CN107104229B - Lithium ion battery cathode material silicon oxide doped manganese oxide/carbon tube and preparation method thereof - Google Patents
Lithium ion battery cathode material silicon oxide doped manganese oxide/carbon tube and preparation method thereof Download PDFInfo
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Abstract
The lithium ion battery cathode material is silicon oxide doped manganese oxide/carbon tube and the preparation method, the material is prepared by the following method: (1) dispersing carbon nano tubes in a low-carbon alcohol solution of N, N-dimethylformamide to obtain a carbon nano tube dispersion solution; (2) dissolving a manganese source, a precipitator and a silicon source in a carbon nano tube dispersion liquid, uniformly stirring, carrying out hydrothermal reaction, naturally cooling to room temperature, filtering, washing, and freeze-drying to obtain black powder; (3) and calcining the black powder in a protective atmosphere, and cooling to room temperature along with the furnace to obtain the silicon oxide doped manganese oxide/carbon tube serving as the cathode material of the lithium ion battery. The material has uniform shape and size, and the manganese oxide grains doped with silicon oxide grow on the surface of the carbon nano tube; the lithium ion battery has the advantages of high electronic conductivity and ionic conductivity, short ion diffusion channel, small volume effect in the process of releasing and embedding lithium ions and the like; the invention has the advantages of simple preparation flow, short period, low reaction temperature, low cost, large-scale synthesis and high product yield.
Description
Technical Field
The invention relates to a lithium ion battery cathode material and a preparation method thereof, in particular to a lithium ion battery cathode material, namely a silicon oxide doped manganese oxide/carbon tube and a preparation method thereof.
Background
With the development of science and technology, the popularization of electronic products such as smart phones and notebook computers and electric vehicles puts higher demands on batteries as energy sources thereof. The lithium ion battery is distinguished by the characteristics of high energy density, environmental friendliness and the like. At present, the negative electrode material of the lithium ion battery mainly adopts a graphite material, the capacity is low, the theoretical specific capacity is only 372mAh/g, the cycle performance is poor, and the development of the lithium ion battery is restricted.
The transition metal oxide manganese oxide is one of the optional materials of the lithium ion battery because of high theoretical capacity and low price. However, because manganese oxide has poor conductivity, large volume effect in the charge and discharge process and poor cycle performance, it is often necessary to coat and modify the manganese oxide, and how to improve the cycle and rate performance of manganese oxide becomes one of the research focuses of researchers.
CN 106252628A discloses a manganese oxide/graphene nanocomposite and a preparation method thereof, and the manganese oxide/graphene nanocomposite is prepared through the working procedures of hydrothermal treatment, compounding, roasting and the like. However, the synthesis process of the material has more steps and longer process time.
CN 105702923A discloses a manganese oxide/carbon nanotube composite material and a preparation method thereof, wherein manganese oxide is dispersed in a thermosetting resin monomer solvent, then carbon nanotubes are introduced, and after double bonds are cured, the manganese oxide/carbon nanotube composite material is crushed and calcined at high temperature. However, the preparation method is complex in preparation steps, and the specific capacity of the prepared material is lower than 500mAh/g, so that the performance is poor.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a silicon oxide doped manganese oxide/carbon tube serving as a negative electrode material of a lithium ion battery and a preparation method thereof, wherein the manganese oxide has the advantages of good conductivity, small volume effect, high discharge capacity, small volume change in the charge-discharge process, good cycle performance and simple preparation process.
The technical scheme adopted by the invention for solving the technical problems is as follows: the lithium ion battery cathode material silicon oxide doped manganese oxide/carbon tube is prepared by the following method:
(1) dispersing carbon nano tubes in a low-carbon alcohol solution of N, N-dimethylformamide to obtain a carbon nano tube dispersion solution;
(2) dissolving a manganese source, a precipitator and a silicon source in the carbon nano tube dispersion liquid obtained in the step (1), uniformly stirring, carrying out hydrothermal reaction, naturally cooling to room temperature, filtering, washing, and freeze-drying to obtain black powder;
(3) and (3) calcining the black powder obtained in the step (2) in a protective atmosphere, and cooling to room temperature along with the furnace to obtain the silicon oxide doped manganese oxide/carbon tube serving as the negative electrode material of the lithium ion battery.
Preferably, in the step (1), the dispersion amount of the carbon nanotubes in the low-carbon alcohol solution of N, N-dimethylformamide is 0.1-0.4 mg/mL.
Preferably, in the step (1), in the low carbon alcohol solution of N, N-dimethylformamide, the volume ratio of the low carbon alcohol to the N-N dimethylformamide is 0.4-1.5: 1 (more preferably 0.5-1.0: 1), and the low carbon alcohol is one or more of methanol, ethanol, propanol, or the like. The precipitation speed of manganese ions and the hydrolysis speed of silicon ions can be controlled by adjusting the proportion of the low-carbon alcohol and the N, N-dimethylformamide, so that manganese carbonate serving as a manganese precipitation product and silicon dioxide serving as a silicon hydrolysis product can uniformly grow on the carbon nano tubes dispersed in the solution.
Preferably, in the step (2), the molar ratio of the manganese element in the manganese source, the precipitant and the silicon element in the silicon source is 4-20: 200-400: 1 (more preferably 5-10: 205-330: 1), and the mass ratio of the carbon nanotube to the manganese source is 1: 10-30 (more preferably 1: 15-25). The manganese source or silicon source mainly provides manganese or silicon in the product. Silica, which is a hydrolysate of doped silicon, can sufficiently utilize its excellent lithium ion conductivity and the plastic properties of lithiated silicon, but since the produced silica is inactive, if the doping amount is too large, the specific discharge capacity is affected. The precipitant can promote the precipitation of manganese and the hydrolysis of silicon by decomposing in the hydrothermal reaction.
Preferably, in the step (2), the molar concentration of the manganese element in the manganese source in the carbon nanotube dispersion liquid is 0.01-0.05 mol/L (more preferably 0.02-0.04 mol/L). The molar concentration of the precipitant in the carbon nanotube dispersion liquid is 0.5-1.5 mol/L. The molar concentration of the silicon element in the silicon source in the carbon nano tube dispersion liquid is 0.001-0.005 mol/L. Under the concentration condition, manganese carbonate serving as a manganese precipitation product and silicon dioxide serving as a silicon hydrolysis product can grow more uniformly, and the size of the grown particles of the manganese carbonate and the silicon dioxide can be influenced by over-concentration or under-concentration.
Preferably, in the step (2), the manganese source is one or more of manganese sulfate, manganese nitrate or manganese chloride.
Preferably, in the step (2), the precipitant is one or more of urea, glycine, alanine, or the like.
Preferably, in the step (2), the silicon source is isopropyl silicate and/or ethyl orthosilicate.
Preferably, in the step (2), the temperature of the hydrothermal reaction is 150-200 ℃ (more preferably 160-180 ℃) and the time is 2-12 h (more preferably 4-6 h). The hydrothermal reaction is mainly a manganese precipitation reaction and a silicon hydrolysis reaction. If the hydrothermal reaction temperature is too low, the precipitant is not easy to decompose, and if the temperature is too high, the product particles are larger and are difficult to form a proper nano-morphology. The hydrothermal reaction is preferably carried out by putting the solution dispersed with the carbon nano tubes into a reaction kettle and putting the reaction kettle into a drying box; the preferable inside lining of the reaction kettle is a stainless steel reaction kettle made of polytetrafluoroethylene.
Preferably, in the step (2), the washing mode is that the precipitate is washed by alcohol and water for more than or equal to 2 times respectively. The alcohol is methanol or ethanol, residual organic matters can be washed away by the alcohol, and residual inorganic matters can be washed away by water.
Preferably, in the step (2), the temperature of the freeze drying is less than-40 ℃, the vacuum degree is less than 50Pa, and the time is 36-48 h. The nano-morphology of the product can be better maintained by adopting freeze drying.
Preferably, in the step (3), the calcining temperature is 600-900 ℃ (more preferably 700-800 ℃) and the calcining time is 1-5 h (more preferably 2-3 h). The calcination decomposes manganese carbonate, which is a precipitation product of manganese, into manganese oxide, and if the calcination temperature is too low, the reaction is difficult to proceed, and if the calcination temperature is too high, side reactions may occur.
Preferably, in the step (3), the protective atmosphere is argon or argon/hydrogen mixed gas, wherein the volume fraction of hydrogen in the argon/hydrogen mixed gas is 3-10%. The protective atmosphere used in the method is high-purity gas with the purity of more than or equal to 99.99 percent.
According to the preparation method of the silicon oxide doped manganese oxide/carbon tube serving as the negative electrode material of the lithium ion battery, the silicon oxide doped manganese oxide particles are grown on the surface of the carbon nano tube, so that the carbon nano tube provides excellent electronic conductivity and a lithium ion diffusion channel, and simultaneously has a large specific surface area, and the silicon dioxide also has excellent lithium ion conductivity and the plastic property of lithiated silicon, so that the electrochemical performance of the manganese oxide can be remarkably improved by adopting the carbon nano tube and the silicon dioxide.
The invention has the following beneficial effects:
(1) the silicon oxide doped manganese oxide/carbon tube product as the negative electrode material of the lithium ion battery has uniform appearance and size, the diameter of the carbon nanotube is less than 50nm, the particle size of silicon oxide doped manganese oxide particles is 10-100 nm, and the particles uniformly grow on the surface of the carbon nanotube;
(2) the silicon oxide doped manganese oxide/carbon tube serving as the negative electrode material of the lithium ion battery has the advantages of high electronic conductivity and ionic conductivity, short ion diffusion channel, small volume effect in the process of releasing and inserting lithium ions and the like; the lithium ion battery cathode material silicon oxide doped manganese oxide/carbon tube is assembled into a battery, the first discharge gram capacity can reach 881.6mAh/g under the voltage range of 0.01-3.00V and the current density of 70mA/g, the capacity is stabilized at more than 600mAh/g after 10 times of circulation, the coulombic efficiency is more than 95%, the capacity is stabilized at more than 570mAh/g under the current density of 140mA/g and the current density is 10 times of circulation, and the coulombic efficiency is more than 95%;
(3) the invention has the advantages of simple preparation flow, short period, low reaction temperature, low cost, large-scale synthesis and high product yield.
Drawings
FIG. 1 is an SEM image of a silicon oxide-doped manganese oxide/carbon tube as a negative electrode material of a lithium ion battery obtained in example 1 of the present invention;
FIG. 2 is a first charge-discharge curve diagram of a silicon oxide-doped manganese oxide/carbon tube as a negative electrode material of a lithium ion battery obtained in example 1 of the present invention;
FIG. 3 is a graph showing the cycle charge/discharge curves of the lithium ion battery negative electrode material silicon oxide doped manganese oxide/carbon tube obtained in example 1 of the present invention;
FIG. 4 is an SEM image of the silicon oxide doped manganese oxide/carbon tube as the negative electrode material of the lithium ion battery obtained in example 2 of the present invention.
Detailed Description
The invention is further illustrated by the following examples and figures.
The carbon nano tube model TNMC8 used in the embodiment of the invention is purchased from China times; the purity of the high-purity argon used in the embodiment of the invention is 99.99 percent; the chemical reagents used in the examples of the present invention, unless otherwise specified, are commercially available in a conventional manner.
Example 1
(1) Dispersing 10mg of carbon nano tube in a low-carbon alcohol solution of N, N-dimethylformamide (which is formed by mixing 25mL of ethanol and 25mL of N, N-dimethylformamide) to obtain a carbon nano tube dispersion solution;
(2) dissolving 151mg of manganese sulfate (1 mmol), 2g of urea (33.30 mmol) and 35 mu L of ethyl orthosilicate (0.16 mmol) in the carbon nano tube dispersion liquid obtained in the step (1), uniformly stirring, then loading into a 100 mL stainless steel reaction kettle with a polytetrafluoroethylene lining, placing in a drying box, carrying out hydrothermal reaction at 180 ℃ for 4h, naturally cooling to room temperature, filtering, washing precipitates with absolute ethyl alcohol and deionized water for 3 times respectively, and freeze-drying at-45 ℃ and a vacuum degree of 35Pa for 48h to obtain black powder;
(3) and (3) calcining the black powder obtained in the step (2) in high-purity argon at 800 ℃ for 2h, and cooling to room temperature along with the furnace to obtain the silicon oxide doped manganese oxide/carbon tube serving as the cathode material of the lithium ion battery.
As shown in fig. 1, in the lithium ion battery negative electrode material silicon oxide doped manganese oxide/carbon tube obtained in the embodiment of the present invention, the diameter of the carbon nanotube is less than 50nm, and the particle size of the silicon oxide doped manganese oxide particle is 10-100 nm, and the silicon oxide doped manganese oxide particle uniformly grows on the surface of the carbon nanotube.
Assembling the battery: weighing 0.14 g of silicon oxide doped manganese oxide/carbon tube serving as the negative electrode material of the lithium ion battery obtained in the embodiment of the invention, adding 0.02g of acetylene black serving as a conductive agent, 0.04g of polyvinylidene fluoride serving as a binder, using N-methyl pyrrolidone as a dispersing agent, uniformly mixing, coating the mixture on copper foil to prepare a negative electrode sheet, and assembling the negative electrode sheet into a CR2025 button cell by using a metal lithium sheet as a positive electrode, a pe and pp composite film as a diaphragm and 1mol/L lithium hexafluorophosphate/DMC: EC (volume ratio 1: 1) as electrolyte in a vacuum glove box.
As shown in FIG. 2, the first discharge gram capacity of the battery is 881.6mAh/g under the voltage range of 0.01-3.00V and the current density of 70 mA/g.
As shown in FIG. 3, the detection shows that the capacity of the battery is stabilized at more than 600mAh/g and the coulombic efficiency is more than 95% after the battery is cycled for 10 times at 70mA/g current density within the voltage range of 0.01-3.00V, and immediately after the battery is cycled for 10 times at 140mAh/g current density, the capacity can still be stabilized at about 600mAh/g, and the coulombic efficiency is more than 98%.
Example 2
(1) Dispersing 20mg of carbon nano tube in a low-carbon alcohol solution of N, N-dimethylformamide (prepared by mixing 20mL of ethanol and 30mL of N, N-dimethylformamide) to obtain a carbon nano tube dispersion solution;
(2) dissolving 357.9mg of manganese nitrate (2 mmol), 5g of glycine (66.60 mmol) and 55 mu L of ethyl orthosilicate (0.25 mmol) in the carbon nano tube dispersion liquid obtained in the step (1), uniformly stirring, then loading into a 100 mL stainless steel reaction kettle with a polytetrafluoroethylene lining, placing in a drying oven, carrying out hydrothermal reaction at 180 ℃ for 6h, naturally cooling to room temperature, filtering, washing precipitates with absolute ethyl alcohol and deionized water successively for 3 times respectively, and freeze-drying at-45 ℃ and under the vacuum degree of 35Pa for 48h to obtain black powder;
(3) and (3) calcining the black powder obtained in the step (2) in high-purity argon at 750 ℃ for 3h, and cooling to room temperature along with the furnace to obtain the silicon oxide doped manganese oxide/carbon tube serving as the cathode material of the lithium ion battery.
As shown in fig. 4, in the lithium ion battery negative electrode material silicon oxide doped manganese oxide/carbon tube obtained in the embodiment of the present invention, the diameter of the carbon nanotube is less than 50nm, and the particle size of the silicon oxide doped manganese oxide particle is 10 to 100nm, and the silicon oxide doped manganese oxide particle uniformly grows on the surface of the carbon nanotube.
Assembling the battery: weighing 0.14 g of silicon oxide doped manganese oxide/carbon tube serving as the negative electrode material of the lithium ion battery obtained in the embodiment of the invention, adding 0.02g of acetylene black serving as a conductive agent, 0.04g of polyvinylidene fluoride serving as a binder, using N-methyl pyrrolidone as a dispersing agent, uniformly mixing, coating the mixture on copper foil to prepare a negative electrode sheet, and assembling the negative electrode sheet into a CR2025 button cell by using a metal lithium sheet as a positive electrode, a pe and pp composite film as a diaphragm and 1mol/L lithium hexafluorophosphate/DMC: EC (volume ratio 1: 1) as electrolyte in a vacuum glove box.
Through detection, the first discharge gram capacity of the battery is 850.1mAh/g under the voltage range of 0.01-3.00V and the current density of 70mA/g, and the coulombic efficiency is more than 95%.
Example 3
(1) Dispersing 10mg of carbon nano tube in a low-carbon alcohol solution of N, N-dimethylformamide (formed by mixing 20mL of methanol and 40mL of N, N-dimethylformamide) to obtain a carbon nano tube dispersion solution;
(2) 214.74mg of manganese nitrate (1.2 mmol), 2.5g of urea (41.63 mmol) and 40 mu L of isopropyl silicate (0.13 mmol) are dissolved in the carbon nano tube dispersion liquid obtained in the step (1), the mixture is uniformly stirred, then the mixture is put into a 100 mL stainless steel reaction kettle with a polytetrafluoroethylene lining, the reaction kettle is placed in a drying oven, after hydrothermal reaction is carried out for 4 hours at 160 ℃, the mixture is naturally cooled to room temperature, filtered, the precipitate is washed by absolute methanol and deionized water for 2 times respectively, and the mixture is frozen and dried for 36 hours at-50 ℃ and under the vacuum degree of 40Pa to obtain black powder;
(3) and (3) calcining the black powder obtained in the step (2) in argon/hydrogen mixed gas (wherein the volume fraction of hydrogen is 8%) at 700 ℃ for 3h, and cooling to room temperature along with the furnace to obtain the silicon oxide doped manganese oxide/carbon tube serving as the cathode material of the lithium ion battery.
Assembling the battery: weighing 0.14 g of silicon oxide doped manganese oxide/carbon tube serving as the negative electrode material of the lithium ion battery obtained in the embodiment of the invention, adding 0.02g of acetylene black serving as a conductive agent, 0.04g of polyvinylidene fluoride serving as a binder, using N-methyl pyrrolidone as a dispersing agent, uniformly mixing, coating the mixture on copper foil to prepare a negative electrode sheet, and assembling the negative electrode sheet into a CR2025 button cell by using a metal lithium sheet as a positive electrode, a pe and pp composite film as a diaphragm and 1mol/L lithium hexafluorophosphate/DMC: EC (volume ratio 1: 1) as electrolyte in a vacuum glove box.
Through detection, after the battery is cycled for 10 times within the voltage range of 0.01-3.00V and under the current density of 140mA/g, the capacity is stabilized to be more than 570mAh/g, and the coulombic efficiency is more than 95%.
Claims (9)
1. The lithium ion battery cathode material silicon oxide doped manganese oxide/carbon tube is characterized by being prepared by the following method:
(1) dispersing carbon nanotubes in a low-carbon alcohol solution of N, N-dimethylformamide to obtain a carbon nanotube dispersion solution, wherein the volume ratio of the low-carbon alcohol to the N-dimethylformamide is 0.4-1.5: 1;
(2) dissolving a manganese source, a precipitator and a silicon source in the carbon nano tube dispersion liquid obtained in the step (1), uniformly stirring, carrying out hydrothermal reaction, naturally cooling to room temperature, filtering, washing, and freeze-drying to obtain black powder;
(3) calcining the black powder obtained in the step (2) in a protective atmosphere, and cooling to room temperature along with the furnace to obtain a silicon oxide doped manganese oxide/carbon tube serving as a negative electrode material of the lithium ion battery;
in the step (2), the manganese source is one or more of manganese sulfate, manganese nitrate or manganese chloride; the precipitator is one or more of urea, glycine or alanine; the silicon source is isopropyl silicate and/or ethyl orthosilicate.
2. The lithium ion battery cathode material of claim 1, silicon oxide doped manganese oxide/carbon tube, characterized in that: in the step (1), the dispersion amount of the carbon nano tube in the low-carbon alcohol solution of the N, N-dimethylformamide is 0.1-0.4 mg/mL.
3. The lithium ion battery negative electrode material silicon oxide doped manganese oxide/carbon tube according to claim 1 or 2, characterized in that: in the step (1), the lower alcohol is one or more of methanol, ethanol or propanol.
4. The lithium ion battery cathode material of claim 3, wherein the silicon oxide-doped manganese oxide/carbon tube is characterized in that: in the step (2), the molar ratio of manganese element in the manganese source, the precipitator and silicon element in the silicon source is 4-20: 200-400: 1, and the mass ratio of the carbon nano tube to the manganese source is 1: 10-30.
5. The lithium ion battery cathode material of claim 4, wherein the silicon oxide-doped manganese oxide/carbon tube is characterized in that: in the step (2), the molar concentration of manganese element in the manganese source in the carbon nano tube dispersion liquid is 0.01-0.05 mol/L; the molar concentration of the precipitant in the carbon nanotube dispersion liquid is 0.5-1.5 mol/L; the molar concentration of the silicon element in the silicon source in the carbon nano tube dispersion liquid is 0.001-0.005 mol/L.
6. The lithium ion battery cathode material of claim 5, wherein the silicon oxide-doped manganese oxide/carbon tube is characterized in that: in the step (2), the temperature of the hydrothermal reaction is 150-200 ℃ and the time is 2-12 h.
7. The lithium ion battery cathode material of claim 6, wherein the silicon oxide-doped manganese oxide/carbon tube is characterized in that: in the step (2), the washing mode is that alcohol and water are used for washing the precipitate for more than or equal to 2 times respectively; the temperature of the freeze drying is lower than-40 ℃, the vacuum degree is lower than 50Pa, and the time is 36-48 h.
8. The lithium ion battery cathode material of claim 7, which is a silicon oxide-doped manganese oxide/carbon tube, characterized in that: in the step (3), the calcining temperature is 600-900 ℃, and the time is 1-5 h.
9. The lithium ion battery cathode material of claim 8, wherein the silicon oxide-doped manganese oxide/carbon tube is characterized in that: in the step (3), the protective atmosphere is argon or argon/hydrogen mixed gas, wherein the volume fraction of hydrogen in the argon/hydrogen mixed gas is 3-10%.
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| CN114050247A (en) * | 2021-11-16 | 2022-02-15 | 欣旺达电动汽车电池有限公司 | Modified silicon-based material, preparation method thereof and lithium battery negative electrode material |
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