CN115863643A - Dispersing and softening agent for lithium ion battery anode slurry and application thereof - Google Patents
Dispersing and softening agent for lithium ion battery anode slurry and application thereof Download PDFInfo
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- CN115863643A CN115863643A CN202211585169.9A CN202211585169A CN115863643A CN 115863643 A CN115863643 A CN 115863643A CN 202211585169 A CN202211585169 A CN 202211585169A CN 115863643 A CN115863643 A CN 115863643A
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- ion battery
- lithium ion
- slurry
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- 239000004902 Softening Agent Substances 0.000 title claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 18
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 12
- 239000006256 anode slurry Substances 0.000 title claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 32
- 239000002002 slurry Substances 0.000 claims abstract description 29
- 239000006258 conductive agent Substances 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000003112 inhibitor Substances 0.000 claims abstract description 6
- 239000000314 lubricant Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 9
- 229920000570 polyether Polymers 0.000 claims description 9
- 229920002635 polyurethane Polymers 0.000 claims description 8
- 239000004814 polyurethane Substances 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 8
- 239000011267 electrode slurry Substances 0.000 claims description 7
- 150000002191 fatty alcohols Chemical class 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 claims description 6
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 239000000600 sorbitol Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- NDQXKKFRNOPRDW-UHFFFAOYSA-N 1,1,1-triethoxyethane Chemical compound CCOC(C)(OCC)OCC NDQXKKFRNOPRDW-UHFFFAOYSA-N 0.000 claims description 3
- HDPNBNXLBDFELL-UHFFFAOYSA-N 1,1,1-trimethoxyethane Chemical compound COC(C)(OC)OC HDPNBNXLBDFELL-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- -1 polyoxypropylene Polymers 0.000 claims description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 claims description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 2
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 2
- TVFWYUWNQVRQRG-UHFFFAOYSA-N 2,3,4-tris(2-phenylethenyl)phenol Chemical group C=1C=CC=CC=1C=CC1=C(C=CC=2C=CC=CC=2)C(O)=CC=C1C=CC1=CC=CC=C1 TVFWYUWNQVRQRG-UHFFFAOYSA-N 0.000 claims description 2
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 2
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims 1
- 230000001965 increasing effect Effects 0.000 abstract description 12
- 239000007787 solid Substances 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 6
- 238000007731 hot pressing Methods 0.000 abstract description 3
- 238000003825 pressing Methods 0.000 abstract description 3
- 238000004804 winding Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 238000000576 coating method Methods 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007581 slurry coating method Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 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
The invention claims a dispersion softening agent for lithium ion battery anode slurry, which comprises the following components: 10-30wt% of dispersing agent, 20-35wt% of lubricating agent, 0-5wt% of water inhibitor and the balance of solvent; the dispersion softening agent provided by the invention has the beneficial effects that: according to the invention, functional groups which have dispersing and flexibility increasing effects and are difficult to realize in a molecular structure are reasonably compounded, and under the condition that the addition amount is not more than 0.5%, solid particles in slurry can be effectively dispersed, floating of a conductive agent and a binder is avoided, friction among particles during cold pressing can be reduced, the flexibility of the positive diaphragm is further improved, and the risks of winding, hot pressing and folding light leakage of the positive diaphragm are reduced.
Description
Technical Field
The invention relates to a dispersion softening agent for lithium ion battery anode slurry, in particular to a multi-component complex dispersion softening agent particularly suitable for anode slurry taking nickel cobalt lithium manganate as an active material, and belongs to the technical field of lithium batteries.
Background
The lithium ion battery has the advantages of large specific energy, long cycle life, low self-discharge rate, no memory effect, environmental friendliness and the like, and is widely applied to the fields of aerospace, national defense, automobiles, 3C and the like.
The lithium ion battery consists of a positive electrode, a negative electrode, a diaphragm and electrolyte, and during forming, the prepared slurry needs to be respectively coated on an aluminum foil to prepare the positive electrode and the negative electrode, so that the viscosity of the slurry is directly related to the coating quality, and along with the rapid development and increasing requirements of the new energy industry, higher requirements are put forward on the lithium battery, the lithium battery is required to have higher capacity and higher processing efficiency, and therefore the coating thickness and the coating speed of a pole piece need to be improved.
In the process of actual operation, the solid content of slurry needs to be improved in pole piece thick coating, the solid content is improved, and materials such as solid particles and adhesives need to be uniformly dispersed, namely, the dispersibility of the slurry is improved, the coating speed is increased, the pole piece is easy to crack in the drying process, so that the flexibility of the pole piece needs to be increased, the cold pressing pressure of the thick pole piece can be increased after the pole piece is dried, and the ductility of the pole piece also needs to be enhanced. In addition, in the process of thick coating and quick coating, a conductive agent, a binder and the like can float upwards, the flexibility of the pole piece can be influenced, the brittleness of the pole piece is deteriorated, and the risks of hot pressing and light leakage in folding of the pole piece in winding are increased.
In order to solve the above problems, the existing solution in the industry is to add a dispersant into the slurry to improve the dispersion effect of the slurry, the existing dispersant can solve the fluidity problem of the slurry to a certain extent, but the solution effect on the problems of flexibility, ductility and the like of the pole piece is still not ideal, the addition proportion of the additive in the positive pole slurry is very limited, generally not more than 0.5%, and the capacity of the lithium battery can be reduced at a higher level, so that a multifunctional assistant capable of solving the problems of the dispersibility of the slurry and the flexibility and ductility of the pole piece on the premise of not more than 0.5% of the addition amount is urgently needed.
Disclosure of Invention
The invention provides a dispersion softening agent special for lithium battery positive electrode slurry taking ternary nickel cobalt lithium manganate as a positive electrode active material and application thereof, aiming at the problems that the dispersibility of the slurry for lithium battery is not good enough after the solid content is improved, and the flexibility and the ductility of a pole piece are not good in the thick coating and fast coating processes.
The technical scheme for solving the technical problems is as follows:
a dispersion softening agent for lithium ion battery anode slurry comprises the following components: 10-30wt% of dispersant, 20-35wt% of lubricant, 0-5wt% of water inhibitor and the balance of solvent;
the dispersing agent is tristyrylphenol polyether phosphate or modified polyurethane, and the modified polyurethane has a structure shown in a formula I:
wherein R is 1 (NCO) 2 Represents one or more of C6-C10 alkyl diisocyanate, diphenylmethane diisocyanate and toluene diisocyanate;
R 2 represents a C2-C8 alkylene group; r 3 OH represents fatty alcohol polyether, preferably one of fatty alcohol polyoxyethylene ether, fatty alcohol polyoxypropylene ether or lauryl alcohol polyoxyethylene ether;
n represents an integer of 0 to 50, preferably an integer of 10 to 45.
The C2-C8 alkylene group as used herein means a group formed by substituting two hydrogen atoms for a straight or branched alkyl group having 2 to 8 carbon atoms.
The preparation method of the modified polyurethane comprises the following steps:
1) Pretreatment: r is to be 1 (NCO) 2 Vacuumizing and drying to remove water; reacting OH-R 2 -OH and R 3 Placing OH in a vacuum drying oven for drying;
2) Synthesis of a polyurethane prepolymer: adding pretreated OH-R into a three-neck flask 2 OH, stirring uniformly; slowly dripping R within 0.5-1.5h 1 (NCO) 2 ，OH-R 2 -OH：R 1 (NCO) 2 The molar ratio is (0.4-0.6): 1; adding a catalyst dibutyltin dilaurate into the mixture, continuously reacting for 1-3h at room temperature, carrying out the reaction under the protection of nitrogen, and testing NCO to reach a preset value;
3) Modified polyurethane: the polyurethane prepolymer obtained in the step 2) and R 3 OH is added according to a molar ratio of 1: (0.4-0.6), uniformly stirring, reacting for 3-5h at room temperature under the protection of nitrogen, determining that the NCO content is close to 0, namely the reaction end point, recovering to room temperature, and discharging to obtain the product.
Preferably, the lubricant is one or more of stearic acid polyethylene glycol ester, epoxidized soybean oil, cardanol glycidyl ether or sorbitol polyether ester, and more preferably, the sorbitol polyether ester is preferably sorbitol polyether-30 tetraoleate or sorbitol polyether-40 tetraoleate.
Preferably, the water inhibitor is one or a compound of more of trimethyl orthoacetate, triethyl orthoacetate, trimethyl orthoformate, triethyl orthoformate, a sulfur-containing silane coupling agent, an aminosilane coupling agent and an epoxy silane coupling agent.
Preferably, the solvent is N-methylpyrrolidone.
The preparation method of the dispersion softening agent comprises the following steps:
1) Filling the reaction kettle with inert gas, then emptying, and keeping the vacuum degree below 0.1 MPa;
2) Putting the dispersing agent, the lubricating agent, the water inhibiting agent and the solvent into a reaction kettle according to the proportion, starting stirring at the stirring speed of 30-50rpm for 0.5-2h;
3) After being stirred evenly, the mixture is emptied, filtered and demagnetized, and the dispersion softening agent is obtained.
The dispersion softening agent provided by the invention has the beneficial effects that:
1) Functional groups which are difficult to realize in a molecular structure and have the functions of dispersion and flexibility enhancement are reasonably compounded, under the condition that the addition amount is not more than 0.5%, solid particles in the slurry can be effectively dispersed, floating of a conductive agent and a binder is avoided, friction among the particles during cold pressing can be reduced, the flexibility of the positive diaphragm is further improved, and the risks of winding and hot pressing of the positive diaphragm and light leakage in folding are reduced;
2) The water inhibitor can avoid the phenomena of gelation, poor thermal stability and the like caused by water absorption of the main material particles;
3) The dispersion softening agent does not influence the adhesive force and does not deteriorate the performance of the battery cell in the using process.
The invention also claims a lithium ion battery anode slurry containing the dispersion softening agent.
Preferably, the lithium ion battery positive electrode slurry further comprises a positive electrode active material, a conductive agent and a binder.
Preferably, the positive active substance is nickel cobalt lithium manganate, the conductive agent is selected from one or a combination of more of conductive carbon black, superconducting carbon black, conductive graphite, acetylene black, ketjen black, graphene and carbon nanotubes, and the binder is one or a combination of vinylidene fluoride homopolymer and vinylidene fluoride copolymer.
The invention also claims a lithium ion battery anode piece, wherein the surface of the anode piece is coated with the lithium ion battery anode slurry.
The invention also claims a lithium ion battery, which comprises the positive pole piece.
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are included to illustrate the invention and not to limit the scope of the invention.
TABLE 1 Dispersion flexibilizing agent formulations used in examples 1-5 and comparative examples 1-2
Wherein the structural formula of the first modified polyurethane is as follows:
the structural formula of the second modified polyurethane is as follows: />
R 3 OH represents polyoxyethylene lauryl ether, and n =10-45.
Example 1: effect of wet pulping process
The specific preparation steps of the lithium battery positive electrode pastes of examples 1 to 5 and comparative examples 1 to 5 were as follows:
1) The adhesive and the organic solvent are mixed and stirred evenly, obtaining a glue solution A;
2) Respectively adding the dispersion flexibility-increasing agents listed in the table 1 into the glue solution A and uniformly stirring to obtain a glue solution B;
3) Adding a conductive agent into the glue solution B to obtain conductive agent slurry;
4) And adding the positive electrode active material into the conductive agent slurry to obtain positive electrode slurry.
In the method, the weight ratio of each raw material is as follows: conductive agent: dispersing and softening agent: binder = 92; the positive active material is nickel cobalt lithium manganate, the conductive agent is formed by mixing conductive carbon black and carbon nanotubes according to a mass ratio of 1.
In comparative example 3, no dispersion flexibilizing agent was added, in comparative example 4, polyethylene glycol 400 was used as the dispersion flexibilizing agent, in comparative example 5, triphenyl phosphate was used as the dispersion flexibilizing agent, and in comparative example, other components of the dispersion slurry were the same as in examples 1 to 5.
The test procedure was as follows:
1. in the positive electrode film folding test, the positive electrode film is folded in half and then rolled back and forth for 3 times by using a press roller with the weight of 2Kg, then the positive electrode film is laid flat, the operation is repeated until the light leaks at the folded position, and the folding times are recorded. Each group was tested 5 times and the average was taken.
2. Resistance test of the positive diaphragm the resistance of the positive diaphragm was tested using a CRM-01 pole piece resistance tester. Each group was tested 5 times and the average was taken.
Table 2 test effect of slurry and positive electrode film obtained by wet pulping
As can be seen from the data in Table 1, after the dispersion flexibilizer of the present invention is added in examples 1-5, compared with comparative examples 1 and 2, the stability of the slurry is higher, and the flexibility and ductility of the obvious pole piece are enhanced, compared with comparative examples 3-5, the solid content of the freshly prepared slurry is increased by 2.5-5%, and after 24h, the viscosity of the slurry of comparative examples 1-3 is greatly increased, while the viscosity of the slurry of examples 1-5 is not changed greatly, the fluidity is still good, the slurry coating process effect is better, and the number of light leakage in half folding is obviously increased, which indicates that the flexibility and ductility of the pole piece are obviously improved.
Example 2: effect of dry pulping process
The concrete preparation process of the lithium battery positive electrode slurry of examples 1 to 5 and comparative examples 1 to 5 is as follows:
1) Dry-mixing the binder, the conductive agent and the positive active substance to obtain uniformly-mixed powder;
2) Adding part of organic solvent into the powder, and uniformly stirring to obtain initial slurry A;
3) Respectively adding the dispersion softening agent into the initial slurry A, and uniformly stirring;
4) And 3) adding the residual organic solvent on the basis of the step 3), and uniformly stirring to obtain the anode slurry.
Wherein the weight ratio of each raw material is that the positive active material: conductive agent: dispersing and softening agent: binder =94, 4.5; the positive active material is nickel cobalt lithium manganate, the conductive agent is formed by mixing conductive carbon black and carbon nano tubes according to the mass ratio of 1.
In comparative example 3, no dispersion flexibilizing agent was added, in comparative example 4, polyethylene glycol 400 was used as the dispersion flexibilizing agent, in comparative example 5, triphenyl phosphate was used as the dispersion flexibilizing agent, and the other components of the slurry were the same as in examples 1 to 5.
The test procedure was as follows:
1. in the positive electrode film folding test, the positive electrode film is folded in half and then rolled back and forth for 3 times by using a press roller with the weight of 2Kg, then the positive electrode film is laid flat, the operation is repeated until the folded part leaks light, and the folding times are recorded. Each group was tested 5 times and the average was taken.
2. Resistance test of the positive diaphragm the resistance of the positive diaphragm was tested using a CRM-01 pole piece resistance tester. Each group was tested 5 times and the average was taken.
TABLE 3 test results for slurries and positive membranes obtained from dry pulping
As can be seen from the data in Table 1, after the dispersion flexibilizer of the present invention is added in examples 1-5, compared with comparative examples 1 and 2, the stability of the slurry is higher, and the flexibility and ductility of the electrode plate are obviously enhanced, compared with comparative examples 3-5, the solid content of the slurry prepared freshly is increased by 2-5%, and the viscosity of the slurry of comparative examples 1-3 is greatly increased after 24h, while the viscosity of the slurry of examples 1-5 is not changed greatly, the fluidity is still good, the slurry coating process effect is better, and the number of light leakage in half folding is obviously increased, which indicates that the flexibility and ductility of the electrode plate are obviously improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A dispersion softening agent for lithium ion battery anode slurry comprises the following components: 10-30wt% of dispersing agent, 20-35wt% of lubricating agent, 0-5wt% of water inhibitor and the balance of solvent;
the dispersing agent is tristyrylphenol polyether phosphate or modified polyurethane, and the modified polyurethane has a structure shown in a formula I:
wherein R is 1 (NCO) 2 Represents C6-C10 alkyl diisocyanate, diphenylmethane diisocyanate, toluene diisocyanateOne or more of the above;
R 2 represents a C2-C8 alkylene group; r 3 OH represents fatty alcohol polyether;
n represents an integer of 0 to 50.
2. The dispersion softening agent of claim 1, wherein the fatty alcohol polyether is one of fatty alcohol polyoxyethylene ether, fatty alcohol polyoxypropylene ether or lauryl alcohol polyoxyethylene ether, and n represents an integer of 10-45.
3. The dispersion softening agent according to claim 1 or 2, wherein the lubricant is a compound of one or more of stearic acid polyethylene glycol ester, epoxidized soybean oil, cardanol glycidyl ether or sorbitol polyether ester.
4. The dispersion flexibilizing agent of claim 3, wherein said sorbitan polyether ester is sorbitan polyether-30 tetraoleate or sorbitan polyether-40 tetraoleate.
5. A dispersion flexibilizing agent according to any of claims 1, 2 or 4, characterized in that said water-suppressing agent is one or a combination of more of trimethyl orthoacetate, triethyl orthoacetate, trimethyl orthoformate, triethyl orthoformate, sulfur-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, and said solvent is N-methylpyrrolidone.
6. The dispersion softening agent according to claim 3, wherein the water inhibitor is one or more of trimethyl orthoacetate, triethyl orthoacetate, trimethyl orthoformate, triethyl orthoformate, sulfur-containing silane coupling agent, aminosilane coupling agent and epoxy silane coupling agent, and the solvent is N-methylpyrrolidone.
7. A positive electrode slurry for a lithium ion battery, comprising the dispersion softening agent according to any one of claims 1 to 6.
8. The lithium ion battery positive electrode slurry according to claim 7, further comprising a positive electrode active material, a conductive agent, and a binder.
9. The lithium ion battery positive electrode slurry according to claim 8, wherein the positive electrode active material is lithium nickel cobalt manganese oxide, the conductive agent is one or a combination of several selected from conductive carbon black, superconducting carbon black, conductive graphite, acetylene black, ketjen black, graphene and carbon nanotubes, and the binder is one or a combination of vinylidene fluoride homopolymer and vinylidene fluoride copolymer.
10. A lithium ion battery positive pole piece, characterized in that, the surface of the positive pole piece is coated with the lithium ion battery positive pole slurry of any one of claims 7 to 9.
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