WO2022121280A1 - 一种类石榴结构硅基复合材料、其制备方法及其应用 - Google Patents
一种类石榴结构硅基复合材料、其制备方法及其应用 Download PDFInfo
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- WO2022121280A1 WO2022121280A1 PCT/CN2021/101984 CN2021101984W WO2022121280A1 WO 2022121280 A1 WO2022121280 A1 WO 2022121280A1 CN 2021101984 W CN2021101984 W CN 2021101984W WO 2022121280 A1 WO2022121280 A1 WO 2022121280A1
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- based composite
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 63
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000010703 silicon Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 52
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 37
- 239000010439 graphite Substances 0.000 claims abstract description 37
- 230000004048 modification Effects 0.000 claims abstract description 18
- 238000012986 modification Methods 0.000 claims abstract description 18
- 238000011049 filling Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000007773 negative electrode material Substances 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims description 39
- 239000002243 precursor Substances 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 239000010410 layer Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 15
- 230000001681 protective effect Effects 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 239000011268 mixed slurry Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000002210 silicon-based material Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000010426 asphalt Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 108010028773 Complement C5 Proteins 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- -1 lithium transition metal Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Images
Classifications
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- 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
- C01B32/20—Graphite
- C01B32/21—After-treatment
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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Definitions
- the invention relates to the field of electrode and negative electrode materials, in particular to a garnet-like structure silicon-based composite material, a preparation method and application thereof.
- anode materials are mainly natural graphite, artificial graphite and intermediate graphite-like materials, but due to their low theoretical capacity (372mAh/g), they cannot meet the needs of the market.
- new high specific capacity anode materials lithium storage metals and their oxides (such as Sn, Si) and lithium transition metal phosphides.
- Si has become one of the most potential alternative graphite materials due to its high theoretical specific capacity (4200mAh/g), but silicon-based has a huge volume effect during the charge and discharge process.
- silicon-based materials have low intrinsic conductivity and poor rate performance. Therefore, reducing the volume expansion effect and improving the cycle performance and rate performance are of great significance for the application of silicon-based materials in lithium-ion batteries.
- the existing silicon-carbon negative electrode material adopts nano-silicon, graphite and carbon granulation to obtain a composite material. Since nano-silicon is coated on the surface of graphite particles to form a core-shell structure, the micron-scale graphite particles cannot release the stress during the discharge process well, resulting in local structural damage and affecting the overall performance of the material. Therefore, how to reduce the volume expansion effect and improve the cycle performance is of great significance for the application of silicon-based materials in Li-ion batteries.
- a garnet-like structure silicon-based composite material and a preparation method thereof are provided, which can reduce the volume expansion effect and improve the cycle performance and rate performance.
- the invention also provides the application of the pomegranate-like structure silicon-based composite material, the product performance is stable, and the application prospect is good.
- a pomegranate-like structure silicon-based composite material is composed of nano-silicon, expanded graphite and a filling and modification layer; the nano-silicon is dispersed in the pores inside the expanded graphite; the filling and modification layer is filled with nanometer silicon. Silicon particles or filled between nano-silicon and expanded graphite.
- a further improvement to the above technical solution is that the particle size D50 of the pomegranate-like structure silicon-based composite material is 2-40 ⁇ m; the specific surface area of the pomegranate-like structure silicon-based composite material is 0.5-15m2/g; The oxygen content of the structural silicon-based composite material is 0-20%; the carbon content of the pomegranate-like structure silicon-based composite material is 20-90%; the silicon content of the pomegranate-like structure silicon-based composite material is 5-90%.
- a further improvement to the above technical solution is that the expanded graphite is powder or emulsion.
- the filling modification layer is a carbon modification layer
- the carbon modification layer is at least one layer
- the thickness of the single layer is 0.2-1.0 ⁇ m.
- the nano-silicon is SiOx, wherein X is 0-0.8; the oxygen content of the nano-silicon is 0-31%; the grain size of the nano-silicon is 1-40 nm, so The nano-silicon is one or both of polycrystalline nano-silicon and amorphous nano-silicon; the particle size D50 of the nano-silicon is 30-150 nm.
- a preparation method of a pomegranate-like structure silicon-based composite material comprising the following steps: S0: mixing and dispersing nano-silicon, a carbon source and a dispersant in an organic solvent uniformly to obtain slurry A; S1: under negative pressure The emulsified graphite is added to the slurry A, and the uniformly mixed slurry A is filled into the gap of the expanded/emulsified graphite by using negative pressure to obtain the slurry B; S2: the slurry B is spray-dried to obtain the precursor C; S3: the The precursor C and the carbon source are mechanically mixed and mechanically fused to obtain the precursor D; S4: the precursor D is subjected to heat treatment and screening treatment to obtain the garnet-like structure silicon matrix composite material.
- the negative pressure is one or more of a vacuum stirring process, an emulsification process, and an online dispersion process.
- the heat treatment is one of static heat treatment or dynamic heat treatment.
- a further improvement to the above technical solution is that the static heat treatment is to place the precursor D in a box furnace or a roller kiln, and under a protective atmosphere, the temperature is raised to 400-1000°C at 1-5°C/min, and the temperature is kept for 0.5°C. -20h, naturally cooled to room temperature; the dynamic heat treatment is to place the precursor D in a rotary furnace, under a protective atmosphere, raise the temperature to 400-1000°C at 1-5°C/min, and pass the temperature at 0-20.0L/min.
- the organic carbon source gas was introduced into the gas at a rate of input, kept for 0.5-20 h, and cooled to room temperature naturally.
- pomegranate-like structure silicon-based composite material is applied to a negative electrode material of a lithium ion battery.
- the expanded graphite inside the garnet-like structure silicon-based composite material of the present invention can play a good conductive network, the carbon conductive network can effectively improve the conductivity of the silicon-based material, and the flexible porous structure of the expanded graphite can effectively alleviate the charging and discharging process. It can effectively avoid the pulverization of the material during the cycle, alleviate the volume expansion effect of the silicon-based material, improve the cycle performance, and improve the conductivity and rate performance of the material. Filling the modified layer can avoid the direct contact between the nano-silicon and the electrolyte to reduce side reactions, and at the same time, it can further effectively improve the conductivity of the silicon-based material and relieve the volume effect energy during the charging and discharging process.
- FIG. 1 is an electron microscope image of the material prepared in Example 4 of the garnet-like structure silicon-based composite material of the present invention.
- Example 2 is a first charge-discharge curve diagram of the material prepared in Example 4 of the garnet-like structure silicon-based composite material of the present invention.
- a pomegranate-like structure silicon-based composite material is composed of nano-silicon, expanded graphite and a filling and modification layer; the nano-silicon is dispersed in the pores inside the expanded graphite; the filling and modification layer is filled with nanometer silicon. Silicon particles or filled between nano-silicon and expanded graphite.
- the particle size D50 of the pomegranate-like structure silicon-based composite material is 2-40 ⁇ m, more preferably 2-20 ⁇ m, particularly preferably 2-10 ⁇ m; the specific surface area of the pomegranate-like structure silicon-based composite material is 0.5-15m2/g , more preferably 0.5-10m2/g, particularly preferably 0.5-5m2/g; the oxygen content of the pomegranate-like structure silicon-based composite material is 0-20%, more preferably 0-10%, particularly preferably 0- 5%; the carbon content of the pomegranate-like structure silicon-based composite material is 20-90%, more preferably 20-60%, particularly preferably 20-50%; the silicon content of the pomegranate-like structure silicon-based composite material is 5-90%, more preferably 20-70%, particularly preferably 30-60%.
- the expanded graphite is powder or emulsion.
- the filling modification layer is a carbon modification layer, the carbon modification layer is at least one layer, and the thickness of the single layer is 0.2-1.0 ⁇ m.
- the nano-silicon is SiOx, wherein X is 0-0.8; the oxygen content of the nano-silicon is 0-31%, more preferably 0-20%, particularly preferably 0-15%; the crystal grains of the nano-silicon are The size is 1-40nm, and the nano-silicon is one or both of polycrystalline nano-silicon or amorphous nano-silicon; the particle size D50 of the nano-silicon is 30-150nm, more preferably 30-110nm, particularly preferably 50-100nm.
- a preparation method of a pomegranate-like structure silicon-based composite material comprising the following steps: S0: mixing and dispersing nano-silicon, a carbon source and a dispersant in an organic solvent uniformly to obtain slurry A; S1: under negative pressure The emulsified graphite is added to the slurry A, and the uniformly mixed slurry A is filled into the gap of the expanded/emulsified graphite by using negative pressure to obtain the slurry B; S2: the slurry B is spray-dried to obtain the precursor C; S3: the The precursor C and the carbon source are mechanically mixed and mechanically fused to obtain the precursor D; S4: the precursor D is subjected to heat treatment and screening treatment to obtain the garnet-like structure silicon matrix composite material.
- the preparation method of the present invention utilizes negative pressure to fill the nano-silicon and carbon source with the inner pores of the expanded graphite; then spray drying and mechanical pressure make the nano-silicon and the carbon source fill the pores of the expanded graphite; finally heat treatment is performed to make the carbon source pyrolyzed to be filled Retouch layer.
- the negative pressure is one or more of a vacuum stirring process, an emulsification process, and an online dispersion process.
- the heat treatment is one of static heat treatment or dynamic heat treatment.
- the static heat treatment is to place the precursor D in a box furnace or roller kiln, and under a protective atmosphere, raise the temperature to 400-1000°C at 1-5°C/min, keep the temperature for 0.5-20h, and naturally cool to room temperature;
- the dynamic heat treatment is to place the precursor D in a rotary furnace, under a protective atmosphere, raise the temperature to 400-1000°C at 1-5°C/min, and feed the organic carbon source gas at a rate of 0-20.0L/min, Incubate for 0.5-20h, and cool to room temperature naturally.
- pomegranate-like structure silicon-based composite material is applied to a negative electrode material of a lithium ion battery.
- Example 1 1. Mix and disperse 1000g of nano-silicon with a particle size D50 of 100nm and 100g of citric acid in alcohol to obtain a slurry A1; 2. Add 50g of expanded graphite to the slurry A1, and vacuumize while dispersing and stirring to obtain Slurry B1; 3. The slurry B1 is spray-dried to obtain the precursor C1; 4. The precursor C1 and the asphalt are mixed and fused at a mass ratio of 10:3, and then sintered in a nitrogen protective atmosphere , the heating rate is 1°C/min, the heat treatment temperature is 1000°C, the temperature is kept for 5h, and after cooling, sieving treatment is performed to obtain a garnet-like structure silicon matrix composite material.
- Example 2 1. Mix and disperse 1000g of nano-silicon with a particle size D50 of 100nm and 100g of citric acid in alcohol to obtain slurry A2; 2. Use an online dispersion system to add 50g of expanded graphite to slurry A2 to obtain slurry B2 3. The slurry B2 is spray-dried to obtain the precursor C2; 4. The precursor C2 and the asphalt are mixed and fused at a mass ratio of 10:3, and then sintered under a nitrogen protective atmosphere. The heat treatment temperature is 1000 °C, the temperature is 1000 °C, and the temperature is kept for 5 hours.
- Example 3 1. Mix and disperse 1000 g of nano-silicon with a particle size D50 of 100 nm and 100 g of citric acid in alcohol to obtain slurry A3; 2. Use an online dispersion system to add 100 g of expanded graphite to slurry A3 to obtain slurry B3 3. The slurry B3 is spray-dried to obtain the precursor C3; 4. The precursor C3 and the asphalt are mixed and fused at a mass ratio of 10:3, and then sintered under a nitrogen protective atmosphere. The temperature is 1°C/min, the heat treatment temperature is 1000°C, and the temperature is kept for 5 hours.
- Example 4 1. Mix and disperse 1000g of nano-silicon with a particle size D50 of 100nm and 50g of citric acid in alcohol to obtain a slurry A4; 2. Use an online dispersion system to add 100g of expanded graphite to the slurry A4 to obtain a slurry B4 3. The slurry B4 is spray-dried to obtain the precursor C4; 4. The precursor C4 and the asphalt are mixed and fused at a mass ratio of 10:4, and then sintered under a nitrogen protective atmosphere. The temperature is 1°C/min, the heat treatment temperature is 1000°C, and the temperature is kept for 5 hours.
- Example 5 1. Mix and disperse 1000g of nano-silicon with a particle size D50 of 100nm and 50g of citric acid in alcohol to obtain slurry A5; 2. Use an online dispersion system to add 100g of expanded graphite to slurry A5 to obtain slurry B5 3. The slurry B5 is spray-dried to obtain the precursor C5; 4. The precursor C5 and the asphalt are mixed and fused at a mass ratio of 10:3, and then sintered under a nitrogen protective atmosphere. 5. Take 1000g of the obtained precursor D5 and put it in a CVD furnace, and heat it up to 1000°C at 5°C/min, respectively at 4.0L/min. High-purity nitrogen was introduced at a rate of 0.5 L/min, and methane gas was introduced at a rate of 0.5 L/min for 0.5 h. After cooling, sieving treatment was performed to obtain a garnet-like structure silicon matrix composite material.
- Example 6 1. Mix and disperse 1000g of nano-silicon with a particle size D50 of 50nm and 50g of citric acid in alcohol to obtain slurry A6; 2. Use an online dispersion system to add 100g of expanded graphite to slurry A6 to obtain slurry B6 3. The slurry B6 is spray-dried to obtain the precursor C6; 4. The precursor C6 and the asphalt are mixed and fused at a mass ratio of 10:3, and then sintered under a nitrogen protective atmosphere. 1°C/min, heat treatment temperature of 900°C, holding for 5h to obtain precursor D6; 5.
- Comparative example 1. Mix and disperse 1000g of nano-silicon with a particle size D50 of 100nm and 100g of citric acid in alcohol to obtain a slurry A0; 2. Mix and fuse the slurry A0 with asphalt in a mass ratio of 10:3, and then The sintering treatment was carried out under nitrogen protective atmosphere, the heating rate was 1 °C/min, the heat treatment temperature was 1000 °C, and the temperature was kept for 5 h. After cooling, the silicon matrix composite material was obtained by screening treatment.
- Test conditions Take the materials prepared in the comparative examples and examples as negative electrode materials, mix them with binder polyvinylidene fluoride (PVDF) and conductive agent (Super-P) in a mass ratio of 80:10:10, and add an appropriate amount of N-methylpyrrolidone (NMP) was used as a solvent to prepare a slurry, which was coated on copper foil, and vacuum-dried and rolled to prepare a negative electrode sheet; a metal lithium sheet was used as the counter electrode, and 1 mol/L LiPF6 trioxide was used.
- PVDF binder polyvinylidene fluoride
- Super-P conductive agent
- NMP N-methylpyrrolidone
- the charge-discharge test of the button battery was carried out on the battery test system of Wuhan Landian Electronics Co., Ltd., under normal temperature conditions, 0.1C constant current charge and discharge, and the charge-discharge voltage was limited to 0.005-1.5V.
- the composite material with a capacity of 500mAh/g was prepared by compounding the prepared silicon carbon composite material with graphite to test its cycle performance. Thickness)/(The thickness of the pole piece before the cycle - the thickness of the copper foil)*100%.
- Table 1 is the first week test results of the Comparative Examples and Examples, and Table 2 is the cyclic expansion test results.
- the expanded graphite inside the garnet-like structure silicon-based composite material of the present invention can play a good conductive network, the carbon conductive network can effectively improve the conductivity of the silicon-based material, and the flexible porous structure of the expanded graphite can effectively alleviate the charging and discharging process. It can effectively avoid the pulverization of the material during the cycle, alleviate the volume expansion effect of the silicon-based material, improve the cycle performance, and improve the conductivity and rate performance of the material. Filling the modified layer can avoid the direct contact between the nano-silicon and the electrolyte to reduce side reactions, and at the same time, it can further effectively improve the conductivity of the silicon-based material and relieve the volume effect energy during the charging and discharging process.
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Abstract
Description
Claims (10)
- 一种类石榴结构硅基复合材料,其特征在于,所述类石榴结构硅基复合材料由纳米硅、膨化石墨和填充修饰层构成;所述纳米硅分散于膨化石墨内部的孔洞;所述填充修饰层填充于纳米硅颗粒中或填充于纳米硅与膨化石墨之间。
- 根据权利要求1所述的类石榴结构硅基复合材料,其特征在于,所述类石榴结构硅基复合材料的粒径D50为2-40μm;所述类石榴结构硅基复合材料的比表面积为0.5-15m2/g;所述类石榴结构硅基复合材料的氧含量为0-20%;所述类石榴结构硅基复合材料的碳含量为20-90%;所述类石榴结构硅基复合材料的硅含量为5-90%。
- 根据权利要求1所述的类石榴结构硅基复合材料,其特征在于,所述膨化石墨为粉体或乳液。
- 根据权利要求1所述的类石榴结构硅基复合材料,其特征在于,所述填充修饰层为碳修饰层,所述碳修饰层至少为一层,单层厚度为0.2-1.0μm。
- 根据权利要求1所述的类石榴结构硅基复合材料,其特征在于,所述纳米硅为SiOx,其中X为0-0.8;所述纳米硅的氧含量为0-31%;所述纳米硅的晶粒大小为1-40nm,所述纳米硅为多晶纳米硅或非晶纳米硅中的一种或两种;所述纳米硅的粒度D50为30-150nm。
- 一种类石榴结构硅基复合材料的制备方法,其特征在于,包括如下步骤:S0:将纳米硅、碳源和分散剂在有机溶剂中混合分散均匀,得到浆料A;S1:在负压状态下将膨化/乳化石墨加入浆料A,利用负压将混合均匀的浆料A填充到膨化/乳化石墨缝隙中,得到浆料B;S2:将浆料B进行喷雾干燥处理,得到前驱体C;S3:将前驱体C和碳源进行机械混合及机械融合,得到前驱体D;S4:将前驱体D进行热处理和筛分处理,得到所述的类石榴结构硅基复合材料。
- 根据权利要求6所述的类石榴结构硅基复合材料的制备方法,其特征在于,在所述步骤S1中,所述负压为真空搅拌工艺、乳化工艺、在线分散工艺中的一种或几种。
- 根据权利要求6所述的类石榴结构硅基复合材料的制备方法,其特征在于,在所述步骤S4中,所述热处理为静态热处理或动态热处理中的一种。
- 根据权利要求8所述的类石榴结构硅基复合材料的制备方法,其特征在于,所述静态热处理为将前驱体D置于箱式炉或辊道窑内,在保护气氛下,以1-5℃/min升温至400-1000℃,保温0.5-20h,自然冷却至室温;所述动态热处理为将前驱体D置于回转炉内,在保护气氛下,以1-5℃/min升温至400-1000℃,以0-20.0L/min通入速率通入有机碳源气体,保温0.5-20h,自然冷却至室温。
- 一种类石榴结构硅基复合材料的应用,其特征在于,所述类石榴结构硅基复合材料应用于锂离子电池负极材料。
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CN105355870A (zh) * | 2015-10-22 | 2016-02-24 | 清华大学深圳研究生院 | 膨胀石墨与纳米硅复合材料及其制备方法、电极片、电池 |
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DE102013204799A1 (de) | 2013-03-19 | 2014-09-25 | Wacker Chemie Ag | Si/C-Komposite als Anodenmaterialien für Lithium-Ionen-Batterien |
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CN104577084A (zh) * | 2015-01-20 | 2015-04-29 | 深圳市贝特瑞新能源材料股份有限公司 | 一种锂离子电池用纳米硅复合负极材料、制备方法及锂离子电池 |
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CN112563501A (zh) * | 2020-12-07 | 2021-03-26 | 广东凯金新能源科技股份有限公司 | 一种类石榴结构硅基复合材料、其制备方法及其应用 |
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