CN115224242A - Preparation method and application of lithium battery positive plate - Google Patents
Preparation method and application of lithium battery positive plate Download PDFInfo
- Publication number
- CN115224242A CN115224242A CN202210659559.XA CN202210659559A CN115224242A CN 115224242 A CN115224242 A CN 115224242A CN 202210659559 A CN202210659559 A CN 202210659559A CN 115224242 A CN115224242 A CN 115224242A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- core
- magnetic
- solution
- shell structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011258 core-shell material Substances 0.000 claims abstract description 34
- 239000007774 positive electrode material Substances 0.000 claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 239000011267 electrode slurry Substances 0.000 claims abstract description 22
- 229920000767 polyaniline Polymers 0.000 claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 239000006258 conductive agent Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000011084 recovery Methods 0.000 claims abstract description 13
- 238000004064 recycling Methods 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims abstract description 8
- 230000009286 beneficial effect Effects 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 6
- 230000005012 migration Effects 0.000 claims abstract description 6
- 238000013508 migration Methods 0.000 claims abstract description 6
- 238000004904 shortening Methods 0.000 claims abstract description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 239000006249 magnetic particle Substances 0.000 claims description 15
- 239000000839 emulsion Substances 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 12
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 239000010405 anode material Substances 0.000 claims description 3
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- 238000007885 magnetic separation Methods 0.000 claims description 2
- 230000001737 promoting effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 230000008595 infiltration Effects 0.000 abstract 1
- 238000001764 infiltration Methods 0.000 abstract 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 17
- 239000006256 anode slurry Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- 239000012467 final product Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
-
- 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
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M2004/028—Positive 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method and application of a lithium battery positive plate, which comprises the following specific steps: using polyaniline as shell and Fe 3 O 4 Uniformly mixing a core-shell structure magnetic nano template serving as a core with a positive electrode material, a binder, a conductive agent and a solvent NMP to prepare positive electrode slurry, coating the positive electrode slurry on the surface of a current collector, then loading a magnetic field to ensure that the core-shell structure magnetic nano template is directionally assembled on the surface of the current collector, finally recovering and recycling the core-shell structure magnetic nano template in a thick electrode through a magnetic recovery device, and simultaneously constructing a three-dimensional network channel with high conductivity in the thick electrode for effectively improving the conductivity of the electrode, shortening the migration path of ions and electrons and providing a multidimensional migration pathThe infiltration channel is opened, the wettability of electrolyte is enhanced, the tortuosity of the electrode is reduced, the gradient porosity is generated, a molecular channel which is beneficial to lithium ion transportation is formed, and the high-speed conduction of lithium ions is promoted.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method and application of a lithium battery positive plate.
Background
With the use of high-power and high-energy devices such as electric bicycles and electric automobiles, people have made higher and higher demands on the energy density and power density of lithium ion batteries. In particular, extremely fast charging (i.e. up to 80% storage capacity in 15 min) is an urgent requirement for the development of current lithium ion battery technology, which also impacts the planning of the charging infrastructure. An extremely fast charging electric car should be able to fully charge the battery in less than 10 minutes to provide a driving range of 200 miles. This presents a tremendous challenge and opportunity for researchers and enterprises.
The preparation of the ultra-thick pole piece with high coating weight is the most direct method for improving the specific energy of the battery. However, as the thickness of the electrode increases, the utilization rate of the electrode material in the deep layer is low, and most batteries cannot maintain high capacity at a high rate. Therefore, for thick electrode sheets, it is necessary to ensure a high loading and also to ensure a lithium ion diffusion rate and to fully utilize active materials. However, thick electrodes also have problems of poor electrolyte wettability, long lithium ion transport path, and large concentration polarization.
Therefore, it is very important to design and optimize the microstructure of the thick electrode and solve the problems of low porosity, poor wettability and long electron and ion migration paths of the thick electrode.
Disclosure of Invention
The invention solves the technical problem of providing a preparation method and application of a lithium battery positive plate, and the thick electrode with a three-dimensional conductive network channel constructed by the method is applied to a lithium ion battery, so that the problems existing in the design of the thick electrode are effectively solved and the quick charge and discharge of the lithium ion battery are realized on the premise of not sacrificing the utilization rate or the capacity of an active material.
The invention adopts the following technical scheme for solving the technical problems: system for positive plate of lithium batteryThe preparation method is characterized by comprising the following specific steps: using polyaniline as shell and Fe 3 O 4 Uniformly mixing a core-shell structure magnetic nano template serving as a core with a positive electrode material, a binder, a conductive agent and a solvent NMP to prepare positive electrode slurry, coating the positive electrode slurry on the surface of a current collector, then loading a magnetic field to ensure that the core-shell structure magnetic nano template is directionally assembled on the surface of the current collector, finally recycling the core-shell structure magnetic nano template in a thick electrode through a magnetic recycling device, and simultaneously constructing a three-dimensional network channel with high conductivity in the thick electrode for effectively improving the conductivity of the electrode, shortening the migration path of ions and electrons, providing a multi-dimensional open permeation channel, enhancing the wettability of electrolyte, reducing the tortuosity of the electrode and generating gradient porosity, forming a molecular-level channel beneficial to lithium ion transportation and promoting the high-speed conduction of lithium ions;
the preparation method of the lithium battery positive plate comprises the following specific steps:
step S1: feCl is added 3 Solution and FeSO 4 The solution is stirred and mixed evenly by oil bath at 60 ℃ under the protection of nitrogen, and then NH is added 3 ·H 2 Adjusting the pH value of the mixed system to 11 by O, cooling to room temperature, and separating black nano Fe by adopting a magnetic field 3 O 4 Washing the particles with ethanol and deionized water alternately for several times, and drying to obtain nano Fe 3 O 4 Particles;
step S2: nano Fe prepared in the step S1 3 O 4 Uniformly mixing the particles, dodecylbenzene sulfonic acid (DBSA) and hydrochloric acid in deionized water, adding aniline, dropwise adding an ammonium persulfate solution into a reaction solution for reaction, carrying out magnetic separation on the solution after the reaction is finished, washing the magnetic particles for three times by using sulfuric acid and acetone respectively, and then washing the magnetic particles by using deionized water until the pH of an eluent is =7 to obtain Fe with polyaniline as a shell 3 O 4 A core-shell structure magnetic nano template as a core;
and step S3: according to the positive electrode material: binder PVDF: respectively weighing raw materials of 90% to 5% of conductive agent SP, adding the core-shell structure magnetic nano template prepared in the step S2 into a suspension containing a positive electrode material, uniformly mixing, and uniformly mixing with binder PVDF, conductive agent SP and solvent NMP to obtain positive electrode slurry;
and step S4: transferring the positive electrode slurry prepared in the step S3 into a mold with a current collector placed at the bottom, adjusting the coating thickness to be 100-1000 microns by using a scraper, loading a magnetic field, directionally assembling a core-shell structure magnetic nano template on the surface of the current collector by adjusting the magnetic field strength to be 50mT-7T, transferring the mold into a drying box, pre-drying at 40 ℃, forming the positive electrode slurry, and removing the specific magnetic field to finally obtain a thick electrode;
step S5: and (4) recycling the core-shell structure magnetic nano template in the thick electrode prepared in the step (S4) by adopting a magnetic recycling device, and finally transferring the thick electrode into a vacuum drying oven to be dried at 120 ℃ to obtain the lithium battery positive plate.
Further limiting, the specific preparation process of the core-shell structure magnetic nano template in the step S2 is as follows: 1 mol. L −1 FeCl 3 ·6H 2 O solution and 0.5 mol. L −1 FeSO 4 ·7H 2 50mL of each O solution is added into a three-neck round-bottom flask, stirred for 30min in oil bath at 60 ℃ under the protection of nitrogen, and then 10mL of solution with the concentration of 1 mol.L is added -1 NH of (2) 3 ·H 2 Adjusting the pH value of the mixed system to 11 by O, cooling to room temperature, and separating black nano Fe by adopting a magnetic field 3 O 4 Washing the particles with ethanol and deionized water alternately for several times, and drying at 60 deg.C to obtain nanometer Fe 3 O 4 Particles; 0.03g of nano Fe 3 O 4 The particles are evenly mixed with 0.04mmol of dodecyl benzene sulfonic acid and 0.0267mmol of hydrochloric acid in deionized water, and then 20mL of solution with the concentration of 0.5 mol.L is added -1 Aniline, the emulsion quickly turns white with the addition of aniline, stirring is continued for 30min, and 30mL of 1 mol. L concentration is added dropwise into the reaction solution -1 The ammonium persulfate solution changes the emulsion from white to light blue with the addition of oxidant ammonium persulfate, and finally turns to dark green, after the reaction is finished, the solution is magnetically separated, and the magnetic particles are treated by 1 mol.L -1 Washing with sulfuric acid and acetone for three times, washing with deionized water until the pH of the eluate is =7, and obtaining the final product with polyaniline as shell and Fe 3 O 4 A core-shell structure magnetic nano template as a core.
Further limiting, in the step S3, the mass ratio of the core-shell structure magnetic nano template to the positive electrode material is 0.2-0.5%.
Further limiting, in the step S3, the positive electrode material is one or more of a high nickel ternary positive electrode material, lithium cobaltate, lithium manganate, lithium nickel cobalt manganate, or lithium iron phosphate.
Further, the viscosity of the positive electrode slurry in step S4 is 4000 to 9000mPa · S.
Further, in the step S4, the coating thickness is adjusted to be 200 to 400 μm by using a scraper.
Further, in step S5, the magnetic recovery device sets the magnetic field strength to 0.5 to 2t.
The lithium battery positive plate prepared by the invention is applied to the preparation of the lithium battery.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. hydrochloric acid is used as a medium, and when aniline is subjected to oxidative polymerization reaction, aniline monomers can be efficiently subjected to oxidative polymerization on the surfaces of the magnetic nanoparticles, so that the effect of well coating the magnetic nanoparticles is achieved. In addition, in an acidic environment, the surface of the magnetic nanoparticles is easily positively charged, and therefore it also absorbs a certain amount of the heterocharged ions while reacting. As the reaction continues, aniline monomer continuously interacts with the magnetic particles on the surfaces of the magnetic particles. The interaction comprises both electrostatic interaction and hydrogen bond interaction of polyaniline molecular chains on the surfaces of the magnetic nanoparticles, so that strong bonding action of polyaniline and the magnetic nanoparticles is ensured to promote stable and good coating of the magnetic nanoparticles in the oxidation polymerization process of aniline monomers.
2. DBSA not only is used as a doping agent to improve the conductivity of polyaniline, but also is used as a surface modifier in the reaction, so that the magnetic nanoparticles can be uniformly dispersed in an acidic liquid phase environment. Meanwhile, the DBSA is beneficial to charge delocalization of polyaniline molecular chains, and the form and the size of polyaniline-coated magnetic nanoparticles can be well controlled. In addition, the electric conductivity of the polyaniline can be further improved by adopting the synergistic effect with the hydrochloric acid.
3. Under the action of a magnetic field, the easy magnetization axes of the magnetic nano templates are oriented and arranged along the direction of a magnetic line, and meanwhile, the interaction between magnetic coupling polar moments promotes the oriented arrangement of the magnetic nano templates. By regulating the size and direction of the magnetic field, an ordered structure with multi-dimensional assembly can be prepared. The magnetic nano template only accounts for 0.5 percent of the mass of the anode material at most, and can not influence the utilization rate of the active material and further the electrochemical performance of the electrode. When the magnetic recovery device is used for recovering the magnetic nanoparticles, the polyaniline of the shell of the magnetic nano template can be dissolved in the NMP solution, so that the shell of the magnetic nano template with the core-shell structure is broken, and the magnetic nanoparticles are exposed, and thus the magnetic nanoparticles can well adsorb metal impurities which are not removed in the anode material. And finally, impurity metal and magnetic particles are removed through a magnetic recovery device, so that potential safety hazards caused by the fact that magnetic impurities pierce the diaphragm in the charging and discharging processes are avoided.
4. After the magnetic nanoparticles are recovered, polyaniline dissolved by solvent NMP can generate a layer of compact film on a channel wall in situ after an electrode is dried, and a three-dimensional network channel with high conductivity is constructed, so that the conductivity of the electrode is improved, high-speed conduction of ions and electrons can be promoted, a mechanical support effect can be generated on the channel wall, and the circulation stability of the battery is effectively improved.
5. The constructed three-dimensional conductive network channel reduces the electrode curvature, and the uniform gradient porosity and low tortuosity formed in the active material in the low-curvature electrode accelerate the reaction kinetics in the high-load electrode, so that the capacity under high multiplying power is improved by shortening the integral diffusion path of lithium ions on the electrode. Meanwhile, a multi-dimensional open permeation channel is provided, so that the electrolyte can be infiltrated from the surface of the dressing layer to the direction of the current collector, the multiplying power and the cycle performance of the thick electrode battery are improved, and the lithium precipitation risk under high-multiplying-power charging and discharging is reduced.
In conclusion, the thick electrode of the three-dimensional conductive network channel constructed by the invention reduces the tortuosity of the electrode and the gradient porosity, forms a molecular channel beneficial to lithium ion transportation, and promotes the high-speed conduction of lithium ions. The lithium ion battery shows lower concentration polarization and rapid lithium ion transmission kinetics, and is beneficial to obtaining a good electrode-electrolyte interface and excellent rate performance.
Drawings
FIG. 1 is SEM images of core-shell structure magnetic nano-templates prepared in examples and comparative examples;
FIG. 2 is a graph showing the rate charge and discharge characteristics of the positive electrode sheets of lithium batteries manufactured in examples and comparative examples.
Detailed Description
The invention directionally assembles the magnetic nano template in the slurry by the external magnetic field, further recovers the magnetic nano particles to construct the thick electrode with the three-dimensional conductive network channel, effectively solves the problems of poor wettability of the thick electrode electrolyte, long lithium ion migration path and large concentration polarization, and realizes the comprehensive promotion of the high-magnification charge-discharge performance and stability of the thick electrode.
In order to better explain the technical solutions, the technical solutions are described in detail with reference to specific embodiments. It should be understood that the scope of the above-described subject matter of the present invention is not limited to the following examples, and any techniques implemented based on the above-described contents of the present invention are within the scope of the present invention.
Electrochemical test is to assemble button cell, and charge and discharge test cabinet is adopted to test electrical property.
Examples
Step S1: 1 mol. L −1 FeCl 3 ·6H 2 O solution and 0.5 mol. L −1 FeSO 4 ·7H 2 Adding 50mL of O solution into a three-neck round-bottom flask, stirring in an oil bath at 60 ℃ for 30min under the protection of nitrogen, and adding 10mL of 1 mol. L -1 NH of 3 ·H 2 Adjusting the pH value of the mixed system to 11 by O, cooling to room temperature, and separating black nano Fe by adopting a magnetic field 3 O 4 Washing the particles with ethanol and deionized water alternately for several times, and drying at 60 deg.C to obtain nanometer Fe 3 O 4 Particles;
step S2: 0.03g of nano Fe 3 O 4 The particles are evenly mixed with 0.04mmol of dodecyl benzene sulfonic acid and 0.0267mmol of hydrochloric acid in deionized water, and then added20mL of the solution with a concentration of 0.5 mol.L -1 Aniline, the emulsion quickly turned white with the addition of aniline, stirring was continued for 30min, and 30mL of 1 mol. L concentration was added dropwise to the reaction mixture -1 The ammonium persulfate solution changes the emulsion from white to light blue with the addition of oxidant ammonium persulfate, and finally turns to dark green, after the reaction is finished, the solution is magnetically separated, and the magnetic particles are treated by 1 mol.L -1 Washing with sulfuric acid and acetone for three times, washing with deionized water until the pH of the eluate is =7, and finally obtaining the Fe-B composite material with polyaniline as a shell 3 O 4 A core-shell structure magnetic nano template as a core;
and step S3: 30g of ncm811 high nickel ternary positive electrode material was dispersed in 500mL of ethanol solution, 0.09g of the magnetic nano template prepared in step S2 was added to the suspension containing the positive electrode material, stirred for 2h, the suspension was centrifuged and dried in a vacuum oven at 80 ℃ for 12h. Then, 1.667g of binder PVDF, 1.667g of conductive agent SP and solvent NMP are uniformly mixed to prepare positive electrode slurry with the viscosity of 7000 mPas;
and step S4: adjusting the coating thickness to 300 mu m by a scraper, coating the anode slurry prepared in the step S3 in a mold with an aluminum foil placed at the bottom, directionally assembling the core-shell structure magnetic nano template on the surface of a current collector by regulating the magnetic field intensity to 5T, transferring the mold into a drying oven for pre-drying at 40 ℃, forming the slurry and removing the specific magnetic field to prepare a thick electrode;
step S5: and (5) setting the magnetic field intensity to be 1T by adopting a magnetic recovery device, recovering and recycling the magnetic nanoparticles with the core-shell structure in the thick electrode prepared in the step (S4), and finally transferring the thick electrode into a vacuum drying oven to dry for 12 hours at 120 ℃ to obtain the lithium battery positive plate.
Comparative example 1 (without magnetic nano template)
Step S1: 30g of NCM811 high-nickel ternary positive electrode material, 1.667g of binder PVDF, 1.667g of conductive agent SP and solvent NMP are mixed uniformly to prepare positive electrode slurry with the viscosity of 7000mPa & s;
step S2: and (3) adjusting the coating thickness to 300 mu m by a scraper, coating the positive electrode slurry prepared in the step (S1) on an aluminum foil, and drying to obtain the lithium battery positive electrode plate.
Comparative example 2 (with magnetic particles, without polyaniline shell)
Step S1: 1 mol. L −1 FeCl 3 ·6H 2 O solution and 0.5 mol. L −1 FeSO 4 ·7H 2 Adding 50mL of O solution into a three-neck round-bottom flask, stirring in an oil bath at 60 ℃ for 30min under the protection of nitrogen, and adding 10mL of 1 mol. L -1 NH of (2) 3 ·H 2 Adjusting the pH value of the mixed system to 11 by O, cooling to room temperature, and separating black nano Fe by adopting a magnetic field 3 O 4 Washing the particles with ethanol and deionized water alternately for several times, and drying at 60 deg.C to obtain nanometer Fe 3 O 4 Particles;
step S2: 30g of ncm811 high nickel ternary positive electrode material was dispersed in 500mL of ethanol solution, 0.09g of the magnetic nano template prepared in step S1 was added to the suspension containing the positive electrode material, stirred for 2h, the suspension was centrifuged and dried in a vacuum oven at 80 ℃ for 12h. Then 1.667g of binder PVDF, 1.667g of conductive agent SP and solvent NMP are mixed uniformly to prepare positive electrode slurry with the viscosity of 7000 mPas;
and step S3: adjusting the coating thickness to 300 mu m by a scraper, coating the anode slurry prepared in the step S2 in a mold with an aluminum foil placed at the bottom, directionally assembling a magnetic nano template on the surface of a current collector by regulating the magnetic field intensity to 5T, transferring the mold into a drying oven for pre-drying at 40 ℃, forming the anode slurry and withdrawing the specific magnetic field to prepare the thick electrode.
And step S4: and (4) setting the magnetic field intensity to be 1T by adopting a magnetic recovery device, recovering the magnetic nano template in the thick electrode prepared in the step (S3), and finally transferring the electrode into a vacuum drying oven to dry for 12 hours at 120 ℃ to obtain the lithium battery positive plate.
Comparative example 3 (without hydrochloric acid)
Step S1: 1 mol. L −1 FeCl 3 ·6H 2 O solution and 0.5 mol. L −1 FeSO 4 ·7H 2 50mL of each O solution is added into a three-neck round-bottom flask, stirred for 30min in oil bath at 60 ℃ under the protection of nitrogen, and then 10mL of solution with the concentration of 1 mol.L is added -1 NH of 3 ·H 2 Adjusting the pH value of the mixed system to 11 by O, cooling to room temperature, and separating black nano Fe by adopting a magnetic field 3 O 4 Washing the particles with ethanol and deionized water alternately for several times, and drying at 60 deg.C to obtain nanometer Fe 3 O 4 Particles;
step S2: 0.03g of nano Fe prepared in the step S1 3 O 4 The particles are evenly mixed with 0.04mmol of dodecylbenzene sulfonic acid in deionized water, and then 20ml of the mixture with the concentration of 0.5 mol.L is added -1 Aniline, the emulsion quickly turned white as aniline was added. Stirring was continued for 30min. 30mL of 1 mol. L concentration was added dropwise to the reaction mixture -1 Ammonium persulfate solution. With the addition of the oxidant ammonium persulfate, the emulsion changed from white to light blue, and finally turned into greenish black. After the reaction is finished, the solution is magnetically separated, and 1 mol.L of magnetic particles are used -1 Washing with sulfuric acid and acetone for three times, and washing with deionized water until the pH of the eluate is =7 to obtain the final product containing polyaniline as shell and Fe 3 O 4 A core-shell structure nano magnetic template as a core;
and step S3: 30g of ncm811 high nickel ternary positive electrode material was dispersed in 500mL of ethanol solution, and 0.09g of the magnetic nano template prepared in step S2 was added to the suspension containing the positive electrode material. The suspension was stirred for 2h, centrifuged and dried in a vacuum oven at 80 ℃ for 12h. Then 1.667g of binder PVDF, 1.667g of conductive agent SP and solvent NMP are mixed uniformly to prepare positive electrode slurry with the viscosity of 7000 mPas;
and step S4: adjusting the coating thickness to 300 mu m by a scraper, coating the anode slurry prepared in the step S3 in a mold with an aluminum foil placed at the bottom, directionally assembling a magnetic nano template on the surface of a current collector by regulating the magnetic field intensity to be 5T, transferring the mold into a drying oven for pre-drying at 40 ℃, forming the anode slurry and removing the specific magnetic field to prepare a thick electrode;
step S5: and (4) setting the magnetic field intensity to be 1T by adopting a magnetic recovery device, recovering the magnetic particles in the thick electrode prepared in the step (S4), and finally transferring the thick electrode into a vacuum drying oven to dry for 12 hours at 120 ℃ to obtain the lithium battery positive plate.
COMPARATIVE EXAMPLE 4 (without DBSA)
Step S1: 1 mol. L −1 FeCl 3 ·6H 2 O solution and 0.5 mol. L −1 FeSO 4 ·7H 2 Adding 50mL of O solution into a three-neck round-bottom flask, stirring in an oil bath at 60 ℃ for 30min under the protection of nitrogen, and adding 10mL of 1 mol. L -1 NH of 3 ·H 2 Adjusting the pH value of the mixed system to 11 by O, cooling to room temperature, and separating black nano Fe by adopting a magnetic field 3 O 4 Washing the particles with ethanol and deionized water alternately for several times, and drying at 60 deg.C to obtain nanometer Fe 3 O 4 Particles;
step S2: 0.03g of nano Fe prepared in the step S1 3 O 4 The particles are mixed evenly with 0.0267mmol hydrochloric acid in deionized water, 20mL of hydrochloric acid with the concentration of 0.5 mol.L is added -1 Aniline, the emulsion turned white rapidly with the addition of aniline. Stirring was continued for 30min. 30mL of 1 mol. L concentration was added dropwise to the reaction mixture -1 Ammonium persulfate solution. With the addition of the oxidant ammonium persulfate, the emulsion changed from white to light blue, and finally turned into greenish black. After the reaction is finished, the solution is magnetically separated, and 1 mol.L of magnetic particles are used -1 Washing with sulfuric acid and acetone for three times, and washing with deionized water until the pH of the eluate is =7 to obtain the final product containing polyaniline as shell and Fe 3 O 4 A core-shell structure magnetic nano template as a core;
and step S3: 30g of ncm811 high nickel ternary positive electrode material was dispersed in 500mL of ethanol solution, and 0.09g of the magnetic nano template prepared in step S2 was added to the suspension containing the positive electrode material. The suspension was stirred for 2h, centrifuged and dried in a vacuum oven at 80 ℃ for 12h. Then 1.667g of binder PVDF, 1.667g of conductive agent SP and solvent NMP are mixed uniformly to prepare positive electrode slurry with the viscosity of 7000 mPas;
and step S4: adjusting the coating thickness to 300 mu m by a scraper, coating the anode slurry prepared in the step S3 in a mold with an aluminum foil placed at the bottom, directionally assembling a magnetic nano template on the surface of a current collector by regulating the magnetic field intensity to be 5T, transferring the mold into a drying oven for pre-drying at 40 ℃, forming the anode slurry and removing the specific magnetic field to prepare a thick electrode;
step S5: and (5) setting the magnetic field intensity to be 1T by adopting a magnetic recovery device, recovering the magnetic nanoparticles in the thick electrode prepared in the step (S4), and finally transferring the thick electrode into a vacuum drying oven to dry for 12 hours at 120 ℃ to prepare the lithium battery positive plate.
Comparative example 5 (changing the order of addition of NMP)
Step S1: 1 mol. L −1 FeCl 3 ·6H 2 O solution and 0.5 mol. L −1 FeSO 4 ·7H 2 Adding 50mL of O solution into a three-neck round-bottom flask, stirring in an oil bath at 60 ℃ for 30min under the protection of nitrogen, and adding 10mL of 1 mol. L -1 NH of (2) 3 ·H 2 Adjusting the pH value of the mixed system to 11 by O, cooling to room temperature, and separating black nano Fe by adopting a magnetic field 3 O 4 Washing the particles with ethanol and deionized water alternately for several times, and drying at 60 deg.C to obtain nanometer Fe 3 O 4 Particles;
step S2: 0.03g of nano Fe 3 O 4 The particles are evenly mixed with 0.04mmol of dodecyl benzene sulfonic acid and 0.0267mmol of hydrochloric acid in deionized water, and then 20mL of solution with the concentration of 0.5 mol.L is added -1 Aniline, the emulsion quickly turns white with the addition of aniline, stirring is continued for 30min, and 30mL of 1 mol. L concentration is added dropwise into the reaction solution -1 The ammonium persulfate solution changes the emulsion from white to light blue with the addition of oxidant ammonium persulfate, and finally turns to dark green, after the reaction is finished, the solution is magnetically separated, and the magnetic particles are treated by 1 mol.L -1 Washing with sulfuric acid and acetone for three times, washing with deionized water until the pH of the eluate is =7, and obtaining the final product with polyaniline as shell and Fe 3 O 4 A core-shell structure magnetic nano template as a core;
and step S3: 30g of ncm811 high nickel ternary positive electrode material was dispersed in 500mL of ethanol solution, 0.09g of the magnetic nano template prepared in step S2 was added to the suspension containing the positive electrode material, stirred for 2h, the suspension was centrifuged and dried in a vacuum oven at 80 ℃ for 12h. Then, uniformly mixing the solid powder with 1.667g of conductive agent SP, mixing 1.667g of binder PVDF with solvent NMP to prepare a solution with a solid content of 5%, then adding the solid powder, mixing for a certain time, adding the rest solvent NMP, and uniformly mixing to prepare positive electrode slurry with the viscosity of 7000 mPas; (ii) a
And step S4: adjusting the coating thickness to 300 mu m by a scraper, coating the anode slurry prepared in the step S3 in a mold with an aluminum foil placed at the bottom, directionally assembling the core-shell structure magnetic nano template on the surface of a current collector by regulating the magnetic field intensity to 5T, transferring the mold into a drying oven for pre-drying at 40 ℃, forming the slurry and removing the specific magnetic field to prepare a thick electrode;
step S5: and (5) setting the magnetic field intensity to be 1T by adopting a magnetic recovery device, recovering the magnetic nanoparticles in the thick electrode prepared in the step (S4), and finally transferring the thick electrode into a vacuum drying oven to dry for 12 hours at 120 ℃ to prepare the lithium battery positive plate.
Comparative example 6 (direct vacuum drying of electrode)
Step S1: 1 mol. L −1 FeCl 3 ·6H 2 O solution and 0.5 mol. L −1 FeSO 4 ·7H 2 Adding 50mL of O solution into a three-neck round-bottom flask, stirring in an oil bath at 60 ℃ for 30min under the protection of nitrogen, and adding 10mL of 1 mol. L -1 NH of (2) 3 ·H 2 Adjusting the pH value of the mixed system to 11 by O, cooling to room temperature, and separating black nano Fe by adopting a magnetic field 3 O 4 Washing the particles with ethanol and deionized water alternately for several times, and drying at 60 deg.C to obtain nanometer Fe 3 O 4 Particles;
step S2: 0.03g of nano Fe 3 O 4 The particles are evenly mixed with 0.04mmol of dodecyl benzene sulfonic acid and 0.0267mmol of hydrochloric acid in deionized water, and then 20mL of solution with the concentration of 0.5 mol.L is added -1 Aniline, the emulsion quickly turns white with the addition of aniline, stirring is continued for 30min, and 30mL of 1 mol. L concentration is added dropwise into the reaction solution -1 The ammonium persulfate solution changes the emulsion from white to light blue with the addition of oxidant ammonium persulfate, and finally turns to dark green, after the reaction is finished, the solution is magnetically separated, and the magnetic particles are treated by 1 mol.L -1 Washing with sulfuric acid and acetone for three times, washing with deionized water until the pH of the eluate is =7, and obtaining the final product with polyaniline as shell and Fe 3 O 4 A core-shell structure magnetic nano template as a core;
and step S3: 30g of ncm811 high nickel ternary positive electrode material was dispersed in 500mL of ethanol solution, 0.09g of the magnetic nano template prepared in step S2 was added to the suspension containing the positive electrode material, stirred for 2h, the suspension was centrifuged and dried in a vacuum oven at 80 ℃ for 12h. Then 1.667g of binder PVDF, 1.667g of conductive agent SP and solvent NMP are mixed uniformly to prepare positive electrode slurry with the viscosity of 7000 mPas;
and step S4: adjusting the coating thickness to 300 mu m by a scraper, coating the anode slurry prepared in the step S3 in a mold with an aluminum foil placed at the bottom, and directionally assembling the core-shell structure magnetic nano template on the surface of a current collector by regulating the magnetic field intensity to 5T to prepare a thick electrode;
step S5: and (5) setting the magnetic field intensity to be 1T by adopting a magnetic recovery device, recovering the magnetic nanoparticles in the thick electrode prepared in the step (S4), and finally transferring the thick electrode into a vacuum drying oven to be dried for 12 hours at 120 ℃ to obtain the lithium battery positive plate.
The lithium battery positive plate prepared by the embodiment of the invention has better rate capability and cycle stability. As can be seen from the electrical property test result in fig. 2, the positive plate of the lithium battery prepared in the example has better rate capability and capacity recovery capability.
Through analyzing the examples and comparative examples 1 to 6, it can be found that the control of the magnetic template ratio, the strength of the magnetic coupling between the magnetic template and the current collector, the recovery of the magnetic template and other key factors can have different degrees of influence on the transmission capability of ions and electrons. The invention can realize the comprehensive improvement of the high-rate charge-discharge performance and stability of the thick electrode by the integrated realization technical scheme of the regulation and control of the microstructure property of the thick electrode, the construction reinforcement of the dressing layer, the electrolyte and the current collector interface, and the improvement of the integral electron and ion conduction.
While the foregoing embodiments have described the general principles, features and advantages of the present invention, it will be understood by those skilled in the art that the present invention is not limited thereto, and that the foregoing embodiments and descriptions are only illustrative of the principles of the present invention, and various changes and modifications can be made without departing from the scope of the principles of the present invention, and these changes and modifications are within the scope of the present invention.
Claims (8)
1. A preparation method of a lithium battery positive plate is characterized by comprising the following specific steps: using polyaniline as shell and Fe 3 O 4 Uniformly mixing a core-shell structure magnetic nano template with a core with a positive electrode material, a binder, a conductive agent and a solvent NMP to prepare positive electrode slurry, coating the positive electrode slurry on the surface of a current collector, then directionally assembling the core-shell structure magnetic nano template on the surface of the current collector by loading a magnetic field, finally recycling the core-shell structure magnetic nano template in a thick electrode by a magnetic recycling device, and simultaneously constructing a three-dimensional network channel with high conductivity in the thick electrode for effectively improving the conductivity of the electrode, shortening the migration path of ions and electrons, providing a multi-dimensional open permeation channel, enhancing the wettability of electrolyte, reducing the tortuosity of the electrode and generating gradient porosity, forming a molecular channel beneficial to lithium ion transportation and promoting the high-speed conduction of lithium ions;
the preparation method of the lithium battery positive plate comprises the following specific steps:
step S1: feCl 3 Solution and FeSO 4 The solution is stirred and mixed evenly by oil bath at 60 ℃ under the protection of nitrogen, and then NH is added 3 ·H 2 Adjusting the pH value of the mixed system to 11 by O, cooling to room temperature, and separating black nano Fe by adopting a magnetic field 3 O 4 Washing the particles with ethanol and deionized water alternately for several times, and drying to obtain nano Fe 3 O 4 Particles;
step S2: nano Fe prepared in step S1 3 O 4 Uniformly mixing particles, dodecylbenzene sulfonic acid and hydrochloric acid in deionized water, adding aniline, then dropwise adding an ammonium persulfate solution into a reaction solution for reaction, carrying out magnetic separation on the solution after the reaction is finished, washing the magnetic particles with sulfuric acid and acetone for three times respectively, and then washing with deionized water until the pH of an eluent is =7 to obtain Fe with polyaniline as a shell 3 O 4 A core-shell structure magnetic nano template as a core;
and step S3: according to the positive electrode material: binder PVDF: respectively weighing raw materials of 90% to 5% of conductive agent SP, adding the core-shell structure magnetic nano template prepared in the step S2 into a suspension containing a positive electrode material, uniformly mixing, and uniformly mixing with binder PVDF, conductive agent SP and solvent NMP to obtain positive electrode slurry;
and step S4: transferring the positive electrode slurry prepared in the step S3 into a mold with a current collector placed at the bottom, adjusting the coating thickness to be 100 to 1000 micrometers by using a scraper, loading a magnetic field, directionally assembling the magnetic nano template with the core-shell structure on the surface of the current collector by adjusting the magnetic field strength to be 50mT to 7T, transferring the mold into a drying box, pre-drying at 40 ℃, forming the positive electrode slurry, removing the specific magnetic field, and finally obtaining a thick electrode;
step S5: and (5) recycling the magnetic nano template with the core-shell structure in the thick electrode prepared in the step (S4) by adopting a magnetic recycling device, and finally transferring the thick electrode into a vacuum drying oven to be dried at 120 ℃ to obtain the lithium battery positive plate.
2. The method for preparing the positive plate of the lithium battery according to claim 1, wherein the specific preparation process of the magnetic nano template with the core-shell structure in the step S2 comprises the following steps: 1 mol. L −1 FeCl 3 ·6H 2 O solution and 0.5 mol. L −1 FeSO 4 ·7H 2 50mL of each O solution is added into a three-neck round-bottom flask, stirred for 30min in oil bath at 60 ℃ under the protection of nitrogen, and then 10mL of solution with the concentration of 1 mol.L is added -1 NH of (2) 3 ·H 2 Adjusting the pH value of the mixed system to 11 by O, cooling to room temperature, and separating black nano Fe by adopting a magnetic field 3 O 4 Washing the particles with ethanol and deionized water alternately for several times, and drying at 60 deg.C to obtain nanometer Fe 3 O 4 Particles; 0.03g of nano Fe 3 O 4 The particles are evenly mixed with 0.04mmol of dodecyl benzene sulfonic acid and 0.0267mmol of hydrochloric acid in deionized water, and then 20mL of solution with the concentration of 0.5 mol.L is added -1 Aniline, the emulsion quickly turns white with the addition of aniline, stirring is continued for 30min, and 30mL of 1 mol. L concentration is added dropwise into the reaction solution -1 Ammonium persulfate solution, withAdding oxidant ammonium persulfate to change the emulsion from white to light blue and finally to dark green, magnetically separating the solution after the reaction is finished, and using 1 mol.L for magnetic particles -1 Washing with sulfuric acid and acetone for three times, washing with deionized water until the pH of the eluate is =7, and finally obtaining the Fe-B composite material with polyaniline as a shell 3 O 4 A core-shell structure magnetic nano template as a core.
3. The method for preparing a positive electrode sheet for a lithium battery according to claim 1, wherein: in the step S3, the mass ratio of the magnetic nano template with the core-shell structure to the anode material is 0.2-0.5%.
4. The method for producing a positive electrode sheet for a lithium battery according to claim 1, characterized in that: in the step S3, the positive electrode material is one or more of a high-nickel ternary positive electrode material, lithium cobaltate, lithium manganate, lithium nickel cobalt manganate or lithium iron phosphate.
5. The method for producing a positive electrode sheet for a lithium battery according to claim 1, characterized in that: the viscosity of the positive electrode slurry in step S4 is 4000 to 9000mPa · S.
6. The method for producing a positive electrode sheet for a lithium battery according to claim 1, characterized in that: in the step S4, a scraper is adopted to adjust the coating thickness to be 200-400 mu m.
7. The method for producing a positive electrode sheet for a lithium battery according to claim 1, characterized in that: and S5, setting the magnetic field intensity of the magnetic recovery device to be 0.5-2T.
8. The use of the positive electrode sheet for a lithium battery prepared by the method according to any one of claims 1 to 7 in the preparation of a lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210659559.XA CN115224242B (en) | 2022-06-13 | 2022-06-13 | Preparation method and application of lithium battery positive plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210659559.XA CN115224242B (en) | 2022-06-13 | 2022-06-13 | Preparation method and application of lithium battery positive plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115224242A true CN115224242A (en) | 2022-10-21 |
| CN115224242B CN115224242B (en) | 2024-03-05 |
Family
ID=83608565
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210659559.XA Active CN115224242B (en) | 2022-06-13 | 2022-06-13 | Preparation method and application of lithium battery positive plate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115224242B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013159471A1 (en) * | 2012-04-26 | 2013-10-31 | 宁波杉杉新材料科技有限公司 | Porous thin film silicon-based negative electrode material of high-performance lithium ion cell and preparation method thereof |
| CN108417839A (en) * | 2018-03-19 | 2018-08-17 | 成都新柯力化工科技有限公司 | A method of cathode of lithium battery electrode high rate performance is improved by magnetic effect |
| CN109461910A (en) * | 2018-10-19 | 2019-03-12 | 浙江大学 | A kind of lithium battery anode and preparation method thereof based on graphene-sulfur composite material |
| CN112002950A (en) * | 2020-08-21 | 2020-11-27 | 江苏海基新能源股份有限公司 | Lithium ion battery positive electrode slurry and preparation method thereof, positive plate and lithium ion battery |
| CN113555541A (en) * | 2021-07-21 | 2021-10-26 | 凤凰新能源(惠州)有限公司 | High-energy-density lithium ion battery |
| US20210376310A1 (en) * | 2020-05-29 | 2021-12-02 | The Regents Of The University Of Michigan | Atomic layer deposition of ionically conductive coatings for lithium battery fast charging |
-
2022
- 2022-06-13 CN CN202210659559.XA patent/CN115224242B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013159471A1 (en) * | 2012-04-26 | 2013-10-31 | 宁波杉杉新材料科技有限公司 | Porous thin film silicon-based negative electrode material of high-performance lithium ion cell and preparation method thereof |
| CN108417839A (en) * | 2018-03-19 | 2018-08-17 | 成都新柯力化工科技有限公司 | A method of cathode of lithium battery electrode high rate performance is improved by magnetic effect |
| CN109461910A (en) * | 2018-10-19 | 2019-03-12 | 浙江大学 | A kind of lithium battery anode and preparation method thereof based on graphene-sulfur composite material |
| US20210376310A1 (en) * | 2020-05-29 | 2021-12-02 | The Regents Of The University Of Michigan | Atomic layer deposition of ionically conductive coatings for lithium battery fast charging |
| CN112002950A (en) * | 2020-08-21 | 2020-11-27 | 江苏海基新能源股份有限公司 | Lithium ion battery positive electrode slurry and preparation method thereof, positive plate and lithium ion battery |
| CN113555541A (en) * | 2021-07-21 | 2021-10-26 | 凤凰新能源(惠州)有限公司 | High-energy-density lithium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| 巫湘坤;詹秋设;张兰;张锁江;: "锂电池极片微结构优化及可控制备技术进展", 应用化学, no. 09, 24 August 2018 (2018-08-24) * |
| 魏磊;王伟;: "具有分级结构的Co_3O_4绣球花状微米球的构筑及其锂离子电池负极性能研究", 山东科学, no. 06, 15 December 2017 (2017-12-15) * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115224242B (en) | 2024-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111463403A (en) | Negative electrode material modified by composite artificial solid electrolyte interface film and battery application thereof | |
| CN106558729B (en) | A kind of lithium ion battery of graphene as anode sizing agent conductive agent | |
| WO2017124439A1 (en) | Three-dimensional na3v2(po4)3 nanowire network electrode material, preparation method therefor and use thereof | |
| CN108172744B (en) | Sb for lithium-sulfur battery diaphragm2Se3Method for preparing composite material | |
| CN108878893B (en) | Modified current collector for negative electrode of quick-charging lithium ion battery and preparation method thereof | |
| CN111540868A (en) | Preparation method and application of two-dimensional manganese dioxide modified polypropylene diaphragm | |
| US20230348274A1 (en) | Silicon-doped graphene-based composite material, preparation method and application thereof | |
| CN113451576A (en) | Graphite composite material, preparation method thereof and lithium ion battery | |
| CN115799608A (en) | Method for improving interface between inorganic phase filler and polymer in composite solid electrolyte and application thereof | |
| CN109830670B (en) | Hollow sandwich type SiO for lithium ion battery cathode material2/C/MoS2Hybrid microspheres | |
| CN113611854B (en) | Prussian blue derived core-shell cubic material, and preparation method and application thereof | |
| CN114759164B (en) | Preparation method and application of lithium battery negative plate | |
| CN110233254B (en) | Bell-shaped Fe for lithium ion battery cathode material3O4/C/MoS2Hybrid microparticles | |
| KR20130014796A (en) | Preparation method for lithium-ion battery anode by direct formation of metal oxide particles in porous carbons | |
| CN110165201B (en) | Preparation method of Si @ Cu hollow core-shell composite material | |
| WO2019241509A9 (en) | Fast charge feof cathode for lithium ion batteries | |
| CN115224242B (en) | Preparation method and application of lithium battery positive plate | |
| CN113921812B (en) | Ultra-high power density sodium ion battery and preparation method thereof | |
| CN113264516B (en) | Preparation method of lithium iron vanadium phosphate carbon nanotube modified ternary cathode material | |
| CN110492089B (en) | Carbon-coated ferric oxide and potassium pentavanadate composite material and preparation method thereof | |
| CN114171711A (en) | Electrode preparation method of water-based zinc ion battery, electrode and battery | |
| CN107342413B (en) | Cobalt tetraoxydi-ferrate nano particle and preparation method and application thereof | |
| CN112331812A (en) | MoO (MoO)2Preparation method of nanorod negative electrode material | |
| CN110690415A (en) | Preparation method of three-dimensional self-supporting sulfur/graphene positive electrode material and lithium-sulfur battery positive electrode | |
| CN116885200B (en) | Lithium metal battery negative electrode current collector material prepared in magnetic field and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |