CN111146430B - Porous core-shell structure silicon-carbon negative electrode material for lithium ion battery and preparation method thereof - Google Patents
Porous core-shell structure silicon-carbon negative electrode material for lithium ion battery and preparation method thereof Download PDFInfo
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 36
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000011258 core-shell material Substances 0.000 title claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
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- 239000002002 slurry Substances 0.000 claims description 50
- 239000005543 nano-size silicon particle Substances 0.000 claims description 36
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- 239000002904 solvent Substances 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 238000005056 compaction Methods 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
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- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- BSWXAWQTMPECAK-UHFFFAOYSA-N 6,6-diethyloctyl dihydrogen phosphate Chemical class CCC(CC)(CC)CCCCCOP(O)(O)=O BSWXAWQTMPECAK-UHFFFAOYSA-N 0.000 claims description 2
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- LCSPTLBPHFPXFQ-UHFFFAOYSA-N n,n-dihydroxy-2-phenylethanamine Chemical compound ON(O)CCC1=CC=CC=C1 LCSPTLBPHFPXFQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
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- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical class [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
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- 239000010703 silicon Substances 0.000 description 8
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- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
The invention belongs to the field of lithium ion battery negative electrode materials and electrochemistry, and particularly relates to a porous core-shell structure silicon-carbon negative electrode material for a lithium ion battery and a preparation method thereof.
Description
Technical Field
The invention belongs to the field of lithium ion battery cathode materials and electrochemistry, and particularly relates to a porous core-shell structure silicon-carbon cathode material for a lithium ion battery and a preparation method thereof.
Background
The conventional negative electrode material in the market is a graphite negative electrode, which has good cycle performance and safety performance and is widely applied to the production and application of lithium ion batteries, but the theoretical specific capacity of the graphite negative electrode is only 372mAh/g, and the requirement of a high-specific-capacity lithium battery cannot be met. Silicon has ultrahigh theoretical specific capacity (4200mAh/g) and lower delithiation potential (<0.5V), the voltage platform of the silicon is slightly higher than that of graphite, surface lithium precipitation is difficult to cause during charging, the safety performance is better, and the silicon becomes a negative electrode candidate material of next-generation high-capacity batteries which are attracted attention. However, silicon expands up to 300% in volume during charge and discharge, so that the silicon electrode is pulverized and falls off during charge and discharge cycles, and loses electrical contact with a current collector, and finally, the battery fails, and extremely poor cycle performance is shown.
Therefore, developing a silicon-carbon negative electrode material with simple process, excellent performance and environmental friendliness is an important research direction in the field of lithium ion batteries.
Disclosure of Invention
In view of the above, the present invention provides a porous core-shell structure silicon-carbon negative electrode material for a lithium ion battery, which is characterized in that the silicon-carbon negative electrode material is a porous core-shell structure, the core is formed by uniformly compounding nano-silicon and porous carbon, and the shell is coated with carbon formed by an organic cracking carbon source, and the method specifically comprises the following steps:
the particle size of the nano silicon is 50-300 nm, preferably 50-100 nm;
the porosity of the porous carbon is greater than 40%;
the thickness of the carbon coating layer is 0.1-10 μm, preferably 5-10 μm.
Preferably, the porous core-shell structure silicon-carbon negative electrode material contains 30 wt% -60 wt% of nano silicon, 30 wt% -45 wt% of low-carbon-residue carbon source and 5 wt% -30 wt% of carbon coating layer.
Preferably, the median particle size of the negative electrode material is 10-20 μm; the specific surface area of the negative electrode material is 3-5 m 2 (ii)/g; the powder compaction density of the negative electrode material is 1.4-1.6 g/cm 3 。
The invention also relates to a preparation method of the porous core-shell structure silicon-carbon negative electrode material for the lithium ion battery, which is characterized by comprising the following steps of:
(1) preparing nano silicon slurry: adding a silicon powder raw material and a dispersing agent into an organic solvent, uniformly mixing, introducing into a high-energy ball mill, and grinding for 5-100 hours under the protection of inert gas to obtain nano silicon slurry;
(2) preparation of porous carbon: placing a carbon precursor in a muffle furnace, introducing a nitrogen-oxygen mixed gas in a proper proportion, heating to 700-1000 ℃, and controlling the combustion degree of the carbon precursor to obtain porous carbon;
(3) slurry compounding and homogeneous dispersion: adding the porous carbon obtained in the step (2) into the nano silicon slurry obtained in the step (1), performing ultrasonic oscillation, and uniformly dispersing the composite slurry by using a high-speed dispersion machine;
(4) atomizing and drying: performing spray drying on the composite slurry obtained in the step (3) to obtain a precursor;
(5) carbon coating: and (4) carrying out homogeneous phase compounding on the precursor obtained in the step (4) and a carbon source, introducing inert gas for protection, and sintering at a high temperature to obtain the porous core-shell structure silicon-carbon negative electrode material.
Preferentially, the silicon powder raw material in the step (1) is monocrystalline silicon or polycrystalline silicon, the purity is more than 99.9%, the median particle size is 10-100 nm, and preferably 50-100 nm;
the dispersing agent is one or the combination of at least two of sodium pyrophosphate, polyvinylpyrrolidone, triethylhexyl phosphoric acid, sodium dodecyl sulfate, cellulose derivatives, polyacrylamide, Guel gum, fatty acid polyglycol ester and polyacrylic dihydroxy phenethylamine;
the organic solvent is one or the combination of at least two of methanol, ethanol, propanol, isopropanol, acetone, furan and amide;
the mass ratio of the silicon powder raw material to the dispersing agent is 100: (0.5 to 10), preferably 100: (1-5); after the solvent is added, the solid content of the mixed solution is 10-40%, and the preferable content is 20-30%;
the high-energy ball mill is a planetary ball mill, a tube mill, a cone mill, a rod mill or a sand mill; the material of the ball milling beads is selected from stainless steel, agate, ceramic, zirconia, alumina or hard alloy.
Preferably, the carbon precursor in the step (2) is sucrose, starch, glucose or lignite; in the nitrogen-oxygen mixed gas, the volume ratio of oxygen is 20-80%.
Preferably, the frequency of the ultrasonic wave in the step (3) is more than 10000Hz, and the ultrasonic time is more than 1 h; the rotating speed of the high-speed dispersion machine is more than 2000rpm, and the dispersion time is more than 1 h.
Preferably, the hot air inlet temperature of the spray dryer in the step (4) is 160-300 ℃, and the hot air outlet temperature is 80-150 ℃.
Preferably, the carbon source material in step (5) is one or a combination of at least two of asphalt, epoxy resin, phenolic resin, furfural resin, urea resin and polyvinyl alcohol;
the sintering reactor is a vacuum furnace, a box furnace, a rotary furnace, a roller kiln or a tubular furnace;
the sintering protective gas is one or the combination of at least two of nitrogen, helium and argon.
The invention also relates to a lithium ion battery which is characterized by comprising the porous core-shell structure silicon-carbon negative electrode material for the lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, micron-sized silicon powder is ground into nano silicon with the granularity D50 less than 100nm through superfine grinding, so that the absolute volume expansion of silicon in the charging and discharging processes is greatly reduced, and meanwhile, the dynamics is improved, so that the lithium atom migration rate is improved;
(2) the carbon precursor is prepared into porous carbon with controllable porosity by a combustion method, so that space is reserved for volume expansion of silicon, the problem of volume expansion of a silicon cathode can be obviously solved, the homogeneous dispersibility of nano silicon can be improved, and the transmission channel and speed of electrons and lithium ions can be ensured;
(3) the carbon coating improves the conductivity of the surface of the composite cathode material, isolates the electrolyte from etching the cathode material, and improves the long-cycle and large-rate performance of the composite cathode material;
(4) the prepared lithium ion battery cathode material has the advantages of cheap raw materials, simple process, environmental friendliness, no pollution and suitability for large-scale production.
Drawings
The invention is further described below with reference to the accompanying drawings.
Fig. 1 is a schematic structural diagram of a porous core-shell structured silicon-carbon negative electrode material prepared in an embodiment.
1 is a carbon coating layer; 2 is porous carbon; 3 is nano silicon.
Detailed Description
The present invention will be further described with reference to the following examples. The described embodiments and their results are only intended to illustrate the invention and should not be taken as limiting the invention described in detail in the claims.
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 porous core-shell structure silicon-carbon negative electrode material for a lithium ion battery comprises the following steps:
(1) preparing nano silicon slurry: 500g of polycrystalline silicon powder with the median particle size of 10 mu m and 5g of polyvinylpyrrolidone are mixed according to the mass ratio of the silicon powder: polyvinylpyrrolidone ═ 100: 1, adding the mixture into absolute ethyl alcohol, wherein the solid content of the mixed solution is 10%, introducing the mixed slurry into a sand mill, and grinding for 100 hours under the protection of nitrogen to obtain nano silicon slurry with the median particle size of 50nm, wherein the diameter of a grinding zirconium ball is 0.1mm, and the mass ratio of the zirconium ball to silicon powder is 10: 1;
(2) preparation of porous carbon: placing 900g of sucrose in a muffle furnace, introducing nitrogen-oxygen mixed gas, wherein the volume ratio of oxygen is 80%, heating to 700 ℃, and controlling the combustion degree of the sucrose to obtain 270g of porous carbon with the porosity of 70%;
(3) slurry compounding and homogeneous dispersion: adding the porous carbon obtained in the step (2) into the nano silicon slurry obtained in the step (1), and starting ultrasonic waves, wherein the frequency of the ultrasonic waves is 15000Hz, and the ultrasonic time is 4 h; introducing the ultrasonically-treated slurry into a high-speed dispersion machine, controlling the rotating speed of the high-speed dispersion machine to be 2200rpm, and dispersing for 2 hours to obtain homogeneously-dispersed composite slurry;
(4) atomizing and drying: spray drying the composite slurry obtained in the step (3) to obtain a precursor, wherein the hot air inlet temperature of a spray dryer is 300 ℃, and the hot air outlet temperature of the spray dryer is 140 ℃;
(5) carbon coating: and (3) mixing the precursor obtained in the step (4) with phenolic resin according to a mass ratio of 9: 1, performing homogeneous phase compounding, then placing in a high-temperature box type furnace, introducing nitrogen for protection, heating to 600 ℃, preserving heat for 2 hours, and cooling to room temperature to obtain the porous core-shell structure silicon-carbon cathode material.
Example 2
A preparation method of a porous core-shell structure silicon-carbon negative electrode material for a lithium ion battery comprises the following steps:
(1) preparing nano silicon slurry: 400g of polycrystalline silicon powder with the median particle size of 30 mu m and 2g of sodium dodecyl sulfate are mixed according to the mass ratio of silicon powder: sodium lauryl sulfate ═ 100: 0.5, adding the mixture into propanol, wherein the solid content of the mixed solution is 20%, introducing the mixed slurry into a sand mill, and grinding for 80 hours under the protection of nitrogen to obtain nano silicon slurry with the median particle size of 100nm, wherein the diameter of a grinding zirconium ball is 0.2mm, and the mass ratio of the zirconium ball to silicon powder is 10: 1;
(2) preparation of porous carbon: putting 1000g of starch in a muffle furnace, introducing nitrogen-oxygen mixed gas, wherein the volume ratio of oxygen is 70%, heating to 800 ℃, and controlling the combustion degree of the starch to obtain 350g of porous carbon with the porosity of 65%;
(3) slurry compounding and homogeneous dispersion: adding the porous carbon obtained in the step (2) into the nano silicon slurry obtained in the step (1), and starting ultrasonic waves, wherein the frequency of the ultrasonic waves is 15000Hz, and the ultrasonic time is 4 h; guiding the ultrasonically treated slurry into a high-speed dispersion machine, and controlling the rotating speed of the high-speed dispersion machine to be 2200rpm and the dispersion time to be 2h to obtain homogeneously dispersed composite slurry;
(4) atomizing and drying: spray drying the composite slurry obtained in the step (3) to obtain a precursor, wherein the hot air inlet temperature of a spray dryer is 260 ℃ and the hot air outlet temperature of the spray dryer is 130 ℃;
(5) carbon coating: and (5) mixing the precursor obtained in the step (4) with pitch according to the mass ratio of 8.5: 1.5, performing homogeneous phase compounding, then placing in a high-temperature box type furnace, introducing helium for protection, heating to 700 ℃, preserving heat for 3 hours, and cooling to room temperature to obtain the porous core-shell structure silicon-carbon cathode material.
Example 3
A preparation method of a porous core-shell structure silicon-carbon negative electrode material for a lithium ion battery comprises the following steps:
(1) preparing nano silicon slurry: 300g of polycrystalline silicon powder with the median particle size of 50 mu m and 15g of Guergen, according to the mass ratio of the silicon powder: 100 of Guerban: 5, adding the mixed solution into acetone, wherein the solid content of the mixed solution is 30%, introducing the mixed slurry into a star-type ball mill, and grinding for 50 hours under the protection of nitrogen to obtain nano silicon slurry with the median particle size of 100nm, wherein the diameter of a grinding zirconium ball is 0.3mm, and the mass ratio of the zirconium ball to silicon powder is 10: 1;
(2) preparation of porous carbon: placing 675g of glucose in a muffle furnace, introducing nitrogen-oxygen mixed gas, wherein the volume ratio of oxygen is 50%, heating to 900 ℃, and controlling the combustion degree of the glucose to obtain 270g of porous carbon with the porosity of 60%;
(3) slurry compounding and homogeneous dispersion: adding the porous carbon obtained in the step (2) into the nano silicon slurry obtained in the step (1), and starting ultrasonic waves, wherein the frequency of the ultrasonic waves is 15000Hz, and the ultrasonic time is 4 h; introducing the ultrasonically-treated slurry into a high-speed dispersion machine, controlling the rotating speed of the high-speed dispersion machine to be 2200rpm, and dispersing for 2 hours to obtain homogeneously-dispersed composite slurry;
(4) atomizing and drying: spray drying the composite slurry obtained in the step (3) to obtain a precursor, wherein the hot air inlet temperature of a spray dryer is 220 ℃, and the hot air outlet temperature of the spray dryer is 110 ℃;
(5) carbon coating: and (3) mixing the precursor obtained in the step (4) with epoxy resin according to a mass ratio of 8: 2, performing homogeneous phase compounding, then placing the silicon carbide anode material in a high-temperature box type furnace, introducing argon for protection, heating to 800 ℃, preserving heat for 4 hours, and then cooling to room temperature to obtain the porous core-shell structure silicon carbon anode material.
Example 4
A preparation method of a porous core-shell structure silicon-carbon negative electrode material for a lithium ion battery comprises the following steps:
(1) preparing nano silicon slurry: 300g of polycrystalline silicon powder with the median particle size of 100 mu m and 30g of fatty acid polyglycol ester are mixed according to the mass ratio of the silicon powder: fatty acid polyglycol ester 100: 10, adding the mixture into isopropanol, wherein the solid content of the mixed solution is 40%, introducing the mixed slurry into a sand mill, and grinding for 20 hours under the protection of nitrogen to obtain nano silicon slurry with the median particle size of 300nm, wherein the diameter of a grinding zirconium ball is 0.4mm, and the mass ratio of the zirconium ball to silicon powder is 10: 1;
(2) preparation of porous carbon: placing 560g of lignite in a muffle furnace, introducing nitrogen-oxygen mixed gas, wherein the volume ratio of oxygen is 40%, heating to 900 ℃, and controlling the combustion degree of the lignite to obtain 280g of porous carbon with the porosity of 50%;
(3) slurry compounding and homogeneous dispersion: adding the porous carbon obtained in the step (2) into the nano silicon slurry obtained in the step (1), and starting ultrasonic waves, wherein the frequency of the ultrasonic waves is 15000Hz, and the ultrasonic time is 4 h; introducing the ultrasonically-treated slurry into a high-speed dispersion machine, controlling the rotating speed of the high-speed dispersion machine to be 2200rpm, and dispersing for 2 hours to obtain homogeneously-dispersed composite slurry;
(4) atomizing and drying: spray drying the composite slurry obtained in the step (3) to obtain a precursor, wherein the hot air inlet temperature of a spray dryer is 160 ℃, and the hot air outlet temperature of the spray dryer is 80 ℃;
(5) carbon coating: and (3) mixing the precursor obtained in the step (4) with furfural resin according to a mass ratio of 7: and 3, performing homogeneous phase compounding, then placing in a high-temperature box type furnace, introducing argon for protection, heating to 900 ℃, preserving heat for 4 hours, and cooling to room temperature to obtain the porous core-shell structure silicon-carbon cathode material.
Comparative example 1
The difference from example 1 is that in step (1), the particle size D50 of nano-silicon is controlled to 400nm by controlling the grinding time, and the rest is the same as example 1, and will not be described again.
Comparative example 2
The difference from example 1 is that in step (1), the particle size D50 of nano-silicon is controlled to be 500nm by controlling the grinding time, and the rest is the same as example 1, which is not repeated herein.
Comparative example 3
The difference from example 1 is that in step (2), the porosity of the porous carbon is 35% by controlling the combustion degree of the carbon source, and the rest is the same as example 1, and the detailed description is omitted here.
Comparative example 4
The difference from example 1 is that in step (2), the porosity of the porous carbon is 25% by controlling the combustion degree of the carbon source, and the rest is the same as example 1, and the detailed description is omitted here.
Comparative example 5
The difference from example 1 is that in step (3), the composite slurry is not subjected to ultrasonic oscillation and high-speed dispersion treatment, 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 (4), the composite slurry is not dried by atomization, but dried by conventional heating, and the rest is the same as example 1, and will not be described again.
Comparative example 7
The difference from example 1 is that in step (5), the precursor obtained by atomization and drying is not coated with carbon, and the rest is the same as example 1, and is not described herein again.
Mixing and dissolving a negative electrode material, a conductive agent and a binder in a solvent according to a mass ratio of 93:2:5, controlling solid content to be 45%, coating the mixture on a copper foil current collector, and drying in vacuum to obtain a negative electrode plate; then, a ternary positive pole piece prepared by a traditional mature process, 1mol/L LiPF6/EC + DMC + EMC (v/v is 1:1:1) electrolyte, a Celgard2400 diaphragm and an outer shell are assembled into the 18650 cylindrical single-cell 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) charging and discharging at constant current of 0.2C at normal temperature, wherein the charging and discharging voltage is limited to 3.2V-4.3V.
The test results are shown in table 1:
table 1 results of performance testing of examples and comparative examples:
as can be seen from Table 1, the porous core-shell structure silicon-carbon anode material prepared by the method can adjust the comprehensive performance of the anode material by adjusting the conditions of the size of nano-silicon, the size of porous carbon pores, the proportion and the thickness of a coating layer and the like, and has a low specific surface area (3.8-4.7 m) 2 The powder compaction density is high (1.40-1.51 g/cm) 3 ) The discharge capacity can be more than 1800mAh/g, the first coulombic efficiency can be more than 91 percent, and the capacity retention rate can reach more than 91 percent after 300 cycles. In comparative examples 1 and 2, the particle size D50 of the nano-silicon is controlled to be 400nm and 500nm by controlling the grinding time, and the obtained anode material has high reversible capacity, but the first coulombic efficiency and the cycle performance are obviously reduced, and the performance tends to be gradually reduced along with the gradual increase of the size of the nano-silicon. In comparative examples 3 and 4, the porosity of the prepared porous carbon is 35% and 25% by controlling the combustion degree of the carbon source, the reversible capacity of the obtained anode material is high, but the coulombic efficiency and the cycle performance are reduced for the first time, and the performance is reduced gradually along with the gradual reduction of the porosity of the porous carbon. In comparative example 5, the composite slurry was not subjected to ultrasonic oscillation and high-speed dispersion treatment, the reversible capacity of the obtained negative electrode material was reduced to 1653.1mAh/g, the first coulombic efficiency was also reduced to 85.2%, and the capacity retention rate was only 83.6% after 300 cycles. In comparative example 6, the reversible capacity of the obtained negative electrode material was reduced to 1571.8mAh/g without drying the composite slurry by atomization, and the first coulombic efficiency and the capacity retention rate at 300 cycles were significantly deteriorated. In comparative example 7, the precursor obtained by atomization and drying was not carbon-coated, and the reversible capacity of the obtained negative electrode material was not significantly reduced, but the first coulombic efficiency was only 74.6%, and the capacity retention rate after 300 cycles was only 65.0%.
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 modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (11)
1. A porous core-shell structure silicon-carbon negative electrode material for a lithium ion battery is characterized in that the silicon-carbon negative electrode material is of a porous core-shell structure, an inner core is formed by compounding nano-silicon and porous carbon homogeneous phases, and a shell is coated by carbon formed by an organic cracking carbon source;
the particle size of the nano silicon is 50-300 nm;
the porosity of the porous carbon is greater than 40%;
the thickness of the carbon coating layer is 0.1-10 mu m;
the preparation method of the porous core-shell structure silicon-carbon negative electrode material comprises the following steps:
(1) preparing nano silicon slurry: adding a silicon powder raw material and a dispersing agent into an organic solvent, uniformly mixing, introducing into a high-energy ball mill, protecting by nitrogen or inert gas, and grinding for 5-100 hours to obtain nano silicon slurry;
(2) preparation of porous carbon: placing the carbon precursor in a muffle furnace, introducing a nitrogen-oxygen mixed gas in a proper proportion, heating to 700-1000 ℃, and controlling the combustion degree of the carbon precursor to obtain porous carbon; the carbon precursor is sucrose, starch, glucose or lignite; in the nitrogen-oxygen mixed gas, the volume ratio of oxygen is 20-80%;
(3) slurry compounding and homogeneous dispersion: adding the porous carbon obtained in the step (2) into the nano silicon slurry obtained in the step (1), performing ultrasonic oscillation, and uniformly dispersing the composite slurry by using a high-speed dispersion machine;
(4) atomizing and drying: spray drying the composite slurry obtained in the step (3) to obtain a precursor;
(5) carbon coating: and (4) carrying out homogeneous phase compounding on the precursor obtained in the step (4) and a carbon source, introducing nitrogen or inert gas for protection, and sintering at a high temperature to obtain the porous core-shell structure silicon-carbon negative electrode material.
2. The silicon-carbon anode material with the porous core-shell structure for the lithium ion battery, according to claim 1, wherein the particle size of the nano silicon is 50-100 nm; the thickness of the carbon coating layer is 5 to 10 μm.
3. The porous core-shell structure silicon-carbon negative electrode material for the lithium ion battery according to claim 1, wherein the porous core-shell structure silicon-carbon negative electrode material contains 30-60 wt% of nano silicon, 30-45 wt% of porous carbon and 5-30 wt% of a carbon coating layer.
4. The silicon-carbon anode material with the porous core-shell structure for the lithium ion battery, according to claim 1, wherein the median particle size of the anode material is 10-20 μm; the specific surface area of the negative electrode material is 3-5 m 2 (ii)/g; the powder compaction density of the negative electrode material is 1.4-1.6 g/cm 3 。
5. A preparation method of the porous core-shell structure silicon-carbon negative electrode material for the lithium ion battery according to any one of claims 1 to 4, characterized by comprising the following steps:
(1) preparing nano silicon slurry: adding a silicon powder raw material and a dispersing agent into an organic solvent, uniformly mixing, introducing into a high-energy ball mill, protecting by nitrogen or inert gas, and grinding for 5-100 hours to obtain nano silicon slurry;
(2) preparation of porous carbon: placing a carbon precursor in a muffle furnace, introducing a nitrogen-oxygen mixed gas in a proper proportion, heating to 700-1000 ℃, and controlling the combustion degree of the carbon precursor to obtain porous carbon; the carbon precursor is sucrose, starch, glucose or lignite; in the nitrogen-oxygen mixed gas, the volume ratio of oxygen is 20-80%;
(3) slurry compounding and homogeneous dispersion: adding the porous carbon obtained in the step (2) into the nano silicon slurry obtained in the step (1), performing ultrasonic oscillation, and uniformly dispersing the composite slurry by using a high-speed dispersion machine;
(4) atomizing and drying: spray drying the composite slurry obtained in the step (3) to obtain a precursor;
(5) carbon coating: and (4) carrying out homogeneous phase compounding on the precursor obtained in the step (4) and a carbon source, introducing nitrogen or inert gas for protection, and sintering at a high temperature to obtain the porous core-shell structure silicon-carbon negative electrode material.
6. The preparation method according to claim 5, wherein the silicon powder raw material in the step (1) is one of monocrystalline silicon or polycrystalline silicon, the purity is more than 99.9%, and the median particle size is 10-100 μm;
the dispersing agent is one or the combination of at least two of sodium pyrophosphate, polyvinylpyrrolidone, triethylhexyl phosphoric acid, sodium dodecyl sulfate, cellulose derivatives, polyacrylamide, Guel gum, fatty acid polyglycol ester and polyacrylic dihydroxy phenethylamine;
the organic solvent is one or the combination of at least two of methanol, ethanol, propanol, isopropanol, acetone, furan and amide;
the mass ratio of the silicon powder raw material to the dispersing agent is 100: (0.5 to 10); after the solvent is added, the solid content of the mixed solution is 10-40%;
the high-energy ball mill is a planetary ball mill, a tube mill, a cone mill, a rod mill or a sand mill; the material of the ball milling beads is selected from stainless steel, agate, ceramic, zirconia, alumina or hard alloy.
7. The preparation method according to claim 6, wherein the median particle diameter of the silicon powder raw material is 50-100 μm; the mass ratio of the silicon powder raw material to the dispersing agent is 100: (1-5); after the solvent is added, the solid content of the mixed solution is 20-30%.
8. The method according to claim 5, wherein the frequency of the ultrasound in step (3) is > 10000Hz, and the ultrasound time is > 1 h; the rotating speed of the high-speed dispersion machine is more than 2000rpm, and the dispersion time is more than 1 h.
9. The method according to claim 5, wherein the hot air inlet temperature of the spray drying in the step (4) is 160 to 300 ℃ and the outlet temperature is 80 to 150 ℃.
10. The preparation method according to claim 5, wherein the carbon source in step (5) is one or a combination of at least two of asphalt, epoxy resin, phenolic resin, furfural resin, urea resin and polyvinyl alcohol;
the sintering reactor is a vacuum furnace, a box furnace, a rotary furnace, a roller kiln or a tubular furnace;
the inert gas is helium or argon.
11. A lithium ion battery is characterized by comprising the porous core-shell structure silicon-carbon negative electrode material in any one of claims 1 to 4 or the porous core-shell structure silicon-carbon negative electrode material prepared by the preparation method in any one of claims 5 to 10.
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| CN111960421B (en) * | 2020-08-27 | 2021-11-05 | 北京理工大学 | Preparation method of coated carbon-silicon negative electrode material |
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| CN114144909A (en) * | 2021-03-31 | 2022-03-04 | 宁德新能源科技有限公司 | Negative pole piece, electrochemical device comprising same and electronic device |
| CN114122372B (en) * | 2021-11-10 | 2024-03-29 | 云南中晟新材料有限责任公司 | Low-expansion silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104393284A (en) * | 2014-11-17 | 2015-03-04 | 天津大学 | Nickel oxide nano-particle loaded porous hard carbon sphere negative electrode material and preparation method thereof |
| CN104953122B (en) * | 2015-06-30 | 2017-09-19 | 深圳清华大学研究院 | Nano-silicone wire/carbon composite negative pole material and preparation method and its lithium ion battery |
| CN105932245B (en) * | 2016-05-20 | 2019-07-16 | 北京壹金新能源科技有限公司 | A kind of high compacted density silicon-carbon cathode material and its preparation method and application |
| CN106450192A (en) * | 2016-10-14 | 2017-02-22 | 浙江天能能源科技股份有限公司 | Silicon/carbon composite material for lithium ion battery and preparation method and application thereof |
| US10084182B2 (en) * | 2017-02-23 | 2018-09-25 | Nanotek Instruments, Inc. | Alkali metal-sulfur secondary battery containing a protected sulfur cathode and manufacturing method |
| CN107416819B (en) * | 2017-06-15 | 2019-11-29 | 北京理工大学 | A method of the porous carbon nanomaterial of N doping is prepared using carbon dioxide |
| EP3476475B1 (en) * | 2017-10-27 | 2022-04-06 | Heraeus Battery Technology GmbH | Production of a porous carbon product |
| CN108258230B (en) * | 2018-02-06 | 2021-02-26 | 马鞍山科达普锐能源科技有限公司 | Hollow-structure silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
| CN108933250B (en) * | 2018-08-28 | 2020-09-15 | 大同新成新材料股份有限公司 | Preparation process of silicon-carbon composite negative electrode material |
| CN109449432A (en) * | 2018-09-14 | 2019-03-08 | 深圳市卓能新能源股份有限公司 | Battery anode slice and its manufacturing method and lithium ion battery and its manufacturing method |
| CN110400930A (en) * | 2019-08-15 | 2019-11-01 | 马鞍山科达普锐能源科技有限公司 | A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof |
| CN110732314B (en) * | 2019-09-26 | 2022-12-02 | 湖南中科星城石墨有限公司 | Composite porous carbon for sulfur fixation and preparation method thereof |
-
2020
- 2020-02-10 CN CN202010084393.4A patent/CN111146430B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 掺氮多孔碳在二氧化碳吸附分离中的应用;陈爱兵等;《无机材料学报》;20150116;第30卷(第01期);9-16 * |
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