CN115536810B - Photo-curing aqueous polyurethane emulsion, lithium ion battery anode material, preparation method and application thereof - Google Patents
Photo-curing aqueous polyurethane emulsion, lithium ion battery anode material, preparation method and application thereof Download PDFInfo
- Publication number
- CN115536810B CN115536810B CN202211361913.7A CN202211361913A CN115536810B CN 115536810 B CN115536810 B CN 115536810B CN 202211361913 A CN202211361913 A CN 202211361913A CN 115536810 B CN115536810 B CN 115536810B
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- aqueous polyurethane
- curing
- ion battery
- diisocyanate
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
-
- 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
- H01M4/13—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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of electrochemistry, and discloses a photo-curing aqueous polyurethane emulsion, a lithium ion battery anode material, and a preparation method and application thereof. Mainly uses polyethylene glycol (PEG) with different molecular weights and diisocyanate as reaction main bodies, adds dimethylolbutyric acid as a chain extender, and finally uses hydroxyethyl acrylate for end capping. On one hand, the composite material utilizes the excellent physical properties and ion conducting capacity of the polyurethane material, and can well relieve the volume expansion effect of silicon particles; on the other hand, the double bond end capped structure can form a three-dimensional network structure with stronger coating property under the effect of ultraviolet light curing, so that the electrochemical performance of the battery can be obviously improved compared with a commercial binder. The invention comprises a synthetic preparation method of the material, and a binder and a lithium ion battery prepared by using the material.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a photo-curing aqueous polyurethane emulsion, a lithium ion battery anode material, a preparation method and application thereof.
Background
Lithium ion batteries are a high energy density and lightweight mobile battery with very wide application in the information age today. Not only portable electronic products such as mobile phones and notebook computers, but also new energy automobiles using lithium ion batteries as driving force sources have been frequently used. With the continuous expansion of application fields, the conventional graphite cathode lithium ion battery has difficulty in meeting the requirements of the industry for the lithium ion battery. In this context, the silicon anode material (3590 mAh.g -1 ) Because it is 10 times that of graphite cathode (372 mAh.g) -1 ) Is expected to be a theoretical specific capacity of (c). However, silicon anode materials have some tripping stones on commercial application roads, which are embodied as: the silicon material has poor conductivity, can generate 200 to 300 percent of huge volume expansion in the charge and discharge process, continuously consumes electrolyte to generate an unstable Solid Electrolyte Interface (SEI) layer, and the like. The existence of these problems makes the stability and safety of the silicon negative electrode during the battery cycle significantly impaired. For this reason, researchers have proposed different solutions from three points of view of electrode material, binder and artificial SEI, respectively, and have all made some progress.
From the existing research and development results, in order to cope with the volume change of the silicon anode material and the damage to the electrode structure, besides researching and improving the silicon material, a more convenient and efficient mode is often to introduce an organic polymer material. Among many organic high molecular polymers, the most attention is paid to the fact that the natural high molecular polymers are used as binders to relieve the volume expansion of silicon particles, and a series of natural high molecules such as sodium carboxymethylcellulose (CMC), arabic Gum (GA), guar Gum (GG), and Karaya Gum (KG) are applied to a silicon negative electrode system, so that good research results are obtained due to the advantages of strong binding capacity, low cost, environmental protection and the like. However, it should be ignored that natural polymers often have poor mechanical properties and weak ion conducting capability due to structural similarity, and this also makes the application of natural polymers in silicon negative electrode systems more limited.
Disclosure of Invention
The invention aims to provide a photocuring aqueous polyurethane emulsion, a lithium ion battery anode material, and a preparation method and application thereof, and solves the problem of insufficient expressive force of the conventional commercial adhesive.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a photo-curing aqueous polyurethane emulsion, which comprises the following steps:
(1) Mixing diisocyanate, polyethylene glycol, a catalyst and a solvent, and performing a prepolymerization reaction to obtain a prepolymerized product;
(2) Adding a chain extender into the prepolymerization product to perform a chain extension reaction to obtain a chain extension product;
(3) Adding hydroxyethyl acrylate into the chain extension product to carry out end capping reaction to obtain polyurethane;
(4) Adding LiOH solution into polyurethane to obtain lithiated polyurethane, and then emulsifying to obtain aqueous polyurethane emulsion;
(5) And adding a photoinitiator into the emulsion to obtain the photo-curing aqueous polyurethane emulsion.
Preferably, in the preparation method of the photo-curing aqueous polyurethane emulsion, the diisocyanate is one of isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate and hexamethylene diisocyanate;
the catalyst is stannous iso-octoate, stannous octoate or dibutyl tin dilaurate; the solvent is acetone, N-dimethylformamide, tetrahydrofuran or N, N-dimethylacetamide; the chain extender is dimethylolbutyric acid or dimethylolpropionic acid; the photoinitiator is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone or phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide;
the lithiation degree of the lithiated polyurethane is 50-100%.
Preferably, in the above-mentioned preparation method of a photocurable aqueous polyurethane emulsion,
the dosage ratio of the diisocyanate, the polyethylene glycol, the catalyst and the solvent is 1-3 mol:0.3 to 0.8mol:0.3 to 1g: 1-4L;
the molar volume ratio of the diisocyanate, the chain extender, the hydroxyethyl acrylate, the LiOH solution and the photoinitiator is 1-3 mol:0.3 to 0.8mol:0.6 to 2mol: 1-3L: 10-30 mmol, wherein the concentration of the LiOH solution is 0.1-0.3 mol/L.
Preferably, in the above-mentioned preparation method of a photocurable aqueous polyurethane emulsion,
the time of the prepolymerization reaction is 1-3 h, the time of the chain extension reaction is 1-3 h, and the time of the end capping reaction is 5-7 h;
the temperature of the prepolymerization reaction, the chain extension reaction and the end capping reaction is independently 50-70 ℃.
The invention also provides a photo-curing aqueous polyurethane emulsion prepared by the preparation method of the photo-curing aqueous polyurethane emulsion, wherein the solid content of the photo-curing aqueous polyurethane emulsion is 30-35 wt%.
The invention also provides a preparation method of the lithium ion battery anode material, which comprises the following steps:
(1) Lithiation is carried out on polyacrylic acid to obtain lithiated polyacrylic acid; mixing the lithiated polyacrylic acid with the photo-curing aqueous polyurethane emulsion, and curing to obtain a binder;
(2) Adding a negative electrode active material and conductive carbon powder into the binder to prepare a lithium battery negative electrode material;
the light-cured aqueous polyurethane emulsion is prepared by a preparation method of the light-cured aqueous polyurethane emulsion.
Preferably, in the preparation method of the lithium ion battery anode material, the lithiation degree of the lithiated polyacrylic acid is 10-100%, the conductive carbon powder is SuperP, the anode active material is nano silicon powder, and the particle size of the nano silicon powder is 20-200 nm; the mass ratio of the polyacrylic acid to the photo-curing aqueous polyurethane emulsion is 0.04-0.12: 1g; the mass ratio of the binder to the anode active material to the SuperP is 5-7: 1 to 3:1 to 3.
Preferably, in the preparation method of the lithium ion battery anode material, the ultraviolet wavelength of the curing is 200-350 nm, the power of the curing is 5-400W, and the curing time is 10-20 min.
The invention also provides a lithium ion battery anode material prepared by the preparation method of the lithium ion battery anode material.
The invention also provides application of the lithium ion battery cathode material in a lithium ion secondary battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) The photocuring aqueous polyurethane emulsion is the photocuring aqueous polyurethane suitable for a lithium ion battery silicon negative electrode system, a double bond end-capped structure of the photocuring aqueous polyurethane can be initiated by ultraviolet light to form a three-dimensional network structure with stronger coating, the reaction is efficient and quick, the photocuring aqueous polyurethane emulsion is suitable for a water system, can act on various water system commercial binders, and is in accordance with the development concept of green chemistry.
(2) The photo-curing aqueous polyurethane emulsion has good mechanical properties, can relieve the volume expansion effect of silicon particles, ensures that an electrode system is more stable, and can adjust the physical properties of commercial binders to ensure that the properties of the commercial binders are more stable.
(3) The ether oxygen chain segment and the carboxylic acid lithium group of the photo-curing aqueous polyurethane emulsion can play a role in conducting lithium ions, so that the lithium ion battery containing the material can obtain more efficient ion transmission.
(4) Compared with a lithium ion battery using pure polyacrylic acid as a binder, the lithium ion battery assembled by the lithium ion battery cathode material has the advantages of smaller impedance, better multiplying power performance and cycle stability performance and better comprehensive performance.
(5) The lithium ion battery assembled by the lithium ion battery cathode material has excellent comprehensive performance, can be applied to portable handheld electronic products or electric vehicles, and has good market prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a graph showing peel strength of a negative electrode tab of a lithium battery in example 1;
FIG. 2 is a graph showing peel strength of a negative electrode tab of a lithium battery in comparative example 1;
FIG. 3 is a graph showing peel strength of a negative electrode tab of a lithium battery in comparative example 2;
fig. 4 is an impedance test chart of the CR2025 button cell in example 1 and comparative example 1;
FIG. 5 is a graph showing diffusion coefficients of CR2025 button cells in example 1 and comparative example 1;
fig. 6 is a graph showing the rate performance of CR2025 button cells in example 1 and comparative example 1;
FIG. 7 shows the CR2025 button cell of example 1 and comparative example 1 at 2A.g -1 Long cycle performance plots for the tests at current densities of (3).
Detailed Description
The invention provides a preparation method of a photo-curing aqueous polyurethane emulsion, which comprises the following steps:
(1) Mixing diisocyanate, polyethylene glycol, a catalyst and a solvent, and performing a prepolymerization reaction to obtain a prepolymerized product;
(2) Adding a chain extender into the prepolymerization product to perform a chain extension reaction to obtain a chain extension product;
(3) Adding hydroxyethyl acrylate into the chain extension product to carry out end capping reaction to obtain polyurethane;
(4) Adding LiOH solution into polyurethane to obtain lithiated polyurethane, and then emulsifying to obtain aqueous polyurethane emulsion;
(5) And adding a photoinitiator into the emulsion to obtain the photo-curing aqueous polyurethane emulsion.
In the invention, the specific mixing process in the step (1) is as follows: after diisocyanate, polyethylene glycol and a catalyst are mixed, an anhydrous and anaerobic reaction device is built, then the reaction device is filled with protective gas by pumping air, and then a solvent is added, wherein the protective gas is argon.
In the present invention, the amount ratio of diisocyanate, polyethylene glycol, catalyst and solvent in the step (1) is preferably 1 to 3mol:0.3 to 0.8mol:0.3 to 1g:1 to 4L, more preferably 1.25 to 2.8mol:0.4 to 0.75mol:0.4 to 0.8g:1.5 to 3.5L, more preferably 1.5mol:0.5mol:0.5g:2L.
In the present invention, the diisocyanate in the step (1) is preferably one of isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, and hexamethylene diisocyanate, more preferably one of isophorone diisocyanate, diphenylmethane diisocyanate, and dicyclohexylmethane diisocyanate, and still more preferably isophorone diisocyanate.
In the present invention, the polyethylene glycol in the step (1) is preferably HO- [ CH ] 2 CH 2 O] n -H, n is 1 to 250, more preferably polyethylene glycol 800, n=18.
In the present invention, the catalyst in the step (1) is preferably stannous iso-octoate, stannous octoate or dibutyltin dilaurate, more preferably stannous iso-octoate or stannous octoate, and still more preferably stannous iso-octoate.
In the present invention, the solvent in the step (1) is preferably acetone, N-dimethylformamide, tetrahydrofuran or N, N-dimethylacetamide, more preferably acetone, N-dimethylformamide or tetrahydrofuran, and still more preferably acetone.
In the present invention, the time of the prepolymerization reaction in the step (1) is preferably 1 to 3 hours, more preferably 1, 1.5, 2, 2.5 or 3 hours, still more preferably 1.5, 2 or 2.5 hours; the temperature of the prepolymerization is preferably 50 to 70℃and more preferably 50, 54, 58, 60, 62, 66 or 70℃and still more preferably 58, 60 or 62 ℃.
In the present invention, the molar volume ratio of the diisocyanate in the step (1), the chain extender in the step (2), the hydroxyethyl acrylate in the step (3), the LiOH solution in the step (4) and the photoinitiator in the step (5) is preferably 1 to 3mol:0.3 to 0.8mol:0.6 to 2mol: 1-3L: 10 to 30mmol, more preferably 1.25 to 2.8mol:0.45 to 0.7mol:0.7 to 2.7mol:1.3 to 2.7L:12 to 27mmol, more preferably 1.5mol:0.5mol:1mol:2L:15mmol.
In the present invention, the chain extender in the step (2) is preferably dimethylolbutyric acid or dimethylolpropionic acid, more preferably dimethylolbutyric acid.
In the present invention, the chain extender is added in the step (2), and further preferably, a mixed solution of the chain extender and a solvent is added, wherein the solvent is the same as the solvent in the step (1), and the molar volume of the chain extender and the mixed solution is preferably 0.3 to 0.8mol: 2-5 mL.
In the present invention, the time of the chain extension reaction in the step (2) is preferably 1 to 3 hours, more preferably 1, 1.2, 1.6, 1.8, 2, 2.4, 2.8 or 3 hours, still more preferably 1.6, 1.8 or 2 hours, and the temperature of the chain extension reaction in the step (2) is the same as the temperature of the prepolymerization reaction in the step (1).
In the present invention, the time of the end-capping reaction in the step (3) is preferably 5 to 7 hours, more preferably 5, 5.5, 6, 6.5 or 7 hours, still more preferably 5.5, 6 or 6.5 hours, and the temperature of the end-capping reaction in the step (3) is the same as the temperature of the prepolymerization reaction in the step (1).
In the present invention, the structural general formula of the polyurethane in the step (3) is:
wherein R comprises one of A, B, C, D, E, wherein A, B, C, D, E are each:
in the present invention, the concentration of the LiOH solution in the step (4) is preferably 0.1 to 0.3mol/L, more preferably 0.15 to 0.27mol/L, and still more preferably 0.2mol/L.
In the present invention, the lithiation degree of the polyurethane after the lithiation in the step (4) is preferably 50 to 100%, more preferably 50, 55, 60, 65, 70, 75, 80, 85, 90 or 100%, still more preferably 50, 55, 60, 65 or 70%.
In the invention, the specific process of emulsification in the step (4) is as follows: the lithiated polyurethane is subjected to shear emulsification, the rate of shear is preferably 300 to 2000rpm, more preferably 300, 400, 500, 600, 700, 800, 900, 1000, 1100 or 1200rpm, more preferably 500, 600, 700 or 800rpm, and the time of shear emulsification is preferably 20 to 40min, more preferably 20, 25, 30, 35 or 40min, more preferably 25 or 30min.
In the present invention, the step (4) further includes: the emulsion obtained after emulsification is transferred to a rotary evaporator, and acetone is removed by rotary evaporation.
In the present invention, the photoinitiator in the step (5) is preferably 2-hydroxy-4 '- (2-hydroxyethoxy) -2-methylpropenyl acetone or phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, more preferably 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropenyl acetone.
The invention also provides a light-cured aqueous polyurethane emulsion prepared by the preparation method of the light-cured aqueous polyurethane emulsion, wherein the solid content of the light-cured aqueous polyurethane emulsion is preferably 30-35 wt%, more preferably 30, 31, 32, 33, 34 or 35wt%, and even more preferably 32 or 33wt%.
The invention also provides a preparation method of the lithium ion battery anode material, which comprises the following steps:
(1) Lithiation is carried out on polyacrylic acid to obtain lithiated polyacrylic acid; mixing the lithiated polyacrylic acid with the photo-curing aqueous polyurethane emulsion, and curing to obtain a binder;
(2) Adding a negative electrode active material and conductive carbon powder into the binder to prepare a lithium battery negative electrode material;
the light-cured aqueous polyurethane emulsion is prepared by a preparation method of the light-cured aqueous polyurethane emulsion.
In the invention, the specific process of lithiation of the polyacrylic acid in the step (1) is as follows: mixing polyacrylic acid, water and lithium hydroxide to obtain lithiated polyacrylic acid, wherein the molar volume ratio of the lithium hydroxide to the polyacrylic acid to the water is 1mol:1 to 5mol:10 to 30L, more preferably 1mol:1.5 to 4.5mol:15 to 28L, more preferably 1mol:2mol:22L.
In the present invention, the lithiation degree of the polyacrylic acid after the lithiation in the step (1) is preferably 10 to 100%, more preferably 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100%, still more preferably 40, 50 or 60%.
In the invention, the mass ratio of the polyacrylic acid to the photo-curing aqueous polyurethane emulsion in the step (1) is preferably 0.04-0.12: 1, more preferably 0.05 to 0.1:1, more preferably 0.08:1.
in the present invention, the ultraviolet wavelength cured in the step (1) is preferably 200 to 350nm, more preferably 200, 220, 240, 260, 290, 300, 330 or 350nm, and still more preferably 260, 290 or 300nm; the curing power in the step (1) is preferably 5 to 400W, more preferably 5, 10, 20, 50, 100, 150, 200, 250, 300, 350, 400W, still more preferably 250, 300 or 350W; the curing time in the step (1) is preferably 10 to 20 minutes, more preferably 10, 13, 15, 17 or 20 minutes, and still more preferably 13, 15 or 17 minutes.
In the present invention, after adding the negative electrode active material and the conductive carbon powder to the binder in the step (2), the method further includes: heating at 80 ℃ for 30min, stopping heating, and continuously stirring for 12h to obtain uniform slurry, namely the lithium battery anode material.
In the present invention, the conductive carbon powder in the step (2) is preferably SuperP.
In the present invention, the negative electrode active material in the step (2) is preferably nano silicon powder having a particle diameter of preferably 20 to 200nm, more preferably 20, 30, 50, 70, 100, 120, 140, 160, 180 or 200nm, and still more preferably 50, 70 or 100nm.
In the present invention, the mass ratio of the binder in the step (1), the negative electrode active material in the step (2), and the super p in the step (2) is preferably 5 to 7:1 to 3:1 to 3, more preferably 5.5 to 6.5:1.5 to 2.7:1.5 to 2.7, more preferably 6:2:2.
in the invention, the method for preparing the lithium battery negative electrode material into the lithium battery negative electrode plate comprises the following steps: coating the prepared lithium battery negative electrode material on a copper foil, removing the solvent, cutting into round electrode slices, removing the solvent again to obtain the lithium battery negative electrode slice, wherein the thickness of the copper foil is preferably 9 mu m, the diameter of the round electrode slice is preferably 15mm, and the solvent removing process is as follows: removing the solvent in a blast oven at 60 ℃; the process of removing the solvent again is as follows: the solvent was thoroughly removed by drying in a vacuum oven at 120℃for 24 h.
The invention also provides application of the lithium ion battery cathode material in a lithium ion secondary battery.
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the photo-curing aqueous polyurethane emulsion comprises the following steps:
(1) 3.330g (0.015 mol) isophorone diisocyanate, 4.000g (0.005 mol) polyethylene glycol 800 and 1 drop (0.005 g) stannous isooctanoate are added into a three-neck flask, an anhydrous anaerobic reaction device is built, the system is filled with argon gas by pumping and ventilating for 3 times, 20mL of acetone is added, and the prepolymerization reaction is carried out for 2 hours at 60 ℃ to obtain a prepolymerization product;
(2) Adding 2mL of an acetone solution of dimethylolbutyric acid into the prepolymerization product, wherein the content of dimethylolbutyric acid is 0.740g (0.005 mol), and carrying out chain extension reaction for 2h to obtain a chain extension product;
(3) Adding 1.16g (0.010 mol) of hydroxyethyl acrylate into the chain extension product, carrying out end-capping reaction for 6 hours, stopping heating and cooling to room temperature to obtain polyurethane;
(4) To the polyurethane was added 20mL of LiOH solution, wherein LiOH.H 2 O content is 0.168g (0.004 mol) to obtain lithiated polyurethane, then shearing and emulsifying for 30min at a stirring speed of 600rpm, transferring the emulsified emulsion to a rotary evaporator, and removing acetone by rotary evaporation for 2h at 40 ℃ to obtain aqueous polyurethane emulsion;
(5) To the emulsion was added 0.030g (0.150 mmol) of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionacetone, and the mixture was uniformly mixed to obtain a photocurable aqueous polyurethane emulsion.
The solid content in the photo-curing aqueous polyurethane emulsion is 32.049wt% calculated by adopting a differential method.
The preparation method of the lithium ion anode material comprises the following steps:
(1) 0.008g (0.180 mmol) of polyacrylic acid was dissolved in 2mL of deionized water, and 0.004g (0.095 mmol) of LiOH H was added 2 O, uniformly mixing to obtain lithiated polyacrylic acid, adding 0.100g of the prepared aqueous polyurethane emulsion, uniformly mixing, and curing in a 290nm and 300W ultraviolet oven for 15min to obtain a binder;
(2) Adding 0.120g of 50nm nano silicon powder and 0.040g of Super P into the binder, uniformly mixing, heating at 80 ℃ for 30min, stopping heating, and continuously stirring for 12h to obtain uniform slurry, namely the lithium battery anode material.
The prepared lithium battery negative electrode material is coated on a copper foil with the thickness of 9 mu m, the solvent is removed in a blast oven at 60 ℃, then the copper foil is cut into round electrode slices with the diameter of 15mm, and the round electrode slices are dried in a vacuum oven at 120 ℃ for 24 hours to thoroughly remove the solvent, so that the lithium battery negative electrode slices are obtained.
The prepared negative electrode plate is assembled into a CR2025 button cell, the counter electrode is a lithium plate,the separator material is Celgard2400 type polypropylene film (PP), and the electrolyte solution is 1M LiPF 6 in EC/DEC (1:1, vol%) with 10% FEC. The assembled CR2025 button cell was left to stand for 24 hours and then subjected to electrochemical performance testing in a incubator at 25 ℃.
Comparative example 1
The preparation method of the lithium ion battery negative electrode plate comprises the following steps:
2mL of deionized water was taken, 0.040g (0.909 mmol) of polyacrylic acid was added, and 0.019g (0.455 mmol) of LiOH H was added 2 O is stirred and dissolved uniformly to obtain a binder, 0.120g of nano silicon powder and 0.040g of Super P are added into the binder, the mixture is stirred uniformly to prepare slurry, and the slurry is coated on copper foil with the thickness of 9 mu m, dried and cut into circular electrode plates with the diameter of 15 mm.
The prepared cathode material is assembled into a CR2025 button cell, the counter electrode is a metal lithium sheet, the diaphragm is Celgard2400 type polypropylene film (PP), and the electrolyte solution is 1M LiPF 6 in EC/DEC (1:1, vol%) with 10% FEC. The assembled button cell was allowed to stand for 24 hours and then subjected to electrochemical performance testing in a incubator at 25 ℃.
Comparative example 2
The preparation method of the lithium ion battery negative electrode plate comprises the following steps:
2mL of deionized water is taken, 0.128g of the photo-curing aqueous polyurethane emulsion prepared in the example 1 is added, the mixture is stirred uniformly and then cured in a 290nm/300W ultraviolet oven for 15min, a binder is obtained after curing, 0.120g of nano silicon powder and 0.040g of Super P are added into the binder, the mixture is stirred uniformly to prepare slurry, and the slurry is coated on copper foil with the thickness of 9 mu m, dried and cut into round electrode slices with the diameter of 15 mm.
The prepared cathode material is assembled into a CR2025 button cell, the counter electrode is a metal lithium sheet, the diaphragm is Celgard2400 type polypropylene film (PP), and the electrolyte solution is 1M LiPF 6 in EC/DEC (1:1, vol%) with 10% FEC. The assembled button cell was allowed to stand for 24 hours and then subjected to electrochemical performance testing in a incubator at 25 ℃.
18 were carried out on CR2025 button cells prepared in example 1, comparative example 1, and comparative example 2The 0 ° peel test, the test results are shown in fig. 1 to 3. As shown in the graph, the average peel strength of CR2025 button cell prepared in example 1, comparative example 1, and comparative example 2 was 0.31 kN.multidot.m -1 、0.25kN·m -1 And 0.10 kN.m -1 . The binding capacity of the binder in example 1 is obviously better than that of the binders in comparative examples 1 and 2, and the fact that the polyacrylic acid and the aqueous polyurethane material are not simply mechanically blended in a system, but form a more complex network structure under the influence of acting forces such as hydrogen bonds and the like, so that the binding capacity of the material is enhanced.
The CR2025 coin cells prepared in example 1 and comparative example 1 were subjected to an impedance test before charge and discharge cycles and an ion diffusion coefficient calculated from the impedance, and the test results are shown in fig. 4 and 5. As shown in fig. 4, the CR2025 button cell prepared in example 1 had an initial charge transfer resistance slightly lower than that of the cell prepared in comparative example 1. Fig. 5 can be deduced from fig. 4, and the slope of the fitted curve of the CR2025 button cell prepared in example 1 and comparative example 1 in fig. 5 is brought into the formula:
the calculated lithium ion diffusion coefficients are respectively 1.96 multiplied by 10 -14 cm 2 s -1 And 1.89×10 -15 cm 2 s -1 I.e., the lithium ion diffusion coefficient of example 1 is much greater than that of comparative example 1, and exhibits better electrochemical cycle performance and stability.
The CR2025 button cell prepared in example 1 and comparative example 1 was subjected to a rate performance test and a cycle performance test, and the test results are shown in fig. 6 and 7. Current density during the test 1 c=4200 mah·g -1 The multiplying power performance test process includes multiplying power of 0.1C, 0.2C, 0.5C, 1C and 0.1C respectively (the multiplying power of 0.1C is from 1C back to 0.1C), and the current density during long-cycle test is 0.5C. As can be seen from FIGS. 6 and 7, the CR2025 button cell prepared in example 1 had better rate performance and cycle stability at high current density than the C prepared in comparative example 1R2025 button cell, and as shown in FIG. 7, the CR2025 button cell had a specific discharge capacity of 1129.9 mAh.g after 100 cycles at a current density of 0.5C -1 . By combining the comparison of the diffusion coefficient calculation results of fig. 5, it is proved that the photo-curing aqueous polyurethane emulsion prepared in example 1 can better promote lithium ion transmission in a lithium ion battery silicon negative electrode system by taking the photo-curing aqueous polyurethane emulsion as a binder, and a more stable solid electrolyte contact interface is constructed, so that more stable electrochemical performance can be shown.
Example 2
The preparation method of the photo-curing aqueous polyurethane emulsion comprises the following steps:
(1) 3.750g (0.015 mol) of diphenylmethane diisocyanate, 4.000g (0.005 mol) of polyethylene glycol 800 and 1 drop of stannous isooctanoate (0.005 g) are added into a three-neck flask, an anhydrous and anaerobic reaction device is built, the system is filled with argon gas by pumping and ventilating for 3 times, 20mL of acetone is added, and the prepolymerization reaction is carried out for 2 hours at 60 ℃ to obtain a prepolymerization product;
(2) Adding 2mL of an acetone solution of dimethylolbutyric acid into the prepolymerization product, wherein the content of dimethylolbutyric acid is 0.740g (0.005 mol), and carrying out chain extension reaction for 2h to obtain a chain extension product;
(3) Adding 1.16g (0.010 mol) of hydroxyethyl acrylate into the chain extension product, carrying out end-capping reaction for 6 hours, stopping heating and cooling to room temperature to obtain polyurethane;
(4) To the polyurethane was added 20mL of LiOH solution, wherein LiOH.H 2 O content is 0.168g (0.004 mol) to obtain lithiated polyurethane, then shearing and emulsifying for 30min at a stirring speed of 600rpm, transferring the emulsified emulsion to a rotary evaporator, and removing acetone by rotary evaporation for 2h at 40 ℃ to obtain aqueous polyurethane emulsion;
(5) To the emulsion was added 0.030g (0.150 mmol) of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionacetone, and the mixture was uniformly mixed to obtain a photocurable aqueous polyurethane emulsion.
The solid content in the photo-curing aqueous polyurethane emulsion is 33.005wt% calculated by adopting a differential method.
The preparation method of the lithium ion anode material comprises the following steps:
(1) 0.008g (0.180 mol) of polyacrylic acid was dissolved in 2mL of deionized water, and 0.004g (0.095 mol) of LiOH H was added 2 O, uniformly mixing to obtain lithiated polyacrylic acid, then adding 0.0097g of the prepared photo-curing aqueous polyurethane emulsion, uniformly mixing, and curing in a 290nm and 300W ultraviolet oven for 15min to obtain a binder;
(2) Adding 0.120g of 50nm nano silicon powder and 0.040g of Super P into the binder, uniformly mixing, heating at 80 ℃ for 30min, stopping heating, and continuously stirring for 12h to obtain uniform slurry, namely the lithium battery anode material.
The prepared lithium battery negative electrode material is coated on a copper foil with the thickness of 9 mu m, the solvent is removed in a blast oven at 60 ℃, then the copper foil is cut into round electrode slices with the diameter of 15mm, and the round electrode slices are dried in a vacuum oven at 120 ℃ for 24 hours to thoroughly remove the solvent, so that the lithium battery negative electrode slices are obtained.
The prepared negative electrode plate is assembled into a CR2025 button cell, the counter electrode is a lithium plate, the used diaphragm material is Celgard2400 type polypropylene film (PP), and the electrolyte solution is 1M LiPF 6 in EC/DEC (1:1, vol%) with 10% FEC. The assembled CR2025 button cell was left to stand for 24 hours and then subjected to electrochemical performance testing in a incubator at 25 ℃. After the CR2025 button cell is cycled for 100 circles under the current density of 0.5C, the specific discharge capacity is 1058.6 mAh.g -1 。
Example 3
The preparation method of the photo-curing aqueous polyurethane emulsion comprises the following steps:
(1) 2.520g (0.015 mol) of hexamethylene diisocyanate, 4.000g (0.005 mol) of polyethylene glycol 800 and 1 drop of stannous isooctanoate (0.005 g) are added into a three-neck flask, an anhydrous and anaerobic reaction device is built, the system is filled with argon gas by pumping and ventilating for 3 times, 20mL of acetone is added, and the prepolymerization reaction is carried out for 2 hours at 60 ℃ to obtain a prepolymerization product;
(2) Adding 2mL of an acetone solution of dimethylolbutyric acid into the prepolymerization product, wherein the content of dimethylolbutyric acid is 0.740g (0.005 mol), and carrying out chain extension reaction for 2h to obtain a chain extension product;
(3) Adding 1.16g (0.010 mol) of hydroxyethyl acrylate into the chain extension product, carrying out end-capping reaction for 6 hours, stopping heating and cooling to room temperature to obtain polyurethane;
(4) To the polyurethane was added 20mL of LiOH solution, wherein LiOH.H 2 O content is 0.168g (0.004 mol) to obtain lithiated polyurethane, then shearing and emulsifying for 30min at a stirring speed of 600rpm, transferring the emulsified emulsion to a rotary evaporator, and removing acetone by rotary evaporation for 2h at 40 ℃ to obtain aqueous polyurethane emulsion;
(5) To the emulsion was added 0.030g (0.150 mmol) of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionacetone, and the mixture was uniformly mixed to obtain a photocurable aqueous polyurethane emulsion.
The solid content in the photo-curing aqueous polyurethane emulsion is 30.126wt% calculated by adopting a differential method.
The preparation method of the lithium ion anode material comprises the following steps:
(1) 0.008g (0.180 mmol) of polyacrylic acid was dissolved in 2mL of deionized water, and 0.004g (0.095 mmol) of LiOH H was added 2 O, uniformly mixing to obtain lithiated polyacrylic acid, adding 0.106g of the prepared aqueous polyurethane emulsion, uniformly mixing, and curing in a 290nm and 300W ultraviolet oven for 15min to obtain a binder;
(2) Adding 0.120g of 50nm nano silicon powder and 0.040g of Super P into the binder, uniformly mixing, heating at 80 ℃ for 30min, stopping heating, and continuously stirring for 12h to obtain uniform slurry, namely the lithium battery anode material.
The prepared lithium battery negative electrode material is coated on a copper foil with the thickness of 9 mu m, the solvent is removed in a blast oven at 60 ℃, then the copper foil is cut into round electrode slices with the diameter of 15mm, and the round electrode slices are dried in a vacuum oven at 120 ℃ for 24 hours to thoroughly remove the solvent, so that the lithium battery negative electrode slices are obtained.
The prepared negative electrode plate is assembled into a CR2025 button cell, the counter electrode is a lithium plate, the used diaphragm material is Celgard2400 type polypropylene film (PP), and the electrolyte solution is 1M LiPF 6 in EC/DEC (1:1, vol%) with 10% FEC. The assembled CR2025 button cell was left to stand for 24 hours and then subjected to electrochemical performance testing in a incubator at 25 ℃. The CR2025 button cell described above cycled at a current density of 0.5CAfter 100 circles, the specific discharge capacity is 989.5 mAh.g -1 。
Example 4
The preparation method of the photo-curing aqueous polyurethane emulsion comprises the following steps:
(1) 2.612g (0.015 mol) of toluene diisocyanate, 4.000g (0.005 mol) of polyethylene glycol 800 and 1 drop of stannous isooctanoate (0.005 g) are added into a three-neck flask, an anhydrous and anaerobic reaction device is built, the system is filled with argon gas by pumping and ventilating for 3 times, 20mL of acetone is added, and the prepolymerization reaction is carried out for 2 hours at 60 ℃ to obtain a prepolymerization product;
(2) Adding 2mL of an acetone solution of dimethylolbutyric acid into the prepolymerization product, wherein the content of dimethylolbutyric acid is 0.740g (0.005 mol), and carrying out chain extension reaction for 2h to obtain a chain extension product;
(3) Adding 1.16g (0.010 mol) of hydroxyethyl acrylate into the chain extension product, carrying out end-capping reaction for 6 hours, stopping heating and cooling to room temperature to obtain polyurethane;
(4) To the polyurethane was added 20mL of LiOH solution, wherein LiOH.H 2 O content is 0.168g (0.004 mol) to obtain lithiated polyurethane, then shearing and emulsifying for 30min at a stirring speed of 600rpm, transferring the emulsified emulsion to a rotary evaporator, and removing acetone by rotary evaporation for 2h at 40 ℃ to obtain aqueous polyurethane emulsion;
(5) To the emulsion was added 0.030g (0.150 mmol) of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionacetone, and the mixture was uniformly mixed to obtain a photocurable aqueous polyurethane emulsion.
The solid content in the photo-curing aqueous polyurethane emulsion is 30.350wt% calculated by adopting a differential method.
The preparation method of the lithium ion anode material comprises the following steps:
(1) 0.008g (0.180 mmol) of polyacrylic acid was dissolved in 2mL of deionized water, and 0.004g (0.095 mmol) of LiOH H was added 2 O, uniformly mixing to obtain lithiated polyacrylic acid, adding 0.105g of the prepared aqueous polyurethane emulsion, uniformly mixing, and curing in a 290nm and 300W ultraviolet oven for 15min to obtain a binder;
(2) Adding 0.120g of 50nm nano silicon powder and 0.040g of Super P into the binder, uniformly mixing, heating at 80 ℃ for 30min, stopping heating, and continuously stirring for 12h to obtain uniform slurry, namely the lithium battery anode material.
The prepared lithium battery negative electrode material is coated on a copper foil with the thickness of 9 mu m, the solvent is removed in a blast oven at 60 ℃, then the copper foil is cut into round electrode slices with the diameter of 15mm, and the round electrode slices are dried in a vacuum oven at 120 ℃ for 24 hours to thoroughly remove the solvent, so that the lithium battery negative electrode slices are obtained.
The prepared negative electrode plate is assembled into a CR2025 button cell, the counter electrode is a lithium plate, the used diaphragm material is Celgard2400 type polypropylene film (PP), and the electrolyte solution is 1M LiPF 6 in EC/DEC (1:1, vol%) with 10% FEC. The assembled CR2025 button cell was left to stand for 24 hours and then subjected to electrochemical performance testing in a incubator at 25 ℃. After the CR2025 button cell is cycled for 100 circles under the current density of 0.5C, the specific discharge capacity is 1032.7 mAh.g -1 。
Example 5
The preparation method of the photo-curing aqueous polyurethane emulsion comprises the following steps:
(1) 3.935g (0.015 mol) dicyclohexylmethane diisocyanate, 4.000g (0.005 mol) polyethylene glycol 800 and 1 drop of stannous isooctanoate (0.005 g) are added into a three-neck flask, an anhydrous and anaerobic reaction device is built, the system is filled with argon gas by pumping and ventilating for 3 times, 20mL of acetone is added, and the prepolymerization reaction is carried out for 2 hours at 60 ℃ to obtain a prepolymerization product;
(2) Adding 2mL of an acetone solution of dimethylolbutyric acid into the prepolymerization product, wherein the content of dimethylolbutyric acid is 0.740g (0.005 mol), and carrying out chain extension reaction for 2h to obtain a chain extension product;
(3) Adding 1.16g (0.010 mol) of hydroxyethyl acrylate into the chain extension product, carrying out end-capping reaction for 6 hours, and stopping heating to obtain polyurethane;
(4) To the polyurethane was added 20mL of LiOH solution, wherein LiOH.H 2 O content is 0.168g (0.004 mol) to obtain lithiated polyurethane, then shearing and emulsifying for 30min at a stirring speed of 600rpm, transferring the emulsified emulsion to a rotary evaporator, and removing acetone by rotary evaporation for 2h at 40 ℃ to obtain aqueous polyurethane emulsion;
(5) To the emulsion was added 0.030g (0.150 mmol) of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionacetone, and the mixture was uniformly mixed to obtain a photocurable aqueous polyurethane emulsion.
The solid content in the photo-curing aqueous polyurethane emulsion is 33.418wt% calculated by adopting a differential method.
The preparation method of the lithium ion anode material comprises the following steps:
(1) 0.008g (0.180 mol) of polyacrylic acid was dissolved in 2mL of deionized water, and 0.004g (0.095 mol) of LiOH H was added 2 O, uniformly mixing to obtain lithiated polyacrylic acid, adding 0.096g of the prepared aqueous polyurethane emulsion, uniformly mixing, and curing in a 290nm and 300W ultraviolet oven for 15min to obtain a binder;
(2) Adding 0.120g of 50nm nano silicon powder and 0.040g of Super P into the binder, uniformly mixing, heating at 80 ℃ for 30min, stopping heating, and continuously stirring for 12h to obtain uniform slurry, namely the lithium battery anode material.
The prepared lithium battery negative electrode material is coated on a copper foil with the thickness of 9 mu m, the solvent is removed in a blast oven at 60 ℃, then the copper foil is cut into round electrode slices with the diameter of 15mm, and the round electrode slices are dried in a vacuum oven at 120 ℃ for 24 hours to thoroughly remove the solvent, so that the lithium battery negative electrode slices are obtained.
The prepared negative electrode plate is assembled into a CR2025 button cell, the counter electrode is a lithium plate, the used diaphragm material is Celgard2400 type polypropylene film (PP), and the electrolyte solution is 1M LiPF 6 in EC/DEC (1:1, vol%) with 10% FEC. The assembled CR2025 button cell was left to stand for 24 hours and then subjected to electrochemical performance testing in a incubator at 25 ℃. After the CR2025 button cell is cycled for 100 circles under the current density of 0.5C, the specific discharge capacity is 856.5 mAh.g -1 。
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. The preparation method of the lithium ion battery anode material is characterized by comprising the following steps of:
(1) Lithiation is carried out on polyacrylic acid to obtain lithiated polyacrylic acid; mixing the lithiated polyacrylic acid with the photo-curing aqueous polyurethane emulsion, and curing to obtain a binder;
(2) Adding a negative electrode active material and conductive carbon powder into the binder to prepare a lithium battery negative electrode material;
the lithiation degree of the lithiated polyacrylic acid is 10-100%;
the ultraviolet wavelength of the curing is 200-350 nm, the power of the curing is 5-400W, and the curing time is 10-20 min;
the preparation method of the photo-curing aqueous polyurethane emulsion comprises the following steps:
a. mixing diisocyanate, polyethylene glycol, a catalyst and a solvent, and performing a prepolymerization reaction to obtain a prepolymerized product;
b. adding a chain extender into the prepolymerization product to perform a chain extension reaction to obtain a chain extension product;
c. adding hydroxyethyl acrylate into the chain extension product to carry out end capping reaction to obtain polyurethane;
d. adding LiOH solution into polyurethane to obtain lithiated polyurethane, and then emulsifying to obtain aqueous polyurethane emulsion;
e. adding a photoinitiator into the emulsion to obtain a photo-curing aqueous polyurethane emulsion;
the chain extender is dimethylolbutyric acid or dimethylolpropionic acid;
the lithiation degree of the lithiated polyurethane is 50-100%.
2. The method for preparing the lithium ion battery anode material according to claim 1, wherein the diisocyanate is one of isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate and hexamethylene diisocyanate;
the catalyst is stannous iso-octoate, stannous octoate or dibutyl tin dilaurate; the solvent is acetone, N-dimethylformamide, tetrahydrofuran or N, N-dimethylacetamide; the photoinitiator is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone or phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide.
3. The method for preparing a negative electrode material for a lithium ion battery according to claim 1 or 2, wherein,
the dosage ratio of the diisocyanate, the polyethylene glycol, the catalyst and the solvent is 1-3 mol:0.3 to 0.8mol:0.3 to 1g: 1-4L;
the molar volume ratio of the diisocyanate, the chain extender, the hydroxyethyl acrylate, the LiOH solution and the photoinitiator is 1-3 mol:0.3 to 0.8mol:0.6 to 2mol: 1-3L: 10-30 mmol, wherein the concentration of the LiOH solution is 0.1-0.3 mol/L.
4. The method for preparing a negative electrode material for a lithium ion battery according to claim 1 or 2, wherein,
the time of the prepolymerization reaction is 1-3 h, the time of the chain extension reaction is 1-3 h, and the time of the end capping reaction is 5-7 h;
the temperature of the prepolymerization reaction, the chain extension reaction and the end capping reaction is independently 50-70 ℃.
5. The method for preparing the lithium ion battery anode material according to claim 4, wherein the conductive carbon powder is SuperP, the anode active material is nano silicon powder, and the particle size of the nano silicon powder is 20-200 nm; the mass ratio of the polyacrylic acid to the photo-curing aqueous polyurethane emulsion is 0.04-0.12: 1g; the mass ratio of the binder to the anode active material to the SuperP is 5-7: 1 to 3:1 to 3.
6. The lithium ion battery anode material prepared by the preparation method of the lithium ion battery anode material of any one of claims 1 to 5.
7. The use of the negative electrode material for lithium ion batteries of claim 6 in lithium ion secondary batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211361913.7A CN115536810B (en) | 2022-11-02 | 2022-11-02 | Photo-curing aqueous polyurethane emulsion, lithium ion battery anode material, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211361913.7A CN115536810B (en) | 2022-11-02 | 2022-11-02 | Photo-curing aqueous polyurethane emulsion, lithium ion battery anode material, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115536810A CN115536810A (en) | 2022-12-30 |
| CN115536810B true CN115536810B (en) | 2023-09-15 |
Family
ID=84720627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211361913.7A Active CN115536810B (en) | 2022-11-02 | 2022-11-02 | Photo-curing aqueous polyurethane emulsion, lithium ion battery anode material, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115536810B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118027894A (en) * | 2024-04-15 | 2024-05-14 | 深圳好电科技有限公司 | Adhesive, negative electrode slurry and lithium ion battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974307A (en) * | 2010-08-13 | 2011-02-16 | 上海材料研究所 | Polyurethane acrylate adhesive containing ionic groups and preparation method thereof |
| CN110364734A (en) * | 2019-06-06 | 2019-10-22 | 华南理工大学 | High-performance water-based compounding negative electrode of lithium ion battery binder and preparation method and application |
| CN111106353A (en) * | 2019-12-30 | 2020-05-05 | 华东理工大学 | Water-based binder for lithium-sulfur battery and preparation method thereof |
| CN113736064A (en) * | 2021-09-29 | 2021-12-03 | 江苏睿浦树脂科技有限公司 | Water-emulsifiable UV (ultraviolet) photocuring anionic resin and preparation method thereof |
-
2022
- 2022-11-02 CN CN202211361913.7A patent/CN115536810B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974307A (en) * | 2010-08-13 | 2011-02-16 | 上海材料研究所 | Polyurethane acrylate adhesive containing ionic groups and preparation method thereof |
| CN110364734A (en) * | 2019-06-06 | 2019-10-22 | 华南理工大学 | High-performance water-based compounding negative electrode of lithium ion battery binder and preparation method and application |
| CN111106353A (en) * | 2019-12-30 | 2020-05-05 | 华东理工大学 | Water-based binder for lithium-sulfur battery and preparation method thereof |
| CN113736064A (en) * | 2021-09-29 | 2021-12-03 | 江苏睿浦树脂科技有限公司 | Water-emulsifiable UV (ultraviolet) photocuring anionic resin and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Poly(urethane acrylate)-based gel polymer films for mechanically stable, transparent, and highly conductive polymer electrolyte applications;Eun-Jin Lee等;JOURNAL OF APPLIED POLYMER SCIENCE;第134卷(第26期) * |
| 水性聚氨酯功能性研究进展;许戈文;鲍俊杰;钟达非;;涂料技术与文摘(03);4-8,11 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115536810A (en) | 2022-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| He et al. | Polyvinyl alcohol grafted poly (acrylic acid) as water-soluble binder with enhanced adhesion capability and electrochemical performances for Si anode | |
| Zheng et al. | A high-resilience and conductive composite binder for lithium-sulfur batteries | |
| WO2017141735A1 (en) | Solid electrolytic composition, electrode sheet for full-solid secondary batteries, full-solid secondary battery, and method for manufacturing electrode sheet for full-solid secondary batteries and full-solid secondary battery | |
| CN107482221B (en) | Polymer crosslinked binder and preparation method and application thereof | |
| CN110061238B (en) | Water-soluble self-healing binder, preparation method thereof and lithium ion battery | |
| CN110350196B (en) | Composite binder, silicon-based negative plate and preparation method thereof | |
| CN111373590A (en) | Method for manufacturing all-solid-state battery | |
| CN115536810B (en) | Photo-curing aqueous polyurethane emulsion, lithium ion battery anode material, preparation method and application thereof | |
| CN105703003A (en) | Comb-shaped polymer, electrolyte and composite electrode for lithium battery, and applications of electrolyte and composite electrode | |
| CN110627997A (en) | Thermoplastic polyurethane adhesive for lithium ion battery and preparation method and application thereof | |
| Zhang et al. | Polydopamine blended with polyacrylic acid for silicon anode binder with high electrochemical performance | |
| Wu et al. | Ionic network for aqueous-polymer binders to enhance the electrochemical performance of Li-Ion batteries | |
| CN113809333B (en) | Organic coating layer, electrode material containing coating layer and lithium ion battery | |
| CN111697217A (en) | Preparation method of silicon/graphite composite cathode of lithium ion battery | |
| Wan et al. | Peach gum as an efficient binder for high-areal-capacity lithium–sulfur batteries | |
| Zheng et al. | PAAS-β-CDp-PAA as a high-performance easily prepared and water-soluble composite binder for high-capacity silicon anodes in lithium-ion batteries | |
| CN111900335A (en) | Silicon-based negative electrode with self-repairing property and preparation method and application thereof | |
| WO2023046155A1 (en) | Organic coating layer and electrode active material containing same, electrode, and battery | |
| CN116404246A (en) | Self-assembled titanium carbide doped polymer solid electrolyte and preparation and application thereof | |
| EP4231404A1 (en) | Composite electrolyte and solid-state battery comprising same | |
| CN115799621A (en) | Composite halide solid electrolyte membrane and solid battery prepared from same | |
| CN113611820A (en) | Solid-state battery pole piece, and preparation method and application thereof | |
| CN115207307A (en) | Lithium/silicon/carbon composite cathode and lithium ion battery comprising same | |
| CN114335495A (en) | Method for preparing silicon-carbon negative electrode material by using waste graphite of lithium ion battery | |
| CN117525575B (en) | Solid electrolyte and preparation method and application 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 |