CN114094034A - Method for manufacturing multilayer long-cycle silicon-carbon negative electrode material - Google Patents
Method for manufacturing multilayer long-cycle silicon-carbon negative electrode material Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 239000007773 negative electrode material Substances 0.000 title claims description 23
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- 238000002156 mixing Methods 0.000 claims abstract description 57
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- 238000000227 grinding Methods 0.000 claims abstract description 52
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 47
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- 239000002041 carbon nanotube Substances 0.000 claims abstract description 22
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- 239000002904 solvent Substances 0.000 claims abstract description 21
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
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- 239000010406 cathode material Substances 0.000 abstract 1
- 239000002210 silicon-based material Substances 0.000 description 22
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- 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
A method for preparing a multilayer long-cycle silicon-carbon cathode material comprises the steps of taking pure silicon and a first masterbatch, wherein the first masterbatch comprises a solvent and a dispersant; then mixing pure silicon with first master batch to form a first mixture, and grinding to form a first grinding body; then taking graphene and the other first masterbatch, mixing the graphene and the other first masterbatch, and grinding the mixture to form a second grinding body; then mixing the first grinding body and the second grinding body to form a second mixture, and then carrying out planetary mixing, emulsification and homogenization and defoaming planetary mixing; then mixing the carbon nano-tubes and a second masterbatch, putting the mixture into a blade stirring tank for stirring, and then putting the mixture into an emulsifying machine for stirring to form a third mixture; the second masterbatch comprises a solvent and a coating agent; planetary mixing and stirring the treated second mixture and the treated third mixture to form a fourth mixture; and finally, carrying out spray drying operation on the fourth mixture to form the silicon-carbon composite structure mixture.
Description
Technical Field
The invention relates to a method for manufacturing a negative electrode material, in particular to a method for manufacturing a multilayer long-cycle silicon-carbon negative electrode material.
Background
In the negative electrode material of the lithium battery, graphite is used as a negative electrode to carry out lithium ion intercalation reaction in the prior mature technology; however, the capacitance of graphite is limited, and the 3C market with increasing capacitance demand and the vehicle market with long endurance cannot meet the future demand, so improving the capacitance of the negative electrode material is an important development direction. Among them, silicon materials are expected to be commercially available due to their excellent lithium storage capacity. The silicon is a non-metal amorphous material, has the advantages of high purity, small particle size, uniform distribution, large specific surface area, high surface activity, low packaging density and the like, and is non-toxic and tasteless. Therefore, the silicon-carbon composite material formed by the silicon material and the graphite material can be used as a negative electrode material of the lithium ion battery, and the electric capacity of the lithium ion battery is greatly improved. It is therefore preferred to use silicon material (pure silicon, silicon oxide) partly in combination with graphite. Since the silicon material has a higher capacity than graphite, the entire negative electrode can have a larger capacity to increase the storage capacity of the battery.
In a lithium ion battery, lithium ions are electrochemically inserted into the crystal structure of a silicon material by the difference between an external potential and the potential energy of the material. When the lithium battery is discharged in an electrochemical manner, lithium ions with electrochemical activity leave the silicon crystal structure to form a discharge mechanism so as to meet the electric energy requirement for communicating with an external circuit. In theory, developers and users want to reduce the loss of all lithium ions as much as possible during charging and discharging, but during the operation of the battery, some active lithium will generate electrochemical side reactions with the active lithium due to increase and decrease of the reaction interface, impurities in the electrolyte or the material, and further cause precipitation and loss of inactive lithium salt, so that the inactive lithium salt is precipitated around the material to form an irreversible thin film, i.e. SEI film. The SEI phenomenon is particularly obvious in silicon materials, when the silicon materials are charged, the silicon materials contain a large amount of lithium ions, so that the crystal structure of the silicon materials is loose and expanded (the structure is much larger than the structure of the original silicon materials), after the silicon materials contain lithium and expand, the expansion effect breaks through the surface stress of the original structure of the materials, the particle surfaces are cracked, a new reaction interface is formed, the BET of the specific surface area of the materials is changed, and then the new reaction interface can react with the residual active lithium in an irreversible manner, so that the lithium ions are consumed; on the other hand, active lithium leaves the silicon lattice structure during discharging to leave voids, so that the whole material is soft and causes collapse, and new reaction interface generation after collapse reacts with active lithium ions to cause loss. After many times of charging and discharging, the expansion, the rupture, the collapse and the lithium consumption occur repeatedly, so that the large capacity decay is caused by the consumption of a large amount of active lithium, and the service life and the usability of the battery are reduced.
In addition, the silicon material itself does not have the corresponding conductive capability, and needs to be assisted by the conductive material to perform electron conduction and ion conduction, and the conductive carbon is often attached to the conductive carbon in an additional form, so that the connection is easily lost in the expansion and rupture charging and discharging processes to cause the loss of conductivity, and the corresponding capacity also generates huge decay after the loss of conductivity.
Therefore, the present invention provides a novel method for manufacturing a long-lasting silicon-carbon negative electrode material with high conductivity, high capacity, expansion buffer property and enhanced cycle life, so as to solve the above-mentioned drawbacks of the prior art.
Disclosure of Invention
Therefore, the present invention is directed to solve the above problems of the prior art, and the present invention provides a manufacturing method with high conductivity, high capacity, expansion buffer property and enhanced cycle life, wherein a dispersing agent (comprising a polymer propping agent, a small molecule anchoring agent and a thickening agent) is added into the original silicon material, and the composite dispersing agent is used for dispersing and supporting nano-micro silicon material, so as to prevent the silicon material from losing the dispersing benefit due to reverse agglomeration in the dispersing process; and a specific number of layers of high-purity refined graphene is added into the material, and the graphene, a special carbon material and a nano-micro silicon material are combined to form a special 3D structure so as to increase a conductive communication bridge among the silicon materials. In the dispersion process, a grinding machine is used for grinding sheets and zirconium beads, and a special planetary mixing machine is used for cooperating in each stage process to ensure that the composite materials can be fully dissolved and uniformly mixed by a special binder formula, and granulation spraying equipment is used for endowing the composite materials with structural morphology; the mixing produces a highly cyclic silicon carbon structure with better conductivity and expansion retarding ability.
In order to achieve the above object, the present invention provides a method for manufacturing a multilayer long-cycle silicon-carbon negative electrode material, comprising the following steps: step A: taking pure silicon; and B: taking a first masterbatch, wherein the components of the first masterbatch are a solvent and a dispersant; wherein the solvent comprises ethanol, acetone and water; the components of the dispersant are a macromolecular propping agent, a small molecular anchoring agent and a thickening agent; and C: mixing 10 wt% of pure silicon and 90 wt% of first masterbatch to form a first mixture, and grinding the first mixture in a grinding machine to form a first grinding body; step D: taking graphene (graphene); step E: additionally taking first masterbatch; mixing 10 wt% of graphene and 90 wt% of first masterbatch, and then grinding in the grinder to form a second grinding body; step F: mixing the first grinding body and the second grinding body with equal weight to form a second mixture, and then carrying out planetary mixing, emulsification and homogenization and defoaming planetary mixing; step G: mixing Carbon Nanotubes (CNT) and a second masterbatch, wherein the carbon nanotubes are arrayed carbon nanotubes, and the second masterbatch comprises a solvent and a coating agent, wherein the solvent is water; step H: placing the mixture of the carbon nanotubes and the second masterbatch into a blade stirring tank, wherein the blade stirring tank comprises blades, stirring for a preset time by the blades, and then placing the mixture into an emulsifying machine to stir for a preset time to form a third mixture; step I: c, planetary mixing and stirring the second mixture and the third mixture which are processed in the step F to form a fourth mixture; step J: then carrying out spray drying operation on the fourth mixture to form a silicon-carbon composite structure mixture; wherein the numerical values of the above components can be varied by + -20%.
Further, in the step A, the pure silicon is metal reduced silicon, and the primary particle size is 10-15 mm.
Further, in the step B, the proportion of the solvent of the first masterbatch is 98.8% wt; the proportion of the dispersant of the first masterbatch is 1.2 wt%; wherein the solvent comprises 40 wt% of ethanol, 2 wt% of acetone and 58 wt% of water; the dispersing agent comprises 0.6-1.2 wt% of high-molecular propping agent, 0.1-0.3 wt% of small-molecular anchoring agent and 0.1-0.4 wt% of thickening agent; wherein the numerical values of the above components can be varied by + -20%.
Further, the polymer proppant is selected from PVP or PVA, and the molecular weight of the polymer proppant is 20000-30000 g/mole; the small molecular anchoring agent is selected from unsaturated ether ketones or benzene sulfonate; the thickening agent is selected from carboxyethyl or sodium carboxymethyl cellulose, or polysaccharide polymer.
Further, in the step C, the grinding machine comprises a grinding sheet and zirconium beads, the grinding sheet rotates at a rotating speed of 3000-3400 rpm, the particle size of the zirconium beads is 0.2-0.4 mm, and the grinding is performed for 12-16 hours in an environment of 16-23 ℃, wherein the ratio of the zirconium beads to the first mixture is 70-78 wt% of the zirconium beads; and in the step E, the grinding machine comprises a grinding sheet and zirconium beads, wherein the grinding condition is to use the zirconium beads with the particle size of 0.6-1.0 mm, the grinding sheet rotates at the rotating speed of 2200-2600 rpm, and the grinding is carried out for 20-24 hours in the environment of 18-25 ℃, wherein the proportion of the zirconium beads and the first mixture body is 70-78 wt% of the zirconium beads.
Further, the planetary mixing in step F is performed by placing the second mixture into a planetary mixer for mixing, wherein the planetary mixer comprises:
an inner barrel for placing the second mixture and stirring the second mixture;
an outer barrel for accommodating the inner barrel, cooling water is arranged between the outer barrel and the inner barrel to cool the second mixture in the inner barrel, and the cooling water is externally connected with a circulating cooling system to achieve the effects of cooling water circulation and heat exchange;
a revolution type stirrer which is arranged in the inner barrel and is externally connected with a driving mechanism, wherein the revolution type stirrer is used for stirring the second mixture in a large path so as to ensure that the second mixture forms displacement of a larger area in the inner barrel;
the self-rotating stirrer is used for fully stirring the second mixture locally, and mainly makes the block-shaped body rotate along the axis of the self-rotating stirrer so as to form a vortex of the second mixture around the self-rotating stirrer; wherein the self-rotating stirrer is at least one rotating ball, is suspended by an iron suspension column and is driven by a driving mechanism.
Further, in the planetary mixing in the step F, the revolution speed of the planetary mixer is 10 to 30rpm, and the rotation speed is 3500 to 5000 rpm.
Further, the emulsification and homogenization in the step F are carried out by putting the second mixture subjected to planetary mixing into an emulsifying machine; the emulsifying machine comprises an emulsifying barrel, and a second mixture subjected to planetary mixing is arranged in the emulsifying barrel; the emulsifying barrel is internally provided with a stirring barrel, the bottom of the stirring barrel comprises a plurality of input holes, and the second mixture can be placed into the stirring barrel; a stirrer is arranged in the stirring barrel and is used for stirring the second mixture in the stirring barrel to make the second mixture uniform and scattering particles of the second mixture into particles with small particle size; the lower side of the stirring barrel comprises a plurality of first output holes, and the stirred second mixture and the particles with small particle size are output to the emulsifying barrel through the first output holes; the upper side of the stirring barrel comprises a plurality of second output holes, and the stirred second mixture is further stirred in the stirring barrel and is output to the emulsifying barrel through the second output holes, and the particles output through the first output holes are output to the emulsifying barrel; wherein the second mixture output to the emulsification barrel from the first output hole and the second output hole is input into the stirring barrel from the input hole, so that the second mixture is repeatedly and circularly stirred and agglomerated in the emulsification barrel to form an emulsification state; and the inner side of the emulsifying barrel is positioned above the second output hole for pumping air so as to guide the second mixture to flow from bottom to top.
Further, when emulsification and homogenization are carried out in the step F, the rotating speed of the emulsifying machine during emulsification is 9000-11000 rpm; and is
The defoaming planetary mixing in the step F is carried out by putting the emulsified and homogenized second mixture into a planetary mixer for defoaming planetary mixing; wherein, air is pumped in the inner barrel to finish the treatment of the second mixture; and is
And F, when the defoaming planetary mixing is carried out, the rotation speed of the planetary mixing machine is 0rpm, the revolution speed is 30rpm, and the mixing is carried out for 30 minutes.
Further, in the step G, the proportion of the coating agent in the second masterbatch is 2-6.8 wt%, and the rest is solvent; the coating agent is prepared from oligosaccharide high polymers and a small amount of oligosaccharaide ketones, wherein the weight ratio of the oligosaccharide high polymers to the oligosaccharaide ketones is 3-6: 1; wherein the weight ratio of the carbon nanotubes to the second masterbatch is as follows: the carbon nanotubes account for 0.1-0.18 wt%, and the rest is the second masterbatch; wherein the numerical values of the above components can be varied by + -20%.
Further, the spray drying operation in step J is performed by putting the fourth mixture into an inner barrel of the planetary mixer for mixing, and pumping the fourth mixture to a four-fluid nozzle to spray out the fourth mixture after a predetermined time to form a spray; wherein the fourth mixture is heated in the four-fluid nozzle; thus forming the silicon-carbon composite structure mixture.
Further, when the spray drying operation is performed in step J, the rotation speed of the planetary mixer is 0rpm, and the revolution speed is 10 rpm; pumping the fourth mixture to the four-fluid spray head after 2-4 hours; wherein the air pressure of the four-fluid spray head is 3kg/cm 2; wherein the temperature for the heat drying in the four-fluid nozzle is 170-185 ℃, and the temperature at the heat drying outlet is 150-160 ℃.
Further, the grain diameter D50 of this silicon carbon composite structure mixture is between 3~10 microns, wherein 50% silicon carbon composite structure mixture's grain diameter is between 3~10 microns. A further understanding of the nature and advantages of the present invention will become apparent from the following description when read in conjunction with the accompanying drawings.
Drawings
FIG. 1 is a schematic flow chart of the manufacturing process of a first polishing body and a second polishing body according to the present invention;
FIG. 2 is a schematic flow chart of planetary mixing, emulsification, homogenization and debubbling of the second mixture according to the present invention;
fig. 3 is a schematic flow chart of the third hybrid according to the present invention;
FIG. 4 is a schematic view of a planetary mixer of the present invention;
FIG. 5 is a schematic view of an emulsion machine of the present invention;
fig. 6 is a schematic flow chart of the process for manufacturing the silicon-carbon composite structure mixture by using the second mixture and the third mixture according to the present invention.
Description of the reference numerals
1. A first masterbatch; 2. a first masterbatch; 3. a second masterbatch; 4. pure silicon; 5. graphene; 6. a carbon nanotube; 9. a silicon carbon composite structure mixture; 10. a first mixing body; 15. a first abrasive body; 16. a second abrasive body; 20. a second mixing body; 30. a third mixture; 40. a fourth mixture; 50. a grinder; 51. a polishing sheet; 52. zirconium beads; 60. four fluid ejection heads; 70. a blade stirring tank; 71. a blade; 80. a planetary mixer; 81. an inner barrel; 82. an outer tub; 83. a revolving type stirrer; 84. a self-rotating agitator; 85. a drive mechanism; 86. a drive mechanism; 90. an emulsifying machine; 91. an emulsification barrel; 92. a stirring barrel; 93. a stirrer; 100. cooling water; 831. a frame; 832. a blade; 841. rotating the ball; 842. suspending an iron column; 921. an input aperture; 922. a first output aperture; 923. a second output aperture.
Detailed Description
The present invention will now be described in detail with reference to the drawings, wherein the same reference numerals are used to designate the same elements, structures, and advantages.
Referring to fig. 1 to 6, a method for manufacturing a multi-layer long-cycle silicon-carbon negative electrode material according to the present invention is shown, which includes the following steps:
taking pure silicon 4 (metal reduced silicon), wherein the purity of the pure silicon 4 is 99.999%, and the primary particle size is 10-15 mm.
A first masterbatch 1 is taken, and the components of the first masterbatch 1 are 98.8 wt% of solvent and 1.2 wt% of dispersant. Wherein the solvent comprises 40 wt% of ethanol, 2 wt% of acetone and 58 wt% of water. The dispersant comprises 0.6-1.2 wt% of a polymeric proppant (such as PVP or PVA with a molecular weight of about 20000-30000 g/mole, preferably 25000g/mole), 0.1-0.3 wt% of a small molecular anchoring agent (such as unsaturated ether ketone or benzenesulfonate), and 0.1-0.4 wt% of a thickening agent (such as carboxyethyl or sodium carboxypropyl cellulose, or polysaccharide polymer).
As shown in fig. 1, 10 wt% of pure silicon 4 and 90 wt% of first masterbatch 1 are mixed to form a first mixture 10, and then ground, in a manner that the first mixture 10 enters a grinding machine 50 for grinding, wherein the grinding machine 50 includes a grinding sheet 51 and zirconium beads 52, the grinding sheet 51 rotates at a rotation speed of 3000-3400 rpm, the particle size of the zirconium beads 52 is 0.2-0.4 mm (preferably 0.3mm), and grinding is performed at 16-23 ℃ for 12-16 hours, wherein the ratio of the zirconium beads 52 to the first mixture 10 is 70-78 wt% of the zirconium beads 52. Thereby forming the first abrasive 15.
Taking graphene (graphene) 5.
And taking the first masterbatch 2, which is the same as the first masterbatch 1 in composition. Mixing 10 wt% of graphene 5 and 90 wt% of first masterbatch 2, and then grinding in the grinder 50, wherein the grinding conditions include using zirconium beads 52 with a particle size of 0.6-1.0 mm (preferably 0.8mm), rotating the grinding sheet 51 at a speed of 2200-2600 rpm, and grinding at 18-25 ℃ for 20-24 hours, wherein the ratio of the zirconium beads 52 to the first mixture 10 is 70-78 wt% of the zirconium beads 52. Thereby forming the second abrasive body 16.
As shown in fig. 2, the first milling bodies 15 and the second milling bodies 16 are mixed by equal weight to form a second mixture 20, and then planetary mixing, emulsification homogenization and defoaming planetary mixing are performed. A in fig. 2 corresponds to the position of the a point in the flow in fig. 1, and a 'in fig. 2 corresponds to the position of the a' in the flow in fig. 1. The method comprises the following steps:
the second mixture 20 is first put into a planetary mixer 80, wherein the revolution speed of the planetary mixer 80 is 10-30 rpm (preferably 20rpm), the rotation speed is 3500-5000 rpm, and the operation time is 1 hour.
As shown in fig. 4, the planetary mixer 80 mainly comprises:
an inner tub 81 for placing the second mixture 20 and stirring the second mixture 20.
An outer tub 82 for accommodating the inner tub 81, and cooling water 100 disposed between the outer tub 82 and the inner tub 81 for cooling the second mixture 20 inside the inner tub 81, wherein the cooling water 100 can be externally connected to a circulating cooling system (conventional prior art, detailed structure thereof is not described) to achieve the effect of circulating and heat exchanging of the cooling water 100.
A revolution type agitator 83 disposed in the inner tub 81 and externally connected to the driving mechanism 85, wherein the revolution type agitator 83 is used for agitating the second mixture 20 in a large path so that the second mixture 20 forms a large area of displacement inside the inner tub 81. The revolving agitator 83 is a substantially U-shaped or V-shaped frame 831, and a plurality of blades 832 are disposed on the side of the frame 831. The revolution type stirrer 83 rotates along the axis of the frame 831 while stirring, so that the second mixture 20 forms a large path of displacement. Preferably, the revolution type pulsator 83 rotates to sweep out a volume more than a half of the volume of the inner tub 81.
A rotation type stirrer 84 for partially and fully stirring the second mixture 20, mainly the block-shaped body rotates along its own axis, so that the second mixture 20 around the rotation type stirrer 84 forms a vortex. The self-rotating agitator 84 is at least one rotating ball 841, and is suspended by a suspension iron column 842 and driven by the driving mechanism 86. The rotating ball 841 rotates about an axis passing through its center of sphere while forming a vortex flow to the second mixture 20.
The at least one rotating ball 841 can be a plurality of rotating balls 841, each rotating ball 841 is suspended by a suspension iron column 842, and the rotating directions of the rotating balls 841 can be the same or different. Two rotary balls 841 are illustrated in fig. 4.
The purpose of the rotation in the present invention is to form a local vortex in the second mixture 20, mainly to break up the second mixture 20. The revolution is to form a large-displacement convection of the second mixing body 20 of the inner tub 81, so that the second mixing body 20 can be uniformly distributed as a whole. The second mixture 20 is sufficiently fused by revolution and rotation.
The planetary-mixed second mixture 20 is then placed into an emulsifying machine 90. As shown in fig. 5, the emulsifying machine 90 includes an emulsifying barrel 91, and the emulsifying barrel 91 includes the second mixture 20 mixed by the planetary mixing.
The inside of the emulsifying barrel 91 further includes a stirring barrel 92, the bottom of the stirring barrel 92 includes a plurality of input holes 921, and the second mixture 20 can be placed into the stirring barrel 92. The agitator 93 is disposed inside the agitator 92 for agitating the second mixture 20 in the agitator 92 to make it uniform and break up the particles into smaller particles. The lower side of the mixing barrel 92 includes a plurality of first output holes 922, and the mixed particles of the second mixture 20 with small particle size can be output to the emulsifying barrel 91 through the first output holes 922. The upper side of this agitator 92 includes a plurality of second delivery port 923, and the second mixture 20 through the stirring and the granule of not exporting through this first delivery port 922 are through further stirring in this agitator 92, and this second delivery port 923 output to this emulsification barrel 91 of rethread. The second mixture 20 output from the first output hole 922 and the second output hole 923 to the emulsification barrel 91 is input into the stirring barrel 92 from the input hole 921, so that the second mixture 20 is repeatedly and circularly stirred in the emulsification barrel 91 to be de-agglomerated to form an emulsified state. The inside of the emulsification barrel 91 above the second output hole 923 can be pumped to guide the second mixture 20 to flow from bottom to top.
The rotation speed of the emulsifying machine 90 for emulsifying is 9000-11000 rpm (preferably 10000rpm), and the emulsifying time is 1 hour.
Then the emulsified and homogenized second mixture 20 is put into the planetary mixer 80 for deaeration planetary mixing. Wherein the air is extracted from the inner tub 81, and the rotation speed is 0rpm and the revolution speed is 30rpm for 30 minutes, thereby completing the processing of the second mixture 20.
As shown in fig. 3, a Carbon Nanotube (CNT)6 and a second masterbatch 3 are mixed, the carbon nanotube 6 is an array carbon nanotube, and the second masterbatch 3 comprises a solvent and a coating agent, the coating agent is 2-6.8 wt% of the coating agent, and the rest is the solvent. The solvent is water. The coating agent is prepared from oligosaccharide macromolecules and a small amount of oligosaccharaide ketones, wherein the weight ratio of the oligosaccharide macromolecules to the oligosaccharaide ketones is 3-6: 1. and the weight ratio of the carbon nano-tubes 6 to the second masterbatch 3 is: the carbon nanotubes 6 account for 0.1-0.18 wt%, and the balance is the second masterbatch 3.
The mixture of the carbon nanotube 6 and the second masterbatch 3 is placed in a blade stirring tank 70, the blade stirring tank 70 includes a blade 71, and the mixture is stirred for 30 minutes by the blade 71 and then placed in an emulsifying machine 90 to be stirred for 30 minutes to form a third mixture 30.
As shown in fig. 6, the treated second mixture 20 and the treated third mixture 30 are planetary-mixed using the planetary mixer 80, wherein the revolution speed is 25rpm and the rotation speed is 2500rpm, and are mixed for 3 hours to form a fourth mixture 40. B in fig. 6 corresponds to the B position in the flow in fig. 2, and C in fig. 6 corresponds to the C position in the flow in fig. 3.
The fourth mixture 40 is then subjected to a spray drying operation. The method comprises the following steps:
the fourth mixture 40 is first mixed in an inner tub 81 of the planetary mixer 80 at a rotation speed of 0rpm and a revolution speed of 10 rpm. After 2-4 hours, the fourth mixture 40 is pumped to a four-fluid nozzle 60 by a pump to be sprayed out to form a spray. Wherein the air pressure of the four fluid nozzles 60 is 3kg/cm2. Wherein the fourth mixture 40 is thermally baked inside the four fluid head 60. The baking temperature is 170-185 ℃. And the temperature at the hot drying outlet is 150-160 ℃. Therefore, the silicon-carbon composite structure mixture 9 required by the invention is formed, wherein the particle size D50 of the silicon-carbon composite structure mixture 9 falls between 3 and 10 micrometers, namely 50 percent of the silicon-carbon composite structure mixture is formedThe particle size of the body 9 falls between 3 and 10 microns.
The numerical values of the above components can be varied by + -20% in the present invention, and the results of the present invention are not affected.
In the invention, a composite dispersant (the components of which are a macromolecular propping agent, a small molecular anchoring agent and a thickening agent) is added into an original silicon material, and the composite dispersant is used for dispersing and supporting a nano-micro silicon material, so that the silicon material is prevented from being reversely agglomerated and losing the dispersing benefit in the dispersing process; and a specific number of layers of high-purity refined graphene is added into the material, and the graphene, a special carbon material and a nano-micro silicon material are combined to form a special 3D structure so as to increase a conductive communication bridge among the silicon materials. In the dispersion process, a grinding machine is used for grinding sheets and zirconium beads, a special planetary mixing machine is used, the processes at all stages cooperate to ensure that the composite materials can be fully dissolved and uniformly mixed by a special binder formula, and granulation spraying equipment is used for endowing the composite materials with structural morphology; the sum results in a highly cyclic silicon carbon structure with better conductivity and expansion buffering capacity.
The above detailed description is specific to one possible embodiment of the present invention, but the embodiment is not intended to limit the scope of the present invention, and equivalent implementations or modifications without departing from the technical spirit of the present invention are intended to be included in the scope of the claims of the present invention.
Claims (13)
1. A method for manufacturing a multilayer long-cycle silicon-carbon negative electrode material is characterized by comprising the following steps:
step A: taking pure silicon;
and B: taking a first masterbatch, wherein the components of the first masterbatch are a solvent and a dispersant; wherein the solvent comprises ethanol, acetone and water; the components of the dispersant are a macromolecular propping agent, a small molecular anchoring agent and a thickening agent;
and C: mixing 10 wt% of pure silicon and 90 wt% of first masterbatch to form a first mixture, and grinding the first mixture in a grinding machine to form a first grinding body;
step D: taking graphene;
step E: taking first master batch, mixing 10 wt% of graphene and 90 wt% of the first master batch, and then grinding in the grinder to form a second grinding body;
step F: mixing the first grinding body and the second grinding body with equal weight to form a second mixture, and then carrying out planetary mixing, emulsification and homogenization and defoaming planetary mixing;
step G: mixing carbon nanotubes and a second masterbatch, wherein the carbon nanotubes are arrayed carbon nanotubes, and the second masterbatch comprises a solvent and a coating agent, wherein the solvent is water;
step H: placing the mixture of the carbon nanotubes and the second masterbatch into a blade stirring tank, wherein the blade stirring tank comprises blades, stirring for a preset time by the blades, and then placing the mixture into an emulsifying machine to stir for a preset time to form a third mixture;
step I: c, planetary mixing and stirring the second mixture and the third mixture which are processed in the step F to form a fourth mixture;
step J: then carrying out spray drying operation on the fourth mixture to form a silicon-carbon composite structure mixture;
wherein the numerical values of the above components are varied by + -20%.
2. The method for producing a multilayered long-cycle silicon-carbon negative electrode material according to claim 1, characterized in that: in the step A, the pure silicon is metal reduced silicon, and the primary particle size is 10-15 mm.
3. The method for producing a multilayered long-cycle silicon-carbon negative electrode material according to claim 1, characterized in that: in step B, the solvent of the first masterbatch is 98.8 wt%; the proportion of the dispersant of the first masterbatch is 1.2 wt%; wherein the solvent comprises 40 wt% of ethanol, 2 wt% of acetone and 58 wt% of water; the dispersing agent comprises 0.6-1.2 wt% of high-molecular propping agent, 0.1-0.3 wt% of small-molecular anchoring agent and 0.1-0.4 wt% of thickening agent; wherein the numerical values of the above components are varied by + -20%.
4. The method for producing a multilayered long-cycle silicon-carbon negative electrode material according to claim 3, characterized in that: the polymer proppant is selected from PVP or PVA, and the molecular weight of the polymer proppant is 20000-30000 g/mole; the small molecular anchoring agent is selected from unsaturated ether ketones or benzene sulfonate; the thickening agent is selected from carboxyethyl or sodium carboxymethyl cellulose, or polysaccharide polymer.
5. The method for producing a multilayered long-cycle silicon-carbon negative electrode material according to claim 1, characterized in that: in the step C, the grinding machine comprises a grinding sheet and zirconium beads, the grinding sheet rotates at the rotating speed of 3000-3400 rpm, the particle size of the zirconium beads is 0.2-0.4 mm, grinding is carried out for 12-16 hours in the environment of 16-23 ℃, and the proportion of the zirconium beads to the first mixture is that the zirconium beads account for 70-78 wt%; and in the step E, the grinding machine comprises a grinding sheet and zirconium beads, wherein the grinding condition is to use the zirconium beads with the particle size of 0.6-1.0 mm, the grinding sheet rotates at the rotating speed of 2200-2600 rpm, and the grinding is carried out for 20-24 hours in the environment of 18-25 ℃, wherein the proportion of the zirconium beads and the first mixture body is 70-78 wt% of the zirconium beads.
6. The method for producing a multilayered long-cycle silicon-carbon negative electrode material according to claim 1, characterized in that: and F, performing planetary mixing in a mode of putting the second mixture into a planetary mixer for mixing, wherein the planetary mixer comprises:
an inner barrel for placing the second mixture and stirring the second mixture;
an outer barrel for accommodating the inner barrel, cooling water is arranged between the outer barrel and the inner barrel to cool the second mixture in the inner barrel, and the cooling water is externally connected with a circulating cooling system to achieve the effects of cooling water circulation and heat exchange;
a revolution type stirrer which is arranged in the inner barrel and is externally connected with a driving mechanism, wherein the revolution type stirrer is used for stirring the second mixture in a large path so as to ensure that the second mixture forms displacement of a larger area in the inner barrel;
the self-rotating stirrer is used for fully stirring the second mixture locally, and mainly makes the block-shaped body rotate along the axis of the self-rotating stirrer so as to form a vortex of the second mixture around the self-rotating stirrer; wherein the self-rotating stirrer is at least one rotating ball, is suspended by an iron suspension column and is driven by a driving mechanism.
7. The method for producing a multilayered long-cycle silicon-carbon negative electrode material according to claim 7, wherein: and F, when planetary mixing is carried out, the revolution speed of the planetary mixer is 10-30 rpm, and the rotation speed is 3500-5000 rpm.
8. The method for producing a multilayered long-cycle silicon-carbon negative electrode material according to claim 1, characterized in that: the emulsification and homogenization in the step F are carried out by putting the second mixture subjected to planetary mixing into an emulsifying machine; the emulsifying machine comprises an emulsifying barrel, and a second mixture subjected to planetary mixing is arranged in the emulsifying barrel;
the emulsifying barrel is internally provided with a stirring barrel, the bottom of the stirring barrel comprises a plurality of input holes, and the second mixture is placed into the stirring barrel; a stirrer is arranged in the stirring barrel and is used for stirring the second mixture in the stirring barrel to make the second mixture uniform and scattering particles of the second mixture into particles with small particle size; the lower side of the stirring barrel comprises a plurality of first output holes, and the stirred second mixture and particles with small particle size can be output to the emulsifying barrel through the first output holes; the upper side of the stirring barrel comprises a plurality of second output holes, and the stirred second mixture is further stirred in the stirring barrel and is output to the emulsifying barrel through the second output holes, wherein the particles which are not output through the first output holes are not output through the second output holes; wherein the second mixture output to the emulsification barrel from the first output hole and the second output hole is input into the stirring barrel from the input hole, so that the second mixture is repeatedly and circularly stirred and agglomerated in the emulsification barrel to form an emulsification state; and the inner side of the emulsifying barrel is positioned above the second output hole for pumping air so as to guide the second mixture to flow from bottom to top.
9. The method for producing a multilayered long-cycle silicon-carbon negative electrode material according to claim 8, characterized in that: when emulsification and homogenization are carried out in the step F, the rotating speed of the emulsifying machine during emulsification is 9000-11000 rpm; and is
The defoaming planetary mixing in the step F is carried out by putting the emulsified and homogenized second mixture into a planetary mixer for defoaming planetary mixing; wherein, air is pumped in the inner barrel to finish the treatment of the second mixture; and is
And F, when the defoaming planetary mixing is carried out, the rotation speed of the planetary mixing machine is 0rpm, the revolution speed is 30rpm, and the mixing is carried out for 30 minutes.
10. The method for producing a multilayered long-cycle silicon-carbon negative electrode material according to claim 1, characterized in that: in the step G, the proportion of the coating agent in the second masterbatch is 2-6.8 wt%, and the rest is solvent; the coating agent is prepared from oligosaccharide high polymers and a small amount of oligosaccharaide ketones, wherein the weight ratio of the oligosaccharide high polymers to the oligosaccharaide ketones is 3-6: 1; wherein the weight ratio of the carbon nanotubes to the second masterbatch is as follows: the carbon nanotubes account for 0.1-0.18 wt%, and the rest is the second masterbatch; wherein the numerical values of the above components are varied by + -20%.
11. The method for producing a multilayered long-cycle silicon-carbon negative electrode material according to claim 1, characterized in that: the spray drying operation in step J is performed by putting the fourth mixture into an inner barrel of the planetary mixer for mixing, and pumping the fourth mixture to a four-fluid nozzle to spray out to form spray after a predetermined time; wherein the fourth mixture is heated in the four-fluid nozzle; thus forming the silicon-carbon composite structure mixture.
12. The method for producing a multilayered long-cycle silicon-carbon negative electrode material according to claim 11, characterized in that: when the spray drying operation is performed in the step J, the rotation speed of the planetary mixer is 0rpm, and the revolution speed is 10 rpm; pumping the fourth mixture to the four-fluid spray head after 2-4 hours; wherein the air pressure of the four-fluid spray head is 3kg/cm 2; wherein the temperature for the heat drying in the four-fluid nozzle is 170-185 ℃, and the temperature at the heat drying outlet is 150-160 ℃.
13. The method for producing a multilayered long-cycle silicon-carbon negative electrode material according to claim 1, characterized in that: the particle size D50 of this silicon carbon composite structure mixture is between 3~10 microns, and wherein 50% silicon carbon composite structure mixture's particle size is between 3~10 microns.
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