CN117603637A - Preparation method and application of adhesive - Google Patents
Preparation method and application of adhesive Download PDFInfo
- Publication number
- CN117603637A CN117603637A CN202311565394.0A CN202311565394A CN117603637A CN 117603637 A CN117603637 A CN 117603637A CN 202311565394 A CN202311565394 A CN 202311565394A CN 117603637 A CN117603637 A CN 117603637A
- Authority
- CN
- China
- Prior art keywords
- binder
- negative electrode
- sodium
- stirring
- mixed solution
- 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.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000001070 adhesive effect Effects 0.000 title claims description 34
- 239000000853 adhesive Substances 0.000 title claims description 33
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011230 binding agent Substances 0.000 claims abstract description 39
- 239000011259 mixed solution Substances 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 30
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011267 electrode slurry Substances 0.000 claims abstract description 22
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 229920001577 copolymer Polymers 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims abstract description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 9
- AZQGFVRDZTUHBU-UHFFFAOYSA-N isocyanic acid;triethoxy(propyl)silane Chemical compound N=C=O.CCC[Si](OCC)(OCC)OCC AZQGFVRDZTUHBU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000006258 conductive agent Substances 0.000 claims description 12
- 239000006245 Carbon black Super-P Substances 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- 239000011871 silicon-based negative electrode active material Substances 0.000 claims description 2
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 21
- 230000008569 process Effects 0.000 abstract description 9
- 238000009831 deintercalation Methods 0.000 abstract description 7
- 238000009830 intercalation Methods 0.000 abstract description 7
- 230000002687 intercalation Effects 0.000 abstract description 7
- 230000008859 change Effects 0.000 abstract description 6
- 239000013543 active substance Substances 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 16
- 229910052710 silicon Inorganic materials 0.000 description 16
- 239000010703 silicon Substances 0.000 description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 14
- 229910052744 lithium Inorganic materials 0.000 description 14
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 12
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- -1 siloxane chain Chemical group 0.000 description 8
- 239000010405 anode material Substances 0.000 description 7
- 229910001290 LiPF6 Inorganic materials 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000012982 microporous membrane Substances 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011856 silicon-based particle Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229920005596 polymer binder Polymers 0.000 description 2
- 239000002491 polymer binding agent Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000002409 silicon-based active material Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIIGJRVNDNCPLB-UHFFFAOYSA-M C1(=CC=CC=C1)S(=O)(=O)[O-].C=CC1=CC=CC=C1.[Na+] Chemical compound C1(=CC=CC=C1)S(=O)(=O)[O-].C=CC1=CC=CC=C1.[Na+] NIIGJRVNDNCPLB-UHFFFAOYSA-M 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000005414 inactive ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000011866 silicon-based anode active material Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/24—Homopolymers or copolymers of amides or imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
-
- 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
-
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Electrochemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a binder, which comprises the steps of adding N-hydroxyethyl acrylamide and sodium p-styrenesulfonate into deionized water, and continuously introducing N 2 Adding ammonium persulfate aqueous solution, heating, stirring, reacting, washing and drying the product to obtain a copolymer; adding the mixture and isocyanate propyl triethoxysilane into dimethyl sulfoxide, then adding dibutyl tin dilaurate, stirring and reacting to obtain a mixed solution, dripping the mixed solution into tetrahydrofuran, centrifugally collecting precipitate, washing and drying to obtain a binder; batteries using the binder are also disclosed; the invention can effectively adapt to the negativeThe volume change of the electrode active material in the lithium ion intercalation/deintercalation process ensures that the electrode slurry does not fall off from the current collector, effectively reduces the loss of active substances and the attenuation of battery capacity, and improves the cycle stability and the cycle life of the battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a binder and a battery using the binder.
Background
Lithium ion batteries have made great progress since commercialization in 1991, and are widely applied to the fields of various portable electronic devices, new energy automobiles and the like, and are the most widely applied chemical power supplies at present. With the application of lithium ion batteries from portable electronic devices to large-scale energy storage systems, it is important to further increase the energy density of lithium ion batteries. The traditional lithium ion battery uses graphite as a negative electrode, the theoretical specific capacity of the graphite is only 372mAh/g, and the energy density of the lithium ion battery is difficult to realize great improvement. Silicon has ultrahigh theoretical specific capacity (4200 mAh/g at high temperature) and high volumetric specific capacity (9786 mAh/cm) 3 ) The advantages of low lithium intercalation and deintercalation potential (less than 0.5V vs. Li/Li+), high storage, low pollution and the like become one of the next-generation anode materials with the highest potential. However, the silicon-based negative electrode material has some defects, such as huge volume change in the lithium intercalation and deintercalation process, the generated stress easily causes the cracking and pulverization of silicon particles and the inactivation of the silicon particles, and in addition, the large volume change also causes the continuous cracking and recombination of a solid electrolyte interface film (SEI), so that the consumption of active lithium is caused, the capacity of the silicon-based negative electrode is comprehensively caused to be suddenly attenuated in the circulation, and the practical application of the silicon-based negative electrode is severely limited.
The binder is an important inactive ingredient of the lithium ion battery, which adheres the electrode active material and the conductive agent to the current collector, and the performance of the binder directly influences the electrochemical performance of the battery. The aqueous binder for the lithium ion battery is mainly as follows: styrene Butadiene Rubber (SBR)/sodium carboxymethylcellulose (CMC), polyacrylic acid (PAA), sodium alginate (NaAlg), polyvinyl alcohol (PVA), and the like. SBR is used as a binder, CMC must be added as a thickener at the same time, but CMC is generally viscous, brittle and poor in flexibility, and the pole piece is prone to cracking during charge and discharge. PAA is adopted as a binder, and the polymer has high glass transition temperature and is harder at normal temperature, so that the pole piece prepared from the binder can be broken due to volume change of active substances in the lithium intercalation process, and the active substances fall off from the pole piece.
The polyhydroxy polymer has good thermal stability and film forming property, and can form hydrogen bond action with hydroxyl functional groups on the silicon surface, so that the volume expansion of the silicon anode can be buffered to a certain extent.
The Chinese patent document CN202310814397.7 provides a modified polyvinyl alcohol binder, a preparation method thereof and a modified composite current collector, wherein the preparation method comprises the following steps: alternately freezing and thawing the polyvinyl alcohol aqueous solution to obtain pre-crosslinked polyvinyl alcohol; and (3) placing the pre-crosslinked polyvinyl alcohol into a lithium salt solution for treatment to obtain the modified polyvinyl alcohol binder, wherein the modified polyvinyl alcohol binder has a double crosslinked network and a rich branched structure, and has high extensibility, excellent adhesive property and lithium supplementing effect.
However, the single polyhydroxy polymer binder has the defects of low viscosity, poor functionality and poor dispersibility of electrode materials, so that the electrochemical performance of the silicon anode still has a large improvement space. Therefore, there is an urgent need to develop a polymer binder having high adhesion, high flexibility, and high electron transport efficiency to maintain the electrode structure stable and to improve the cycle life of the battery.
Disclosure of Invention
In order to solve the defects in the prior art, one of the purposes of the invention is to provide a preparation method of a binder, and the prepared binder can effectively adapt to the volume change of a negative electrode active material in the lithium ion intercalation/deintercalation process, ensure that electrode slurry does not fall off from a current collector, effectively reduce the loss of active substances and the attenuation of battery capacity, and improve the cycle stability and the cycle life of a battery.
The technical scheme adopted for solving the technical problems is as follows: a method for preparing an adhesive, comprising the steps of:
(1) Adding N-hydroxyethyl acrylamide and sodium p-styrenesulfonate into deionized water, stirring uniformly to obtain monomer mixed solution, and continuously introducing N 2 Preheating the monomer mixed solution, adding a part of ammonium persulfate aqueous solution, heating, adding the rest ammonium persulfate aqueous solution, stirring for reaction, washing the product with ethanol and acetone, and drying to obtain an N-hydroxyethyl acrylamide-sodium p-styrenesulfonate copolymer;
(2) Adding N-hydroxyethyl acrylamide-sodium p-styrenesulfonate copolymer and isocyanate propyl triethoxysilane into dimethyl sulfoxide, then adding dibutyl tin dilaurate, stirring and reacting to obtain a mixed solution, dripping the mixed solution into tetrahydrofuran, centrifugally collecting precipitate, washing and drying to obtain the adhesive.
The preparation method of the adhesive comprises the following steps of (1) mixing 3-6 g of N-hydroxyethyl acrylamide, sodium p-styrenesulfonate and deionized water in percentage by weight and volume: 1-3 g: 50-80 mL.
Further, the ammonium persulfate in the step (1) is added in an amount of 0.5-2% of the total monomer mixture.
Further, in the step (1), the mixture is preheated to 30-55 ℃, heated to 45-70 ℃ and stirred for 3-6 hours under the stirring reaction condition of 300-500 r/min.
The preparation method of the adhesive comprises the following steps of (2) preparing an N-hydroxyethyl acrylamide-sodium p-styrenesulfonate copolymer, isocyanate propyl triethoxysilane, dimethyl sulfoxide and dibutyl tin dilaurate in a weight-volume ratio of 7-11 g: 0.1-2 g: 60-80 mL: 0.005-0.1 g; the volume ratio of dimethyl sulfoxide to tetrahydrofuran is 1:10 to 20.
Further, in the step (2), stirring reaction conditions are 300-400 r/min, and stirring reaction is carried out for 10-16 h at 40-70 ℃.
The second purpose of the invention is to provide a binder prepared by the preparation method.
The invention further provides a battery, which comprises a negative electrode plate, wherein the negative electrode plate comprises a negative electrode slurry, the negative electrode slurry comprises a conductive agent, a negative electrode active material and the binder, and the mass ratio of the binder in the negative electrode slurry is 5-10%.
The negative electrode active material of the battery is a silicon-based negative electrode active material or a graphite negative electrode active material.
The conductive agent of the battery is one or more of Super-P, ketjen black, acetylene black and KS-6.
Compared with the prior art, the invention has the following beneficial effects:
the adhesive disclosed by the invention can be used for improving the lithium ion conductivity of the adhesive and improving the ion transmission capacity of an electrode, has good mechanical property, film forming property and cohesiveness, is suitable for a silicon-based anode active material, can form hydrogen bond action and chemical bond connection with hydroxyl functional groups on the surface of silicon, can effectively adapt to the volume change of the anode active material in the lithium ion intercalation/deintercalation process, ensures that electrode slurry does not fall off from a current collector, effectively reduces the loss of active substances and the attenuation of battery capacity, and improves the cycle stability and cycle life of a battery.
2, the adhesive takes N-hydroxyethyl acrylamide and sodium p-styrenesulfonate as monomers, under the initiation of ammonium persulfate, the N-hydroxyethyl acrylamide-sodium p-styrenesulfonate copolymer is obtained, and the obtained polymer has two structural units, one is an acrylamide structural unit with a hydroxyl group on a side chain, and the other is a styrenestructural unit with a sulfonic acid group on a side chain; polar groups such as hydroxyl, amido and the like can form hydrogen bonds with the surfaces of silicon particles, so that the bonding capability of the silicon-based active material is improved; the introduction of the rigid benzene ring can increase the glass transition temperature of the binder, and improve the Young modulus and mechanical property of the binder, so that the volume expansion of silicon is better inhibited and the cracking of the pole piece is relieved; the sulfonic acid group has stronger affinity with lithium ions, so that the ion conductivity of the battery can be remarkably improved, the ion transmission capacity of the binder can be improved, and the specific capacity and the cycle life of the battery can be improved; and then, the DBTDL is used as a catalyst, isocyanate radical of the isocyanatopropyl triethoxysilane reacts with hydroxyl in a copolymer side chain, and a siloxane chain segment is introduced to prepare the adhesive, wherein the siloxane chain segment can be subjected to condensation reaction with hydroxyl on the surfaces of an active material and a current collector after hydrolysis, and the silicon-based active material and a conductive agent are tightly adhered to the current collector in the charging and discharging process, so that the adhesive strength of the adhesive can be further improved, the volume expansion of the anode active material in the lithium deintercalation process can be obviously inhibited, the pulverization and the falling of the anode active material are avoided, and the cycle performance of the lithium ion battery is further prolonged.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following examples. Of course, the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Unless otherwise specified, both chemical reagents and materials in the present invention are purchased through a market route or synthesized from raw materials purchased through a market route.
The invention will be further illustrated by the following examples.
Example 1
The preparation method of the adhesive comprises the following steps:
(1) Adding 6g N-hydroxyethyl acrylamide and 3g of sodium p-styrenesulfonate into 80mL of deionized water, uniformly stirring to obtain a monomer mixed solution, and continuously introducing N 2 Preheating the monomer mixture to 55 ℃, adding 0.05g of ammonium persulfate, heating to 70 ℃, adding 0.05g of ammonium persulfate, stirring at 500r/min for reaction for 6 hours, washing the product with ethanol and acetone, and drying to obtain the N-hydroxyethyl acrylamide-sodium p-styrenesulfonate copolymer.
(2) 1.1-g N-hydroxyethyl acrylamide-sodium p-styrenesulfonate copolymer and 0.2g of isocyanate propyl triethoxysilane are added into 8mL of dimethyl sulfoxide, then 0.01g of dibutyl tin dilaurate is added, stirring reaction is carried out for 16 hours at the temperature of 400r/min to obtain a mixed solution, the mixed solution is dripped into 80mL of tetrahydrofuran, and the sediment is centrifugally collected, washed and dried to obtain the adhesive.
The preparation method of the lithium ion battery adopting the adhesive comprises the following steps:
a, silicon-based anode material silicon oxide, conductive agent Super-P and binder are mixed according to the mass ratio of 80:10:10, and controlling the solid content of the mixture to 40% by weight with a 20wt% ethanol aqueous solution to prepare a negative electrode slurry.
And B, uniformly coating the negative electrode slurry on a copper foil current collector, vacuum drying in an oven for 12 hours, and cutting into round pole pieces with the diameter of 10 mm.
And C, taking a metal lithium sheet as a counter electrode, taking 1mol/L LiPF6 (a solvent is a mixed solution of Ethylene Carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1:1, adding 5% by volume of fluoroethylene carbonate (FEC)) as an electrolyte, and assembling a polypropylene microporous membrane into a 2032 type button cell in a glove box in an argon atmosphere.
Example 2
The preparation method of the adhesive comprises the following steps:
(1) Adding 5g N-hydroxyethyl acrylamide and 2.5g sodium p-styrenesulfonate into 70mL deionized water, stirring to obtain monomer mixed solution, and continuously introducing N 2 Preheating the monomer mixture to 50 ℃, adding 0.05g of ammonium persulfate, heating to 65 ℃, adding 0.05g of ammonium persulfate, stirring at 450r/min for reaction for 5 hours, washing the product with ethanol and acetone, and drying to obtain the N-hydroxyethyl acrylamide-sodium p-styrenesulfonate copolymer.
(2) 1.0g N-hydroxyethyl acrylamide-sodium p-styrenesulfonate copolymer and 0.15g of isocyanate propyl triethoxysilane are added into 8mL of dimethyl sulfoxide, then 0.01g of dibutyl tin dilaurate is added, stirring reaction is carried out for 14h at the temperature of 400r/min to obtain a mixed solution, the mixed solution is dripped into 80mL of tetrahydrofuran, and the precipitate is centrifugally collected, washed and dried to obtain the adhesive.
The preparation method of the lithium ion battery adopting the adhesive comprises the following steps:
a, silicon-based anode material silicon oxide, conductive agent Super-P and binder are mixed according to the mass ratio of 80:10:10, and controlling the solid content of the mixture to 40% by weight with a 20wt% ethanol aqueous solution to prepare a negative electrode slurry.
And B, uniformly coating the negative electrode slurry on a copper foil current collector, vacuum drying in an oven for 12 hours, and cutting into round pole pieces with the diameter of 10 mm.
And C, taking a metal lithium sheet as a counter electrode, taking 1mol/L LiPF6 (a solvent is a mixed solution of Ethylene Carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1:1, adding 5% by volume of fluoroethylene carbonate (FEC)) as an electrolyte, and assembling a polypropylene microporous membrane into a 2032 type button cell in a glove box in an argon atmosphere.
Example 3
The preparation method of the adhesive comprises the following steps:
(1) Adding 4g N-hydroxyethyl acrylamide and 2g of sodium p-styrenesulfonate into 60mL of deionized water, uniformly stirring to obtain a monomer mixed solution, and continuously introducing N 2 Preheating the monomer mixture to 45 ℃, adding 0.05g of ammonium persulfate, heating to 60 ℃, adding 0.05g of ammonium persulfate, stirring at 400r/min for reaction for 4 hours, washing the product with ethanol and acetone, and drying to obtain the N-hydroxyethyl acrylamide-sodium p-styrenesulfonate copolymer.
(2) Adding 0.9g N-hydroxyethyl acrylamide-sodium p-styrenesulfonate copolymer and 0.1g of isocyanate propyl triethoxysilane into 7mL of dimethyl sulfoxide, then adding 0.01g of dibutyl tin dilaurate, stirring at 400r/min and 50 ℃ for reaction for 12 hours to obtain a mixed solution, dripping the mixed solution into 80mL of tetrahydrofuran, centrifugally collecting precipitate, washing and drying to obtain the adhesive.
The preparation method of the lithium ion battery adopting the adhesive comprises the following steps:
a, silicon-based anode material silicon oxide, conductive agent Super-P and binder are mixed according to the mass ratio of 80:10:10, and controlling the solid content of the mixture to 40% by weight with a 20wt% ethanol aqueous solution to prepare a negative electrode slurry.
And B, uniformly coating the negative electrode slurry on a copper foil current collector, vacuum drying in an oven for 12 hours, and cutting into round pole pieces with the diameter of 10 mm.
And C, taking a metal lithium sheet as a counter electrode, taking 1mol/L LiPF6 (a solvent is a mixed solution of Ethylene Carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1:1, adding 5% by volume of fluoroethylene carbonate (FEC)) as an electrolyte, and assembling a polypropylene microporous membrane into a 2032 type button cell in a glove box in an argon atmosphere.
Example 4
The preparation method of the adhesive comprises the following steps:
(1) Adding 3g N-hydroxyethyl acrylamide and 1g of sodium p-styrenesulfonate into 50mL of deionized water, uniformly stirring to obtain a monomer mixed solution, and continuously introducing N 2 Preheating the monomer mixture to 30 ℃, adding 0.05g of ammonium persulfate, heating to 45 ℃, adding 0.05g of ammonium persulfate, stirring at 300r/min for reaction for 3 hours, washing the product with ethanol and acetone, and drying to obtain the N-hydroxyethyl acrylamide-sodium p-styrenesulfonate copolymer.
(2) Adding 0.7g N-hydroxyethyl acrylamide-sodium p-styrenesulfonate copolymer and 0.1g of isocyanate propyl triethoxysilane into 6mL of dimethyl sulfoxide, then adding 0.005g of dibutyl tin dilaurate, stirring at 300r/min and 40 ℃ for reaction for 10 hours to obtain a mixed solution, dripping the mixed solution into 80mL of tetrahydrofuran, centrifugally collecting precipitate, washing and drying to obtain the adhesive.
The preparation method of the lithium ion battery adopting the adhesive comprises the following steps:
a, silicon-based anode material silicon oxide, conductive agent Super-P and binder are mixed according to the mass ratio of 80:10:10, and controlling the solid content of the mixture to 40% by weight with a 20wt% ethanol aqueous solution to prepare a negative electrode slurry.
And B, uniformly coating the negative electrode slurry on a copper foil current collector, vacuum drying in an oven for 12 hours, and cutting into round pole pieces with the diameter of 10 mm.
And C, taking a metal lithium sheet as a counter electrode, taking 1mol/L LiPF6 (a solvent is a mixed solution of Ethylene Carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1:1, adding 5% by volume of fluoroethylene carbonate (FEC)) as an electrolyte, and assembling a polypropylene microporous membrane into a 2032 type button cell in a glove box in an argon atmosphere.
Comparative example 1. A method for preparing an adhesive, comprising the steps of: will beAdding 6g N-hydroxyethyl acrylamide and 3g of sodium p-styrenesulfonate into 80mL of deionized water, uniformly stirring to obtain a monomer mixed solution, and continuously introducing N 2 Preheating the monomer mixed solution to 55 ℃, adding 0.05g of ammonium persulfate, heating to 70 ℃, adding 0.05g of ammonium persulfate, stirring at 500r/min for reaction for 6 hours, washing the product with ethanol and acetone, and drying to obtain the binder.
A preparation method of a lithium ion battery comprises the following steps: A. silicon-based anode material silicon oxide, conductive agent Super-P and binder according to the mass ratio of 80:10:10, mixing, and controlling the solid content of the mixture to be 40% by weight through a 20wt% ethanol aqueous solution to prepare negative electrode slurry; B. uniformly coating the negative electrode slurry on a copper foil current collector, vacuum drying in an oven for 12 hours, and cutting into round pole pieces with the diameter of 10 mm; C. a2032 type button cell was assembled in a glove box under an argon atmosphere using a metallic lithium sheet as a counter electrode, 1mol/L LiPF6 (solvent is a mixture of Ethylene Carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1:1, 5% by volume of fluoroethylene carbonate (FEC)) was added as an electrolyte, and a polypropylene microporous separator.
Comparative example 2. A method for preparing an adhesive, comprising the steps of: adding 6g N-hydroxyethyl acrylamide into 80mL of deionized water, uniformly stirring to obtain a monomer mixed solution, and continuously introducing N 2 Preheating the monomer mixed solution to 55 ℃, adding 0.05g of ammonium persulfate, heating to 70 ℃, adding 0.05g of ammonium persulfate, stirring at 500r/min for reaction for 6 hours, washing the product with ethanol and acetone, and drying to obtain the binder.
A preparation method of a lithium ion battery comprises the following steps: A. silicon-based anode material silicon oxide, conductive agent Super-P and binder according to the mass ratio of 80:10:10, mixing, and controlling the solid content of the mixture to be 40% by weight through a 20wt% ethanol aqueous solution to prepare negative electrode slurry; B. uniformly coating the negative electrode slurry on a copper foil current collector, vacuum drying in an oven for 12 hours, and cutting into round pole pieces with the diameter of 10 mm; C. a2032 type button cell was assembled in a glove box under an argon atmosphere using a metallic lithium sheet as a counter electrode, 1mol/L LiPF6 (solvent is a mixture of Ethylene Carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1:1, 5% by volume of fluoroethylene carbonate (FEC)) was added as an electrolyte, and a polypropylene microporous separator.
The adhesive prepared in examples 1 to 4 and comparative examples 1 to 2 was tested for performance, and the test method for peel strength was carried out by using a universal tensile machine with reference to GB/T2790-1995 "test method for peel strength of 180 degree adhesive for Flexible Material to rigid Material", which is: taking out two copper foils with the specification of 40mm multiplied by 100mm, and scrubbing with alcohol before use; in the test, one end of each copper foil is coated with enough electrode slurry, the coating area is 5.5cm multiplied by 1.3cm, and the copper foil is placed in a 60 ℃ oven for 2 hours to be dried after the coating is finished; and finally, fixing one end of the sample on a tension probe, peeling at 180 degrees at a constant speed of 10mm/min, and testing the peeling force in the peeling process to represent the cohesive strength of the adhesive.
The batteries prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to performance test, and constant current charge-discharge cycle test was performed at 50℃using a LAND-CT2001A tester, with a discharge cutoff voltage of 0.005V and a charge cutoff voltage of 1.5V, and were first respectively subjected to charge-discharge cycles at a current density of 100mA/g for 3 times, and then subjected to charge-discharge cycles at a current density of 500 mA/g. Specific data are shown in the following table.
。
From the data in the table, the peel strength of the adhesive prepared by the embodiment is obviously better than that of the comparative example, and the cycling stability is better, which indicates that the adhesive provided by the invention can effectively inhibit the volume expansion of the silicon-based negative electrode in the lithium intercalation and deintercalation process, and obviously improve the cycling performance of the lithium battery. The binder modified by sodium styrene benzenesulfonate (comparative example 1) can effectively improve the lithium ion conduction efficiency, so the electrochemical performance of the battery prepared in comparative example 1 is also obviously better than that of the battery prepared in comparative example 2.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. A preparation method of an adhesive is characterized in that: comprises the following steps of
(1) Adding N-hydroxyethyl acrylamide and sodium p-styrenesulfonate into deionized water, stirring uniformly to obtain monomer mixed solution, and continuously introducing N 2 Preheating the monomer mixed solution, adding a part of ammonium persulfate aqueous solution, heating, adding the rest ammonium persulfate aqueous solution, stirring for reaction, washing the product with ethanol and acetone, and drying to obtain an N-hydroxyethyl acrylamide-sodium p-styrenesulfonate copolymer;
(2) Adding N-hydroxyethyl acrylamide-sodium p-styrenesulfonate copolymer and isocyanate propyl triethoxysilane into dimethyl sulfoxide, then adding dibutyl tin dilaurate, stirring and reacting to obtain a mixed solution, dripping the mixed solution into tetrahydrofuran, centrifugally collecting precipitate, washing and drying to obtain the adhesive.
2. The method of claim 1, wherein 1-3 g sodium p-styrenesulfonate and 50-80 mL deionized water are added to each 3-6-g N-hydroxyethyl acrylamide in the step (1).
3. The method for preparing a binder according to claim 1, wherein the ammonium persulfate in the step (1) is added in an amount of 0.5 to 2% of the monomer mixture.
4. The method for preparing a binder according to claim 1, wherein in the step (1), the binder is preheated to 30-55 ℃, heated to 45-70 ℃ and stirred for 3-6 hours under the stirring reaction condition of 300-500 r/min.
5. The method for preparing a binder according to claim 1, wherein in the step (2), each 7 to 11g N of the sodium hydroxyethyl acrylamide-p-styrenesulfonate copolymer corresponds to 0.1 to 2g of isocyanatopropyl triethoxysilane, 60 to 80mL of dimethyl sulfoxide and 0.005 to 0.1g of dibutyltin dilaurate; the volume ratio of dimethyl sulfoxide to tetrahydrofuran is 1:10 to 20.
6. The method for preparing a binder according to claim 1, wherein the stirring reaction condition in the step (2) is 300-400 r/min and the stirring reaction is carried out at 40-70 ℃ for 10-16 h.
7. A binder prepared by the method of any of claims 1 to 6.
8. A battery comprising a negative electrode sheet, the negative electrode sheet comprising a negative electrode slurry, characterized in that the negative electrode slurry comprises a conductive agent, a negative electrode active material and the binder of claim 7, and the mass ratio of the binder in the negative electrode slurry is 5-10%.
9. The battery of claim 8, wherein the negative electrode active material is a silicon-based negative electrode active material or a graphite negative electrode active material.
10. The battery of claim 8, wherein the conductive agent is one or more of Super-P, ketjen black, acetylene black, KS-6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311565394.0A CN117603637A (en) | 2023-11-22 | 2023-11-22 | Preparation method and application of adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311565394.0A CN117603637A (en) | 2023-11-22 | 2023-11-22 | Preparation method and application of adhesive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117603637A true CN117603637A (en) | 2024-02-27 |
Family
ID=89957249
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311565394.0A Pending CN117603637A (en) | 2023-11-22 | 2023-11-22 | Preparation method and application of adhesive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117603637A (en) |
-
2023
- 2023-11-22 CN CN202311565394.0A patent/CN117603637A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| 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 | |
| CN105958075B (en) | Pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders and the application in electrochemical energy storing device | |
| CN109004220B (en) | Boric acid compound modified lithium ion battery silicon cathode and preparation method thereof | |
| CN109888170B (en) | Three-dimensional network adhesive for secondary battery, preparation method of three-dimensional network adhesive, negative electrode slurry and negative electrode material | |
| CN111916645B (en) | Pole piece, preparation method of pole piece and battery | |
| CN102237527B (en) | Lithium ion battery and lithium ion battery electrode as well as electrode material and paste for lithium ion battery | |
| CN110890545A (en) | PEDOT (polyethylene glycol terephthalate)/PSS (Polybutylece terephthalate)/CMC (carboxymethyl cellulose) composite binder as well as preparation method and application thereof | |
| CN102437369B (en) | Lithium ion battery | |
| CN111647345B (en) | Lithium ion battery negative electrode polymer protective coating and preparation method and application thereof | |
| CN115295802A (en) | Adhesive, preparation method thereof and application thereof in lithium ion battery | |
| CN115172753A (en) | Novel lithium ion battery water-soluble binder and preparation method and application thereof | |
| CN110128650B (en) | Conductive polymer binder and preparation method and application thereof | |
| CN113629250B (en) | Polyimide binder for lithium battery cathode and silicon-based cathode plate | |
| CN112142890A (en) | Cyclic carbonate polymer binder and preparation method and application thereof | |
| CN112457805A (en) | Adhesive, preparation method thereof, silicon-carbon negative electrode material and lithium battery | |
| CN114242990B (en) | Polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder and preparation method and application thereof | |
| US20230114529A1 (en) | Negative electrode piece and secondary battery including same | |
| CN116731635A (en) | Conductive adhesive and preparation method and application thereof | |
| CN116014079A (en) | Lignin water-based composite battery binder and preparation method and application of silicon-based negative plate thereof | |
| CN114122398B (en) | Integrated conductive adhesive and preparation method and application thereof | |
| CN115939398A (en) | Conductive adhesive, preparation method and application thereof | |
| CN117603637A (en) | Preparation method and application of adhesive | |
| CN114400323A (en) | Preparation method of novel disulfide bond sulfur-containing polymer positive active substance | |
| CN113980174A (en) | Coordinate bond enhanced cathode adhesive 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 |