CN111755677B - Core-shell structure porous silicon negative electrode material for lithium ion battery and preparation method thereof - Google Patents
Core-shell structure porous silicon negative electrode material for lithium ion battery and preparation method thereof Download PDFInfo
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- CN111755677B CN111755677B CN202010639804.1A CN202010639804A CN111755677B CN 111755677 B CN111755677 B CN 111755677B CN 202010639804 A CN202010639804 A CN 202010639804A CN 111755677 B CN111755677 B CN 111755677B
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a core-shell structure porous silicon negative electrode material for a lithium ion battery and a preparation method thereof; the porous silicon negative electrode material is of a core-shell structure, the inner core comprises nano porous silicon, graphite and amorphous carbon, and the shell is made of amorphous carbon; the negative electrode material contains 30-70 wt% of nano-porous silicon, 20-45 wt% of graphite and 10-40 wt% of amorphous carbon; the micro-porous silicon raw material contains 1-10 wt.% of oxygen, and the oxygen content in the nano-porous silicon obtained by wet grinding is 12-35 wt.%; when the cathode material is used as a cathode active material of a lithium ion battery, the battery capacity can be obviously increased, the cathode material has excellent cycle performance, the raw materials are low in price, the preparation process and equipment are mature, and the cathode material is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a core-shell structure porous silicon negative electrode material for a lithium ion battery and a preparation method thereof.
Background
At present, the conventional lithium ion negative electrode material mainly adopts a graphite negative electrode, but the theoretical specific capacity of the graphite negative electrode is only 372mAh/g, and the urgent needs of users cannot be met. The theoretical capacity of silicon is up to 4200mAh/g, which is more than 10 times of the capacity of a graphite cathode material, and simultaneously, the coulomb efficiency of the silicon-carbon composite product is close to that of the graphite cathode, and the silicon-carbon composite product is low in price, environment-friendly, rich in earth reserves, and is the optimal choice of a new generation of high-capacity cathode material. However, since the silicon material has poor conductivity and the volume expansion of silicon reaches up to 300% during charging, the volume expansion during charging and discharging easily causes the collapse of the material structure and the peeling and pulverization of the electrode, resulting in the loss of the active material, further causing the sharp reduction of the battery capacity and the serious deterioration of the cycle performance.
In order to stabilize the structure of silicon in the charging and discharging process, relieve the expansion and achieve the effect of improving the electrochemical performance, a carbon material with high conductivity and high specific surface area is urgently needed, and the carbon material is mixed with silicon to be used as a lithium battery negative electrode material.
Disclosure of Invention
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a core-shell structure porous silicon negative electrode material for a lithium battery and a preparation method thereof, wherein the core-shell structure porous silicon negative electrode material is characterized in that: the core-shell structure porous silicon negative electrode material is of a core-shell structure, the core comprises nano porous silicon, graphite and amorphous carbon, and the shell is made of amorphous carbon. The preparation process of the cathode material comprises an atomization granulation technology. The nano-porous silicon is prepared by a wet grinding process, then is compounded with graphite particles and is dispersed in the negative electrode material, and at least one part of the surfaces of the nano-porous silicon and the graphite is covered by amorphous carbon. At least a part of the surface of the anode material is covered with an amorphous carbon layer. The nano-silicon porous silicon in the core-shell structure porous silicon cathode material prepared by the invention has a smaller volume expansion effect in the charge and discharge processes. The powder and the pure solvent in the composite slurry are separated by the atomization granulation technology, the powder is recycled, the pure steam enters the condenser to be recycled, the cost is saved, the environment is protected, and on the other hand, the particle size and the particle morphology of atomized particles can be adjusted by changing the technological parameters of the closed spray dryer and the state of the composite slurry. Therefore, when the cathode material is used as a cathode active material of a lithium ion battery, the cathode material can obviously increase the battery capacity, has excellent cycle performance, is cheap in raw materials, mature in preparation process and equipment, and is suitable for large-scale production.
Specifically, the invention relates to a core-shell structure porous silicon negative electrode material for a lithium ion battery, which is characterized in that: the porous silicon negative electrode material is of a core-shell structure, the inner core comprises nano porous silicon, graphite and amorphous carbon, and the shell is made of amorphous carbon; the proportion of the nano porous silicon in the negative electrode material is 30-70 wt.%, preferably 40-50 wt.%; the ratio of the graphite is 20-45 wt.%, preferably 30-40 wt.%, and the ratio of the amorphous carbon is 10-40 wt.%, preferably 20-30 wt.%.
Preferably, the specific surface area of the negative electrode material is 1-10 m2(ii)/g; the median particle diameter D50 of the negative electrode material is 6-30 μm.
Preferably, the nano silicon porous silicon is prepared by a wet grinding process; the raw material for wet grinding is micron porous silicon with the median particle size of 1-200 mu m; and (3) grinding the micro porous silicon by a wet method to obtain the nano porous silicon, wherein the median particle size D50 of the nano porous silicon is 70-100 nm.
Preferably, the microporous silicon raw material contains 1-10 wt.% of oxygen, and the nano-porous silicon obtained by wet grinding contains 12-35 wt.% of oxygen.
Preferably, the graphite is one or more of artificial graphite, natural graphite, isostatic pressure graphite, mould pressing graphite, extruded graphite, dense crystalline graphite, crystalline flake graphite, aphanitic graphite, micron graphite and nano silicon graphite; the median particle size D50 of micron graphite is 1-20 μm, and the median particle size of nano graphite is 90-900 nm.
Preferably, the amorphous carbon is formed by thermal decomposition of a carbon source material, the surface of the negative electrode material is partially covered with the amorphous carbon formed by thermal decomposition, and the average thickness of the amorphous carbon layer is 10 to 1000 nm; the amorphous carbon is also present in the interior of the anode material and is filled in partial pores of the partially porous silicon;
the thermally decomposed carbon source material is one or more of methane, ethane, ethylene, acetylene, propane, propylene, acetone, butane, butylene, pentane, hexane, benzene, toluene, xylene, styrene, naphthalene, phenol, furan, pyridine, anthracene, liquefied gas, citric acid, triose, tetrose, pentose, hexose, glucose, sucrose, asphalt, epoxy resin, phenol resin, furfural resin, acrylic resin, polyvinyl chloride resin, polyether polyester resin, polyamide resin, polyimide resin, formaldehyde resin, polyoxymethylene, polyamide, polysulfone, polyethylene glycol, bismaleimide, polyethylene, polyvinyl chloride, polytetrafluoroethylene, polystyrene, polypropylene and polyacrylonitrile;
the thermal decomposition temperature is 600-1000 ℃, and the decomposition time is 1-6 hours.
The invention also relates to a preparation method of the core-shell structure porous silicon negative electrode material, which comprises the following steps:
(1) preparing nano porous silicon: adding porous silicon powder with the median particle size of 1-200 mu m and the purity of more than 99% and a grinding solvent into a dispersion tank of a sand mill, controlling the solid content of a mixed solution to be 10-30%, and starting stirring uniformly; the grinding beads are made of one of zirconium silicate, aluminum oxide, stainless steel, agate, ceramic, zirconium oxide and hard alloy, the mass ratio of the grinding beads to silicon powder is (10-30): 1, the mixed solution in the stirring tank is introduced into a sand mill, the linear velocity of the sand mill is more than 14m/s, and the grinding time is 30-70 h, so that porous silicon slurry is obtained;
(2) atomizing and granulating: adding graphite and carbon source materials into the porous silicon slurry obtained in the step (1), adjusting the solid content of the mixed slurry to be 10% -50%, measuring the viscosity of the mixed slurry to be lower than 100Pa & s, and stirring at a high speed of 400-800 rpm for 1-6 h; introducing inert gas into a closed spray dryer, and starting to drive oxygen until the detected oxygen content is lower than 2%; controlling the inlet temperature of the closed spray dryer to be 160-220 ℃, the outlet temperature to be 85-120 ℃ and the rotating speed of an atomizing disc to be more than 12000 rpm; introducing the mixed slurry, and carrying out atomization drying to obtain dry powder with the median particle size D50 of 4-30 micrometers;
(3) preparing a porous silicon negative electrode material: putting the dry powder obtained in the step (2) into a vapor deposition furnace, introducing inert gas for protection, heating to 600-1000 ℃, introducing a carbon source material for vapor deposition, depositing for 1-4 hours, and thermally decomposing the carbon source material to form amorphous carbon which not only covers the surface of the negative electrode material but also exists in the negative electrode material to obtain the core-shell structure porous silicon negative electrode material;
wherein, the step (1):
the wet grinding equipment is a sand mill, and the structural shape of a stirring shaft of the sand mill is one of a disc type, a rod type or a rod disc type;
the grinding solvent is one or more of methanol, benzyl alcohol, ethanol, ethylene glycol, propanol, isopropanol, propylene glycol, butanol, n-butanol, isobutanol, pentanol, neopentyl alcohol and octanol; the purity of the alcohol solvent is more than or equal to 99 percent;
and (3) the inert gas in the step (2) or (3) is one of nitrogen, argon and neon.
The invention also relates to a lithium ion battery, which is characterized in that the lithium ion battery cathode material is any one of the core-shell structure porous silicon cathode materials.
Compared with the prior art, the invention has the advantages that:
(1) in the core-shell structure porous silicon cathode material prepared by the invention, the median particle size D50 of the nano porous silicon is 70-100 nm, the porous silicon has a smaller volume expansion effect in the charge and discharge processes, and the nano energy greatly reduces the absolute volume expansion of the silicon in the charge and discharge processes;
(2) according to the core-shell structure porous silicon negative electrode material prepared by the invention, the powder and the pure solvent in the composite slurry are separated by an atomization granulation technology, the powder is recovered, the pure steam enters a condenser for recovery and reuse, the cost is saved, the environment is protected, and on the other hand, the particle size and the particle morphology of atomized particles can be adjusted by changing the process parameters of a closed spray dryer and the state of the composite slurry;
(3) in the core-shell structure porous silicon negative electrode material prepared by the method, on one hand, the carbon material can obviously improve the conductivity and ion transmission rate of the negative electrode material, and on the other hand, the formed carbon coating layer can isolate the erosion of electrolyte, stabilize the structure of the negative electrode material and improve the electrochemical performance of the negative electrode material;
(4) the raw materials used by the porous silicon cathode material with the core-shell structure prepared by the invention are low in price, and the preparation process and equipment are mature, so that the porous silicon cathode material is suitable for large-scale production;
(5) the core-shell structure porous silicon negative electrode material prepared by the invention has excellent electrochemical performance, high specific capacity (934.7-1420 mAh/g), high primary efficiency (83.6-87%), and excellent cycle performance (18650 cylindrical battery with capacity of 500, and the capacity retention rate of 900 cycles can reach 86% under the charge-discharge rate of 1C/1C).
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a cross-sectional view of a porous silicon powder in example 1 of the present invention;
FIG. 2 is an SEM image of a porous silicon anode material prepared in example 1 of the present invention;
FIG. 3 is an XRD pattern of the porous silicon anode material prepared in example 1 of the present invention;
fig. 4 is a first charging and discharging curve of the button cell made of the porous silicon negative electrode material in example 1 of the present invention;
FIG. 5 is a cycle curve of the porous silicon anode material prepared in example 1 of the present invention in 18650 cylindrical cells at 1C/1C rate.
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 core-shell structure porous silicon negative electrode material for a lithium ion battery comprises the following steps:
(1) preparing nano porous silicon: adding 1000g of porous silicon powder with the median particle size of 1 mu m and the purity of 99.99 percent and ethanol into a dispersion tank of a sand mill, controlling the solid content of the mixed solution to be 10 percent, and starting stirring for 30 minutes; the grinding beads are made of hard alloy, and the mass ratio of the grinding beads to the silicon powder is 30: 1; introducing the mixed solution in the stirring tank into a sand mill, wherein the linear speed of the sand mill is 16m/s, and the grinding time is 70h, so as to obtain porous silicon slurry; detecting to obtain that the mass content of oxygen element in the nano porous silicon is 32 percent, and the median particle size of the nano porous silicon is 77 nm;
(2) atomizing and granulating: adding nano graphite with the median particle size of 400nm and a carbon source material, namely glucose, into the porous silicon slurry obtained in the step (1), adjusting the solid content of the mixed slurry to be 10%, measuring the viscosity of the mixed slurry to be 15Pa s, stirring at a high speed for 1h, and stirring at a speed of 600 rpm; introducing high-purity nitrogen into a closed spray dryer, and starting to drive oxygen until the detected oxygen content is lower than 2%; controlling the inlet temperature of the closed spray dryer to be 220 ℃, the outlet temperature to be 120 ℃ and the rotating speed of the atomizing disc to be 20000 rpm; introducing the mixed slurry, and carrying out atomization drying to obtain dry powder with the median particle size of 6.4 microns;
(3) preparing a porous silicon negative electrode material: putting the dry powder obtained in the step (2) into a vapor deposition furnace, introducing nitrogen for protection, heating to 700 ℃ at a heating rate of 3 ℃/min, introducing methane for vapor deposition, and depositing for 4 hours to obtain a core-shell structure porous silicon anode material, wherein the median particle size D50 of the anode material is 7.2 mu m;
in the core-shell structure porous silicon negative electrode material, the proportion of nano porous silicon is 50 wt.%, the proportion of graphite is 20 wt.%, the proportion of carbon formed by thermal decomposition of glucose is 15 wt.%, and the proportion of carbon formed by thermal decomposition of methane is 15 wt.%.
Example 2
(1) Preparing nano porous silicon: adding 1000g of porous silicon powder with the median particle size of 70 mu m and the purity of 99.9 percent and ethanol into a dispersion tank of a sand mill, controlling the solid content of the mixed solution to be 15 percent, and starting stirring for 30 minutes; the grinding beads are made of hard alloy, and the mass ratio of the grinding beads to the silicon powder is 30: 1; introducing the mixed solution in the stirring tank into a sand mill, wherein the linear speed of the sand mill is 16m/s, and the grinding time is 55h, so as to obtain porous silicon slurry; detecting to obtain that the mass content of oxygen element in the nano porous silicon is 27 percent, and the median particle size of the nano porous silicon is 82 nm;
(2) atomizing and granulating: adding natural graphite with the median particle size of 2 mu m and carbon source material-epoxy resin into the porous silicon slurry obtained in the step (1), adjusting the solid content of the mixed slurry to be 20%, measuring the viscosity of the mixed slurry to be 34 Pa.s, stirring at a high speed for 1h, and stirring at a speed of 600 rpm; introducing high-purity nitrogen into a closed spray dryer, and starting to drive oxygen until the detected oxygen content is lower than 2%; controlling the inlet temperature of the closed spray dryer to be 200 ℃, the outlet temperature to be 110 ℃ and the rotating speed of the atomizing disc to be 18000 rpm; introducing the mixed slurry, and carrying out atomization drying to obtain dry powder with the median particle size of 10.7 microns;
(3) preparing a porous silicon negative electrode material: placing the dry powder obtained in the step (2) in a fluidized bed, wherein the adopted fluidizing gas is argon, the carbon source gas is acetylene, the treatment temperature is 700 ℃, and the reaction time is 1.5h, so as to obtain the core-shell structure porous silicon anode material, wherein the median particle size D50 of the anode material is 13.6 microns;
in the core-shell structure porous silicon negative electrode material, the ratio of nano porous silicon is 70 wt.%, the ratio of graphite is 20 wt.%, the ratio of carbon thermally decomposed by epoxy resin is 5 wt.%, and the ratio of carbon thermally decomposed by acetylene is 5 wt.%.
Example 3
(1) Preparing nano porous silicon: adding 1000g of porous silicon powder with the median particle size of 130 mu m and the purity of 99.2 percent and ethanol into a dispersion tank of a sand mill, controlling the solid content of the mixed solution to be 20 percent, and starting stirring for 30 minutes; the grinding beads are made of hard alloy, and the mass ratio of the grinding beads to the silicon powder is 30: 1; introducing the mixed solution in the stirring tank into a sand mill, wherein the linear speed of the sand mill is 16m/s, and the grinding time is 40h, so as to obtain porous silicon slurry; detecting to obtain that the mass content of oxygen element in the nano porous silicon is 21 percent, and the median particle size of the nano porous silicon is 88 nm;
(2) atomizing and granulating: adding artificial graphite with a median particle size of 12 microns and a carbon source material, namely acrylic resin into the porous silicon slurry obtained in the step (1), adjusting the solid content of the mixed slurry to be 30%, measuring the viscosity of the mixed slurry to be 57Pa & s, stirring at a high speed for 1h, and stirring at a speed of 600 rpm; introducing high-purity nitrogen into a closed spray dryer, and starting to drive oxygen until the detected oxygen content is lower than 2%; controlling the inlet temperature of the closed spray dryer to be 180 ℃, the outlet temperature to be 100 ℃ and the rotating speed of an atomizing disc to be 16000 rpm; introducing the mixed slurry, and carrying out atomization drying to obtain dry powder with the median particle size of 19.2 microns;
(3) preparing a porous silicon negative electrode material: mixing the dry powder obtained in the step (2) with carbon source material-asphalt, and then placing the mixture into a box furnace for calcination, wherein nitrogen is introduced for protection, the sintering temperature is 800 ℃, the sintering time is 1h, and the porous silicon anode material with the core-shell structure is obtained, wherein the median particle size D50 of the anode material is 22.8 mu m;
in the core-shell structure porous silicon negative electrode material, the proportion of nano porous silicon is 40 wt.%, the proportion of graphite is 45 wt.%, the proportion of carbon decomposed by acrylic resin is 7 wt.%, and the proportion of carbon decomposed by asphalt is 8 wt.%.
Example 4
(1) Preparing nano porous silicon: adding 1000g of porous silicon powder with the median particle size of 190 mu m and the purity of 99.1 percent and ethanol into a dispersion tank of a sand mill, controlling the solid content of the mixed solution to be 30 percent, and starting stirring for 30 minutes; the grinding beads are made of hard alloy, and the mass ratio of the grinding beads to the silicon powder is 30: 1; introducing the mixed solution in the stirring tank into a sand mill, wherein the linear speed of the sand mill is 16m/s, and the grinding time is 30h, so as to obtain porous silicon slurry; the mass content of the oxygen element in the nano porous silicon is 13 percent through detection, and the median particle size of the nano porous silicon is 99 nm.
(2) Atomizing and granulating: adding aphanitic graphite with the median particle size of 20 microns and a carbon source material, namely formaldehyde resin, into the porous silicon slurry obtained in the step (1), adjusting the solid content of the mixed slurry to be 50%, measuring the viscosity of the mixed slurry to be 86Pa s, stirring at a high speed for 1h, and stirring at a speed of 600 rpm; introducing high-purity nitrogen into a closed spray dryer, and starting to drive oxygen until the detected oxygen content is lower than 2%; controlling the inlet temperature of the closed spray dryer to be 160 ℃, the outlet temperature to be 90 ℃ and the rotating speed of the atomizing disc to be 13000 rpm; introducing the mixed slurry, and carrying out atomization drying to obtain dry powder with the median particle size of 27.1 microns;
(3) preparing a porous silicon negative electrode material: mixing the dry powder obtained in the step (2) with a carbon source material-polyacrylonitrile, and then placing the mixture into a box furnace for calcination, wherein nitrogen is introduced for protection, the sintering temperature is 500 ℃, the sintering time is 1h, and the core-shell structure porous silicon anode material is obtained, and the median particle size D50 of the anode material is 29.8 mu m;
in the core-shell structure porous silicon negative electrode material, the proportion of nano porous silicon is 30 wt.%, the proportion of carbon nano tubes is 30 wt.%, the proportion of carbon thermally decomposed by formaldehyde resin is 10 wt.%, and the proportion of carbon thermally decomposed by polyacrylonitrile is 30 wt.%.
Comparative example 1
The difference from example 1 is that in step (1), the porous silicon powder is not subjected to nanocrystallization, and the rest is the same as example 1, and is not described herein again.
The following results are obtained by testing: the porous silicon had an oxygen content of 2.7% by mass and a median particle diameter of 1 μm.
Comparative example 2
The difference from example 1 is that in step (2), the atomization drying technique is not used, but conventional heating stirring drying is used, and the rest is the same as example 1, and the description is omitted here.
The powder after stirring and heating was dried into a block, and the median particle diameter D50 after scattering was 57.9 μm, and the median particle diameter of the finally obtained negative electrode material was 63.1 μm.
Comparative example 3
The difference from example 1 is that in step (2), the rotation speed of the atomizing disk in the spray dryer is adjusted to 10000rpm, and the rest is the same as example 1, and will not be described again.
The following results are obtained by testing: after the mixed slurry is atomized and dried, the median particle size of the obtained dry powder is 31.2 μm, and the median particle size of the finally prepared negative electrode material is 34.8 μm.
Comparative example 4
The difference from example 1 is that in step (2), the solid content of the mixed slurry was adjusted to 50%, and the viscosity of the mixed slurry at this time was 104 pas, and the description is omitted as in example 1.
The following results are obtained by testing: after the mixed slurry is atomized and dried, the median particle size of the obtained dry powder is 34.6 microns, and the median particle size of the finally prepared negative electrode material is 38.3 microns.
Comparative example 5
The difference from example 1 is that in step (2), no graphite is added to the composite slurry, and the rest is the same as example 1, and is not described herein again.
Comparative example 6
The difference from example 1 is that in step (2), no carbon source is added to the composite slurry, and the rest is the same as example 1, and will not be described herein.
Comparative example 7
The difference from example 1 is that step (3) is not performed, i.e. the carbon source coating is not performed on the atomized and dried powder, and the rest is the same as example 1, and the description is omitted here.
The core-shell structure porous silicon anode materials in examples 1 to 4 and comparative examples 1 to 7 were tested by the following methods:
the particle size range of the material was tested using a malvern laser particle sizer Mastersizer 3000.
The morphology and the graphical processing of the material were analyzed using a field emission Scanning Electron Microscope (SEM) (JSM-7160).
The morphology of the material and the state of the amorphous carbon were analyzed using a field emission Transmission Electron Microscope (TEM) (JEM-F200).
An oxygen-nitrogen-hydrogen analyzer (ONH) is adopted to accurately and rapidly measure the oxygen element content in the material.
The material was subjected to phase analysis using an XRD diffractometer (X' Pert3 Powder) to determine the grain size of the material.
A cross-sectional plane sample of the negative electrode material was prepared using an argon ion cutter (IB-19530CP) for SEM imaging observation and microscopic analysis.
The specific surface area and porosity of the negative electrode material were determined using a U.S. Mach Chart and pore Analyzer (TriStar II 3020).
The specific surface area of the anode material of the embodiment 1-4 is detected to be 1-10 m2(ii)/g; the median particle diameter D50 of the negative electrode material is 6-30 μm.
Scanning the whole composite material by using a TEM (transmission electron microscope), and measuring that the surface layer part of the negative electrode material is covered by amorphous carbon, wherein the thickness of the amorphous carbon layer is 10-1000 nm.
Mixing the core-shell structure porous silicon negative electrode materials obtained in the examples 1 to 4 and the comparative examples 1 to 7 in pure solvent water according to the mass ratio of 91:2:2:5 of the negative electrode material, carbon black (Super P), carbon nano tubes and LA133 glue, homogenizing, controlling the solid content to be 45%, coating the mixture on a copper foil current collector, and drying in vacuum to obtain a negative electrode piece. Button cells were assembled in an argon atmosphere glove box using a separator Celgard2400, an electrolyte of 1mol/L LiPF6/EC + DMC + EMC (v/v 1:1:1), and a metallic lithium plate as the counter electrode. And (3) performing charge and discharge tests on the button cell, wherein the voltage interval is 5 mV-1.5V, and the current density is 80 mA/g. The first reversible capacity and efficiency of the core-shell structure porous silicon anode materials in the examples and the comparative examples were measured.
Assembling the ternary positive pole piece prepared by the mature process, 1mol/L LiPF6/EC + DMC + EMC (v/v is 1:1:1) electrolyte, Celgard2400 diaphragm and an outer shell into a 18650 cylindrical single battery by adopting a conventional production process. On a LanD battery test system of Wuhanjinnuo electronics Co Ltd, the charge and discharge performance of the prepared cylindrical battery is tested, and the test conditions are as follows: and (3) constant current charging and discharging at 0.2C at normal temperature, wherein the charging and discharging voltage is limited to 2.75V-4.2V.
According to the first reversible capacity measured in the button cell, the core-shell structure porous silicon negative electrode materials in the examples and the comparative examples are mixed with the same stable artificial graphite, and the first reversible capacity tested by the button cell of the mixed powder is 480 +/-5 mAh/g. And preparing a negative pole piece from the mixed powder by a button cell process, and assembling a 18650 cylindrical single cell by using a ternary pole piece prepared by a mature process as a positive pole, an isolating film and electrode liquid unchanged. The 18650 cylindrical single battery is subjected to charge and discharge tests, the voltage interval is 2.5 mV-4.2V, and the current density is 480mA/g
The test equipment of the button cell and the 18650 cylindrical single cell are both the LAND battery test system of Wuhanjinnuo electronics, Inc.
The performance test results of the nano porous silicon and core-shell structure porous silicon anode materials of examples 1 to 4 and comparative examples 1 to 7 are as follows:
table 1 milling important parameters and nanoporous silicon test data in examples 1 to 4 and comparative examples 1 to 7:
table 2 important parameters for spray drying and powder test data in examples 1 to 4 and comparative examples 1 to 7:
table 3 mass ratios and performance test data of the core-shell structure silicon-containing anode materials in examples 1 to 4 and comparative examples 1 to 7:
as can be seen from Table 1, the core-shell porous silicon anode material prepared by the method of the present application can be used for preparing anode materials with different properties by combining wet grinding and atomization drying technologies. Wherein, various parameter indexes of the nano porous silicon, such as median particle diameter D50, oxygen content and the like, can be changed by adjusting wet grinding process parameters; by adjusting the technological parameters of atomization and drying, the particle size of the atomized dry powder can be changed, thereby affecting the performance of the cathode material. In examples 1 to 4, the first efficiency of the porous silicon negative electrode material gradually decreases, 86.0 to 80.5%, with the gradual decrease of the content of the nanosilicon oxide, the gradual increase of the median particle size, and the gradual increase of the particle size of the atomized dry powder. The first reversible capacity and the first efficiency are exerted, so that the first reversible capacity and the first efficiency are in great relation with the components of the negative electrode material, and when the porous silicon content is higher, the first reversible capacity of the negative electrode material is the highest, 1420.4 mAh/g; when the graphite content is higher, the first efficiency of the negative electrode material is higher, namely 87.8 percent.
In comparative example 1, the silicon powder raw material is not subjected to nanocrystallization, and the first reversible capacity, the first coulombic efficiency and the cycle performance of the obtained core-shell structure porous silicon anode material are poorer than those of the anode material prepared in example 1;
in comparative example 2, the median particle diameter D50 of the obtained porous silicon negative electrode material was significantly large, 57.9 μm, not by the spray drying process, but by the conventional heat drying, when the particle size was large, the lithium ion diffusion path was increased, and at the same time, the distribution of each component inside the negative electrode material particles was not uniform, and not only was the first reversible capacity (983.1mAh/g) and the first coulombic efficiency poor (80.6%), but also the cycle performance was significantly reduced.
In comparative examples 3 to 4, the adjustment of the rotation speed of the atomizer to a low level and the adjustment of the solid content of the mixed slurry to a high level both affect the median diameter of the atomized powder, resulting in a decrease in electrochemical performance, and have the same mechanism as in comparative example 2.
In comparative example 5, graphite was not added to the composite slurry, and the first efficiency of the obtained porous silicon negative electrode material was significantly reduced, mainly because the porous silicon itself had poor conductivity, and the resistance and polarization inside the negative electrode material were increased, resulting in an increase in irreversible loss of lithium ions.
In comparative example 6, no carbon source was added to the composite slurry, and the first capacity of the obtained porous silicon negative electrode material was high, but the cycle performance was significantly reduced, mainly because the carbon source was not added to the liquid phase and may not be well filled in a part of the pores of the porous silicon, thereby causing the reduction of the cycle performance.
In comparative example 7, the powder after the atomization drying was not coated with a carbon source, and the porous silicon was in direct contact with the electrolyte, which resulted in the continuous loss of lithium ions, thereby significantly decreasing the cycle performance.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (9)
1. A preparation method of a core-shell structure porous silicon negative electrode material for a lithium ion battery is characterized by comprising the following steps:
(1) preparing nano porous silicon: adding porous silicon powder with the median particle size of 1-200 mu m and the purity of more than 99% and a grinding solvent into a dispersion tank of a sand mill, controlling the solid content of a mixed solution to be 10-30%, and starting stirring uniformly; the grinding beads are made of one of zirconium silicate, aluminum oxide, stainless steel, agate, ceramic, zirconium oxide and hard alloy, the mass ratio of the grinding beads to silicon powder is (10-30): 1, the mixed solution in the stirring tank is introduced into a sand mill, the linear velocity of the sand mill is more than 14m/s, and the grinding time is 30-70 h, so that porous silicon slurry is obtained;
(2) atomizing and granulating: adding graphite and carbon source materials into the porous silicon slurry obtained in the step (1), adjusting the solid content of the mixed slurry to be 10% -50%, measuring the viscosity of the mixed slurry to be lower than 100Pa & s, and stirring at a high speed of 400-800 rpm for 1-6 h; introducing inert gas into a closed spray dryer, and starting to drive oxygen until the detected oxygen content is lower than 2%; controlling the inlet temperature of the closed spray dryer to be 160-220 ℃, the outlet temperature to be 85-120 ℃ and the rotating speed of an atomizing disc to be more than 12000 rpm; introducing the mixed slurry, and carrying out atomization drying to obtain dry powder with the median particle size D50 of 4-30 micrometers;
(3) preparing a porous silicon negative electrode material: putting the dry powder obtained in the step (2) into a vapor deposition furnace, introducing inert gas for protection, heating to 600-1000 ℃, introducing a carbon source material for vapor deposition, depositing for 1-4 hours, and thermally decomposing the carbon source material to form amorphous carbon which not only covers the surface of the negative electrode material but also exists in the negative electrode material to obtain the core-shell structure porous silicon negative electrode material;
wherein, the step (1):
the structure shape of the stirring shaft of the sand mill is one of a disc type, a rod type or a rod disc type;
the grinding solvent is one or more of methanol, benzyl alcohol, ethanol, ethylene glycol, propanol, isopropanol, propylene glycol, butanol, n-butanol, isobutanol, pentanol, neopentyl alcohol and octanol; the purity of the alcohol solvent is more than or equal to 99 percent;
the inert gas in the steps (2) and (3) is one of nitrogen, argon and neon;
the porous silicon negative electrode material is of a core-shell structure, the inner core comprises nano porous silicon, graphite and amorphous carbon, and the shell is made of amorphous carbon; the proportion of the nano porous silicon in the negative electrode material is 30-70 wt.%; the ratio of the graphite is 20-45 wt.%, and the ratio of the amorphous carbon is 10-40 wt.%.
2. The preparation method of the core-shell structure porous silicon anode material according to claim 1, characterized in that: the proportion of the nano porous silicon in the negative electrode material is 40-50 wt.%; the ratio of the graphite is 30-40 wt.%, and the ratio of the amorphous carbon is 20-30 wt.%.
3. The preparation method of the core-shell structure porous silicon anode material according to claim 1, characterized in that: the specific surface area of the negative electrode material is 1-10 m2(ii)/g; the median particle diameter D50 of the negative electrode material is 6-30 μm.
4. The preparation method of the core-shell structure porous silicon anode material according to claim 1, characterized in that: the nano-porous silicon is prepared by a wet grinding process; the raw material for wet grinding is micron porous silicon with the median particle size of 1-200 mu m; and (3) grinding the micro porous silicon by a wet method to obtain the nano porous silicon, wherein the median particle size D50 of the nano porous silicon is 70-100 nm.
5. The preparation method of the core-shell structure porous silicon anode material according to claim 4, characterized in that: the microporous silicon raw material contains 1-10 wt.% of oxygen, and the oxygen content in the nano-porous silicon obtained by wet grinding is 12-35 wt.%.
6. The preparation method of the core-shell structure porous silicon anode material according to claim 1, characterized in that: the graphite is artificial graphite and/or natural graphite, and comprises one or more of isostatic pressure graphite, mould pressing graphite, extruded graphite, dense crystalline graphite, crystalline flake graphite, aphanitic graphite, micron graphite and nano graphite; the median particle size D50 of micron graphite is 1-20 μm, and the median particle size of nano graphite is 90-900 nm.
7. The preparation method of the core-shell structure porous silicon anode material according to claim 1, characterized in that: the amorphous carbon is formed by thermal decomposition of a carbon source material, the surface part of the negative electrode material is covered by the amorphous carbon formed by thermal decomposition, and the average thickness of an amorphous carbon layer is 10-1000 nm; the amorphous carbon is also present in the interior of the anode material and is filled in partial pores of the partially porous silicon;
the thermally decomposed carbon source material is one or more of methane, ethane, ethylene, acetylene, propane, propylene, acetone, butane, butylene, pentane, hexane, benzene, toluene, xylene, styrene, naphthalene, phenol, furan, pyridine, anthracene, liquefied gas, citric acid, triose, tetrose, pentose, hexose, glucose, sucrose, asphalt, epoxy resin, phenol resin, furfural resin, acrylic resin, polyvinyl chloride resin, polyether polyester resin, polyamide resin, polyimide resin, formaldehyde resin, polyoxymethylene, polyamide, polysulfone, polyethylene glycol, bismaleimide, polyethylene, polyvinyl chloride, polytetrafluoroethylene, polystyrene, polypropylene and polyacrylonitrile;
the thermal decomposition temperature is 600-1000 ℃, and the decomposition time is 1-6 hours.
8. A porous silicon negative electrode material with a core-shell structure for a lithium ion battery is characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. A lithium ion battery is characterized in that the lithium ion battery negative electrode material is the core-shell structure porous silicon negative electrode material of claim 8.
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