CN116875234A - Preparation method of cathode binder of cathode and anode polymer composite battery - Google Patents
Preparation method of cathode binder of cathode and anode polymer composite battery Download PDFInfo
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- CN116875234A CN116875234A CN202310917727.5A CN202310917727A CN116875234A CN 116875234 A CN116875234 A CN 116875234A CN 202310917727 A CN202310917727 A CN 202310917727A CN 116875234 A CN116875234 A CN 116875234A
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- anionic
- polymer
- positive electrode
- cationic
- binder
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- 229920000642 polymer Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 239000003013 cathode binding agent Substances 0.000 title claims description 8
- 229920006317 cationic polymer Polymers 0.000 claims abstract description 53
- 229920006318 anionic polymer Polymers 0.000 claims abstract description 47
- 125000000129 anionic group Chemical group 0.000 claims abstract description 36
- 239000011883 electrode binding agent Substances 0.000 claims abstract description 34
- 125000002091 cationic group Chemical group 0.000 claims abstract description 20
- -1 ethyl bromide- (4-vinyl) pyridine Chemical compound 0.000 claims abstract description 12
- XESUCHPMWXMNRV-UHFFFAOYSA-M sodium;2-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1C=C XESUCHPMWXMNRV-UHFFFAOYSA-M 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 18
- 239000003995 emulsifying agent Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000011267 electrode slurry Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 9
- FKKAGFLIPSSCHT-UHFFFAOYSA-N 1-dodecoxydodecane;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC FKKAGFLIPSSCHT-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000011888 foil Substances 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 230000005587 bubbling Effects 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 abstract description 9
- 239000011230 binding agent Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000008358 core component Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000011884 anode binding agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C09J125/00—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 an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
-
- 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
- C09J139/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
- C09J139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
-
- 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)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a positive electrode binder of a cathode-anode polymer composite battery, which specifically comprises the following steps: step 1, preparing a cationic polymer by adopting ethyl bromide- (4-vinyl) pyridine; step 2, preparing an anionic polymer by using sodium vinylbenzenesulfonate; and 3, preparing the positive electrode binder of the anionic and cationic multi-branched polymer according to the products obtained in the step 1 and the step 2. The adhesive prepared by the invention can improve the thermal expansion coefficient and the bonding strength of the adhesive.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a preparation method of an anionic-cationic polymer composite battery positive electrode binder.
Background
With the rapid development of society, green and environment-friendly new energy sources such as solar energy, wind energy, hydrogen energy and the like are favored, and the efficient use of these energy sources depends on the success of technologies such as solar cells, fuel cells, lithium batteries and the like. Up to now, lithium batteries have been widely used, such as new energy automobiles, electric vehicles, and the like. However, battery price, service life, and safety are to be further improved.
The core component of the lithium battery mainly comprises three positive electrodes, a negative electrode and a separator, wherein the positive electrode is one of the core components of the lithium battery. The positive electrode material has an important influence on the manufacturing cost and the service life of the battery. The positive electrode of the lithium battery is formed by mixing multiple components such as carbon black, lithium salt and other auxiliary agents. In order to improve battery performance, the conductive carbon black exists in the form of powder, and then the conductive carbon black, lithium salt, etc. are effectively bonded together with a binder. The existing adhesive has small thermal expansion coefficient, so that the physical and chemical properties of the electrode material are easy to change in the charging and discharging process of the lithium battery, and the bonding strength of the adhesive is weakened.
Disclosure of Invention
The invention aims to provide a preparation method of a positive electrode binder of a cathode and anode polymer composite battery, and the binder prepared by the method can improve the thermal expansion coefficient and the bonding strength of the binder.
The technical scheme adopted by the invention is that the preparation method of the positive electrode binder of the anionic and cationic polymer composite battery specifically comprises the following steps:
step 1, preparing a cationic polymer by adopting ethyl bromide- (4-vinyl) pyridine;
step 2, preparing an anionic polymer by using sodium vinylbenzenesulfonate;
and 3, preparing the positive electrode binder of the anionic and cationic multi-branched polymer according to the products obtained in the step 1 and the step 2.
The invention is also characterized in that:
the specific process of the step 1 is as follows:
step 1.1, taking 3g-5g of ethyl bromide- (4-vinyl) pyridine and 0.1g-0.2g of azodiisobutyronitrile, vacuumizing, filling nitrogen to remove oxygen, and repeating for 3-5 times;
step 1.2, adding 3mL-5 mLN-hydroxyethyl acrylamide and 10mL-15mL of N, N-dimethylformamide into the product obtained in the step 1.1, bubbling nitrogen for 10-30 minutes, reacting for 12h-36h at 80-120 ℃, cooling to room temperature after the reaction is finished, pouring the reaction solution into 100mL-300mL of ethanol, and collecting solid powdery cationic polymer.
The specific process of the step 2 is as follows:
step 2.1, taking 3g-5g of sodium vinylbenzenesulfonate and 0.1g-0.2g of azodiisobutyronitrile, vacuumizing, filling nitrogen to remove oxygen, and repeating for 3-5 times;
step 2.2, adding 3mL-5mL of 2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester and 10mL-15mLN, N-dimethylformamide into the product obtained in the step 1.1, bubbling nitrogen for 10-30 minutes, reacting for 12h-36h at 80-120 ℃, cooling to room temperature after the reaction is finished, pouring the reaction solution into 100mL-300mL of ethanol, and collecting solid powdery anionic polymer.
The specific process of the step 3 is as follows:
step 3.1, taking 0.8g-1.2g of the cationic polymer prepared in the step 1 and 0.8g-1.2g of the anionic polymer, and sequentially adding the cationic polymer and the anionic polymer into 6mL-8mL of deionized water to obtain an anionic-cationic polymer mixed solution;
step 3.2, dissolving 40mg-60mg of sodium dodecyl ether sulfate in 4mL-6mL of deionized water to obtain an emulsifier solution;
and 3.3, dropwise adding the emulsifier solution obtained in the step 3.2 into the mixed solution of the anionic and cationic polymers obtained in the step 3.1, continuously stirring for 30-60min after the dropwise adding is finished, and freeze-drying at-70 ℃ to-40 for 36-72h to obtain the anionic and cationic multi-branched polymer positive electrode binder.
The specific process for preparing the positive electrode of the anionic multi-branched polymer battery by adopting the positive electrode binder of the anionic multi-branched polymer prepared in the step 3 is as follows:
adding 0.7g-1g of lithium iron phosphate, 0.1g-0.15g of conductive carbon black and 0.1g-0.15g of polyvinylpyrrolidone into 2.0mL-3.0mL of deionized water, stirring for 30min-60min, then adding 0.1g-0.15g of anionic and cationic multi-branched polymer positive electrode binder, stirring and dispersing to obtain positive electrode slurry, coating the positive electrode slurry on carbon-coated aluminum foil, drying at 90-110 ℃, and rolling and cutting into positive electrode plates with the thickness of 50mm multiplied by 50 mm.
The invention has the beneficial effects that the invention constructs the multi-substituent or branched anionic polymer and the cationic polymer, and the multi-substituent or branched anionic polymer and the cationic polymer are compounded, so that on one hand, the characteristic of the multi-substituent or branched polymer is utilized to improve the molecular asymmetry, reduce the crystallization performance and reduce the thermal expansion coefficient of the battery, and solve the problem of thermal expansion and cold contraction of the battery. On the other hand, the bond strength is improved by the ionic bond to reduce breakage and to improve conductivity.
The multi-substituent or branched anionic and cationic polymer is used as the positive electrode binder of the battery, so that the problems of poor conductivity, easiness in crystallization, weak bonding strength, low thermal expansion coefficient and the like of the positive electrode binder of the lithium battery electrode are solved.
Drawings
Fig. 1 is a thermal expansion coefficient test chart of example 1 and comparative examples 1-2, which are the preparation method of the cathode binder for a polymer electrolyte and cathode composite battery according to the present invention.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The invention relates to a preparation method of an anode binder of a cathode-anode polymer composite battery, which specifically comprises the following steps:
1) Preparation of cationic polymers
3-5g of ethyl bromide- (4-vinyl) pyridine and azodiisobutyronitrile (0.1-0.2 g) are taken, vacuum pumping and nitrogen filling are carried out to remove oxygen, the steps are repeated for 3-5 times, then 3-5mL of N-hydroxyethyl acrylamide and 10-15mL of N, N-Dimethylformamide (DMF) are added, and nitrogen bubbling is carried out for 10-30 minutes. Further reacting at 80-120 deg.C for 12-36 hr. After the reaction was completed, the reaction mixture was cooled to room temperature, and the reaction solution was poured into 100 to 300mL of industrial ethanol, and the solid powdery cationic polymer was collected.
2) Preparation of anionic polymers
Taking 3-5g of sodium vinylbenzenesulfonate and 0.1-0.2g of azodiisobutyronitrile, vacuumizing, filling nitrogen to remove oxygen, and repeating for 3-5 times; then, 3-5mL of 2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester and 10-15mL of N, N-Dimethylformamide (DMF) were added, and nitrogen was bubbled for 10-30 minutes. Further reacting at 80-120 deg.C for 12-36 hr. After the reaction was completed, the reaction mixture was cooled to room temperature, poured into 100-300mL of industrial ethanol, and the solid powdery anionic polymer was collected.
3) Preparation of positive electrode binder of anionic and cationic multi-branched polymer
Taking 0.8-1.2g of cationic polymer and 0.8-1.2g of anionic polymer, and sequentially adding into 6-8mL of deionized water to obtain an anionic-cationic polymer mixed solution. 40-60mg of sodium dodecyl ether sulfate was dissolved in 4-6mL of deionized water to obtain an emulsifier solution. And further dropwise adding the emulsifier solution (dropwise adding time is 30 min) into the mixed solution of the anionic and cationic polymers, continuously stirring for 30-60min after the dropwise adding is finished, and freeze-drying at-70 ℃ to-40 for 36-72h to obtain the anionic and cationic multi-branched polymer positive electrode binder. 4) Preparation of positive electrode of multi-branched polymer battery based on anions and cations
Adding 0.7-1g of lithium iron phosphate, 0.1-0.15g of conductive carbon black and 0.1-0.15g of polyvinylpyrrolidone into 2.0-3.0mL of deionized water, stirring for 30-60min, further adding 0.1-0.15g of anionic-cationic multi-branched polymer positive electrode binder, and stirring and dispersing to obtain the positive electrode slurry. And further coating the positive electrode slurry on a carbon-coated aluminum foil, drying at 90-110 ℃, and rolling and cutting into positive electrode plates with the thickness of 50mm multiplied by 50 mm.
Example 1
1) Preparation of cationic polymers
Ethyl bromide- (4-vinyl) pyridine 5g and azobisisobutyronitrile (0.2 g) were taken, evacuated and purged with nitrogen to remove oxygen, and repeated 3 times, then 5mL of N-hydroxyethyl acrylamide and 15mL of N, N-Dimethylformamide (DMF) were added, and nitrogen was bubbled for 10 minutes. The reaction was further carried out at 80℃for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, poured into 100mL of industrial ethanol, and the solid powdery cationic polymer was collected.
2) Preparation of anionic polymers
Taking 5g of sodium vinylbenzenesulfonate and 0.2g of azobisisobutyronitrile, vacuumizing, filling nitrogen to remove oxygen, and repeating for 3 times; then, 5mL of 2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester and 15mL of N, N-Dimethylformamide (DMF) were added, and nitrogen was bubbled for 10 minutes. The reaction was further carried out at 80℃for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, poured into 100mL of industrial ethanol, and the solid powdery anionic polymer was collected.
3) Preparation of positive electrode binder of anionic and cationic multi-branched polymer
1.2g of cationic polymer and 0.8g of anionic polymer were taken and added to 6mL of deionized water in sequence to obtain an anionic-cationic polymer mixed solution. 60mg of sodium dodecyl ether sulfate was dissolved in 4mL of deionized water to obtain an emulsifier solution. And further dropwise adding the emulsifier solution (dropwise adding time is 30 min) into the mixed solution of the anionic and cationic polymers, continuously stirring for 30min after the dropwise adding is finished, and freeze-drying at-40 ℃ for 72h to obtain the anionic and cationic multi-branched polymer positive electrode binder.
4) Preparation of positive electrode of multi-branched polymer battery based on anions and cations
Adding 0.7g of lithium iron phosphate, 0.1g of conductive carbon black and 0.1g of polyvinylpyrrolidone into 2.0mL of deionized water, stirring for 30min, further adding 0.1g of anionic-cationic multi-branched polymer positive electrode binder, and stirring and dispersing to obtain the positive electrode slurry. The positive electrode slurry is further coated on carbon-coated aluminum foil, dried at 90 ℃, rolled and cut into positive electrode plates with the thickness of 50mm multiplied by 50 mm.
Comparative example 1 (binder contains only anionic polymer, the polymeric branch type is half that of example 1)
1) Preparation of anionic polymeric positive electrode binder
0.8g of anionic polymer was taken and added to 6mL of deionized water successively to obtain an anionic polymer mixed solution. 60mg of sodium dodecyl ether sulfate was dissolved in 4mL of deionized water to obtain an emulsifier solution. And further dropwise adding the emulsifier solution (dropwise adding time is 30 min) into the polymer mixed solution, continuously stirring for 30min after the dropwise adding is finished, and freeze-drying at-40 ℃ for 72h to obtain the anionic polymer positive electrode binder.
2) Preparation of positive pole piece of lithium ion battery based on anionic polymer positive pole binder
Adding 0.7g of lithium iron phosphate, 0.1g of conductive carbon black and 0.1g of polyvinylpyrrolidone into 2.0mL of deionized water, stirring for 30min, further adding 0.1g of anionic polymer positive electrode binder, and stirring and dispersing to obtain the positive electrode slurry. The positive electrode slurry is further coated on carbon-coated aluminum foil, dried at 90 ℃, rolled and cut into positive electrode plates with the thickness of 50mm multiplied by 50 mm.
Comparative example 2 (binder contains only cationic polymer, the polymeric branch type is half that of example 1)
1) Preparation of cationic Polymer Positive electrode Binder
1.2g of cationic polymer was taken and added to 6mL of deionized water in sequence to obtain a cationic polymer mixed solution. 60mg of sodium dodecyl ether sulfate was dissolved in 4mL of deionized water to obtain an emulsifier solution. And further dropwise adding the emulsifier solution (dropwise adding time is 30 min) into the polymer mixed solution, continuously stirring for 30min after the dropwise adding is finished, and freeze-drying at-40 ℃ for 72h to obtain the cationic polymer positive electrode binder.
2) Preparation of positive pole piece of lithium ion battery based on positive pole binder of cationic polymer
Adding 0.7g of lithium iron phosphate, 0.1g of conductive carbon black and 0.1g of polyvinylpyrrolidone into 2.0mL of deionized water, stirring for 30min, further adding 0.1g of cationic polymer positive electrode binder, and stirring and dispersing to obtain the positive electrode slurry. The positive electrode slurry is further coated on carbon-coated aluminum foil, dried at 90 ℃, rolled and cut into positive electrode plates with the thickness of 50mm multiplied by 50 mm.
The following table 1 shows the performance test results of the adhesive and positive electrode sheet prepared in example 1, comparative example 1 and comparative example 2:
TABLE 1 Performance test results of adhesive and Positive Pole piece
The crystallinity test shows that the binder in example 1 has lower crystallinity, and the main reason is that the cationic polymer branched chain contains a large amount of ammonium bromide ions, so that positive charge repulsive force exists in the cationic polymer chain and is difficult to accumulate, the anionic polymer branched chain contains benzenesulfonate anions, and the negative charge repulsive force prevents the anionic polymer from crystallizing, and meanwhile, the flexibility and asymmetry of the polymer chain are greatly improved, so that the crystallinity of the binder is reduced.
Example 1 the binder polymer structure has different types of branches (functional groups) and flexible branches, so that the crystallinity is reduced, the amorphous area is increased, and the thermal expansion coefficient is improved. The binder is beneficial to the practical use of the lithium battery, such as volume change caused by temperature.
The positive electrode binder prepared by the anionic and cationic polymers can reduce the resistivity of the electrode plate and the resistivity to be 47 ohm cm.
The pole piece flexibility test is carried out by adopting a 2mm winding needle to wind, and the pole piece powder falling phenomenon in the embodiment 1 is found; the pole pieces in the comparative example 1 and the comparative example 2 not only have the phenomenon of falling off, which shows that the bonding effect of the positive electrode adhesive of the anionic and cationic multi-branched polymer is best.
The peel strength of the pole pieces was tested using a tensile tester, and when the tensile angle was 180℃and the tensile rate was 20mm/min, the peel strength in example 1 reached 23N/m, which is far higher than the proportional strength of comparative examples 1 and 2, because the binder in example 1 was compounded with an anionic polymer, which resulted in a strong force between the anionic polymer and the cationic polymer.
As can be seen from FIG. 1, the thermal expansion coefficients of comparative examples 1-2 are small, and the thermal expansion coefficient of example 1 is large, which is beneficial to practical application, and avoids the weakening of the adhesive strength of the adhesive due to the small thermal expansion coefficient, so that the adhered object is peeled off.
Example 2
1) Preparation of cationic polymers
Ethyl bromide- (4-vinyl) pyridine 3g and azobisisobutyronitrile (0.1 g) were taken, evacuated and purged with nitrogen to remove oxygen, repeated 5 times, and then 3mL of N-hydroxyethyl acrylamide and 10mL of N, N-Dimethylformamide (DMF) were added thereto, followed by bubbling with nitrogen for 30 minutes. The reaction was further carried out at 120℃for 36 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, poured into 300mL of industrial ethanol, and the solid powdery cationic polymer was collected.
2) Preparation of anionic polymers
Taking 3g of sodium vinylbenzenesulfonate and 0.1g of azobisisobutyronitrile, vacuumizing, filling nitrogen to remove oxygen, and repeating for 5 times; then, 3mL of 2- (2-methoxyethoxy) ethyl 2-methyl-2-propenoate and 10mL of N, N-Dimethylformamide (DMF) were added, and nitrogen was bubbled for 30 minutes. The reaction was further carried out at 120℃for 36 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, poured into 300mL of industrial ethanol, and the solid powdery anionic polymer was collected.
3) Preparation of positive electrode binder of anionic and cationic multi-branched polymer
0.8g of cationic polymer and 1.2g of anionic polymer were taken and added to 8mL of deionized water in sequence to obtain an anionic-cationic polymer mixed solution. 40mg of sodium dodecyl ether sulfate was dissolved in 6mL of deionized water to obtain an emulsifier solution. And further dropwise adding the emulsifier solution (dropwise adding time is 30 min) into the mixed solution of the anionic and cationic polymers, continuously stirring for 60min after the dropwise adding is finished, and freeze-drying at-70 ℃ for 36h to obtain the anionic and cationic multi-branched polymer positive electrode binder.
4) Preparation of positive electrode of multi-branched polymer battery based on anions and cations
1g of lithium iron phosphate, 0.15g of conductive carbon black and 0.15g of polyvinylpyrrolidone are added into 3.0mL of deionized water and stirred for 60min, and 0.15g of anionic-cationic multi-branched polymer positive electrode binder is further added, and the positive electrode slurry is obtained through stirring and dispersing. And further coating the positive electrode slurry on a carbon-coated aluminum foil, drying at 110 ℃, and rolling and cutting into positive electrode plates with the thickness of 50mm multiplied by 50 mm.
Example 3
1) Preparation of cationic polymers
Ethyl bromide- (4-vinyl) pyridine 4g and azobisisobutyronitrile (0.15 g) were taken, evacuated and purged with nitrogen to remove oxygen, and repeated 4 times, then 4mL of N-hydroxyethyl acrylamide and 12mL of N, N-Dimethylformamide (DMF) were added, and nitrogen bubbling was performed for 20 minutes. The reaction was further carried out at 100℃for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, poured into 200mL of industrial ethanol, and the solid powdery cationic polymer was collected.
2) Preparation of anionic polymers
Taking 4g of sodium vinylbenzenesulfonate and 0.2g of azobisisobutyronitrile, vacuumizing, filling nitrogen to remove oxygen, and repeating for 4 times; then, 4mL of 2- (2-methoxyethoxy) ethyl 2-methyl-2-propenoate and 12mL of N, N-Dimethylformamide (DMF) were added, and nitrogen was bubbled for 20 minutes. The reaction was further carried out at 100℃for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, poured into 200mL of industrial ethanol, and the solid powdery anionic polymer was collected.
3) Preparation of positive electrode binder of anionic and cationic multi-branched polymer
1.0g of cationic polymer and 1.0g of anionic polymer were taken and added to 7mL of deionized water in sequence to obtain an anionic-cationic polymer mixed solution. 50mg of sodium dodecyl ether sulfate was dissolved in 5mL of deionized water to obtain an emulsifier solution. And further dropwise adding the emulsifier solution (dropwise adding time is 30 min) into the mixed solution of the anionic and cationic polymers, continuously stirring for 50min after the dropwise adding is finished, and freeze-drying at-50 ℃ for 48h to obtain the anionic and cationic multi-branched polymer positive electrode binder.
4) Preparation of cathode electrode of anionic and cationic multi-branched polymer battery, adding 0.8g of lithium iron phosphate, 0.12g of conductive carbon black and 0.12g of polyvinylpyrrolidone into 2.5mL of deionized water, stirring for 50min, further adding 0.12g of anionic and cationic multi-branched polymer cathode binder, stirring and dispersing to obtain the cathode slurry. And further coating the positive electrode slurry on a carbon-coated aluminum foil, drying at 100 ℃, and rolling and cutting into positive electrode plates with the thickness of 50mm multiplied by 50 mm.
Claims (5)
1. The preparation method of the cathode binder of the anionic polymer composite battery is characterized by comprising the following steps: the method specifically comprises the following steps:
step 1, preparing a cationic polymer by adopting ethyl bromide- (4-vinyl) pyridine;
step 2, preparing an anionic polymer by using sodium vinylbenzenesulfonate;
and 3, preparing the positive electrode binder of the anionic and cationic multi-branched polymer according to the products obtained in the step 1 and the step 2.
2. The method for preparing the cathode binder of the anionic and cationic polymer composite battery according to claim 1, which is characterized in that: the specific process of the step 1 is as follows:
step 1.1, taking 3g-5g of ethyl bromide- (4-vinyl) pyridine and 0.1g-0.2g of azodiisobutyronitrile, vacuumizing, filling nitrogen to remove oxygen, and repeating for 3-5 times;
step 1.2, adding 3mL-5 mLN-hydroxyethyl acrylamide and 10mL-15mL of N, N-dimethylformamide into the product obtained in the step 1.1, bubbling nitrogen for 10-30 minutes, reacting for 12-36 hours under the condition of 80-120 ℃, cooling to room temperature after the reaction is finished, pouring the reaction solution into 100mL-300mL of ethanol, and collecting solid powdery cationic polymer.
3. The method for preparing the cathode binder of the anionic and cationic polymer composite battery according to claim 1, which is characterized in that: the specific process of the step 2 is as follows:
step 2.1, taking 3g-5g of sodium vinylbenzenesulfonate and 0.1g-0.2g of azodiisobutyronitrile, vacuumizing, filling nitrogen to remove oxygen, and repeating for 3-5 times;
step 2.2, 3mL-5mL of 2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester and 10mL-15mLN, N-dimethylformamide are added to the product obtained in the step 1.1, nitrogen bubbling is carried out for 10-30 minutes, the reaction is carried out for 12h-36h under the condition of 80 ℃ to 120 ℃, after the reaction is finished, the reaction solution is cooled to room temperature, and the reaction solution is poured into 100mL-300mL of ethanol, so as to collect solid powdery anionic polymer.
4. The method for preparing the cathode binder of the anionic and cationic polymer composite battery according to claim 1, which is characterized in that: the specific process of the step 3 is as follows:
step 3.1, taking 0.8g-1.2g of the cationic polymer prepared in the step 1 and 0.8g-1.2g of the anionic polymer, and sequentially adding the cationic polymer and the anionic polymer into 6mL-8mL of deionized water to obtain an anionic-cationic polymer mixed solution;
step 3.2, dissolving 40mg-60mg of sodium dodecyl ether sulfate in 4mL-6mL of deionized water to obtain an emulsifier solution;
and 3.3, dropwise adding the emulsifier solution obtained in the step 3.2 into the mixed solution of the anionic and cationic polymers obtained in the step 3.1, continuously stirring for 30-60min after the dropwise adding is finished, and freeze-drying for 36-72h at-70 ℃ to-40 to obtain the anionic and cationic multi-branched polymer positive electrode binder.
5. The method for preparing the positive electrode binder of the anionic and cationic polymer composite battery, according to claim 4, which is characterized in that: the specific process for preparing the positive electrode of the anionic and cationic multi-branched polymer battery by adopting the positive electrode binder of the anionic and cationic multi-branched polymer prepared in the step 3 is as follows:
adding 0.7g-1g of lithium iron phosphate, 0.1g-0.15g of conductive carbon black and 0.1g-0.15g of polyvinylpyrrolidone into 2.0mL-3.0mL of deionized water, stirring for 30min-60min, then adding 0.1g-0.15g of anionic and cationic multi-branched polymer positive electrode binder, stirring and dispersing to obtain positive electrode slurry, coating the positive electrode slurry on carbon-coated aluminum foil, drying at 90-110 ℃, and rolling and cutting into positive electrode plates with the thickness of 50mm multiplied by 50 mm.
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