
Lithium ion battery cathode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a lithium ion battery cathode material and a preparation method and application thereof, the cathode material has a unique indium nitride coated silicon particle and carbon nanofiber composite structure, the carbon nanofiber is used as a structural carrier and is connected with a plurality of silicon particles in series, and the current collector and the volume buffer function are realized; the presence of indium nitride improves overall conductivity, its high acid resistance and structural stability reduces the generation of unstable SEI films; the inner layer silicon particles and the nano carbon fibers are protected, the structural stability of the material is improved, the whole material has good conductivity, the structural stability is kept excellently in the lithium intercalation and deintercalation process, and good multiplying power and cycle performance are realized.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a lithium ion battery cathode material and a preparation method and application thereof.
Background
The lithium ion battery is the battery system with the best comprehensive performance in the market at present. Compared with other secondary batteries, such as lead-acid batteries, nickel-chromium batteries, metal hydride nickel batteries and the like, lithium ion batteries have the advantages of low cost, high energy density and the like, and are widely applied to portable electronic equipment such as mobile phones, digital cameras, notebook computers and the like. With the rapid growth of the electric automobile market, the development of the lithium ion battery is met with a new opportunity.
The silicon element and the carbon element are rich in natural contents and respectively occupy the third place and the seventh place, so that the commercialization of the two materials has a very considerable prospect; when the silicon is used as a negative electrode material of a lithium ion battery, silicon is used as a negative electrode material (up to 4200 mA · h/g) with ultrahigh theoretical lithium intercalation capacity and is always a hot door developed in the industry, but the unstable SEI film and the huge volume expansion (more than or equal to 400%) in the lithium intercalation and deintercalation process cause the problems of huge irreversible capacity loss, poor cycle performance and the like, so that the application of silicon materials is limited; in contrast, although the conventional graphite cathode material has the characteristics of low price, rich raw materials, long service life and the like, the theoretical capacity (372 mA · h/g) is low, the requirement of high energy density is difficult to meet under the condition of low compaction density, and meanwhile, the rate capability of the graphite cathode is poor, so that the application of the graphite cathode in high-power charging and discharging occasions is greatly limited, and particularly when a high-capacity anode ternary material is matched, the overall energy density of a system is greatly reduced by adopting graphite as the cathode.
In view of the above, a lithium ion battery cathode material with stable structure and good conductivity is needed to realize high rate performance and ultra-long cycle life.
Disclosure of Invention
The first technical problem to be solved by the invention is as follows: the negative electrode material of the lithium ion battery is stable in structure and good in conductivity.
The second technical problem to be solved by the invention is as follows: the preparation method of the lithium ion battery cathode material is provided.
The third technical problem to be solved by the invention is as follows: the application of the lithium ion battery negative electrode material is provided.
In order to solve the first technical problem, the invention adopts the technical scheme that: the lithium ion battery cathode material comprises a plurality of silicon particles and carbon nanofibers, wherein the silicon particles are connected through the carbon nanofibers;
indium nitride is formed on the surfaces of the silicon particles and the surfaces of the carbon nanofibers;
the silicon particles are connected through the carbon nanofibers to form a plurality of chain-shaped structures.
The negative electrode material of the lithium ion battery implemented according to the invention has at least the following beneficial effects: the cathode material has a unique indium nitride coated silicon particle and carbon nanofiber composite structure, the carbon nanofiber is used as a structural carrier, and a plurality of silicon particles are connected in series, so that the current collector and the volume buffer effect are achieved; the presence of indium nitride improves overall conductivity, its high acid resistance and structural stability reduces the generation of unstable SEI films; the inner layer silicon particles and the nano carbon fibers are protected, the structural stability of the material is improved, the whole material has good conductivity, the structural stability is kept in the lithium intercalation and deintercalation process, and good multiplying power and cycle performance are realized.
In order to solve the second technical problem, the invention adopts the technical scheme that: the preparation method of the lithium ion battery negative electrode material comprises the following steps:
s1, preparing carbon nanofibers;
s2, preparing a precursor: oxidizing the carbon nanofibers to obtain surface oxidized carbon nanofibers; adding silicate ester and a surfactant into the surface oxidized nano carbon fiber for reaction, carrying out solid-liquid separation, and collecting a solid phase to obtain a precursor;
s3, reducing the precursor: mixing the precursor with metal magnesium, reacting under a protective atmosphere, cleaning, performing solid-liquid separation, and collecting a solid phase to obtain a reduction precursor;
s4, immersion treatment: adding the reduction precursor into an indium nitrate solution, carrying out solid-liquid separation, and collecting a solid phase to obtain powder;
s5, nitriding: and nitriding the powder to obtain the lithium ion battery cathode material.
According to some embodiments of the present invention, in the step S1, the filamentous nanocarbon is prepared using an electrospinning method.
According to some embodiments of the invention, the electrospinning process comprises the following processes:
(1) adding PAN into a solvent, and stirring for 2-4 h to obtain a PAN solution;
(2) horizontally spinning the PAN solution to obtain PAN fiber;
(3) pre-oxidizing the PAN fiber to obtain pre-oxidized PAN fiber;
(4) and carbonizing the pre-oxidized PAN fiber at high temperature in an inert atmosphere.
According to some embodiments of the invention, the PAN (polyacrylonitrile) has a molecular weight of 10000 to 25000.
According to some embodiments of the invention, the solvent is N, N-Dimethylformamide (DMF).
According to some embodiments of the invention, the concentration of PAN in the PAN solution is 0.05g/mL to 0.3 g/mL.
According to some embodiments of the invention, the horizontal spinning is performed using a horizontal spinning device.
According to some embodiments of the invention, the horizontal spinning device comprises the following components: the device comprises an injector, an injection pump and a metal receiving plate; the syringe is connected with the injection pump, and further comprises a syringe needle point which is vertical to the metal receiving plate.
According to some embodiments of the invention, the injection pump flow rate is 0.2-0.5 mL/h.
According to some embodiments of the invention, the distance between the tip of the syringe needle and the metal receiving plate is 10-30 cm.
According to some embodiments of the invention, the syringe needle tip is further connected to a high voltage power supply.
According to some embodiments of the invention, the high voltage of the high voltage power supply is set to 10-15 kV.
According to some embodiments of the present invention, the horizontal spinning process further requires turning on a tungsten-iodine lamp to assist drying.
According to some embodiments of the invention, the power of the iodine-tungsten lamp is 200-250 w.
According to some embodiments of the invention, the pre-oxidation process is: heating the PAN fiber to 200-300 ℃ in the air atmosphere, and preserving the heat for 2-3 h; preferably, the temperature rise speed is 2-4 ℃/min.
According to some embodiments of the invention, the temperature increase process of the carbonization is: heating to 300-400 ℃ for the first time, and keeping the temperature for 2-4 h; heating to 700-900 ℃ for the second time, and preserving heat for 2-4 hours; preferably, the first temperature rise speed is 3-5 ℃/min; preferably, the speed of the second temperature rise is 3-5 ℃/min.
According to some embodiments of the invention, the oxidation system in the oxidation process is a chlorate and acid mixed solution.
According to some embodiments of the invention, the chlorate salt is at least one of sodium chlorate and potassium chlorate.
According to some embodiments of the invention, the acid is at least one of phosphoric acid or sulfuric acid.
According to some embodiments of the invention, the KClO3The mass fraction is 5-15%.
According to some embodiments of the invention, the H2SO4The mass fraction is 15-30%.
According to some embodiments of the present invention, the mass concentration of the filamentous nanocarbon is 1% to 5%.
According to some embodiments of the invention, the oxidation process requires stirring for 1-2 hours.
According to some embodiments of the invention, the temperature during the oxidation is 65 to 85 ℃.
According to some embodiments of the invention, the reaction time in the oxidation process is 1-2 h.
According to some embodiments of the invention, the washing is washing with water for 5-8 times.
According to some embodiments of the invention, the silicate is an alkyl orthosilicate.
According to some embodiments of the invention, the alkyl orthosilicate is Tetraethylorthosilicate (TEOS).
According to some embodiments of the invention, the mass ratio of water to surfactant in the precursor preparation process is 50: 1-5.
According to some embodiments of the invention, the surfactant is a cationic surfactant.
According to some embodiments of the invention, the cationic surfactant is a quaternary ammonium cationic surfactant.
According to some embodiments of the invention, the quaternary ammonium salt cationic surfactant comprises at least one of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, octadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, and tetradecyltrimethylammonium chloride.
According to some embodiments of the invention, the mass ratio of the surface oxidized nano carbon fiber to the surfactant in the precursor preparation process is 20: 2-5.
According to some embodiments of the invention, the reaction during the preparation of the precursor comprises a solution reaction and a hydrothermal reaction.
According to some embodiments of the invention, the solution reaction temperature is 65 to 85 ℃.
According to some embodiments of the invention, the solution reaction time is 6 to 10 hours.
According to some embodiments of the invention, the silicate is added dropwise at a rate of 0.05-0.1 mL/min during the precursor preparation.
According to some embodiments of the invention, the ratio of the surface oxidized nano carbon fiber to the ethyl orthosilicate in the precursor preparation process is 1: 75-750.
According to some embodiments of the invention, the hydrothermal reaction is carried out at a temperature of 180 to 200 ℃.
According to some embodiments of the invention, the hydrothermal reaction time is 8-12 h.
According to some embodiments of the invention, the precursor preparation process is performed 4-6 times after solid-liquid separation.
According to some embodiments of the invention, the solid phase is collected during the preparation of the precursor and then dried; preferably, the drying temperature is 80-90 ℃, and the drying time is 10-12 h.
According to some embodiments of the invention, the mass ratio of the precursor to the metal magnesium is 1:1 to 1.5.
According to some embodiments of the invention, the time of the reaction in the process of reducing the precursor is 2-4 h.
According to some embodiments of the invention, the temperature of the reaction during the reduction of the precursor is 650 to 750 ℃.
According to some embodiments of the invention, the temperature ramp rate during the reduction of the precursor is 5 ℃/min.
According to some embodiments of the present invention, the precursor is reduced by hydrochloric acid with a concentration of about 1 mol/L; preferably, the time for the cleaning is about 30 min.
According to some embodiments of the invention, the molar ratio of magnesium metal to hydrogen chloride in the precursor reduction process is 1: 1.5-2.
According to some embodiments of the invention, the solid phase is collected during the reduction of the precursor and dried; preferably, the drying temperature is 80-90 ℃, and the drying time is 10-12 h.
According to some embodiments of the invention, the concentration of indium ions in the indium nitrate solution is 1 to 1.5 mol/L.
According to some embodiments of the invention, the mass ratio of the reducing precursor to the metal ions is 100: 1-5.
According to some embodiments of the invention, the solid phase is collected during the impregnation treatment and dried; preferably, the drying temperature is 80-90 ℃, and the drying time is 10-12 h.
The silicon particles after the magnesium thermal reduction are connected by the carbon nanofibers, the carbon nanofibers play a role of a current collector at the moment, the overall conductivity of the material is greatly improved, the silicon particles are connected by the carbon nanofibers, and the accumulated carbon nanofibers play a structural buffering role, so that the volume expansion of silicon in the charging and discharging process can be effectively relieved; the silicon particles subjected to magnesium thermal reduction have a porous structure, the porous structure can buffer volume expansion and can adsorb subsequent impregnation solution, so that the indium nitride precursor is mainly adsorbed on the inner surface and the outer surface of the silicon particles, and a better coating effect is realized.
The indium nitride has good conductivity, can greatly improve the conductivity of the material, has excellent acid resistance and structural stability, can protect the surface of silicon particles, effectively reduces the generation of redundant SEI films, and reduces irreversible capacity; the inner layer silicon particles and the nano carbon fibers are protected, the structural stability of the material is improved, the whole material has good conductivity, the structural stability is kept excellently in the lithium intercalation and deintercalation process, and good multiplying power and cycle performance are realized.
According to some embodiments of the invention, the nitriding process is a nitriding reaction of the powder under a nitrogen atmosphere.
According to some embodiments of the present invention, the nitridation reaction temperature is 650 to 750 ℃, and the reaction time is 3 to 6 hours.
The preparation method of the lithium ion negative electrode material provided by the embodiment of the invention has at least the following beneficial effects: the invention adopts an electrostatic spinning method to prepare the carbon nanofibers, and carboxyl is introduced by oxidizing the surface of the carbon nanofibers; adding a surfactant (quaternary ammonium salt cationic surfactant) into the oxidized carbon nanofibers, and forming a template by utilizing the electrostatic adsorption effect of carboxyl and the surfactant; adding silicate ester, and hydrolyzing and polymerizing the silicate ester under the guidance of a template; after hydrothermal reaction, polymerizing on the carbon nanofibers to form silica particles; then preparing carbon nanofibers serving as connecting wires by reducing metal magnesium, and connecting a plurality of porous silicon particle composite materials in series; and soaking the surface of the composite material with indium ions by a soaking method, and nitriding the impregnated composite material to form the indium nitride-coated silicon particle/nano carbon fiber composite material.
In order to solve the third technical problem, the invention adopts the technical scheme that: the lithium ion negative electrode material is applied to the preparation of a lithium ion battery.
According to some embodiments of the invention, the mass ratio of the lithium ion negative electrode material, the conductive agent, and the binder in the lithium ion battery is about 8:1: 1.
The application of the lithium ion negative electrode material according to the embodiment of the invention has at least the following beneficial effects: according to the invention, the silicon particles are connected by the carbon nanofibers, the carbon nanofibers play a role of a current collector, the overall conductivity of the material is greatly improved, the silicon particles are linked by the carbon nanofibers, and the accumulated carbon nanofibers play a structural buffering role, so that the volume expansion of the silicon particles in the charging and discharging processes can be effectively relieved; the indium nitride has good conductivity, the conductivity of the material is greatly improved, the surface of silicon particles is protected, the generation of redundant SEI films is effectively reduced, and the irreversible capacity is reduced; the inner layer silicon particles and the nano carbon fibers are protected, the structural stability of the material is improved, the whole material has good conductivity, the structural stability is kept excellently in the lithium intercalation and deintercalation process, and good multiplying power and cycle performance are realized. The material effectively realizes good structural stability, reduces the generation of irreversible capacity, obtains super-long cycle life, and simultaneously realizes extremely high rate performance by the unique current collector structure and the coating of high-conductivity substances on the surface.
Drawings
FIG. 1 is a schematic structural diagram of a negative electrode material of a lithium ion battery prepared according to an embodiment of the present invention;
FIG. 2 is an SEM image (low magnification) of a negative electrode material of a lithium ion battery prepared according to a first embodiment of the invention;
fig. 3 is an SEM image (high magnification) of a negative electrode material of a lithium ion battery according to an embodiment of the present invention.
Detailed Description
In order to explain technical contents, achieved objects, and effects of the present invention in detail, the following description is made with reference to the accompanying drawings in combination with the embodiments. The test methods used in the examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available reagents and materials unless otherwise specified.
The structural schematic diagram of the lithium ion battery cathode material prepared by the embodiment of the invention is shown in fig. 1, and the lithium ion battery cathode material comprises carbon nanofibers and at least one silicon particle from the diagram 1; indium nitride is formed on the surfaces of the silicon particles and the surfaces of the carbon nanofibers; the silicon particles are connected through the nano carbon fibers to form a plurality of chain-shaped structures.
The preparation process of the cathode material comprises the steps of preparing the carbon nanofibers, carrying out hydrothermal reaction, carrying out magnesiothermic reduction, carrying out dipping treatment and nitriding:
step 1: adding polyacrylonitrile (PAN, the molecular weight of 10000-25000) into N, N-Dimethylformamide (DMF), controlling the concentration of PAN in the solution to be 0.05-0.3 g/mL, and stirring for 2-6 h after the addition is finished.
Adding the PAN solution into an injector of a horizontal spinning device, starting horizontal spinning after the addition is finished, and collecting a sample after the spinning is finished to obtain PAN fiber; wherein, the flow rate of a jet pump in the horizontal spinning device is controlled to be 0.2-0.5 mL/h, the distance between the needle point of the injector and the metal receiving plate is 10-30 cm, a high-voltage power supply is connected with the needle point, the high voltage is set to be 10-15 kV, and a tungsten iodine lamp (200-250 w) is started for auxiliary drying.
Pre-oxidizing the PAN fiber in an air atmosphere, wherein the initial temperature in the pre-oxidation process is room temperature, the target temperature is 200-300 ℃, the temperature rise speed is 2-4 ℃/min, and after the temperature rise is finished, the temperature is kept for 2-3 h to obtain the pre-oxidized PAN fiber.
Carrying out high-temperature carbonization on the pre-oxidized PAN fiber under the protection of inert atmosphere to obtain nano carbon fiber; the temperature of the first stage of high-temperature carbonization is increased to 300-400 ℃, the temperature increasing speed is 3-5 ℃/min, and the temperature is maintained for 2-4 h after temperature increase; the target temperature of the second-stage heating is 700-900 ℃, the heating speed is 3-5 ℃/min, and the temperature is kept for 2-4 h after the heating is finished.
Step 2: adding the carbon nanofibers obtained in the step 1 into a mixed solution of potassium chlorate and sulfuric acid, stirring and reacting for 1-2 hours at 65-85 ℃, filtering after the reaction is finished, and washing for 5-8 times by using deionized water to obtain surface oxidized carbon nanofibers; wherein, KClO35-15% of H2SO4The mass fraction is 15-30%, and the addition amount of the carbon nanofibers is 1-5% of solid content.
Adding the surface oxidized nano carbon fiber into water (the mass ratio of the surface oxidized nano carbon fiber to deionized water is 1: 5-50), adding a surfactant (the mass ratio of the surface oxidized nano carbon fiber to the surfactant is 20: 2-5), stirring at 65-85 ℃, and adding tetraethoxysilane (the mass ratio of the surface oxidized nano carbon fiber to Tetraethoxysilane (TEOS)) at a dropping speed of 0.05-0.1 mL/min; after the addition is finished, the reaction time is 6-10 h, the reacted mixture is transferred to a hydrothermal reaction kettle, after hydrothermal reaction is carried out for 8-12 h at 180-200 ℃, centrifugation, filtration and deionized water cleaning are carried out for 4-6 times, and drying is carried out for 10-12 h at 80-90 ℃ to obtain a precursor; wherein the surfactant comprises at least one of cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, stearyl trimethyl ammonium chloride, lauryl trimethyl ammonium bromide, lauryl trimethyl ammonium chloride, myristyl trimethyl ammonium bromide and myristyl trimethyl ammonium chloride.
And step 3: mixing the precursor with metal magnesium powder (the mass ratio of the precursor to the metal magnesium is 1: 1-1.5), and calcining for 2-4 h at 650-750 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃/min.
After the reaction is finished, adding 1mol/L hydrochloric acid, cleaning for 30min, centrifugally filtering, drying, and drying at 80-90 ℃ for 10-12 h to obtain a reduction precursor; wherein the molar ratio of Mg to HCl is 1: 1.5-2.
And 4, step 4: dipping treatment: adding the reduction precursor to 1-1.5 mol/L indium nitrate (In (NO)3)3) Soaking the solution, filtering, and drying at 80-90 ℃ for 10-12 h to obtain powder; wherein the mass ratio of the reduction precursor to the indium element is 100: 1-5.
And 5: nitriding: carrying out nitridation reaction on the obtained powder in a nitrogen atmosphere to obtain a lithium ion negative electrode material; wherein the temperature of the nitridation reaction is 650-750 ℃, and the time of the nitridation reaction is 3-6 h.
In order to test that the lithium ion negative electrode material prepared in the embodiment has good multiplying power and cycle performance, the obtained negative electrode material is prepared according to the following steps: conductive agent: the mass ratio of the binder is about 8:1:1, lithium metal is adopted as a negative electrode to form the button cell, the discharging gram capacity is measured according to current densities of 1A/g, 2A/g and 5A/g, and the cycle performance is measured under the current density of 5A/g.
The first embodiment of the invention is as follows: a preparation method of a lithium ion negative electrode material comprises the following steps:
step 1: adding polyacrylonitrile (PAN, molecular weight of 10000-15000) into N, N-Dimethylformamide (DMF), controlling the concentration of PAN in the solution to be 0.05g/mL, and stirring for 2h after the addition is finished.
Adding the PAN solution into an injector of a horizontal spinning device, starting horizontal spinning, and collecting a sample after the spinning is finished to obtain PAN fiber; wherein, the flow rate of a jet pump in the horizontal spinning device is controlled to be 0.2mL/h, the distance between the needle point of the injector and the metal receiving plate is 10cm, a high-voltage power supply is connected with the needle point, the high voltage is set to be 10kV, and an iodine tungsten lamp (200 w) is started for auxiliary drying.
Pre-oxidizing the PAN fiber in the air atmosphere, wherein the initial temperature in the pre-oxidation process is room temperature, the target temperature is 200 ℃, the temperature rise speed is 2 ℃/min, and after the temperature rise is finished, the temperature is kept for 2h to obtain the pre-oxidized PAN fiber.
Carrying out high-temperature carbonization on the pre-oxidized PAN fiber under the protection of argon to obtain nano carbon fiber; the temperature rise target temperature of the first stage of high-temperature carbonization is 300 ℃, the temperature rise speed is 3 ℃/min, and the temperature is kept for 2h after the temperature rise is finished; the second stage heating target temperature is 700 ℃, the heating speed is 3 ℃/min, and the temperature is kept for 2h after the heating is finished.
Step 2: adding the carbon nanofibers obtained in the step 1 into a mixed solution of potassium chlorate and sulfuric acid, stirring and reacting for 1h at 65 ℃, filtering after the reaction is finished, and washing for 5 times by using deionized water to obtain surface oxidized carbon nanofibers; wherein, KClO35% by mass of H2SO4The mass fraction is 15 percent, and the adding amount of the carbon nanofiber is 1 percent of the solid content.
Adding the surface oxidized nano carbon fiber into water (the mass ratio of the surface oxidized nano carbon fiber to the deionized water is 1: 50), adding hexadecyl trimethyl ammonium bromide (the mass ratio of the surface oxidized nano carbon fiber to the hexadecyl trimethyl ammonium bromide is 20: 2), stirring at 65 ℃, and adding tetraethoxysilane (the mass ratio of the surface oxidized nano carbon fiber to the Tetraethoxysilane (TEOS)) at the dropping speed of 0.05 mL/min; and after the addition is finished, the reaction time is 6h, the reacted mixture is transferred to a hydrothermal reaction kettle, after hydrothermal reaction is carried out for 8h at 180 ℃, centrifugation, filtration and deionized water cleaning are carried out for 4 times, and drying is carried out for 10h at 80 ℃ to obtain the precursor.
And step 3: mixing the precursor with metal magnesium powder (the mass ratio of the precursor to the metal magnesium is 1: 1), and calcining for 2h at 650 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃/min.
After the reaction is finished, adding 1mol/L hydrochloric acid to clean for 30min, drying after centrifugal filtration, and drying for 10h at 80 ℃ to obtain a reduction precursor; wherein the molar ratio of Mg to HCl is 1: 1.5.
And 4, step 4: dipping treatment: adding the reduction precursor to 1mol/L indium nitrate (In (NO)3)3) Soaking the solution, filtering, and drying at 80 deg.C for 10 hr to obtain powder; wherein the mass ratio of the reduction precursor to the indium element is 100: 1.
And 5: nitriding: carrying out nitridation reaction on the obtained powder in a nitrogen atmosphere to obtain a lithium ion negative electrode material; wherein the temperature of the nitridation reaction is 650 ℃, and the time of the nitridation reaction is 3 h.
Example two: a preparation method of a lithium ion negative electrode material comprises the following steps:
step 1: adding polyacrylonitrile (PAN, molecular weight of 20000-25000) into N, N-Dimethylformamide (DMF), controlling the concentration of PAN in the solution to be 0.3g/mL, and stirring for 6h after the addition is finished.
Adding the PAN solution into an injector of a horizontal spinning device, starting horizontal spinning after the addition is finished, and collecting a sample after the spinning is finished to obtain PAN fiber; wherein, the flow rate of a jet pump in the horizontal spinning device is controlled to be 0.5mL/h, the distance between the needle point of the injector and the metal receiving plate is 30cm, a high-voltage power supply is connected with the needle point, the high voltage is set to be 15kV, and an iodine tungsten lamp (250 w) is started for auxiliary drying.
Pre-oxidizing the PAN fiber in the air atmosphere, wherein the initial temperature in the pre-oxidation process is room temperature, the target temperature is 300 ℃, the temperature rise speed is 4 ℃/min, and after the temperature rise is finished, the temperature is kept for 3h to obtain the pre-oxidized PAN fiber.
Carrying out high-temperature carbonization on the pre-oxidized PAN fiber under the protection of argon to obtain nano carbon fiber; the temperature rise target temperature of the first stage of high-temperature carbonization is 400 ℃, the temperature rise speed is 5 ℃/min, and the temperature is kept for 4h after the temperature rise is finished; the target temperature of the second stage of heating is 900 ℃, the heating speed is 5 ℃/min, and the temperature is kept for 4h after the heating is finished.
Step 2: adding the carbon nanofibers obtained in the step 1 into a mixed solution of potassium chlorate and sulfuric acid, stirring and reacting for 2 hours at 85 ℃, filtering after the reaction is finished, and washing for 8 times by using deionized water to obtain surface oxidized carbon nanofibers; wherein, KClO315% by mass of H2SO4The mass fraction is 30 percent, and the adding amount of the carbon nanofiber is 5 percent of the solid content.
Adding the surface oxidized nano carbon fiber into water (the mass ratio of the surface oxidized nano carbon fiber to the deionized water is 5: 50), adding hexadecyl trimethyl ammonium chloride (the mass ratio of the surface oxidized nano carbon fiber to the hexadecyl trimethyl ammonium chloride is 20: 5), stirring at 85 ℃, and adding tetraethoxysilane (the mass ratio of the surface oxidized nano carbon fiber to the Tetraethoxysilane (TEOS)) at a dropping speed of 0.1 mL/min; and after the addition is finished, the reaction time is 10h, the reacted mixture is transferred to a hydrothermal reaction kettle, after hydrothermal reaction is carried out for 12h at 200 ℃, centrifugation, filtration and deionized water cleaning are carried out for 6 times, and drying is carried out for 12h at 90 ℃ to obtain the precursor.
And step 3: mixing the precursor with metal magnesium powder (the mass ratio of the precursor to the metal magnesium is 1: 1.5), and calcining for 4h at 750 ℃ in an argon atmosphere, wherein the temperature rise speed is 5 ℃/min.
After the reaction is finished, adding 1mol/L hydrochloric acid to clean for 30min, drying after centrifugal filtration, and drying at 90 ℃ for 12h to obtain a reduction precursor; wherein the molar ratio of Mg to HCl is 1: 2.
And 4, step 4: dipping treatment: the reduction precursor was added to 1.5mol/L indium nitrate (In (NO)3)3) Soaking the solution, filtering, and drying at 90 deg.C for 12 hr to obtain powder; wherein the mass ratio of the reduction precursor to the indium element is 100: 5.
And 5: nitriding: carrying out nitridation reaction on the powder in a nitrogen atmosphere to obtain a lithium ion negative electrode material; wherein the temperature of the nitridation reaction is 750 ℃, and the time of the nitridation reaction is 6 h.
The third embodiment of the invention is as follows: a preparation method of a lithium ion negative electrode material comprises the following steps:
step 1: adding polyacrylonitrile (PAN, the molecular weight of 15000-20000) into N, N-Dimethylformamide (DMF), controlling the concentration of PAN in the solution to be 0.2g/mL, and stirring for 4h after the addition is finished.
Adding the PAN solution into an injector of a horizontal spinning device, starting horizontal spinning after the addition is finished, and collecting a sample after the spinning is finished to obtain PAN fiber; wherein, the flow rate of a jet pump in the horizontal spinning device is controlled to be 0.3mL/h, the distance between the needle point of the injector and the metal receiving plate is 20cm, a high-voltage power supply is connected with the needle point, the high voltage is set to be 12kV, and an iodine tungsten lamp (220 w) is started for auxiliary drying.
Pre-oxidizing the PAN fiber in the air atmosphere, wherein the initial temperature in the pre-oxidation process is room temperature, the target temperature is 250 ℃, the temperature rise speed is 3 ℃/min, and after the temperature rise is finished, the temperature is kept for 2.5h to obtain the pre-oxidized PAN fiber.
Carrying out high-temperature carbonization on the pre-oxidized PAN fiber under the protection of argon to obtain nano carbon fiber; the temperature rise target temperature of the first stage of high-temperature carbonization is 350 ℃, the temperature rise speed is 4 ℃/min, and the temperature is kept for 3h after the temperature rise is finished; the second stage heating target temperature is 800 ℃, the heating speed is 4 ℃/min, and the temperature is kept for 3h after the heating is finished.
Step 2: adding the carbon nanofibers obtained in the step 1 into a mixed solution of potassium chlorate and sulfuric acid, stirring and reacting for 1.5 hours at 70 ℃, filtering after the reaction is finished, and washing for 6 times by using deionized water to obtain surface oxidized carbon nanofibers; wherein, KClO310% by mass of H2SO4The mass fraction is 20 percent, and the adding amount of the carbon nanofiber is 3 percent of the solid content.
Adding the surface oxidized nano carbon fiber into water (the mass ratio of the surface oxidized nano carbon fiber to the deionized water is 3: 50), adding octadecyl trimethyl ammonium bromide (the mass ratio of the surface oxidized nano carbon fiber to the octadecyl trimethyl ammonium bromide is 20: 3), stirring at 70 ℃, and adding tetraethoxysilane (the mass ratio of the surface oxidized nano carbon fiber to the Tetraethoxysilane (TEOS) is 1: 500) at the dropping speed of 0.08 mL/min; and after the addition is finished, the reaction time is 8h, the reacted mixture is transferred to a hydrothermal reaction kettle, after hydrothermal reaction is carried out for 10h at 190 ℃, centrifugation, filtration and deionized water cleaning are carried out for 5 times, and drying is carried out for 11h at 85 ℃ to obtain the precursor.
And step 3: mixing the precursor with metal magnesium powder (the mass ratio of the precursor to the metal magnesium is 1: 1.2), and calcining for 3h at 700 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃/min.
After the reaction is finished, adding 1mol/L hydrochloric acid to clean for 30min, drying after centrifugal filtration, and drying for 11h at 85 ℃ to obtain a reduction precursor; wherein the molar ratio of Mg to HCl is 1: 1.8.
And 4, step 4: dipping treatment: the reduction precursor was added to 1.2mol/L indium nitrate (In (NO)3)3) Soaking the solution, filtering, and drying at 85 deg.C for 11 hr to obtain powder; wherein the mass ratio of the reduction precursor to the indium element is 100: 3.
And 5: nitriding: carrying out nitridation reaction on the obtained powder in a nitrogen atmosphere to obtain a lithium ion negative electrode material; wherein the temperature of the nitridation reaction is 700 ℃, and the time of the nitridation reaction is 4 h.
The first comparative example of the present invention is: a preparation method of a lithium ion negative electrode material comprises the following steps:
step 1: adding polyacrylonitrile (PAN, molecular weight of 10000-15000) into N, N-Dimethylformamide (DMF), controlling the concentration of PAN in the solution to be 0.05g/mL, and stirring for 2h after the addition is finished.
Adding the PAN solution into an injector of a horizontal spinning device, starting horizontal spinning after the addition is finished, and collecting a sample after the spinning is finished to obtain PAN fiber; wherein, the flow rate of a jet pump in the horizontal spinning device is controlled to be 0.2mL/h, the distance between the needle point of the injector and the metal receiving plate is 10cm, a high-voltage power supply is connected with the needle point, the high voltage is set to be 10kV, and an iodine tungsten lamp (200 w) is started for auxiliary drying.
Pre-oxidizing the PAN fiber in the air atmosphere, wherein the initial temperature in the pre-oxidation process is room temperature, the target temperature is 200 ℃, the temperature rise speed is 2 ℃/min, and after the temperature rise is finished, the temperature is kept for 2h to obtain the pre-oxidized PAN fiber.
Carrying out high-temperature carbonization on the pre-oxidized PAN fiber under the protection of argon to obtain nano carbon fiber; the temperature rise target temperature of the first stage of high-temperature carbonization is 300 ℃, the temperature rise speed is 3 ℃/min, and the temperature is kept for 2h after the temperature rise is finished; the second stage heating target temperature is 700 ℃, the heating speed is 3 ℃/min, and the temperature is kept for 2h after the heating is finished.
Step 2: adding the carbon nanofibers obtained in the step 1 into a mixed solution of potassium chlorate and sulfuric acid, stirring and reacting for 1h at 65 ℃, filtering after the reaction is finished, and washing for 5 times by using deionized water to obtain surface oxidized carbon nanofibers; wherein, KClO35% by mass of H2SO4The mass fraction is 15 percent, and the adding amount of the carbon nanofiber is 1 percent of the solid content.
Adding the surface oxidized nano carbon fiber into water (the mass ratio of the surface oxidized nano carbon fiber to the deionized water is 1: 50), adding hexadecyl trimethyl ammonium bromide (the mass ratio of the surface oxidized nano carbon fiber to the hexadecyl trimethyl ammonium bromide is 20: 2), stirring at 65 ℃, and adding tetraethoxysilane (the mass ratio of the surface oxidized nano carbon fiber to the Tetraethoxysilane (TEOS)) at the dropping speed of 0.05 mL/min; and after the addition is finished, the reaction time is 6h, the reacted mixture is transferred to a hydrothermal reaction kettle, after hydrothermal reaction is carried out for 8h at 180 ℃, centrifugation, filtration and deionized water cleaning are carried out for 4 times, and drying is carried out for 10h at 80 ℃ to obtain the precursor.
And step 3: mixing the precursor with metal magnesium powder (the mass ratio of the precursor to the metal magnesium is 1: 1), and calcining for 2h at 650 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃/min.
After the reaction is finished, adding 1mol/L hydrochloric acid to clean for 30min, drying after centrifugal filtration, and drying for 10h at 80 ℃ to obtain a reduction precursor; wherein the molar ratio of Mg to HCl is 1: 1.5.
And 4, step 4: nitriding: carrying out nitridation reaction on the obtained powder in a nitrogen atmosphere to obtain a lithium ion negative electrode material; wherein the temperature of the nitridation reaction is 650 ℃, and the time of the nitridation reaction is 3 h.
In order to measure the multiplying power and the cycling performance of the first embodiment, the lithium ion negative electrode materials obtained in the first embodiment, the third embodiment and the first comparative embodiment are combined into slurry according to the mass ratio of the lithium ion negative electrode materials, the conductive agent and the binder being 8:1:1, the negative electrode adopts lithium metal to form a button cell, the discharge gram capacity performance is measured according to the current densities of 1A/g, 2A/g and 5A/g, and the cycling stability is measured by cycling under the current density of 5A/g. The results of the gram discharge capacity, the first efficiency and the cycle performance under different multiplying factors of the first to third embodiments of the invention and the first comparative embodiment are shown in table 1.
Table 1 table of results of different rates of charge gram capacity, first efficiency and cycle performance of examples one to three and comparative example one
From table 1, it is known that the gram discharge capacity, the first efficiency and the cycle performance of the first, second and third examples are far superior to those of the first comparative example; the lithium ion negative electrode materials prepared in the first embodiment, the second embodiment and the third embodiment all show excellent rate and cycle performance, and have high first efficiency and low irreversible capacity. Therefore, the lithium ion battery anode material is very suitable for being used as a high-performance lithium ion battery anode material.
In conclusion, according to the lithium ion negative electrode material provided by the invention, the silicon particles are connected by the carbon nanofibers, the carbon nanofibers play a role of a current collector, the overall conductivity of the material is greatly improved, the particles are linked by the carbon nanofibers, and the accumulated carbon nanofibers play a structural buffering role, so that the volume expansion of silicon in the charging and discharging process can be effectively relieved; the indium nitride has good conductivity, can greatly improve the conductivity of the material, has excellent acid resistance and structural stability, can protect the silicon surface, effectively reduces the generation of redundant SEI films, and reduces the irreversible capacity. The material effectively realizes good structural stability, reduces the generation of irreversible capacity, obtains super-long cycle life, and simultaneously realizes extremely high rate performance by the unique current collector structure and the coating of high-conductivity substances on the surface.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to the related technical fields, are included in the scope of the present invention.
Claims (12)
1. A lithium ion battery negative electrode material is characterized in that: the silicon particles are connected with each other through the carbon nanofibers;
indium nitride is formed on the surfaces of the silicon particles and the surfaces of the carbon nanofibers;
the silicon particles are connected through the nano carbon fibers to form a plurality of chain structures;
the preparation method of the lithium ion battery negative electrode material comprises the following steps:
s1, preparing carbon nanofibers;
s2, preparing a precursor: oxidizing the carbon nanofibers, carrying out solid-liquid separation, and collecting a solid phase to obtain surface oxidized carbon nanofibers; adding silicate ester and a surfactant into the surface oxidized nano carbon fiber for reaction, carrying out solid-liquid separation, and collecting a solid phase to obtain a precursor;
s3, reducing the precursor: mixing the precursor with metal magnesium, reacting under a protective atmosphere, carrying out solid-liquid separation, and collecting a solid phase to obtain a reduction precursor;
s4, immersion treatment: adding the reduction precursor into an indium nitrate solution, carrying out solid-liquid separation, and collecting a solid phase to obtain powder;
s5, nitriding: and nitriding the powder to obtain the lithium ion battery cathode material.
2. A method of preparing the negative electrode material of the lithium ion battery of claim 1, wherein: comprises the following steps:
s1, preparing carbon nanofibers;
s2, preparing a precursor: oxidizing the carbon nanofibers, carrying out solid-liquid separation, and collecting a solid phase to obtain surface oxidized carbon nanofibers; adding silicate ester and a surfactant into the surface oxidized nano carbon fiber for reaction, carrying out solid-liquid separation, and collecting a solid phase to obtain a precursor;
s3, reducing the precursor: mixing the precursor with metal magnesium, reacting under a protective atmosphere, carrying out solid-liquid separation, and collecting a solid phase to obtain a reduction precursor;
s4, immersion treatment: adding the reduction precursor into an indium nitrate solution, carrying out solid-liquid separation, and collecting a solid phase to obtain powder;
s5, nitriding: and nitriding the powder to obtain the lithium ion battery cathode material.
3. The method of claim 2, wherein: in the step S1, the carbon nanofibers are prepared by an electrospinning method.
4. The method of claim 3, wherein: the electrospinning method comprises the following processes:
(1) adding PAN into a solvent to obtain a PAN solution;
(2) horizontally spinning the PAN solution to obtain PAN fiber;
(3) pre-oxidizing the PAN fiber to obtain pre-oxidized PAN fiber;
(4) and carbonizing the pre-oxidized PAN fiber under a protective atmosphere.
5. The method of claim 4, wherein: the molecular weight of the PAN is 10000-25000.
6. The method of claim 2, wherein: the oxidant in the oxidation process is a mixed solution of chlorate and acid.
7. The method of claim 2, wherein: the temperature in the oxidation process is 65-85 ℃.
8. The method of claim 2, wherein: the reaction time in the oxidation process is 1-2 h.
9. The method of claim 2, wherein: the surfactant is a cationic surfactant.
10. The method of claim 9, wherein: the cationic surfactant is a quaternary ammonium salt cationic surfactant.
11. The method of claim 10, wherein: the quaternary ammonium salt cationic surfactant comprises at least one of hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium bromide and tetradecyl trimethyl ammonium chloride.
12. The use of the lithium ion battery anode material of claim 1 in a lithium ion battery.
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