CN108258227B - Preparation method of silicon-carbon composite material based on silicon-based molecular sieve structure and lithium battery - Google Patents
Preparation method of silicon-carbon composite material based on silicon-based molecular sieve structure and lithium battery Download PDFInfo
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Abstract
The invention relates to a silicon-carbon composite material based on a silicon-based molecular sieve structure, a preparation method thereof and a lithium ion battery containing the material.
Description
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a silicon-carbon composite material based on a silicon-based molecular sieve structure, a preparation method thereof and a lithium ion battery containing the material.
Background
Lithium ion batteries have attracted attention because of their high energy density, environmental friendliness, and excellent cycle performance. With the shift from the automobile industry to electric vehicles and the development of miniaturized batteries, the development and application of high energy density batteries are urgently needed. However, the energy density of the graphite cathode commercialized at present is very low (only 372 mAh/g), and the requirement of people on the endurance mileage of the electric automobile is difficult to meet.
Silicon has a relatively high theoretical capacity (4200 mAh/g, about 10 times that of graphite negative electrodes), and thus, silicon has been extensively and intensively studied as a negative electrode of a lithium ion battery. Unfortunately, although silicon has a high theoretical capacity, since silicon itself is a semiconductor and has poor conductivity, it exhibits a large volume change (> 300%) during charge and discharge, so that the contact between the material and the conductive agent, electrolyte is deteriorated, resulting in a sharp decline in capacity.
Researchers have done a lot of work to improve the conductivity of silicon materials and reduce the volume change of silicon during the charge and discharge processes to improve the cycle performance of silicon cathodes. Such as: nano-sizing of silicon particles (nanowires, nanotubes, porous silicon, hollow silicon, silicon thin films), composite (amorphous carbon, carbon nanotubes, graphene, titanium dioxide), alloying (FeSi, NiSi), use of novel conductive agents and electrolyte additives (self-healing polymers, conductive polymers), and the like.
The construction of porous silicon is one of the effective ways to mitigate the volume change of silicon. For example, patent CN104254490A discloses a silicon carbon material containing mesoporous silicon, which has a reversible capacity of about 1400mAh/g at a current density of 100 mA/g; when the current density became 300mA/g, a reversible capacity of about 1180mAh/g was obtained. After 240 cycles, the capacity retention rate was 82.8%, thereby obtaining a specific capacity of 977 mAh/g.
The invention is the result of research on the silicon-carbon composite material under the technical background.
Disclosure of Invention
The invention provides a silicon-carbon composite material based on a silicon-based molecular sieve structure, a preparation method thereof and a lithium ion battery containing the material through research on the silicon-carbon composite material.
The technical scheme of the invention is as follows:
a silicon-carbon composite material based on a silicon-based molecular sieve structure takes a silicon-based molecular sieve as a raw material, silicon atoms in an oxidation state are reduced into a silicon simple substance, and the pore channel structure of the silicon-based molecular sieve is not damaged during reduction reaction (the pore channel comprises a cage, the pore channel structure is not damaged in the invention, namely the spatial position is unchanged, but a chemical bond is not broken), and the carbon simple substance is distributed in the pore channel of the silicon-based molecular sieve.
Further, the silicon-based molecular sieve is any one or more selected from pure silicon molecular sieves, silicon-aluminum molecular sieves and titanium-silicon molecular sieves. Further, the pure silicon molecular sieve is selected from one or more of SBA and KIT; the silicon-aluminum molecular sieve is any one or more selected from SAPO, ZSM, MCM, mordenite, beta-molecular sieve, MOR and SSZ; the titanium-silicon molecular sieve is selected from any one or more of TS and TPSO.
Further, the reducing agent used for reducing the silicon atoms in the oxidation state into the simple silicon substance is a metal reducing agent, the metal reducing agent is magnesium or aluminum, the mass of the magnesium or the aluminum is 0.05-2 times of that of the silicon-based molecular sieve, the reduction reaction is carried out in an inert atmosphere, the reaction temperature is 500-900 ℃, and the temperature rise rate of the reaction system is 0.5-3 ℃/min.
Further, the carbon distributed in the pore channels of the silicon-based molecular sieve is generated by carbonizing saccharides or hydrocarbons.
A method of preparing a silicon carbon composite material as described in any one of the preceding claims, comprising the steps of: uniformly mixing a silicon-based molecular sieve with a metal reducing agent which is 0.05-2 times of the mass of the silicon-based molecular sieve, wherein the metal reducing agent is magnesium or aluminum, uniformly mixing, and roasting at the temperature of 900 ℃ for 0.5-6h in an inert atmosphere at the heating rate of 0.5-3 ℃/min; cooling the roasted mixture, and stirring the mixture in an acid solution with hydrogen ion concentration of 0.1-5mol/L for 2-48 h; filtering and washing to obtain an intermediate material containing a silicon simple substance; dispersing the intermediate material containing the silicon simple substance in a saccharide solution and carbonizing the saccharide, or carbonizing the intermediate material containing the silicon simple substance in hydrocarbon atmosphere and hydrocarbon to obtain the silicon-carbon composite material.
Further, the saccharide solution is any one or more of glucose, sucrose and chitosan, the concentration of the saccharide solution is 0.1-3mol/L, and the mass of the saccharide solute is 1-10 times of the mass of the intermediate material containing the silicon simple substance, the intermediate material containing the silicon simple substance is dispersed in the saccharide solution through ultrasonic waves, reacts for 1-48 hours at the temperature of 100-250 ℃, is filtered, washed and dried, and is then carbonized for 0.5-12 hours at the temperature of 600-1200 ℃ at the speed of 0.1-10 ℃/min in an inert atmosphere to obtain the silicon-carbon composite material.
Further, the hydrocarbon atmosphere is methane, ethane and ethylene, and the intermediate material containing the silicon simple substance is carbonized for 0.1-2h at the temperature of 300-1200 ℃ at the speed of 0.1-3 ℃/min in the hydrocarbon atmosphere to obtain the silicon-carbon composite material.
A lithium ion battery, the negative electrode of which contains the silicon-carbon composite material or the silicon-carbon composite material prepared by the method.
Further, the preparation method of the lithium ion battery cathode comprises the following steps: mixing the silicon-carbon composite material, acetylene black and polyvinylidene fluoride according to the mass ratio of 7:2:1, preparing negative electrode slurry by taking N-methyl pyrrolidone as a solvent, uniformly coating the slurry on a metal foil, and drying and slicing to obtain a negative electrode sheet.
Has the advantages that:
1. in the reduction reaction process of the silicon-based molecular sieve, a silicon-oxygen bond is broken, silicon in an oxidation state is reduced into a simple substance, only oxygen is combined with a reducing agent, the space position of a silicon atom is basically kept unchanged, the pore space of the silicon-based molecular sieve is basically not damaged, carbon simple substances are distributed in the pore spaces, the conductivity of the material can be increased, the loose structure of the molecular sieve can improve the volume change in the silicon charging process, and the two aspects enable the silicon-carbon material to have excellent cycle performance;
2. the silicon carbon material prepared by the method can dissolve excessive metal reducing agent and oxide generated by the metal reducing agent by adding acid solution; for the molecular sieve containing other metal elements such as aluminum, titanium and the like in the silicon-based molecular sieve, the metal elements exist in a simple substance or oxide form after silicon is reduced, the metal simple substance or metal oxide can be dissolved by acid, and the occupied space position is released, so that space can be provided for the volume change of silicon in the charging and discharging process; because the silicon-based molecular sieve raw material is granular, in the carbonization process, the carbon simple substance is not only distributed in the pore channel, but also distributed outside the granules.
Drawings
FIG. 1 is a schematic view (nanoscale) of the microstructure of a silicon-carbon material according to the present invention, in which reference numeral 1 is a carbon simple substance and reference numeral 2 is a basic skeleton (silicon simple substance layer);
FIG. 2 is an X-ray diffraction pattern of an elemental silicon-containing intermediate material (upper) and a silicon-carbon material (lower) prepared in example 3 of the present invention, with diffraction angle angles on the abscissa and diffraction intensity on the ordinate;
FIG. 3 is a charge-discharge curve of the intermediate material containing elemental silicon prepared in example 3 of the present invention by multiple charge-discharge, with the abscissa representing gram capacity (mAh/g) and the ordinate representing voltage (V);
fig. 4 is a charge and discharge curve of the silicon carbon composite prepared in example 3 of the present invention by multiple charge and discharge, with gram capacity (mAh/g) on the abscissa and voltage (V) on the ordinate.
Detailed Description
A silicon-carbon composite material based on a silicon-based molecular sieve structure takes a silicon-based molecular sieve as a raw material, silicon atoms in an oxidation state are reduced into a silicon simple substance, and the pore channel structure of the silicon-based molecular sieve is not damaged during reduction reaction (the pore channel comprises a cage, the pore channel structure is not damaged in the invention, namely the spatial position is unchanged, but a chemical bond is not broken), and the carbon simple substance is distributed in the pore channel of the silicon-based molecular sieve.
Further, the silicon-based molecular sieve is any one or more selected from pure silicon molecular sieves, silicon-aluminum molecular sieves and titanium-silicon molecular sieves. Further, the pure silicon molecular sieve is selected from one or more of SBA and KIT; the silicon-aluminum molecular sieve is any one or more selected from SAPO, ZSM, MCM, mordenite, beta-molecular sieve, MOR and SSZ; the titanium-silicon molecular sieve is selected from any one or more of TS and TPSO.
Further, the reducing agent used for reducing the silicon atoms in the oxidation state into the simple silicon substance is a metal reducing agent, the metal reducing agent is magnesium or aluminum, the mass of the magnesium or the aluminum is 0.05-2 times of that of the silicon-based molecular sieve, the reduction reaction is carried out in an inert atmosphere, the reaction temperature is 500-900 ℃, and the temperature rise rate of the reaction system is 0.5-3 ℃/min.
Further, the carbon distributed in the pore channels of the silicon-based molecular sieve is generated by carbonizing saccharides or hydrocarbons.
A method of preparing a silicon carbon composite material as described in any one of the preceding claims, comprising the steps of: uniformly mixing a silicon-based molecular sieve with a metal reducing agent which is 0.05-2 times of the mass of the silicon-based molecular sieve, wherein the metal reducing agent is magnesium or aluminum, uniformly mixing, and roasting at the temperature of 900 ℃ for 0.5-6h in an inert atmosphere at the heating rate of 0.5-3 ℃/min; cooling the roasted mixture, and stirring the mixture in an acid solution with hydrogen ion concentration of 0.1-5mol/L for 2-48 h; filtering and washing to obtain an intermediate material containing a silicon simple substance; dispersing the intermediate material containing the silicon simple substance in a saccharide solution and carbonizing the saccharide, or carbonizing the intermediate material containing the silicon simple substance in hydrocarbon atmosphere and hydrocarbon to obtain the silicon-carbon composite material.
Further, the saccharide solution is any one or more of glucose, sucrose and chitosan, the concentration of the saccharide solution is 0.1-3mol/L, and the mass of the saccharide solute is 1-10 times of the mass of the intermediate material containing the silicon simple substance, the intermediate material containing the silicon simple substance is dispersed in the saccharide solution through ultrasonic waves, reacts for 1-48 hours at the temperature of 100-250 ℃, is filtered, washed and dried, and is then carbonized for 0.5-12 hours at the temperature of 600-1200 ℃ at the speed of 0.1-10 ℃/min in an inert atmosphere to obtain the silicon-carbon composite material.
Further, the hydrocarbon atmosphere is methane, ethane and ethylene, and the intermediate material containing the silicon simple substance is carbonized for 0.1-2h at the temperature of 300-1200 ℃ at the speed of 0.1-3 ℃/min in the hydrocarbon atmosphere to obtain the silicon-carbon composite material.
A lithium ion battery, the negative electrode of which contains the silicon-carbon composite material or the silicon-carbon composite material prepared by the method.
Further, the preparation method of the lithium ion battery cathode comprises the following steps: mixing the silicon-carbon composite material, acetylene black and polyvinylidene fluoride according to the mass ratio of 7:2:1, preparing negative electrode slurry by taking N-methyl pyrrolidone as a solvent, uniformly coating the slurry on a metal foil, and drying and slicing to obtain a negative electrode sheet.
Example 1
A preparation method of a silicon-carbon composite material based on a silicon-based molecular sieve structure comprises the following steps of: magnesium = 1: 1.6, uniformly mixing Mg and SSZ, and then heating the obtained mixture to 650 ℃ at a heating rate of 0.5 ℃/min in an inert atmosphere for roasting for 3 hours; preparing a hydrochloric acid solution with the molar concentration of 1 mol/L, and stirring the materials in the acid solution (the molar quantity of hydrogen ions is more than 2 times of that of magnesium powder) for 24 hours; washing with deionized water, and filtering until the pH of the filtrate is =7 to obtain an intermediate material containing silicon simple substance; and (3) placing the intermediate material containing the silicon simple substance in a muffle furnace, heating to 900 ℃ at the speed of 0.5 ℃/min under the atmosphere of ethylene and the like, and carbonizing for 1 h to obtain the silicon-carbon composite material.
Example 2
A preparation method of a silicon-carbon composite material based on a silicon-based molecular sieve structure comprises the following steps of: magnesium = 1: mixing magnesium and SAPO uniformly according to the proportion of 0.2, and then heating the obtained mixture to 900 ℃ at the heating rate of 0.5 ℃/min in an inert atmosphere for roasting for 0.5 h; preparing a nitric acid solution with the molar concentration of 0.1 mol/L, and placing the materials in an acid solution (the molar weight of the acid is 2 times of that of the magnesium powder) to stir for 48 hours; washing with deionized water, and filtering until the pH of the filtrate is =7 to obtain an intermediate material containing silicon simple substance; preparing 3mol/L glucose solution, wherein the glucose solution is an intermediate material containing silicon simple substance according to the mass ratio: glucose = 1: 1 (wherein the mass of the glucose refers to the mass of solute in the glucose solution), and ultrasonically dispersing the silicon simple substance into the saccharide solution for 4 hours; reacting the obtained suspension in a polytetrafluoroethylene reaction kettle for 1 h at the temperature of 250 ℃; the obtained sample is washed by deionized water, filtered until the pH of the filtrate is =7, dried for 24h at 40 ℃, and then carbonized for 0.5h at the temperature of 1200 ℃ at the speed of 0.1 ℃/min in an inert atmosphere to obtain the silicon-carbon composite material.
Example 3
A preparation method of a negative electrode of a lithium ion battery comprises the following steps:
step one, the mass ratio is SSZ: magnesium = 1: 1.6, uniformly mixing magnesium and SSZ, and then heating the obtained mixture to 650 ℃ at a heating rate of 0.5 ℃/min in an inert atmosphere for roasting for 3 hours; preparing a hydrochloric acid solution with the molar concentration of 1 mol/L, and stirring the materials in the acid solution (the molar weight of the acid is 2 times of that of the magnesium powder) for 24 hours; washing with deionized water, and filtering until the pH of the filtrate is =7 to obtain an intermediate material containing silicon simple substance;
step two, preparing 3mol/L of sucrose solution, wherein the sucrose solution is a silicon-containing simple substance material according to the mass ratio: sucrose = 1: 1, ultrasonically dispersing a silicon simple substance into a sucrose solution for 4 hours; reacting the obtained suspension in a polytetrafluoroethylene reaction kettle for 5 hours at 190 ℃; filtering the obtained sample by using deionized water until the pH is =7, drying the sample at 80 ℃ for 24h, and then heating the sample to 800 ℃ at the speed of 1 ℃/min in an inert atmosphere for carbonizing the sample for 3h to obtain a silicon-carbon composite material;
step three, according to the silicon-carbon material: acetylene black: mixing polyvinylidene fluoride according to the mass ratio of 7:2:1, preparing negative electrode slurry by taking N-methyl pyrrolidone as a solvent, uniformly coating the slurry on copper foil, and drying and slicing to obtain a negative electrode sheet with the diameter of 12 mm;
the lithium ion battery takes a lithium sheet as a counter electrode, and the battery is assembled in a glove box;
performing electrical property test on a Xinwei tester, wherein the charging and discharging voltage is 0.05-3V; when the current density is 500 mA/g, the initial discharge capacity and the charge capacity of the material are 1200 mAh/g and 905 mAh/g respectively; after 500 cycles, the discharge and charge capacities of the cells were 614 mAh/g and 585 mAh/g, respectively.
Example 4
A preparation method of a silicon-carbon composite material based on a silicon-based molecular sieve structure comprises the following steps of: magnesium = 1: 2, uniformly mixing magnesium and ZSM, and then heating the obtained mixture to 500 ℃ at a heating rate of 3 ℃/min in an inert atmosphere to roast for 6 hours; preparing a sulfuric acid solution with the molar concentration of 5mol/L, and stirring the materials in an acid solution (the molar weight of the acid is 2 times that of the magnesium powder) for 2 hours; filtering with deionized water to pH =7 to obtain a material containing elemental silicon; preparing 0.1 mol/L chitosan solution, wherein the chitosan solution is prepared from silicon-containing simple substance materials according to the mass ratio: chitosan = 1: 10, dispersing the silicon simple substance into the chitosan solution by ultrasonic for 0.3 h; reacting the obtained suspension in a polytetrafluoroethylene reaction kettle for 48 hours at 100 ℃; the resulting sample was filtered with deionized water to pH =7,120 ℃ and dried for 2h, followed by carbonization at 10 ℃/min up to 600 ℃ for 12h in an inert atmosphere to yield a silicon-carbon composite.
In examples 1 to 4, a silicon-carbon composite material was produced, and the microstructure of the pore channel thereof can be seen in fig. 1, wherein the spatial distribution of the silicon-based molecular sieve was not substantially destroyed, and carbon simple substance was distributed in the pore channel, and in addition, carbonization reaction occurred outside the molecular sieve particles, so that carbon simple substance was also present.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. A preparation method of a silicon-carbon composite material based on a silicon-based molecular sieve structure is characterized by comprising the following steps: uniformly mixing a silicon-based molecular sieve and a metal reducing agent with the mass 0.05-2 times of that of the silicon-based molecular sieve, wherein the silicon-based molecular sieve is any one of SAPO, ZSM and SSZ, the metal reducing agent is magnesium or aluminum, and after uniform mixing, the temperature is increased to 500-900 ℃ at the heating rate of 0.5-3 ℃/min in an inert atmosphere for roasting for 0.5-6h, so that silicon atoms in an oxidation state are reduced into a silicon simple substance, and the pore structure of the silicon-based molecular sieve is not damaged during reduction reaction; cooling the roasted mixture, and stirring the mixture in an acid solution with the hydrogen ion concentration of 0.1-5mol/L for 2-48h, wherein the acid solution is hydrochloric acid, sulfuric acid or nitric acid; filtering and washing to obtain an intermediate material containing a silicon simple substance; dispersing an intermediate material containing a silicon simple substance in a saccharide solution and carbonizing the saccharide to obtain a silicon-carbon composite material; the pore canal formed by the pore canal of the corresponding silicon-based molecular sieve in the obtained silicon-carbon composite material is distributed with carbon simple substance, and the outer part of the particle formed by the particle of the corresponding silicon-based molecular sieve in the obtained silicon-carbon composite material is distributed with carbon simple substance.
2. The method of claim 1, wherein the method comprises the steps of: the saccharide solution is any one or more of glucose, sucrose and chitosan, the concentration of the saccharide solution is 0.1-3mol/L, the mass of the saccharide solute is 1-10 times of the mass of the intermediate material containing the silicon simple substance, the intermediate material containing the silicon simple substance is dispersed in the saccharide solution by ultrasonic waves and reacts for 1-48 hours at the temperature of 100-250 ℃, then the intermediate material is heated to the temperature of 600-1200 ℃ at the speed of 0.1-10 ℃/min in an inert atmosphere and carbonized for 0.5-12 hours, and the silicon-carbon composite material is obtained after filtration, washing and drying.
3. A lithium ion battery having a negative electrode comprising the silicon-carbon composite prepared by the method of claim 1 or 2.
4. The lithium ion battery of claim 3, wherein the preparation method of the lithium ion battery cathode comprises the following steps: mixing the silicon-carbon composite material, acetylene black and polyvinylidene fluoride according to the mass ratio of 7:2:1, preparing negative electrode slurry by taking N-methyl pyrrolidone as a solvent, uniformly coating the slurry on a metal foil, and drying and slicing to obtain a negative electrode sheet.
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| CN107628622A (en) * | 2017-08-31 | 2018-01-26 | 中国科学院上海硅酸盐研究所 | A kind of lithium ion battery porous silicon negative material and its preparation method and application |
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