CN110767863A - Porous SiO for lithium ion battery diaphragm2Preparation method and application of microspheres - Google Patents
Porous SiO for lithium ion battery diaphragm2Preparation method and application of microspheres Download PDFInfo
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- CN110767863A CN110767863A CN201911057803.XA CN201911057803A CN110767863A CN 110767863 A CN110767863 A CN 110767863A CN 201911057803 A CN201911057803 A CN 201911057803A CN 110767863 A CN110767863 A CN 110767863A
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- sio
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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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 provides porous SiO for a lithium ion battery diaphragm2A preparation method and application of microspheres belong to the technical field of battery diaphragm coating. The invention relates to porous SiO used for lithium ion battery diaphragm2The preparation method of the microsphere comprises the following steps: preparation of spherical SiO2Particles; prepared spherical SiO2Adding the particles into water, adding a protective agent, adding an alkali solution, stirring, etching for a certain time, centrifuging, and cleaning to obtain porous SiO2And (3) microspheres. In addition, the invention also provides porous SiO for the lithium ion battery diaphragm2The application of the microspheres comprises taking a certain amount of porous SiO2Dispersing the microspheres with a dispersing agent, adding a certain amount of a binding agent to prepare a coating solution, and coating the base film with the coating solution. The porous SiO prepared by the invention2The preparation of the microspheres is simple; completion of coatingThe diaphragm has good air permeability, good thermal stability and good application prospect.
Description
Technical Field
The invention belongs to the technical field of battery diaphragm coating, and particularly relates to porous SiO for a lithium ion battery diaphragm2A preparation method and application of the microsphere.
Background
In recent years, with the rapid development of electric vehicles and portable electronic products and the use of large lithium ion power batteries, the lithium battery industry is rapidly developed. As the application fields expand and the demand increases, the outer shape and size of the battery change, and the lithium secondary battery is required to have better durability and safety than the existing small-sized battery.
From the perspective of lithium battery safety, more and more battery enterprises begin to aim at the field of coating and modifying the diaphragm to produce the composite lithium ion battery diaphragm. The existing coating diaphragm is mainly coated with PP, PE and non-woven fabrics; common membrane-modifying layers are boehmite, Al2O3Inorganic particles with the size of more than 500nm, the thickness of the coating layer is more than 2 microns, and the density of the coating layer is 4g/m2Above, although improving battery performance, it can affect the volume and mass energy density of the battery. A heavy separator coating may also partially impede the transport of lithium ions. On the other hand, if the inorganic particles of the coating layer are small, they are easily accumulated and agglomerated, and it is difficult to obtain a coating layer having uniform stability. Therefore, the battery diaphragm is coated to improve the battery performance, the air permeability of the diaphragm is improved, the lithium ion transmission effect is ensured, and the method has important significance.
Chinese patent 109336148A discloses alumina for coating ceramic diaphragm of lithium battery and its preparation method, the content of alumina is not less than 99.9%; particle size and distribution of alumina: d50 particle size is 0.5-1.2 μm; and satisfies the following conditions: d10 is more than or equal to 1/2D 50; d90 is less than or equal to 3D 50; d99 is not more than 5D 50. The proportion of the magnetic substance in the total mass of the product is less than 0.5 ppm; the specific surface area of the alumina is 5.5-7.5m2The aluminum oxide has the characteristics of moderate median diameter particles and narrow particle size distribution range, meets the requirement of coating a lithium battery diaphragm to prepare a ceramic diaphragm, has low content of magnetic substances, and ensures that the product has safety in use, and the prepared aluminum oxide has small primary crystal particle size, good dispersibility, 0.95 percent of longitudinal thermal shrinkage at 130 ℃ and 0.6 percent of transverse thermal shrinkage.
Chinese patent 201711485007.7 discloses a lithium ion battery separator coated with nanoparticles and a method for preparing the same. The lithium ion battery diaphragm coated with the nano particles comprises a base film and the nano particles coated on at least one surface of the base film, wherein the nano particles have a porous structure, at least part of pore channels penetrate through the surface of the nano particles, the coating is prepared by the nano particles with the porous structure, the nano particles with the porous structure have developed pore channel structures, and lithium ions can be diffused in gaps among the nano particles and can also be freely diffused in pore channels inside the porous structure of the nano particles. The lithium ion conductivity was improved by coating the porous silica particles, but the permeability value of the PP-based film coated with the porous silica particles was 205s, and although the permeability value was reduced (i.e., the permeability was improved) relative to the PP-based film coated with the non-porous silica particles, there was still a large room for improvement in the permeability compared to the original permeability of the uncoated base film.
The invention prepares SiO with microporous structure2The microsphere solves the problem of dispersibility in the solution, enables the coating to be uniformly coated, reduces the density and thickness of the coating, and provides a good lithium ion transmission channel effect. The method has the advantages of light and thin coating and the like, and has very wide application prospect.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of porous SiO2 microspheres for lithium ion battery separators, and the prepared SiO2 microspheres2The microsphere has good dispersibility in the solution and simple preparation; meanwhile, the application of the porous SiO2 microspheres for the lithium ion battery diaphragm is provided, and the coated diaphragm has good air permeability and good application prospect.
In order to achieve the above object, the present invention provides the following technical solutions:
porous SiO for lithium ion battery diaphragm2The preparation method of the microsphere comprises the following specific steps:
(1) preparation of spherical SiO with particle size of 150-300nm2And (3) particle: a certain dosage is addedMixing TEOS with ethanol to obtain a mixture 1; adding the mixture 1 into a mixed solvent consisting of ethanol, ammonia water and water to obtain a mixture 2; heating the mixture 2, stirring, centrifuging and cleaning to obtain spherical SiO2Particles;
(2) the spherical SiO prepared in the step (1) is used2Adding the particles into water in a certain proportion, adding a certain mass of protective agent, heating, refluxing for a period of time, cooling to room temperature, adding a certain mass of alkaline solution, stirring, etching for a certain period of time, centrifuging, and cleaning to obtain porous SiO2And (3) microspheres.
Wherein the content of the first and second substances,
in the step (1), the concentration of the ammonia water is 25 to 28 percent
In the step (1), the volume ratio of TEOS to ethanol in the mixture 1 is 1: 1-5;
in the step (1), the volume ratio of ethanol, ammonia water and water in the mixed solvent is 15:1-3: 4;
in the step (1), the volume ratio of the mixture 1 to the mixed solvent is 1: 2-3.5;
in the step (1), the temperature rise is 25-50 ℃;
in the step (1), the stirring step is: stirring at 1100rpm for 8-12 min, and then at 400rpm for 100-140 min;
in the step (2), the spherical SiO2The particles are added into water with a certain proportion, and the proportion is spherical SiO2The mass ratio of the particles to the water is 1: 100;
in the step (2), the protective agent is spherical SiO22-3 times of the mass of the particles;
in the step (2), the protective agent may be polyvinylpyrrolidone (PVP), polydopamine, or polyoxyethylene (PEO, Mw ═ 10)4-106) One or more of;
in the step (2), the temperature rise is 85-95 ℃;
in the step (2), the reflux time is 1.5 to 2.5 hours;
the above-mentioned step (2) Wherein the alkali solution is spherical SiO22-3 times of the mass of the particles;
in the step (2), the concentration of the alkali solution is 0.5-2 mol/L;
in the step (2), the alkali solution may be one or more of a NaOH solution, a LiOH solution, and a KOH solution;
in the step (2), the etching time is 30-60 min;
in addition, the invention also provides the porous SiO for the lithium ion battery diaphragm2The application of the microspheres is as follows:
(1) taking a certain amount of the porous SiO2Dispersing the microspheres in a solvent, adding a certain amount of binder, and preparing a coating solution;
(2) and coating the base film with the coating solution, and drying to form the diaphragm with a certain coating thickness for the lithium ion battery.
Wherein the content of the first and second substances,
in the step (1), the solvent may be one or more of NMP, water, ethanol, DMF and DMAc;
in the above step (1), SiO2The mass fraction in the coating solution is 15-20%;
in the step (1), the binder may be one or more of polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), sodium alginate, chitosan, and sodium carboxymethylcellulose (CMC);
in the step (1), the mass fraction of the binder in the coating solution is 5-10%;
in the step (2), the base film may be any one of PP, PE, and nonwoven film;
in the step (2), the coating method includes blade coating, dip coating, spray coating, spin coating;
in the step (2), the coating may be one of single-sided coating and double-sided coating;
in the step (2), the coating thickness of the lithium ion battery separator is 500-2000 nm.
The invention has the following beneficial effects:
(1) the invention prepares porous SiO2The microspheres are simple to operate and can be prepared at normal temperature;
(2) the thickness and density of the coating are reduced, so that the coated diaphragm keeps good air permeability;
(3) the battery diaphragm prepared by the invention has improved thermal stability, liquid absorption rate and ionic conductivity.
Detailed Description
The present invention will be further explained with reference to specific examples in order to make the technical means, the technical features, the technical objectives and the effects of the present invention easier to understand, but the following examples are only preferred embodiments of the present invention, and not all embodiments of the present invention. Based on the embodiments in the implementation, other embodiments obtained by those skilled in the art without any creative efforts belong to the protection scope of the present invention.
The experimental methods in the following examples are conventional methods unless otherwise specified, and materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The water in the following examples may be tap water, purified water, distilled water, or drinking water.
Tetraethyl silicate (TEOS) is available from Alantin under the designation T110593
Polyvinylpyrrolidone (PVP) was purchased from Aladdin under the trade designation P110607
NMP purchased from Aladdin under the trade designation M100588
PVDF is available from Akema under the trade designation HSV900
PVA available from Alantin having a commercial number P139543
CMC purchased from Shenzhen Kejing, Inc. with the serial number EQ-Lib-CMC
Sodium alginate is available from Aladdin, Inc. under the product number S100128
The viscosity of chitosan in the following examples was 0.8 pa.s.
Example 1
(1) Preparation of spherical SiO2And (3) particle: 5mL of TEOS was mixed with 5mL of ethanol,obtaining a mixture 1; adding the mixture 1 into a mixed solvent consisting of 3mL of ammonia water, 15mL of ethanol and 4mL of water to obtain a mixture 2; heating the mixture 2 to 50 ℃, firstly stirring at 1100rpm for 10min, then stirring at 400rpm for 2 h, centrifuging, and cleaning to obtain spherical SiO2Particles;
example 2
The difference between the present example and example 1 is that (1) TEOS is 1mL, ammonia water is 1 mL; (1) the mixture 2 was warmed to 25 ℃ and the rest was the same as in example 1.
Example 3
The spherical SiO prepared in example 12Adding 0.5g of particles into 50g of water, adding 1g of PVP, heating to 90 ℃, refluxing for 2 hours, cooling to room temperature, adding 1g of 2mol/L NaOH solution, stirring for 30 minutes, centrifuging, and cleaning to obtain porous SiO2And (3) microspheres.
Example 4
The spherical SiO prepared in example 12Adding 0.5g of particles into 50g of water, adding 1g of polydopamine, heating to 85 ℃, refluxing for 2.5 hours, cooling to room temperature, adding 1g of 1mol/L LiOH solution, stirring for 30 minutes, centrifuging, and cleaning to obtain porous SiO2And (3) microspheres.
Example 5
The spherical SiO prepared in example 120.5g of the granulate was added to 50g of water, and 1.5g of PEO (Mw 10) was added6) Heating to 95 ℃, refluxing for 1.5 hours, cooling to room temperature, then adding 1.5g of 0.5mol/L KOH solution, stirring for 30 minutes, centrifuging, and cleaning to obtain porous SiO2And (3) microspheres.
Example 6
The stirring time was 60 minutes, which is different from example 3, and the same as example 3 was repeated.
For the porous SiO obtained in examples 1 to 62The particle size and porosity of the microspheres were measured, and the experimental results are shown in table 1.
TABLE 1 examples 1-6 porous SiO2Particle size and porosity of microspheres
| Porosity of the material | SiO2Mean diameter of sphere | |
| Example 1 | 0 | 150nm |
| Example 2 | 0 | 350nm |
| Example 3 | 15％ | 150nm |
| Example 4 | 18％ | 150nm |
| Example 5 | 47％ | 150nm |
| Example 6 | 35％ | 150nm |
As can be seen from Table 1, the SiO prepared according to the invention2The average size of the microspheres is in a stable range, and porous SiO is obtained after etching2The porosity of the microspheres can be properly controlled. Relative to before etchingSiO of (2)2Microspheres, etched SiO2The microspheres can retain their original size.
Comparative example 1
Untreated virgin PE film.
Example 7
(1) Taking the non-porous SiO prepared in example 12Dispersing the microspheres in NMP, adding PVDF to prepare a coating solution, wherein SiO is220% by mass of PVDF, 10% by mass of PVDF;
(2) and (3) coating one side of the PE film scraper with the coating solution, and drying to form the lithium ion battery diaphragm with the coating thickness of 500 nm.
Example 8
(1) Taking the non-porous SiO prepared in example 22Dispersing the microspheres in water, adding CMC, and preparing coating solution containing SiO2The mass fraction of the CMC is 15 percent, and the mass fraction of the CMC is 5 percent;
(2) the PE film is subjected to double-sided dip coating by using the coating solution, and a lithium ion battery separator with the coating thickness (thickness of one side) of 500nm is formed after drying.
Example 9
Unlike example 8, example 9 in which the porous SiO prepared in example 32The microspheres were otherwise the same as in example 8.
Example 10
(1) The porous SiO prepared in example 4 was taken2Dispersing the microspheres in water, adding sodium alginate to obtain a coating solution containing SiO2The mass fraction of the sodium alginate is 20 percent, and the mass fraction of the sodium alginate is 10 percent;
(2) and (3) coating one side of the PE film scraper with the coating solution, and drying to form the lithium ion battery diaphragm with the coating thickness of 1000 nm.
Example 11
(1) The porous SiO prepared in example 5 was taken2Dispersing the microspheres in water, adding chitosan to obtain a coating solution containing SiO2The mass fraction of the chitosan is 20 percent, and the mass fraction of the chitosan is 10 percent;
(2) and (3) coating the PP film on one side by using the coating solution by using a spraying method, and drying to form the diaphragm for the lithium ion battery with the coating thickness of 1500 nm.
Example 12
Unlike example 11, example 12 is a porous SiO prepared in example 62Microspheres, 500nm thick, were prepared as in example 11.
Example 13
Unlike example 9, example 13, the porous SiO prepared in example 62The microspheres were coated at a thickness of 2000nm and the rest was the same as in example 9.
The air permeability, the surface density, the heat shrinkage at 150 degrees/1 h, the ionic conductivity, and the liquid absorption rate of the separators for lithium ion batteries prepared in comparative examples 7 to 13 were measured, and the results are shown in table 2.
TABLE 2 test results of comparative example and examples 7 to 13
It can be seen that SiO was added to the untreated raw PE film2The air permeability, the thermal stability, the ionic conductivity and the liquid absorption rate of the microsphere-coated diaphragm are obviously improved, and in addition, the porous SiO prepared by the method2Microsphere coated membranes vs. non-porous SiO2The air permeability, the thermal stability, the ionic conductivity and the liquid absorption rate of the diaphragm coated by the microspheres are obviously improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. Porous SiO for lithium ion battery diaphragm2The preparation method of the microsphere is characterized by comprising the following steps:
(1) preparing spherical SiO with the particle size of 150-350nm2Particles;
(2) the spherical SiO prepared in the step (1) is used2Adding the particles into water in a certain proportion, adding a certain mass of protective agent, heating, refluxing for a period of time, cooling to room temperature, adding a certain amount of alkaline solution, stirring, etching for a certain period of time, centrifuging, and cleaning to obtain porous SiO2And (3) microspheres.
2. The method of claim 1, wherein the step (1) of preparing the spherical SiO2The method of granulation comprises the steps of:
a. mixing TEOS and ethanol according to the volume ratio of 1:1-5 to obtain a mixture 1;
b. mixing ethanol, 25-28% of ammonia water and water according to the volume ratio of 15:1-3:4 to obtain a mixed solvent;
c. mixing the mixture 1 and the mixed solvent according to the volume ratio of 1:2-3.5 to obtain a mixture 2;
d. heating the mixture 2 to 25-50 ℃, firstly stirring at 1100rpm for 10 minutes, then stirring at 400rpm for 2 hours, centrifuging and cleaning to obtain the spherical SiO2And (3) granules.
3. The method according to claim 1, wherein in the step (2), the SiO is spherical2The particles are added into water with a certain proportion, and the proportion is spherical SiO2The mass ratio of the particles to the water is 1: 100; the protective agent is spherical SiO22-3 times of the mass of the particles; the mass of the alkali solution is spherical SiO22-3 times of the mass of the particles.
4. A method according to any one of claims 1 and 3, wherein the protective agent is polyvinylpyrrolidone (PVP), polydopamine, polyoxyethylene (PEO, Mw ═ 10)4-106) One or more of;
5. the method as claimed in any one of claims 1 and 3, wherein the alkali solution is one or more of NaOH solution, LiOH solution and KOH solution, and the concentration is 0.5-2 mol/L.
6. The method according to claim 1, wherein in the step (2), the etching time is 30-60 minutes;
7. porous SiO for lithium ion battery separator prepared by the method of any of claims 1 to 62The application of the microspheres is characterized in that the porous SiO used for the lithium ion battery diaphragm2The microsphere is applied to coating of the diaphragm for the lithium ion battery, and comprises the following steps:
(1) taking a certain amount of porous SiO2Dispersing the microspheres in a solvent, adding a certain amount of binder, and preparing a coating solution;
(2) and coating the base film with the coating solution, and drying to form the diaphragm with a certain coating thickness for the lithium ion battery.
8. The method according to claim 7, wherein the solvent in step (1) can be one or more of NMP, water, ethanol, DMF, DMAc; the binder can be one or more of polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), sodium alginate, chitosan and sodium carboxymethylcellulose (CMC).
9. The method of claim 7, wherein in the coating solution of step (1), porous SiO is present2The mass fraction of the microspheres is 15-20%, and the mass fraction of the binder is 5-10%.
10. The method as claimed in claim 7, wherein the coating thickness of the lithium ion battery separator in the step (2) is 500-2000 nm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113013549A (en) * | 2021-01-28 | 2021-06-22 | 清华大学 | Coating material for light-weight lithium ion battery diaphragm, preparation method of coating material and light-weight lithium ion battery composite diaphragm |
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| CN103579556A (en) * | 2012-07-24 | 2014-02-12 | 海洋王照明科技股份有限公司 | Electrochemical power-supply composite membrane and preparation method thereof |
| CN108336279A (en) * | 2017-12-29 | 2018-07-27 | 武汉中兴创新材料技术有限公司 | A kind of lithium ion battery separator and preparation method thereof of nano-particle coating |
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- 2019-11-01 CN CN201911057803.XA patent/CN110767863A/en active Pending
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| CN103579556A (en) * | 2012-07-24 | 2014-02-12 | 海洋王照明科技股份有限公司 | Electrochemical power-supply composite membrane and preparation method thereof |
| CN108336279A (en) * | 2017-12-29 | 2018-07-27 | 武汉中兴创新材料技术有限公司 | A kind of lithium ion battery separator and preparation method thereof of nano-particle coating |
Non-Patent Citations (1)
| Title |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113013549A (en) * | 2021-01-28 | 2021-06-22 | 清华大学 | Coating material for light-weight lithium ion battery diaphragm, preparation method of coating material and light-weight lithium ion battery composite diaphragm |
| CN113013549B (en) * | 2021-01-28 | 2021-11-02 | 清华大学 | Coating material for light-weight lithium ion battery diaphragm, preparation method of coating material and light-weight lithium ion battery composite diaphragm |
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