CN107611406B - Preparation method of silicon/graphene/carbon composite negative electrode material - Google Patents
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Abstract
A preparation method of a silicon/graphene/carbon composite negative electrode material comprises the following steps: (1) uniformly dispersing silicon nanoparticles into absolute ethyl alcohol under ultrasonic treatment; (2) adding aminopropyl trimethoxy silane by stirring to perform surface modification treatment on silicon; (3) centrifuging and drying the dispersion to obtain APS modified silicon nanoparticles, dispersing the APS modified silicon nanoparticles in absolute ethyl alcohol to form dispersion, dropwise adding a graphene solution under stirring, centrifuging, washing, and freeze-drying; (4) uniformly mixing the polyvinylidene fluoride and the mixed solution, coating the mixture on a copper current collector to form a composite material with consistent thickness, and drying the composite material in a vacuum drying oven; (5) and carrying out high-temperature heat treatment in an inert atmosphere. The obtained negative electrode material has high discharge specific capacity, good charge-discharge characteristics and high cycle stability; the process flow is simple, the silicon content in the material is large, and the method is easy to implement and suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a silicon/graphene/carbon composite negative electrode material.
Background
The lithium ion battery has the characteristics of high voltage, high specific energy, long cycle life, environmental friendliness and the like, and becomes an ideal matching power supply for portable electronics, mobile products and electric automobiles. Due to the development requirements of miniaturization, high energy density and portability of electronic products, especially the development of smart phones and new energy batteries, the energy density requirement of lithium ion batteries is higher and higher, the improvement of the performance of the lithium ion batteries mainly depends on the improvement of the energy density and the cycle life of lithium-embedded materials, the theoretical capacity of the lithium ion batteries taking graphite and other materials as the negative electrode is only 372 mAh/g at present, the requirements of people on energy storage equipment in daily life can not be met far away, and the development of novel high-performance negative electrode materials is urgent. Researches show that the silicon-based material has extremely high specific capacity when applied to the lithium ion battery cathode, wherein the theoretical capacity can reach 3579 mAh/g, so that the silicon-based material is more and more concerned as the lithium ion battery cathode material.
However, when a silicon material is used as a negative electrode of a lithium ion battery, during the charge and discharge cycle of the battery, the reversible generation and decomposition of L i-Si alloy is accompanied by huge volume changes, which may cause differentiation and cracks of the silicon negative electrode material, resulting in collapse of the material structure and falling of the electrode material, further resulting in separation of the electrode material from the conductive network, increased internal resistance, rapid attenuation of reversible capacity, and rapid decrease of the cycle performance of the lithium ion battery with the silicon negative electrode.
CN180094A discloses a graphene-coated silicon negative electrode material and a preparation method thereof, in which a static self-assembly method is adopted to coat graphene on the surface of the silicon negative electrode material, so as to improve the lithium storage specific capacity and the battery cycle performance of the graphene-coated silicon negative electrode lithium ion battery. Graphene does not provide good protection against pulverization of the nano-silicon particles.
CN105024076A discloses a lithium ion battery cathode material and its preparation method and application, the material is divided into two layers: the carbon core layer and the silicon coating layer can effectively relieve the expansion of the silicon material, thereby improving the cycle performance of the battery material, but the pure carbon coating has a limited capability of improving the conductivity of the composite material.
The method can not fundamentally solve the problem of rapid volume expansion of the silicon material cathode lithium ion battery in the charging and discharging processes.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a silicon/graphene/carbon composite cathode material, and the silicon/graphene/carbon composite cathode material prepared by the method can fundamentally solve the problem of rapid volume expansion of a silicon material cathode lithium ion battery in the charge and discharge process, thereby improving the charge and discharge efficiency of the silicon material cathode lithium ion battery and prolonging the service life.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a silicon/graphene/carbon composite negative electrode material comprises the following steps:
(1) uniformly dispersing silicon nanoparticles into absolute ethyl alcohol under ultrasonic treatment to form silicon nanoparticle dispersion liquid;
(2) adding Aminopropyltrimethoxysilane (APS) into the silicon nanoparticle dispersion liquid obtained in the step (1) by stirring to perform surface modification treatment on silicon;
(3) centrifuging and drying the dispersion liquid obtained in the step (2) to obtain APS modified silicon nanoparticles, dispersing the APS modified silicon nanoparticles in absolute ethyl alcohol to form a dispersion liquid, dropwise adding a graphene solution under stirring, and carrying out centrifugal washing and freeze drying treatment to obtain a silicon nanoparticle/graphene composite material;
(4) uniformly mixing the silicon nanoparticle/graphene composite material obtained in the step (3) with polyvinylidene fluoride (PVDF), coating the mixture on a copper current collector to form a composite material with consistent thickness, and drying the composite material in a vacuum drying oven;
(5) and (4) carrying out high-temperature heat treatment on the dried composite material in the step (4) in an inert atmosphere to obtain the silicon/graphene/carbon composite anode material.
Preferably, in the step (1), the particle size of the silicon nanoparticles ranges from 30 nm to 70 nm.
Preferably, in the step (1), the concentration of the silicon nanoparticle dispersion liquid is 0.5mg/m L-2 mg/m L.
Preferably, in the step (2), the volume percentage of the APS added (the ratio of the volume of the APS to the volume of the silicon nanoparticle dispersion) is 0.5% to 2%.
Preferably, in the step (3), the concentration of the dispersion of APS-modified silicon nanoparticles is 0.5mg/m L to 2 mg/m L.
Preferably, in the step (3), the concentration of the added graphene solution is 1mg/m L-2.5 mg/m L.
Preferably, in the step (3), when the graphene solution is added, the mass ratio of the silicon nanoparticles to the graphene in the dispersion liquid is controlled to be 9-11: 1.
Preferably, in the step (4), the mass ratio of the silicon nanoparticle/graphene composite material to the polyvinylidene fluoride is 1-3: 1.
Preferably, in the step (4), the temperature of the vacuum drying is 60-120 ℃.
Preferably, in the step (5), the inert atmosphere is one or more of argon-hydrogen mixed gas, argon gas and nitrogen gas.
Preferably, in the step (5), the high-temperature heat treatment temperature is 500 ℃ to 850 ℃.
The silicon/graphene/carbon composite negative electrode material prepared by the invention has high specific discharge capacity (0.5A g)-1The first discharge capacity was 3932.5mAh/g and the charge-discharge characteristics were good (0.5A g)-1The first coulombic efficiency is 81.47 percent under the circulating current of (1), and the circulating stability is high (0.5A g)-1Is circulatedThe specific capacity of 2010 mAh/g is still kept after 30 times of charge and discharge under the ring current).
Compared with the prior art, the silicon cathode lithium ion battery prepared by the invention has the advantages that on one hand, the surface coating of the silicon particles is directly carried out by using the adhesive polyvinylidene fluoride (PVDF) as a carbon source, and a fully-packaged carbon coating layer is formed on the surface of the silicon particles, so that the lithiation rate of an electrode material is improved by 3-4.5 times in the charging and discharging process of the battery, and the charging and discharging efficiency is improved; and the elastic and amorphous carbon structure coating layer converts the 'multi-crack pulverization' process of the silicon particles in the charging and discharging process into the 'single-crack pulverization' process, thereby prolonging the service life of the battery. On the other hand, the graphene-coated silicon particles can increase the conductivity of the material, so that the charge and discharge efficiency of the silicon cathode lithium ion battery is further increased. The silicon cathode lithium ion battery is 0.5A g-1The specific capacity of 2010 mAh/g is still kept after 30 times of charging and discharging under the circulating current; at 4A g-1The specific capacity of 750 mAh/g was maintained even after charging and discharging 100 times under the circulating current of (2).
Drawings
Fig. 1 is an SEM electron micrograph of the silicon negative electrode tab prepared in example 1 of the present invention;
fig. 2 shows that the silicon/graphene/carbon composite negative electrode material prepared in example 1 of the present invention is 0.5A g-1The charge-discharge performance of the first 3 times under the current density;
fig. 3 shows that the silicon/graphene/carbon composite negative electrode material prepared in example 1 of the present invention is 0.5A g-1Cycling performance curve at current density.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and improvements without departing from the principle of the embodiments of the present invention, and such modifications and improvements are considered to be within the scope of the embodiments of the present invention.
Example 1
(1) Uniformly dispersing 80 mg of silicon nanoparticles (40 nm-60 nm) into 100 ml of absolute ethyl alcohol under ultrasonic treatment to form silicon nanoparticle dispersion liquid with the concentration of 0.8mg/m L;
(2) adding L m Aminopropyltrimethoxysilane (APS) into the silicon nanoparticle dispersion liquid obtained in the step (1) by magnetic stirring to perform surface modification treatment on silicon;
(3) centrifuging and drying the dispersion liquid obtained in the step (2) to obtain APS modified silicon nanoparticles, dispersing the APS modified silicon nanoparticles in absolute ethyl alcohol to form a dispersion liquid with the concentration of 0.8mg/m L, dropwise adding a graphene solution (1.26 mg/m L) under magnetic stirring to enable the mass ratio of the silicon nanoparticles to the graphene to be 10:1, and carrying out centrifugal washing and freeze drying treatment to obtain a silicon nanoparticle/graphene composite material;
(4) uniformly mixing a silicon nanoparticle/graphene composite material and polyvinylidene fluoride (PVDF) according to a mass ratio of 6:4, coating the mixture on a copper current collector to form a composite material with consistent thickness, and drying the composite material in a vacuum drying oven at 120 ℃;
(5) and carrying out heat treatment on the dried composite material at 550 ℃ in an argon atmosphere to obtain the silicon/graphene/carbon composite negative electrode material.
An SEM electron microscope image of the silicon negative electrode sheet prepared from the silicon/graphene/carbon composite negative electrode material obtained in this example is shown in fig. 1. In the figure, the graphene and the nano-Si particles can be observed to be uniformly mixed, and the graphene can well coat the nano-Si particles.
The battery assembly is that the composite material after the calcination treatment is dried in a vacuum drying box, and is put in a closed glove box filled with argon gas, the metal lithium is used as a counter electrode, a microporous polypropylene film is used as a diaphragm, and the diaphragm is 1.0M L iPF6The mixed solvent of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) dissolved in the volume ratio of 1:1 is used as electrolyte, and metal lithium is used as a counter electrode, so that the CR2025 button cell is assembled. And testing the charge and discharge performance of the battery within the voltage range of 0.02-1V.
At 0.5A g-1As shown in fig. 2, the charge/discharge performance of the silicon/graphene carbon/composite negative electrode material at the current density for the first 3 times is high in specific capacity (0.5A g) as shown in fig. 2-1Under the circulating current ofThe first discharge specific capacity can reach 3932.5mAh/g, and the first coulombic efficiency is 81.47%. )
At 0.5A g-1The cyclic performance curve at current density, as shown in FIG. 3, is 0.5A g-1The specific capacity of 2010 mAh/g was maintained even after 30 times of charging and discharging.
Example 2
(1) Uniformly dispersing 80 mg of silicon nanoparticles (40-55 nm) into 100 ml of absolute ethyl alcohol under ultrasonic treatment to form silicon nanoparticle dispersion liquid with the concentration of 0.8mg/m L;
(2) adding L m Aminopropyltrimethoxysilane (APS) into the silicon nanoparticle dispersion liquid by magnetic stirring to perform surface modification treatment on silicon;
(3) centrifuging and drying the dispersion liquid obtained in the step (2) to obtain APS modified silicon nanoparticles, dispersing the APS modified silicon nanoparticles in absolute ethyl alcohol to form a dispersion liquid with the concentration of 0.8mg/m L, dropwise adding a graphene solution (1.26 mg/m L) under magnetic stirring to enable the mass ratio of the silicon nanoparticles to the graphene to be 10:1, and carrying out centrifugal washing and freeze drying treatment to obtain a silicon nanoparticle/graphene composite material;
(4) uniformly mixing a silicon nanoparticle/graphene composite material and polyvinylidene fluoride (PVDF) according to a mass ratio of 6:4, coating the mixture on a copper current collector to form a composite material with consistent thickness, and drying the composite material in a vacuum drying oven at 120 ℃;
(5) and carrying out heat treatment on the composite material at 800 ℃ in argon-hydrogen atmosphere to obtain the silicon/graphene/carbon composite negative electrode material.
The battery assembly is that the composite material after the calcination treatment is dried in a vacuum drying box, and is put in a closed glove box filled with argon gas, the metal lithium is used as a counter electrode, a microporous polypropylene film is used as a diaphragm, and the diaphragm is 1.0M L iPF6The mixed solvent of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) dissolved in the volume ratio of 1:1 is used as electrolyte, and metal lithium is used as a counter electrode, so that the CR2025 button cell is assembled. And testing the charge and discharge performance of the battery within the voltage range of 0.02-1V.
Obtained in this exampleThe specific capacity of the silicon/graphene carbon/composite negative electrode material is high (0.5A g)-1Under the circulating current, the first discharge specific capacity can reach 3234.5 mAh/g, and the first coulombic efficiency is 80.47 percent); 0.5A g-1The specific capacity of 1845 mAh/g was maintained even after 30 times of charging and discharging.
Example 3
(1) Uniformly dispersing 80 mg of silicon nanoparticles (45-60 nm) into 100 ml of absolute ethyl alcohol under ultrasonic treatment to form silicon nanoparticle dispersion liquid with the concentration of 0.8mg/m L;
(2) adding L m Aminopropyltrimethoxysilane (APS) into the silicon nanoparticle dispersion liquid by magnetic stirring to perform surface modification treatment on silicon;
(3) centrifuging and drying the dispersion liquid obtained in the step (2) to obtain APS modified silicon nanoparticles, dispersing the APS modified silicon nanoparticles in absolute ethyl alcohol to form a dispersion liquid with the concentration of 0.8mg/m L, dropwise adding a graphene solution (1.26 mg/m L) under magnetic stirring to enable the mass ratio of the silicon nanoparticles to the graphene to be 10:1, and carrying out centrifugal washing and freeze drying treatment to obtain a silicon nanoparticle/graphene composite material;
(4) uniformly mixing a silicon nanoparticle/graphene composite material and polyvinylidene fluoride (PVDF) according to the mass ratio of 6:4, coating the mixture on a copper current collector to form a composite material with consistent thickness, and drying the composite material in a vacuum drying oven at 120 ℃;
(5) and (3) carrying out high-temperature heat treatment on the composite material at 850 ℃ in a nitrogen atmosphere to obtain the silicon/graphene/carbon composite anode material.
The battery assembly is that the composite material after the calcination treatment is dried in a vacuum drying box, and is put in a closed glove box filled with argon gas, the metal lithium is used as a counter electrode, a microporous polypropylene film is used as a diaphragm, and the diaphragm is 1.0M L iPF6The mixed solvent of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) dissolved in the volume ratio of 1:1 is used as electrolyte, and metal lithium is used as a counter electrode, so that the CR2025 button cell is assembled. And testing the charge and discharge performance of the battery within the voltage range of 0.02-1V.
Silicon/graphite obtained in this exampleThe alkene/carbon composite negative electrode material has high specific capacity (0.5 Ag) and the negative electrode material has high specific capacity-1Under the circulating current, the first discharge specific capacity can reach 3136.5mAh/g, and the first coulombic efficiency is 79.7 percent; 0.5A g-1The specific capacity of 1789 mAh/g is still maintained after 30 times of charging and discharging under the circulating current of (2).
Claims (5)
1. A preparation method of a silicon/graphene/carbon composite negative electrode material is characterized by comprising the following steps:
(1) uniformly dispersing silicon nanoparticles into absolute ethyl alcohol under ultrasonic treatment to form silicon nanoparticle dispersion liquid, wherein the particle size range of the silicon nanoparticles is 30-70 nm, and the concentration of the silicon nanoparticle dispersion liquid is 0.5mg/m L-2 mg/m L;
(2) adding aminopropyl trimethoxy silane into the silicon nanoparticle dispersion liquid obtained in the step (1) by stirring to perform surface modification treatment on silicon; the volume percentage of the added aminopropyl trimethoxy silane is 0.5-2%, and the volume percentage refers to the volume ratio of the aminopropyl trimethoxy silane to the volume of the silicon nanoparticle dispersion liquid;
(3) centrifuging and drying the dispersion liquid obtained in the step (2) to obtain APS modified silicon nanoparticles, dispersing the APS modified silicon nanoparticles in absolute ethyl alcohol to form a dispersion liquid, dropwise adding a graphene solution under stirring, and carrying out centrifugal washing and freeze drying treatment to obtain a silicon nanoparticle/graphene composite material; when the graphene solution is added, controlling the mass ratio of the silicon nanoparticles to the graphene in the dispersion liquid to be 9-11: 1;
(4) uniformly mixing the silicon nanoparticle/graphene composite material obtained in the step (3) with polyvinylidene fluoride, coating the mixture on a copper current collector to form a composite material with consistent thickness, and drying the composite material in a vacuum drying oven; the mass ratio of the silicon nano-particle/graphene composite material to the PVDF is 0.25-4.5;
(5) and (4) carrying out high-temperature heat treatment on the dried composite material in the step (4) in an inert atmosphere to obtain the silicon/graphene/carbon composite anode material.
2. The method for preparing the silicon/graphene/carbon composite anode material according to claim 1, wherein in the step (3), the concentration of the APS-modified silicon nanoparticle dispersion liquid is 0.5mg/m L-2 mg/m L.
3. The preparation method of the silicon/graphene/carbon composite anode material as claimed in claim 1 or 2, wherein in the step (3), the concentration of the added graphene is 1mg/m L-2.5 mg/m L.
4. The method for preparing a silicon/graphene/carbon composite anode material according to claim 1 or 2, characterized in that: in the step (4), the temperature of the vacuum drying is 60-120 ℃.
5. The method for preparing a silicon/graphene/carbon composite anode material according to claim 1 or 2, characterized in that: in the step (5), the high-temperature heat treatment temperature is 500-850 ℃.
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