CN108365208B - Preparation method of nano-silicon composite negative electrode material for lithium ion battery - Google Patents
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Abstract
The invention relates to a nano-silicon composite negative electrode material for a lithium ion battery, which is of an egg model structure, wherein egg yolk is a graphite matrix, nano-silicon materials are uniformly dispersed in the graphite matrix and on the surface of the graphite matrix, egg white is graphene uniformly dispersed on the surfaces of the graphite matrix and the nano-silicon, and egg shells are conductive carbon coating layers. The invention combines the nano-composite, surface modification and surface coating technologies to prepare the silicon alloy cathode material with an egg model structure, and the silicon alloy cathode material has high specific capacity, high first charge-discharge efficiency and excellent cycle stability. The invention has simple preparation process, environmental protection and no pollution.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a nano silicon composite negative electrode material for a lithium ion battery, a preparation method of the nano silicon composite negative electrode material, and the lithium ion battery prepared by using the negative electrode material.
Background
At present, with the shortage of global petroleum resources and the continuous deterioration of climate environment, the development of clean and energy-saving new energy automobiles is highly valued by countries in the world. The development of new energy automobiles is critical to power sources thereof. At present, a commercial lithium ion battery mainly adopts a graphite negative electrode material, but the theoretical specific capacity of the lithium ion battery is only 372mAh/g, and the requirement of the future lithium ion battery on high energy density cannot be met. Therefore, the development of high-performance novel electrode materials becomes a research focus.
Silicon has ultrahigh theoretical specific capacity (4200 mAh/g) and lower lithium removal potential (< 0.5V), the voltage platform of silicon is slightly higher than that of graphite, surface lithium precipitation is difficult to cause during charging, the safety performance is better, silicon becomes one of the potential-rich choices for the replacement of carbon-based negative electrodes of lithium ion batteries, but silicon has the defects as the negative electrode material of the lithium ion batteries: (1) the silicon material is easy to generate volume expansion in the charging and discharging processes, so that a conductive network collapses and the electrical cycle performance is influenced; (2) silicon is a semiconductor material, the self conductivity is low, and in the charge-discharge cycle process, the de-intercalation of lithium ions can cause the volume expansion and shrinkage of the material to be more than 300%, so that the structure of the material is damaged and pulverized, the capacity is rapidly attenuated, and the cycle performance is deteriorated. (3) The silicon material is easy to corrode and has capacity attenuation in the circulating process; (4) due to the volume effect of silicon materials, it is difficult to form a stable Solid Electrolyte Interface (SEI) film in an electrolyte, and a new SEI film is continuously formed on the exposed silicon surface along with the destruction of an electrode structure, which aggravates the corrosion and capacity fading of silicon.
Analysis shows that the larger volume expansion and contraction of the silicon material in the lithium extraction process is the cause of material damage and pulverization, and is the main reason for the faster capacity decay. For example, CN 103474667a discloses a silicon-carbon composite negative electrode material, which comprises nano silicon/graphite particles, a first carbon coating layer and an organic cracking layer, wherein the nano silicon/graphite particles are spherical or spheroidal composite particles formed by coating a nano silicon particle layer with graphite as a core.
CN 104617269 discloses a silicon alloy composite negative electrode material, which is prepared by using graphite and silicon alloy coated on the surface of the graphite as an inner core and cracking carbon as an outer shell and combining nano-compounding, surface modification and coating modification technologies. However, the composite material prepared by the method has high content of metal impurities, is easy to generate self-discharge and has poor high-temperature storage.
CN 105070894A discloses a porous silicon-based composite negative electrode material for a lithium ion battery, wherein the negative electrode material is in a capsule structure, a capsule core is made of amorphous porous silicon, a capsule wall is made of a conductive carbon material, the particle size of the amorphous porous silicon is 10-300nm, the pore size of the amorphous porous silicon is 0.5-100 nm, and the thickness of the capsule wall is 0.5-10 mu m. However, the composite material prepared by the method has more internal pores, lower tap density and low volume energy density.
Therefore, developing a preparation method of the nano silicon-based composite anode material with simple process, excellent performance and environmental friendliness is an important research direction in the field of lithium ion batteries.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a nano silicon-based composite negative electrode material for a lithium ion battery and a preparation method thereof.
A preparation method of a nano silicon composite negative electrode material for a lithium ion battery comprises the following steps:
a1, carrying out liquid phase compounding on graphite powder and nano silicon powder in an alcohol medium to obtain a first precursor;
a2, coating graphene on the surface of the first precursor to obtain a second precursor;
a3, coating, modifying and sintering the second precursor to obtain the nano silicon composite anode material;
further, the method also comprises the step A4: and D, crushing, screening and demagnetizing the composite negative electrode material obtained in the step A3 to obtain the nano silicon composite negative electrode material with the medium particle size of 5.0-20 microns.
Preferably, in the step a1, before liquid phase compounding, the nano silicon powder is prepared by using a powder material surface modification method: adding a silane coupling agent into a flask of the alcohol-based nano silicon slurry, then putting the flask into an ultrasonic cleaner for ultrasonic treatment for 4-8 hours, and finally performing freeze drying to obtain the modified nano silicon powder.
Preferably, the silane coupling agent is aminopropyltrimethoxysilane, isobutyltriethoxysilane, methacryloxysilane, preferably aminopropyltrimethoxysilane. The adding amount of the silane coupling agent is 1.0-10.0%.
Preferably, in the step a1, adding graphite powder into a flask filled with the modified nano silicon powder slurry, then performing planetary ball milling for 1-20 hours, and finally performing spray drying to obtain the spheroidal nano silicon/graphite composite material, namely the first precursor.
Preferably, in the step a2, the graphene coating step is: dispersing the nano silicon/graphite in an alcohol solvent, adding graphene oxide into the nano silicon/graphite solution, uniformly dispersing, and performing spray granulation to obtain a precursor compound.
Preferably, in step a3, the coating is mechanical solid phase coating, or liquid phase coating, or gas phase coating.
Preferably, in the step A3, the sintering temperature is 600-1000 ℃, and the thermal reduction time is 10-240 min.
Preferably, the temperature rise rate of the thermal reduction is 0.5-15.0 ℃/min.
A lithium ion battery is characterized by comprising the nano silicon composite negative electrode material prepared by any one of the preparation methods 1-9.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention breaks through the prior art, adopts the above unique and novel preparation method to prepare the lithium ion battery nano-silicon composite cathode material with an egg model structure, combines the advantages of the existing silicon-carbon material, simultaneously sets nano-silicon/graphite into egg yolk to enable the nano-silicon to be uniformly adhered to the inner pores and the surface of the graphite, so that the nano-silicon composite cathode material has better conductivity and can be used as a matrix of the whole composite material, and sets graphene into egg white to enable the composite material to form a four-way eight-reach conductive network and a buffer zone, thereby effectively relieving the volume expansion and contraction effect of the nano-silicon in the charge-discharge process, and improving the comprehensive performance (the capacity retention rate of the whole battery is more than 82 percent in 800 weeks) and the first coulomb efficiency (> 92 percent); by providing the conductive carbon layer as an eggshell, which has a lower specific surface area, it is determined whether a robust "egg" model structure and an ideal specific capacity can be obtained.
(2) The nano-silicon composite negative electrode material for the lithium ion battery provided by the invention has the advantages of high specific capacity, high first charge-discharge efficiency, excellent cycle stability, simple preparation process, environmental friendliness and no pollution.
Drawings
FIG. 1 is a structural diagram model of a nano-silicon composite anode material prepared by the method of the invention.
Fig. 2 is a Scanning Electron Microscope (SEM) image of the nano silicon composite negative electrode material prepared by the method of the present invention.
FIG. 3 is an XRD diagram of the nano-silicon composite anode material prepared by the method of the invention.
FIG. 4 is a first charge-discharge curve of the nano-silicon composite anode material prepared by the method of the present invention.
FIG. 5 is a cycle performance curve of the nano-silicon composite anode material prepared by the method of the present invention.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A preparation method of a nano silicon composite negative electrode material for a lithium ion battery comprises the following steps:
a1, adding aminopropyltrimethoxysilane into a nano silicon powder flask with the medium particle size of 100nm dispersed in an ethanol solvent, mixing in a mass ratio of 1:20, then putting into an ultrasonic cleaner for ultrasonic treatment for 4 hours, and adjusting the ultrasonic frequency to 40kHZ to obtain the modified nano silicon slurry.
A2, adding artificial graphite powder with the medium particle size of 10 microns into the modified nano-silicon slurry, mixing in a mixing mass ratio of 1:1, putting the mixture into a planetary ball mill of a 5L stainless steel tank, introducing argon protective gas, performing high-energy ball milling for 10 hours at the rotation speed of 200r/min, and performing spray drying treatment to obtain the nano-silicon/graphite precursor.
A3, stirring and dispersing the nano silicon/graphite in an ethanol solvent for 1h, adding 50 layers of graphene oxide into the nano silicon/graphite solution, and mixing according to a mixing ratio of 2: and 8, continuously stirring for 10 hours, and then carrying out spray granulation to obtain the nano silicon/graphite/graphene composite material.
A4, mixing the nano silicon/graphite/graphene composite particles with asphalt with the particle size of 3 microns according to the mass ratio of 9:1, uniformly mixing, placing in a VC mixer, adjusting the frequency to 35HZ, mixing for 1h, placing in a crucible, carrying out carbonization treatment in a carbonization furnace, using nitrogen as protective gas, heating at the speed of 5 ℃/min, keeping the temperature at 900 ℃ for 4h, and cooling to room temperature. And then sieving with a 400-mesh sieve to obtain the finished product of the nano silicon composite negative electrode material. The particle size of the egg-shaped nano silicon composite negative electrode material is 16 microns; the particle size of the yolk nano silicon/graphite composite material is 12 micrometers, the thickness of the albumen graphene is 3 micrometers, and the thickness of the eggshell conductive carbon is 1 micrometer.
Fig. 1 is a structural diagram model of a nano silicon composite negative electrode material of the present invention, fig. 2 is a Scanning Electron Microscope (SEM) diagram of the nano silicon composite negative electrode material prepared in example 1, fig. 3 is an XRD diagram of the nano silicon composite negative electrode material prepared in example 1, and fig. 4 is a first charge and discharge curve of the nano silicon composite negative electrode material prepared in example 1, as can be seen from the diagram, the first charge and discharge capacity of the material is high.
Example 2
A preparation method of a nano silicon composite negative electrode material for a lithium ion battery comprises the following steps:
a1, adding a silane coupling agent into a nano silicon powder flask with a medium particle size of 100nm dispersed in an ethanol solvent, mixing in a mass ratio of 1:15, then putting into an ultrasonic cleaner, and carrying out ultrasonic treatment for 6 hours, wherein the ultrasonic frequency is adjusted to 40kHZ, so as to obtain the modified nano silicon slurry.
A2, adding artificial graphite powder with the medium particle size of 10 microns into the modified nano silicon slurry, mixing in a mixing mass ratio of 2:1, putting the mixture into a planetary ball mill of a 5L stainless steel tank, introducing argon protective gas, performing high-energy ball milling for 20 hours at the rotation speed of 200r/min, and performing spray drying treatment to obtain the nano silicon/graphite.
A3, stirring and dispersing the nano silicon/graphite in an ethanol solvent for 1h, adding 100 layers of graphene oxide into the nano silicon/graphite solution, and mixing according to a mixing ratio of 1: continuously stirring for 10 hours, and then carrying out spray granulation to obtain the nano silicon/graphite/graphene composite material;
a4, mixing the nano silicon/graphite/graphene composite particles with asphalt with the particle size of 3 microns according to the mass ratio of 8:2, uniformly mixing, placing in a VC mixer, adjusting the frequency to 35HZ, mixing for 1h, placing in a crucible, carrying out carbonization treatment in a carbonization furnace, using nitrogen as protective gas, heating at the speed of 5 ℃/min, keeping the temperature at 800 ℃ for 4h, and cooling to room temperature. Then sieving with a 400-mesh sieve to obtain a finished product of the nano silicon composite negative electrode material; the particle size of the egg-shaped nano silicon composite negative electrode material is 15 micrometers; the particle size of the yolk nano silicon/graphite composite material is 11 micrometers, the thickness of the albumen graphene is 2 micrometers, and the thickness of the eggshell conductive carbon is 2 micrometers.
Example 3
A preparation method of a nano silicon composite negative electrode material for a lithium ion battery comprises the following steps:
a1, adding a silane coupling agent into a nano silicon powder flask with the medium particle size of 200nm dispersed in an ethylene-propylene alcohol solvent, mixing in a mass ratio of 1:20, then putting into an ultrasonic cleaner, performing ultrasonic treatment for 8 hours, and adjusting the ultrasonic frequency to 40kHZ to obtain the modified nano silicon slurry.
A2, adding artificial graphite powder with a medium particle size of 15 microns into the modified nano silicon slurry, mixing in a mixing mass ratio of 3:1, putting the mixture into a planetary ball mill of a 5L stainless steel tank, introducing argon protective gas, performing high-energy ball milling for 10 hours at a rotation speed of 500r/min, and performing spray drying treatment to obtain the nano silicon/graphite.
A3, stirring and dispersing the nano silicon/graphite in an ethanol solvent for 3 hours, adding the graphene oxide with 200 layers into the nano silicon/graphite solution, and mixing according to a mixing ratio of 3: and 7, continuously stirring for 10 hours, and then carrying out spray granulation to obtain the nano silicon/graphite/graphene composite material.
A4, mixing the nano silicon/graphite/graphene composite particles with phenolic aldehyde with the particle size of 5 microns according to the mass ratio of 8:2, uniformly mixing, placing in a VC mixer, adjusting the frequency to 35HZ, mixing for 2h, placing in a crucible, carrying out carbonization treatment in a carbonization furnace, using nitrogen as protective gas, heating at the speed of 2 ℃/min, keeping the temperature at 950 ℃ for 4h, and cooling to room temperature. Then sieving with a 400-mesh sieve to obtain a finished product of the nano silicon composite negative electrode material; the particle size of the egg-shaped nano silicon composite negative electrode material is 22 mu m; the particle size of the yolk nano silicon/graphite composite material is 17 micrometers, the thickness of the albumen graphene is 3 micrometers, and the thickness of the eggshell conductive carbon is 2 micrometers.
Example 4
A preparation method of a nano silicon composite negative electrode material for a lithium ion battery comprises the following steps:
a1, adding a silane coupling agent into a nano silicon powder flask with the medium particle size of 50nm dispersed in an ethylene-propylene alcohol solvent, mixing in a mass ratio of 1:20, then putting into an ultrasonic cleaner, performing ultrasonic treatment for 8 hours, and adjusting the ultrasonic frequency to 40kHZ to obtain the modified nano silicon slurry.
A2, adding artificial graphite powder with the medium particle size of 18 microns into the modified nano silicon slurry, mixing in a mixing mass ratio of 1:1, putting the mixture into a planetary ball mill of a 5L stainless steel tank, introducing argon protective gas, performing high-energy ball milling for 10 hours at the rotation speed of 500r/min, and performing spray drying treatment to obtain the nano silicon/graphite.
A3, stirring and dispersing the nano silicon/graphite in an ethylene-propylene alcohol solvent for 3 hours, adding the oxidized graphene with 20 layers into the nano silicon/graphite solution, and mixing according to a mixing ratio of 3: and 7, continuously stirring for 10 hours, and then carrying out spray granulation to obtain the nano silicon/graphite/graphene composite material.
A4, dissolving phenolic aldehyde with the particle size of 5 microns in alcohol, proportioning the nano silicon/graphite/graphene composite particles and the phenolic aldehyde solution according to the mass ratio of 8:2, uniformly mixing, stirring for 10 hours at the rotating speed of 1000r/min, carrying out spray drying, then placing in a crucible, carrying out carbonization treatment in a carbonization furnace, using nitrogen as protective gas, heating at the speed of 5 ℃/min, keeping the temperature at 950 ℃ for 4 hours, and cooling to room temperature. Then sieving with a 400-mesh sieve to obtain a finished product of the nano silicon composite negative electrode material; the particle size of the egg-shaped nano silicon composite negative electrode material is 25 micrometers; the particle size of the yolk nano silicon/graphite composite material is 20 micrometers, the thickness of the albumen graphene is 3 micrometers, and the thickness of the eggshell conductive carbon is 2 micrometers.
Comparative example 1
The difference from example 1 is that step A1 and step A3 were not performed.
Comparative example 2
The difference from example 1 is that step a2 is not performed.
Firstly, performance testing:
the preparation of the battery by using the negative electrode materials provided by the embodiment and the comparative example comprises the following specific steps:
mixing and dissolving a negative electrode material, a conductive agent and a binder in a solvent according to a mass ratio of 94:2:4, controlling solid content to be 50%, coating the mixture on a copper foil current collector, and drying in vacuum to obtain a negative electrode plate and 1mol/L LiPF6The button cell comprises electrolyte of/EC + DMC + EMC (v/v =1:1:1), SK diaphragm, lithium sheet and shell, and is assembled by adopting conventional production process.
On the Shenzhen Xinwei Limited battery test system, the test conditions are as follows: at normal temperature, the constant current charge and discharge is carried out at 0.1C, and the charge and discharge cutoff voltage is 0.01V-1.5V.
Secondly, the test results are shown in table 1:
table 1 results of performance testing of examples and comparative examples:
Claims (5)
1. a preparation method of a nano silicon composite negative electrode material for a lithium ion battery is characterized by comprising the following steps:
a1, preparing nano silicon powder by adopting a powder material surface modification method: adding a silane coupling agent into a flask of alcohol-based nano silicon slurry, then putting the flask into an ultrasonic cleaner for ultrasonic treatment for 4-8 hours, and finally performing freeze drying to obtain modified nano silicon powder; then carrying out liquid phase compounding on the modified nano silicon powder and graphite powder in an alcohol medium, then carrying out planetary ball milling for 1-20 h, and finally carrying out spray drying to obtain a spheroidal nano silicon/graphite composite material, namely a first precursor; wherein the silane coupling agent is aminopropyltrimethoxysilane, isobutyl triethoxy silicon and methacryloxy silane; the adding amount of the silane coupling agent is 1.0-10.0%;
a2, coating graphene on the surface of the first precursor: dispersing the nano silicon/graphite composite material in an alcohol solvent, adding graphene oxide into the nano silicon/graphite solution, uniformly dispersing, and performing spray granulation to obtain a second precursor;
and A3, coating and sintering the second precursor to obtain the nano silicon composite anode material.
2. The method for preparing the nano-silicon composite anode material for the lithium ion battery according to claim 1, further comprising the step of A4: and D, crushing, screening and demagnetizing the composite negative electrode material obtained in the step A3 to obtain the nano silicon composite negative electrode material with the medium particle size of 5.0-20 microns.
3. The preparation method of the nano-silicon composite anode material for the lithium ion battery according to claim 1, characterized by comprising the following steps: in step a3, the coating is mechanical solid phase coating, liquid phase coating or gas phase coating.
4. The preparation method of the nano-silicon composite anode material for the lithium ion battery according to claim 1, characterized by comprising the following steps: in the step A3, the sintering temperature is 600-1000 ℃, and the thermal reduction time is 10-240 min.
5. The preparation method of the nano-silicon composite anode material for the lithium ion battery according to claim 4, characterized by comprising the following steps: the temperature rise rate of the thermal reduction is 0.5-15.0 ℃/min.
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| CN109755521B (en) * | 2018-12-29 | 2020-09-29 | 湖南中科星城石墨有限公司 | SiO with three-dimensional net structure2Preparation method of/C negative electrode material |
| CN110729471B (en) * | 2019-10-24 | 2021-10-26 | 湖南金硅科技有限公司 | Silicon @ graphene/CVD carbon composite anode material for lithium ion battery and preparation method and application thereof |
| CN110931756A (en) * | 2019-12-13 | 2020-03-27 | 成都爱敏特新能源技术有限公司 | High-performance silicon-carbon composite negative electrode material with adjustable particle size and preparation method thereof |
| CN111697218A (en) * | 2020-06-30 | 2020-09-22 | 陕西煤业化工技术研究院有限责任公司 | Silicon-carbon negative electrode material and preparation method thereof |
| CN111916718A (en) * | 2020-07-30 | 2020-11-10 | 内蒙古凯金新能源科技有限公司 | Spherical lithium ion battery surface coating material and preparation method thereof |
| CN113363479A (en) * | 2021-03-31 | 2021-09-07 | 万向一二三股份公司 | Double-layer carbon-coated silicon oxide negative electrode material and preparation method and application thereof |
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| CN103474667A (en) * | 2013-08-16 | 2013-12-25 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon-carbon composite negative electrode material for lithium ion battery and preparation method thereof |
| CN106935834A (en) * | 2017-04-21 | 2017-07-07 | 山东大学 | A kind of porous silicon negative material of compound carbon coating and preparation method thereof |
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| CN103474667A (en) * | 2013-08-16 | 2013-12-25 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon-carbon composite negative electrode material for lithium ion battery and preparation method thereof |
| CN106935834A (en) * | 2017-04-21 | 2017-07-07 | 山东大学 | A kind of porous silicon negative material of compound carbon coating and preparation method thereof |
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