CN117199292A - Preparation method of porous silicon-carbon anode material - Google Patents
Preparation method of porous silicon-carbon anode material Download PDFInfo
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- CN117199292A CN117199292A CN202311184077.4A CN202311184077A CN117199292A CN 117199292 A CN117199292 A CN 117199292A CN 202311184077 A CN202311184077 A CN 202311184077A CN 117199292 A CN117199292 A CN 117199292A
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- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000010405 anode material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 24
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000003763 carbonization Methods 0.000 claims abstract description 7
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 239000000725 suspension Substances 0.000 claims abstract description 3
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- 239000004642 Polyimide Substances 0.000 claims abstract 6
- 229920001721 polyimide Polymers 0.000 claims abstract 6
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 238000005530 etching Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000005253 cladding Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 5
- 238000010000 carbonizing Methods 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 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
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion batteries, and provides a preparation method of a porous silicon-carbon anode material for a lithium ion battery, which comprises the following steps: (1) For nanometer Si powder and nanometer Al (OH) 3 Ultrasonic dispersion is carried out on the mixed water-based suspension liquid of the (B), and the Si/Al (OH) is obtained through freeze drying 3 Mixing the powder; (2) Adding 4,4' -diaminodiphenyl ether (ODA) and pyromellitic anhydride (PMDA) in dimethylacetamide solution into Si/Al (OH) 3 Mixing the powder, stirring uniformly, placing in a muffle furnace, completely volatilizing dimethylacetamide and synthesizing Polyimide (PI) to obtain Si/Al (OH) 3 PI compositeA material; (3) For Si/Al (OH) under inert atmosphere 3 High temperature carbonization of PI to obtain Si/Al 2 O 3 a/C composite; (4) To Si/Al 2 O 3 Adding excessive diluted hydrochloric acid into the composite material, and carrying out suction filtration, washing and drying to obtain a porous silicon-carbon anode material; the invention utilizes nano Si powder to carry negative charge and nano Al (OH) 3 The porous silicon-carbon anode material is prepared by carbonization cladding of PI and hydrochloric acid etching.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a preparation method of a porous silicon-carbon anode material for a lithium ion battery.
Background
Silicon materials having theoretical capacities up to 4200 mAh/g and lower operating potentials are considered one of the most promising negative electrode materials for next generation lithium ion batteries. However, silicon particles undergo significant volume expansion during lithium intercalation, resulting in structural fracture that rapidly attenuates battery capacity, thereby limiting the practical use of silicon in lithium ion batteries. According to the invention, the porous silicon-carbon material is prepared by the hard template method, so that the volume expansion caused by lithium intercalation is effectively relieved, and the stability of the material structure is ensured, thereby improving the cycle performance of the battery.
Disclosure of Invention
The invention aims to overcome the existing defects and provide a preparation method of a porous silicon-carbon anode material, which uses nano Si and nano Al (OH) 3 ODA and PMDA are used as raw materials, and the silicon-carbon anode material with a porous structure is prepared through the procedures of ultrasonic dispersion, freeze drying, crosslinking solidification, high-temperature carbonization, hydrochloric acid etching, washing drying and the like, so that the problems in the background technology can be effectively solved.
In order to achieve the above purpose, the present invention provides the following technical solutions: the preparation method of the porous silicon-carbon anode material comprises the following steps:
(1) For nanometer Si powder and nanometer Al (OH) 3 Ultrasonic dispersion is carried out on the mixed water-based suspension liquid of the (B), and the Si/Al (OH) is obtained through freeze drying 3 Mixing the powder;
(2) Adding Si/Al (OH) into the dimethylacetamide solution of ODA and PMDA 3 Mixing the powder, stirring uniformly, placing in a muffle furnace, completely volatilizing dimethylacetamide and synthesizing PI to obtain Si/Al (OH) 3 PI composite;
(3) For Si/Al (OH) under inert atmosphere 3 High temperature carbonization of PI to obtain Si/Al 2 O 3 a/C composite;
(4) To Si/Al 2 O 3 And adding excessive diluted hydrochloric acid into the/C composite material, and finally carrying out suction filtration, washing and drying to obtain the porous silicon-carbon anode material.
The purity of the nano Si powder is more than or equal to 99.9%, and the maximum granularity is less than or equal to 150 nm; the nanometer Al (OH) 3 Purity is more than or equal to 99.9%, maximum granularity is less than or equal to 200 nm; the Si and the Al (OH) 3 The mass ratio of (2) is 1:1 to 1:2; the molar ratio of the ODA to the PMDA is 1:1, and the concentration of the solution is 15%; the Si/Al (OH) 3 The mass ratio of the catalyst to the ODA/PMDA is 1:1 to 1:2; the muffle furnace temperature is 250-280 ℃ and the heating time is 1-3 hours; the carbonization temperature is 800-1200 ℃ and the time is 1-2 hours; the inert atmosphere is at least one of nitrogen, argon and helium.
Compared with the prior art, the invention has the beneficial effects that: the preparation method of the porous silicon-carbon anode material has the following advantages:
the gram capacity of the silicon-carbon anode material prepared by the method is more than 750 mAh/g, the initial coulombic efficiency is more than 90%, and the capacity retention rate after 300 weeks circulation is more than 80%, so that the problem of poor circulation performance of the silicon-based anode material is effectively solved.
Description of the embodiments
The invention is further illustrated by the following specific examples.
Example 1: nanometer Si powder (purity is more than or equal to 99.9 percent, maximum granularity is less than or equal to 150 nm) and nanometer Al (OH) 3 (purity is more than or equal to 99.9%, maximum particle size is less than or equal to 200 and nm), and Si powder and Al (OH) are simply mixed 3 The mass ratio of (2) is 1:1, and after adding a proper amount of water, ultrasonic dispersion is carried out, and the Si/Al (OH) is obtained through freeze drying 3 Mixing the powder; ODA and PMDA were dissolved in dimethylacetamide at a molar ratio of 1:1 to prepare a 15% strength solution, and Si/Al (OH) was added thereto 3 Mixed powder, si/Al (OH) 3 The mass ratio of the catalyst to the ODA/PMDA is 1:1, the mixture is stirred uniformly and then is placed in a muffle furnace at 260 ℃ for heat preservation for 2 hours, and the dimethylacetamide is completely volatilized and synthesized into PI to obtain Si/Al (OH) 3 PI composite; carbonizing the composite material for 1 hour at 1000 ℃ in nitrogen atmosphere to obtain Si/Al 2 O 3 a/C composite; si-Al 2 O 3 And adding excessive diluted hydrochloric acid into the/C composite material, and finally carrying out suction filtration, washing and drying to obtain the porous silicon-carbon anode material.
Example 2: nanometer Si powder (purity is more than or equal to 99.9 percent, maximum granularity is less than or equal to 150 nm) and nanometer Al (OH) 3 (purity is more than or equal to 99.9%, maximum particle size is less than or equal to 200 and nm), and Si powder and Al (OH) are simply mixed 3 The mass ratio of (2) is 1:2, and after adding a proper amount of water, ultrasonic dispersion is carried out, and the Si/Al (OH) is obtained through freeze drying 3 Mixing the powder; ODA and PMDA were dissolved in dimethylacetamide at a molar ratio of 1:1 to prepare a 15% strength solution, and Si/Al (OH) was added thereto 3 Mixed powder, si/Al (OH) 3 The mass ratio of the catalyst to the ODA/PMDA is 1:1, the mixture is stirred uniformly and then is placed in a muffle furnace at 260 ℃ for heat preservation for 2 hours, and the dimethylacetamide is completely volatilized and synthesized into PI to obtain Si/Al (OH) 3 PI composite; carbonizing the composite material for 1 hour at 1000 ℃ in nitrogen atmosphere to obtain Si/Al 2 O 3 a/C composite; to Si/Al 2 O 3 And adding excessive diluted hydrochloric acid into the/C composite material, and finally carrying out suction filtration, washing and drying to obtain the porous silicon-carbon anode material.
Example 3: nanometer Si powder (purity is more than or equal to 99.9 percent, maximum granularity is less than or equal to 150 nm) and nanometer Al (OH) 3 (purity is more than or equal to 99.9%, maximum particle size is less than or equal to 200 and nm), and Si powder and Al (OH) are simply mixed 3 The mass ratio of (2) is 1:1, and after adding a proper amount of water, ultrasonic dispersion is carried out, and the Si/Al (OH) is obtained through freeze drying 3 Mixing the powder; ODA and PMDA were dissolved in dimethylacetamide at a molar ratio of 1:1 to prepare a 15% strength solution, and Si/Al (OH) was added thereto 3 Mixed powder, si/Al (OH) 3 The mass ratio of the catalyst to the ODA/PMDA is 1:2, the mixture is stirred uniformly and then is placed in a muffle furnace at 260 ℃ for heat preservation for 2 hours, and the dimethylacetamide is completely volatilized and synthesized into PI to obtain Si/Al (OH) 3 PI composite; carbonizing the composite material for 1 hour at 1000 ℃ in nitrogen atmosphere to obtain Si/Al 2 O 3 a/C composite; to Si/Al 2 O 3 And adding excessive diluted hydrochloric acid into the/C composite material, and finally carrying out suction filtration, washing and drying to obtain the porous silicon-carbon anode material.
Example 4: nano Si powder(purity is more than or equal to 99.9%, maximum particle size is less than or equal to 150 nm) and nano Al (OH) 3 (purity is more than or equal to 99.9%, maximum particle size is less than or equal to 200 and nm), and Si powder and Al (OH) are simply mixed 3 The mass ratio of (2) is 1:2, and after adding a proper amount of water, ultrasonic dispersion is carried out, and the Si/Al (OH) is obtained through freeze drying 3 Mixing the powder; ODA and PMDA were dissolved in dimethylacetamide at a molar ratio of 1:1 to prepare a 15% strength solution, and Si/Al (OH) was added thereto 3 Mixed powder, si/Al (OH) 3 The mass ratio of the catalyst to the ODA/PMDA is 1:2, the mixture is stirred uniformly and then is placed in a muffle furnace at 260 ℃ for heat preservation for 2 hours, and the dimethylacetamide is completely volatilized and synthesized into PI to obtain Si/Al (OH) 3 PI composite; carbonizing the composite material for 1 hour at 1000 ℃ in nitrogen atmosphere to obtain Si/Al 2 O 3 a/C composite; to Si/Al 2 O 3 And adding excessive diluted hydrochloric acid into the/C composite material, and finally carrying out suction filtration, washing and drying to obtain the porous silicon-carbon anode material.
The silicon-carbon anode material prepared in the embodiment is used for preparing a button cell, and specifically comprises the following steps:
mixing the silicon-carbon anode material, sodium carboxymethyl cellulose and acetylene black according to the mass ratio of 80/10/10, dripping a proper amount of deionized water, grinding into uniform slurry, and then coating the slurry on a copper foil. The water was evaporated at room temperature and dried in a vacuum oven at 100 c for 12 h to prepare a working electrode. The assembly of CR2016 type button-type analog cells was performed in a glove box filled with high purity argon (less than 5 ppm water oxygen content). Wherein the counter electrode and the reference electrode are metal lithium sheets, the diaphragm is a porous polypropylene film (Celgard 2400), and the electrolyte is 1 mol/L LiPF 6 Mixed liquid (95:5, volume ratio) with vinylene carbonate, liPF 6 The solvent of (2) is a mixed solution of ethylene carbonate and dimethyl carbonate (1:1, volume ratio). Constant current charge-discharge and cycle performance test of button cell with blue electric test system (LAND CT2001A, wuhan Jinno electron) with voltage range of 0.01-2V vs. Li/Li + The current density was 200 mA/g.
The results of the tests of examples 1-4 are as follows:
| examples | Gram capacity (mAh/g) | First coulombic efficiency (%) | Capacity retention at 300 weeks (%) |
| 1 | 1524.5 | 91.9 | 81.2 |
| 2 | 1247.9 | 91.7 | 82.5 |
| 3 | 1045.7 | 91.8 | 83.4 |
| 4 | 775.5 | 91.1 | 84.2 |
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related arts are included in the scope of the present invention.
Claims (8)
1. A preparation method of a porous silicon-carbon anode material is characterized by comprising the following steps: the method comprises the following steps:
(1) For nanometer Si powder and nanometer Al (OH) 3 Ultrasonic dispersion is carried out on the mixed water-based suspension liquid of the (B), and the Si/Al (OH) is obtained through freeze drying 3 Mixing the powder;
(2) Adding Si/Al (OH) into the dimethylacetamide solution of 4,4' -diaminodiphenyl ether ODA and pyromellitic anhydride PMDA 3 Mixing the powder, stirring uniformly, placing in a muffle furnace, completely volatilizing dimethylacetamide and synthesizing polyimide PI to obtain Si/Al (OH) 3 PI composite;
(3) For Si/Al (OH) under inert atmosphere 3 High temperature carbonization of PI to obtain Si/Al 2 O 3 a/C composite;
(4) To Si/Al 2 O 3 And adding excessive diluted hydrochloric acid into the/C composite material, and finally carrying out suction filtration, washing and drying to obtain the porous silicon-carbon anode material.
2. The method for preparing the porous silicon-carbon anode material according to claim 1, wherein the method comprises the following steps: the purity of the nano Si powder in the step (1) is more than or equal to 99.9%, and the maximum granularity is less than or equal to 150 nm; nanometer Al (OH) 3 The purity is more than or equal to 99.9 percent, and the maximum granularity is less than or equal to 200 nm.
3. The method for preparing the porous silicon-carbon anode material according to claim 1, wherein the method comprises the following steps: si and Al (OH) in the step (1) 3 The mass ratio of (2) is 1:1-1:2.
4. The method for preparing the porous silicon-carbon anode material according to claim 1, wherein the method comprises the following steps: the molar ratio of ODA to PMDA in the step (2) is 1:1, and the concentration of the solution is 15%.
5. The method for preparing the porous silicon-carbon anode material according to claim 1, wherein the method comprises the following steps: si/Al (OH) in the step (2) 3 The mass ratio of the catalyst to the ODA/PMDA is 1:1 to1:2。
6. The method for preparing the porous silicon-carbon anode material according to claim 1, wherein the method comprises the following steps: the muffle furnace temperature in the step (2) is 250-280 ℃, and the heating time is 1-3 hours.
7. The method for preparing the porous silicon-carbon anode material according to claim 1, comprising the following steps: the method is characterized in that the carbonization temperature in the step (3) is 800-1200 ℃ and the time is 1-2 hours.
8. The method for preparing the porous silicon-carbon anode material according to claim 1, wherein the method comprises the following steps: and (3) the inert atmosphere in the step (3) is at least one of nitrogen, argon and helium.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311184077.4A CN117199292A (en) | 2023-09-14 | 2023-09-14 | Preparation method of porous silicon-carbon anode material |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311184077.4A CN117199292A (en) | 2023-09-14 | 2023-09-14 | Preparation method of porous silicon-carbon anode material |
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| CN117199292A true CN117199292A (en) | 2023-12-08 |
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| CN202311184077.4A Withdrawn CN117199292A (en) | 2023-09-14 | 2023-09-14 | Preparation method of porous silicon-carbon anode material |
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- 2023-09-14 CN CN202311184077.4A patent/CN117199292A/en not_active Withdrawn
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Application publication date: 20231208 |