CN115745609A - Continuous sintering process and sintering furnace for silicon-based negative electrode material - Google Patents
Continuous sintering process and sintering furnace for silicon-based negative electrode material Download PDFInfo
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- 238000005245 sintering Methods 0.000 title claims abstract description 86
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 31
- 239000010703 silicon Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000008569 process Effects 0.000 title claims abstract description 26
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 23
- 230000007246 mechanism Effects 0.000 claims abstract description 72
- 239000000463 material Substances 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010426 asphalt Substances 0.000 claims abstract description 22
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000010405 anode material Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000011068 loading method Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims description 14
- 238000009826 distribution Methods 0.000 claims description 11
- 230000001681 protective effect Effects 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 14
- 230000008901 benefit Effects 0.000 abstract description 9
- 239000000377 silicon dioxide Substances 0.000 abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 5
- 230000005484 gravity Effects 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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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Abstract
The invention relates to a continuous sintering process of a silicon-based anode material and a sintering furnace thereof, which comprises the following steps: 1) Preparing materials: preparing high-purity graphite powder, high-purity silicon powder and modified asphalt; 2) Mixing: taking high-purity graphite powder and high-purity silicon powder, fully mixing and stirring uniformly, adding modified asphalt into the rest, fully stirring and mixing uniformly again: 3) And (3) sintering: and (4) loading the mixed materials into a high-temperature-resistant crucible. This continuous sintering process of silica-based negative electrode material and fritting furnace thereof, through setting up first slewing mechanism, the framework, second slewing mechanism, box body and crucible, first slewing mechanism drives the framework, second slewing mechanism, box body and crucible carry out vertical direction rotatory, second slewing mechanism drives box body and crucible and carries out horizontal direction rotatory, it is rotatory with horizontal direction to make the crucible carry out vertical direction simultaneously, it is more even to make the inside material of different positions crucible be heated, the off-the-shelf quality of silica-based negative electrode material has been improved, thereby possess the advantage of even heating, the use is made things convenient for.
Description
Technical Field
The invention relates to the technical field of silicon-based anode material production, in particular to a continuous sintering process of a silicon-based anode material and a sintering furnace thereof.
Background
Along with the enhancement of awareness of environmental protection and energy crisis, the lithium ion battery is more and more popular as an environment-friendly energy storage technology, the lithium ion battery can be widely used due to the characteristics of high capacity density, long cycle and high stability, the market of the lithium ion battery is increasingly wide along with the wide application of electronic products and the vigorous development of electric automobiles, and meanwhile, higher requirements are put forward on the safety of the lithium ion battery.
At present, artificial graphite is mainly used as a negative electrode material in the domestic lithium battery industry, compared with a common artificial graphite negative electrode, a silicon-based negative electrode benefits from higher energy density (4200 mAh/g) of silicon, a commercial lithium ion battery mainly adopts a graphite negative electrode material, but the theoretical specific capacity of the lithium ion battery is only 372mAh/g, the requirement of the market on the high capacity density of the lithium ion battery cannot be met, and 9 times of lithium ions can be stored, so that the energy density of the battery is greatly improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a continuous sintering process of a silicon-based anode material and a sintering furnace thereof, which have the advantages of uniform heating and the like, and solve the problems that when the silicon-based anode material is produced, the material needs to be loaded into a crucible and then put into the sintering furnace for processing, but the crucible is usually kept still in the sintering furnace, so that the material in the crucible at different positions is heated unevenly, and the quality of the finished product of the silicon-based anode material is influenced.
In order to achieve the purpose, the invention provides the following technical scheme: a continuous sintering process of a silicon-based negative electrode material comprises the following steps:
1) Preparing materials: preparing high-purity graphite powder, high-purity silicon powder and modified asphalt;
2) Mixing: taking high-purity graphite powder and high-purity silicon powder, fully mixing and stirring uniformly, adding modified asphalt into the rest, and fully stirring and mixing uniformly again;
3) And (3) sintering: loading the mixed material into a high-temperature-resistant crucible, then putting the crucible into a continuous high-temperature oxygen-free sintering furnace, slowly heating the crucible in the furnace, fully melting the modified asphalt at 200-300 ℃ to uniformly heat the edge of the crucible to the central part, uniformly coating the asphalt on the surfaces of the high-purity graphite and the high-purity silicon powder, continuously heating the coated product to 1200-1300 ℃, and then fully sintering the coated product at the constant temperature of 1200-1300 ℃ in an oxygen-free manner;
4) And (3) cooling: and the sintered material is cooled by protective gas and is slowly and indirectly cooled and then discharged out of the furnace, and the lithium battery negative electrode material product with high energy density and short charging time can be directly formed.
Further, the high-purity graphite powder accounts for 70-80% by mass, and the high-purity silicon powder accounts for 10-15% by mass.
Further, the sintering time at 200-300 ℃ is 8-10 hours, the sintering time in the process of continuously heating to 1200-1300 ℃ is 20-30 hours, and the sintering time in the region of 1200-1300 ℃ is 10-15 hours.
The invention also provides a sintering furnace for silicon-based negative electrode materials, which comprises a sintering furnace body, wherein a first rotating mechanism is arranged inside the sintering furnace body, a frame body is arranged on the first rotating mechanism, a second rotating mechanism is arranged on the inner bottom wall of the frame body, a plurality of box bodies are arranged at the top of the second rotating mechanism, crucibles are arranged inside the box bodies, and a positioning mechanism is arranged inside the box bodies.
Further, first rotation mechanism includes first motor, first motor fixed connection is at the back of fritting furnace body, the output of first motor runs through and extends to the inside of fritting furnace body, the output fixed mounting of first motor has first pivot, the front fixed mounting of first pivot has first carousel, the front fixed mounting of first carousel has a plurality of horizontal poles, the outside of horizontal pole is rotated and is installed first sleeve, the front fixed mounting of horizontal pole has the baffle, the outside fixed mounting of first sleeve has the connecting rod with framework fixed connection.
Further, the back fixed mounting of fritting furnace body has the protection casing, the protection casing is located the outside of first motor, and is a plurality of the horizontal pole is the front at first carousel of annular equidistance distribution.
Further, second slewing mechanism includes the second motor, the output end fixed mounting of second motor has the second carousel, the bottom fixed mounting of second carousel has a plurality of montants, the bottom fixed mounting of montant has the pulley of the inner bottom wall contact in with the framework.
Further, it is a plurality of montant symmetric distribution is in the bottom of second carousel, the quantity of montant is the even number, and is a plurality of the box body is the top of annular equidistance distribution at the second carousel.
Further, positioning mechanism includes four diaphragms, two guide bars and two annular plates, four diaphragm symmetric distribution is on the inner wall of box body, two the guide bar is located respectively between four diaphragms, two reset spring have been cup jointed in the outside of guide bar, the outside slidable mounting of guide bar has two second sleeves, two one side that reset spring carried on the back mutually is respectively with two relative one side fixed connection of diaphragm, two one side that reset spring is relative respectively with one side fixed connection that two second sleeves carried on the back mutually, the telescopic outside of second articulates there is the down tube, two one side that the second sleeve was kept away from to the down tube is articulated mutually with one side that two annular plates carried on the back mutually respectively, two one side that the annular plate is relative all contacts with the outside of crucible.
Compared with the prior art, the technical scheme of the application has the following beneficial effects:
1. this continuous sintering process of silica-based negative electrode material and fritting furnace thereof, through setting up first slewing mechanism, the framework, second slewing mechanism, box body and crucible, first slewing mechanism drives the framework, second slewing mechanism, box body and crucible carry out vertical direction rotatory, second slewing mechanism drives box body and crucible and carries out horizontal direction rotatory, it is rotatory with horizontal direction to make the crucible carry out vertical direction simultaneously, it is more even to make the inside material of different positions crucible be heated, the off-the-shelf quality of silica-based negative electrode material has been improved, thereby possess the advantage of even heating, the use is made things convenient for.
2. According to the continuous sintering process of the silicon-based negative electrode material and the sintering furnace thereof, the positioning mechanism is arranged, the positioning mechanism can position the crucible, when materials in the crucible are sintered, the crucible is not easy to fall off from the inside of the box body, loss is reduced, and therefore the continuous sintering process has the advantages of falling prevention and convenience in use.
3. According to the continuous sintering process for the silicon-based anode material and the sintering furnace thereof, the crucible can be disassembled and assembled by the positioning mechanism, the operation mode is simple, the crucible can be conveniently and quickly installed or taken out, time and labor are saved, the working efficiency is improved, the continuous sintering process has the advantage of convenience in disassembly and assembly, and the use is facilitated.
Drawings
FIG. 1 is a schematic view of the structure of the present invention;
FIG. 2 is a right side cross-sectional view of the inventive structure;
FIG. 3 is an enlarged view taken at A of FIG. 1 in accordance with the present invention;
FIG. 4 is a schematic structural diagram of a frame body according to the present invention;
FIG. 5 is a schematic view of the connection between the second turntable and the box body according to the present invention;
FIG. 6 is a schematic view of the connection between the box body, the crucible and the mounting mechanism according to the present invention;
FIG. 7 is a schematic view of the construction of the annular plate of the present invention.
In the figure: 1 sintering furnace body, 2 first rotating mechanism, 21 first motor, 22 first rotating shaft, 23 first rotating disc, 24 transverse bar, 25 first sleeve, 26 baffle, 27 connecting rod, 3 frame body, 4 second rotating mechanism, 41 second motor, 42 second rotating disc, 43 vertical bar, 44 pulley, 5 box body, 6 crucible, 7 positioning mechanism, 71 transverse plate, 72 guide bar, 73 reset spring, 74 second sleeve, 75 diagonal bar, 76 annular plate.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
referring to fig. 1-7, the continuous sintering process of the silicon-based negative electrode material in the present embodiment includes the following steps:
1, preparing materials: preparing high-purity graphite powder, high-purity silicon powder and modified asphalt;
2, mixing: taking high-purity graphite powder and high-purity silicon powder, fully mixing and stirring uniformly, adding modified asphalt into the rest, and fully stirring and mixing uniformly again;
3, sintering: loading the mixed material into a high-temperature-resistant crucible, then putting the crucible into a continuous high-temperature oxygen-free sintering furnace, slowly heating the crucible in the furnace, fully melting the modified asphalt at 200-300 ℃ to uniformly heat the edge of the crucible to the central part, uniformly coating the asphalt on the surfaces of the high-purity graphite and the high-purity silicon powder, continuously heating the coated product to 1200-1300 ℃, and then fully sintering the coated product at the constant temperature of 1200-1300 ℃ in an oxygen-free manner;
and 4, cooling: and the sintered material is cooled by the protective gas and is slowly and indirectly cooled and then discharged out of the furnace, so that the lithium battery negative electrode material product with high energy density and short charging time can be directly formed.
In the embodiment, the mass percent of the high-purity graphite powder is 70%, and the mass percent of the high-purity silicon powder is 10%.
In this example, the sintering time was 8 hours at 200-300 ℃,20 hours during the continuous temperature rise to 1200-1300 ℃, and 10 hours in the region of 1200-1300 ℃.
Specifically, the crucible products are in an oxygen-free state in the whole process of entering the furnace and heating to cooling and discharging, the heating of the products is the heating radiation heat transfer of the partition wall of the hearth, the fuel combustion is completed in the partition wall of the hearth, the smoke gas is discharged through the partition wall channel of the hearth, and after the heating and sintering of the products in the furnace are completed, the cooling is also the indirect cooling through the cavity of the partition wall of the hearth.
The invention also aims to provide a sintering furnace for silicon-based negative electrode materials, which comprises a sintering furnace body 1, wherein a first rotating mechanism 2 is arranged inside the sintering furnace body 1, a frame body 3 is arranged on the first rotating mechanism 2, a second rotating mechanism 4 is arranged on the inner bottom wall of the frame body 3, a plurality of box bodies 5 are arranged at the top of the second rotating mechanism 4, crucibles 6 are arranged inside the box bodies 5, and a positioning mechanism 7 is arranged inside the box bodies 5.
It is specific, put into the inside of crucible 6 with the material earlier, then install crucible 6 in the inside of box body 5 through positioning mechanism 7, operation is simple, be convenient for install or take out crucible 6 fast, time saving and labor saving, work efficiency is improved, first slewing mechanism 2 drives framework 3, second slewing mechanism 4, box body 5 and crucible 6 carry out vertical direction rotatory, second slewing mechanism 4 drives box body 5 and crucible 6 and carries out horizontal direction rotatory, make crucible 6 carry out vertical direction rotatory and horizontal direction rotatory simultaneously, positioning mechanism 7 can fix a position crucible 6, when sintering the material to in the crucible 6, crucible 6 is difficult for dropping from the inside of box body 5, the loss has been reduced, make the inside material of different positions crucible 6 be heated more evenly, the off-the-shelf quality of silica-based cathode material has been improved.
In this embodiment, the first rotating mechanism 2 includes a first motor 21, the first motor 21 is fixedly connected to the back of the sintering furnace body 1, the output end of the first motor 21 penetrates through and extends to the inside of the sintering furnace body 1, the output end of the first motor 21 is fixedly provided with a first rotating shaft 22, the front of the first rotating shaft 22 is fixedly provided with a first rotating disc 23, the front of the first rotating disc 23 is fixedly provided with a plurality of cross bars 24, the outside of the cross bar 24 is rotatably provided with a first sleeve 25, the front of the cross bar 24 is fixedly provided with a baffle 26, and the outside of the first sleeve 25 is fixedly provided with a connecting rod 27 fixedly connected with the frame 3.
Specifically, through opening first motor 21, first motor 21 drives first pivot 22, first carousel 23 and a plurality of horizontal pole 24 and carries out vertical direction rotation, and first sleeve 25 is connected with framework 3 through connecting rod 27, receives the influence of gravity, and framework 3 drives connecting rod 27 down all the time, makes first sleeve 25 rotate in horizontal pole 24 outside, prevents through baffle 26 that first sleeve 25 from droing from horizontal pole 24's outside.
In this embodiment, a protective cover is fixedly mounted on the back of the sintering furnace body 1, the protective cover is located outside the first motor 21, the protective cover protects the first motor 21, and the plurality of cross bars 24 are distributed on the front surface of the first rotating disc 23 in an annular and equidistant manner.
In this embodiment, the second rotating mechanism 4 includes a second motor 41, a second rotating disk 42 is fixedly mounted at an output end of the second motor 41, a plurality of vertical rods 43 are fixedly mounted at a bottom of the second rotating disk 42, and pulleys 44 in contact with a bottom wall of the frame 3 are fixedly mounted at bottoms of the vertical rods 43.
Specifically, by opening the second motor 41, the second motor 41 drives the second turntable 42 to rotate in the horizontal direction, and the second turntable 42 drives the vertical rod 43 and the pulley 44 to rotate in the horizontal direction in the inner bottom wall of the frame body 3, so that the second turntable 42 is rotated more stably.
In this embodiment, the plurality of vertical rods 43 are symmetrically distributed at the bottom of the second turntable 42, the number of the vertical rods 43 is even, when the plurality of pulleys 44 rotate, the second turntable 42 can be supported, and the plurality of box bodies 5 are annularly and equidistantly distributed at the top of the second turntable 42.
In this embodiment, the positioning mechanism 7 includes four transverse plates 71, two guide rods 72 and two annular plates 76, the four transverse plates 71 are symmetrically distributed on the inner wall of the box body 5, the two guide rods 72 are respectively located between the four transverse plates 71, two return springs 73 are sleeved outside the guide rods 72, two second sleeves 74 are slidably mounted outside the guide rods 72, one sides of the two return springs 73 opposite to each other are respectively and fixedly connected with one sides of the two transverse plates 71, one sides of the two return springs 73 opposite to each other are respectively and fixedly connected with one sides of the two second sleeves 74 opposite to each other, the outside of the second sleeves 74 is hinged with an inclined rod 75, one side of the two inclined rods 75 far away from the second sleeves 74 is respectively and hinged with one side of the two annular plates 76 opposite to each other, and one side of the two annular plates 76 opposite to each other is in contact with the outside of the crucible 6.
Through moving two annular plates 76 back to back, two annular plates 76 drive and all drive two second sleeves 74 through two down tube 75 and move back to back in the outside of guide bar 72, two second sleeves 74 extrude two reset springs 73 and produce deformation, then place crucible 6 at the inner bottom wall of box body 5, loosen two annular plates 76 at last, two reset springs 73 resume deformation and drive two second sleeves 74 and carry out relative movement in the outside of guide bar 72, two second sleeves 74 drive annular plate 76 through two down tube 75 and reset, make two annular plates 76 carry out the centre gripping to crucible 6, make crucible 6 install in the inside of box body 5.
Example 2:
referring to fig. 1-7, the continuous sintering process of the silicon-based negative electrode material in the present embodiment includes the following steps:
1, preparing materials: preparing high-purity graphite powder, high-purity silicon powder and modified asphalt;
2, mixing: taking high-purity graphite powder and high-purity silicon powder, fully mixing and stirring uniformly, adding modified asphalt into the rest, and fully stirring and mixing uniformly again;
3, sintering: loading the mixed material into a high-temperature-resistant crucible, then putting the crucible into a continuous high-temperature oxygen-free sintering furnace, slowly heating the crucible in the furnace, fully melting the modified asphalt at 200-300 ℃ to uniformly heat the edge of the crucible to the central part, uniformly coating the asphalt on the surfaces of the high-purity graphite and the high-purity silicon powder, continuously heating the coated product to 1200-1300 ℃, and then fully sintering the coated product at the constant temperature of 1200-1300 ℃ in an oxygen-free manner;
and 4, cooling: and the sintered material is cooled by the protective gas and is slowly and indirectly cooled and then discharged out of the furnace, so that the lithium battery negative electrode material product with high energy density and short charging time can be directly formed.
In the embodiment, the mass percent of the high-purity graphite powder is 75%, and the mass percent of the high-purity silicon powder is 12.5%.
In this example, the sintering time was 9 hours at 200 to 300 ℃, 25 hours during the continuous temperature rise to 1200 to 1300 ℃, and 12.5 hours in the region of 1200 to 1300 ℃.
Specifically, the crucible products are in an oxygen-free state in the whole process of entering the furnace and heating to cooling and discharging, the products are heated by heating radiation heat transfer of the dividing wall of the hearth, fuel combustion is completed in the dividing wall of the hearth, smoke gas is discharged through the dividing wall channel of the hearth, and after the products are heated and sintered in the furnace, cooling is also performed through indirect cooling of the cavity of the dividing wall of the hearth.
The invention also aims to provide a sintering furnace for silicon-based negative electrode materials, which comprises a sintering furnace body 1, wherein a first rotating mechanism 2 is arranged inside the sintering furnace body 1, a frame body 3 is arranged on the first rotating mechanism 2, a second rotating mechanism 4 is arranged on the inner bottom wall of the frame body 3, a plurality of box bodies 5 are arranged at the top of the second rotating mechanism 4, crucibles 6 are arranged inside the box bodies 5, and a positioning mechanism 7 is arranged inside the box bodies 5.
Specific, put into the inside of crucible 6 with the material earlier, then install crucible 6 in the inside of box body 5 through positioning mechanism 7, the operation is simple, be convenient for install or take out crucible 6 fast, save time and labor, work efficiency is improved, first slewing mechanism 2 drives framework 3, second slewing mechanism 4, box body 5 and crucible 6 carry out vertical direction rotatory, second slewing mechanism 4 drives box body 5 and crucible 6 and carries out horizontal direction rotatory, make crucible 6 carry out vertical direction rotatory and horizontal direction rotatory simultaneously, positioning mechanism 7 can fix a position crucible 6, when sintering the material to in the crucible 6, crucible 6 is difficult for dropping from the inside of box body 5, the loss has been reduced, make the inside material of different positions crucible 6 be heated more evenly, the off-the-shelf quality of silica-based cathode material has been improved.
In this embodiment, the first rotating mechanism 2 includes a first motor 21, the first motor 21 is fixedly connected to the back of the sintering furnace body 1, the output end of the first motor 21 penetrates through and extends to the inside of the sintering furnace body 1, the output end of the first motor 21 is fixedly provided with a first rotating shaft 22, the front of the first rotating shaft 22 is fixedly provided with a first rotating disc 23, the front of the first rotating disc 23 is fixedly provided with a plurality of cross bars 24, the outside of the cross bar 24 is rotatably provided with a first sleeve 25, the front of the cross bar 24 is fixedly provided with a baffle 26, and the outside of the first sleeve 25 is fixedly provided with a connecting rod 27 fixedly connected with the frame 3.
Specifically, through opening first motor 21, first motor 21 drives first pivot 22, first carousel 23 and a plurality of horizontal pole 24 and carries out vertical direction rotation, and first sleeve 25 is connected with framework 3 through connecting rod 27, receives the influence of gravity, and framework 3 drives connecting rod 27 down all the time, makes first sleeve 25 rotate in horizontal pole 24 outside, prevents through baffle 26 that first sleeve 25 from droing from horizontal pole 24's outside.
In this embodiment, a protective cover is fixedly mounted on the back of the sintering furnace body 1, the protective cover is located outside the first motor 21, the protective cover protects the first motor 21, and the plurality of cross bars 24 are distributed on the front surface of the first rotating disc 23 in an annular and equidistant manner.
In this embodiment, the second rotating mechanism 4 includes a second motor 41, a second rotating disk 42 is fixedly mounted at an output end of the second motor 41, a plurality of vertical rods 43 are fixedly mounted at a bottom of the second rotating disk 42, and pulleys 44 in contact with a bottom wall of the frame 3 are fixedly mounted at bottoms of the vertical rods 43.
Specifically, by opening the second motor 41, the second motor 41 drives the second turntable 42 to rotate in the horizontal direction, and the second turntable 42 drives the vertical rod 43 and the pulley 44 to rotate in the horizontal direction in the inner bottom wall of the frame body 3, so that the second turntable 42 is rotated more stably.
In this embodiment, a plurality of montants 43 symmetric distribution is in the bottom of second carousel 42, and the quantity of montant 43 is the even number, and when a plurality of pulleys 44 rotated, can also support second carousel 42, and a plurality of box bodys 5 are the top of annular equidistance distribution at second carousel 42.
In this embodiment, the positioning mechanism 7 includes four transverse plates 71, two guide rods 72 and two annular plates 76, the four transverse plates 71 are symmetrically distributed on the inner wall of the box body 5, the two guide rods 72 are respectively located between the four transverse plates 71, two return springs 73 are sleeved outside the guide rods 72, two second sleeves 74 are slidably mounted outside the guide rods 72, one sides of the two return springs 73 opposite to each other are respectively and fixedly connected with one sides of the two transverse plates 71, one sides of the two return springs 73 opposite to each other are respectively and fixedly connected with one sides of the two second sleeves 74 opposite to each other, the outside of the second sleeves 74 is hinged with an inclined rod 75, one side of the two inclined rods 75 far away from the second sleeves 74 is respectively and hinged with one side of the two annular plates 76 opposite to each other, and one side of the two annular plates 76 opposite to each other is in contact with the outside of the crucible 6.
Through two annular plates 76 of moving back to back, two annular plates 76 drive and all drive two second sleeves 74 through two sloping poles 75 and move back to back in the outside of guide bar 72, two second sleeves 74 extrude two reset springs 73 and produce deformation, then place crucible 6 at the inner diapire of box body 5, loosen two annular plates 76 at last, two reset springs 73 resume deformation and drive two second sleeves 74 and carry out relative movement in the outside of guide bar 72, two second sleeves 74 drive annular plate 76 through two sloping poles 75 and reset, make two annular plates 76 carry out the centre gripping to crucible 6, make crucible 6 install in the inside of box body 5.
Example 3:
referring to fig. 1-7, the continuous sintering process of the silicon-based negative electrode material in the present embodiment includes the following steps:
1, preparing materials: preparing high-purity graphite powder, high-purity silicon powder and modified asphalt;
2, mixing: taking high-purity graphite powder and high-purity silicon powder, fully mixing and stirring uniformly, adding modified asphalt into the rest, and fully stirring and mixing uniformly again;
3, sintering: loading the mixed material into a high-temperature-resistant crucible, then putting the crucible into a continuous high-temperature oxygen-free sintering furnace, slowly heating the crucible in the furnace, fully melting the modified asphalt at 200-300 ℃ to uniformly heat the edge of the crucible to the central part, uniformly coating the asphalt on the surfaces of the high-purity graphite and the high-purity silicon powder, continuously heating the coated product to 1200-1300 ℃, and then fully sintering the coated product at the constant temperature of 1200-1300 ℃ in an oxygen-free manner;
and 4, cooling: and the sintered material is cooled by protective gas and is slowly and indirectly cooled and then discharged out of the furnace, and the lithium battery negative electrode material product with high energy density and short charging time can be directly formed.
In the embodiment, the mass percent of the high-purity graphite powder is 80%, and the mass percent of the high-purity silicon powder is 15%.
In this example, the sintering time was 10 hours at 200-300 ℃, 30 hours during the continuous temperature rise to 1200-1300 ℃, and 15 hours in the region of 1200-1300 ℃.
Specifically, the crucible products are in an oxygen-free state in the whole process of entering the furnace and heating to cooling and discharging, the products are heated by heating radiation heat transfer of the dividing wall of the hearth, fuel combustion is completed in the dividing wall of the hearth, smoke gas is discharged through the dividing wall channel of the hearth, and after the products are heated and sintered in the furnace, cooling is also performed through indirect cooling of the cavity of the dividing wall of the hearth.
The invention also aims to provide a sintering furnace for silicon-based negative electrode materials, which comprises a sintering furnace body 1, wherein a first rotating mechanism 2 is arranged inside the sintering furnace body 1, a frame body 3 is arranged on the first rotating mechanism 2, a second rotating mechanism 4 is arranged on the inner bottom wall of the frame body 3, a plurality of box bodies 5 are arranged at the top of the second rotating mechanism 4, crucibles 6 are arranged inside the box bodies 5, and a positioning mechanism 7 is arranged inside the box bodies 5.
Specific, put into the inside of crucible 6 with the material earlier, then install crucible 6 in the inside of box body 5 through positioning mechanism 7, the operation is simple, be convenient for install or take out crucible 6 fast, save time and labor, work efficiency is improved, first slewing mechanism 2 drives framework 3, second slewing mechanism 4, box body 5 and crucible 6 carry out vertical direction rotatory, second slewing mechanism 4 drives box body 5 and crucible 6 and carries out horizontal direction rotatory, make crucible 6 carry out vertical direction rotatory and horizontal direction rotatory simultaneously, positioning mechanism 7 can fix a position crucible 6, when sintering the material to in the crucible 6, crucible 6 is difficult for dropping from the inside of box body 5, the loss has been reduced, make the inside material of different positions crucible 6 be heated more evenly, the off-the-shelf quality of silica-based cathode material has been improved.
In this embodiment, the first rotating mechanism 2 includes a first motor 21, the first motor 21 is fixedly connected to the back of the sintering furnace body 1, the output end of the first motor 21 penetrates through and extends to the inside of the sintering furnace body 1, the output end of the first motor 21 is fixedly provided with a first rotating shaft 22, the front of the first rotating shaft 22 is fixedly provided with a first rotating disc 23, the front of the first rotating disc 23 is fixedly provided with a plurality of cross bars 24, the outside of the cross bar 24 is rotatably provided with a first sleeve 25, the front of the cross bar 24 is fixedly provided with a baffle 26, and the outside of the first sleeve 25 is fixedly provided with a connecting rod 27 fixedly connected with the frame 3.
Specifically, through opening first motor 21, first motor 21 drives first pivot 22, first carousel 23 and a plurality of horizontal pole 24 and carries out vertical direction rotation, and first sleeve 25 is connected with framework 3 through connecting rod 27, receives the influence of gravity, and framework 3 drives connecting rod 27 down all the time, makes first sleeve 25 rotate in horizontal pole 24 outside, prevents through baffle 26 that first sleeve 25 from droing from horizontal pole 24's outside.
In this embodiment, the protection cover is fixedly installed on the back surface of the sintering furnace body 1, the protection cover is located outside the first motor 21, the protection cover protects the first motor 21, and the plurality of cross bars 24 are annularly and equidistantly distributed on the front surface of the first rotating disc 23.
In this embodiment, the second rotating mechanism 4 includes a second motor 41, a second rotating disk 42 is fixedly mounted at an output end of the second motor 41, a plurality of vertical rods 43 are fixedly mounted at a bottom of the second rotating disk 42, and pulleys 44 in contact with a bottom wall of the frame 3 are fixedly mounted at a bottom of the vertical rods 43.
Specifically, by opening the second motor 41, the second motor 41 drives the second turntable 42 to rotate in the horizontal direction, and the second turntable 42 drives the vertical rod 43 and the pulley 44 to rotate in the horizontal direction in the inner bottom wall of the frame body 3, so that the second turntable 42 is rotated more stably.
In this embodiment, a plurality of montants 43 symmetric distribution is in the bottom of second carousel 42, and the quantity of montant 43 is the even number, and when a plurality of pulleys 44 rotated, can also support second carousel 42, and a plurality of box bodys 5 are the top of annular equidistance distribution at second carousel 42.
In this embodiment, the positioning mechanism 7 includes four transverse plates 71, two guide rods 72 and two annular plates 76, the four transverse plates 71 are symmetrically distributed on the inner wall of the box body 5, the two guide rods 72 are respectively located between the four transverse plates 71, two return springs 73 are sleeved outside the guide rods 72, two second sleeves 74 are slidably mounted outside the guide rods 72, one sides of the two return springs 73 opposite to each other are respectively and fixedly connected with one sides of the two transverse plates 71 opposite to each other, one sides of the two return springs 73 opposite to each other are respectively and fixedly connected with one sides of the two second sleeves 74 opposite to each other, the outside of the second sleeves 74 is hinged with the diagonal rods 75, one sides of the two diagonal rods 75 far away from the second sleeves 74 are respectively and hinged with one sides of the two annular plates 76 opposite to each other, and one sides of the two annular plates 76 opposite to each contact with the outside of the crucible 6.
Through two annular plates 76 of moving back to back, two annular plates 76 drive and all drive two second sleeves 74 through two sloping poles 75 and move back to back in the outside of guide bar 72, two second sleeves 74 extrude two reset springs 73 and produce deformation, then place crucible 6 at the inner diapire of box body 5, loosen two annular plates 76 at last, two reset springs 73 resume deformation and drive two second sleeves 74 and carry out relative movement in the outside of guide bar 72, two second sleeves 74 drive annular plate 76 through two sloping poles 75 and reset, make two annular plates 76 carry out the centre gripping to crucible 6, make crucible 6 install in the inside of box body 5.
The working principle of the embodiment is as follows:
(1) Firstly, materials are put into the crucible 6, the two annular plates 76 are moved in a reverse manner, the two annular plates 76 drive the two second sleeves 74 to move in a reverse manner outside the guide rod 72 through the two inclined rods 75, the two second sleeves 74 extrude the two return springs 73 to generate deformation, then the crucible 6 is placed on the inner bottom wall of the box body 5, finally the two annular plates 76 are loosened, the two return springs 73 recover the deformation to drive the two second sleeves 74 to move relatively outside the guide rod 72, the two second sleeves 74 drive the annular plates 76 to reset through the two inclined rods 75, the two annular plates 76 clamp the crucible 6, the crucible 6 is installed inside the box body 5, the operation mode is simple, the crucible 6 is conveniently and quickly installed or taken out, time and labor are saved, the working efficiency is improved, and the crucible box has the advantage of being convenient to disassemble and assemble, and is convenient to use;
(2) By starting the first motor 21, the first motor 21 drives the first rotating shaft 22, the first rotating disc 23 and the plurality of cross bars 24 to rotate in the vertical direction, the first sleeve 25 is connected with the frame body 3 through the connecting rod 27 and is influenced by gravity, the frame body 3 always drives the connecting rod 27 to face downwards, so that the first sleeve 25 rotates outside the cross bars 24, the first sleeve 25 is prevented from falling off from the outside of the cross bars 24 through the baffle 26, by starting the second motor 41, the second motor 41 drives the second rotating disc 42, the plurality of box bodies 5 and the plurality of crucibles 6 to rotate in the horizontal direction, the second rotating disc 42 drives the vertical rod 43 and the pulleys 44 to rotate in the horizontal direction on the inner bottom wall of the frame body 3, so that the second rotating disc 42 rotates more stably, the crucibles 6 rotate in the vertical direction and the horizontal direction simultaneously, so that materials in the crucibles 6 at different positions are heated more uniformly, the quality of finished silicon-based cathode materials is improved, and the silicon-based cathode material has the advantage of uniform heating and is convenient to use;
(3) Two annular plates 76 position crucible 6, when sintering the material in crucible 6, crucible 6 is difficult for dropping from the inside of box body 5, has reduced the loss to the advantage that has the anti-drop has made things convenient for the use.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising a … …" does not exclude the presence of another identical element in a process, method, article, or apparatus that comprises the element.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A continuous sintering process of a silicon-based negative electrode material is characterized by comprising the following steps:
1) Preparing materials: preparing high-purity graphite powder, high-purity silicon powder and modified asphalt;
2) Mixing: taking high-purity graphite powder and high-purity silicon powder, fully mixing and stirring uniformly, adding modified asphalt into the rest, and fully stirring and mixing uniformly again;
3) And (3) sintering: loading the mixed material into a high-temperature-resistant crucible, then putting the crucible into a continuous high-temperature oxygen-free sintering furnace, slowly heating the crucible in the furnace, fully melting the modified asphalt at 200-300 ℃ to uniformly heat the edge of the crucible to the central part, uniformly coating the asphalt on the surfaces of the high-purity graphite and the high-purity silicon powder, continuously heating the coated product to 1200-1300 ℃, and then fully sintering the coated product at the constant temperature of 1200-1300 ℃ in an oxygen-free manner;
4) And (3) cooling: and the sintered material is cooled by protective gas and is slowly and indirectly cooled and then discharged out of the furnace, and the lithium battery negative electrode material product with high energy density and short charging time can be directly formed.
2. The continuous sintering process of silicon-based anode material according to claim 1, characterized in that: the high-purity graphite powder accounts for 70-80% by mass, and the high-purity silicon powder accounts for 10-15% by mass.
3. The continuous sintering process of the silicon-based anode material as claimed in claim 1, wherein: the sintering time at 200-300 ℃ is 8-10 hours, the sintering time in the process of continuously heating to 1200-1300 ℃ is 20-30 hours, and the sintering time in the region of 1200-1300 ℃ is 10-15 hours.
4. The utility model provides a fritting furnace of silicon-based negative pole material, includes fritting furnace body (1), its characterized in that: the sintering furnace is characterized in that a first rotating mechanism (2) is arranged inside the sintering furnace body (1), a frame body (3) is arranged on the first rotating mechanism (2), a second rotating mechanism (4) is arranged on the inner bottom wall of the frame body (3), a plurality of box bodies (5) are arranged at the top of the second rotating mechanism (4), a crucible (6) is arranged inside each box body (5), and a positioning mechanism (7) is arranged inside each box body (5).
5. The sintering furnace of silicon-based anode material according to claim 4, characterized in that: first rotation mechanism (2) include first motor (21), first motor (21) fixed connection is at the back of fritting furnace body (1), the output of first motor (21) runs through and extends to the inside of fritting furnace body (1), the output fixed mounting of first motor (21) has first pivot (22), the front fixed mounting of first pivot (22) has first carousel (23), the front fixed mounting of first carousel (23) has a plurality of horizontal poles (24), first sleeve (25) are installed in the outside rotation of horizontal pole (24), the front fixed mounting of horizontal pole (24) has baffle (26), the outside fixed mounting of first sleeve (25) has connecting rod (27) with framework (3) fixed connection.
6. The sintering furnace of silicon-based anode material according to claim 5, characterized in that: the back fixed mounting of fritting furnace body (1) has the protection casing, the protection casing is located the outside of first motor (21), and a plurality of horizontal pole (24) are the front of annular equidistance distribution at first carousel (23).
7. The sintering furnace of silicon-based anode material according to claim 4, characterized in that: second slewing mechanism (4) include second motor (41), the output fixed mounting of second motor (41) has second carousel (42), the bottom fixed mounting of second carousel (42) has a plurality of montants (43), the bottom fixed mounting of montant (43) has pulley (44) with the contact of inner bottom wall in framework (3).
8. The sintering furnace of silicon-based anode material according to claim 7, characterized in that: a plurality of montant (43) symmetric distribution is in the bottom of second carousel (42), the quantity of montant (43) is the even number, and is a plurality of box body (5) are the top of annular equidistance distribution at second carousel (42).
9. The sintering furnace of silicon-based anode material according to claim 4, characterized in that: the positioning mechanism (7) comprises four transverse plates (71), two guide rods (72) and two annular plates (76), the four transverse plates (71) are symmetrically distributed on the inner wall of the box body (5), the two guide rods (72) are respectively located between the four transverse plates (71), two return springs (73) are sleeved on the outer portion of each guide rod (72), two second sleeves (74) are slidably mounted on the outer portion of each guide rod (72), one sides of the two return springs (73) opposite to each other are respectively fixedly connected with one sides of the two transverse plates (71), one sides of the two return springs (73) opposite to each other are respectively fixedly connected with one sides of the two second sleeves (74) opposite to each other, inclined rods (75) are hinged to the outer portions of the two annular plates (76), one sides of the inclined rods (75) far away from the second sleeves (74) are respectively hinged to one sides of the two annular plates (76) opposite to each other, and one sides of the two annular plates (76) opposite to each other are in contact with the outer portion of the crucible (6).
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0275614A1 (en) * | 1987-01-20 | 1988-07-27 | The Carborundum Company | System for preventing decomposition of silicon carbide articles during sintering |
| CN103633307A (en) * | 2013-12-20 | 2014-03-12 | 大连宏光锂业股份有限公司 | Method for producing silicon-carbon composite negative electrode material of lithium ion battery |
| CN111342035A (en) * | 2020-03-11 | 2020-06-26 | 西安越遴新材料研究院有限公司 | Method for modifying silicon-carbon composite negative electrode by asphalt modification process derivative |
| US20210399290A1 (en) * | 2018-11-27 | 2021-12-23 | Guangzhou Automobile Group Co., Ltd. | Silicon-based composite negative electrode material and preparation method thereof, and negative electrode of lithium ion battery |
| CN215572111U (en) * | 2021-05-11 | 2022-01-18 | 宁波晨鑫维克工业科技有限公司 | Crucible tilting mechanism of fritting furnace |
| CN114472833A (en) * | 2022-01-04 | 2022-05-13 | 河南科技大学 | Rotary furnace body type hot continuous casting device for horizontal continuous casting |
-
2022
- 2022-09-27 CN CN202211179026.8A patent/CN115745609B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0275614A1 (en) * | 1987-01-20 | 1988-07-27 | The Carborundum Company | System for preventing decomposition of silicon carbide articles during sintering |
| CN103633307A (en) * | 2013-12-20 | 2014-03-12 | 大连宏光锂业股份有限公司 | Method for producing silicon-carbon composite negative electrode material of lithium ion battery |
| US20210399290A1 (en) * | 2018-11-27 | 2021-12-23 | Guangzhou Automobile Group Co., Ltd. | Silicon-based composite negative electrode material and preparation method thereof, and negative electrode of lithium ion battery |
| CN111342035A (en) * | 2020-03-11 | 2020-06-26 | 西安越遴新材料研究院有限公司 | Method for modifying silicon-carbon composite negative electrode by asphalt modification process derivative |
| CN215572111U (en) * | 2021-05-11 | 2022-01-18 | 宁波晨鑫维克工业科技有限公司 | Crucible tilting mechanism of fritting furnace |
| CN114472833A (en) * | 2022-01-04 | 2022-05-13 | 河南科技大学 | Rotary furnace body type hot continuous casting device for horizontal continuous casting |
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