CN114613545A - Preparation method of composite conductive slurry with excellent electrical property - Google Patents
Preparation method of composite conductive slurry with excellent electrical property Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 58
- 239000002002 slurry Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 109
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 61
- 239000010439 graphite Substances 0.000 claims abstract description 61
- 239000011521 glass Substances 0.000 claims abstract description 58
- 239000011324 bead Substances 0.000 claims abstract description 51
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 51
- 239000006185 dispersion Substances 0.000 claims abstract description 49
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 229910021426 porous silicon Inorganic materials 0.000 claims abstract description 37
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 46
- 229910001416 lithium ion Inorganic materials 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 46
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical class [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 45
- 238000005530 etching Methods 0.000 claims description 45
- 238000000227 grinding Methods 0.000 claims description 45
- 238000001035 drying Methods 0.000 claims description 38
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 27
- 238000004140 cleaning Methods 0.000 claims description 27
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 27
- 229910052710 silicon Inorganic materials 0.000 claims description 27
- 239000010703 silicon Substances 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000002270 dispersing agent Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 18
- 238000009210 therapy by ultrasound Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000012530 fluid Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000138 intercalating agent Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 229920000128 polypyrrole Polymers 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 238000010008 shearing Methods 0.000 claims description 9
- 239000004005 microsphere Substances 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 5
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229940116411 terpineol Drugs 0.000 claims description 5
- -1 graphite alkene Chemical class 0.000 abstract description 13
- 239000007772 electrode material Substances 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 4
- 239000002052 molecular layer Substances 0.000 abstract description 4
- 238000005253 cladding Methods 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/18—Conductive material dispersed in non-conductive inorganic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a preparation method of composite conductive slurry with excellent electrical property, which comprises the following steps: the preparation method comprises the following steps of pretreatment of graphite, preparation of compound dispersion liquid, preparation of porous silicon, preparation of modified glass beads coated by graphene oxide, preparation of primary slurry and preparation of conductive slurry. Through at glass bead surface cladding graphite oxide alkene, glass bead and graphite alkene compatibility between the two are better, make graphite alkene and glass bead dispersion more even in the system, the phenomenon that glass bead and graphite alkene reunite respectively is difficult for appearing, the thick liquids performance is more even stable, the deuterogamy forms the compound conductive paste for the lithium cell through high-pressure pulse jet technology, adopt mechanical stripping technique can furthest's remain graphite alkene and molybdenum disulfide layer piece integrality, keep its higher conducting capacity, effectively prevent piling up again of nanolayer simultaneously, can promote electric conductivity by a wide margin, improve electrode material surface area rate of utilization, solve, the cyclic electric capacity low grade defect reunion.
Description
Technical Field
The invention relates to the technical field of electrodes, in particular to a preparation method of composite conductive slurry with excellent electrical property.
Background
A lithium battery is a type of battery using a non-aqueous electrolyte solution, with lithium metal or a lithium alloy as a positive/negative electrode material. Lithium metal batteries were first proposed and studied by Gilbert n.lewis in 1912. In the 70 s of the 20 th century, m.s.whitetingham proposed and began to study lithium ion batteries. Because the chemical characteristics of lithium metal are very active, the requirements on the environment for processing, storing and using the lithium metal are very high. In recent decades, with the wide application and rapid development of various portable electronic devices and electric vehicles, the demand and performance requirements for a chemical power source, which is a power system, have been increased rapidly, and lithium batteries have become mainstream due to their advantages such as high power characteristics and their wide application in the field of mobile electronic terminal devices. Meanwhile, the graphene has the advantages of large theoretical specific surface area, outstanding mechanical property and thermal conductivity, high conductivity at room temperature and the like, and has low cost and good processability, so that the graphene has potential application prospects in various fields such as nano electronic devices, sensors, hydrogen storage materials, lithium batteries, super capacitors and the like.
However, since the graphene slurry or powder is unstable and easy to agglomerate and the nanolayers are easy to re-stack in the storage and use processes, the electrical conductivity of the electrode material is reduced, and the surface area utilization rate of the electrode material is reduced, so that the performance advantages of high specific surface area, high electrical conductivity and high thermal conductivity of the graphene material cannot be fully achieved. Therefore, there is a need to provide a new conductive paste method to improve the above-mentioned drawbacks.
Disclosure of Invention
In view of the above, the present invention is directed to the defects existing in the prior art, and a main object of the present invention is to provide a method for preparing a composite conductive paste with excellent electrical properties, wherein the composite conductive paste is easy to agglomerate, and a nanolayer is not piled up again, so that the electrical conductivity of an electrode material is greatly improved, and the utilization rate of the surface area of the electrode material is improved, so that the performance advantages of the graphene material, such as high specific surface area, high electrical conductivity and high thermal conductivity, can be fully utilized.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of composite conductive paste with excellent electrical property comprises the following steps:
(1) pretreatment of graphite
Placing graphite in a mixed solution composed of an oxidant and an intercalator, performing ultrasonic stirring treatment for 0.5-5h at 20-60 ℃, washing, filtering and drying the obtained product, placing the obtained product in a muffle furnace, treating the product for 0.1-6h at 600-1200 ℃ in a nitrogen atmosphere to obtain an expanded graphite product, placing the expanded graphite product, lithium ions or magnesium ion salts and molybdenum disulfide in a reaction kettle, continuously stirring, heating to 600-800 ℃, and keeping the temperature for 1-12h to obtain a graphite-molybdenum disulfide compound intercalated by the lithium ions or the magnesium ions;
(2) preparation of Compound Dispersion
Dissolving the graphite-molybdenum disulfide compound intercalated with lithium ions or magnesium ions obtained in the step (1) in an organic solvent, and carrying out ultrasonic treatment for 0.5-2h to obtain a compound dispersion liquid;
(3) preparation of porous silicon
Cleaning and drying a silicon wafer by using a cleaning solution and deionized water in sequence, putting the dried silicon wafer into an etching solution for etching treatment, wherein the etching current is 10-15A, the etching time is 30-50 minutes, and cleaning and drying the silicon wafer by using deionized water after etching is finished to obtain porous silicon;
(4) preparation of modified glass beads coated with graphene oxide
Adding the modified glass beads into the graphene oxide dispersion liquid, stirring, standing, filtering, washing and drying to obtain modified glass beads coated by graphene oxide;
(5) preparation of preliminary slurry
Placing the porous silicon obtained in the step (3), the modified glass microspheres coated by the graphene oxide in the step (4) and the grinding balls in a grinding tank according to the mass ratio of (1-50) to 1, adding a dispersing agent, vacuumizing the system by using a vacuum pump, and introducing a protective atmosphere; stirring and grinding at the system temperature of-50-0 ℃, adding a carbon binder after grinding for 0.5-5h, and continuously stirring and grinding for 0.5-1 h; then adding compound dispersion liquid, and carrying out ultrasonic treatment for 0.1-3h to obtain primary slurry;
(6) preparation of electroconductive paste
And (3) adding the primary slurry obtained in the step (5) into a high-pressure pulse jet machine, controlling the driving pressure to be 70-100MPa, adopting a counter-jet device, accelerating the primary slurry in jet fluid, enabling the particles of the graphite-molybdenum disulfide compound intercalated by the lithium ions or the magnesium ions to collide at high speed, and shearing and stripping to obtain the composite conductive slurry for the lithium battery.
Preferably, the mass ratio of the compound dispersion liquid to the modified glass microspheres coated by porous silicon and graphene oxide is (1-50): 0.5-0.8.
Preferably, the organic solvent is one or more of N-methylpyrrolidone (NMP), Ethylene Glycol (EG), N-butanol and terpineol.
Preferably, the mass ratio of the lithium ion or magnesium ion salt, the molybdenum disulfide and the expanded graphite product is (3-12): (38-49): 52.
As a preferable mode, the dispersant in the step (5) is polypyrrole.
Compared with the prior art, the invention has obvious advantages and beneficial effects, and specifically, the technical scheme includes that:
through at glass bead surface cladding graphite oxide alkene, glass bead and graphite alkene compatibility between the two are better, make graphite alkene and glass bead dispersion more even in the system, the phenomenon that glass bead and graphite alkene reunite respectively is difficult for appearing, the thick liquids performance is more even stable, the deuterogamy forms the compound conductive paste for the lithium cell through high-pressure pulse jet technology, adopt mechanical stripping technique can furthest's remain graphite alkene and molybdenum disulfide layer piece integrality, keep its higher conducting capacity, effectively prevent piling up again of nanolayer simultaneously, can promote electric conductivity by a wide margin, improve electrode material surface area rate of utilization, solve, the cyclic electric capacity low grade defect reunion.
To more clearly illustrate the features and effects of the present invention, the present invention is described in detail below with reference to specific examples.
Detailed Description
The invention discloses a preparation method of composite conductive paste with excellent electrical property, which comprises the following steps:
(1) pretreatment of graphite
Placing graphite in a mixed solution composed of an oxidant and an intercalator, performing ultrasonic stirring treatment for 0.5-5h at 20-60 ℃, washing, filtering and drying the obtained product, placing the obtained product in a muffle furnace, treating the product for 0.1-6h at 600-1200 ℃ in a nitrogen atmosphere to obtain an expanded graphite product, placing the expanded graphite product, lithium ions or magnesium ion salts and molybdenum disulfide in a reaction kettle, continuously stirring, heating to 600-800 ℃, and keeping the temperature for 1-12h to obtain a graphite-molybdenum disulfide compound intercalated by the lithium ions or the magnesium ions; the mass ratio of the lithium ion or magnesium ion salt, the molybdenum disulfide and the expanded graphite product is (3-12): 38-49): 52.
(2) Preparation of Compound Dispersion
Dissolving the graphite-molybdenum disulfide compound intercalated with lithium ions or magnesium ions obtained in the step (1) in an organic solvent, and carrying out ultrasonic treatment for 0.5-2h to obtain a compound dispersion liquid; the organic solvent is one or more of N-methyl pyrrolidone (NMP), Ethylene Glycol (EG), N-butanol and terpineol.
(3) Preparation of porous silicon
Cleaning and drying a silicon wafer by using a cleaning solution and deionized water in sequence, putting the dried silicon wafer into an etching solution for etching treatment, wherein the etching current is 10-15A, the etching time is 30-50 minutes, and cleaning and drying the silicon wafer by using deionized water after etching is finished to obtain porous silicon.
(4) Preparation of modified glass beads coated with graphene oxide
And adding the modified glass beads into the graphene oxide dispersion liquid, stirring, standing, filtering, washing and drying to obtain the modified glass beads coated by the graphene oxide.
(5) Preparation of preliminary slurry
Placing the porous silicon obtained in the step (3), the modified glass microspheres coated by the graphene oxide in the step (4) and the grinding balls in a grinding tank according to the mass ratio of (1-50) to 1, adding a dispersing agent, vacuumizing the system by using a vacuum pump, and introducing a protective atmosphere; stirring and grinding at the system temperature of-50-0 ℃, adding a carbon binder after grinding for 0.5-5h, and continuously stirring and grinding for 0.5-1 h; then adding compound dispersion liquid, and carrying out ultrasonic treatment for 0.1-3h to obtain primary slurry; the mass ratio of the compound dispersion liquid to the modified glass microspheres coated by the porous silicon and the graphene oxide is (1-50): 0.5-0.8; the dispersant is polypyrrole.
(6) Preparation of electroconductive paste
And (3) adding the primary slurry obtained in the step (5) into a high-pressure pulse jet machine, controlling the driving pressure to be 70-100MPa, adopting a counter-jet device, accelerating the primary slurry in jet fluid, enabling the particles of the graphite-molybdenum disulfide compound intercalated by the lithium ions or the magnesium ions to collide at high speed, and shearing and stripping to obtain the composite conductive slurry for the lithium battery.
Example 1
(1) Pretreatment of graphite
Placing graphite in a mixed solution composed of an oxidant and an intercalator, performing ultrasonic stirring treatment for 5 hours at the temperature of 20 ℃, washing, filtering and drying the obtained product, placing the obtained product in a muffle furnace, treating the product for 6 hours at the high temperature of 600 ℃ in a nitrogen atmosphere to obtain an expanded graphite product, placing the expanded graphite product, lithium ions or magnesium ion salts and molybdenum disulfide in a reaction kettle, continuously stirring, heating to 600 ℃, and keeping the temperature for 12 hours to obtain a graphite-molybdenum disulfide compound intercalated by the lithium ions or the magnesium ions; the mass ratio of the lithium ions or magnesium ions salts, the molybdenum disulfide and the expanded graphite product is 3:38: 52.
(2) Preparation of Compound Dispersion
Dissolving the graphite-molybdenum disulfide compound intercalated with lithium ions or magnesium ions obtained in the step (1) in an organic solvent, and carrying out ultrasonic treatment for 0.5h to obtain a compound dispersion liquid; the organic solvent is N-methylpyrrolidone (NMP).
(3) Preparation of porous silicon
And cleaning and drying the silicon wafer by using a cleaning solution and deionized water in sequence, putting the dried silicon wafer into an etching solution for etching treatment, wherein the etching current is 12A, the etching time is 40 minutes, and cleaning and drying the silicon wafer by using the deionized water after etching is finished to obtain the porous silicon.
(4) Preparation of modified glass beads coated with graphene oxide
And adding the modified glass beads into the graphene oxide dispersion liquid, stirring, standing, filtering, washing and drying to obtain the modified glass beads coated by the graphene oxide.
(5) Preparation of preliminary slurry
Placing the porous silicon obtained in the step (3), the modified glass beads coated by the graphene oxide obtained in the step (4) and the grinding balls in a grinding tank according to the mass ratio of 26:21:1, adding a dispersing agent, vacuumizing the system by using a vacuum pump, and introducing a protective atmosphere; stirring and grinding at the system temperature of-30 ℃, adding a carbon binder after grinding for 4 hours, and continuously stirring and grinding for 0.7 hour; then adding a compound dispersion liquid, and carrying out ultrasonic treatment for 0.3h to obtain primary slurry; the mass ratio of the compound dispersion liquid to the modified glass beads coated with porous silicon and graphene oxide is 26:21: 0.6; the dispersant is polypyrrole.
(6) Preparation of electroconductive paste
And (3) adding the primary slurry obtained in the step (5) into a high-pressure pulse jet machine, controlling the driving pressure to be 80MPa, adopting an opposite jet device, accelerating the primary slurry in jet fluid, enabling the particles of the graphite-molybdenum disulfide compound intercalated by the lithium ions or the magnesium ions to collide at high speed, and shearing and stripping to obtain the composite conductive slurry for the lithium battery.
Example 2
(1) Pretreatment of graphite
Placing graphite in a mixed solution composed of an oxidant and an intercalator, performing ultrasonic stirring treatment for 0.5h at 60 ℃, washing, filtering and drying the obtained product, placing the obtained product in a muffle furnace, treating for 0.1h at 1200 ℃ in a nitrogen atmosphere to obtain an expanded graphite product, placing the expanded graphite product, lithium ions or magnesium ion salts and molybdenum disulfide in a reaction kettle, continuously stirring, heating to 800 ℃, and keeping the temperature for 1h to obtain a graphite-molybdenum disulfide compound intercalated by the lithium ions or the magnesium ions; the mass ratio of the lithium ions or magnesium ion salts, the molybdenum disulfide and the expanded graphite product is 12:49: 52.
(2) Preparation of Compound Dispersion
Dissolving the graphite-molybdenum disulfide compound intercalated with lithium ions or magnesium ions obtained in the step (1) in an organic solvent, and carrying out ultrasonic treatment for 2 hours to obtain a compound dispersion liquid; the organic solvent is Ethylene Glycol (EG).
(3) Preparation of porous silicon
And cleaning and drying the silicon wafer by using a cleaning solution and deionized water in sequence, putting the dried silicon wafer into an etching solution for etching treatment, wherein the etching current is 11A, the etching time is 35 minutes, and cleaning and drying the silicon wafer by using the deionized water after etching is finished to obtain the porous silicon.
(4) Preparation of modified glass beads coated with graphene oxide
And adding the modified glass beads into the graphene oxide dispersion liquid, stirring, standing, filtering, washing and drying to obtain the modified glass beads coated by the graphene oxide.
(5) Preparation of preliminary slurry
Placing the porous silicon obtained in the step (3), the modified glass beads coated by the graphene oxide obtained in the step (4) and the grinding balls in a grinding tank according to the mass ratio of 13:28:1, adding a dispersing agent, vacuumizing the system by using a vacuum pump, and introducing a protective atmosphere; stirring and grinding at the system temperature of-36 ℃, adding a carbon binder after grinding for 1.5h, and continuously stirring and grinding for 0.9 h; then adding a compound dispersion liquid, and carrying out ultrasonic treatment for 2.1h to obtain primary slurry; the mass ratio of the compound dispersion liquid to the modified glass beads coated with porous silicon and graphene oxide is 13:28: 0.7; the dispersant is polypyrrole.
(6) Preparation of electroconductive paste
And (3) adding the primary slurry obtained in the step (5) into a high-pressure pulse jet machine, controlling the driving pressure to be 90MPa, adopting an opposite jet device, accelerating the primary slurry in jet fluid, enabling the particles of the graphite-molybdenum disulfide compound intercalated by the lithium ions or the magnesium ions to collide at high speed, and shearing and stripping to obtain the composite conductive slurry for the lithium battery.
Example 3
(1) Pretreatment of graphite
Placing graphite in a mixed solution composed of an oxidant and an intercalator, performing ultrasonic stirring treatment for 2.6 hours at 30 ℃, washing, filtering and drying the obtained product, placing the obtained product in a muffle furnace, treating the product for 0.6 hour at 650 ℃ in a nitrogen atmosphere to obtain an expanded graphite product, placing the expanded graphite product, lithium ions or magnesium ion salts and molybdenum disulfide in a reaction kettle, continuously stirring, heating to 700 ℃, and keeping the temperature for 10 hours to obtain a graphite-molybdenum disulfide compound intercalated by the lithium ions or the magnesium ions; the mass ratio of the lithium ion or magnesium ion salt, the molybdenum disulfide and the expanded graphite product is 10:41: 52.
(2) Preparation of Compound Dispersion
Dissolving the graphite-molybdenum disulfide compound intercalated with lithium ions or magnesium ions obtained in the step (1) in an organic solvent, and performing ultrasonic treatment for 1.7h to obtain a compound dispersion liquid; the organic solvent is n-butanol.
(3) Preparation of porous silicon
Cleaning and drying a silicon wafer by using a cleaning solution and deionized water in sequence, placing the dried silicon wafer into an etching solution for etching treatment, wherein the etching current is 10A, the etching time is 50 minutes, and cleaning and drying the silicon wafer by using deionized water after etching is finished to obtain porous silicon.
(4) Preparation of modified glass beads coated with graphene oxide
And adding the modified glass beads into the graphene oxide dispersion liquid, stirring, standing, filtering, washing and drying to obtain the modified glass beads coated by the graphene oxide.
(5) Preparation of preliminary slurry
Placing the porous silicon obtained in the step (3), the modified glass beads coated by the graphene oxide obtained in the step (4) and the grinding balls in a grinding tank according to the mass ratio of 47:32:1, adding a dispersing agent, vacuumizing the system by using a vacuum pump, and introducing a protective atmosphere; stirring and grinding at the system temperature of-28 ℃, adding a carbon binder after grinding for 0.8h, and continuously stirring and grinding for 0.6 h; then adding a compound dispersion liquid, and carrying out ultrasonic treatment for 0.3h to obtain primary slurry; the mass ratio of the compound dispersion liquid to the modified glass beads coated with porous silicon and graphene oxide is 47:32: 0.7; the dispersant is polypyrrole.
(6) Preparation of electroconductive paste
And (3) adding the primary slurry obtained in the step (5) into a high-pressure pulse jet machine, controlling the driving pressure to be 78MPa, adopting a counter-jet device, accelerating the primary slurry in jet fluid, enabling the particles of the graphite-molybdenum disulfide compound intercalated by the lithium ions or the magnesium ions to collide at high speed, and shearing and stripping to obtain the composite conductive slurry for the lithium battery.
Example 4
(1) Pretreatment of graphite
Placing graphite in a mixed solution composed of an oxidant and an intercalator, performing ultrasonic stirring treatment for 3.5 hours at 54 ℃, washing, filtering and drying the obtained product, placing the product in a muffle furnace, treating the product for 5 hours at 930 ℃ in a nitrogen atmosphere to obtain an expanded graphite product, placing the expanded graphite product, lithium ions or magnesium ion salts and molybdenum disulfide in a reaction kettle, continuously stirring, heating to 700 ℃, and keeping the temperature for 10 hours to obtain a lithium ion or magnesium ion intercalated graphite-molybdenum disulfide compound; the mass ratio of the lithium ions or magnesium ion salts, the molybdenum disulfide and the expanded graphite product is 11:43: 52.
(2) Preparation of Compound Dispersion
Dissolving the graphite-molybdenum disulfide compound intercalated with lithium ions or magnesium ions obtained in the step (1) in an organic solvent, and performing ultrasonic treatment for 1.8 hours to obtain a compound dispersion liquid; the organic solvent is terpineol.
(3) Preparation of porous silicon
And cleaning and drying the silicon wafer by using a cleaning solution and deionized water in sequence, putting the dried silicon wafer into an etching solution for etching treatment, wherein the etching current is 15A, the etching time is 50 minutes, and cleaning and drying the silicon wafer by using the deionized water after etching is finished to obtain the porous silicon.
(4) Preparation of modified glass beads coated with graphene oxide
And adding the modified glass beads into the graphene oxide dispersion liquid, stirring, standing, filtering, washing and drying to obtain the modified glass beads coated by the graphene oxide.
(5) Preparation of preliminary slurry
Placing the porous silicon obtained in the step (3), the modified glass microspheres coated with the graphene oxide in the step (4) and the grinding balls in a mass ratio of 17:42:1 into a grinding tank, adding a dispersing agent, vacuumizing the system by using a vacuum pump, and introducing protective atmosphere; stirring and grinding at the system temperature of-50-0 ℃, adding a carbon binder after grinding for 0.5-5h, and continuously stirring and grinding for 0.5-1 h; then adding compound dispersion liquid, and carrying out ultrasonic treatment for 0.1-3h to obtain primary slurry; the mass ratio of the compound dispersion liquid to the modified glass beads coated with porous silicon and graphene oxide is 17:42: 0.65; the dispersant is polypyrrole.
(6) Preparation of electroconductive paste
And (3) adding the primary slurry obtained in the step (5) into a high-pressure pulse jet machine, controlling the driving pressure to be 86MPa, adopting a counter-jet device, accelerating the primary slurry in jet fluid, enabling the particles of the graphite-molybdenum disulfide compound intercalated by the lithium ions or the magnesium ions to collide at high speed, and shearing and stripping to obtain the composite conductive slurry for the lithium battery.
Example 5
(1) Pretreatment of graphite
Placing graphite in a mixed solution composed of an oxidant and an intercalator, performing ultrasonic stirring treatment for 3.7h at 56 ℃, washing, filtering and drying the obtained product, placing the obtained product in a muffle furnace, treating the product for 3h at 1100 ℃ in a nitrogen atmosphere to obtain an expanded graphite product, placing the expanded graphite product, lithium ions or magnesium ion salts and molybdenum disulfide in a reaction kettle, continuously stirring, heating to 680 ℃, and keeping the temperature for 9.5h to obtain a graphite-molybdenum disulfide compound intercalated by the lithium ions or the magnesium ions; the mass ratio of the lithium ions or magnesium ion salts, the molybdenum disulfide and the expanded graphite product is 6:47: 52.
(2) Preparation of Compound Dispersion
Dissolving the graphite-molybdenum disulfide compound intercalated with lithium ions or magnesium ions obtained in the step (1) in an organic solvent, and performing ultrasonic treatment for 1.6h to obtain a compound dispersion liquid; the organic solvent is N-methylpyrrolidone (NMP).
(3) Preparation of porous silicon
And cleaning and drying the silicon wafer by using a cleaning solution and deionized water in sequence, putting the dried silicon wafer into an etching solution for etching treatment, wherein the etching current is 11A, the etching time is 36 minutes, and cleaning and drying the silicon wafer by using the deionized water after etching is finished to obtain the porous silicon.
(4) Preparation of modified glass beads coated with graphene oxide
And adding the modified glass beads into the graphene oxide dispersion liquid, stirring, standing, filtering, washing and drying to obtain the modified glass beads coated by the graphene oxide.
(5) Preparation of preliminary slurry
Placing the porous silicon obtained in the step (3), the modified glass beads coated by the graphene oxide obtained in the step (4) and the grinding balls in a grinding tank according to the mass ratio of 1:50:1, adding a dispersing agent, vacuumizing the system by using a vacuum pump, and introducing a protective atmosphere; stirring and grinding at the system temperature of-50 ℃, adding a carbon binder after grinding for 5 hours, and continuously stirring and grinding for 1 hour; then adding a compound dispersion liquid, and carrying out ultrasonic treatment for 3h to obtain a primary slurry; the mass ratio of the compound dispersion liquid to the modified glass beads coated with porous silicon and graphene oxide is 1:50: 0.5; the dispersant is polypyrrole.
(6) Preparation of electroconductive paste
And (3) adding the primary slurry obtained in the step (5) into a high-pressure pulse jet machine, controlling the driving pressure to be 70MPa, adopting an opposite jet device, accelerating the primary slurry in jet fluid, enabling the particles of the graphite-molybdenum disulfide compound intercalated by the lithium ions or the magnesium ions to collide at high speed, and shearing and stripping to obtain the composite conductive slurry for the lithium battery.
Example 6
(1) Pretreatment of graphite
Placing graphite in a mixed solution composed of an oxidant and an intercalator, performing ultrasonic stirring treatment for 1.5h at 51 ℃, washing, filtering and drying the obtained product, placing the obtained product in a muffle furnace, treating the product for 3.8h at 840 ℃ in a nitrogen atmosphere to obtain an expanded graphite product, placing the expanded graphite product, lithium ions or magnesium ion salts and molybdenum disulfide in a reaction kettle, continuously stirring, heating to 700 ℃, and keeping the temperature for 10h to obtain a graphite-molybdenum disulfide compound intercalated by the lithium ions or the magnesium ions; the mass ratio of the lithium ion or magnesium ion salt, the molybdenum disulfide and the expanded graphite product is 4:39: 52.
(2) Preparation of Compound Dispersion
Dissolving the graphite-molybdenum disulfide compound intercalated with lithium ions or magnesium ions obtained in the step (1) in an organic solvent, and performing ultrasonic treatment for 1.2h to obtain a compound dispersion liquid; the organic solvent is terpineol.
(3) Preparation of porous silicon
And cleaning and drying the silicon wafer by using a cleaning solution and deionized water in sequence, putting the dried silicon wafer into an etching solution for etching treatment, wherein the etching current is 13A, the etching time is 45 minutes, and cleaning and drying the silicon wafer by using the deionized water after etching is finished to obtain the porous silicon.
(4) Preparation of modified glass beads coated with graphene oxide
And adding the modified glass beads into the graphene oxide dispersion liquid, stirring, standing, filtering, washing and drying to obtain the modified glass beads coated by the graphene oxide.
(5) Preparation of preliminary slurry
Placing the porous silicon obtained in the step (3), the modified glass beads coated by the graphene oxide obtained in the step (4) and the grinding balls in a grinding tank according to the mass ratio of 50:1:1, adding a dispersing agent, vacuumizing the system by using a vacuum pump, and introducing a protective atmosphere; stirring and grinding at the system temperature of 0 ℃, adding a carbon binder after grinding for 5 hours, and continuously stirring and grinding for 1 hour; then adding a compound dispersion liquid, and carrying out ultrasonic treatment for 3h to obtain a primary slurry; the mass ratio of the compound dispersion liquid to the modified glass beads coated with porous silicon and graphene oxide is 50:1: 0.8; the dispersant is polypyrrole.
(6) Preparation of electroconductive paste
And (3) adding the primary slurry obtained in the step (5) into a high-pressure pulse jet machine, controlling the driving pressure to be 100MPa, adopting an opposite jet device, accelerating the primary slurry in jet fluid, enabling the particles of the graphite-molybdenum disulfide compound intercalated by the lithium ions or the magnesium ions to collide at high speed, and shearing and stripping to obtain the composite conductive slurry for the lithium battery.
Performance testing
And stirring and diluting the composite conductive slurry for the lithium battery into uniform paste, and coating the paste on foamed nickel to form the negative plate. And (3) drying the pole piece in a vacuum drying oven at 80 ℃, tabletting on a tabletting machine under the pressure of 10MPa, and drying the pole piece in a vacuum drying oven at 120 ℃ for 12 hours. And transferring the dried pole piece into a glove box, taking a metal lithium piece as a counter electrode, and assembling the metal lithium piece into a simulated button cell in the glove box filled with dry argon. The diaphragm is a porous polypropylene film, and the electrolyte is LiPF with the concentration of 1mol/L6A solution in which the electrolyte solvent is a mixed solvent of Ethylene Carbonate (EC) and diethyl carbonate (DEC). And testing the charge and discharge performance of the battery under different conditions by using a Land battery tester. The charging and discharging voltage test range is 0-2V, and the cycle number is 100 cycles. The test results are shown in table 1.
TABLE 1
The design of the invention is characterized in that: through at glass bead surface cladding graphite oxide, compatibility between glass bead and the graphite alkene is better, make graphite alkene and glass bead dispersion more even in the system, the phenomenon that glass bead and graphite alkene reunite respectively is difficult for appearing, the thick liquids performance is more even stable, it forms the compound conductive paste for the lithium cell through the high-voltage pulse efflux technique to cooperate again, adopt mechanical stripping technique can furthest remain graphite alkene and molybdenum disulfide lamella integrality, keep its higher conducting capacity, effectively prevent piling up again of nanolayer simultaneously, can promote electric conductivity by a wide margin, improve electrode material surface area rate of utilization, solve the reunion, defects such as cyclic capacitance low.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that any minor modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the technical scope of the present invention.
Claims (5)
1. A preparation method of composite conductive paste with excellent electrical property is characterized by comprising the following steps: the method comprises the following steps:
(1) pretreatment of graphite
Placing graphite in a mixed solution composed of an oxidant and an intercalator, performing ultrasonic stirring treatment for 0.5-5h at 20-60 ℃, washing, filtering and drying the obtained product, placing the obtained product in a muffle furnace, treating the product for 0.1-6h at 600-1200 ℃ in a nitrogen atmosphere to obtain an expanded graphite product, placing the expanded graphite product, lithium ions or magnesium ion salts and molybdenum disulfide in a reaction kettle, continuously stirring, heating to 600-800 ℃, and keeping the temperature for 1-12h to obtain a graphite-molybdenum disulfide compound intercalated by the lithium ions or the magnesium ions;
(2) preparation of Compound Dispersion
Dissolving the graphite-molybdenum disulfide compound intercalated with lithium ions or magnesium ions obtained in the step (1) in an organic solvent, and carrying out ultrasonic treatment for 0.5-2h to obtain a compound dispersion liquid;
(3) preparation of porous silicon
Cleaning and drying a silicon wafer by using a cleaning solution and deionized water in sequence, putting the dried silicon wafer into an etching solution for etching treatment, wherein the etching current is 10-15A, the etching time is 30-50 minutes, and cleaning and drying the silicon wafer by using deionized water after etching is finished to obtain porous silicon;
(4) preparation of modified glass beads coated with graphene oxide
Adding the modified glass beads into the graphene oxide dispersion liquid, stirring, standing, filtering, washing and drying to obtain modified glass beads coated by graphene oxide;
(5) preparation of preliminary slurry
Placing the porous silicon obtained in the step (3), the modified glass microspheres coated by the graphene oxide in the step (4) and the grinding balls in a grinding tank according to the mass ratio of (1-50) to 1, adding a dispersing agent, vacuumizing the system by using a vacuum pump, and introducing a protective atmosphere; stirring and grinding at the system temperature of-50-0 ℃, adding a carbon binder after grinding for 0.5-5h, and continuously stirring and grinding for 0.5-1 h; then adding compound dispersion liquid, and carrying out ultrasonic treatment for 0.1-3h to obtain primary slurry;
(6) preparation of electroconductive paste
And (3) adding the primary slurry obtained in the step (5) into a high-pressure pulse jet machine, controlling the driving pressure to be 70-100MPa, adopting a counter-jet device, accelerating the primary slurry in jet fluid, enabling the particles of the graphite-molybdenum disulfide compound intercalated by the lithium ions or the magnesium ions to collide at high speed, and shearing and stripping to obtain the composite conductive slurry for the lithium battery.
2. The method of preparing a composite conductive paste having excellent electrical properties as claimed in claim 1, wherein: the mass ratio of the compound dispersion liquid to the modified glass microspheres coated by the porous silicon and the graphene oxide is (1-50): (1-50): 0.5-0.8.
3. The method of preparing a composite conductive paste having excellent electrical properties as claimed in claim 1, wherein: the organic solvent is one or more of N-methyl pyrrolidone (NMP), Ethylene Glycol (EG), N-butanol and terpineol.
4. The method of claim 1, wherein the composite conductive paste has excellent electrical properties, and the method comprises the steps of: the mass ratio of the lithium ion or magnesium ion salt, the molybdenum disulfide and the expanded graphite product is (3-12): 38-49): 52.
5. The method of preparing a composite conductive paste having excellent electrical properties as claimed in claim 1, wherein: the dispersant in the step (5) is polypyrrole.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106025202A (en) * | 2016-05-25 | 2016-10-12 | 福建翔丰华新能源材料有限公司 | Preparation method of silicon-graphene compound conductive paste |
| CN106384827A (en) * | 2016-10-19 | 2017-02-08 | 成都新柯力化工科技有限公司 | Graphene-molybdenum disulfide composite conductive paste for lithium battery and preparation method thereof |
| CN109256546A (en) * | 2018-09-03 | 2019-01-22 | 山西煤炭进出口集团科学技术研究院有限公司 | A kind of molybdenum disulfide/graphene composite material and its preparation method and application |
| CN112750992A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Molybdenum disulfide/titanium dioxide/graphene composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106025202A (en) * | 2016-05-25 | 2016-10-12 | 福建翔丰华新能源材料有限公司 | Preparation method of silicon-graphene compound conductive paste |
| CN106384827A (en) * | 2016-10-19 | 2017-02-08 | 成都新柯力化工科技有限公司 | Graphene-molybdenum disulfide composite conductive paste for lithium battery and preparation method thereof |
| CN109256546A (en) * | 2018-09-03 | 2019-01-22 | 山西煤炭进出口集团科学技术研究院有限公司 | A kind of molybdenum disulfide/graphene composite material and its preparation method and application |
| CN112750992A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Molybdenum disulfide/titanium dioxide/graphene composite material |
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