CN108493387B - Adhesive for battery diaphragm coating and preparation method thereof - Google Patents
Adhesive for battery diaphragm coating and preparation method thereof Download PDFInfo
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- CN108493387B CN108493387B CN201810368741.3A CN201810368741A CN108493387B CN 108493387 B CN108493387 B CN 108493387B CN 201810368741 A CN201810368741 A CN 201810368741A CN 108493387 B CN108493387 B CN 108493387B
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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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- 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
-
- 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 relates to an adhesive for a battery diaphragm coating and a preparation method thereof, wherein the adhesive comprises a high molecular polymer with a core-shell structure, wherein the high molecular polymer takes vinyl-POSS as a core and hydrophilic polymer as a shell; the preparation method comprises the step of carrying out emulsion polymerization reaction on vinyl-POSS and a hydrophilic polymer monomer to grow a hydrophilic high-molecular chain segment on the vinyl-POSS so as to form the adhesive for the hydrophilic battery diaphragm coating, which takes the vinyl-POSS as a core and the hydrophilic polymer as a shell and has an adhesive effect. The adhesive is used for the lithium battery ceramic diaphragm, can effectively improve the liquid absorption/retention capacity of the diaphragm, and effectively inhibit the shedding of ceramic powder; after the diaphragm is assembled into the battery, the battery has the advantages of superior cycle performance, high ionic conductivity, excellent rate performance and the like.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to an adhesive for a battery diaphragm coating and a preparation method thereof.
Background
The diaphragm is an important component of the lithium ion battery, and the performance of the diaphragm determines the interface structure, internal resistance and the like of the battery and directly influences the capacity, cycle performance, safety and the like of the battery. The ceramic diaphragm is a novel high-safety diaphragm material developed on the conventional polyolefin diaphragm, and the main preparation method of the ceramic diaphragm is to use inorganic powder (such as Al)2O3、SiO2、TiO2Etc.), an adhesive, etc. are dispersed in a solvent, and a ceramic coating is formed on the surface of the polyolefin separator base material by a casting method or an immersion method. The heat shrinkage performance, the liquid absorption rate and the wettability of the electrolyte and the ionic conductivity, the capacity retention and the rate capability of the lithium battery using the ceramic diaphragm are influenced by the inorganic powder, the adhesive and the manufacturing process.
At present, the main research directions on ceramic diaphragm coatings include inorganic powder and a manufacturing process thereof, and modification and synthesis of adhesives, for example, patent CN106186008A discloses boehmite for lithium battery diaphragm coatings and a hydrothermal preparation method thereof, and patent CN103560219A discloses a preparation method of ceramic diaphragms using polydopamine as adhesives.
The traditional adhesive, such as polyvinylidene fluoride and polyvinylidene fluoride-hexafluoropropylene, has good mechanical properties, chemical resistance and adhesiveness, but has a space for improving the wettability of a diaphragm and the electrochemical performance of a battery due to the hydrophobicity of the traditional adhesive; for example, polymethyl methacrylate adhesives have a certain liquid absorption property, but have poor adhesion performance, and easily cause separation of ceramic powder of a separator, thereby causing a safety problem of a battery. Therefore, modification treatment of the conventional adhesive is inevitably required.
Disclosure of Invention
The invention aims to: aiming at the problems of poor wettability of a ceramic diaphragm, easy falling of ceramic powder and the like caused by poor hydrophilicity and weak bonding capability of the existing battery ceramic diaphragm adhesive, the adhesive for the battery diaphragm coating, which has high hydrophilicity, high adhesion and high electrochemical stability, and the preparation process thereof are provided.
In order to achieve the purpose, the invention adopts the following technical scheme:
the adhesive for the battery diaphragm coating comprises a high-molecular polymer with a core-shell structure, wherein the high-molecular polymer takes vinyl-POSS as a core and hydrophilic polymer as a shell.
Wherein the polyhedral oligomeric silsesquioxane (POSS) is an inorganic core (SiO) composed of silicon (Si) and oxygen (O)3/2)nThe organic/inorganic hybrid material formed by the organic arms has a nanometer size effect, and the inorganic core endows the material with good thermal stability and mechanical property, such as a preparation method of POSS-based nanometer hybrid micelle disclosed in CN 105670004A. For vinyl hydrophilic polymer monomers such as acrylic acid, acrylonitrile and the like, a hydrophilic high molecular chain can be grown on vinyl silsesquioxane through emulsion polymerization, so that the synthesis design of the hydrophilic high molecular polymer with the spherical-like core-shell structure is realized, for example, vinyl-POSS is used as a core, a shell is the core-shell structure high molecular polymer of polyacrylonitrile, the periphery has a plurality of polar groups, multi-point bonding can be formed, just like the tentacle of octopus, and ceramic particles in the diaphragm coating and the base film are well bonded together.
The preparation method of the adhesive for the battery diaphragm coating comprises the following steps:
step (1): preparing a mixed solution of an initiator, an emulsifier and vinyl-POSS: adding an initiator and an emulsifier into 100-150ml of deionized water according to the weight ratio of 0.02-0.05:2-4, adding a sodium hydroxide aqueous solution with the mass fraction of 5% to adjust the pH to be alkalescent, and adding a vinyl-POSS monomer after completely dissolving, wherein the weight ratio of the vinyl-POSS to the initiator is 0.02-0.03: 0.04-0.09;
step (2): preparation of vinyl-POSS/hydrophilic polymer core-shell structure: adding a hydrophilic polymer monomer into the mixed solution obtained in the step (1) at a proper stirring speed, wherein the weight ratio of the vinyl-POSS to the hydrophilic polymer monomer is 2-4: 200-; then reacting for 4-8 hours at a constant temperature of 85-90 ℃;
and (3): and (3) after the reaction in the step (2) is finished, cooling to 30-40 ℃, demulsifying with concentrated hydrochloric acid, filtering, washing, and drying to obtain a white powdery vinyl-POSS/hydrophilic polymer core-shell structure high polymer.
Preferably, in the step (1), the initiator is at least one of azobisisobutyronitrile, sodium persulfate and ammonium persulfate.
Preferably, in step (1), the emulsifier is at least one of sodium stearate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
Preferably, in the step (1), the vinyl-POSS is at least one of pentahedral vinyl-POSS, hexahedral vinyl-POSS, and octahedral vinyl-POSS.
Preferably, in the step (2), the hydrophilic polymer monomer is at least one of acrylic acid and acrylonitrile.
Preferably, in the step (3), the weight average molecular weight of the vinyl-POSS/hydrophilic polymer core-shell structure high molecular polymer is 100000-150000.
Compared with the prior art, the invention grows the hydrophilic high molecular chain segment on the vinyl-POSS through the emulsion polymerization reaction of the vinyl-POSS and the hydrophilic polymer monomer to form the adhesive for the hydrophilic battery diaphragm coating which takes the vinyl-POSS as the core and the hydrophilic polymer as the shell and has the adhesive effect, and the adhesive is used for the lithium battery ceramic diaphragm, can effectively improve the liquid absorption/retention capacity of the diaphragm and effectively inhibit the falling of ceramic powder; after the diaphragm is assembled into the battery, the battery has the advantages of superior cycle performance, high ionic conductivity, excellent rate performance and the like.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Sodium persulfate and sodium dodecyl sulfate are mixed according to the weight ratio of 0.04: 3, adding the mixture into 150ml of deionized water, and then adding a sodium hydroxide aqueous solution with the mass fraction of 5% to adjust the pH value to 8; then adding hexahedral vinyl-POSS, wherein the weight ratio of the hexahedral vinyl-POSS to the sodium persulfate is 0.02: 0.04; adding acrylic acid in a weight ratio of 250:1 to vinyl-POSS with proper stirring; and then reacting for 4 hours at a constant temperature of 90 ℃, cooling to 40 ℃ after the reaction is finished, demulsifying with concentrated hydrochloric acid, filtering, washing and drying to obtain white powdery hexahedral vinyl-POSS/polyacrylic acid core-shell structure polymer adhesive.
Adding the adhesive powder, the aluminum oxide nano particles and the carboxymethyl cellulose into the aqueous solution according to the weight ratio of 5:1:90 to prepare a mixed solution with the solid content of 50%, and mixing for 1h at the rotating speed of 20000 to obtain the coating slurry. Coating the slurry on the surface of a polypropylene diaphragm by adopting a blade coating mode, drying at 80 ℃ to obtain a lithium battery ceramic diaphragm coating with the thickness of 5 mu m, and fully infiltrating LiPF6Electrolyte with surface lithium ion conductivity of 3.9 × 10 measured by electrochemical workstation-3Scm-1The coating adhesion is 41Nm-1(ii) a Assembled into LiFePO4a/C lithium battery. Testing the cycle performance by using an electrochemical workstation, and still maintaining 92% of initial discharge capacity after 400 cycles of cycle; as a comparison sample, polyvinylidene fluoride, carboxymethyl cellulose and aluminum oxide nanoparticles are prepared into slurry and a coating according to the same proportion, and the lithium ions on the surface of the slurry and the coating are measuredSub-conductivity of 5.7X 10-4Scm-1The coating adhesion is 21Nm-1After 400 cycles, the capacity retention was only 79%.
Example 2
Mixing azodiisobutyronitrile and sodium dodecyl benzene sulfonate according to the weight ratio of 0.02: 3, adding the mixture into 120ml of deionized water, and then adding a sodium hydroxide aqueous solution with the mass fraction of 5% to adjust the pH value to 8; then adding pentahedral vinyl-POSS, wherein the weight ratio of the pentahedral vinyl-POSS to the azobisisobutyronitrile is 0.03: 0.05; adding acrylonitrile in a weight ratio of 300:1 to vinyl-POSS with proper stirring; and then reacting for 6 hours at a constant temperature of 70 ℃, cooling to 35 ℃ after the reaction is finished, demulsifying with concentrated hydrochloric acid, filtering, washing and drying to obtain a white powdery pentahedral vinyl-POSS/polyacrylonitrile core-shell structure polymer adhesive.
Adding the adhesive powder, the aluminum oxide nanoparticles and the hydroxypropyl methyl cellulose into the aqueous solution according to the weight ratio of 5:2:90 to prepare a mixed solution with the solid content of 45%, and mixing for 1h at the rotating speed of 15000 to obtain the slurry for the coating. Coating the slurry on the surface of a polypropylene diaphragm by adopting a blade coating mode, drying at 60 ℃ to obtain a lithium battery ceramic diaphragm coating with the thickness of 5 mu m, and fully soaking LiPF6Electrolyte with surface lithium ion conductivity of 3.6 × 10 measured by electrochemical workstation-3Scm-1The coating adhesion is 43Nm-1(ii) a Assembled into LiFePO4a/C lithium battery. Testing the cycle performance by using an electrochemical workstation, and still maintaining 93 percent of initial discharge capacity after 400 cycles of cycle; as a comparison sample, polymethyl methacrylate, hydroxypropyl methyl cellulose and aluminum oxide nanoparticles are prepared into slurry and a coating according to the same proportion, and the lithium ion conductivity of the surface of the slurry and the coating is measured to be 5.7 multiplied by 10- 4Scm-1The coating adhesion is 15Nm-1After 400 cycles, the capacity retention was only 80%.
Example 3
Ammonium persulfate and sodium stearate are mixed according to the weight ratio of 0.03: 2.5, adding the mixture into 130ml of deionized water, and then adding a sodium hydroxide aqueous solution with the mass fraction of 5% to adjust the pH value to 7.5; then adding octahedral vinyl-POSS, wherein the weight ratio of the octahedral vinyl-POSS to the ammonium persulfate is 0.03: 0.08; adding acrylic acid in a weight ratio to vinyl POSS of 300:1 with proper stirring; reacting at 80 ℃ for 5 hours at constant temperature, cooling to 30 ℃ after the reaction is finished, demulsifying with concentrated hydrochloric acid, filtering, washing and drying to obtain white powdery octahedral vinyl-POSS/polyacrylic acid core-shell structure polymer adhesive.
Adding the adhesive powder, the titanium dioxide nano particles and the hydroxypropyl methyl cellulose into the aqueous solution according to the weight ratio of 6:2:90 to prepare a mixed solution with the solid content of 45%, and mixing for 2 hours at the rotating speed of 20000 to obtain the slurry for the coating. Coating the slurry on the surface of a polypropylene diaphragm by adopting a blade coating mode, drying at 80 ℃ to obtain a lithium battery ceramic diaphragm coating with the thickness of 5 mu m, and fully infiltrating LiPF6Electrolyte with surface lithium ion conductivity of 3.7 × 10 measured by electrochemical workstation-3Scm-1The coating adhesion is 42Nm-1(ii) a Assembled into LiFePO4a/C lithium battery. Testing the cycle performance by using an electrochemical workstation, and after circulating for 400 circles, still keeping 91% of the initial discharge capacity; as a comparison sample, polyvinylidene fluoride-hexafluoropropylene copolymer, hydroxypropyl methyl cellulose and titanium dioxide nanoparticles are prepared into slurry and a coating according to the same proportion, and the lithium ion conductivity of the surface of the slurry and the coating is measured to be 4.1 multiplied by 10-4Scm-1The coating adhesion is 22Nm-1After 400 cycles, the capacity retention was only 78%.
Example 4
Mixing sodium persulfate and sodium stearate in a weight ratio of 0.05: 4, adding the mixture into 150ml of deionized water, and then adding a sodium hydroxide aqueous solution with the mass fraction of 5% to adjust the pH value to 7.5; then adding hexahedron vinyl-POSS, wherein the weight ratio of the hexahedron vinyl-POSS to the sodium persulfate is 0.03: 0.09; adding acrylic acid in a weight ratio of 250:1 to the octahedral vinyl-POSS with proper stirring; reacting at the constant temperature of 75 ℃ for 5 hours, cooling to 35 ℃ after the reaction is finished, demulsifying with concentrated hydrochloric acid, filtering, washing and drying to obtain white powdery octahedral vinyl-POSS/polyacrylic acid core-shell structure polymer adhesive.
Adding the adhesive powder, the titanium dioxide nano particles and the hydroxypropyl methyl cellulose into the aqueous solution according to the weight ratio of 5:3:90 to prepare a mixed solution with the solid content of 46%, and mixing for 2.5 hours at the rotating speed of 15000 to obtain the slurry for the coating. Coating the slurry on the surface of a polypropylene diaphragm by adopting a blade coating mode, drying at 70 ℃ to obtain a lithium battery ceramic diaphragm coating with the thickness of 5 mu m, and fully soaking LiPF6Electrolyte with surface lithium ion conductivity of 3.8 × 10 measured by electrochemical workstation-3Scm-1The coating adhesion is 47Nm-1(ii) a Assembled into LiFePO4a/C lithium battery. Testing the cycle performance by using an electrochemical workstation, and still maintaining 92% of initial discharge capacity after 400 cycles of cycle; as a comparison sample, polymethyl methacrylate, hydroxypropyl methylcellulose and titanium dioxide nano particles are prepared into slurry and a coating according to the same proportion, and the lithium ion conductivity of the surface of the slurry and the coating is measured to be 5.1 multiplied by 10-4Scm-1The coating adhesion is 16Nm-1After 400 cycles, the capacity retention was only 78%.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (6)
1. An adhesive for coating a battery separator, characterized in that: the adhesive comprises a high molecular polymer with a core-shell structure, wherein the high molecular polymer takes vinyl-POSS as a core and hydrophilic polymer as a shell; the monomer of the hydrophilic polymer is at least one of acrylic acid and acrylonitrile;
the preparation method of the adhesive comprises the following steps:
step (1): preparing a mixed solution of an initiator, an emulsifier and vinyl-POSS: adding an initiator and an emulsifier into 100-150ml of deionized water according to the weight ratio of 0.02-0.05:2-4, adding a sodium hydroxide aqueous solution with the mass fraction of 5% to adjust the pH to be alkalescent, and adding vinyl-POSS after completely dissolving, wherein the weight ratio of the vinyl-POSS to the initiator is 0.02-0.03: 0.04-0.09;
step (2): preparation of vinyl-POSS/hydrophilic polymer core-shell structure: adding a hydrophilic polymer monomer into the mixed solution obtained in the step (1) under stirring, wherein the weight ratio of the vinyl-POSS to the hydrophilic polymer monomer is 2-4: 200-; then reacting for 4-8 hours at a constant temperature of 85-90 ℃;
and (3): and (3) after the reaction in the step (2) is finished, cooling to 30-40 ℃, demulsifying with concentrated hydrochloric acid, filtering, washing, and drying to obtain a white powdery vinyl-POSS/hydrophilic polymer core-shell structure high polymer.
2. The method for preparing the adhesive for coating the battery separator according to claim 1, comprising the steps of:
step (1): preparing a mixed solution of an initiator, an emulsifier and vinyl-POSS: adding an initiator and an emulsifier into 100-150ml of deionized water according to the weight ratio of 0.02-0.05:2-4, adding a sodium hydroxide aqueous solution with the mass fraction of 5% to adjust the pH to be alkalescent, and adding vinyl-POSS after completely dissolving, wherein the weight ratio of the vinyl-POSS to the initiator is 0.02-0.03: 0.04-0.09;
step (2): preparation of vinyl-POSS/hydrophilic polymer core-shell structure: adding a hydrophilic polymer monomer into the mixed solution obtained in the step (1) under stirring, wherein the weight ratio of the vinyl-POSS to the hydrophilic polymer monomer is 2-4: 200-; then reacting for 4-8 hours at a constant temperature of 85-90 ℃;
and (3): and (3) after the reaction in the step (2) is finished, cooling to 30-40 ℃, demulsifying with concentrated hydrochloric acid, filtering, washing, and drying to obtain a white powdery vinyl-POSS/hydrophilic polymer core-shell structure high polymer.
3. The method for preparing the adhesive for coating the battery separator according to claim 2, wherein: in the step (1), the initiator is at least one of azobisisobutyronitrile, sodium persulfate and ammonium persulfate.
4. The method for preparing the adhesive for coating the battery separator according to claim 2, wherein: in the step (1), the emulsifier is at least one of sodium stearate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
5. The method for preparing the adhesive for coating the battery separator according to claim 2, wherein: in the step (1), the vinyl-POSS is at least one of pentahedral vinyl-POSS, hexahedral vinyl-POSS and octahedral vinyl-POSS.
6. The method for preparing the adhesive for coating the battery separator according to claim 2, wherein: in the step (3), the weight average molecular weight of the vinyl-POSS/hydrophilic polymer core-shell structure high molecular polymer is 100000-150000.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR102658100B1 (en) | 2019-12-03 | 2024-04-16 | 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 | Secondary battery, device containing secondary battery, manufacturing method of secondary battery, and adhesive composition |
| CN113785439B (en) * | 2020-03-27 | 2024-03-26 | 宁德新能源科技有限公司 | Separator, electrode assembly, battery and electronic device |
| EP3916901A4 (en) * | 2020-03-31 | 2022-04-13 | Ningde Amperex Technology Ltd. | Separator, electrode assembly, battery, and electronic apparatus |
| CN112341961B (en) * | 2020-10-28 | 2023-01-13 | 欣旺达电动汽车电池有限公司 | Adhesive, diaphragm and preparation method thereof |
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| CN102977253A (en) * | 2012-11-06 | 2013-03-20 | 中科院广州化学有限公司 | Silicone modified acrylate hybrid emulsion and preparation method and application thereof |
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| CN107221625A (en) * | 2017-05-10 | 2017-09-29 | 西北工业大学 | The gel electrolyte and preparation method of the high nano combined POSS polyacrylate-coateds improved polyalkene diaphragm of thermomechanical property |
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| CN102977253A (en) * | 2012-11-06 | 2013-03-20 | 中科院广州化学有限公司 | Silicone modified acrylate hybrid emulsion and preparation method and application thereof |
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