CN114094034B - Method for manufacturing multi-layer long-cycle silicon-carbon anode material - Google Patents
Method for manufacturing multi-layer long-cycle silicon-carbon anode material Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 21
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 239000010405 anode material Substances 0.000 title claims description 17
- 239000000203 mixture Substances 0.000 claims abstract description 145
- 238000003756 stirring Methods 0.000 claims abstract description 55
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 48
- 238000000227 grinding Methods 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 43
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 238000004945 emulsification Methods 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
- 239000002153 silicon-carbon composite material Substances 0.000 claims abstract description 15
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000001694 spray drying Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims description 35
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 22
- 239000011324 bead Substances 0.000 claims description 22
- 229910052726 zirconium Inorganic materials 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000012530 fluid Substances 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000498 cooling water Substances 0.000 claims description 10
- 230000007246 mechanism Effects 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- 239000002562 thickening agent Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000004873 anchoring Methods 0.000 claims description 8
- 229920001542 oligosaccharide Polymers 0.000 claims description 8
- -1 unsaturated ether ketone Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 6
- 150000002482 oligosaccharides Chemical class 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 6
- 238000000265 homogenisation Methods 0.000 claims description 5
- 238000006073 displacement reaction Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 claims description 3
- 229940077388 benzenesulfonate Drugs 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 150000004676 glycans Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229920001282 polysaccharide Polymers 0.000 claims description 3
- 239000005017 polysaccharide Substances 0.000 claims description 3
- 150000003384 small molecules Chemical class 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229920002521 macromolecule Polymers 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 abstract description 7
- 239000002210 silicon-based material Substances 0.000 description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 239000002131 composite material Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000003139 buffering effect Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- JLQUFIHWVLZVTJ-UHFFFAOYSA-N carbosulfan Chemical compound CCCCN(CCCC)SN(C)C(=O)OC1=CC=CC2=C1OC(C)(C)C2 JLQUFIHWVLZVTJ-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—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
-
- 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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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
A method for preparing multi-layer long-cycle silicon-carbon negative electrode material comprises taking a pure silicon and a first masterbatch, wherein the first masterbatch comprises solvent and dispersant; then mixing pure silicon and a first masterbatch to form a first mixture, and grinding to form a first grinding body; then taking graphene and another first masterbatch, mixing the graphene and the another first masterbatch, and grinding the two to form a second grinding body; then mixing the first grinding body and the second grinding body to form a second mixture, and then performing planetary mixing, emulsification homogenizing and defoaming planetary mixing; then mixing the carbon nano-tube and a second masterbatch, then placing the mixture into a blade stirring tank for stirring, and then placing the mixture into an emulsifying machine for stirring to form a third mixture; the second masterbatch comprises a solvent and a coating agent; then, planetary mixing is carried out on the second mixture and the third mixture after treatment 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 manufacturing method of a negative electrode material, in particular to a manufacturing method of a multi-layer long-cycle silicon-carbon negative electrode material.
Background
In the prior art, graphite is used as a negative electrode for lithium ion intercalation reaction in a negative electrode material of a lithium battery; however, due to the limited capacitance of graphite, the 3C market and the vehicle market with continuous marshal, which are increasingly required to meet the demands of the capacitance, cannot meet the future demands, so the improvement of the capacitance of the negative electrode material is an important development direction. Among them, silicon materials are expected to be commercially available because of their excellent lithium storage capacity. The silicon content in the crust is the most element except oxygen, and the silicon material is a nonmetallic amorphous material, and 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 nontoxic and odorless. Therefore, the silicon-carbon composite material formed by the silicon material and the graphite material can be used as a negative electrode material of a lithium ion battery, and the capacitance of the lithium ion battery is greatly improved. It is preferred to use silicon material (pure silicon, silicon oxide) partially in combination with graphite. Because the silicon material has a higher capacitance than graphite, the entire negative electrode can be made to have a larger capacitance to increase the storage capacity of the battery.
In lithium ion batteries, lithium ions are electrochemically intercalated into the crystal structure of a silicon material by the difference in external potential and potential energy of the material. When the lithium battery discharges in an electrochemical mode, lithium ions with electrochemical activity leave the silicon crystal structure to form a discharge mechanism so as to meet the electric energy requirement of communicating an external circuit. In theory, developers and users hope that all lithium ions can reduce the loss as much as possible in the charge and discharge process, however, during the battery operation, a part of active lithium can have electrochemical side reaction with active lithium due to the increase or decrease of the reaction interface and the impurities in the electrolyte or the material, so that the precipitation and loss of inactive lithium salt are caused, and the inactive lithium salt is precipitated around the material to form an irreversible film, namely SEI film. The SEI phenomenon is particularly obvious in a silicon material, when the silicon material is charged, the crystal structure of the silicon material is loosely expanded due to the fact that a large amount of lithium ions are contained in the silicon material (the structure is much larger than that of the original silicon material), after the silicon material is expanded, the expansion effect breaks through the surface stress of the original structure of the material, the surface of particles is broken, a new reaction interface is formed, the specific surface area BET of the material is changed, and then the new reaction interface can irreversibly react with residual active lithium, so that lithium ions are consumed; on the other hand, active lithium leaves the silicon lattice structure and leaves a cavity during discharge, so that the whole material is soft to collapse, and a new reaction interface is generated after the collapse and reacts with active lithium ions to cause loss. After multiple charge and discharge, the expansion, rupture, collapse and lithium consumption repeatedly occur, so that a large amount of active lithium is consumed to cause great decay of capacitance, and the service life and usability of the battery are reduced.
In addition, the silicon material itself does not have the corresponding conductivity, and the electron conduction and the ion conduction are needed to be carried out by the aid of the conductive material, and the conductive carbon is often attached to the silicon material in an additional form, so that the connection is easily lost in the charge and discharge process of expansion and rupture to cause the loss of conductivity, and the corresponding capacity also has great decay after the loss of conductivity.
Therefore, the present invention provides a novel method for manufacturing a long-acting silicon-carbon negative electrode material with high conductivity, high capacity, enhanced expansion buffering property and enhanced cycle life, so as to solve the above-mentioned drawbacks in the prior art.
Disclosure of Invention
Therefore, the present invention aims to solve the above problems in the prior art, and proposes a manufacturing method with high conductivity, high capacity, expansion buffering property and cycle life enhancement, which adds a dispersing agent (which comprises a polymer proppant, a small-molecule anchor agent and a thickener) into an original silicon material, wherein the composite dispersing agent is used for dispersing and supporting the nano-micro silicon material, so as to avoid the silicon material from losing dispersion benefit due to agglomeration during the dispersion process; and a specific layer number 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 the conductive communication bridge between the silicon materials. In the dispersing process, grinding sheets and zirconium beads are applied by a grinder, a special planetary mixer is applied, and the composite materials can be fully and uniformly mixed through a special binder formula in cooperation in the process of each stage, and the structural morphology of the composite materials is endowed by granulating and spraying equipment; mixing produces a highly cyclic silicon carbon structure with better conductivity and expansion buffering capability.
In order to achieve the above object, the present invention provides a method for manufacturing a multi-layer long-cycle silicon-carbon anode material, comprising the following steps: step A: taking pure silicon; and (B) step (B): in addition, a first masterbatch is taken, and the components of the first masterbatch are a solvent and a dispersing agent; wherein the solvent comprises ethanol, acetone and water; the dispersing agent comprises the components of a high polymer propping agent, a small polymer anchoring agent and a thickening agent; step C: mixing 10% by weight of pure silicon with 90% by weight of a first masterbatch to form a first mixture, and grinding the first mixture in such a way that the first mixture is fed into a grinder to be ground, thereby forming a first ground body; step D: taking graphene; step E: additionally taking a first masterbatch; mixing 10% wt of graphene with 90% wt of the first masterbatch and then grinding the mixture in the grinder, thereby forming a second grind; step F: mixing the first grinding body and the second grinding body with equal weight to form a second mixture, and then performing the procedures of planetary mixing, emulsification homogenizing and defoaming planetary mixing; step G: mixing Carbon Nanotubes (CNT) with a second masterbatch, wherein the carbon nanotubes are array carbon nanotubes, and the second masterbatch comprises a solvent and a coating agent, and 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 for stirring for a preset time to form a third mixture; step I: f, performing planetary mixing on the second mixture and the third mixture 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 components can be changed by +/-20 percent.
Further, in the step A, the pure silicon is metal reduced silicon, and the original particle size is 10-15 mm.
Further, in step B, the solvent of the first masterbatch is present in a proportion of 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 the following components of 0.6-1.2% by weight of polymer propping agent, 0.1-0.3% by weight of small molecular anchoring agent and 0.1-0.4% by weight of thickening agent; wherein the numerical values of the components can be changed by +/-20 percent.
Further, the polymer propping agent is selected from PVP or PVA, and the molecular weight of the polymer propping agent is 20000-30000 g/mole; the small molecule anchoring agent is selected from unsaturated ether ketone or benzenesulfonate; the thickener is selected from carboxyethyl or sodium carboxypropyl 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, grinding is carried out for 12-16 hours at the temperature of 16-23 ℃, and the ratio of the zirconium beads to the first mixture is 70-78%wt; and in the step E, the grinding machine comprises a grinding sheet and zirconium beads, wherein the grinding condition is that the zirconium beads with the particle size of 0.6-1.0 mm are used, the grinding sheet rotates at the rotating speed of 2200-2600 rpm, the grinding is carried out for 20-24 hours at the temperature of 18-25 ℃, and the proportion of the zirconium beads to the first mixture is 70-78%wt.
Further, the planetary mixing in the 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, wherein 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;
the revolution stirrer is arranged in the inner barrel and is externally connected with the driving mechanism, and the revolution stirrer is used for stirring the second mixture in a large path so as to enable the second mixture to form displacement of a larger area in the inner barrel;
the self-rotating stirrer is used for fully stirring the second mixture locally, and mainly comprises a block body which rotates along the axis of the block body so that the second mixture around the self-rotating stirrer forms vortex; wherein the self-rotation stirrer is at least one rotating ball, is suspended by a suspending iron column and is driven by a driving mechanism.
Further, in the step F, the planetary mixer is rotated at a revolution speed of 10 to 30rpm and a rotation speed of 3500 to 5000rpm.
Further, in the step F, the emulsifying and homogenizing manner is to put the second mixture after planetary mixing into an emulsifying machine; wherein the emulsifying machine comprises an emulsifying barrel, and the interior of the emulsifying barrel comprises a second mixture which is mixed by the planetary mixer; wherein the emulsifying barrel also comprises 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; the stirrer is arranged in the stirring barrel and used for stirring the second mixture in the stirring barrel uniformly and scattering the particles 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 diameters 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 particles which are stirred by the second mixture and output through the first output holes are further stirred in the stirring barrel and then output to the emulsifying barrel through the second output holes; the second mixture output from the first output hole and the second output hole to the emulsifying barrel is input into the stirring barrel from the input hole, so that the second mixture is repeatedly and circularly stirred and agglomerated in the emulsifying barrel to form an emulsifying state; and pumping air at the position above the second output hole on the inner side of the emulsifying barrel so as to guide the second mixture to flow from bottom to top.
Further, in the step F, when emulsification and homogenization are carried out, the rotation speed of the emulsifying machine is 9000-11000 rpm when emulsification is carried out; and is also provided with
F, the defoaming planetary mixing is carried out in the mode that the second mixture after emulsification and homogenization is placed into a planetary mixer for defoaming planetary mixing operation; wherein, the air suction is carried out in the inner barrel to finish the treatment of the second mixture; and is also provided with
In the deaeration planetary mixing in the step F, the rotation speed of the planetary mixer was 0rpm, and the revolution speed was 30rpm 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 balance is solvent; the material of the coating agent is oligosaccharide polymer and a small amount of oligosaccharinones, wherein the weight ratio of the oligosaccharide polymer to the oligosaccharinones is 3-6: 1, a step of; wherein the weight ratio of the carbon nanotube to the second masterbatch is as follows: the carbon nano-tube accounts for 0.1-0.18 wt% and the balance is the second masterbatch; wherein the numerical values of the components can be changed by +/-20 percent.
Further, in the step J, the spray drying operation is performed by firstly placing the fourth mixture into an inner barrel of the planetary mixer for mixing, and after a predetermined time, pumping the fourth mixture to a four-fluid nozzle by using a pump to spray to form spray; wherein the fourth mixture is thermally baked inside the four fluid ejection head; thus forming the silicon-carbon composite structure mixture.
Further, in the spray drying operation in the step J, the rotation speed of the planetary mixer was 0rpm and the revolution speed was 10rpm; then pumping the fourth mixture to the four fluid nozzle after 2-4 hours; wherein the air pressure of the four fluid ejection heads is 3kg/cm 2; wherein the temperature of the interior of the four fluid spray heads for heat drying is 170-185 ℃, and the temperature of the interior of the four fluid spray heads for heat drying is 150-160 ℃.
Further, the particle diameter D50 of the silicon-carbon composite structure mixture is 3-10 microns, namely 50% of the silicon-carbon composite structure mixture has the particle diameter of 3-10 microns. A further understanding of the nature and advantages of the present invention will become apparent from the following description, read in conjunction with the accompanying drawings.
Drawings
FIG. 1 is a schematic view of a 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 homogenizing and defoaming planetary mixing of a second mixture according to the present invention;
FIG. 3 is a schematic illustration of a manufacturing process of a third mixture 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 emulsifying machine of the present invention;
FIG. 6 is a schematic flow chart of the process for producing the silicon-carbon composite structure by using the second mixture and the third mixture.
Description of the reference numerals
1. A first masterbatch; 2. a first masterbatch; 3. a second masterbatch; 4. pure silicon; 5. a graphene; 6. a carbon nanotube; 9. a silicon-carbon composite structure mixture; 10. a first mixture; 15. a first abrasive body; 16. a second abrasive body; 20. a second mixture; 30. a third mixture; 40. a fourth mixture; 50. a grinder; 51. grinding sheets; 52. zirconium beads; 60. a fourth fluid ejection head; 70. a blade stirring tank; 71. a blade; 80. a planetary mixer; 81. an inner barrel; 82. an outer tub; 83. a revolution type stirrer; 84. a self-rotating agitator; 85. a driving mechanism; 86. a driving mechanism; 90. an emulsifying machine; 91. an emulsifying barrel; 92. a stirring barrel; 93. a stirrer; 100. cooling water; 831. a frame; 832. a blade; 841. rotating ball; 842. suspending iron columns; 921. an input hole; 922. a first output aperture; 923. and a second output hole.
Detailed Description
The structural composition, and the resulting efficacy and advantages of the present invention will now be described in detail, along with the accompanying figures, by way of a preferred embodiment of the invention.
Referring to fig. 1 to 6, the method for manufacturing the multi-layer long-cycle silicon-carbon anode material of the present invention comprises the following steps:
and taking pure silicon 4 (metal reduced silicon), wherein the purity of the pure silicon is 99.999%, and the original particle size is 10-15 mm.
A first masterbatch 1 was taken, the composition of the first masterbatch 1 being 98.8% wt (weight percent) solvent plus 1.2% wt 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 polymer propping agent (such as PVP or PVA, with molecular weight of about 20000-30000 g/mole, preferably 25000 g/mole), 0.1-0.3% wt of small molecular anchoring agent (such as unsaturated ether ketone or benzenesulfonate), and 0.1-0.4% wt of thickening agent (such as carboxyethyl or sodium carboxypropyl cellulose, or polysaccharide polymer).
As shown in fig. 1, 10% by weight of pure silicon 4 and 90% by weight of a first masterbatch 1 are mixed to form a first mixture 10, and then the first mixture 10 is ground by feeding the first mixture 10 into a grinder 50, wherein the grinder 50 comprises a grinding sheet 51 and zirconium beads 52, the grinding sheet 51 rotates at 3000-3400 rpm, the zirconium beads 52 have a particle size of 0.2-0.4 mm (preferably 0.3 mm), and the grinding is performed for 12-16 hours at 16-23 ℃, wherein the ratio of the zirconium beads 52 to the first mixture 10 is 70-78% by weight of the zirconium beads 52. Thus forming the first abrasive body 15.
A graphene 5 was taken.
In addition, the first masterbatch 2 is taken, and the components of the first masterbatch are the same as those of the first masterbatch 1. 10% by weight of graphene 5 and 90% by weight of first masterbatch 2 are mixed and then enter the grinder 50 for grinding, but the grinding condition is that zirconium beads 52 with the particle size of 0.6-1.0 mm (preferably 0.8 mm) are used, a grinding sheet 51 rotates at a rotating speed of 2200-2600 rpm, grinding is carried out for 20-24 hours at the temperature of 18-25 ℃, and the ratio of the zirconium beads 52 to the first mixture 10 is 70-78% by weight of the zirconium beads 52. Thus forming the second abrasive body 16.
As shown in fig. 2, the first polishing body 15 and the second polishing body 16 having equal weights are mixed to form a second mixture 20, and then the planetary mixing, emulsification, homogenization, and deaeration planetary mixing are performed. A in fig. 2 corresponds to the position of a point a of the flow in fig. 1, and a 'in fig. 2 corresponds to the position of a' of the flow in fig. 1. The method comprises the following steps:
the second mixture 20 is first placed in a planetary mixer 80, wherein the revolution speed of the planetary mixer 80 is 10-30 rpm (preferably 20 rpm), the rotation speed is 3500-5000 rpm, and the operation time is 1 hour.
As shown in fig. 4, the planetary mixer 80 mainly includes:
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, wherein cooling water 100 is disposed between the outer tub 82 and the inner tub 81 to cool the second mixture 20 inside the inner tub 81, and the cooling water 100 can be externally connected to a circulating cooling system (which is a conventional prior art and detailed structure thereof is not repeated) to achieve the effects of circulating the cooling water 100 and heat exchange.
A revolution agitator 83 disposed in the inner tub 81 and externally connected to a driving mechanism 85, wherein the revolution agitator 83 is used for agitating the second mixture 20 in a large path so as to form a displacement of the second mixture 20 in a large area inside the inner tub 81. Wherein the revolution type pulsator 83 has a substantially U-shaped or V-shaped frame 831, and a plurality of blades 832 are disposed at sides of the frame 831. The revolution stirrer 83 rotates along the axis of the frame 831 while stirring, so that the second mixing body 20 is displaced in a large path. Preferably, the volume swept by the revolution type agitator 83 when rotated exceeds half the volume of the inner tub 81.
A self-rotating agitator 84 is used to fully agitate the second mixture 20 locally, and the second mixture 20 around the self-rotating agitator 84 is formed by the self-rotation of the block along its own axis. The self-rotating agitator 84 is at least one rotating ball 841, and is suspended by a suspension strut 842 and driven by a driving mechanism 86. The rotating ball 841 rotates around the axis passing through the center of the ball, and forms a vortex to the second mixture 20.
The at least one rotary ball 841 may be a plurality of rotary balls 841, each rotary ball 841 is respectively suspended by a suspension iron 842, and the rotation directions of the rotary balls 841 may be the same or different. In fig. 4, two swivel balls 841 are illustrated.
The purpose of the autorotation in the present invention is to form local vortex flow in the second mixture 20, mainly to break up the second mixture 20. The revolution aims to make the second mixture 20 of the inner tub 81 form a large displacement convection so that the second mixture 20 as a whole can be uniformly distributed. The second mixture 20 is fully fused by revolution and rotation.
The planetary-blended second mixture 20 is then placed in 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 after planetary stirring.
Wherein the emulsifying barrel 91 further comprises a stirring barrel 92, and the bottom of the stirring barrel 92 comprises a plurality of input holes 921, and the second mixture 20 can be placed into the stirring barrel 92. The stirring vessel 92 is internally provided with a stirrer 93 for stirring the second mixture 20 in the stirring vessel 92 to be uniform and to break up particles thereof into particles of smaller particle size. The lower side of the stirring vessel 92 includes a plurality of first output holes 922, and the stirred particles of the second mixture 20 and small particle size can be output to the emulsification vessel 91 through the first output holes 922. The upper side of the stirring barrel 92 includes a plurality of second output holes 923, and the particles which are not output through the first output holes 922 by the second mixed body 20 after stirring are further stirred in the stirring barrel 92 and then output to the emulsifying barrel 91 through the second output holes 923. The second mixture 20 outputted from the first output hole 922 and the second output hole 923 to the emulsification barrel 91 is inputted 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 deagglomerated to form an emulsified state. Suction may be applied to the inside of the emulsification barrel 91 above the second output hole 923 to guide the second mixture 20 to flow from bottom to top.
In the present invention, the emulsifying machine 90 performs emulsification at a rotational speed of 9000 to 11000rpm (preferably 10000 rpm) for 1 hour.
Then, the emulsified and homogenized second mixture 20 is put into the planetary mixer 80 again for defoaming planetary mixing operation. Wherein the air suction is performed in the inner tub 81 and the rotation speed is 0rpm and the revolution speed is 30rpm for 30 minutes, thereby completing the process of the second mixture 20.
As shown in fig. 3, carbon Nanotubes (CNTs) 6 and a second masterbatch 3 are mixed, wherein the carbon nanotubes 6 are array carbon nanotubes, the second masterbatch 3 comprises a solvent and a coating agent, the weight percentage of the coating agent is 2-6.8 wt%, and the balance is the solvent. The solvent is water. The material of the coating agent is oligosaccharide polymer and a small amount of oligosaccharinones, wherein the weight ratio of the oligosaccharide polymer to the oligosaccharinones is 3-6: 1. the weight ratio of the carbon nanotubes 6 to the second masterbatch 3 is: the carbon nano-tube 6 accounts for 0.1-0.18 wt% and the balance is the second masterbatch 3.
The mixture of the carbon nanotubes 6 and the second masterbatch 3 is placed in a blade agitation tank 70, the blade agitation tank 70 includes a blade 71, and is agitated by the blade 71 for 30 minutes, and then placed in an emulsifying machine 90 for 30 minutes to form a third mixture 30.
As shown in fig. 6, the second mixture 20 and the third mixture 30 which were treated as described above were subjected to planetary stirring by using the planetary stirring machine 80, in which the revolution speed was 25rpm and the rotation speed was 2500rpm, and were mixed for 3 hours, to form a fourth mixture 40. B in fig. 6 corresponds to the B position of the flow in fig. 2, and C in fig. 6 corresponds to the C position of 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 mix body 40 was first put into the inner tub 81 of the planetary mixer 80 to be mixed, wherein the rotation speed was 0rpm and the revolution speed was 10rpm. After 2-4 hours, the fourth mixture 40 is pumped to a four-fluid nozzle 60 by a pump to spray. Wherein the air pressure of the four fluid ejection heads 60 is 3kg/cm 2 . Wherein the fourth mixture 40 is thermally baked inside the four fluid ejection head 60. The baking temperature is 170-185 ℃. The temperature at the hot-baking outlet is 150-160 ℃. Thus, the silicon-carbon composite structure mixture 9 required by the invention is formed, wherein the particle diameter D50 of the silicon-carbon composite structure mixture 9 is between 3 and 10 microns, namely that 50% of the particle diameters of the silicon-carbon composite structure mixture 9 are between 3 and 10 microns.
The values of the above components in the present invention may vary by + -20% without affecting the results of the present invention.
In the invention, a composite dispersing agent (which comprises a macromolecule propping agent, a micromolecule anchoring agent and a thickening agent) is added into an original silicon material, and the composite dispersing agent is used for dispersing and supporting a nano-micro silicon material, so that the silicon material is prevented from losing dispersing benefit due to anti-agglomeration in the dispersing process; and a specific layer number 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 the conductive communication bridge between the silicon materials. In the dispersing process, grinding sheets and zirconium beads are applied by a grinder, a special planetary mixer is applied, and the composite materials can be fully mutually dissolved and uniformly mixed by a special binder formula in the process of each stage, and the structural morphology is given to the composite materials by a granulating and spraying device; the sum results in a highly cyclic silicon carbon structure with better conductivity and expansion buffering capability.
The foregoing detailed description is directed to a practical embodiment of the present invention, but the embodiment is not intended to limit the scope of the invention, and all equivalent implementations or modifications that do not depart from the spirit of the invention are intended to be included in the scope of the appended claims.
Claims (13)
1. The manufacturing method of the multi-layer long-cycle silicon-carbon anode material is characterized by comprising the following steps of:
step A: taking pure silicon;
and (B) step (B): in addition, a first masterbatch is taken, and the components of the first masterbatch are a solvent and a dispersing agent; wherein the solvent comprises ethanol, acetone and water; the components of the dispersing agent are a high polymer propping agent, a small polymer anchoring agent and a thickening agent, wherein the high polymer propping agent is selected from PVP or PVA; the small molecule anchoring agent is selected from unsaturated ether ketone or benzenesulfonate; the thickener is selected from carboxyethyl or sodium carboxypropyl cellulose or polysaccharide polymer;
step C: mixing 10% by weight of pure silicon with 90% by weight of a first masterbatch to form a first mixture, and grinding the first mixture in such a way that the first mixture is fed into a grinder to be ground, thereby forming a first ground body;
step D: taking graphene;
step E: in addition, taking the first masterbatch, mixing 10% by weight of graphene with 90% by weight of the first masterbatch, and then grinding the mixture 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 performing the procedures of planetary mixing, emulsification homogenizing and defoaming planetary mixing;
step G: mixing a carbon nanotube and a second masterbatch, wherein the carbon nanotube is an array carbon nanotube, the second masterbatch comprises a solvent and a coating agent, the solvent is water, and the coating agent is prepared from oligosaccharide polymers and oligosaccharide ketones;
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 for stirring for a preset time to form a third mixture;
step I: f, performing planetary mixing on the second mixture and the third mixture 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 components are changed by +/-20 percent.
2. The method for producing a multi-layer long-circulating silicon-carbon anode material according to claim 1, wherein: in the step A, the pure silicon is metal reduced silicon, and the original particle size is 10-15 mm.
3. The method for producing a multi-layer long-circulating silicon-carbon anode material according to claim 1, wherein: in step B, the solvent of the first masterbatch in a proportion of 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; wherein the numerical values of the components are changed by +/-20 percent; the dispersing agent comprises 0.6-1.2 wt% of polymer propping agent, 0.1-0.3 wt% of small molecular anchoring agent and 0.1-0.4 wt% of thickening agent.
4. The method for producing a multi-layer long-circulating silicon-carbon anode material according to claim 3, wherein: the molecular weight of the polymer propping agent is 20000-30000 g/mole.
5. The method for producing a multi-layer long-circulating silicon-carbon anode material according to claim 1, wherein: in the step C, the grinding machine comprises a grinding sheet and zirconium beads, wherein 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, grinding is carried out for 12-16 hours at the temperature of 16-23 ℃, and the ratio of the zirconium beads to the first mixture is 70-78%wt; and in the step E, the grinding machine comprises a grinding sheet and zirconium beads, wherein the grinding condition is that the zirconium beads with the particle size of 0.6-1.0 mm are used, the grinding sheet rotates at the rotating speed of 2200-2600 rpm, the grinding is carried out for 20-24 hours at the temperature of 18-25 ℃, and the proportion of the zirconium beads to the first mixture is 70-78%wt.
6. The method for producing a multi-layer long-circulating silicon-carbon anode material according to claim 1, wherein: the planetary mixing in the 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, wherein 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;
the revolution stirrer is arranged in the inner barrel and is externally connected with the driving mechanism, and the revolution stirrer is used for stirring the second mixture in a large path so as to enable the second mixture to form displacement of a larger area in the inner barrel;
the self-rotating stirrer is used for fully stirring the second mixture locally, and mainly comprises a block body which rotates along the axis of the block body so that the second mixture around the self-rotating stirrer forms vortex; wherein the self-rotation stirrer is at least one rotating ball, is suspended by a suspending iron column and is driven by a driving mechanism.
7. The method for producing a multi-layer long-circulating silicon-carbon anode material according to claim 1, wherein: and F, when planetary mixing is performed in the step F, 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 multi-layer long-circulating silicon-carbon anode material according to claim 1, wherein: f, the second mixture subjected to planetary mixing is put into an emulsifying machine; wherein the emulsifying machine comprises an emulsifying barrel, and the interior of the emulsifying barrel comprises a second mixture which is mixed by the planetary mixer;
wherein the emulsifying barrel also comprises a stirring barrel, the bottom of the stirring barrel comprises a plurality of input holes, and the second mixture is put into the stirring barrel; the stirrer is arranged in the stirring barrel and used for stirring the second mixture in the stirring barrel uniformly and scattering the particles into particles with small particle size; the lower side of the stirring barrel comprises a plurality of first output holes, and the particles with small particle sizes of the second mixture can be output to the emulsifying barrel through the first output holes after being stirred; the upper side of the stirring barrel comprises a plurality of second output holes, and the particles which are not output by the first output holes of the stirred second mixture are further stirred in the stirring barrel and then output to the emulsifying barrel through the second output holes; the second mixture output from the first output hole and the second output hole to the emulsifying barrel is input into the stirring barrel from the input hole, so that the second mixture is repeatedly and circularly stirred and agglomerated in the emulsifying barrel to form an emulsifying state; and pumping air at the position above the second output hole on the inner side of the emulsifying barrel so as to guide the second mixture to flow from bottom to top.
9. The method for producing a multi-layer long-circulating silicon-carbon anode material according to claim 6, wherein: f, when emulsification and homogenization are carried out in the step F, the rotation speed of the emulsifying machine is 9000-11000 rpm when emulsification is carried out; and is also provided with
F, the defoaming planetary mixing is carried out in the mode that the second mixture after emulsification and homogenization is placed into a planetary mixer for defoaming planetary mixing operation; wherein, the air suction is carried out in the inner barrel to finish the treatment of the second mixture; and is also provided with
In the deaeration planetary mixing in the step F, the rotation speed of the planetary mixer was 0rpm, and the revolution speed was 30rpm for 30 minutes.
10. The method for producing a multi-layer long-circulating silicon-carbon anode material according to claim 1, wherein: in the step G, the proportion of the coating agent in the second masterbatch is 2-6.8 wt%, and the rest is solvent; wherein the weight ratio of the oligosaccharide macromolecule to the oligosaccharide ketone is 3-6: 1, a step of; wherein the weight ratio of the carbon nanotube to the second masterbatch is as follows: the carbon nano-tube accounts for 0.1-0.18 wt% and the balance is the second masterbatch.
11. The method for producing a multi-layer long-circulating silicon-carbon anode material according to claim 1, wherein: the spray drying operation in the step J is carried out by firstly placing the fourth mixture into an inner barrel of the planetary mixer for mixing, and after a preset time, pumping the fourth mixture to a four-fluid nozzle by a pump to spray to form spray; wherein the fourth mixture is thermally baked inside the four fluid ejection head; thus forming the silicon-carbon composite structure mixture.
12. The method for producing a multi-layer long-circulating silicon-carbon anode material according to claim 11, wherein: in the spray drying operation in the step J, the rotation speed of the planetary mixer was 0rpm, and the revolution speed was 10rpm; then pumping the fourth mixture to the four fluid nozzle after 2-4 hours; wherein the air pressure of the four fluid ejection heads is 3kg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the temperature of the interior of the four fluid spray heads for heat drying is 170-185 ℃, and the temperature of the interior of the four fluid spray heads for heat drying is 150-160 ℃.
13. The method for producing a multi-layer long-circulating silicon-carbon anode material according to claim 1, wherein: the particle size D50 of the silicon-carbon composite structure mixture is 3-10 microns, namely 50% of the silicon-carbon composite structure mixture has the particle size of 3-10 microns.
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