CN107611425B - Fusiform zinc ferrite/carbon lithium ion battery nano composite negative electrode material and preparation method and application thereof - Google Patents
Fusiform zinc ferrite/carbon lithium ion battery nano composite negative electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a fusiform zinc ferrite/carbon lithium ion battery nano composite negative electrode material, a preparation method and application thereof, the composite negative electrode material is a fusiform structure and is formed by compounding carbon skeleton zinc ferrite secondary nano particles, wherein the content of zinc ferrite is 60-90% of the mass of the zinc ferrite/carbon lithium ion battery nano composite negative electrode material. The preparation method of the material comprises the following steps: an organic metal framework is used as a linking agent and a carbon source, and is mixed with metal salt to carry out hydrothermal reaction, and after a precursor is obtained by centrifugal washing and drying, the precursor is annealed to obtain the spindle zinc ferrite/carbon lithium ion battery nano composite negative electrode material; the spindle-shaped structure zinc ferrite/carbon lithium ion battery nano composite negative electrode material has stable structure and good conductivity, and has excellent cycle stability and rate capability when being used as a lithium ion battery negative electrode material; the method is simple to operate, convenient to control, low in cost, environment-friendly, and suitable for industrial mass production, and the practical application of the lithium ion battery is realized.
Description
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a nano composite negative electrode material of a fusiform zinc ferrite/carbon lithium ion battery, and a preparation method and application thereof.
Background
With the increasing demand for energy in the current society, the increasing energy crisis and environmental problems are caused, and the continuous research on new energy and energy storage and conversion technology is stimulated. Lithium ion batteries, which have been successfully commercialized by sony corporation at the end of the 20 th century, attract the attention of most people, and are now being used in various electronic devices such as computers and mobile phones due to their unique advantages in energy storage and conversion. However, with the further development of electric vehicles and energy storage technologies, higher requirements are put forward on lithium ion batteries, and high energy density is required to be realized, and meanwhile, good rate performance and cycle stability are maintained, and the lithium ion batteries are lighter, safer and more environment-friendly. This situation can be improved by studying electrode materials of important components in view of the composition of lithium ion batteries.
The negative electrode material is used as a main body of lithium storage and is an important component of a lithium ion battery, and the commercialized graphite negative electrode is only 372 mAh g-1Such a relatively low theoretical specific capacity of (a) is far from meeting the future development requirements. And the anode material having the advantages at presentIn the lithium battery, nanometer-sized Transition Metal Oxides (TMOs) greatly attract attention of people, on one hand, nanometer-sized particles have larger specific surface area and provide more reactive active sites, and meanwhile, a reaction path is shortened for lithium ion transmission, and on the other hand, the transition metal oxides generally have higher theoretical specific capacity, and particularly, the double transition metal oxides have higher theoretical specific capacity.
Iron-based double transition metal oxides having a relatively cobalt-based double metal oxide (MFe) as promising negative electrode materials for lithium batteries2O4M = Ni, Mn, Zn, Co), lower toxicity, cheaper and more environmentally friendly, while at the same time ensuring a high theoretical specific capacity. Among these, ZnFe2O4But also from other iron-based double transition metals because not only the conversion reaction but also Zn exists in the process of storing lithium2+With Li+The generated alloy reaction improves the lithium storage capacity and increases the specific capacity. However, like other transition metal oxides, ZnFe2O4There is also a large capacity fade, i.e., low capacity retention and volume change of the material during charge and discharge, resulting in a material having low cycle stability and reversibility. In view of the above-mentioned drawbacks, researchers have made great efforts to improve the defects, for example, Won et al synthesized ZnFe with core/hollow/shell by spray drying at 450 deg.C2O4The materials obtained at different synthesis temperatures have different structures and different electrochemical properties, and undergo 200 cycles at a current density of 0.5 ℃, and ZnFe of a core/hollow/shell2O4The discharge capacity is 862 mAh g-1Solid ZnFe obtained at a temperature much higher than 350 DEG C2O4ZnFe with core-shell structure obtained at 400 DEG C2O4（J. M.Won, S. H. Choi, et al. Electrochemical properties of yolk-shell structuredZnFe(2)O(4) powders prepared by a simple spray drying process as anodematerial for lithium-ion battery[J]Scientific reports, 2014, 4: 5857.); xing et al successfully prepared single-crystal phase octahedron ZnFe by low-temperature hydrothermal reaction method2O4FromThe scanning electron microscope picture can show that the octahedron has a uniform appearance and a smooth surface, the size is 100-350 nm, and the electrochemical performance test shows that the octahedron ZnFe2O4The first discharge capacity at 0.06C current density is 1350 mAh g-1And the specific capacity after 80 cycles is 910 mAh g-1When the test is also carried out under the high current density of 1C, the discharge capacity of 300 cycles still has 730 mAh g-1Exhibits a good cycle stability and high capacity performance at high rate (P.F. Teh, Y. Sharma, et al. NanoWeb odor composition of one-dimensional, high aspect ratio, size-tunable electrospinner ZnFe)2O4nanofibers for lithium ion batteries[J]. J. Mater. Chem., 2011, 21,14999–15008.）。
The spindle-shaped zinc ferrite/carbon lithium ion battery nano composite material is prepared by combining an organic metal framework method with a hydrothermal reaction process, and no related synthetic method report exists so far, and no report exists for preparing a lithium ion battery cathode material by using a related structure composite material.
Disclosure of Invention
Aiming at the defects that the conventional commercial lithium ion battery graphite cathode material is low in theoretical capacity, poor in conductivity of a transition metal oxide cathode material, too fast in specific capacity attenuation in the charge-discharge cycle process of the battery and the like, the invention provides the fusiform zinc ferrite/carbon lithium ion battery nano composite cathode material, and the preparation method and the application thereof, so that the structural stability and the electrochemical performance of the lithium ion battery cathode material can be improved, and the cycle stability and the rate capability of the material in the charge-discharge process can be improved. In addition, the zinc ferrite/carbon preparation method provided by the invention is simple, the process is easy to control, the cost is low, the environment is friendly, the large-scale production of the lithium ion battery cathode material can be promoted, and the method is suitable for industrial application.
The invention is realized by the following technical scheme.
A preparation method of a nano composite negative electrode material of a fusiform zinc ferrite/carbon lithium ion battery comprises the following steps:
(1) dissolving fumaric acid in dimethylformamide, and uniformly stirring to obtain a dispersion liquid;
(2) adding iron metal salt and zinc metal salt into the dispersion liquid obtained in the step (1), and uniformly stirring to obtain a mixed liquid;
(3) transferring the mixed solution obtained in the step (2) into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an electric heating constant-temperature air-blowing drying oven for hydrothermal reaction, cooling to room temperature, centrifugally washing and drying;
(4) and (4) putting the powder obtained after drying in the step (3) into a porcelain boat, then putting into a tube furnace, carrying out annealing reaction in a nitrogen atmosphere, and cooling to room temperature to obtain the spindle-shaped zinc ferrite/carbon lithium ion battery nano composite negative electrode material.
Preferably, the fumaric acid used in the step (1) is 4 to 32 mmol.
Preferably, the time for stirring and uniformly mixing in the step (1) is 2 to 4 hours.
Preferably, the adding amount of the iron metal salt and the zinc metal salt in the step (2) is controlled in such a way that the molar ratio of Fe to Zn is 1.5-3: 0.75 to 1.5, and more preferably 2: 1.
preferably, the iron metal salt in the step (2) is one of ferric nitrate and ferric trichloride; the zinc metal salt is one of zinc nitrate and zinc acetate.
Preferably, the time for stirring uniformly in the step (2) is 2 to 5 hours.
Preferably, the hydrothermal reaction kettle in the step (3) has a volume of 50 mL.
Preferably, the drying in the step (3) is drying in an oven at 60-80 ℃.
Preferably, the temperature of the hydrothermal reaction in the step (3) is 100-150 ℃, and more preferably 100 ℃; the time of the hydrothermal reaction is 10-12 hours.
Preferably, the centrifugal washing in step (3) is washing with absolute ethyl alcohol for 2-3 times, then washing with dimethylformamide for 1-2 times, and finally washing with absolute ethyl alcohol for 2-3 times.
Preferably, the temperature of the annealing reaction in the step (4) is 500-600 ℃, and the time is 1-2 hours.
The zinc ferrite/carbon lithium ion battery nano composite negative electrode material with the fusiform structure prepared by the method is a polyhedral structure with the fusiform structure, namely a structure similar to a Chinese date core, two pointed ends and a thick middle part, the fusiform structure is formed by compounding secondary nano zinc ferrite particles with a carbon framework, and the content of zinc ferrite in the nano composite negative electrode material is 60-90 wt%.
Preferably, the particle size of the zinc ferrite secondary nanoparticles in the nano composite negative electrode material is 200-900 nm.
The application of the fusiform zinc ferrite/carbon lithium ion battery nano composite negative electrode material in the preparation of a lithium ion battery is provided.
Compared with the prior art, the invention has the following characteristics:
1) the carbon material has good conductivity and skeleton function, so that the spindle zinc ferrite/carbon lithium ion battery nano composite negative electrode material solves the problem of poor conductivity of pure zinc ferrite metal oxide in the charging and discharging process, promotes the rapid transmission of carriers, and effectively relieves the volume change of the metal material so as to keep the stability of the structure.
2) Due to the action of the organic metal framework fumaric acid, the material has a unique fusiform structure, the size of hundreds of nanometers is maintained, the contact area between the electrolyte and particles is well increased, the diffusion path of lithium ions is shortened, and therefore ideal electrochemical performance of the battery is achieved.
3) The preparation method is simple to operate, easy to control the process, low in cost and environment-friendly, and can promote the practical application of the lithium ion battery cathode material and realize industrial large-scale production.
Drawings
FIG. 1 is an SEM image of a nano-composite negative electrode material of a spindle-shaped zinc ferrite/carbon lithium ion battery obtained in example 1 of the invention.
FIG. 2 is a TEM image of the nano-composite negative electrode material of the spindle zinc ferrite/carbon lithium ion battery obtained in example 1 of the present invention.
Fig. 3 is an XRD chart of the nano composite cathode material of spindle zinc ferrite/carbon lithium ion battery obtained in example 1 of the present invention.
FIG. 4 is a Raman spectrum of the nano-composite negative electrode material of the spindle zinc ferrite/carbon lithium ion battery obtained in example 1 of the present invention.
Fig. 5 is a constant current charge and discharge performance diagram of a battery assembled by using the fusiform zinc ferrite/carbon nanocomposite obtained in the embodiment 1 of the invention as a lithium ion battery cathode material.
Fig. 6 is a rate performance diagram of a battery assembled by using the fusiform zinc ferrite/carbon nanocomposite obtained in example 1 of the invention as a negative electrode material of a lithium ion battery.
Detailed Description
The invention is further explained below with reference to examples and figures. The following examples are provided only for illustrating the present invention and are not intended to limit the scope of the invention.
Example 1
(1) 1.8571 g of fumaric acid (C) were weighed out4H4O499.0%) was added to 20 mL of dimethylformamide (HCON (CH)3)2AR), magnetically stirred at 750 rpm for 2 hours to give a transparent dispersion. 0.4040g of iron nitrate (Fe (NO) was weighed out3)3·9H2O, 98.5%) with 0.1487 g of zinc nitrate (Zn (NO)3)2·6H299.0%) was added to the dispersion, stirred at 750 rpm for 3 hours, mixed well and transferred to a 50 mL hydrothermal kettle sealed steel shell, and reacted in an electric heating constant temperature forced air drying oven at 100 ℃ for 12 hours. After the temperature is reduced to room temperature, carrying out solid-liquid separation on a hydrothermal reaction product, washing the obtained solid with absolute ethyl alcohol for 2 times, then washing with dimethylformamide for 1 time, and finally washing with absolute ethyl alcohol for 2 times, wherein the washing process is realized by carrying out centrifugal separation on a centrifuge at the rotating speed of 8000 rpm for 2 min, and drying the washed product in a constant-temperature drying oven at the temperature of 60 ℃ for 12 h to obtain dried precursor solid powder;
(2) uniformly placing the precursor powder in a 30 x 60 mm ceramic boat, then placing the ceramic boat in a constant-temperature area of a tube furnace, and firstly introducingThe air in the tube furnace was purged with nitrogen for 50 min, and then at 2 deg.C for min under the same nitrogen atmosphere-1Heating at a heating rate of 500 deg.C for 1h, and heating at 3 deg.C for min-1The temperature of the tube furnace is naturally reduced to the room temperature after the temperature is reduced to 400 ℃, and the nitrogen flow in the whole process is maintained at 10 mL min-1(ii) a Finally, the spindle-shaped zinc ferrite/carbon lithium ion battery nano composite negative electrode material with the zinc ferrite content of 75.2wt% is obtained.
FIG. 1 is an SEM image of the zinc ferrite/carbon nanocomposite prepared in this example. The figure shows that the composite material obtained through the processes has a fusiform structure, good dispersibility is kept among particles, the size distribution is uniform, and the size is 300-450 nm.
FIG. 2 is a TEM image of the fusiform zinc ferrite/carbon nanocomposite prepared in this example. As can be seen from the figure, the spindle-shaped zinc ferrite/carbon nanocomposite material prepared in the embodiment has the carbon component, plays a role in maintaining a structural framework in the whole particle, and comprises two-stage zinc ferrite particles with the particle size of 10-20 nm in the middle.
FIG. 3 is an XRD pattern of the fusiform zinc ferrite/carbon nanocomposite prepared in this example. The zinc ferrite with a cubic crystal structure is obtained by comparing each diffraction peak in the graph with a PDF card, and no mixed peak appears. However, no significant carbon diffraction peak was observed, which was probably not detectable due to the low carbon content.
FIG. 4 is a Raman spectrum of the fusiform zinc ferrite/carbon nanocomposite prepared in this example. 100-1000 cm in the figure-1Several characteristic peaks within the range are just vibration models of zinc ferrite substances; 1200-1600 cm-1The existence of a plurality of characteristic peaks in the range proves that the material contains carbon components, and the comparison of the peak intensity of the two peaks shows that the carbon material in the zinc ferrite/carbon nano composite material has a certain graphitization degree.
(3) Taking the spindle zinc ferrite/carbon lithium ion battery nano composite negative electrode material obtained in the step (2) as an active material, taking acetylene black as a conductive agent, taking polyvinylidene fluoride as a binder, and mixing the active material: conductive agent:binder = 7: 2: 1, then 0.5 mL of azomethylpyrrolidone is dripped into a penicillin bottle with the mass ratio of 1, the mixture is stirred for 4 hours to form slurry, the slurry is uniformly coated on a copper foil, then the copper foil is placed into a constant-temperature drying box with the temperature of 120 ℃ for drying for 12 hours, a small wafer with the thickness of 14mm is punched by a sheet punching machine after the slurry is dried to constant weight, the small wafer is taken as a working electrode, the small wafer is placed into a glove box filled with argon under the condition of ensuring no water, the purchased lithium wafer is taken as a counter electrode and a reference electrode, the used Celgard 2400 type diaphragm is provided, and the electrolyte is 1 mol L-1LiPF of6Mixed with Ethylene Carbonate (EC), dimethyl carbonate (DMC) (EC: DMC = 1: 2, v/v) and finally assembled into a button cell type CR2025 in a glove box, which must be kept at an oxygen and water vapour content of less than 1 ppm throughout the process. Thus obtaining the lithium ion battery of the spindle-shaped zinc ferrite/carbon lithium ion battery nano composite cathode material.
FIG. 5 is a diagram showing the charge-discharge cycle performance of the nanocomposite negative electrode material of the fusiform zinc ferrite/carbon lithium ion battery prepared in this embodiment. At 25 ℃ at 1000 mA g-1The current density of the lithium ion battery is between 0.01 and 3.0V, and the first discharge and charge specific capacities are 1162.3 mAh g respectively-1And 771.6 mAh g-1From the 70 th cycle, the cycle of the battery tends to be stable and is maintained at 650 mAh g-1The left and right have higher reversible specific capacity.
Fig. 6 is a graph of rate performance of the nano composite negative electrode material of the fusiform zinc ferrite/carbon lithium ion battery prepared in the embodiment. The corresponding specific capacities of the nano composite negative electrode material of the shuttle-shaped zinc ferrite/carbon lithium ion battery are 883, 752, 669, 582 and 496 mAh g respectively under the current densities of 0.2, 0.4, 0.8, 1.6 and 3.2C-1(ii) a Even at higher 6.4C rates, the material retained 389 mAh g-1The reversible specific capacity of (a). When the current multiplying power of the circulation returns to 0.2C, the storage capacity returns to 915 mAh g-1And the capacity is gradually increased along with the increase of the number of cycles, which shows that the nano composite negative electrode material of the fusiform zinc ferrite/carbon lithium ion battery has better rate capability and cycling stability.
Example 2
(1) 1.8571 g of fumaric acid (C) were weighed out4H4O499.0%) was added to 20 mL of dimethylformamide (HCON (CH)3)2AR), was stirred and mixed at 750 rpm for 3 hours to obtain a transparent dispersion. 0.8080 g of iron nitrate (Fe (NO) was weighed out3)3·9H2O, 98.5%) with 0.2974 g of zinc nitrate (Zn (NO)3)2·6H299.0%) was added to the dispersion, stirred at 750 rpm for 3 hours, mixed well and transferred to a 50 mL hydrothermal kettle sealed steel shell, and reacted in an electric heating constant temperature forced air drying oven at 100 ℃ for 10 hours. After the temperature is reduced to room temperature, carrying out solid-liquid separation on a hydrothermal reaction product, washing the obtained solid with absolute ethyl alcohol for 2 times, then washing with dimethylformamide for 1 time, and finally washing with absolute ethyl alcohol for 2 times, wherein the washing process is realized by carrying out centrifugal separation on a centrifuge at the rotating speed of 8000 rpm for 2 min, and drying the washed product in a constant-temperature drying oven at the temperature of 60 ℃ for 12 h to obtain dried precursor solid powder;
(2) uniformly placing the precursor powder in a 30 x 60 mm ceramic boat, placing in a constant temperature region of a tube furnace, introducing 50 min nitrogen to remove air in the tube furnace, and then performing 2 deg.C min under the same nitrogen atmosphere-1Heating at a heating rate of 600 deg.C for 1h, and heating at 3 deg.C for min-1The temperature of the tubular furnace is naturally reduced to room temperature after being reduced to 400 ℃, and the nitrogen flow in the whole process is maintained at 10 mLmin-1(ii) a Finally, the spindle-shaped zinc ferrite/carbon lithium ion battery nano composite negative electrode material with 68 percent of zinc ferrite content is obtained.
(3) Taking the spindle zinc ferrite/carbon lithium ion battery nano composite negative electrode material obtained in the step (2) as an active material, taking acetylene black as a conductive agent, taking polyvinylidene fluoride as a binder, and mixing the active material: conductive agent: binder = 7: 2: 1, then adding into a penicillin bottle with the mass ratio of 5 mL, then dropwise adding 0.75 mL of N-methyl pyrrolidone, stirring for 4 hours to form slurry, uniformly coating the slurry on a copper foil, and then putting into a constant-temperature drying oven with the temperature of 120 ℃ for dryingDrying for 12 h, drying to constant weight, punching out a 14mm small wafer serving as a working electrode by using a sheet punching machine, putting the small wafer into a glove box filled with argon under the condition of ensuring no water, using the purchased lithium wafer as a counter electrode and a reference electrode, using a Celgard 2400 type diaphragm, and using 1 mol L of electrolyte-1LiPF of6Mixed with Ethylene Carbonate (EC), dimethyl carbonate (DMC) (EC: DMC = 1: 2, v/v) and finally assembled into a button cell type CR2025 in a glove box, which must be kept at an oxygen and water vapour content of less than 1 ppm throughout the process. Thus obtaining the lithium ion battery assembled by the spindle-shaped zinc ferrite/carbon lithium ion battery nano composite cathode material.
Finally, the spindle-shaped zinc ferrite/carbon lithium ion battery nano composite negative electrode material with the zinc ferrite content of 68 wt% is obtained.
The composite material obtained through the processes has a fusiform structure, good dispersibility among particles is kept, the size distribution is uniform, and the size is 450-600 nm. The corresponding specific capacities of the nano composite cathode material of the fusiform zinc ferrite/carbon lithium ion battery are 847, 743, 637, 569 and 473 mAh g respectively under the current densities of 0.2, 0.4, 0.8, 1.6 and 3.2C-1(ii) a Even at higher 6.4C rate, the material still retained 363 mAh g-1The reversible specific capacity of (a). When the current multiplying power of the circulation returns to 0.2C, the storage capacity returns to 839 mAh g-1And the capacity is gradually increased along with the increase of the number of cycles, which shows that the nano composite negative electrode material of the fusiform zinc ferrite/carbon lithium ion battery has better rate capability and cycling stability.
Example 3
(1) 3.7142 g of fumaric acid (C) were weighed out4H4O499.0%) was added to 40 mL of dimethylformamide (HCON (CH)3)2AR), was stirred and mixed at 750 rpm for 2 hours to obtain a transparent dispersion. 0.8080 g of iron nitrate (Fe (NO) was weighed out3)3·9H2O, 98.5%) with 0.2974 g of zinc nitrate (Zn (NO)3)2·6H299.0%) was added to the dispersion as described aboveStirring for 3 hours at the speed of 750 rpm, uniformly mixing, transferring into a 50 mL sealed steel shell of a hydrothermal kettle, and reacting for 12 hours in an electric heating constant-temperature air-blast drying oven at the temperature of 150 ℃. After the temperature is reduced to room temperature, carrying out solid-liquid separation on a hydrothermal reaction product, washing the obtained solid with absolute ethyl alcohol for 3 times, then washing with dimethylformamide for 2 times, and finally washing with absolute ethyl alcohol for 3 times, wherein the washing process is realized by carrying out centrifugal separation on a centrifuge at the rotating speed of 8000 rpm for 2 min, and drying the washed product in a constant-temperature drying oven at the temperature of 60 ℃ for 12 h to obtain dried precursor solid powder;
(2) uniformly placing the precursor powder in a 30 x 60 mm ceramic boat, placing in a constant temperature region of a tube furnace, introducing 50 min nitrogen to remove air in the tube furnace, and then performing 2 deg.C min under the same nitrogen atmosphere-1Heating at a heating rate of 550 deg.C for 1h, and heating to 3 deg.C for min-1After the temperature is reduced to 400 ℃, the temperature of the tube furnace is naturally reduced to the room temperature, and the nitrogen flow in the whole process is maintained at 10 mL min-1(ii) a Finally, the spindle-shaped zinc ferrite/carbon lithium ion battery nano composite negative electrode material with the zinc ferrite content of 75.2 percent is obtained.
(3) Taking the spindle zinc ferrite/carbon lithium ion battery nano composite negative electrode material obtained in the step (2) as an active material, taking acetylene black as a conductive agent, taking polyvinylidene fluoride as a binder, and mixing the active material: conductive agent: binder = 7: 2: 1, then 0.9 mL of azomethylpyrrolidone is dripped into a penicillin bottle with the mass ratio of 1, the mixture is stirred for 4 hours to form slurry, the slurry is uniformly coated on a copper foil, then the copper foil is placed into a constant-temperature drying box with the temperature of 120 ℃ for drying for 12 hours, a small wafer with the thickness of 14mm is punched by a sheet punching machine after the slurry is dried to constant weight, the small wafer is taken as a working electrode, the small wafer is placed into a glove box filled with argon under the condition of ensuring no water, the purchased lithium wafer is taken as a counter electrode and a reference electrode, the used Celgard 2400 type diaphragm is provided, and the electrolyte is 1 mol L-1LiPF of6Mixed with Ethylene Carbonate (EC) and dimethyl carbonate (DMC) (EC: DMC = 1: 2, v/v), and finally assembled into a button cell type CR2025 in a glove box, wherein the whole glove box must keep oxygenThe water vapor content and the water vapor content are both less than 1 ppm. Thus obtaining the lithium ion battery assembled by the spindle-shaped zinc ferrite/carbon lithium ion battery nano composite cathode material.
Finally, the spindle-shaped zinc ferrite/carbon lithium ion battery nano composite negative electrode material with the zinc ferrite content of 75.2wt% is obtained.
The composite material obtained through the processes has a fusiform structure, good dispersibility among particles is kept, the size distribution is uniform, and the size is 250-400 nm. The corresponding specific capacities of the nano composite negative electrode material of the fusiform zinc ferrite/carbon lithium ion battery are 891, 767, 672, 593 and 506 mAh g respectively under the current densities of 0.2, 0.4, 0.8, 1.6 and 3.2C-1(ii) a Even at higher 6.4C rates, the material retained 397 mAh g-1The reversible specific capacity of (a). When the current multiplying power of the circulation returns to 0.2C, the storage capacity returns to 887 mAh g-1And the capacity is gradually increased along with the increase of the number of cycles, which shows that the nano composite negative electrode material of the fusiform zinc ferrite/carbon lithium ion battery has better rate capability and cycling stability.
Example 4
(1) 3.7142 g of fumaric acid (C) were weighed out4H4O499.0%) was added to 40 mL of dimethylformamide (HCON (CH)3)2AR), was stirred and mixed at 750 rpm for 2 hours to obtain a transparent dispersion. 0.2702 g of ferric chloride (FeCl) were weighed out3·6H2O, AR) with 0.1096 g of Zinc acetate (Zn (Ac)2·2H2O, 97.0%) was added to the dispersion, stirred at 750 rpm for 3 hours, mixed well and transferred to a 50 mL hydrothermal kettle sealed steel shell, and reacted in an electric heating constant temperature forced air drying oven at 125 ℃ for 11 hours. Cooling to room temperature, performing solid-liquid separation on the hydrothermal reaction product, washing the obtained solid with absolute ethyl alcohol for 2 times, then washing with dimethylformamide for 1 time, and finally washing with absolute ethyl alcohol for 2 times, wherein the washing process is realized by centrifuging the obtained product at 8000 rpm for 2 min, and drying the obtained product in a constant-temperature drying oven at 60 ℃ for 12 h to obtain the final productTo a dry precursor solid powder;
(2) uniformly placing the precursor powder in a 30 x 60 mm ceramic boat, placing in a constant temperature region of a tube furnace, introducing 50 min nitrogen to remove air in the tube furnace, and then performing 2 deg.C min under the same nitrogen atmosphere-1Heating at a heating rate of 500 deg.C for 1h, heating to 600 deg.C for 1h, and heating at 3 deg.C for min-1The temperature of the tube furnace is naturally reduced to the room temperature after the temperature is reduced to 400 ℃, and the nitrogen flow in the whole process is maintained at 10 mL min-1(ii) a Finally, the spindle-shaped zinc ferrite/carbon lithium ion battery nano composite negative electrode material with the zinc ferrite content of 60 percent is obtained.
(3) Taking the spindle zinc ferrite/carbon lithium ion battery nano composite negative electrode material obtained in the step (2) as an active material, taking acetylene black as a conductive agent, taking polyvinylidene fluoride as a binder, and mixing the active material: conductive agent: binder = 7: 2: 1, then dropwise adding 1 mL of azomethylpyrrolidone, stirring for 4 hours to form slurry, uniformly coating the slurry on a copper foil, then putting the copper foil into a constant-temperature drying box at 120 ℃ for drying for 12 hours, drying to constant weight, then using a sheet punching machine to punch a small 14mm wafer which is a working electrode, putting the small wafer into a glove box filled with argon under the condition of ensuring no water, using purchased lithium wafers as a counter electrode and a reference electrode, using a Celgard 2400 type diaphragm, and using 1 mol L of electrolyte as a diaphragm-1LiPF of6Mixed with Ethylene Carbonate (EC), dimethyl carbonate (DMC) (EC: DMC = 1: 2, v/v) and finally assembled into a button cell type CR2025 in a glove box, which must maintain oxygen and water vapour contents of less than 1 ppm. Thus obtaining the lithium ion battery assembled by the spindle-shaped zinc ferrite/carbon lithium ion battery nano composite cathode material.
Finally, the spindle-shaped zinc ferrite/carbon lithium ion battery nano composite negative electrode material with the zinc ferrite content of 60 wt% is obtained.
The composite material obtained through the processes has a fusiform structure, good dispersibility among particles is kept, the size distribution is uniform, and the size is 200-350 nm. At a temperature of 0.2, 0.4, 0.8, 1.6,Under the current densities of 3.2C, the corresponding specific capacities of the spindle zinc ferrite/carbon lithium ion battery nano composite negative electrode material are 989, 819, 709, 562 and 456 mAh g-1(ii) a Even at higher 6.4C rate, the material still retained 357 mAh g-1The reversible specific capacity of (a). When the current multiplying power of the circulation returns to 0.2C, the storage capacity returns to 995 mAh g-1And the capacity is gradually increased along with the increase of the number of cycles, which shows that the nano composite negative electrode material of the fusiform zinc ferrite/carbon lithium ion battery has better rate capability and cycling stability.
Example 5
(1) 0.4643 g of fumaric acid (C) were weighed out4H4O499.0%) was added to 5 mL of dimethylformamide (HCON (CH)3)2AR), magnetically stirred at 750 rpm for 2 hours to give a transparent dispersion. 0.4040g of iron nitrate (Fe (NO) was weighed out3)3·9H2O, 98.5%) with 0.1487 g of zinc nitrate (Zn (NO)3)2·6H299.0%) was added to the dispersion, stirred at 750 rpm for 3 hours, mixed well and transferred to a 50 mL hydrothermal kettle sealed steel shell, and reacted in an electric heating constant temperature forced air drying oven at 150 ℃ for 11 hours. After the temperature is reduced to room temperature, carrying out solid-liquid separation on a hydrothermal reaction product, washing the obtained solid with absolute ethyl alcohol for 2 times, then washing with dimethylformamide for 1 time, and finally washing with absolute ethyl alcohol for 3 times, wherein the washing process is realized by carrying out centrifugal separation on a centrifuge at the rotating speed of 8000 rpm for 2 min, and drying the washed product in a constant-temperature drying oven at the temperature of 60 ℃ for 12 h to obtain dried precursor solid powder;
(2) uniformly placing the precursor powder in a 30 x 60 mm ceramic boat, placing in a constant temperature region of a tube furnace, introducing 50 min nitrogen to remove air in the tube furnace, and then performing 2 deg.C min under the same nitrogen atmosphere-1Heating at a heating rate of 600 deg.C for 1h, and heating at 3 deg.C for min-1Cooling to 400 ℃ and then naturally cooling the tube furnace to room temperature, wherein nitrogen in the whole processThe air flow rate is maintained at 10 mL min-1；
(3) Taking the spindle zinc ferrite/carbon lithium ion battery nano composite negative electrode material obtained in the step (2) as an active material, taking acetylene black as a conductive agent, taking polyvinylidene fluoride as a binder, and mixing the active material: conductive agent: binder = 7: 2: 1, then dropwise adding 1 mL of azomethylpyrrolidone, stirring for 4 hours to form slurry, uniformly coating the slurry on a copper foil, then putting the copper foil into a constant-temperature drying box at 120 ℃ for drying for 12 hours, drying to constant weight, then using a sheet punching machine to punch a small 14mm wafer which is a working electrode, putting the small wafer into a glove box filled with argon under the condition of ensuring no water, using purchased lithium wafers as a counter electrode and a reference electrode, using a Celgard 2400 type diaphragm, and using 1 mol L of electrolyte as a diaphragm-1LiPF of6Mixed with Ethylene Carbonate (EC), dimethyl carbonate (DMC) (EC: DMC = 1: 2, v/v) and finally assembled into a button cell type CR2025 in a glove box, which must maintain oxygen and water vapour contents of less than 1 ppm. Thus obtaining the lithium ion battery assembled by the spindle-shaped zinc ferrite/carbon lithium ion battery nano composite cathode material.
Finally, the spindle-shaped zinc ferrite/carbon lithium ion battery nano composite negative electrode material with the zinc ferrite content of 90 wt% is obtained.
The composite material obtained through the processes has a fusiform structure, good dispersibility among particles is kept, the size distribution is uniform, and the size is 700-900 nm. Under the current densities of 0.2, 0.4, 0.8, 1.6 and 3.2C, the corresponding specific capacities of the nano composite negative electrode material of the fusiform zinc ferrite/carbon lithium ion battery are 799, 739, 657, 469 and 397 mAh g respectively-1(ii) a Even at higher 6.4C rate, the material still retained 301 mAh g-1The reversible specific capacity of (a). When the current multiplying power of the circulation returns to 0.2C, the storage capacity returns to 800 mAh g-1And the capacity is gradually increased along with the increase of the number of cycles, which shows that the nano composite negative electrode material of the fusiform zinc ferrite/carbon lithium ion battery has better rate capability and cycling stability.
Claims (10)
1. A preparation method of a nano composite negative electrode material of a fusiform zinc ferrite/carbon lithium ion battery is characterized by comprising the following steps:
(1) dissolving fumaric acid in dimethylformamide, and uniformly stirring to obtain a dispersion liquid;
(2) adding iron metal salt and zinc metal salt into the dispersion liquid obtained in the step (1), and uniformly stirring to obtain a mixed liquid; the molar ratio of the fumaric acid to the metal ions in the metal salt is 2.66:1, 5.33:1, 10.67:1 or 21.33:1, wherein the metal salt comprises an iron metal salt and a zinc metal salt;
(3) transferring the mixed solution obtained in the step (2) into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an electric heating constant-temperature air-blowing drying oven for hydrothermal reaction, cooling to room temperature, centrifugally washing and drying;
(4) and (4) putting the powder obtained after drying in the step (3) into a porcelain boat, then putting into a tube furnace, carrying out annealing reaction in a nitrogen atmosphere, and cooling to room temperature to obtain the spindle-shaped zinc ferrite/carbon lithium ion battery nano composite negative electrode material.
2. The production method according to claim 1, wherein the fumaric acid in the step (1) is used in an amount of 4 to 32 mmol.
3. The method according to claim 1, wherein the amount of the iron metal salt and the zinc metal salt added in the step (2) is controlled so that the molar ratio of Fe to Zn is (1.5-3): (0.75 to 1.5).
4. The method according to claim 1, wherein the iron metal salt in the step (2) is one of ferric nitrate and ferric trichloride; the zinc metal salt is one of zinc nitrate and zinc acetate.
5. The preparation method according to claim 1, wherein the hydrothermal reaction in the step (3) is carried out at a temperature of 100 to 150 ℃ for 10 to 12 hours.
6. The method according to claim 1, wherein the centrifugal washing in step (3) is performed by washing with absolute ethanol for 2-3 times, washing with dimethylformamide for 1-2 times, and washing with absolute ethanol for 2-3 times.
7. The method according to claim 1, wherein the annealing in step (4) is carried out at a temperature of 500 to 600 ℃ for 1 to 2 hours.
8. A nanocomposite negative electrode material of a zinc ferrite/carbon lithium ion battery having a shuttle structure prepared by the method of any one of claims 1 to 7, wherein the content of zinc ferrite in the nanocomposite negative electrode material is 60 to 90 wt%.
9. The nano composite negative electrode material of the fusiform zinc ferrite/carbon lithium ion battery as claimed in claim 8, wherein the secondary zinc ferrite nanoparticles in the nano composite negative electrode material have a particle size of 200-900 nm.
10. The use of the nanocomposite negative electrode material of a fusiform zinc ferrite/carbon lithium ion battery according to claim 9 for preparing a lithium ion battery.
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