CN111129497A - Preparation method of inorganic oxide doped aqueous binder - Google Patents
Preparation method of inorganic oxide doped aqueous binder Download PDFInfo
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- CN111129497A CN111129497A CN201911229675.2A CN201911229675A CN111129497A CN 111129497 A CN111129497 A CN 111129497A CN 201911229675 A CN201911229675 A CN 201911229675A CN 111129497 A CN111129497 A CN 111129497A
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- inorganic oxide
- butadiene rubber
- polyvinyl alcohol
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- aqueous binder
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of an inorganic oxide doped aqueous binder, which mainly comprises the following steps: 1. treating the surface of the inorganic oxide by using a silane coupling agent to enhance the surface polarity of the inorganic oxide; 2. dispersing Styrene Butadiene Rubber (SBR) and polyvinyl alcohol by deionized water; 3. adding the obtained inorganic oxide into the dispersed styrene butadiene rubber-polyvinyl alcohol aqueous dispersion, and stirring for 3-6h to obtain the inorganic oxide doped styrene butadiene rubber-polyvinyl alcohol aqueous binder. According to the invention, inorganic oxide particles are doped in the styrene-butadiene rubber and polyvinyl alcohol with good flexibility under the action of strong polarity, so that the interaction between a styrene-butadiene rubber chain segment and a vinyl alcohol chain segment is improved, a cross-linked structure is formed, the crystallinity of linear polyvinyl alcohol is reduced, and the volume expansion effect of the silicon-carbon negative electrode material can be well inhibited.
Description
Technical Field
The invention belongs to the field of new energy materials, and particularly relates to an inorganic oxide doped aqueous binder.
Background
At present, the negative electrode materials of the lithium battery are mainly carbon materials and non-carbon materials, wherein the research on the carbon materials is very mature, but the theoretical capacity of 372mAh/g cannot meet the pursuit of people for the high-energy-density lithium battery. The silicon negative electrode material is widely concerned due to the fact that the theoretical capacity of the silicon negative electrode material is up to 4200mAh/g, and therefore the silicon negative electrode material becomes a research hotspot. However, the silicon negative electrode material has a natural disadvantage that the volume of the material is easy to expand (300%) during charging and discharging of the silicon negative electrode material, which greatly influences the use of the silicon negative electrode material in a lithium battery.
Therefore, many methods have been tried to solve this problem, such as coating a carbon layer on the silicon surface to suppress the expansion effect of silicon, for example, CN109786666A discloses a nitrogen-doped carbon-coated silicon nanoparticle composite material, which can suppress the expansion of silicon material by coating a nitrogen-doped carbon layer on the silicon nanoparticle surface to obtain better cycle stability. CN110010867A discloses a graphene silicon-based flexible composite lithium battery cathode material, which inhibits the expansion effect of silicon nanoparticles by coating a layer of graphene on the surface of the silicon nanoparticles. However, by coating the active material, the activity of the silicon negative electrode is also lowered to some extent, so that the capacity thereof is lowered. In order not to reduce the activity of the silicon negative electrode material, one also mixes some rigid particles in the silicon negative electrode material to reduce the expansion ratio of the silicon negative electrode, for example, CN109817895A adds ceramic particles in the negative electrode slurry to inhibit the expansion of the silicon material. However, the direct doping of the ceramic particles has the problems of difficult dispersion and easy falling off during the use process. The methods are all used for improving the structure and the composition of the silicon-based negative electrode material, and few binders are improved to inhibit the expansion effect of the silicon-based negative electrode material.
Disclosure of Invention
Aiming at the problem that the existing silicon-carbon binder cannot well inhibit the volume effect of a silicon-carbon cathode in the charging and discharging processes, the invention provides a preparation method of an inorganic oxide doped aqueous binder, wherein inorganic oxide particles are doped in styrene-butadiene rubber and polyvinyl alcohol with good flexibility under the action of strong polarity, so that the volume expansion effect of a silicon-carbon cathode material can be well inhibited.
The technical scheme adopted by the invention for solving the problems is as follows:
a method for preparing an inorganic oxide-doped aqueous binder, comprising the steps of:
(1) hydrolysis of the silane coupling agent: adding a silane coupling agent into deionized water, controlling the solid content of the silane coupling agent to be 0.5-1%, adjusting the pH of the solution to 4-5 by using acetic acid, and stirring for 0.5-2h to obtain a silane coupling agent hydrolysis solution;
(2) surface treatment of inorganic oxide: adding inorganic oxide into the silane coupling agent hydrolysis solution obtained in the step (1), performing ultrasonic dispersion for 0.5-1h, and stirring for 6-8h to obtain an inorganic oxide water dispersion liquid with strong polarity on the surface;
(3) and preparing the aqueous binder: adding styrene butadiene rubber and polyvinyl alcohol into deionized water, and stirring for 0.5-2h to obtain styrene butadiene rubber-polyvinyl alcohol dispersion liquid; and (3) mixing the inorganic oxide aqueous dispersion obtained in the step (2) with styrene butadiene rubber-polyvinyl alcohol dispersion, and stirring for 6-8 hours to obtain the inorganic oxide doped aqueous binder.
According to the scheme, the mass ratio of the styrene butadiene rubber, the polyvinyl alcohol and the inorganic oxide is (5-6) to (3-4) to (1-2).
According to the scheme, the solid content of the inorganic oxide in the inorganic oxide water dispersion liquid is about 8-12%, the solid content of the styrene-butadiene rubber-polyvinyl alcohol in the styrene-butadiene rubber-polyvinyl alcohol dispersion liquid is controlled to be 8-12%, and the solid content of the finally prepared inorganic oxide-doped aqueous binder is also about 8-12%.
According to the scheme, the silane coupling agent is selected from any one of gamma-aminopropyltriethoxysilane (KH-550), gamma-aminopropyltriethoxysilane (A-1100), N- β (aminoethyl) -gamma-aminopropylmethyldimethoxysilane (KH-602), and the like.
According to the scheme, the concentration of the acetic acid is 0.5-1.5 mol/L.
According to the scheme, the inorganic oxide is any one of silicon dioxide, titanium dioxide, aluminum oxide and the like, and the particle size is 50-200 nm.
According to the scheme, the molecular weight of the styrene-butadiene rubber is 200000-500000; the molecular weight of the polyvinyl alcohol is 80000-200000.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, inorganic oxide particles are doped in SBR with good flexibility under the action of strong polarity, and the inorganic oxide with strong polarity on the surface can be used as a stress gathering point in styrene butadiene rubber and polyvinyl alcohol to improve the interaction of a styrene butadiene rubber chain segment and a vinyl alcohol chain segment, so that a cross-linked structure is formed, the crystallinity of linear polyvinyl alcohol is reduced, and the volume expansion effect of a silicon-carbon negative electrode material can be well inhibited.
2. According to the invention, by performing polarity treatment on the surface of the inorganic oxide, the inorganic oxide dispersion liquid with uniform dispersion can be obtained, and can be better dispersed in the preparation of the negative electrode slurry, so that the effect of inhibiting the expansion of the negative electrode active material is better; moreover, the method helps the styrene butadiene rubber to disperse through the oxide subjected to surface polarity treatment, and can obtain the negative electrode slurry with better coating effect.
Drawings
Fig. 1 is a cycle test chart of the battery No. 1 prepared in example 1 and a comparative battery.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the following examples, the particle size of the silica used was 50 to 200 nm; the molecular weight of Styrene Butadiene Rubber (SBR) is 200000-400000; the concentration of the acetic acid is 0.5-1.5 mol/L.
Example 1
A method for preparing an inorganic oxide-doped aqueous binder, comprising the steps of:
(1) adding gamma-aminopropyltriethoxysilane (A-1100) into deionized water, controlling the solid content to be 0.5%, adjusting the pH of the solution to 5 by using acetic acid, and stirring for 1h to obtain gamma-aminopropyltriethoxysilane (A-1100) hydrolysis solution;
(2) adding silicon dioxide into the gamma-aminopropyl triethoxysilane hydrolysis solution obtained in the step (1), ultrasonically dispersing for 1h, and stirring for 6h to obtain a silicon dioxide water dispersion liquid with strong polarity on the surface, wherein the solid content of the silicon dioxide is about 10%;
(3) adding styrene-butadiene rubber and polyvinyl alcohol into deionized water, controlling the solid content of the styrene-butadiene rubber to be 6% and the solid content of the polyvinyl alcohol to be 4%, and stirring for 2 hours to obtain a styrene-butadiene rubber-polyvinyl alcohol dispersion liquid; and (3) mixing the silicon dioxide aqueous dispersion obtained in the step (2) with a styrene-butadiene rubber-polyvinyl alcohol dispersion, and stirring for 8 hours to obtain an inorganic oxide-doped aqueous binder with the total solid content of 10%, wherein the mass ratio of the styrene-butadiene rubber-polyvinyl alcohol (namely the total mass of the styrene-butadiene rubber and the polyvinyl alcohol) to the inorganic oxide (namely the silicon dioxide) is 9: 1.
Mixing and grinding nano silicon and graphite according to a mass ratio of 10:80 for 1h, and adding the mixed powder into the binder aqueous solution prepared in example 1 to obtain electrode slurry, wherein the mass ratio of the nano silicon to the graphite to the binder solution is 10: 80: 100; adding deionized water into the electrode slurry to enable the solid content of the slurry system to reach 20-30 wt%, uniformly stirring, coating on the carbon-coated copper foil, and drying at 80 ℃ and 0.1Mpa for 12h to obtain a negative electrode plate; and assembling the obtained negative electrode plate, a polyethylene diaphragm, a lithium sheet and electrolyte into a CR2016 type button cell which is marked as a No. 1 cell.
Polyacrylic acid is used as a binder, deionized water is used as a solvent, an aqueous binder with the mass fraction of 25 wt% is prepared, a negative electrode plate is prepared according to the method, and the negative electrode plate, a polypropylene diaphragm, a lithium plate and electrolyte are assembled into a CR2016 type button cell which is marked as a comparison sample.
Example 2
A method for preparing an inorganic oxide-doped aqueous binder, comprising the steps of:
(1) adding N- β (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane (KH-602) into deionized water, controlling the solid content to be 1%, adjusting the pH of the solution to 4 by using acetic acid, and stirring for 2h to obtain a gamma-aminopropyl triethoxy silane (A-1100) hydrolysis solution.
(2) Adding silicon dioxide with the particle size of 50-200nm into the hydrolysis solution of N- β (aminoethyl) -gamma aminopropyl methyl dimethoxy silane (KBM-603) obtained in the step 1, ultrasonically dispersing for 1h, and stirring for 6h to obtain a silicon dioxide water dispersion liquid with strong polarity on the surface, wherein the solid content of the silicon dioxide is about 10%.
(3) Adding styrene-butadiene rubber and polyvinyl alcohol into deionized water, controlling the solid content of the styrene-butadiene rubber to be 5% and the solid content of the polyvinyl alcohol to be 5%, and stirring for 2 hours to obtain a styrene-butadiene rubber-polyvinyl alcohol dispersion liquid; and (3) mixing the silicon dioxide aqueous dispersion obtained in the step (2) with a styrene butadiene rubber-polyvinyl alcohol dispersion, and stirring for 8 hours to obtain an inorganic oxide doped aqueous binder with the total solid content of 10%, wherein the mass ratio of the styrene butadiene rubber-polyvinyl alcohol to the inorganic oxide is 9: 1.
Mixing and grinding nano silicon and graphite according to a mass ratio of 10:80 for 1h, and adding the mixed powder into the binder aqueous solution prepared in the embodiment 2 to obtain electrode slurry, wherein the mass ratio of the nano silicon to the graphite to the binder solution is 10: 80: 100; adding deionized water into the electrode slurry to enable the solid content of the slurry system to reach 20-30 wt%, uniformly stirring, coating on the carbon-coated copper foil, and drying at 80 ℃ and 0.1Mpa for 12h to obtain a negative electrode plate; and assembling the obtained negative electrode plate, a polyethylene diaphragm, a lithium sheet and electrolyte into a CR2016 type button cell which is marked as a No. 2 cell.
Example 3
A method for preparing an inorganic oxide-doped aqueous binder, comprising the steps of:
(1) adding N- β (aminoethyl) -gamma-aminopropyl methyl dimethoxysilane (KH-602) into deionized water, controlling the solid content to be 0.8%, adjusting the pH of the solution to 4.5 by using acetic acid, and stirring for 0.5h to obtain a gamma-aminopropyl triethoxysilane (A-1100) hydrolysis solution.
(2) Adding silicon dioxide into the hydrolysis solution of N- β (aminoethyl) -gamma aminopropyl methyl dimethoxysilane (KBM-603) obtained in the step 1, ultrasonically dispersing for 1h, and stirring for 6h to obtain a silicon dioxide water dispersion liquid with strong polarity on the surface, wherein the solid content of the silicon dioxide is about 10%.
(3) Adding styrene-butadiene rubber and polyvinyl alcohol into deionized water, controlling the solid content of the styrene-butadiene rubber to be 4% and the solid content of the polyvinyl alcohol to be 6%, and stirring for 2 hours to obtain a styrene-butadiene rubber-polyvinyl alcohol dispersion liquid; and (3) mixing the silicon dioxide aqueous dispersion obtained in the step (2) with a styrene butadiene rubber-polyvinyl alcohol dispersion, and stirring for 8 hours to obtain an inorganic oxide doped aqueous binder with the total solid content of 10%, wherein the mass ratio of the styrene butadiene rubber-polyvinyl alcohol to the inorganic oxide is 8: 2.
Mixing and grinding nano silicon and graphite for 1h according to a mass ratio of 10:80, and adding the mixed powder into the binder aqueous solution prepared in the scheme 1 to obtain electrode slurry, wherein the mass ratio of the nano silicon to the graphite to the binder solution is 10: 80: 100; adding deionized water into the electrode slurry to enable the solid content of the slurry system to reach 20-30 wt%, uniformly stirring, coating on the carbon-coated copper foil, and drying at 80 ℃ and 0.1Mpa for 12h to obtain a negative electrode plate; and assembling the obtained negative electrode plate, a polyethylene diaphragm, a lithium sheet and electrolyte into a CR2016 type button cell which is marked as a No. 3 cell.
TABLE 1
| Battery numbering | Capacity retention rate after 300 cycles of 200mA/g |
| Sample A | 91.4％ |
| Sample B | 92.5％ |
| Sample C | 90.4& |
| Control sample | 86.6％ |
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and changes can be made without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.
Claims (8)
1. A preparation method of an inorganic oxide doped aqueous binder is characterized by comprising the following steps:
(1) hydrolysis of the silane coupling agent: adding a silane coupling agent into deionized water, controlling the solid content of the silane coupling agent to be 0.5-1%, adjusting the pH of the solution to 4-5 by using acetic acid, and stirring for 0.5-2h to obtain a silane coupling agent hydrolysis solution;
(2) surface treatment of inorganic oxide: adding an inorganic oxide into the silane coupling agent hydrolysis solution obtained in the step (1), performing ultrasonic dispersion for 0.5-1h, and stirring for 6-8h to obtain an inorganic oxide aqueous dispersion;
(3) and preparing the aqueous binder: adding styrene butadiene rubber and polyvinyl alcohol into deionized water, and stirring for 0.5-2h to obtain styrene butadiene rubber-polyvinyl alcohol dispersion liquid; and (3) mixing the inorganic oxide aqueous dispersion obtained in the step (2) with styrene butadiene rubber-polyvinyl alcohol dispersion, and stirring for 6-8 hours to obtain the inorganic oxide doped aqueous binder.
2. The method as claimed in claim 1, wherein the mass ratio of styrene-butadiene rubber, polyvinyl alcohol and inorganic oxide is (5-6): (3-4): 1-2).
3. The method of claim 1, wherein the inorganic oxide-doped aqueous binder comprises 8-12% of inorganic oxide in the aqueous dispersion of inorganic oxide, and the styrene-butadiene rubber-polyvinyl alcohol dispersion comprises 8-12% of styrene-butadiene rubber-polyvinyl alcohol.
4. The method of claim 1, wherein the silane coupling agent is selected from the group consisting of γ -aminopropyltriethoxysilane, N- β (aminoethyl) - γ -aminopropylmethyldimethoxysilane.
5. The method of claim 1, wherein the acetic acid is present in a concentration of 0.5 to 1.5 mol/L.
6. The method according to claim 1, wherein the inorganic oxide is any one of silica, titania and alumina, and the particle size is 50-200 nm.
7. The method as claimed in claim 1, wherein the molecular weight of the styrene-butadiene rubber is 200000-500000.
8. The method as claimed in claim 1, wherein the molecular weight of the polyvinyl alcohol is 80000-200000.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242595A (en) * | 2012-02-09 | 2013-08-14 | 三星Sdi株式会社 | Composite binder for battery, and anode and battery including the composite |
| CN104466180A (en) * | 2014-11-14 | 2015-03-25 | 无锡信大气象传感网科技有限公司 | Lithium ion battery negative electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242595A (en) * | 2012-02-09 | 2013-08-14 | 三星Sdi株式会社 | Composite binder for battery, and anode and battery including the composite |
| CN104466180A (en) * | 2014-11-14 | 2015-03-25 | 无锡信大气象传感网科技有限公司 | Lithium ion battery negative electrode material |
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Application publication date: 20200508 |