CN114447313B - Preparation method and production device of silicon-based anode material - Google Patents
Preparation method and production device of silicon-based anode material Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 117
- 239000010703 silicon Substances 0.000 title claims abstract description 117
- 239000010405 anode material Substances 0.000 title claims abstract description 95
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 82
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000004966 Carbon aerogel Substances 0.000 claims abstract description 37
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 30
- 239000010439 graphite Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 27
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 23
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 23
- 239000002019 doping agent Substances 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 21
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 10
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 10
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 10
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 10
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 91
- 239000000463 material Substances 0.000 claims description 53
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000000227 grinding Methods 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 24
- 238000011084 recovery Methods 0.000 claims description 22
- 239000007921 spray Substances 0.000 claims description 17
- 238000005253 cladding Methods 0.000 claims description 16
- 239000011261 inert gas Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 238000010000 carbonizing Methods 0.000 claims description 6
- 239000011800 void material Substances 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000010413 sodium alginate Nutrition 0.000 claims description 4
- 239000000661 sodium alginate Substances 0.000 claims description 4
- 229940005550 sodium alginate Drugs 0.000 claims description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 abstract description 11
- 238000009792 diffusion process Methods 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 8
- 239000011259 mixed solution Substances 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 7
- 238000005507 spraying Methods 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 238000003860 storage Methods 0.000 description 11
- 230000009286 beneficial effect Effects 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000003139 buffering effect Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- -1 for example Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M4/04—Processes of manufacture in general
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a preparation method and a production device of a silicon-based anode material, wherein the preparation method comprises the following steps: s1: ultrasonically dispersing nano silicon, carbon aerogel, carbon nano tube, graphite, doping agent, dispersing agent and organic solvent for preset time at preset ultrasonic power, and then obtaining first mixed feed liquid by using a sanding process, wherein the doping agent comprises at least one of hydrazine hydrate, ammonium bicarbonate, ammonium chloride, ammonium fluoride and ammonium nitrate; s2: and drying, spraying and granulating the first mixed solution, and simultaneously coating carbon to obtain the silicon-based anode material with the doped spongy framework structure. According to the preparation method of the silicon-based anode material, the silicon-based anode material has a spongy framework structure, the inside of the silicon-based anode material is in a spongy loose structure, the channels and the pores are more, a continuous three-dimensional conductive network is formed, ion diffusion and electron mobility are greatly improved, and the conductivity of the silicon-based anode material and the volume expansion of silicon in the silicon-based anode material are favorably improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method and a production device of a silicon-based negative electrode material.
Background
Along with the rapid expansion of the application range of the lithium ion battery to the fields of power batteries, energy storage batteries and the like, higher requirements are put forward on the energy density and the cycle life of the battery, an electrode material is a key factor for determining the performance of the battery, and the currently commercialized lithium ion battery cathode material is graphite, but the capacity development of the lithium ion battery cathode material is close to a theoretical value, and cannot meet the wide market demands at present.
Silicon is considered as a cathode material of a next-generation high-energy-density lithium ion battery, but has low conductivity and serious volume effect (about 300 percent) in the charge and discharge process, so that the electrode material is pulverized and falls off, a solid-phase electrolyte layer on the surface of the electrode material is continuously formed, a large amount of lithium ions are consumed, and the problems of capacity loss, poor cycle performance and the like are caused, so that the application of the electrode material in the lithium ion battery is greatly limited. Therefore, how to reduce the volume expansion of the internal silicon during the charge and discharge process and improve the conductivity is a technical problem that needs to be solved by those skilled in the art.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a preparation method of the silicon-based anode material, which can lead the silicon-based anode material to have a spongy framework structure, and the inside of the silicon-based anode material is in a spongy loose structure, and has more channels and pores, so as to form a continuous three-dimensional conductive network, greatly improve ion diffusion and electron mobility, be beneficial to improving the conductivity of the silicon-based anode material and buffering the volume expansion of silicon in the silicon-based anode material, and further improve the circulation stability and capacity retention rate of the silicon-based anode material.
The invention also provides a production device of the silicon-based anode material.
The preparation method of the silicon-based anode material comprises the following steps: s1: ultrasonically dispersing nano silicon, carbon aerogel, carbon nano tube, graphite, doping agent, dispersing agent and organic solvent for preset time at preset ultrasonic power, and then obtaining first mixed material liquid by using a sanding process, wherein the weight parts ratio of nano silicon, carbon aerogel, carbon nano tube, graphite, doping agent, dispersing agent and organic solvent is (5-15): (20-30): (1-10): (5-10): (5-10): (1-5): (40-60), wherein the dopant comprises at least one of hydrazine hydrate, ammonium bicarbonate, ammonium chloride, ammonium fluoride and ammonium nitrate; s2: and drying, spraying and granulating the first mixed material liquid and simultaneously coating carbon to obtain the silicon-based anode material with the doped spongy framework structure.
According to the preparation method of the silicon-based anode material, the silicon-based anode material with the spongy skeleton structure formed by nano silicon, carbon aerogel, carbon nano tube, graphite and dopants is beneficial to buffering and buffering the volume expansion of silicon in the silicon-based anode material, reducing cracks and pulverization of an active material, simultaneously, a continuous three-dimensional conductive network can be constructed, the ion diffusion and electron mobility are accelerated, the defect of poor conductivity of the silicon-based material is overcome, in addition, the electron transmission capacity of the carbon material can be improved by adding the dopants, the lithium storage capacity of the material is improved, the specific capacity of a battery is improved, and in addition, a large number of pore channels are constructed in the doping process, so that the volume expansion of the silicon is further buffered, and the circulation stability and the capacity retention rate of the silicon-based anode material are improved.
In some embodiments of the invention, the nanosilicon has a particle size D50 of 30nm to 60nm, the carbon aerogel has a grid colloid particle diameter of 5nm to 30nm, the carbon aerogel has a typical void size of 60nm to 100nm, and the carbon aerogel has a porosity of greater than 75%.
In some embodiments of the invention, the graphite has a particle size of 5 μm to 20 μm and the dispersing agent comprises one or more of cetyltrimethylammonium bromide, polyvinylpyrrolidone, sodium hexametaphosphate, sodium alginate.
In some embodiments of the present invention, in S1, the grinding media used in the sanding process are grinding media having dimensions of 3mm and 5mm, and the mass ratio of the grinding media having dimensions of 3mm and 5mm is 1:1, the weight ratio of the grinding media to the material is 3:1, and the grinding time is 1-3 hours.
In some embodiments of the invention, the method of preparing further comprises: s3: carbonizing the silicon-based anode material, wherein the calcining temperature is 1000-1500 ℃ and the duration is 2-5 h.
According to an embodiment of the invention, a production device of a silicon-based anode material comprises: the liquid conveying module is used for conveying the first mixed liquid, and a liquid outlet end of the liquid conveying module is provided with a spray head; the gas conveying heating module is isolated from the feed liquid conveying module and is used for heating and conveying inert gas, cladding gas and doping gas; the treatment bin module is respectively communicated with the feed liquid conveying module and the gas conveying heating module, and the first mixed feed liquid is dried and sprayed in the treatment bin module for granulation and carbon coating at the same time, so that the silicon-based anode material with the doped spongy framework structure is obtained; and the receiving module is connected with the processing bin module to recycle the silicon-based anode material.
According to the production device of the silicon-based anode material, the first mixed material liquid is subjected to drying and spray granulation in the treatment bin module and simultaneously subjected to carbon coating, so that the silicon-based anode material has a spongy framework structure, the inside of the silicon-based anode material is in a spongy loose structure, and the channels and the pores are more, a continuous three-dimensional conductive network is formed, the ion diffusion and the electron mobility are greatly improved, the conductivity of the silicon-based anode material and the volume expansion of silicon in the buffer are favorably improved, and the comprehensive performance of the silicon-based anode material is favorably improved.
In some embodiments of the invention, the process cartridge module comprises; a bin defining a processing space; the baffle compartment is arranged in the compartment body and is opposite to the air outlet end of the air conveying heating module, doped materials are arranged in the baffle compartment, the doped materials comprise at least one of ammonium bicarbonate, ammonium chloride, ammonium fluoride and ammonium nitrate, and air flowing out of the air conveying heating module can flow into the processing space after being mixed with the doped materials through the baffle compartment.
In some embodiments of the invention, the gas delivery heating module comprises: one end of the first pipe section is connected with an inert gas source, and the first pipe section is provided with a first control valve; one end of the second pipe section is connected with a cladding air source, and the second pipe section is provided with a second control valve; one end of the third pipe section is connected with a doping air source, and the third pipe section is provided with a third control valve; the air inlet end of the air pump is respectively communicated with the other end of the first pipe section, the other end of the second pipe section and the other end of the third pipe section; the air pump is characterized by comprising a heater, one end of the heater is communicated with an air outlet of the air pump, and the other end of the heater is connected with the treatment bin module through an air inlet bin.
In some embodiments of the invention, the production apparatus further comprises: the gas-liquid separation module is provided with a gas outlet at the upper part, the gas outlet is communicated with one end of the gas-liquid separation module, and a first check valve is arranged between the gas outlet and the gas-liquid separation module; the gas recovery module is communicated with the other end of the gas-liquid separation module, and a second check valve is arranged between the gas recovery module and the other end of the gas-liquid separation module.
In some embodiments of the invention, the production apparatus further comprises: and the gas recovery module is provided with an exhaust port, the fourth pipe section is connected between the exhaust port and the air inlet end of the air pump, and the fourth pipe section is provided with a fourth control valve.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a schematic illustration of a method of preparing a silicon-based negative electrode material according to one embodiment of the invention;
FIG. 2 is a schematic view of an apparatus for producing a silicon-based anode material according to an embodiment of the present invention;
fig. 3 is a schematic structural view of a silicon-based anode material according to an embodiment of the present invention.
Reference numerals:
a production apparatus 100;
a feed liquid delivery module 10; a shower head 11; a feed pump 12;
a gas delivery heating module 20; a first pipe section 21; a first control valve 211; a second tube section 22; a second control valve 221; a third pipe section 23; a third control valve 231; an air pump 24; a heater 25; an air inlet bin 26; an air outlet 27;
a process cartridge module 30; a bin body 31; baffle compartment 32; doping material 33;
a receiving module 40; a discharge bin 41; a discharge valve 42;
a gas-liquid separation module 50; a condenser 51; a liquid storage tank 52; a first check valve 53;
a gas recovery module 60; a second check valve 61; a fourth pipe section 62; a fourth control valve 63;
a blower 70;
a silicon-based anode material 200;
nano silicon 201; a carbon aerogel 202; a carbon nanotube 203; graphite 204; a carbon coating 205.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
The following disclosure provides many different embodiments, or examples, for implementing different structures of the invention. In order to simplify the present disclosure, components and arrangements of specific examples are described below. They are, of course, merely examples and are not intended to limit the invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art will recognize the applicability of other processes and/or the use of other materials.
A method of preparing a silicon-based anode material 200 and a production apparatus 100 according to an embodiment of the present invention are described below with reference to fig. 1 to 3.
Referring to fig. 1 and 3, a method for preparing a silicon-based anode material 200 according to an embodiment of the present invention includes the steps of: s1: the nano silicon 201, the carbon aerogel 202, the carbon nanotube 203, the graphite 204, the dopant (not shown), the dispersant (not shown) and the organic solvent (not shown) are ultrasonically dispersed at a preset ultrasonic power for a preset time, for example, the ultrasonic power may be 500W and the ultrasonic dispersion preset time may be 40-100min.
Referring to fig. 1, a sanding process is used to obtain a first mixed solution, wherein the weight parts ratio of nano silicon 201, carbon aerogel 202, carbon nanotube 203, graphite 204, dopant, dispersant and organic solvent is (5-15): (20-30): (1-10): (5-10): (5-10): (1-5): (40-60).
Specifically, the dopant includes at least one of hydrazine hydrate, ammonium bicarbonate, ammonium chloride, ammonium fluoride, and ammonium nitrate, in other words, the dopant may include only one of hydrazine hydrate, ammonium bicarbonate, ammonium chloride, ammonium fluoride, and ammonium nitrate, or the dopant may also include two or more of hydrazine hydrate, ammonium bicarbonate, ammonium chloride, ammonium fluoride, and ammonium nitrate.
Referring to fig. 1, S2: and drying, spraying and granulating the first mixed solution and simultaneously coating carbon to obtain the silicon-based anode material 200 with the doped spongy framework structure. For example, the first mixed solution may be dried, spray-granulated, and carbon-coated by the following production apparatus 100 (see fig. 2) of the silicon-based negative electrode material 200 to obtain the silicon-based negative electrode material 200 having a doped sponge-like skeleton structure. For example, referring to fig. 3, the silicon-based anode material 200 with a spongy skeleton structure is a core-shell structure, the doped inner core portion includes nano silicon 201, carbon aerogel 202, carbon nanotube 203 and graphite 204, and the doped outer shell portion is a carbon coating 205.
It can be understood that the carbon aerogel 202 is a light, porous, amorphous, bulk nano carbon material, the continuous three-dimensional network structure of which can be controlled and cut at nano scale, the carbon aerogel 202 has the characteristics of good conductivity, large specific surface area, porosity and the like, the carbon nanotube 203 can form a conductive channel and a skeleton, the doping material is decomposed by heating during drying and spray granulation to generate doping gas, and the doping material can form gaps, channels and the like in the silicon-based anode material 200, thereby being beneficial to lithium ion transmission and forming a loose sponge structure to relieve silicon expansion.
Specifically, the inventor finds that in practical research, the silicon nanocrystallization is helpful for releasing stress generated in the lithium intercalation process of the silicon negative electrode, and inhibiting the occurrence of cracks and chalking; the nano silicon and carbon composite can promote the electrical contact between silicon-based anode material particles, reduce the contact between the material and electrolyte, inhibit the repeated growth of SEI film, stabilize the interface, provide a certain buffer for the volume expansion of silicon, and relieve the negative effects caused by the volume expansion of silicon by constructing a three-dimensional conductive network structure, a porous structure and the like.
In view of this, according to the preparation method of the silicon-based anode material 200 of the embodiment of the invention, the silicon-based anode material 200 of the spongy skeleton structure formed by the nano silicon 201, the carbon aerogel 202, the carbon nanotube 203, the graphite 204 and the dopant is beneficial to buffering the volume expansion of the silicon in the interior, reducing the cracks and pulverization of the active material, simultaneously constructing a continuous three-dimensional conductive network, accelerating the ion diffusion and the electron mobility, improving the defect of poor conductivity of the silicon-based material, and the addition of the dopant can improve the electron transmission capability of the carbon material and create the lithium storage active site, thereby improving the lithium storage capability of the material, improving the specific capacity of the battery, and in addition, constructing a large number of air hole channels in the doping process is beneficial to further buffering the volume expansion of the silicon.
In some embodiments of the invention, referring to FIG. 3, the particle size D50 of the nano-silicon 201 is 30nm-60nm, in other words, 50% of the nano-silicon 201 has a particle size between 30nm-60nm, the lattice colloid particle diameter of the carbon aerogel 202 is 5nm-30nm, the typical void size of the carbon aerogel 202 is 60nm-100nm, the porosity of the carbon aerogel 202 is greater than 75%, for example, the porosity of the carbon aerogel 202 may be 75%, 78%, 80%, 83%, 85%, 88%, 90%, 91%, 93%, etc.
It can be understood that by making the particle diameter D50 of the nano silicon 201 be 30nm-60nm and the typical void size of the carbon aerogel 202 be 60nm-100nm, part of the nano silicon 201 enters the typical void of the carbon aerogel 202 in the drying and granulating process, which is favorable for improving the composite strength of the nano silicon 201 and the carbon aerogel 202, the structure is more stable, the electrical contact between the particles of the silicon-based anode material 200 can be improved, the contact between the material and the electrolyte can be reduced, the repeated growth of the SEI film can be inhibited, the interface can be stabilized, and a certain buffer can be provided for the volume expansion of silicon.
In some embodiments of the invention, the particle size of the graphite 204 is between 5 μm and 20 μm, in other words, the particle size of the graphite 204 may take any one of 5 μm to 20 μm, wherein the graphite 204 comprises at least one of natural graphite, artificial graphite, and spherical graphite, optionally the graphite 204 is spherical graphite, and the dispersing agent comprises one or more of cetyltrimethylammonium bromide, polyvinylpyrrolidone, sodium hexametaphosphate, and sodium alginate. Therefore, the material liquid can be more uniform, and the comprehensive performance of the silicon-based anode material 200 is further improved.
Alternatively, in some examples, the diameter of the carbon nanotubes 203 is less than 30nm, e.g., the diameter of the carbon nanotubes 203 may be 10nm, 12nm, 15nm, 18nm, 22nm, 26nm, 30nm, etc.
In some embodiments of the present invention, in S1, the grinding media used in the sanding process are grinding media having dimensions of 3mm and 5mm, and the mass ratio of the grinding media having dimensions of 3mm and 5mm is 1:1, the weight ratio of the grinding media (including the grinding media having dimensions of 3mm and 5 mm) to the material is 3:1, and the grinding time is 1 to 3 hours. For example, the ultrasonically dispersed nano-silicon 201, carbon aerogel 202, carbon nanotubes 203, graphite 204, dopant, dispersant and organic solvent may be sanded using a grinder to obtain a first mixed liquor. Therefore, uniformity of various components in the first mixed feed liquid is guaranteed, and blending and mixing are achieved.
In some embodiments of the invention, the method of making further comprises: s3: carbonizing the silicon-based anode material 200, wherein the calcining temperature is 1000-1500 ℃ and the duration is 2-5 h. It can be appreciated that by carbonizing the silicon-based anode material 200, the structural stability of the material is enhanced while the conductivity of the material is increased, thereby prolonging the service life and efficiency of the silicon-based anode material 200.
Referring to fig. 2, an apparatus 100 for producing a silicon-based anode material 200 according to an embodiment of the present invention may include: a feed liquid conveying module 10, a gas conveying heating module 20, a treatment bin module 30 and a material receiving module 40.
Referring to fig. 2, the solution delivery module 10 is configured to deliver the first mixed solution, for example, the ultrasonically dispersed nano silicon 201, carbon aerogel 202, carbon nanotube 203, graphite 204, dopant, dispersant and organic solvent may be sanded by using a grinder to obtain the first mixed solution, where the ratio of parts by weight of nano silicon 201, carbon aerogel 202, carbon nanotube 203, graphite 204, dopant, dispersant and organic solvent is (5-15): (20-30): (1-10): (5-10): (5-10): (1-5): (40-60).
Referring to fig. 2, a spray head 11 is disposed at a liquid outlet end of the liquid delivery module 10, wherein the liquid delivery module 10 includes a feed pump 12 and a corresponding pipeline, the feed pump 12 is communicated with the spray head 11 through the corresponding pipeline, the spray head 11 may be configured as a rotatable spray head, and a rotation speed may be 1000r/min-10000r/min, thereby being beneficial to ensuring uniformity of spraying the first mixed liquid and controlling granularity of the material.
Referring to fig. 2, the gas delivery heating module 20 is isolated from the feed liquid delivery module 10, and the gas delivery heating module 20 is configured to deliver an inert gas, a coating gas, and a doping gas, for example, the inert gas may be nitrogen or argon, the coating gas may include one or more of methane, ethylene, and acetylene, and the doping gas may be ammonia or fluorine-containing gas, etc.
Referring to fig. 2, the treatment bin module 30 is respectively communicated with the feed liquid conveying module 10 and the gas conveying and heating module 20, the first mixed feed liquid is dried and spray granulated in the treatment bin module 30 and simultaneously carbon coated to obtain a silicon-based anode material 200 with a doped spongy skeleton structure, and the material receiving module 40 is connected with the treatment bin module 30 to recover the silicon-based anode material 200.
According to the production device 100 of the silicon-based anode material 200 provided by the embodiment of the invention, the first mixed material liquid is dried and sprayed in the treatment bin module 30 and is subjected to carbon coating, so that the silicon-based anode material 200 has a spongy framework structure, the inside of the silicon-based anode material is in a spongy loose structure, the channels and the pores are more, a continuous three-dimensional conductive network is formed, the ion diffusion and the electron mobility are greatly improved, the conductivity of the silicon-based anode material 200 and the volume expansion of buffered silicon in the silicon-based anode material are improved, the comprehensive performance of the silicon-based anode material 200 is improved, and meanwhile, the production device 100 of the silicon-based anode material 200 integrates drying, granulating, doping and coating, and is simple to operate and high in heat utilization rate.
In some embodiments of the present invention, referring to FIG. 2, a process cartridge module 30 includes; the bin body 31 and the baffle bin 32, the bin body 31 defines a processing space, the baffle bin 32 is arranged in the bin body 31 and is opposite to the air outlet end of the gas conveying heating module 20, the baffle bin 32 is internally provided with a doped material 33, the doped material 33 comprises at least one of ammonium bicarbonate, ammonium chloride, ammonium fluoride and ammonium nitrate, the gas flowing out of the gas conveying heating module 20 can flow into the processing space after being mixed with the doped material 33 through the baffle bin 32, and it is understood that the baffle bin 32 is permeable to the gas, for example, the baffle bin 32 can be provided with a plurality of micropores to form a gas channel. Thus, during granulation and cladding, the gas (inert gas, cladding gas and/or doping gas) can mix part of the doping material 33 into the bin body 31 when passing through the baffle bin 32, which is beneficial to improving the doping effect of the carbon cladding 205.
In some embodiments of the present invention, referring to fig. 2, a gas delivery heating module 20 includes: the first pipe section 21, the second pipe section 22, the third pipe section 23, the air pump 24 and the heater 25, one end of the first pipe section 21 is connected with an inert gas source, the first pipe section 21 is provided with a first control valve 211, the first control valve 211 is used for controlling the on-off of the first pipe section 21, and for example, the inert gas source can be a nitrogen gas source; one end of the second pipe section 22 is connected with a cladding air source, the second pipe section 22 is provided with a second control valve 221, and the second control valve 221 is used for controlling the on-off of the second pipe section 22; one end of the third pipe section 23 is connected with a doping air source, the third pipe section 23 is provided with a third control valve 231, the third control valve 231 is used for controlling the on-off of the third pipe section 23, the air inlet end of the air pump 24 is respectively communicated with the other end of the first pipe section 21, the other end of the second pipe section 22 and the other end of the third pipe section 23, one end of the heater 25 is communicated with an air outlet of the air pump 24, and the other end of the heater 25 is connected with the treatment bin module 30 through an air inlet bin 26.
For example, as shown in fig. 2, the air inlet chambers 26 may be plural, and the plural air inlet chambers 26 may be disposed at intervals and respectively communicate with the heater 25, and the recovery module includes a discharge chamber 41 and a discharge valve 42, and the discharge valve 42 is used to control opening and closing of the discharge chamber 41. Optionally, a blower 70 may be disposed in the bin 31, and the blower 70 may purge the bin to facilitate material collection.
Specifically, the control method of the production apparatus 100 of the silicon-based anode material 200 may be as follows: the first control valve 211 is opened to introduce nitrogen, the heater 25 is controlled to heat for 0.5h to 1h, and the drying temperature is controlled to be 110 ℃ to 200 ℃ to preheat the bin body 31; when the temperature of the bin body 31 reaches 110-200 ℃, a feed pump 12 of the feed liquid conveying module 10 is started, the first mixed feed liquid is pumped in, the speed of the pump is 3-10L/h, and the rotating speed of the spray head 11 can be controlled to be 1000-10000 r/min;
the second control valve 221 and the third control valve 231 are opened, specifically, the second control valve 221 and the third control valve 231 can be opened at the same time, or the second control valve 221 and the third control valve 231 can be opened first, then inert gas, cladding gas and doping gas are introduced at the same time after the second control valve 221 and the third control valve 231 are opened, and the flow of the corresponding control valve is adjusted, so that the mixed mole ratio of the inert gas, the cladding gas and the doping gas is 5:4:1, and carbon cladding and doping of nitrogen and fluorine atoms are performed;
the materials stay in the treatment bin for 1 to 5 hours; the charge pump 12, the air pump 24 and the heater 25 are turned off, and the blower 70 is turned on to purge the material while cooling is achieved; finally, collecting the materials, further carbonizing in a heating device such as a sintering furnace or a tube furnace, wherein the temperature is 1000-1500 ℃ and the duration is 2-5 hours, so as to obtain the carbonized silicon-based anode material 200.
Thus, the silicon-based anode material 200 shown in fig. 3 can be obtained, the inner core part and the carbon coating layer 205 are doped, the inside of the silicon-based anode material 200 can be further ensured to be in a sponge loose structure, channels and pores are increased to form a continuous three-dimensional conductive network, ion diffusion and electron mobility are greatly improved, conductivity of the silicon-based anode material 200 and volume expansion of silicon in the buffer are facilitated to be improved, and meanwhile, the silicon-based anode material has the advantages of good circulation stability, high capacity retention rate and the like.
In some embodiments of the present invention, referring to fig. 2, the production apparatus 100 further includes: the gas-liquid separation module 50 and the gas recovery module 60, the upper portion of the treatment bin module 30 is provided with an air outlet 27, the air outlet 27 is communicated with one end of the gas-liquid separation module 50, a first check valve 53 is arranged between the air outlet 27 and the gas-liquid separation module 50, for example, the gas-liquid separation module 50 can comprise a condenser 51 and a liquid storage tank 52, the air outlet 27 and the condenser 51 are in one-way conduction through the first check valve 53, the gas flowing out from the air outlet 27 flows to the condenser 51 through the first check valve 53, after the condenser 51 is cooled, the gas flows to the liquid storage tank 52 to realize gas-liquid separation, and a recovery solvent is arranged in the liquid storage tank 52 to be beneficial to recovering waste liquid, for example, the recovery solvent can be ethanol.
Referring to fig. 2, the gas recovery module 60 communicates with the other end of the gas-liquid separation module 50, and a second check valve 61 is provided between the gas recovery module 60 and the other end of the gas-liquid separation module 50. It will be appreciated that by providing the second check valve 61, it is advantageous to prevent the recovered gas from flowing back to the gas-liquid separation module 50, and to ensure the reliability of the operation of the production apparatus 100.
In some embodiments of the present invention, referring to fig. 2, the production apparatus 100 further includes: the fourth pipe section 62, the gas recovery module 60 is provided with a gas outlet, the fourth pipe section 62 is connected between the gas outlet and the gas inlet end of the gas pump 24, and the fourth pipe section 62 is provided with a fourth control valve 63.
It can be appreciated that the fourth control valve 63 can control the on-off of the fourth pipe section 62, so that the recovered gas can be timely introduced into the air inlet end of the air pump 24, which is beneficial to improving the utilization rate of the gas and ensuring the production yield of the silicon-based anode material 200. For example, after the first control valve 211, the second control valve 221, and the third control valve 231 are all opened, the fourth control valve 63 is opened to introduce the recovery gas into the intake end of the air pump 24.
The method of preparing the silicon-based anode material 200 and the production apparatus 100 according to the present invention will be described in detail with reference to fig. 1 to 3. It will of course be understood that the following description is intended to be illustrative of the invention and is not to be taken as limiting.
The production apparatus 100 of the silicon-based anode material 200 according to the embodiment of the invention includes: a feed liquid conveying module 10, a gas conveying heating module 20, a treatment bin module 30, a material receiving module 40, a gas-liquid separating module 50, a gas recycling module 60 and a blower 70.
Referring to fig. 2, the feed liquid conveying module 10 is used for conveying a first mixed feed liquid, a spray head 11 is arranged at a liquid outlet end of the feed liquid conveying module 10, the feed liquid conveying module 10 comprises a feed pump 12 and corresponding pipelines, the feed pump 12 is communicated with the spray head 11 through the corresponding pipelines, the spray head 11 is a rotatable spray head, and the rotation speed is 800r/min.
Referring to fig. 2, the gas delivery heating module 20 is isolated from the feed liquid delivery module 10, and the gas delivery heating module 20 is configured to deliver an inert gas, a coating gas, and a doping gas, for example, nitrogen, methane, ethylene, and acetylene, and the doping gas is ammonia and fluorine-containing gas.
Referring to fig. 2, the treatment bin module 30 is respectively communicated with the feed liquid conveying module 10 and the gas conveying and heating module 20, the first mixed feed liquid is dried and spray granulated in the treatment bin module 30 and simultaneously carbon coated to obtain a silicon-based anode material 200 with a doped spongy skeleton structure, and the material receiving module 40 is connected with the treatment bin module 30 to recover the silicon-based anode material 200.
Further, referring to FIG. 2, the process cartridge module 30 includes; the gas treatment device comprises a bin body 31 and a baffle plate bin 32, wherein the bin body 31 defines a treatment space, the baffle plate bin 32 is permeable to gas, the baffle plate bin 32 is arranged in the bin body 31 and is opposite to the gas outlet end of the gas conveying heating module 20, a doped material 33 is arranged in the baffle plate bin 32, the doped material 33 comprises ammonium bicarbonate, ammonium chloride, ammonium fluoride and ammonium nitrate, and the gas flowing out of the gas conveying heating module 20 can flow into the treatment space after being mixed with the doped material 33 through the baffle plate bin 32.
Referring to fig. 2, the gas delivery heating module 20 includes: the air pump comprises a first pipe section 21, a second pipe section 22, a third pipe section 23, an air pump 24 and a heater 25, wherein one end of the first pipe section 21 is connected with an inert gas source, the first pipe section 21 is provided with a first control valve 211, the first control valve 211 is used for controlling the on-off of the first pipe section 21, one end of the second pipe section 22 is connected with a cladding gas source, the second pipe section 22 is provided with a second control valve 221, and the second control valve 221 is used for controlling the on-off of the second pipe section 22; one end of the third pipe section 23 is connected with a doping air source, the third pipe section 23 is provided with a third control valve 231, the third control valve 231 is used for controlling the on-off of the third pipe section 23, the air inlet end of the air pump 24 is respectively communicated with the other end of the first pipe section 21, the other end of the second pipe section 22 and the other end of the third pipe section 23, one end of the heater 25 is communicated with an air outlet of the air pump 24, and the other end of the heater 25 is connected with the treatment bin module 30 through an air inlet bin 26.
Referring to fig. 2, the three air inlet chambers 26 are provided at intervals, and the three air inlet chambers 26 are respectively communicated with the heater 25, and the recovery module includes a discharge chamber 41 and a discharge valve 42, and the discharge valve 42 is used for controlling the opening and closing of the discharge chamber 41. Optionally, a blower 70 may be disposed in the bin 31, and the blower 70 may purge the bin to facilitate material collection.
Referring to fig. 2, an air outlet 27 is provided at an upper portion of the bin body 31, the air outlet 27 is communicated with one end of the gas-liquid separation module 50, a first check valve 53 is provided between the air outlet 27 and the gas-liquid separation module 50, the gas-liquid separation module 50 includes a condenser 51 and a liquid storage tank 52, the air outlet 27 and the condenser 51 are connected in one way by the first check valve 53, air flowing out from the air outlet 27 flows to the condenser 51 through the first check valve 53, after the condenser 51 is cooled, flows to the liquid storage tank 52 to realize gas-liquid separation, and a recovery solvent is provided in the liquid storage tank 52 to facilitate recovery of waste liquid, for example, the recovery solvent may be ethanol.
Referring to fig. 2, the gas recovery module 60 communicates with the gas outlet end of the liquid storage tank 52, and a second check valve 61 is provided between the gas recovery module 60 and the gas outlet end of the gas-liquid separation module 50. The production apparatus 100 further includes: the fourth pipe section 62, the gas recovery module 60 is provided with a gas outlet, the fourth pipe section 62 is connected between the gas outlet and the gas inlet end of the gas pump 24, and the fourth pipe section 62 is provided with a fourth control valve 63.
Specifically, referring to fig. 1 and 2, the preparation method of the silicon-based anode material 200 may be as follows:
s1: dispersing nano silicon 201, carbon aerogel 202, carbon nanotube 203, graphite 204, dopant (not shown), dispersant (not shown) and organic solvent (not shown) at preset ultrasonic power of 500W for 90min, wherein the weight ratio of nano silicon 201, carbon aerogel 202, carbon nanotube 203, graphite 204, dopant, dispersant and organic solvent is 10:25:3:7:7:3:45, the particle diameter D50 of the nano-silica 201 is 50nm, the mesh colloid particle diameter of the carbon aerogel 202 is 5nm-30nm, the typical void size of the carbon aerogel 202 is 80nm, and the porosity of the carbon aerogel 202 is 80%. The diameter of the carbon nanotube 203 is 20nm, the graphite 204 is spherical graphite, the particle size is 10 mu m, the dispersing agent is cetyl trimethyl ammonium bromide, polyvinylpyrrolidone, sodium hexametaphosphate and sodium alginate, and the organic solvent is absolute ethyl alcohol.
And grinding the ultrasonically dispersed nano silicon 201, the carbon aerogel 202, the carbon nano tube 203, the graphite 204, the dopant, the dispersing agent and the organic solvent by using a grinding machine to obtain a first mixed feed liquid, wherein when the first mixed feed liquid is prepared, grinding media adopted in the grinding machine are grinding media with the sizes of 3mm and 5mm, the mass ratio of the grinding media with the sizes of 3mm and 5mm is 1:1, the weight ratio of the grinding media to the materials is 3:1, and the grinding time is 2 hours.
S2: the first mixed solution is dried, spray-granulated, and carbon-coated by the production apparatus 100 (see fig. 2) of the silicon-based anode material 200 to obtain the doped silicon-based anode material 200 having a spongy skeleton structure.
Specifically, the control method of the production apparatus 100 of the silicon-based anode material 200 may be as follows: the first control valve 211 is opened to introduce nitrogen, the heater 25 is controlled to heat for 0.8h, the drying temperature is controlled to be 150 ℃, and the preheating of the bin body 31 is realized; when the temperature of the bin body 31 reaches 150 ℃, a feeding pump 12 of the feed liquid conveying module 10 is started, the first mixed feed liquid is pumped in, the speed of the pumping is 8L/h, and the rotating speed of the spray head 11 can be controlled to 9000r/min;
simultaneously opening the second control valve 221 and the third control valve 231, and then simultaneously introducing inert gas, cladding gas and doping gas after opening, and adjusting the flow of the corresponding control valves to ensure that the mixed molar ratio of the inert gas to the cladding gas to the doping gas is 5:4:1, thereby carrying out carbon cladding and doping nitrogen and fluorine atoms;
the materials stay in the treatment bin for 3 hours; the charge pump 12, air pump 24 and heater 25 are turned off and the blower 70 is turned on to purge the material while cooling is achieved.
S3: and collecting the materials, further carbonizing the materials in a heating device such as a sintering furnace or a tube furnace, wherein the calcining temperature is 1200 ℃ and the duration is 3 hours, so as to obtain the carbonized silicon-based anode material 200. Referring to fig. 3, a silicon-based anode material 200 with a spongy skeleton structure is a material with a core-shell structure, a doped inner core portion includes nano silicon 201, carbon aerogel 202, carbon nanotubes 203 and graphite 204, and a doped outer shell portion is a carbon cladding layer 205.
It can be understood that the doping gas is generated during the thermal decomposition process of drying and spray granulation, and the doping can simultaneously form voids, channels and the like in the silicon-based anode material 200, and the inner core part of the silicon-based anode material 200 and the carbon coating layer 205 are both doped, so that the silicon-based anode material 200 has a spongy skeleton structure, the inside of the silicon-based anode material is in a spongy loose structure, the channels and the pores are more, a continuous three-dimensional conductive network is formed, the ion diffusion and the electron mobility are greatly improved, the conductivity of the silicon-based anode material 200 and the volume expansion of silicon in the buffer are favorably improved, the comprehensive performance of the silicon-based anode material 200 is favorably improved, and meanwhile, the production device 100 of the silicon-based anode material 200 integrates drying, granulation, doping and coating, and is simple to operate and high in heat utilization rate.
Other configurations and operations of the production apparatus 100 of the silicon-based anode material 200 according to the embodiment of the present invention are known to those skilled in the art, and will not be described in detail herein.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; the device can be mechanically connected, electrically connected and communicated; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature "up" or "down" a second feature may be the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "above," "over" and "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is less level than the second feature.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: many changes, modifications, substitutions and variations may be made to the embodiments without departing from the spirit and principles of the invention, the scope of which is defined by the claims and their equivalents.
Claims (8)
1. The preparation method of the silicon-based anode material is characterized by comprising the following steps of:
s1: ultrasonically dispersing nano silicon, carbon aerogel, carbon nano tube, graphite, dopant, dispersing agent and organic solvent for a preset time at preset ultrasonic power, and then obtaining a first mixed material liquid by utilizing a sanding process, wherein the weight parts ratio of nano silicon, carbon aerogel, carbon nano tube, graphite, dopant, dispersing agent and organic solvent is (5-15): (20-30): (1-10): (5-10): (5-10): (1-5): (40-60), wherein the dopant comprises at least one of hydrazine hydrate, ammonium bicarbonate, ammonium chloride, ammonium fluoride and ammonium nitrate, the grain diameter D50 of the nano silicon is 30-60 nm, the grid colloid grain diameter of the carbon aerogel is 5-30 nm, the typical void size of the carbon aerogel is 60-100 nm, and the porosity of the carbon aerogel is more than 75%;
s2: the first mixed material liquid is dried, sprayed and granulated and simultaneously subjected to carbon coating to obtain the silicon-based anode material with a doped spongy framework structure, wherein the silicon-based anode material is a material with a core-shell structure, the doped inner core part comprises nano silicon, carbon aerogel, carbon nano tubes and graphite, and the doped outer shell part is a carbon coating;
s3: and carbonizing the silicon-based anode material, wherein the calcining temperature is 1000-1500 ℃ and the duration is 2-5 h.
2. The method for preparing a silicon-based anode material according to claim 1, wherein the particle size of the graphite is 5-20 μm, and the dispersing agent comprises one or more of cetyltrimethylammonium bromide, polyvinylpyrrolidone, sodium hexametaphosphate and sodium alginate.
3. The preparation method of the silicon-based anode material according to claim 1, wherein in S1, grinding media adopted in the sanding process are grinding media with the size of 3mm and 5mm, the mass ratio of the grinding media with the size of 3mm and 5mm is 1:1, the weight ratio of the grinding media to the materials is 3:1, and the grinding time is 1-3 hours.
4. A production device of a silicon-based anode material, which is characterized by comprising:
a feed liquid conveying module for conveying the first mixed feed liquid according to claim 1, wherein a spray head is arranged at the liquid outlet end of the feed liquid conveying module;
the gas conveying heating module is isolated from the feed liquid conveying module and is used for heating and conveying inert gas, cladding gas and doping gas;
the treatment bin module is respectively communicated with the feed liquid conveying module and the gas conveying heating module, and the first mixed feed liquid is dried and sprayed in the treatment bin module for granulation and carbon coating at the same time, so that the silicon-based anode material with the doped spongy framework structure is obtained;
and the receiving module is connected with the processing bin module to recycle the silicon-based anode material.
5. The apparatus for producing a silicon-based anode material according to claim 4, wherein the process cartridge module comprises;
a bin defining a processing space;
the baffle compartment is arranged in the compartment body and is opposite to the air outlet end of the air conveying heating module, doped materials are arranged in the baffle compartment, the doped materials comprise at least one of ammonium bicarbonate, ammonium chloride, ammonium fluoride and ammonium nitrate, and air flowing out of the air conveying heating module can flow into the processing space after being mixed with the doped materials through the baffle compartment.
6. The apparatus for producing a silicon-based anode material according to claim 5, wherein the gas-feed heating module comprises:
one end of the first pipe section is connected with an inert gas source, and the first pipe section is provided with a first control valve;
one end of the second pipe section is connected with a cladding air source, and the second pipe section is provided with a second control valve;
one end of the third pipe section is connected with a doping air source, and the third pipe section is provided with a third control valve;
the air inlet end of the air pump is respectively communicated with the other end of the first pipe section, the other end of the second pipe section and the other end of the third pipe section;
the air pump is characterized by comprising a heater, one end of the heater is communicated with an air outlet of the air pump, and the other end of the heater is connected with the treatment bin module through an air inlet bin.
7. The apparatus for producing a silicon-based anode material according to claim 6, further comprising:
the gas-liquid separation module is provided with a gas outlet at the upper part, the gas outlet is communicated with one end of the gas-liquid separation module, and a first check valve is arranged between the gas outlet and the gas-liquid separation module;
the gas recovery module is communicated with the other end of the gas-liquid separation module, and a second check valve is arranged between the gas recovery module and the other end of the gas-liquid separation module.
8. The production apparatus of a silicon-based anode material according to claim 7, further comprising:
and the gas recovery module is provided with an exhaust port, the fourth pipe section is connected between the exhaust port and the air inlet end of the air pump, and the fourth pipe section is provided with a fourth control valve.
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