CN117645852A - Oily adhesive system and application thereof - Google Patents
Oily adhesive system and application thereof Download PDFInfo
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- CN117645852A CN117645852A CN202410114649.XA CN202410114649A CN117645852A CN 117645852 A CN117645852 A CN 117645852A CN 202410114649 A CN202410114649 A CN 202410114649A CN 117645852 A CN117645852 A CN 117645852A
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- adhesive
- oily
- acrylonitrile
- adhesive system
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- 239000000853 adhesive Substances 0.000 title claims abstract description 143
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 143
- 239000006258 conductive agent Substances 0.000 claims abstract description 38
- 229920001577 copolymer Polymers 0.000 claims abstract description 38
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011149 active material Substances 0.000 claims abstract description 26
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 22
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- LJTFFORYSFGNCT-UHFFFAOYSA-N Thiocarbohydrazide Chemical compound NNC(=S)NN LJTFFORYSFGNCT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 12
- -1 acrylic ester Chemical class 0.000 claims abstract description 9
- 239000011267 electrode slurry Substances 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 2
- 238000004132 cross linking Methods 0.000 abstract description 21
- 239000001257 hydrogen Substances 0.000 abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 20
- 230000007774 longterm Effects 0.000 abstract description 9
- 229920002239 polyacrylonitrile Polymers 0.000 abstract description 6
- 238000007112 amidation reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 19
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 18
- 239000006256 anode slurry Substances 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 16
- 239000002002 slurry Substances 0.000 description 16
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 14
- 238000007664 blowing Methods 0.000 description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 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 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical group 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
Abstract
An oily adhesive system and application thereof relate to the technical field of secondary battery materials and solve the problems of insufficient cohesiveness and limited long-term stability of the existing adhesive. An oily adhesive system obtained by mixing an acrylonitrile copolymer with thiourea or thiocarbazide in an oily solvent; the acrylonitrile copolymer is polymerized by acrylonitrile, acrylic ester monomer and itaconic acid. The oily binder system of the invention can be applied to a secondary battery as a positive electrode slurry after being mixed with an active material and a conductive agent, is coated on a positive electrode current collector of the battery, and finally functions in a crosslinked structure. Firstly, molecular chain design is carried out on polyacrylonitrile to improve the flexibility of the polyacrylonitrile as an adhesive; the linear adhesive is prepared into the multi-hydrogen bond crosslinking adhesive through amidation reaction, covalent bonds and multiple hydrogen bonds coexist, the effectiveness of a crosslinking structure is ensured, and meanwhile, the long-term stability and the rate capability are improved.
Description
Technical Field
The invention relates to the technical field of secondary battery materials, in particular to an oily adhesive system and application thereof.
Background
With the rapid development of energy structural transformation, secondary batteries are receiving increasing attention. Among the energy storage devices, the lithium ion battery has the advantages of high energy density, long cycle life and the like, and is widely applied to various energy storage power supply systems of electric automobiles, aerospace, wind power, firepower and the like at present. Moreover, as the application of lithium ion batteries is becoming mature, sodium ion batteries and potassium ion batteries having similar operating principles show great development potential due to the abundant sodium/potassium resource reserves. The performance of the battery depends largely on the electrode, and optimizing the battery structure is advantageous in promoting the development of high-performance batteries.
The positive electrode of the above secondary battery is composed of an active material, a binder, a conductive agent, and a current collector. Wherein the binder is used for tightly combining the active material and the conductive agent and fixing the active material and the conductive agent on the current collector. Since the active material and the conductive agent are generally in a powder state and cannot be fixed to the current collector by themselves, powdering and falling off of the electrode sheet may cause capacity loss and interruption of electron and ion transfer, which is fatal to the normal operation of the battery. Thus, the binder is critical to maintaining electrode integrity, ion transfer, and efficient electrochemical reactions.
In order to achieve long-term stable operation of the battery, some patent documents have disclosed the use of some crosslinking binders in secondary batteries. For example, chinese patent document CN117219774a discloses a conductive crosslinking adhesive, which is prepared by using hydroxyl and carboxyl groups on sodium alginate and surface oxygen-containing functional groups of Ti3C2TX MXene through hydrogen bonds, and the adhesive system simplifies the crosslinking process, reduces the use of conductive agents and increases the loading amount of active materials in the application process. Chinese patent document CN114373931a discloses a three-dimensional network structure formed by hydrogen bonding and crosslinking a rigid polyacrylic acid chain and a special polymer soft chain, wherein the polymer soft chain is selected from polyurethane terpolymers. A large number of polar groups can build rich hydrogen bonds, so that the adhesive system forms a cross-linked structure, improves the overall mechanical strength and endows the pole piece with self-healing capability. Chinese patent document CN114142039a discloses an adhesive system comprising two polymers, wherein the two polymers are capable of forming triple hydrogen bonds between carbonyl groups and secondary amine, so that the adhesive system has higher toughness and is capable of releasing stress generated by expansion. The above-mentioned adhesive uses only hydrogen bonds to construct a crosslinking system, but it cannot be confirmed whether or not an effective hydrogen bond crosslinking structure exists in an electrode sheet using such an adhesive. In addition, the application range of aqueous binders such as sodium alginate and polyacrylic acid is limited, and the aqueous binders are applied to the positive electrode sheet, and the capacity of the active material is damaged to a certain extent. Therefore, development of the cross-linked oily adhesive with the coexistence of hydrogen bonds and covalent bonds is significant in realizing the long-term stability of the positive plate and promoting the improvement of the battery performance.
The ideal adhesive should possess the following characteristics: (1) In the process of preparing the adhesive solution, the adhesive can be quickly and fully dissolved; (2) providing sufficient adhesion; (3) stable slurry state; (4) electrochemical stabilization; (5) inhibiting the swelling effect of the electrolyte; (6) good flexibility, etc. Existing adhesives can only meet part of the requirements. The conventional polyvinylidene fluoride adhesive mainly depends on intermolecular van der Waals force to realize bonding force due to the linear structure of the adhesive. Therefore, when the electrode is applied to a battery, the electrode plate can crack or even pulverize when facing large volume change or substance migration; the novel adhesive, such as polyacrylic acid, polyacrylamide and the like, has the problems of larger rigidity and poor flexibility, and even if the novel adhesive is used in a water-inert positive plate, the contraction and cracking of the plate inevitably occur in the preparation process. Therefore, a net-shaped oily adhesive is developed, which is beneficial to the long-term stability of the battery and the improvement of the rate performance.
The polyacrylonitrile has strong adhesion with active materials and current collectors and low cost, and is a promising adhesive. However, polyacrylonitrile has a high crystallinity at room temperature at a temperature below the glass transition temperature. Therefore, the pole piece prepared by using the acrylonitrile homopolymer as the adhesive has poor flexibility and is unfavorable for mass production.
Disclosure of Invention
In order to solve the problems of insufficient cohesiveness and limited long-term stability of the existing adhesive, the invention provides an oily adhesive system and application thereof.
The technical scheme of the application is as follows:
an oily adhesive system, wherein the oily adhesive is obtained by mixing an acrylonitrile copolymer with thiourea or thiocarbazide in an oily solvent;
the acrylonitrile copolymer is polymerized by acrylonitrile, acrylic ester monomers and itaconic acid.
Preferably, the mass ratio of the acrylonitrile copolymer to thiourea or thiocarbazide is 4:0.5 to 4.
Preferably, the oily solvent is N-methylpyrrolidone.
Preferably, the acrylic monomer is one or more of methyl acrylate, butyl acrylate and dodecyl acrylate.
Preferably, the acrylonitrile copolymer is synthesized by the following steps:
s1, adding acrylonitrile, acrylic ester monomers and itaconic acid into water, and introducing nitrogen into a reaction system to remove oxygen;
s2, adding a water-based initiator, heating the reaction system to a first temperature for reaction, heating to a second temperature for the second time, and continuing the reaction;
and S3, filtering and crushing the generated solid, cleaning with deionized water, and drying to obtain the acrylonitrile copolymer.
Preferably, the molar ratio of the acrylonitrile, the acrylic ester monomer and the itaconic acid is 70-98: 1-15: 1-15.
Preferably, the mass ratio of the total mass of the acrylonitrile, the acrylic ester monomer and the itaconic acid to water is 15-20: 100.
preferably, the aqueous initiator is ammonium persulfate; the dosage of the water-based initiator is 2% of the total mass of the acrylonitrile, the acrylic ester monomer and the itaconic acid.
Preferably, in the step S2, the first temperature is 60-70 ℃, and the reaction time at the first temperature is 2.5-3.5 hours; the second temperature is 85-95 ℃, and the reaction time at the second temperature is 2-3 h.
The invention also provides an application of the oily adhesive system, which is used for being applied to a secondary battery as positive electrode slurry after being mixed with an active material and a conductive agent.
Preferably, the mass ratio of the solute in the active material, the conductive agent and the oily adhesive system is 80-95: 10-2: 10-3.
Preferably, the positive electrode slurry is coated on a current collector, placed in a 80 ℃ forced air oven for 8 hours, and then placed in a 120 ℃ vacuum oven for 8 hours to dry, so that the binder system is crosslinked on the current collector.
Compared with the prior art, the invention has the following specific beneficial effects:
1. according to the invention, the acrylonitrile copolymer is used as an oily adhesive main body, and the molecular chain of the acrylonitrile copolymer contains cyano groups with strong polarity, so that the cohesiveness can be improved through dipole-dipole interaction; the lone pair electrons on the nitrogen atoms can be connected with metal ions to promote the dissociation of salt in the electrolyte, so that the conductivity is improved; the structural units of methyl acrylate, butyl acrylate and other lipids are introduced into the polyacrylonitrile chain, so that the flexibility of the acrylonitrile copolymer as an adhesive is improved;
2. according to the invention, itaconic acid is introduced into an acrylonitrile copolymer, so that on one hand, the cohesiveness of an adhesive can be improved, on the other hand, a crosslinking point is introduced for a subsequent crosslinking adhesive, an amidation reaction is carried out between carboxyl in an itaconic acid structural unit and amino in thiourea/thiocarbazide to form a covalent bond crosslinking structure, and a hydrogen bond is formed between thiocarbonyl and secondary amine in the thiourea/thiocarbazide structure, so that a linear adhesive is prepared into a multi-hydrogen bond crosslinking adhesive through amidation reaction, the covalent bond and the multi-hydrogen bond coexist, the formation of the covalent bond ensures the effectiveness of the crosslinking structure, and meanwhile, the multi-hydrogen bond improves the long-term stability and the multiplying power performance;
3. the oily adhesive system provided by the invention can be applied to the anode slurry of the secondary battery, and does not generate crosslinking reaction in the slurry preparation process, so that the smooth preparation of the anode slurry can be ensured, and the slurry stability can be maintained; the crosslinking condition is simple, and the crosslinking of the adhesive can be completed only by utilizing the unavoidable high-temperature stage in the electrode slice drying process.
Drawings
FIG. 1 is a hydrogen nuclear magnetic resonance spectrum of the polymer in example 1;
FIG. 2 is a temperature-variable Fourier infrared spectrum of a film prepared by using the adhesive system of example 2;
FIG. 3 is a graph showing the comparison of the state of the product before and after soaking in the solution corresponding to example 1 and application example 7; wherein A represents the pre-product soaking state in example 1, B represents the post-product soaking state in example 1, C represents the pre-product soaking state in application example 7, and D represents the post-product soaking state in application example 7;
fig. 4 is a graph showing comparison of cycle performance of the batteries of application example 1, application example 7 and comparative example 1;
fig. 5 is a graph showing comparison of the rate performance of the batteries of application example 1, application example 7 and comparative example 1;
FIG. 6 is a cross-linking reaction scheme of an acrylonitrile copolymer with thiocarbazide.
Detailed Description
In order to make the technical solution of the present invention clearer, the technical solution of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the present invention, and it should be noted that the following embodiments are only used for better understanding of the technical solution of the present invention, and should not be construed as limiting the present invention.
Example 1.
Acrylonitrile (83%, 36.70 g), itaconic acid (11%, 11.93 g) and methyl acrylate (6%, 4.30 g) were added to water (264.65 g), and nitrogen was introduced for 1.5 hours to remove oxygen; ammonium persulfate (1.06 g) is added into the mixed system, and after being stirred uniformly, the temperature is raised to 65 ℃ for 3 hours; and (3) raising the temperature of the mixed system to 90 ℃ for the second time, reacting for 2.5h, and protecting the whole process by nitrogen. Filtering and crushing the generated solid, cleaning with deionized water, and drying to obtain the acrylonitrile copolymer.
Example 2.
Acrylonitrile (85%, 37.58 g), itaconic acid (2%, 2.17 g) and methyl acrylate (13%, 9.33 g) were added to the aqueous phase (245.4 g), and nitrogen was purged for 1.5 hours to remove oxygen; ammonium persulfate (0.98 g) is added into the mixed system, and after uniform stirring, the temperature is raised to 65 ℃ and the reaction is carried out for 3 hours; and (3) raising the temperature of the mixed system to 90 ℃ for the second time, reacting for 2.5h, and protecting the whole process by nitrogen. Filtering and crushing the generated solid, cleaning with deionized water, and drying to obtain the acrylonitrile copolymer.
Example 3.
Acrylonitrile (88%, 38.91 g), itaconic acid (6%, 6.51 g) and methyl acrylate (6%, 4.30 g) were added to the aqueous phase (248.6 g), and nitrogen was introduced for 1.5h to remove oxygen; ammonium persulfate (0.99 g) is added into the mixed system, and after uniform stirring, the temperature is raised to 65 ℃ and the reaction is carried out for 3 hours; and (3) raising the temperature of the mixed system to 90 ℃ for the second time, reacting for 2.5h, and protecting the whole process by nitrogen. Filtering and crushing the generated solid, cleaning with deionized water, and drying to obtain the acrylonitrile copolymer.
Example 4.
Acrylonitrile (90%, 39.80 g), itaconic acid (4%, 4.34 g) and methyl acrylate (6%, 4.30 g) were added to the aqueous phase (242.2 g), and nitrogen was introduced for 1.5h to remove oxygen; ammonium persulfate (0.97 g) is added into the mixed system, and after uniform stirring, the temperature is raised to 65 ℃ and the reaction is carried out for 3 hours; and (3) raising the temperature of the mixed system to 90 ℃ for the second time, reacting for 2.5h, and protecting the whole process by nitrogen. Filtering and crushing the generated solid, cleaning with deionized water, and drying to obtain the acrylonitrile copolymer.
Example 5.
Acrylonitrile (98%, 43.33 g), itaconic acid (1%, 1.08 g) and methyl acrylate (1%, 0.72 g) were added to the aqueous phase (225.65 g), and nitrogen was introduced for 1.5h to remove oxygen; ammonium persulfate (0.90 g) is added into the mixed system, and after uniform stirring, the temperature is raised to 65 ℃ and the reaction is carried out for 3 hours; and (3) raising the temperature of the mixed system to 90 ℃ for the second time, reacting for 2.5h, and protecting the whole process by nitrogen. Filtering and crushing the generated solid, cleaning with deionized water, and drying to obtain the acrylonitrile copolymer.
Example 6.
Acrylonitrile (83%, 36.70 g), itaconic acid (11%, 11.93 g) and butyl acrylate (6%, 6.41 g) were added to the aqueous phase (275.2 g), and nitrogen was introduced for 1.5h to remove oxygen; ammonium persulfate (1.10 g) is added into the mixed system, and after uniform stirring, the temperature is raised to 65 ℃ and the reaction is carried out for 3 hours; and (3) raising the temperature of the mixed system to 90 ℃ for the second time, reacting for 2.5h, and protecting the whole process by nitrogen. Filtering and crushing the generated solid, cleaning with deionized water, and drying to obtain the acrylonitrile copolymer.
Application example 1.
The acrylonitrile copolymer prepared in example 1 was mixed with thiourea according to 4: mixing the materials according to the mass ratio of 0.5, and applying the mixture as an adhesive to a lithium iron phosphate positive plate in a lithium ion battery.
Adding an adhesive into an N-methyl pyrrolidone solvent to prepare an adhesive solution with the concentration of 25mg/mL, adding a conductive agent into the adhesive solution, and adding lithium iron phosphate into a mixed system after uniformly mixing, wherein the mass ratio of the adhesive to the conductive agent to the active material is 1:1:8, uniformly stirring to obtain the anode slurry. The positive electrode slurry is coated on a current collector, and the current collector passes through a blowing oven at 80 ℃ for 8 hours and then passes through a vacuum oven at 120 ℃ for 8 hours to dry the pole piece, so that the adhesive system is crosslinked. And assembling the positive plate, the positive and negative electrode shells, the gasket, the elastic sheet, the lithium sheet, the diaphragm and the electrolyte into a button type half battery in a glove box, and standing for 12 hours to ensure that the inside of the battery is fully soaked.
Application example 2.
The acrylonitrile copolymer prepared in example 1 was mixed with thiourea in a mass ratio of 4:1 is mixed and used as an adhesive to be applied to a lithium iron phosphate positive plate in a lithium ion battery.
Adding an adhesive into an N-methyl pyrrolidone solvent, preparing an adhesive solution with the concentration of 25mg/mL, adding a conductive agent into the adhesive solution, and adding lithium iron phosphate into a mixed system after uniformly mixing, wherein the mass ratio of the adhesive to the conductive agent to the active material is 1:1:8, uniformly stirring to obtain the anode slurry. The slurry is coated on a current collector, and the pole piece is dried through a blowing oven at 80 ℃ for 8 hours and a vacuum oven at 120 ℃ for 8 hours, so that the adhesive system is crosslinked. And assembling the positive plate, the positive and negative electrode shells, the gasket, the elastic sheet, the lithium sheet, the diaphragm and the electrolyte into a button type half battery in a glove box, and standing for 12 hours to ensure that the inside of the battery is fully soaked.
Application example 3.
The acrylonitrile copolymer prepared in example 1 was mixed with thiourea in a mass ratio of 4:1.5 mixing and applying the mixture as an adhesive to a lithium iron phosphate positive plate in a lithium ion battery.
Adding an adhesive into an N-methyl pyrrolidone solvent, preparing an adhesive solution with the concentration of 25mg/mL, adding a conductive agent into the adhesive solution, and adding lithium iron phosphate into a mixed system after uniformly mixing, wherein the mass ratio of the adhesive to the conductive agent to the active material is 1:1:8, uniformly stirring to obtain the anode slurry. The slurry is coated on a current collector, and the pole piece is dried through a blowing oven at 80 ℃ for 8 hours and a vacuum oven at 120 ℃ for 8 hours, so that the adhesive system is crosslinked. And assembling the positive plate, the positive and negative electrode shells, the gasket, the elastic sheet, the lithium sheet, the diaphragm and the electrolyte into a button type half battery in a glove box, and standing for 12 hours to ensure that the inside of the battery is fully soaked.
Application example 4.
The acrylonitrile copolymer prepared in example 1 was mixed with thiourea in a mass ratio of 4:2, the mixture is used as an adhesive to be applied to a lithium iron phosphate positive plate in a lithium ion battery.
Adding an adhesive into an N-methyl pyrrolidone solvent, preparing an adhesive solution with the concentration of 25mg/mL, adding a conductive agent into the adhesive solution, and adding lithium iron phosphate into a mixed system after uniformly mixing, wherein the mass ratio of the adhesive to the conductive agent to the active material is 1:1:8, uniformly stirring to obtain the anode slurry. The slurry is coated on a current collector, and the pole piece is dried through a blowing oven at 80 ℃ for 8 hours and a vacuum oven at 120 ℃ for 8 hours, so that the adhesive system is crosslinked. And assembling the positive plate, the positive and negative electrode shells, the gasket, the elastic sheet, the lithium sheet, the diaphragm and the electrolyte into a button type half battery in a glove box, and standing for 12 hours to ensure that the inside of the battery is fully soaked.
Application example 5.
The acrylonitrile copolymer prepared in example 1 was mixed with thiourea in a mass ratio of 4:3, the mixture is used as an adhesive to be applied to a lithium iron phosphate positive plate in a lithium ion battery.
Adding an adhesive into an N-methyl pyrrolidone solvent, preparing an adhesive solution with the concentration of 25mg/mL, adding a conductive agent into the adhesive solution, and adding lithium iron phosphate into a mixed system after uniformly mixing, wherein the mass ratio of the adhesive to the conductive agent to the active material is 1:1:8, uniformly stirring to obtain the anode slurry. The slurry is coated on a current collector, and the pole piece is dried through a blowing oven at 80 ℃ for 8 hours and a vacuum oven at 120 ℃ for 8 hours, so that the adhesive system is crosslinked. And assembling the positive plate, the positive and negative electrode shells, the gasket, the elastic sheet, the lithium sheet, the diaphragm and the electrolyte into a button type half battery in a glove box, and standing for 12 hours to ensure that the inside of the battery is fully soaked.
Application example 6.
The acrylonitrile copolymer prepared in example 1 was mixed with thiourea in a mass ratio of 4:4, the mixture is used as an adhesive to be applied to a lithium iron phosphate positive plate in a lithium ion battery.
Adding an adhesive into an N-methyl pyrrolidone solvent, preparing an adhesive solution with the concentration of 25mg/mL, adding a conductive agent into the adhesive solution, and adding lithium iron phosphate into a mixed system after uniformly mixing, wherein the mass ratio of the adhesive to the conductive agent to the active material is 1:1:8, uniformly stirring to obtain the anode slurry. The slurry is coated on a current collector, and the pole piece is dried through a blowing oven at 80 ℃ for 8 hours and a vacuum oven at 120 ℃ for 8 hours, so that the adhesive system is crosslinked. Assembling the positive plate, the positive and negative electrode shells, the gasket, the elastic sheet, the lithium sheet, the diaphragm and the electrolyte into a button type half cell in a glove box, and standing for 12 hours to ensure that the interior of the cell is fully soaked
Application example 7.
The acrylonitrile copolymer prepared in example 1 and thiocarbazide were mixed according to a mass ratio of 4:1 is mixed and used as an adhesive to be applied to a lithium iron phosphate positive plate in a lithium ion battery.
Adding an adhesive into an N-methyl pyrrolidone solvent, preparing an adhesive solution with the concentration of 25mg/mL, adding a conductive agent into the adhesive solution, and adding lithium iron phosphate into a mixed system after uniformly mixing, wherein the mass ratio of the adhesive to the conductive agent to the active material is 1:1:8, uniformly stirring to obtain the anode slurry. The slurry is coated on a current collector, and the pole piece is dried through a blowing oven at 80 ℃ for 8 hours and a vacuum oven at 120 ℃ for 8 hours, so that the adhesive system is crosslinked. And assembling the positive plate, the positive and negative electrode shells, the gasket, the elastic sheet, the lithium sheet, the diaphragm and the electrolyte into a button type half battery in a glove box, and standing for 12 hours to ensure that the inside of the battery is fully soaked.
Application example 8.
The acrylonitrile copolymer prepared in example 1 and thiocarbazide were mixed according to a mass ratio of 4:2, the mixture is used as an adhesive to be applied to a lithium iron phosphate positive plate in a lithium ion battery.
Adding an adhesive into an N-methyl pyrrolidone solvent, preparing an adhesive solution with the concentration of 25mg/mL, adding a conductive agent into the adhesive solution, and adding lithium iron phosphate into a mixed system after uniformly mixing, wherein the mass ratio of the adhesive to the conductive agent to the active material is 1:1:8, uniformly stirring to obtain the anode slurry. The slurry is coated on a current collector, and the pole piece is dried through a blowing oven at 80 ℃ for 8 hours and a vacuum oven at 120 ℃ for 8 hours, so that the adhesive system is crosslinked. And assembling the positive plate, the positive and negative electrode shells, the gasket, the elastic sheet, the lithium sheet, the diaphragm and the electrolyte into a button type half battery in a glove box, and standing for 12 hours to ensure that the inside of the battery is fully soaked.
Application example 9.
The acrylonitrile copolymer prepared in example 3 was mixed with thiourea in a mass ratio of 4:1 is mixed and applied to a layered oxide positive plate in a sodium ion battery as an adhesive.
Adding an adhesive into an N-methyl pyrrolidone solvent, preparing an adhesive solution with 3% of solid content, adding a conductive agent into the adhesive solution, and adding a layered oxide into a mixed system after uniformly mixing, wherein the mass ratio of the adhesive, the conductive agent and an active material is 3:2: and 95, uniformly stirring to obtain the anode slurry. The slurry is coated on a current collector, and the pole piece is dried through a blowing oven at 80 ℃ for 8 hours and a vacuum oven at 120 ℃ for 8 hours, so that the adhesive system is crosslinked. And assembling the positive plate, the positive and negative electrode shells, the gasket, the elastic sheet, the sodium sheet, the diaphragm and the electrolyte into a button type half cell in a glove box, and standing for 12 hours to ensure that the interior of the cell is fully soaked.
Application example 10.
The acrylonitrile copolymer prepared in example 3 was mixed with thiourea in a mass ratio of 4:2 is mixed and used as an adhesive to be applied to a layered oxide positive plate in a sodium ion battery.
Adding an adhesive into an N-methyl pyrrolidone solvent, preparing an adhesive solution with 3% of solid content, adding a conductive agent into the adhesive solution, and adding a layered oxide into a mixed system after uniformly mixing, wherein the mass ratio of the adhesive, the conductive agent and an active material is 3:2: and 95, uniformly stirring to obtain the anode slurry. The slurry is coated on a current collector, and the pole piece is dried through a blowing oven at 80 ℃ for 8 hours and a vacuum oven at 120 ℃ for 8 hours, so that the adhesive system is crosslinked. And assembling the positive plate, the positive and negative electrode shells, the gasket, the elastic sheet, the sodium sheet, the diaphragm and the electrolyte into a button type half cell in a glove box, and standing for 12 hours to ensure that the interior of the cell is fully soaked.
Application example 11.
The acrylonitrile copolymer prepared in example 3 and thiocarbazide were mixed according to a mass ratio of 4:1 is mixed and applied to a layered oxide positive plate in a sodium ion battery as an adhesive.
Adding an adhesive into an N-methyl pyrrolidone solvent, preparing an adhesive solution with 3% of solid content, adding a conductive agent into the adhesive solution, and adding a layered oxide into a mixed system after uniformly mixing, wherein the mass ratio of the adhesive, the conductive agent and an active material is 3:2: and 95, uniformly stirring to obtain the anode slurry. The slurry is coated on a current collector, and the pole piece is dried through a blowing oven at 80 ℃ for 8 hours and a vacuum oven at 120 ℃ for 8 hours, so that the adhesive system is crosslinked. And assembling the positive plate, the positive and negative electrode shells, the gasket, the elastic sheet, the sodium sheet, the diaphragm and the electrolyte into a button type half cell in a glove box, and standing for 12 hours to ensure that the interior of the cell is fully soaked.
Application example 12.
The acrylonitrile copolymer prepared in example 3 and thiocarbazide were mixed according to a mass ratio of 4:2 is mixed and used as an adhesive to be applied to a layered oxide positive plate in a sodium ion battery.
Adding an adhesive into an N-methyl pyrrolidone solvent, preparing an adhesive solution with 3% of solid content, adding a conductive agent into the adhesive solution, and adding a layered oxide into a mixed system after uniformly mixing, wherein the mass ratio of the adhesive, the conductive agent and an active material is 3:2: and 95, uniformly stirring to obtain the anode slurry. The slurry is coated on a current collector, and the pole piece is dried through a blowing oven at 80 ℃ for 8 hours and a vacuum oven at 120 ℃ for 8 hours, so that the adhesive system is crosslinked. And assembling the positive plate, the positive and negative electrode shells, the gasket, the elastic sheet, the sodium sheet, the diaphragm and the electrolyte into a button type half cell in a glove box, and standing for 12 hours to ensure that the interior of the cell is fully soaked.
Comparative example 1.
And preparing the positive pole piece of the lithium ion battery by using a conventional polyvinylidene fluoride adhesive as an adhesive of lithium iron phosphate.
Adding a polyvinylidene fluoride adhesive into an N-methyl pyrrolidone solvent, preparing an adhesive solution with the concentration of 25mg/mL, adding a conductive agent into the adhesive solution, and adding lithium iron phosphate into a mixed system after uniformly mixing, wherein the mass ratio of the adhesive to the conductive agent to the active material is 1:1:8, uniformly stirring to obtain the anode slurry. The slurry is coated on a current collector, and the pole piece is dried through a blowing oven at 80 ℃ for 8 hours and a vacuum oven at 120 ℃ for 8 hours, so that the adhesive system is crosslinked. And assembling the positive plate, the positive and negative electrode shells, the gasket, the elastic sheet, the lithium sheet, the diaphragm and the electrolyte into a button type half battery in a glove box, and standing for 12 hours to ensure that the inside of the battery is fully soaked.
Comparative example 2.
And preparing the positive electrode plate of the sodium ion battery by using a conventional polyvinylidene fluoride adhesive as the adhesive of the layered oxide.
Adding a polyvinylidene fluoride adhesive into an N-methyl pyrrolidone solvent, preparing an adhesive solution with 3% of solid content, adding a conductive agent into the adhesive solution, and adding a layered oxide into a mixed system after uniformly mixing, wherein the mass ratio of the adhesive, the conductive agent and an active material is 3:2: and 95, uniformly stirring to obtain the anode slurry. The slurry is coated on a current collector, and the pole piece is dried through a blowing oven at 80 ℃ for 8 hours and a vacuum oven at 120 ℃ for 8 hours, so that the adhesive system is crosslinked. And assembling the positive plate, the positive and negative electrode shells, the gasket, the elastic sheet, the sodium sheet, the diaphragm and the electrolyte into a button type half cell in a glove box, and standing for 12 hours to ensure that the interior of the cell is fully soaked.
Characterization example.
The acrylonitrile copolymer obtained in example 1 was subjected to a nuclear magnetic resonance hydrogen spectrum test to obtain signals at 13.04ppm and 12.49ppm corresponding to carboxyl characteristic peaks in the itaconic acid structure of FIG. 1, which indicates successful incorporation of itaconic acid into the polymer chain.
Film was prepared from the adhesive system of application example 2, and a temperature-changing Fourier infrared spectrum test was performed to obtain FIG. 2, and it can be seen that 3200cm -1 ~3500cm -1 Peaks in the range shift with increasing temperature, as the temperature increases break the hydrogen bonds, indicating that the adhesive system is rich in hydrogen bonds; 2240cm -1 The corresponding characteristic peak of cyano group shows that cyano groups in the crosslinking system are stable and no side reaction occurs.
Effect example.
(1) For the copolymer prepared in example 1 and the film prepared by the adhesive system of application example 7, which was immersed in the solvent N-methylpyrrolidone for 24 hours, the state diagram before and after immersion is shown in FIG. 3, and it can be seen that the adhesive film prepared in application example 7 was not dissolved, indicating that the crosslinking reaction was successfully performed.
(2) The button half-cells prepared in application example 1, application example 7 and comparative example 1 were subjected to electrochemical performance tests, and specific test procedures and results are as follows:
the electrochemical cycle performance test was performed at 1C after 3 cycles of activation at a current density of 0.08C, wherein the electrochemical cycle performance tested in application example 1, application example 7 and comparative example 1 is shown in fig. 4 (the number of activation cycles was omitted).
(3) Meanwhile, the button half-cells prepared in the application example 1, the application example 7 and the comparative example 1 were subjected to rate performance test in a current range of 0.02 to 5C, and the test results are shown in FIG. 5 (the activation turns are omitted).
It is evident that there is a clear improvement in the application examples during long-term circulation. In the rate performance test, the battery performance was improved.
(4) Electrochemical cycle performance and multiplying power performance tests were performed on button half batteries prepared in all the above application examples and comparative examples, and electrochemical cycle performance and multiplying power performance comparison results of lithium metal half batteries are shown in table 1, and electrochemical performance and multiplying power performance comparison results of sodium metal half batteries are shown in table 2.
TABLE 1
TABLE 2
Compared with the conventional polyvinylidene fluoride adhesive, the oily adhesive system provided by the application has better cycle stability and improved multiplying power performance.
This is because the carboxyl in the itaconic acid structural unit and the amino in the thiourea/thiocarbazide in the acrylonitrile copolymer used in the application undergo amidation reaction to form a covalent bond crosslinking structure, and hydrogen bonds (the reaction formula is shown in fig. 6) are formed between thiocarbonyl and secondary amine in the thiourea/thiocarbazide structure, the covalent bond and multiple hydrogen bonds coexist, the formation of the covalent bond ensures the effectiveness of the crosslinking structure, and meanwhile, the multiple hydrogen bonds improve the long-term stability and the rate capability.
Claims (10)
1. An oily adhesive system, characterized in that it is obtained by mixing an acrylonitrile copolymer with thiourea or thiocarbazide in an oily solvent;
the acrylonitrile copolymer is polymerized by acrylonitrile, acrylic ester monomers and itaconic acid.
2. The oily adhesive system according to claim 1, wherein the mass ratio of acrylonitrile copolymer to thiourea or thiocarbazide is 4:0.5 to 4.
3. The oily adhesive system according to claim 1, wherein the oily solvent is N-methylpyrrolidone.
4. The oily adhesive system according to claim 1, wherein the acrylonitrile copolymer is synthesized by the following steps:
s1, adding acrylonitrile, acrylic ester monomers and itaconic acid into water, and introducing nitrogen into a reaction system to remove oxygen;
s2, adding a water-based initiator, heating the reaction system to a first temperature for reaction, heating to a second temperature for the second time, and continuing the reaction;
and S3, filtering and crushing the generated solid, cleaning with deionized water, and drying to obtain the acrylonitrile copolymer.
5. The oily adhesive system according to claim 4, wherein the molar ratio of acrylonitrile, acrylic acid ester monomer and itaconic acid is from 70 to 98: 1-15: 1-15.
6. The oily adhesive system according to claim 4, wherein the ratio of the total mass of acrylonitrile, acrylic acid ester monomer and itaconic acid to the mass of water is 15 to 20:100.
7. the oily adhesive system according to claim 4, wherein the aqueous initiator is ammonium persulfate; the dosage of the water-based initiator is 2% of the total mass of the acrylonitrile, the acrylic ester monomer and the itaconic acid.
8. The oily adhesive system according to claim 4, wherein in step S2, the first temperature is 60 ℃ to 70 ℃, and the reaction time at the first temperature is 2.5h to 3.5h; the second temperature is 85-95 ℃, and the reaction time at the second temperature is 2-3 h.
9. The use of an oily binder system according to any one of claims 1 to 8, wherein the oily binder system is used as a positive electrode slurry for a secondary battery after being mixed with an active material and a conductive agent; the mass ratio of the solute in the active material, the conductive agent and the oily adhesive system is 80-95: 10-2: 10-3.
10. The use of an oily binder system according to claim 9, wherein the positive electrode slurry is coated on a current collector, placed in a 80 ℃ forced air oven for 8 hours and then placed in a 120 ℃ vacuum oven for 8 hours to crosslink the binder system on the current collector.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003037945A1 (en) * | 2001-10-29 | 2003-05-08 | Kaneka Corporation | Acrylonitrile-containing block copolymer and thermo- plastic resin compositions |
| CN1602558A (en) * | 2001-10-26 | 2005-03-30 | 日本瑞翁株式会社 | Slurry composition for electrode, electrode and secondary cell |
| US20060228545A1 (en) * | 2005-04-11 | 2006-10-12 | Tesa Aktiengesellschaft | Adhesive |
| CN104538635A (en) * | 2014-12-11 | 2015-04-22 | 江西先材纳米纤维科技有限公司 | High-performance binder for silicon materials for lithium ion batteries and preparation method thereof |
| CN106220779A (en) * | 2016-08-17 | 2016-12-14 | 四川茵地乐科技有限公司 | Acrylonitrile copolymer binder and the application in lithium ion battery thereof |
| US20230141592A1 (en) * | 2020-06-17 | 2023-05-11 | Grst International Limited | Binder composition for secondary battery |
| CN116130658A (en) * | 2022-12-28 | 2023-05-16 | 深圳好电科技有限公司 | Bi-component lithium ion battery positive electrode material and preparation method thereof |
| KR20230170731A (en) * | 2022-06-09 | 2023-12-19 | 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 | Anode slurry, secondary batteries, battery modules, battery packs and electrical devices |
| CN117343670A (en) * | 2023-11-09 | 2024-01-05 | 杭州叁元素赋能新材料有限公司 | Adhesive for negative electrode of water-based lithium ion battery, and preparation method and application thereof |
-
2024
- 2024-01-29 CN CN202410114649.XA patent/CN117645852B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1602558A (en) * | 2001-10-26 | 2005-03-30 | 日本瑞翁株式会社 | Slurry composition for electrode, electrode and secondary cell |
| WO2003037945A1 (en) * | 2001-10-29 | 2003-05-08 | Kaneka Corporation | Acrylonitrile-containing block copolymer and thermo- plastic resin compositions |
| US20060228545A1 (en) * | 2005-04-11 | 2006-10-12 | Tesa Aktiengesellschaft | Adhesive |
| CN104538635A (en) * | 2014-12-11 | 2015-04-22 | 江西先材纳米纤维科技有限公司 | High-performance binder for silicon materials for lithium ion batteries and preparation method thereof |
| CN106220779A (en) * | 2016-08-17 | 2016-12-14 | 四川茵地乐科技有限公司 | Acrylonitrile copolymer binder and the application in lithium ion battery thereof |
| US20230141592A1 (en) * | 2020-06-17 | 2023-05-11 | Grst International Limited | Binder composition for secondary battery |
| KR20230170731A (en) * | 2022-06-09 | 2023-12-19 | 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 | Anode slurry, secondary batteries, battery modules, battery packs and electrical devices |
| CN116130658A (en) * | 2022-12-28 | 2023-05-16 | 深圳好电科技有限公司 | Bi-component lithium ion battery positive electrode material and preparation method thereof |
| CN117343670A (en) * | 2023-11-09 | 2024-01-05 | 杭州叁元素赋能新材料有限公司 | Adhesive for negative electrode of water-based lithium ion battery, and preparation method and application thereof |
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