CN113644252A - Silicon-carbon negative electrode material and preparation method thereof - Google Patents
Silicon-carbon negative electrode material and preparation method thereof Download PDFInfo
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- CN113644252A CN113644252A CN202110890749.8A CN202110890749A CN113644252A CN 113644252 A CN113644252 A CN 113644252A CN 202110890749 A CN202110890749 A CN 202110890749A CN 113644252 A CN113644252 A CN 113644252A
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- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000010426 asphalt Substances 0.000 claims abstract description 59
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 53
- 239000010703 silicon Substances 0.000 claims abstract description 53
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 38
- 238000000498 ball milling Methods 0.000 claims abstract description 29
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 31
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical group CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 22
- 239000007921 spray Substances 0.000 claims description 21
- 239000012298 atmosphere Substances 0.000 claims description 15
- 239000011261 inert gas Substances 0.000 claims description 15
- 239000007833 carbon precursor Substances 0.000 claims description 14
- 238000001694 spray drying Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
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- 238000000576 coating method Methods 0.000 claims description 8
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- 239000010405 anode material Substances 0.000 claims description 7
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- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 4
- LHYBRZAQMRWQOJ-UHFFFAOYSA-N 2-methyl-2-(methylamino)propan-1-ol Chemical compound CNC(C)(C)CO LHYBRZAQMRWQOJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 3
- 239000011301 petroleum pitch Substances 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052744 lithium Inorganic materials 0.000 abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract description 5
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- 238000012360 testing method Methods 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 239000004698 Polyethylene Substances 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910010661 Li22Si5 Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- -1 Polyethylene Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
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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
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a silicon-carbon cathode material and a preparation method thereof, wherein the silicon-carbon cathode material comprises the following components in percentage by mass: 10-50% of micron silicon powder and 90-50% of asphalt, wherein the sum of the mass percentages of the components is 100%; the raw material is micron-sized silicon powder, the price is low, and the nano silicon powder with uniform particle size is obtained through high-energy ball milling, so that the volume effect of silicon in the circulating process can be effectively improved; dispersing agent is added in the ball milling process to inhibit the agglomeration of the nano silicon powder and realize effective dispersion; the asphalt and the silicon powder are uniformly mixed, so that the asphalt derived carbon is uniformly coated, the volume expansion of silicon in the processes of lithium insertion and lithium removal is inhibited, and the electrical contact between the silicon and a current collector is improved; finally, the first reversible capacity of the silicon-carbon negative electrode material for the lithium ion battery is improved, and the cycling stability of the battery is improved; the preparation method of the silicon-carbon cathode composite material is simple to operate, low in cost and easy to realize industrialization.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery preparation, and relates to a silicon-carbon negative electrode material and a preparation method thereof.
Background
Lithium ion batteries have been widely used in the fields of portable consumer electronics, electric tools, medical electronics, and the like because of their excellent properties. Meanwhile, the method has good application prospect in the fields of pure electric vehicles, hybrid electric vehicles, energy storage and the like. The lithium ion battery commercialized at present mainly uses graphite as a negative electrode material. However, in recent years, the demand for energy density of batteries has been rapidly increasing in various fields, and development of lithium ion batteries with higher energy density has been strongly demanded. Therefore, the development of a negative electrode material with higher energy density is urgent.
The highest specific mass capacity of the silicon material can reach 4200mA h g-1(Li22Si5) The lower lithium storage reaction voltage platform is the material which is known to be the highest theoretical specific volume of the negative electrode of the lithium ion battery at present. And the silicon material is environment-friendly, abundant in reserve and low in cost, so that the silicon-based negative electrode material is a novel high-energy material with great development prospect. However, the electronic conductivity and ionic conductivity of silicon are low, resulting in poor kinetics of electrochemical reactions; more importantly, the phase change and volume expansion of silicon in the lithiation process can generate larger stress, so that the electrode is broken and pulverized, the resistance is increased, and the cycle performance is suddenly reduced. The nano silicon and the carbonaceous material are compounded, so that the conductivity of the silicon-carbon cathode material can be improved, and the carbonaceous material can also be used as a buffer matrix to provide a certain buffer effect for the volume change of the silicon. However, the nano silicon has a large specific surface area and is easy to agglomerate, and the silicon in the obtained silicon-carbon composite material is often unevenly distributed, so that the improvement of the electrochemical performance of the negative electrode material is limited.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a silicon-carbon anode material and a preparation method thereof.
One of the purposes of the invention is to provide a silicon-carbon negative electrode material which can effectively improve the cycling stability of a battery;
the second purpose of the invention is to provide a preparation method of the silicon-carbon cathode material, which is simple to operate, low in cost and easy to realize industrialization.
Technical scheme
The silicon-carbon anode material is characterized by comprising the following components in percentage by mass: 10-50% of nano silicon powder and 90-50% of asphalt derived carbon, wherein the sum of the mass percentages of the components is 100%; wherein, the nano silicon powder is embedded in the asphalt derived carbon, and the granularity of the nano silicon powder is not more than 200 nm.
The precursor of the pitch-derived carbon is petroleum pitch with a softening point of 250 ℃.
The method for preparing the silicon-carbon negative electrode material is characterized by comprising the following steps:
step 1: dispersing micron silicon powder in ethanol, adding a dispersing agent, uniformly mixing, adding into a ball milling tank, and carrying out ball milling to obtain a nano silicon powder ethanol mixture; the proportion of the silicon to the ethanol is 20 to 30 percent; the dispersant accounts for 0.5 to 1 percent of the mass of the silicon powder; the particle size of the nano silicon powder is not more than 200 nm;
step 2: weighing asphalt, adding the asphalt into the nano silicon powder ethanol mixture, and stirring to obtain a silicon asphalt mixture; the ratio of the nano silicon powder to the asphalt is 1: 10-1: 1;
and step 3: placing the silicon asphalt mixture into a spray dryer for spray drying to obtain a silicon asphalt spray intermediate; the air inlet temperature of spray drying is 150-190 ℃, and the air outlet temperature is 70-90 ℃;
and 4, step 4: preheating the silicon pitch spray intermediate in a coating machine to obtain a silicon-carbon precursor; the preheating: firstly heating to 600-700 ℃, then preserving heat for 1-2 h, then continuously heating to 750-850 ℃, then preserving heat for 2-4 h, wherein the heating speed is 5-10 ℃/min, and the heating atmosphere is inert gas;
and 5: sintering the silicon-carbon precursor at high temperature to obtain a silicon-carbon negative electrode material; the sintering temperature of the high-temperature sintering is 850-950 ℃, the heat preservation time is 1-3 h, and the heating atmosphere is inert gas.
The granularity of the micron silicon powder in the step 1 is not more than 5 mu m.
The dispersant is AMP-95 aminomethyl propanol.
The AMP-95 aminomethyl propanol comprises the following components: 2-amino-2-methyl-1-propanol, the concentration is not less than 89.0%; 2-methyl-2-methylamino-1-propanol, the concentration is not more than 7.0%; and water at a concentration of 5%.
In the step 1: the ball milling speed is 900r/min to 1200r/min, and the ball milling time is 2h to 6 h.
The high-temperature sintering adopts a rotary furnace.
Advantageous effects
According to the silicon-carbon cathode material and the preparation method thereof, the raw material is micron-sized silicon powder, the price is low, and the nano silicon powder with uniform particle size is obtained through high-energy ball milling, so that the volume effect of silicon in the circulation process can be effectively improved; dispersing agent is added in the ball milling process to inhibit the agglomeration of the nano silicon powder and realize effective dispersion; the asphalt and the silicon powder are uniformly mixed, so that the asphalt derived carbon is uniformly coated, the volume expansion of silicon in the processes of lithium insertion and lithium removal is inhibited, and the electrical contact between the silicon and a current collector is improved; finally, the first reversible capacity of the silicon-carbon negative electrode material for the lithium ion battery is improved, and the cycling stability of the battery is improved; the preparation method of the silicon-carbon cathode composite material is simple to operate, low in cost and easy to realize industrialization.
The invention has the beneficial effects that:
1. the silicon-carbon cathode material is prepared from micron-sized silicon powder and is low in price, and the nano silicon powder with uniform particle size is obtained through high-energy ball milling, so that the volume effect of silicon in the circulating process can be effectively improved; dispersing agent is added in the ball milling process to inhibit the agglomeration of the nano silicon powder and realize effective dispersion; the asphalt and the silicon powder are uniformly mixed, so that the asphalt derived carbon is uniformly coated, the volume expansion of silicon in the processes of lithium insertion and lithium removal is inhibited, and the electrical contact between the silicon and a current collector is improved; finally, the first reversible capacity of the silicon-carbon negative electrode material for the lithium ion battery is improved, and the cycling stability of the battery is improved.
2. The preparation method of the silicon-carbon cathode material is simple to operate, low in cost and easy to realize industrialization.
Drawings
Fig. 1 is an SEM image of a silicon-carbon negative electrode material provided in example 1 of the present invention;
fig. 2 is an SEM cross-sectional view of a silicon-carbon negative electrode material provided in example 1 of the present invention;
FIG. 3 is a TEM image of a silicon-carbon anode material provided in example 1 of the present invention;
fig. 4 is a XRD test result of the silicon-carbon anode material provided in example 1 of the present invention;
fig. 5 shows TG test results of silicon carbon negative electrode materials provided in examples 1 and 2 of the present invention;
fig. 6 shows the capacity retention rate and coulombic efficiency of a lithium battery prepared from the silicon-carbon negative electrode composite material provided in example 1 of the present invention.
Fig. 7 shows the capacity retention rate and coulombic efficiency of a full battery obtained by matching the silicon-carbon negative electrode composite material provided in embodiment 1 of the present invention with NCM 811.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
the invention adopts the technical scheme that the silicon-carbon cathode material comprises the following components in percentage by mass: 10-50% of nano silicon powder and 90-50% of asphalt derived carbon, wherein the sum of the mass percentages of the components is 100%; wherein the nano silicon powder is embedded in the asphalt derived carbon, the particle size of the nano silicon powder is not more than 200nm, and a precursor of the asphalt derived carbon is petroleum asphalt with a softening point of 250 ℃;
the embodiment of the invention provides a preparation method of a silicon-carbon negative electrode material, which is realized by the following steps:
step 1, weighing micron silicon powder, wherein the granularity of the micron silicon powder is not more than 5 microns, dispersing the micron silicon powder in ethanol, the proportion of silicon to ethanol is 20-30%, adding 0.5-1% of dispersing agent, wherein the dispersing agent is AMP-95 aminomethyl propanol, and the specific components are as follows: 2-amino-2-methyl-1-propanol, the concentration is not less than 89.0%; 2-methyl-2-methylamino-1-propanol, the concentration is not more than 7.0%; and water with the concentration of 5 percent, adding the mixture into a ball milling tank for ball milling after uniform mixing, wherein the ball milling rotation speed is 900r/min to 1200r/min, the ball milling time is 2h to 6h, and the granularity of the nano silicon powder obtained by ball milling is not more than 200nm to obtain a nano silicon powder ethanol mixture;
step 2, weighing asphalt, wherein the ratio of the silicon powder to the asphalt is 1: 10-1: 1, adding the nano silicon powder ethanol mixture obtained in the step 1 and stirring to obtain a silicon asphalt mixture;
step 3, placing the silicon asphalt mixture obtained in the step 2 into a spray dryer for spray drying, wherein the air inlet temperature of the spray drying is 150-190 ℃, the air outlet temperature is 70-90 ℃, and a silicon asphalt spray intermediate is obtained;
step 4, placing the silicon asphalt spray intermediate obtained in the step 3 into a coating machine for preheating, heating to 600-700 ℃, then preserving heat for 1-2 h, then continuing to heat to 750-850 ℃, then preserving heat for 2-4 h, wherein the heating speed is 5-10 ℃/min, and the heating atmosphere is inert gas, so as to obtain a silicon-carbon precursor;
and 5, sintering the silicon-carbon precursor prepared in the step 4 at high temperature by using a rotary furnace, wherein the sintering temperature is 850-950 ℃, the heat preservation time is 1-3 h, and the heating atmosphere is inert gas, so that the silicon-carbon cathode material is obtained.
Example 1
Step 1, weighing 1kg of micron silicon powder, dispersing the micron silicon powder in 3kg of ethanol, adding 10g of AMP-95 aminomethyl propanol, uniformly mixing, adding the mixture into a ball milling tank, and carrying out ball milling for 6 hours at the ball milling rotation speed of 900r/min to obtain a nano silicon powder ethanol mixture;
step 2, weighing 1kg of asphalt, adding the asphalt into the nano silicon powder ethanol mixture obtained in the step 1, and stirring to obtain a silicon asphalt mixture;
step 3, placing the silicon asphalt mixture obtained in the step 2 into a spray dryer for spray drying, wherein the air inlet temperature of the spray drying is 150 ℃, the air outlet temperature is 90 ℃, and a silicon asphalt spray intermediate is obtained;
step 4, placing the silicon asphalt spray intermediate obtained in the step 3 into a coating machine for preheating, heating to 600 ℃, then preserving heat for 2 hours, then continuing to heat to 750 ℃, and preserving heat for 3 hours, wherein the heating speed is 10 ℃/min, and the heating atmosphere is inert gas, so as to obtain a silicon-carbon precursor;
and 5, sintering the silicon-carbon precursor prepared in the step 4 at a high temperature, wherein the high-temperature sintering adopts a rotary furnace, the sintering temperature is 850 ℃, the heat preservation time is 3 hours, and the heating atmosphere is inert gas, so that the silicon-carbon cathode material is obtained.
The silicon-carbon negative electrode material obtained in step 5 of example 1 is subjected to electron microscope Scanning (SEM) tests, and as a result, spherical particles with different sizes can be seen as shown in fig. 1. The SEM cross section of the silicon carbon particles shows that the silicon carbon is uniformly mixed and a large number of large pores are formed in the middle, as shown in fig. 2. Further high resolution transmission scanning electron microscopy characterization (HRTEM) was performed, and as shown in fig. 3, it can be seen that silicon particles are uniformly distributed in the carbon substrate, and the lattice spacing of 0.31nm corresponds to the (111) crystal plane of silicon; carbon substrate has carbon microcrystals with lattice spacing of 0.39nm and amorphous carbon, which is characteristic of soft carbon derived from pitch.
When the silicon-carbon negative electrode material prepared in example 1 is subjected to an X-ray diffraction (XRD) test, as shown in fig. 4, a peak of silicon can be seen, which indicates that silicon is pure phase silicon with good crystallinity, has good structural consistency and no other impurities, and soft carbon obtained by pitch diffraction has substantially no peak.
Example 2
Step 1, weighing 1kg of micron silicon powder, dispersing the micron silicon powder in 4kg of ethanol, adding 5g of AMP-95 aminomethyl propanol, uniformly mixing, adding the mixture into a ball milling tank, and carrying out ball milling for 2 hours at the ball milling rotation speed of 1200r/min to obtain a nano silicon powder ethanol mixture;
step 2, weighing 3kg of asphalt, adding the asphalt into the nano silicon powder ethanol mixture obtained in the step 1, and stirring to obtain a silicon asphalt mixture;
step 3, placing the silicon asphalt mixture obtained in the step 2 into a spray dryer for spray drying, wherein the air inlet temperature of the spray drying is 190 ℃, the air outlet temperature is 70 ℃, and a silicon asphalt spray intermediate is obtained;
step 4, placing the silicon asphalt spray intermediate obtained in the step 3 into a coating machine for preheating, heating to 650 ℃, then preserving heat for 1.5h, then continuing to heat to 800 ℃, then preserving heat for 3h, wherein the heating speed is 8 ℃/min, and the heating atmosphere is inert gas, so as to obtain a silicon-carbon precursor;
and 5, sintering the silicon-carbon precursor prepared in the step 4 at a high temperature, wherein the high-temperature sintering adopts a rotary furnace, the sintering temperature is 900 ℃, the heat preservation time is 2 hours, and the heating atmosphere is inert gas, so that the silicon-carbon cathode material is obtained.
Example 3
Step 1, weighing 1kg of micron silicon powder, dispersing the micron silicon powder in 5kg of ethanol, adding 8g of AMP-95 aminomethyl propanol, uniformly mixing, adding the mixture into a ball milling tank, and carrying out ball milling for 4 hours at the ball milling rotation speed of 1000r/min to obtain a nano silicon powder ethanol mixture;
step 2, weighing 10kg of asphalt, adding the asphalt into the nano silicon powder ethanol mixture obtained in the step 1, and stirring to obtain a silicon asphalt mixture;
step 3, placing the silicon asphalt mixture obtained in the step 2 into a spray dryer for spray drying, wherein the air inlet temperature of the spray drying is 170 ℃, the air outlet temperature is 80 ℃, and a silicon asphalt spray intermediate is obtained;
step 4, placing the silicon asphalt spray intermediate obtained in the step 3 into a coating machine for preheating, heating to 700 ℃, then preserving heat for 1h, then continuing to heat to 850 ℃, and preserving heat for 4h, wherein the heating speed is 7 ℃/min, and the heating atmosphere is inert gas, so as to obtain a silicon-carbon precursor;
and 5, sintering the silicon-carbon precursor prepared in the step 4 at a high temperature, wherein the high-temperature sintering adopts a rotary furnace, the sintering temperature is 950 ℃, the heat preservation time is 1h, and the heating atmosphere is inert gas, so that the silicon-carbon cathode material is obtained.
Example 4
Step 1, weighing 1kg of micron silicon powder, dispersing the micron silicon powder in 4kg of ethanol, adding 5g of AMP-95 aminomethyl propanol, uniformly mixing, adding the mixture into a ball milling tank, and carrying out ball milling for 4 hours at the ball milling rotation speed of 1000r/min to obtain a nano silicon powder ethanol mixture;
step 2, weighing 7kg of asphalt, adding the asphalt into the nano silicon powder ethanol mixture obtained in the step 1, and stirring to obtain a silicon asphalt mixture;
step 3, placing the silicon asphalt mixture obtained in the step 2 into a spray dryer for spray drying, wherein the air inlet temperature of the spray drying is 180 ℃, the air outlet temperature is 85 ℃, and a silicon asphalt spray intermediate is obtained;
step 4, placing the silicon asphalt spray intermediate obtained in the step 3 in a coating machine for preheating, heating to 650 ℃, then preserving heat for 1.5h, then continuing to heat to 800 ℃, then preserving heat for 34h, wherein the heating speed is 5 ℃/min, and the heating atmosphere is inert gas, so as to obtain a silicon-carbon precursor;
and 5, sintering the silicon-carbon precursor prepared in the step 4 at a high temperature, wherein the high-temperature sintering adopts a rotary furnace, the sintering temperature is 900 ℃, the heat preservation time is 2.5 hours, and the heating atmosphere is inert gas, so that the silicon-carbon cathode material is obtained.
Thermogravimetric Test (TG): as shown in fig. 5, the silicon carbon negative electrode materials prepared in examples 1 and 2 were placed in a thermogravimetric analyzer and tested in an air atmosphere at a heating rate of 10 ℃/min, and it was found that the silicon content was about 34.6% in example 1 and about 55.0% in example 2.
And (3) testing the charge and discharge performance:
the silicon-carbon negative electrode material obtained in the embodiment 1 is prepared into a lithium ion battery negative electrode piece. The specific method comprises the steps of mixing and grinding the silicon-carbon material, the Super-P and the CMC according to the mass ratio of 8:1:1, using deionized water as a solvent, stirring for 12 hours, coating the mixture on a copper foil by using a scraper, drying in vacuum for 12 hours, slicing into a circular sheet with the diameter of 12mm, wherein the surface density of the negative electrode material loaded on a pole piece is about-1.2 mg cm-2. The cell was set up in a glove box filled with high purity argon, both water and oxygen concentrations were less than 0.1 ppm. For the half cells, 2016 coin cells with metallic lithium foil as the counter electrode were assembled. Wherein the diaphragm adopts a Polyethylene (PE) film, and the electrolyte is 1.0M LiPF6Dissolved in EC/DEC (1:1, Vol%) containing 5.0% FEC. After standing for 12h, the test was carried out by constant current charging and discharging at 0.5C, the charging limit voltage of the battery was 2.0V, and the discharging end voltage was 0.01V. The test results are shown in FIG. 6, the specific discharge capacity is up to 1250mA hg-1The initial coulombic efficiency is about 78.5%, the average coulombic efficiency is kept 98.7%, and the capacity retention rate is as high as 85% at 100 circles. In addition, for a full cell, the silicon carbon negative electrode prepared in example 1 was first blended with graphite to obtain an average specific capacity of about 550mAh g-1The negative electrode of (1). From industrial LiNi0.8Co0.1Mn0.1O2The (NCM811) electrode serves as the positive electrode.The positive electrode was prepared by mixing NCM811, Super-P and polyvinylidene fluoride binder (100: 1: 1.5) in N-methylpyrrolidone to a uniform slurry. The slurry was coated on an aluminum foil current collector and dried in vacuum at 120 ℃ for 12 h. The positive-negative electrode capacity ratio is about 1: 1.1. the charge-discharge voltage window is 2.8V-4.2V, and the current density is 0.5C. As shown in fig. 7, the initial coulombic efficiency is 91.6%, and the capacity retention rate is 82% after 2000 cycles, so that the silicon-carbon material prepared by the technical scheme of the invention is used as the negative electrode material of the lithium battery, and has the advantages of high initial coulombic efficiency, high capacity, good cycle stability and the like in terms of electrical properties.
The ball mill model adopted in the above embodiment is a WSP6 high-speed ball mill; the inert gas adopts nitrogen or argon; the granularity of the micron silicon powder is not more than 5 mu m; the dispersant is AMP-95 aminomethyl propanol: the concrete components are as follows: 2-amino-2-methyl-1-propanol, the concentration is not less than 89.0%; 2-methyl-2-methylamino-1-propanol, the concentration is not more than 7.0%; and water at a concentration of 5%.
The silicon-carbon cathode material provided by the invention has the advantages that the raw material is micron-sized silicon powder, the price is low, and the nano-silicon powder with uniform particle size is obtained through high-energy ball milling, so that the volume effect of silicon in a circulating process can be effectively improved; dispersing agent is added in the ball milling process to inhibit the agglomeration of the nano silicon powder and realize effective dispersion; the asphalt and the silicon powder are uniformly mixed, so that the asphalt derived carbon is uniformly coated, the volume expansion of silicon in the processes of lithium insertion and lithium removal is inhibited, and the electrical contact between the silicon and a current collector is improved; finally, the first reversible capacity of the silicon-carbon negative electrode material for the lithium ion battery is improved, and the cycling stability of the battery is improved; the preparation method of the silicon-carbon cathode material is simple to operate, low in cost and easy to realize industrialization.
Claims (8)
1. The silicon-carbon anode material is characterized by comprising the following components in percentage by mass: 10-50% of nano silicon powder and 90-50% of asphalt derived carbon, wherein the sum of the mass percentages of the components is 100%; wherein, the nano silicon powder is embedded in the asphalt derived carbon, and the granularity of the nano silicon powder is not more than 200 nm.
2. The silicon-carbon anode material according to claim 1, wherein: the precursor of the pitch-derived carbon is petroleum pitch with a softening point of 250 ℃.
3. A method for preparing the silicon-carbon anode material of claim 1 or 2, characterized by the steps of:
step 1: dispersing micron silicon powder in ethanol, adding a dispersing agent, uniformly mixing, adding into a ball milling tank, and carrying out ball milling to obtain a nano silicon powder ethanol mixture; the proportion of the silicon to the ethanol is 20 to 30 percent; the dispersant accounts for 0.5 to 1 percent of the mass of the silicon powder; the particle size of the nano silicon powder is not more than 200 nm;
step 2: weighing asphalt, adding the asphalt into the nano silicon powder ethanol mixture, and stirring to obtain a silicon asphalt mixture; the ratio of the nano silicon powder to the asphalt is 1: 10-1: 1;
and step 3: placing the silicon asphalt mixture into a spray dryer for spray drying to obtain a silicon asphalt spray intermediate; the air inlet temperature of spray drying is 150-190 ℃, and the air outlet temperature is 70-90 ℃;
and 4, step 4: preheating the silicon pitch spray intermediate in a coating machine to obtain a silicon-carbon precursor; the preheating: firstly heating to 600-700 ℃, then preserving heat for 1-2 h, then continuously heating to 750-850 ℃, then preserving heat for 2-4 h, wherein the heating speed is 5-10 ℃/min, and the heating atmosphere is inert gas;
and 5: sintering the silicon-carbon precursor at high temperature to obtain a silicon-carbon negative electrode material; the sintering temperature of the high-temperature sintering is 850-950 ℃, the heat preservation time is 1-3 h, and the heating atmosphere is inert gas.
4. The method of claim 3, wherein: the granularity of the micron silicon powder in the step 1 is not more than 5 mu m.
5. The method of claim 3, wherein: the dispersant is AMP-95 aminomethyl propanol.
6. The method of claim 3, wherein: the AMP-95 aminomethyl propanol comprises the following components: 2-amino-2-methyl-1-propanol, the concentration is not less than 89.0%; 2-methyl-2-methylamino-1-propanol, the concentration is not more than 7.0%; and water at a concentration of 5%.
7. The method of claim 3, wherein: in the step 1: the ball milling speed is 900r/min to 1200r/min, and the ball milling time is 2h to 6 h.
8. The method of claim 3, wherein: the high-temperature sintering adopts a rotary furnace.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114388755A (en) * | 2021-12-14 | 2022-04-22 | 鞍钢化学科技有限公司 | Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof |
CN117205795A (en) * | 2023-10-07 | 2023-12-12 | 博路天成新能源科技有限公司 | Homogeneous mixing process for anisotropic micro-nano particles |
CN117254017A (en) * | 2023-10-30 | 2023-12-19 | 肇庆理士电源技术有限公司 | Silicon-carbon negative electrode material of battery and dry preparation process thereof |
Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102447112A (en) * | 2011-11-30 | 2012-05-09 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material, preparation method thereof and cathode material containing same as well as lithium ion battery |
CN103456954A (en) * | 2013-09-06 | 2013-12-18 | 四川一美能源科技有限公司 | Preparation method of active electrode material |
US20140302396A1 (en) * | 2011-11-10 | 2014-10-09 | General Research Institute For Nonferrous Metals | Nano silicon-carbon composite material and preparation method thereof |
CN104425802A (en) * | 2013-09-11 | 2015-03-18 | 上海杉杉科技有限公司 | Silicon-based composite material and preparation method and application thereof and prepared lithium ion battery |
CN104659333A (en) * | 2015-01-04 | 2015-05-27 | 合肥国轩高科动力能源股份公司 | Preparation method of Mg2Si/SiOx/C composite cathode material membrane electrode of lithium ion secondary battery |
WO2016110110A1 (en) * | 2015-01-08 | 2016-07-14 | 田东 | Preparation method for silicon-carbon composite lithium ion battery negative electrode piece |
CN106299277A (en) * | 2016-08-30 | 2017-01-04 | 浙江超威创元实业有限公司 | A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof |
CN106531980A (en) * | 2015-11-17 | 2017-03-22 | 宁波杉杉新材料科技有限公司 | Negative electrode material for lithium-ion battery and preparation method and application of negative electrode material |
CN107188593A (en) * | 2017-06-06 | 2017-09-22 | 广东工业大学 | A kind of process for dispersing of accuracy controlling alumina whisker draw ratio |
CN107785560A (en) * | 2017-11-15 | 2018-03-09 | 国联汽车动力电池研究院有限责任公司 | A kind of high performance silicon carbon negative pole material and preparation method thereof |
CN107863498A (en) * | 2017-09-20 | 2018-03-30 | 广东省稀有金属研究所 | A kind of preparation method of cathode material of lithium-ion power battery |
CN108172812A (en) * | 2018-01-30 | 2018-06-15 | 郑州中科新兴产业技术研究院 | A kind of silicon-carbon cathode material available for power battery and preparation method thereof |
CN108615866A (en) * | 2018-05-03 | 2018-10-02 | 无锡尼摩新能源科技有限公司 | A kind of agraphitic carbon lithium cell cathode material containing nano-silicon |
CN109873146A (en) * | 2019-02-27 | 2019-06-11 | 陕西煤业化工技术研究院有限责任公司 | A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof |
CN110304926A (en) * | 2019-08-12 | 2019-10-08 | 广东工业大学 | A kind of silicon nitride pug and preparation method thereof and silicon nitride ceramics part |
CN112234179A (en) * | 2020-10-26 | 2021-01-15 | 郑州中科新兴产业技术研究院 | Preparation method of high-capacity silicon-based negative electrode material |
-
2021
- 2021-08-04 CN CN202110890749.8A patent/CN113644252B/en active Active
Patent Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140302396A1 (en) * | 2011-11-10 | 2014-10-09 | General Research Institute For Nonferrous Metals | Nano silicon-carbon composite material and preparation method thereof |
CN102447112A (en) * | 2011-11-30 | 2012-05-09 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material, preparation method thereof and cathode material containing same as well as lithium ion battery |
CN103456954A (en) * | 2013-09-06 | 2013-12-18 | 四川一美能源科技有限公司 | Preparation method of active electrode material |
CN104425802A (en) * | 2013-09-11 | 2015-03-18 | 上海杉杉科技有限公司 | Silicon-based composite material and preparation method and application thereof and prepared lithium ion battery |
CN104659333A (en) * | 2015-01-04 | 2015-05-27 | 合肥国轩高科动力能源股份公司 | Preparation method of Mg2Si/SiOx/C composite cathode material membrane electrode of lithium ion secondary battery |
WO2016110110A1 (en) * | 2015-01-08 | 2016-07-14 | 田东 | Preparation method for silicon-carbon composite lithium ion battery negative electrode piece |
CN106531980A (en) * | 2015-11-17 | 2017-03-22 | 宁波杉杉新材料科技有限公司 | Negative electrode material for lithium-ion battery and preparation method and application of negative electrode material |
CN106299277A (en) * | 2016-08-30 | 2017-01-04 | 浙江超威创元实业有限公司 | A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof |
CN107188593A (en) * | 2017-06-06 | 2017-09-22 | 广东工业大学 | A kind of process for dispersing of accuracy controlling alumina whisker draw ratio |
CN107863498A (en) * | 2017-09-20 | 2018-03-30 | 广东省稀有金属研究所 | A kind of preparation method of cathode material of lithium-ion power battery |
CN107785560A (en) * | 2017-11-15 | 2018-03-09 | 国联汽车动力电池研究院有限责任公司 | A kind of high performance silicon carbon negative pole material and preparation method thereof |
CN108172812A (en) * | 2018-01-30 | 2018-06-15 | 郑州中科新兴产业技术研究院 | A kind of silicon-carbon cathode material available for power battery and preparation method thereof |
CN108615866A (en) * | 2018-05-03 | 2018-10-02 | 无锡尼摩新能源科技有限公司 | A kind of agraphitic carbon lithium cell cathode material containing nano-silicon |
CN109873146A (en) * | 2019-02-27 | 2019-06-11 | 陕西煤业化工技术研究院有限责任公司 | A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof |
CN110304926A (en) * | 2019-08-12 | 2019-10-08 | 广东工业大学 | A kind of silicon nitride pug and preparation method thereof and silicon nitride ceramics part |
CN112234179A (en) * | 2020-10-26 | 2021-01-15 | 郑州中科新兴产业技术研究院 | Preparation method of high-capacity silicon-based negative electrode material |
Non-Patent Citations (6)
Title |
---|
CHO, SANGHUN等: "Synthesis of Copper Oxide/Graphite Composite for High-Performance Rechargeable Battery Anode", CHEMISTRY-A EUROPEAN JOURNAL, vol. 23, no. 48, 25 August 2017 (2017-08-25), pages 11629 - 11635 * |
张莉;赵学波;: "锂离子电池硅基负极材料表面和界面调控的研究进展", 辽宁石油化工大学学报, no. 04, 31 August 2020 (2020-08-31), pages 49 - 58 * |
李晨等: "球磨法制备煤沥青基高性能锂离子电池硅/炭负极材料", 《炭素技术》 * |
李晨等: "球磨法制备煤沥青基高性能锂离子电池硅/炭负极材料", 《炭素技术》, no. 05, 28 October 2020 (2020-10-28), pages 11 - 17 * |
许晓海等, 冶金工业出版社 * |
陈泽森等: "《水性建筑涂料生产技术》", 31 January 2007, pages: 91 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114388755A (en) * | 2021-12-14 | 2022-04-22 | 鞍钢化学科技有限公司 | Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof |
CN117205795A (en) * | 2023-10-07 | 2023-12-12 | 博路天成新能源科技有限公司 | Homogeneous mixing process for anisotropic micro-nano particles |
CN117205795B (en) * | 2023-10-07 | 2024-03-12 | 博路天成新能源科技有限公司 | Homogeneous mixing process for anisotropic micro-nano particles |
CN117254017A (en) * | 2023-10-30 | 2023-12-19 | 肇庆理士电源技术有限公司 | Silicon-carbon negative electrode material of battery and dry preparation process thereof |
CN117254017B (en) * | 2023-10-30 | 2024-05-24 | 肇庆理士电源技术有限公司 | Silicon-carbon negative electrode material of battery and dry preparation process thereof |
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