CN107240680B - hard carbon-metal oxide-soft carbon composite material and preparation method and application thereof - Google Patents
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Abstract
the invention discloses a hard carbon-metal oxide-soft carbon composite material and a preparation method and application thereof.A hard carbon precursor is prepared by a hydro-thermal method of a hydrocarbon in a reaction kettle, then the hard carbon precursor and titanium salt are pre-coated, and asphalt is placed in a muffle furnace for low-temperature pyrolysis reaction to obtain a soft carbon precursor; and finally, fully mixing the pre-coated hard carbon precursor and the soft carbon precursor, and carrying out high-temperature pyrolysis reaction under the protection of inert gas to obtain a product, namely a hard carbon-metal oxide-soft carbon composite material, wherein the material can be used as a negative electrode active material of a sodium ion battery. The raw materials used by the invention have wide sources and low cost; the prepared hard carbon-metal oxide-soft carbon composite material has the advantages of large reversible capacity, high first charge-discharge coulombic efficiency, good cycle performance and the like in a sodium ion battery.
Description
Technical Field
The invention relates to a preparation method of a composite material, in particular to a hard carbon-metal oxide-soft carbon composite material and a preparation method and application thereof.
Background
Compared with traditional secondary batteries such as lead-acid batteries and nickel-cadmium batteries, the lithium ion battery has the advantages of high working voltage, high energy density, long cycle life, environmental friendliness and the like, thereby attracting more and more attention of scientific researchers. However, the global lithium resource is not abundant, the abundance of lithium element in earth crust is only 0.006%, the resource and price problems become a concern for future large-scale application, and the development of a new energy storage battery system with excellent comprehensive performance is urgently needed. Compared with lithium resources, the sodium reserves are very rich, the content in the earth crust is about 2.64 percent, the sodium reserves and the earth crust are the same main group elements, the chemical properties are similar, and the development of the sodium ion battery by using sodium to replace lithium has very wide application prospects.
At present, the cathode materials commonly used in lithium ion batteries are natural graphite, artificial graphite and the like, which have excellent cycle performance, but sodium ions with relatively large radius are difficult to be embedded into the graphite interlayer spacing, so that the development of novel cathode materials for sodium ion batteries has become a focus of research.
hard carbon is pyrolytic carbon of high molecular polymer, which is difficult to graphitize, and has layers which are staggered with each otherThe structure enables sodium ions to be embedded and extracted from various angles, thereby greatly improving the charging and discharging speed; compared with graphite materials, the low-temperature performance of the composite material is also obviously improved, and the hard carbon material generally has higher reversible specific capacity, but the hard carbon material also has the defects of overhigh electrode potential, potential hysteresis, primary irreversibility, large capacity and the like, so that the large-scale application of the composite material is limited. The soft carbon material refers to amorphous carbon capable of being graphitized at a high temperature of 2500 ℃ or more, and has a smaller specific surface area and better electrolyte compatibility than the hard carbon material. Compared with the carbon materials currently used, TiO2the sodium ion battery has the advantages of high dielectric constant, good chemical stability and thermal stability and the like, so that the sodium ion battery has the advantages of small initial irreversible capacity loss, good safety performance and the like. Therefore, the hard carbon material is used as the core, the hard carbon-metal oxide-soft carbon composite material is prepared by double-layer coating of the metal oxide and the soft carbon material, and the lithium ion battery using the composite material as the active material has the advantages of high reversible capacity, good cycle performance, high safety performance and the like, and meanwhile, the preparation method is simple and the cost is low.
Disclosure of Invention
The invention aims to provide a sodium ion battery cathode material with low price, good cycle performance and high capacity and a preparation method thereof.
the invention is realized by the following scheme:
A method for preparing a hard carbon-metal oxide-soft carbon composite material, comprising the steps of:
1) putting a hydrocarbon aqueous solution into a reaction kettle for hydrothermal reaction, then washing with water until the pH value is neutral, and drying to obtain a hard carbon precursor;
2) Adding a hard carbon precursor and a titanium salt into a mixed solution of a solvent and deionized water, stirring, and drying after the titanium salt is fully hydrolyzed to obtain a pre-coated hard carbon precursor;
3) putting the asphalt into a muffle furnace for low-temperature pyrolysis reaction to decompose light components in the asphalt to obtain a soft carbon precursor;
4) and uniformly mixing the pre-coated hard carbon precursor and the soft carbon precursor, and carrying out high-temperature pyrolysis reaction under the protection of inert gas to obtain the hard carbon-metal oxide-soft carbon composite material.
in a further scheme, the hydrocarbon in the step 1) is at least one of glucose, sucrose, lignin and cellulose; the temperature of the hydrothermal reaction is 100-300 ℃.
in a further scheme, the titanium salt in the step 2) is butyl titanate or titanium isopropoxide; the solvent is one of ethanol, ethylene glycol and propylene glycol, the volume ratio of the solvent to the deionized water is 3:7, and the solvent mainly plays a role of a dispersing agent.
In a further scheme, the asphalt in the step 3) is at least one of coal tar asphalt, mesophase asphalt and petroleum asphalt; the temperature of the low-temperature pyrolysis reaction is 25-400 ℃, and the time is 12-48 h.
In a further scheme, the mass ratio of the hard carbon precursor, the titanium salt and the soft carbon precursor in the hard carbon-metal oxide-soft carbon composite material is (60-100): (5-20): (5-20).
Further, the inert gas in the step 4) is nitrogen, argon or helium.
In a further scheme, the temperature of the high-temperature pyrolysis reaction in the step 4) is 700-1200 ℃, and the time is 2-6 hours.
The second object of the present invention is to provide a hard carbon-metal oxide-soft carbon composite material prepared by the above preparation method.
A third object of the present invention is to provide use of a hard carbon-metal oxide-soft carbon composite for a negative active material of a sodium ion secondary battery.
the hard carbon-metal oxide-soft carbon composite material is synthesized by a thermal decomposition method, the inner core is made of hard carbon material, the specific capacity is higher, the interlayer spacing is larger than that of graphite, and the diffusion speed of lithium ions in the hard carbon material is higher, so that the low-temperature performance and the rate capability of the battery can be improved. The coating layer of the composite material is a double-layer coating of the metal oxide and the soft carbon material, the metal oxide coating layer can reduce the first irreversible capacity of the hard carbon material, and the structural stability of the metal oxide coating layer ensures the safety of the negative electrode material; the soft carbon material has smaller specific surface area and good conductivity, on one hand, the reversible capacity of the composite material is improved, on the other hand, the soft carbon material is beneficial to reacting with the electrolyte to generate a stable and compact SEI film, and the better cycle performance and the higher charge-discharge efficiency of the battery are ensured.
The raw materials used by the invention have wide sources and low cost; the hard carbon-metal oxide-soft carbon composite material prepared by the invention has the advantages of large reversible capacity, high first charge-discharge coulombic efficiency, good cycle performance and the like in a sodium ion battery.
Detailed Description
in order to further understand the contents and features of the present invention, the following examples are given, but these examples do not limit the whole contents of the idea of the present invention.
Example 1
1) Adding a 0.5M glucose aqueous solution into a reaction kettle, then placing the reaction kettle into an oven, controlling the temperature of the oven at 180 ℃, and controlling the hydrothermal reaction time to be 8 h;
2) Washing the reactant obtained in the step 1) with deionized water, and performing suction filtration for 3 times until the pH value is neutral, and drying at 80-120 ℃ for more than or equal to 24 hours to obtain a hard carbon precursor material;
3) Adding the hard carbon precursor and tetrabutyl titanate into an ethanol-water solution (the volume ratio of ethanol to deionized water is 3:7), stirring for 4 hours, and filtering and drying after the tetrabutyl titanate is fully hydrolyzed to obtain a pre-coated hard carbon precursor;
4) putting the crucible filled with the asphalt into a muffle furnace, pyrolyzing the crucible at 220 ℃ for 22h, and obtaining a soft carbon precursor after light components in the asphalt are decomposed;
5) and (3) fully mixing the two precursor products obtained in the steps 3) and 4) through a planetary ball mill, wherein the mass ratio of the hard carbon precursor to the titanium salt to the soft carbon precursor is 60:20:20, and carrying out high-temperature carbonization reaction on the mixture under the protection of inert gas, wherein the carbonization temperature is 800 ℃ and the reaction time is 4h, so as to finally obtain the hard carbon-metal oxide-soft carbon composite material.
Example 2
1) adding a 0.5M glucose aqueous solution into a reaction kettle, then placing the reaction kettle into an oven, controlling the temperature of the oven at 100 ℃, and controlling the hydrothermal reaction time to be 16 h;
2) Washing the reactant obtained in the step 1) with deionized water, and performing suction filtration for 3 times until the pH value is neutral, and drying at 80-120 ℃ for more than or equal to 24 hours to obtain a hard carbon precursor material;
3) Adding the hard carbon precursor and titanium isopropoxide into an ethylene glycol-water solution (the volume ratio of ethylene glycol to deionized water is 3:7), stirring for 4 hours, and filtering and drying after titanium isopropoxide is fully hydrolyzed to obtain a pre-coated hard carbon precursor;
4) putting the crucible filled with the asphalt into a muffle furnace, pyrolyzing the crucible at 220 ℃ for 22h, and obtaining a soft carbon precursor after light components in the asphalt are decomposed;
5) And (3) fully mixing the two precursor products obtained in the steps 3) and 4) through a planetary ball mill, wherein the mass ratio of the hard carbon precursor to the titanium salt to the soft carbon precursor is 60:20:20, and carrying out high-temperature carbonization reaction on the mixture under the protection of inert gas, wherein the carbonization temperature is 900 ℃ and the reaction time is 4h, so as to finally obtain the hard carbon-metal oxide-soft carbon composite material.
Example 3
1) Adding a sucrose aqueous solution with the concentration of 0.6M into a reaction kettle, then placing the reaction kettle into an oven, controlling the temperature of the oven at 180 ℃, and performing hydrothermal reaction for 10 hours;
2) Washing the reactant obtained in the step 1) with deionized water, performing suction filtration for 3 times until the pH value is neutral, and drying at 80-120 ℃ for more than or equal to 24 hours to obtain a hard carbon precursor material;
3) Adding a hard carbon precursor and tetrabutyl titanate into a propylene glycol-water solution (the volume ratio of propylene glycol to deionized water is 3:7), stirring for 4 hours, and filtering and drying after the tetrabutyl titanate is fully hydrolyzed to obtain a pre-coated hard carbon precursor;
4) Putting the crucible filled with the asphalt into a muffle furnace, pyrolyzing the crucible at 220 ℃ for 22h, and obtaining a soft carbon precursor after light components in the asphalt are decomposed;
5) And (3) fully mixing the two precursor products obtained in the steps 3) and 4) through a planetary ball mill, wherein the mass ratio of the hard carbon precursor to the titanium salt to the soft carbon precursor is 80:10:10, and carrying out high-temperature carbonization reaction on the mixture under the protection of inert gas, wherein the carbonization temperature is 900 ℃ and the reaction time is 4h, so as to finally obtain the hard carbon-metal oxide-soft carbon composite material.
Example 4
1) Adding a lignin aqueous solution with the concentration of 0.4M into a reaction kettle, then placing the reaction kettle into an oven, controlling the temperature of the oven at 240 ℃, and performing hydrothermal reaction for 10 hours;
2) washing the reactant obtained in the step 1) with deionized water, and performing suction filtration for 3 times until the pH value is neutral, and drying at 80-120 ℃ for more than or equal to 24 hours to obtain a hard carbon precursor material;
3) Adding the hard carbon precursor and tetrabutyl titanate into an ethanol-water solution (the volume ratio of ethanol to deionized water is 3:7), stirring for 4 hours, and filtering and drying after the tetrabutyl titanate is fully hydrolyzed to obtain a pre-coated hard carbon precursor;
4) putting the crucible filled with the asphalt into a muffle furnace, pyrolyzing the crucible at 220 ℃ for 22h, and obtaining a soft carbon precursor after light components in the asphalt are decomposed;
5) And (3) fully mixing the two precursor products obtained in the steps 3) and 4) through a planetary ball mill, wherein the mass ratio of the hard carbon precursor to the titanium salt to the soft carbon precursor is 80:10:10, and carrying out high-temperature carbonization reaction on the mixture under the protection of inert gas, wherein the carbonization temperature is 900 ℃ and the reaction time is 4h, so as to finally obtain the hard carbon-metal oxide-soft carbon composite material.
Example 5
1) Adding a 0.6M cellulose aqueous solution into a reaction kettle, then placing the reaction kettle into an oven, controlling the temperature of the oven at 200 ℃, and controlling the hydrothermal reaction time to be 8 hours;
2) washing the reactant obtained in the step 1) with deionized water, and performing suction filtration for 3 times until the pH value is neutral, and drying at 80-120 ℃ for more than or equal to 24 hours to obtain a hard carbon precursor material;
3) Adding the hard carbon precursor and tetrabutyl titanate into an ethanol-water solution (the volume ratio of ethanol to deionized water is 3:7), stirring for 4 hours, and filtering and drying after the tetrabutyl titanate is fully hydrolyzed to obtain a pre-coated hard carbon precursor;
4) putting the crucible filled with the asphalt into a muffle furnace, pyrolyzing the crucible at 380 ℃ for 12h, and obtaining a soft carbon precursor after decomposing light components in the asphalt;
5) and (3) fully mixing the two precursor products obtained in the steps 3) and 4) through a planetary ball mill, wherein the mass ratio of the hard carbon precursor to the titanium salt to the soft carbon precursor is 90:5:5, and carrying out high-temperature carbonization reaction on the mixture under the protection of inert gas, wherein the carbonization temperature is 1200 ℃ and the reaction time is 4h, so as to finally obtain the hard carbon-metal oxide-soft carbon composite material.
example 6
1) Adding a 0.6M cellulose aqueous solution into a reaction kettle, then placing the reaction kettle into an oven, controlling the temperature of the oven at 300 ℃, and controlling the hydrothermal reaction time to be 6 h;
2) washing the reactant obtained in the step 1) with deionized water, and performing suction filtration for 3 times until the pH value is neutral, and drying at 80-120 ℃ for more than or equal to 24 hours to obtain a hard carbon precursor material;
3) Adding the hard carbon precursor and titanium isopropoxide into an ethanol-water solution (the volume ratio of ethanol to deionized water is 3:7), stirring for 4 hours, and filtering and drying after the titanium isopropoxide is fully hydrolyzed to obtain a pre-coated hard carbon precursor;
4) Putting the crucible filled with the asphalt into a muffle furnace, pyrolyzing the crucible at 380 ℃ for 22h, and obtaining a soft carbon precursor after decomposing light components in the asphalt;
5) and (3) fully mixing the two precursor products obtained in the steps 3) and 4) through a planetary ball mill, wherein the mass ratio of the hard carbon precursor to the titanium salt to the soft carbon precursor is 90:5:5, and carrying out high-temperature carbonization reaction on the mixture under the protection of inert gas, wherein the carbonization temperature is 1200 ℃ and the reaction time is 4h, so as to finally obtain the hard carbon-metal oxide-soft carbon composite material.
Comparative example 1
1) adding a 0.5M glucose aqueous solution into a reaction kettle, then placing the reaction kettle into an oven, controlling the temperature of the oven at 180 ℃, and controlling the hydrothermal reaction time to be 8 h;
2) Washing the reactant obtained in the step 1) with deionized water, and performing suction filtration for 3 times until the pH value is neutral, and drying at 80-120 ℃ for more than or equal to 24 hours to obtain a hard carbon precursor material;
3) putting the crucible filled with the asphalt into a muffle furnace, pyrolyzing the crucible at 220 ℃ for 22h, and obtaining a soft carbon precursor after light components in the asphalt are decomposed;
4) And (3) fully mixing the two precursor products obtained in the steps 2) and 3) through a planetary ball mill, wherein the mass ratio of the hard carbon precursor to the soft carbon precursor is 90:10, and carrying out high-temperature carbonization reaction on the mixture under the protection of inert gas, wherein the carbonization temperature is 800 ℃ and the reaction time is 4h, so as to finally obtain the hard carbon-soft carbon composite material.
comparative example 2
1) adding a 0.5M glucose aqueous solution into a reaction kettle, then placing the reaction kettle into an oven, controlling the temperature of the oven at 180 ℃, and controlling the hydrothermal reaction time to be 8 h;
2) and (2) carrying out high-temperature carbonization reaction on the hard carbon precursor product obtained in the step 1) under the protection of inert gas, wherein the carbonization temperature is 800 ℃, and the reaction time is 4h, so as to finally obtain the hard carbon material.
the materials prepared in the above examples 1 to 6 and comparative examples 1 to 2 were used as negative electrode active materials of sodium ion batteries, and were subjected to normal-temperature charge-discharge and cycle performance tests: mixing a hard carbon material, a conductive agent and a binder according to a mass ratio of 8:1:1 to prepare a pole piece, taking metal sodium as a counter electrode, and taking 1mol/L of NaFP as electrolyte6EC: DMC 1: 1(w: w) and the separator used was PP (Celgard 2400), the button cells were assembled in an argon atmosphere glove box and the button cells were tested for charging and discharging in the voltage range 0.001-2.0V (vs. Na)+Na) with a current density of 50mA g-1. The results of the performance tests of each cell are shown in table 1 below (the data results are averaged after 3 tests were performed).
Table 1: performance testing
note: the battery is subjected to constant current charge and discharge at a cycle test temperature of 25 ℃ and a current density of 50 mA/g.
as can be seen from the above table 1, the composite material of the present invention is a double-layer clad structure of metal oxide and soft carbon, which reduces the first discharge capacity, but improves the first coulombic efficiency and capacity retention rate of the composite material; on the other hand, excessive metal oxide coating may also result in lower electrical conductivity of the composite, thereby reducing the cycle performance of the composite. According to the invention, the ratio of the hard carbon precursor, the titanium salt and the soft carbon precursor is regulated, so that the prepared hard carbon-metal oxide-soft carbon composite material can effectively improve the first coulombic efficiency and the capacity retention rate of the battery.
the hard carbon precursor material prepared in the comparative example 1 is not pre-coated with titanium salt, so that the first coulombic efficiency and the capacity retention rate are poor; the hard carbon material prepared in comparative example 2 has a higher first capacity because it is not coated, but a larger specific surface area causes a higher first irreversible capacity, thereby reducing the first coulombic efficiency and poor cycle stability.
Having thus described in detail preferred embodiments of the present invention, it will be apparent to those skilled in the art that many variations, modifications, and alterations to these embodiments may be practiced based on the teachings of the present invention, which are intended to be covered by the appended claims.
Claims (8)
1. a preparation method of a hard carbon-metal oxide-soft carbon composite material is characterized by comprising the following steps: the method comprises the following steps:
1) Putting a hydrocarbon aqueous solution into a reaction kettle for hydrothermal reaction, then washing with water until the pH is neutral, and drying at 80-120 ℃ for more than or equal to 24 hours to obtain a hard carbon precursor;
2) Adding the hard carbon precursor and titanium salt into a mixed solvent containing deionized water, stirring, and drying after the titanium salt is fully hydrolyzed to obtain a pre-coated hard carbon precursor;
3) Placing the asphalt in a muffle furnace for low-temperature pyrolysis reaction to decompose light components in the asphalt to obtain a soft carbon precursor, wherein the temperature of the low-temperature pyrolysis reaction is 220-400 ℃;
4) Uniformly mixing the pre-coated hard carbon precursor and the soft carbon precursor, and carrying out high-temperature pyrolysis reaction under the protection of inert gas, wherein the temperature of the high-temperature pyrolysis reaction is 700-1200 ℃, so as to obtain a hard carbon-metal oxide-soft carbon composite material; the mass ratio of the hard carbon precursor to the titanium salt to the soft carbon precursor is (60-100): (5-20): (5-20).
2. The method of claim 1, wherein: the hydrocarbon in the step 1) is at least one of glucose, sucrose, lignin and cellulose; the temperature of the hydrothermal reaction is 100-300 ℃.
3. the method of claim 1, wherein: the titanium salt in the step 2) is butyl titanate or titanium isopropoxide; the mixed solvent is formed by mixing deionized water and ethanol or by mixing deionized water and propylene glycol; the volume ratio of the ethanol to the deionized water in the mixed solvent is 3:7, or the volume ratio of the propylene glycol to the deionized water in the mixed solvent is 3: 7.
4. the method of claim 1, wherein: the asphalt in the step 3) is at least one of coal tar asphalt, mesophase asphalt and petroleum asphalt; the time of the low-temperature pyrolysis reaction is 12-48 h.
5. The method of claim 1, wherein: the inert gas in the step 4) is nitrogen, argon or helium.
6. the method of claim 1, wherein: the time of the high-temperature pyrolysis reaction in the step 4) is 2-6 h.
7. A hard carbon-metal oxide-soft carbon composite material prepared by the preparation method of claim 1.
8. Use of the hard carbon-metal oxide-soft carbon composite according to claim 7, wherein: the hard carbon-metal oxide-soft carbon composite material is used as a negative active material of a sodium ion secondary battery.
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| CN115744872B (en) * | 2022-12-16 | 2024-01-09 | 天津理工大学 | Asphalt-based soft carbon composite cellulose hard carbon negative electrode material and preparation method thereof |
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| CN101385163A (en) * | 2006-02-17 | 2009-03-11 | 株式会社Lg化学 | Lithium manganese secondary battery |
| CN103811717A (en) * | 2014-02-19 | 2014-05-21 | 新乡市赛日新能源科技有限公司 | Power lithium-ion battery negative electrode material with core-shell structure and preparation method thereof |
| US9640799B2 (en) * | 2014-05-13 | 2017-05-02 | Samsung Electronics Co., Ltd. | Negative electrode active material for non-lithium secondary battery, method of preparing the same, negative electrode for non-lithium secondary battery including the same, and non-lithium secondary battery including the negative electrode |
| CN104393284A (en) * | 2014-11-17 | 2015-03-04 | 天津大学 | Nickel oxide nano-particle loaded porous hard carbon sphere negative electrode material and preparation method thereof |
| CN106486673A (en) * | 2015-08-25 | 2017-03-08 | 神华集团有限责任公司 | Material with carbon element for lithium ion battery negative and preparation method thereof and lithium ion battery negative and lithium ion battery |
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