CN115785849B - Polymer micro-nano binder and preparation and application thereof - Google Patents
Polymer micro-nano binder and preparation and application thereof Download PDFInfo
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- CN115785849B CN115785849B CN202211628826.3A CN202211628826A CN115785849B CN 115785849 B CN115785849 B CN 115785849B CN 202211628826 A CN202211628826 A CN 202211628826A CN 115785849 B CN115785849 B CN 115785849B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 104
- 239000011230 binding agent Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 75
- 239000006185 dispersion Substances 0.000 claims abstract description 54
- 239000011267 electrode slurry Substances 0.000 claims abstract description 50
- 239000000853 adhesive Substances 0.000 claims abstract description 42
- 230000001070 adhesive effect Effects 0.000 claims abstract description 41
- 229920005596 polymer binder Polymers 0.000 claims abstract description 25
- 239000002491 polymer binding agent Substances 0.000 claims abstract description 25
- 238000010008 shearing Methods 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000000725 suspension Substances 0.000 claims abstract description 9
- 230000008961 swelling Effects 0.000 claims abstract description 7
- 239000002086 nanomaterial Substances 0.000 claims abstract description 6
- 239000002033 PVDF binder Substances 0.000 claims description 76
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 76
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 39
- 239000011231 conductive filler Substances 0.000 claims description 36
- 239000011149 active material Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 25
- 239000002105 nanoparticle Substances 0.000 claims description 25
- 239000004815 dispersion polymer Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 239000002003 electrode paste Substances 0.000 claims description 15
- 239000011888 foil Substances 0.000 claims description 15
- 239000004570 mortar (masonry) Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- 238000005096 rolling process Methods 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 238000001994 activation Methods 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 9
- 239000006183 anode active material Substances 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 239000006182 cathode active material Substances 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 238000010146 3D printing Methods 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 238000010345 tape casting Methods 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- 239000002121 nanofiber Substances 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 229920001410 Microfiber Polymers 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000011246 composite particle Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 238000007731 hot pressing Methods 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 claims description 2
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 2
- LRVBJNJRKRPPCI-UHFFFAOYSA-K lithium;nickel(2+);phosphate Chemical compound [Li+].[Ni+2].[O-]P([O-])([O-])=O LRVBJNJRKRPPCI-UHFFFAOYSA-K 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 239000003658 microfiber Substances 0.000 claims description 2
- 239000011859 microparticle Substances 0.000 claims description 2
- 239000002060 nanoflake Substances 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000006258 conductive agent Substances 0.000 abstract description 17
- 238000003756 stirring Methods 0.000 abstract description 17
- 230000009974 thixotropic effect Effects 0.000 abstract description 5
- 229920003023 plastic Polymers 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 description 60
- 230000000052 comparative effect Effects 0.000 description 38
- 239000002002 slurry Substances 0.000 description 34
- 239000000243 solution Substances 0.000 description 23
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 22
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 22
- 239000007788 liquid Substances 0.000 description 15
- 239000002994 raw material Substances 0.000 description 15
- 239000000919 ceramic Substances 0.000 description 13
- 239000011268 mixed slurry Substances 0.000 description 11
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 238000004080 punching Methods 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 238000009827 uniform distribution Methods 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 5
- 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 4
- 230000003213 activating effect Effects 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
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- 230000000149 penetrating effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 3
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- 238000002844 melting Methods 0.000 description 3
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- 238000011056 performance test Methods 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
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- 238000007719 peel strength test Methods 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002704 solution binder Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
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- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 235000011187 glycerol Nutrition 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
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- 238000001746 injection moulding Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
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- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
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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 provides a polymer micro-nano binder, and preparation and application thereof, and belongs to the field of batteries. The invention provides a polymer micro-nano binder, which is a mixed system of the existing polymer binder and a solvent, wherein the solvent satisfies the following conditions: a temperature of < 60 ℃, which is a non-solvent for the polymer binder but which is capable of forming a uniform stable sol or suspension dispersion with the existing polymer binder; temperatures > 60 ℃, which are capable of swelling or dissolving the existing polymeric binders. The invention selects a specific solvent which does not dissolve the existing polymer adhesive but can realize good dispersion of the polymer adhesive micro-nano material through the actions of strong shearing, ultrasonic, stirring and the like, thereby preparing polymer sol or suspension adhesive, and the adhesive also has good dispersion capability on solid components such as conductive agent, active particles and the like, so as to prepare the plastic electrode slurry with thixotropic rheological characteristics; further, a battery electrode excellent in overall performance is obtained.
Description
Technical Field
The invention provides a polymer micro-nano binder, and preparation and application thereof, and belongs to the field of batteries.
Background
As one of the power sources, lithium ion batteries have been widely used as power sources for consumer electronics (e.g., mobile phones and notebook computers) to the automobile industry and stationary storage systems due to their high energy density, long life span, and light weight. Lithium ion batteries have received much attention for their high energy density and have been successfully used in a variety of fields such as smart automobiles, information technology, mobile devices, etc. It remains highly desirable to design next generation rechargeable batteries with higher energy densities, shapes that can be designed on demand, lower cost, and longer cycle life. For lithium ion battery electrode active materials, which are key to determining battery performance, conventional electrode sheets are typical multicomponent systems composed of active materials, conductive fillers, polymer binders and metal current collectors, the performance of which is determined by the active materials themselves and the assembled structure of the composite electrode sheets. The requirements of the lithium ion battery on energy density and power density are required to be established on a reasonable charge (electron/ion) transmission system, so how to control the microstructure inside the pole piece and how to realize the processing of the high-load electrode are also key to the development of the next-generation high-performance lithium ion battery.
In the conventional electrode preparation, the polymer binder PVDF, PLA, PVA, PAA and the like are dissolved in a good solvent thereof and then blended with the active material and the conductive agent to form a uniform electrode slurry. In the slurry, the polymeric binder is distributed therein on a molecular scale and achieves a relatively uniform distribution over the surface of the other solid component, also referred to as a "uniform distribution" pattern of binder. However, this binder solution-based slurry has the following problems: (1) In electrode processing (heating drying and rolling) after coating is finished, volume shrinkage is large, and meanwhile, polymer molecular chains can crystallize and shrink to cause component separation and uncontrollable aggregation or agglomeration, so that the internal stress of the pole piece is excessive in the drying process, and the thick pole piece is severely cracked. Meanwhile, the bonding effectiveness of the interface between the active material and the conductive agent in the electrode is weakened, and the electron transmission network and the ion transmission network in the electrode are damaged. This disadvantage is ameliorated if a new binder system or new bonding means can be found, which is of significant practical significance in terms of improving electrode performance. (2) In the uniform distribution mode, when the binder content is relatively low, the interfacial binder content of each component is low, and the interfacial bonding effect may be deteriorated by the uniform distribution of the binder based on the solution. Therefore, the development of the novel adhesive system not only aims to solve the problems of controllability and uniformity of the internal structure, but also needs to improve the mechanical strength and stability of the adhesive interface on the premise of lower adhesive loading, and effectively regulate and control the rheological property of the electrode slurry so as to support innovation of the electrode processing technology.
Disclosure of Invention
Aiming at the defects, the invention starts from the initial state of the adhesive, selects a specific solvent which does not dissolve the existing polymer adhesive but can realize good dispersion of the polymer adhesive micro-nano material through the actions of strong shearing, ultrasonic, stirring and the like, so as to prepare a polymer sol or suspension adhesive system, and the adhesive system also has good dispersion capability on solid components such as conductive agent, active particles and the like, thereby preparing the plastic electrode slurry with thixotropic rheological characteristics; the obtained electrode slurry is used for further preparing the battery electrode with low adhesive content (less than or equal to 2wt percent), high active material loading, uniform structure, excellent comprehensive performance and customizable shape and high energy density.
The technical scheme of the invention is as follows:
The first technical problem to be solved by the invention is to provide a polymer micro-nano binder, wherein the polymer micro-nano binder is a mixed system of the existing polymer binder and a solvent, and the solvent satisfies the following conditions: at lower temperatures (< 60 ℃), it is a non-solvent for the polymeric binder, but is capable of forming a uniform stable sol or suspension dispersion with the existing polymeric binder; at higher temperatures (> 60 ℃), it is capable of swelling or dissolving the existing polymeric binder.
Further, the solvent includes at least one of Propylene Carbonate (PC) or Ethylene Carbonate (EC).
Further, the particle diameter of the polymer micro-nano binder is 10 nanometers to 10 micrometers.
Further, the mass fraction of the polymer micro-nano binder is 1-70%, preferably 5-40%; namely the mass of the polymer in the polymer micro-nano binder mixed system accounts for the proportion of the total mass of the binder mixed system.
Further, the morphology of the polymer micro-nano binder includes: at least one of a dispersion of polymer nanoparticles, a sol system of polymer nanoparticles, a dispersion of polymer microparticles, a dispersion of polymer nanoflakes, a dispersion of polymer microflakes, a dispersion of polymer nanofibers, or a dispersion of polymer microfibers.
Further, the existing polymer adhesive includes at least one of polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyacrylamide (PAM), polyethylene oxide (PEO), polyethylene glycol (PEG), polyvinylidene fluoride (PVDF), polyvinyl acetate (PVAc), polytetrafluoroethylene (PTFE), l-polylactic acid (PLLA), polymethyl methacrylate (PMMA), high density Polyethylene (PE), linear Low Density Polyethylene (LLDPE), polypropylene (PP), ethylene-propylene copolymer (EPDM), polycarbonate (PC), polyethylene amide (PEI), polyimide (PI), sodium carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), polyacrylonitrile (PAN), poly 4-methacrylic acid-2, 6-tetramethylpiperidine-1-nitroxide radical (PTMA), polyvinylpyrrolidone (PVP), poly (3, 4-ethylenedioxythiophene) (PEDOT), or poly (styrenesulfonic acid) (PSS).
Further, the solvent includes at least one of the following solvents in addition to PC or EC: dimethylacetamide (DMA), N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), methylene chloride (CH 2Cl2), acetone (C 3H6 O), dimethylsulfoxide (DMSO), acetonitrile (ACN), toluene, carbon tetrachloride, cyclohexane, carbonates, alcohols, ketones, ethers or glycerin, deionized water, and the like.
The second technical problem to be solved by the invention is to provide a preparation method of the polymer micro-nano adhesive, which comprises the following steps: adding the existing polymer binder micro-nano powder into the solvent, and preparing a uniform and stable sol or suspension dispersion system by high-speed shearing (the shearing speed is more than or equal to 100s -1) or ultrasonic dispersing at 0-60 ℃ to obtain the polymer micro-nano binder, wherein the polymer in the polymer micro-nano binder exists in a micro-nano size (the particle diameter is between 10 nanometers and 10 microns).
Further, the time of the high-speed shearing or ultrasonic dispersion treatment is 1 to 30 minutes.
The third technical problem to be solved by the invention is to point out: the polymer micro-nano binder is used for preparing high-quality electrode slurry, an anode plate, a cathode plate, a lithium ion battery, a sodium ion battery, a super capacitor or various electrochemical energy storage devices such as a lithium metal battery and the like.
The fourth technical problem to be solved by the invention is to provide a method for using the polymer micro-nano adhesive, which comprises the following steps: firstly, adding the polymer micro-nano binder into an anode or cathode active material and a conductive filler, and uniformly mixing and dispersing the mixture by a machine to obtain electrode slurry; the obtained electrode slurry is used for preparing a wet electrode blank with uniform structure and customizable shape by the existing processing mode; the wet electrode blank is heated to 100-200 ℃ to enable the polymer micro-nano adhesive in the blank to be fully swelled, melted and permeated, so that the bonding among the components is realized, the volatilization of the solvent is realized, and the electrode plate is prepared by rolling treatment, and can be used for preparing electrodes in various electrochemical energy storage devices.
Further, the existing processing modes comprise flexible and changeable processing modes such as knife coating, extrusion, injection, hot pressing and the like.
Further, in the use method, the temperature is raised to 100-200 ℃ for 3 min-10 h, so that the polymer micro-nano structure (such as micro-nano particles, micro-nano fibers or micro-nano sheets) in the polymer micro-nano binder is swelled, gelled, dissolved or melted in a solvent, thereby fully penetrating and realizing component bonding.
The fifth technical problem to be solved by the invention is to provide an electrode slurry, which is prepared by the following method: and adding the polymer micro-nano binder into the anode or cathode active material and the conductive filler, and uniformly mixing to obtain uniformly dispersed electrode slurry.
Further, the proportion of each component is as follows: 1 to 99 parts by weight of positive electrode active material or negative electrode active material, 0.5 to 50 parts by weight of conductive filler and 0.1 to 50 parts by weight of polymer binder.
Further, the method for uniformly mixing comprises the following steps: the polymer dispersion system is premixed with the active material and the conductive filler, and then dispersed and mixed by adopting grinding, mechanical stirring, a single screw extruder, a double screw extruder or a ball mill.
Further, the mass fraction of the solid content of the electrode slurry is 20-80%, and the high solid content such as 50-80 wt% can be realized.
Further, the electrode slurry is a clay-like electrode slurry, and the shearing yield stress of the electrode slurry is 100-3000 Pa.
Further, the obtained electrode paste has plasticity.
Furthermore, the electrode paste (the electrode paste with the ceramic-like rheological property) can be directly molded by an extruder, an injection machine and a hot press to obtain a blank, and then the adhesive is activated and dried to finally obtain the electrode with the high energy density, wherein the shape of the electrode can be customized.
Still further, the electrode paste can realize 3D printing forming of the electrode: the electrode paste is filled into a storage tank of a 3D printer head, and the electrode paste is extruded onto a current collector matrix at a constant speed by utilizing the pushing of the 3D printer and the control of a computer; and then heating the printed electrode to 100-200 ℃ (high-temperature activation) to realize effective bonding and shaping of each component, and finally obtaining the electrode with customized shape.
Further, the positive electrode active material includes: lithium iron phosphate, lithium manganese phosphate, lithium nickel phosphate, lithium cobalt phosphate, lithium manganese iron phosphate, lithium manganate, lithium nickelate, lithium cobaltate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate or sulfur carbon composite particles.
Further, the anode active material includes: artificial graphite, natural graphite, lithium titanate, silicon-carbon composite material, tin, alloy material thereof and the like.
Further, the conductive filler is at least one of conductive carbon black, conductive graphite, carbon nanofiber, carbon nanotube or graphene.
The sixth technical problem to be solved by the invention is to provide a preparation method of an electrode, which comprises the following steps: firstly, adding the polymer micro-nano binder into an anode or cathode active material and a conductive filler, and uniformly mixing to obtain electrode slurry; preparing electrode blanks with uniform structures and customizable shapes from the electrode slurry in the existing processing mode; heating the electrode blank to 100-200 ℃ to enable polymer micro-nano particles in the binder to be sufficiently melted and permeated, so that bonding among components is realized, and meanwhile, volatilization of a solvent is ensured, and then an electrode plate is manufactured; the polymer micro-nano binder is a mixed system of the existing polymer binder and a solvent, and the solvent satisfies the following conditions: the polymer binder is a non-solvent at lower temperatures (< 60 ℃) and is capable of swelling or dissolving the polymer binder at higher temperatures (> 60 ℃) and forming a uniform sol or suspension dispersion with the polymer binder.
Further, the solvent includes at least one of Propylene Carbonate (PC) or Ethylene Carbonate (EC).
Further, the polymer micro-nano binder is prepared by the following method: adding the existing polymer binder into the solvent, and dispersing by shearing, ultrasonic or stirring to obtain a polymer micro-nano dispersion system.
Specifically, the preparation method of the battery electrode comprises the following steps:
1) Preparing a polymer micro-nano adhesive: adding the weighed existing polymer binder into a specific solvent, and dispersing by using a high-speed shearing machine or an ultrasonic dispersing machine to obtain a uniform polymer micro-nano binder (polymer micro-nano dispersion system);
2) Preparing uniform electrode slurry: fully premixing an anode active material or a cathode active material and a conductive filler, adding the polymer micro-nano adhesive into the mixture, and mixing the mixture by adopting grinding, mechanical mixing or a ball mill until uniform electrode slurry is obtained;
3) Electrode slurry processing: and (3) coating the electrode slurry on the surface of a positive electrode or negative electrode current collector, heating to 100-200 ℃ for 3 min-10 h to swell or dissolve the polymer micro-nano adhesive, volatilizing the solvent and realizing the activation of the adhesive, and finally drying and rolling to obtain the electrode with uniform structure.
Further, in the above battery electrode method, the proportions of the respective components are: 20-98 parts of positive electrode active material or negative electrode active material, 1-50 parts of conductive filler and 1-30 parts of polymer binder.
Further, the current collector is aluminum foil, copper foil, aluminum wire or copper wire.
Further, electrode slurry is obtained by uniformly mixing by using a mortar, a ball mill or a twin-screw extruder.
And further, drying the obtained electrode, and then carrying out rolling treatment to obtain the positive and negative electrode plate of the lithium ion battery, wherein the rolling temperature is 50-300 ℃, the pressure is 1-200 MPa, and the rolling time is 1 second-15 minutes.
The seventh technical problem to be solved by the invention is to provide an electrode, which is manufactured by the method.
The invention has the beneficial effects that:
1) The invention adopts the existing polymer binder and a specific solvent to prepare a novel modified binder with a micro-nano structure, and the polymer nano binder (polymer dispersion system or polymer sol) can be used for distributing the binder more reasonably, thereby effectively strengthening the interface bonding among the electrode active material, the conductive agent and the current collector and ensuring the stability of the result of the whole electrode.
2) Because the polymer nano adhesive does not need to dissolve the polymer, the dispersion system is only prepared by strong shearing or ultrasonic dispersion under the condition of lower temperature, and the preparation process is more efficient and energy-saving compared with the traditional solution type adhesive system.
3) The electrode slurry prepared by the method of the invention can swell, gel and even dissolve dispersed polymer micro-nano particles by using a solvent in a high-temperature activation and drying process, thereby inhibiting uncontrollable aggregation and separation of components, realizing more uniform distribution of active materials and conductive agents, improving the uniformity degree of ion and electron transmission networks in the electrode and reducing the internal resistance of the electrode.
3) The electrode slurry prepared by the invention realizes bonding by in-situ swelling and dissolving of the polymer binder such as PVDF nano particles, and can effectively improve stress cracking caused by concentration, crystallization, uncontrollable aggregation and the like in the drying process of the electrode slurry prepared by the traditional polymer solution binder.
4) The composite electrode prepared by the invention is bonded by in-situ swelling and dissolving of the compound binder such as PVDF nano particles, and under a proper dosage, the binder can form a highly-penetrated skeleton structure inside the electrode, so that not only is the bonding between the components of the electrode effectively ensured, but also the stability of the integral structure of the electrode is ensured, and the preparation of the flexible electrode can be realized under the condition of lower binder dosage (less than 10 wt%).
5) After the half battery is assembled by the composite electrode prepared by the invention, the cycle performance and the multiplying power performance of the battery are obviously improved.
6) The binder can be used for preparing the plastic electrode slurry with high solid content and thixotropic fluid characteristics, and realizes innovation of various processing modes of the electrode slurry, including electrode molding processing by using common polymer molding processing technologies such as extrusion, calendaring, injection molding, pressing and the like.
7) The electrode paste obtained by the invention can be coated on the surface of the positive electrode or the negative electrode current collector by a traditional knife coating mode and a mouth film extrusion method, so that a uniform electrode paste coating with adjustable thickness from 50 to 5000 micrometers is obtained.
8) The binder can be used for improving the electrode load (the surface load of one side of an active material can be improved from 20mg/cm 2 to 50mg/cm 2 without cracking), improving the multiplying power performance and optimizing the cycle performance, and can be used for processing novel batteries with special electrode shapes, thereby laying a foundation for preparing structurally diversified electrodes and batteries.
Drawings
FIG. 1 is a cross-sectional SEM of a composite electrode obtained in example I and comparative example II, wherein (a) is a cross-sectional SEM of example I and (b) is a cross-sectional SEM of comparative example II.
FIG. 2 is an SEM image of the surface of a composite electrode obtained in comparative example one (a/a 1), comparative example two (b/b 1) and example one (c/c 1).
Fig. 3 (a) and (b) are characteristics of the flexural deformation conductivity stability of the composite electrode obtained in comparative example one, comparative example two and example one (a is a graph of comparative example one, comparative example two and example one in order from top to bottom).
FIG. 4 (a) is a graph showing peel strength test of the electrode and aluminum foil in comparative example one, comparative example two and example one; (b) Comparative example one, comparative example two and example one digital photographs of the aluminum foil surface after the adhesive system peel test.
Fig. 5 is a ratio performance test of button half cells prepared from the composite electrodes obtained in comparative example three, comparative example four and example two.
Fig. 6 is a graph showing the results of the cycle performance test of button half cells prepared by using the composite electrode obtained in the second embodiment and the third embodiment.
Fig. 7 is a digital photograph of a four-extrusion electrode of an embodiment.
FIG. 8 is a graph showing the structural evolution of PVDF nanoparticles under different drying conditions in comparative example five, comparative example six and example five.
FIG. 9 is an SEM image of a graphite anode prepared by PVDF-PC binder system in example six.
Fig. 10 is an SEM image of PVDF-EC nanoadhesives in the conductive agent in example seven.
FIG. 11 is a graph of the temperature ramp up rheology of PVDF-EC nanoadhesives in example seven.
Detailed Description
The invention starts from the initial state of the adhesive, selects a specific solvent which does not dissolve the existing polymer adhesive at low temperature but can realize good dispersion of polymer adhesive micro-nano materials through the actions of strong shearing, ultrasonic or stirring and the like, thereby preparing a polymer sol or suspension adhesive dispersion system, and the adhesive system also has good dispersion capability on solid components such as conductive agents, active particles and the like, so as to prepare the plastic electrode slurry with thixotropic rheological characteristics; and then the electrode paste is processed in flexible and changeable modes such as knife coating, extrusion and the like to prepare an electrode blank with uniform structure and customizable shape, and then the electrode blank is dried and shaped to obtain the high-energy-density electrode plate with excellent comprehensive performance, so that the electrode paste can be used for preparing electrodes in various electrochemical energy storage devices.
If the obtained electrode slurry is coated on the surface of the positive electrode or the negative electrode current collector, then the temperature is raised to 100-200 ℃; in the heating process, the system is converted from a low-viscosity dispersion system to a high-viscosity swelling or even dissolving system, and the gelation physical transformation phenomenon occurs; the polymer in the polymer dispersion system is fully melted and permeated, so that the bonding between the components of the electrode is realized, the volatilization of the solvent is ensured, and the battery electrode with low adhesive content, high active material loading, uniform structure, excellent comprehensive performance and customizable shape and high energy density is prepared.
The following examples are provided to further illustrate the invention and are not to be construed as limiting the invention. The technical solution can be reasonably designed by a person skilled in the art with reference to the examples, and the results of the present invention can be obtained as well.
Embodiment one:
(1) Preparing a polymer dispersion: and adding the dried and weighed polyvinylidene fluoride (PVDF) micro-nano agglomerate powder into a Propylene Carbonate (PC) solvent, stirring for about 10-20 min by a high-speed stirrer, and uniformly dispersing the polyvinylidene fluoride (PVDF) in the solvent Propylene Carbonate (PC) in the form of nano particles (100-300 nm) to obtain a nano dispersion with the mass fraction of 5%.
(2) Preparation of composite electrode paste (functional paste): a certain amount of the obtained polymer dispersion liquid is added into weighed lithium nickel cobalt manganese oxide (NCM) or Lithium Cobalt Oxide (LCO) and conductive carbon black, the mass ratio of active material to conductive filler to polymer is 92:4:4, and the raw materials are added into a ceramic mortar for grinding for 20 minutes, so that uniform slurry is obtained.
(3) Preparing a composite electrode: coating the uniformly mixed slurry on the surface of an aluminum foil with a certain thickness (about 500 mu m), activating and drying for 180min at 100 ℃, ensuring that the solvent is completely volatilized, fully melting and penetrating polyvinylidene fluoride (PVDF) to the components of the electrode to realize effective bonding of the interfaces of the components, obtaining the required composite electrode, and obtaining the electrode sheet with a specific shape by using a sheet punching machine for standby.
(4) Electrode plate was assembled with 2032 button cell: the positive electrode plate is the composite electrode, the negative electrode is made of lithium metal, the diaphragm is a Celgard commercial diaphragm, and the electrolyte is an EC/EMC/DMC (volume ratio is 1:1:1) solution of 1MLiPF 6.
The raw material ratios and activation conditions of each example and comparative example are shown in table 1.
Embodiment two:
(1) Preparing a polymer dispersion: the dried and weighed polyvinylidene fluoride (PVDF) powder was added to a Propylene Carbonate (PC) solvent, and the polyvinylidene fluoride (PVDF) was dispersed in the form of nanoparticles in the solvent Propylene Carbonate (PC) with stirring by a high-speed stirrer for about 10 to 20 minutes, to obtain a nanodispersion having a mass dispersion of 5%.
(2) Preparation of composite slurry (functional slurry): a certain amount of the obtained polymer dispersion liquid is added into weighed lithium nickel cobalt manganese oxide (NCM) or Lithium Cobalt Oxide (LCO) and conductive carbon black, the mass ratio of active material to conductive filler to polymer is 94:5:1, and the raw materials are added into a ceramic mortar for mixing for 20 minutes, so that uniform slurry is obtained.
(3) Preparing a composite electrode: coating the uniformly mixed slurry on the surface of an aluminum foil with a certain thickness (about 500 mu m), activating and drying for 120min at 120 ℃ to ensure that the solvent is completely volatilized, and fully melting and penetrating polyvinylidene fluoride (PVDF) to the components of the electrode to realize effective bonding of the interfaces of the components to obtain the required composite electrode, and obtaining the electrode sheet with a specific shape by using a sheet punching machine for standby.
(4) Electrode plate was assembled with 2032 button cell: the positive electrode plate is the composite electrode, the negative electrode is made of lithium metal, the diaphragm is a Celgard commercial diaphragm, and the electrolyte is an EC/EMC/DMC (volume ratio is 1:1:1) solution of 1MLiPF 6.
Embodiment III:
(1) Preparing a polymer dispersion: the dried and weighed polyvinylidene fluoride (PVDF) is added into Propylene Carbonate (PC) solvent, and the polyvinylidene fluoride (PVDF) is dispersed in the solvent Propylene Carbonate (PC) in the form of nano particles along with the stirring of a high-speed stirrer for about 10 to 20 minutes, so that nano dispersion liquid with the mass dispersion of 5% is obtained.
(2) Preparation of composite slurry (functional slurry): adding a certain amount of the obtained polymer dispersion liquid into weighed lithium nickel cobalt manganese oxide (NCM) or Lithium Cobalt Oxide (LCO) and conductive carbon black, wherein the mass ratio of active material to conductive filler to polymer is 93:5:2, and adding the raw materials into a ceramic mortar for mixing for 20 minutes to obtain uniform slurry;
(3) Preparing a composite electrode: coating the uniformly mixed slurry on the surface of an aluminum foil with a certain thickness (about 500 mu m), activating and drying for 60min at 140 ℃, ensuring that the solvent is completely volatilized, and fully melting and penetrating polyvinylidene fluoride (PVDF) to the components of the electrode to realize effective bonding of the interfaces of the components to obtain a required composite electrode, and obtaining an electrode sheet with a specific shape for standby by using a sheet punching machine;
(4) Electrode plate was assembled with 2032 button cell: the positive electrode plate is the composite electrode, the negative electrode is made of lithium metal, the diaphragm is a Celgard commercial diaphragm, and the electrolyte is an EC/EMC/DMC (volume ratio is 1:1:1) solution of 1MLiPF 6.
Embodiment four:
(1) Preparing a polymer dispersion: the dried and weighed polyvinylidene fluoride (PVDF) is added into Propylene Carbonate (PC) solvent, and the polyvinylidene fluoride (PVDF) is dispersed in the solvent Propylene Carbonate (PC) in the form of nano particles along with the stirring of a high-speed stirrer for about 10 to 20 minutes, so as to obtain nano dispersion liquid with the mass dispersion of 20 percent.
(2) Preparation of composite slurry (functional slurry): and adding a certain amount of the obtained polymer dispersion liquid into weighed lithium nickel cobalt manganese oxide (NCM) or Lithium Cobalt Oxide (LCO) and conductive carbon black, wherein the mass ratio of active material to conductive filler to polymer is 85:10:5, and adding the raw materials into a ceramic mortar for mixing for 30 minutes to obtain the high-solid-content 3D printing ink.
(3) Injecting PVDF nano particle-based 'ink' into the injection tube, pushing the injection tube to the forefront end of the injection tube, discharging gas in the ink, installing a nozzle and a piston, fixing the injection tube on a movable arm of a 3D printer, and connecting the injection tube with a gas flow system to enable the whole injection tube to be in a closed state.
(4) The control panel is used for inputting a pre-designed program, the pre-designed program comprises the setting of a printing pattern and the moving speed (namely the printing speed) of a nozzle, the printing program is started to start printing after the air pressure is regulated and the air is introduced, and the ink in the injection tube is extruded at a constant speed under the pushing of uniform air flow.
(5) Finally, the extruded electrode is activated and dried for 30min at 160 ℃ to ensure that the solvent is completely volatilized, and polyvinylidene fluoride (PVDF) is fully melted and permeated to the components of the electrode to realize effective bonding of interfaces of the components.
Fifth embodiment:
(1) Preparing a polymer dispersion: the dried and weighed polyvinylidene fluoride (PVDF) is added into Propylene Carbonate (PC) solvent, and the polyvinylidene fluoride (PVDF) is dispersed in the solvent Propylene Carbonate (PC) in the form of nano particles along with the stirring of a high-speed stirrer for about 10 to 20 minutes, so that nano dispersion liquid with the mass dispersion of 5% is obtained.
(2) Preparation of composite slurry (functional slurry): a certain amount of the polymer dispersion liquid is added into weighed nickel cobalt lithium manganate (NCM) or Lithium Cobalt Oxide (LCO) and conductive carbon black, and the mass ratio of active material/conductive filler/polymer is 80:10:10, adding the raw materials into a ceramic mortar, and mixing for 20 minutes to obtain uniform slurry;
(3) Preparing a composite electrode: coating the uniformly mixed slurry on the surface of an aluminum foil with a certain thickness (about 500 mu m), and activating at 180 ℃ for 20min to ensure that the solvent is completely volatilized, thus obtaining the required composite electrode.
Example six:
(1) Preparing a polymer dispersion: the dried and weighed polyvinylidene fluoride (PVDF) is added into Propylene Carbonate (PC) solvent, and the polyvinylidene fluoride (PVDF) is dispersed in the solvent Propylene Carbonate (PC) in the form of nano particles along with the stirring of a high-speed stirrer for about 10 to 20 minutes, so that nano dispersion liquid with the mass dispersion of 5% is obtained.
(2) Preparation of composite slurry (functional slurry): adding a certain amount of the obtained polymer dispersion liquid into weighed graphite or silicon micropowder and conductive carbon black, wherein the mass ratio of active material/conductive filler/polymer is 80:10:10, adding the raw materials into a ceramic mortar, and mixing for 40 minutes to obtain uniform slurry;
(3) Preparing a composite electrode: the evenly mixed slurry is coated on the surface of copper foil with a certain thickness (about 500 mu m), and the activation treatment is carried out for 20min at 180 ℃ to ensure that the solvent is completely volatilized, thus obtaining the required composite electrode.
Embodiment seven:
(1) Preparing a polymer dispersion: the dried and weighed polyvinylidene fluoride (PVDF) is added into a solvent of Ethylene Carbonate (EC), and the polyvinylidene fluoride (PVDF) is dispersed in the solvent of Ethylene Carbonate (EC) in the form of nano particles along with stirring for about 10 to 20 minutes by a high-speed stirrer, so that a nano dispersion with the mass dispersion of 5% is obtained.
(2) Preparation of conductive paste: a certain amount of the polymer dispersion liquid obtained above was added to the weighed conductive carbon black, and living: the mass ratio of the conductive filler to the polymer is 1:1, and the raw materials are added into a ceramic mortar to be mixed for 20 minutes, so that uniform slurry is obtained; and then coating the uniformly mixed conductive slurry on the surface of an aluminum foil with a certain thickness (about 500 mu m), drying at 60 ℃ for 300min to ensure complete volatilization of the solvent, and observing the distribution state of PVDF nano particles in the conductive agent.
Comparative example one:
(1) Preparing polyvinylidene fluoride solution: dissolving the dried and weighed polyvinylidene fluoride (PVDF) in N, N-Dimethylformamide (DMF), and stirring for 2 hours at normal temperature with magnetic stirring to obtain a uniform polyvinylidene fluoride solution with the mass fraction of 5%;
(2) Preparation of composite slurry: adding a certain amount of the obtained solution into weighed lithium nickel cobalt manganese oxide (NCM) or Lithium Cobalt Oxide (LCO) and conductive carbon black, wherein the mass ratio of active materials to conductive fillers to polymers is 92:4:4, and adding the raw materials into a ceramic mortar for mixing for 10 minutes to obtain uniform slurry;
(3) Preparing a composite electrode: coating the uniformly mixed slurry on the surface of an aluminum foil with a certain thickness (about 500 mu m), drying for 30min at 160 ℃ to ensure that the solvent is completely volatilized, obtaining a required composite electrode, and obtaining an electrode sheet with a specific shape for standby by using a sheet punching machine;
(4) Electrode plate was assembled with 2032 button cell: the positive electrode plate is the composite electrode, the negative electrode is made of lithium metal, the diaphragm is a Celgard commercial diaphragm, and the electrolyte is an EC/EMC/DMC (volume ratio is 1:1:1) solution of 1MLiPF 6.
Comparative example two:
(1) Preparing polyvinylidene fluoride solution: dissolving the dried and weighed polyvinylidene fluoride (PVDF) in N-methyl pyrrolidone (NMP), and stirring for 2 hours at normal temperature with magnetic stirring to obtain a uniform polyvinylidene fluoride solution with the mass fraction of 5%;
(2) Preparation of composite slurry: adding a certain amount of the obtained solution into weighed lithium nickel cobalt manganese oxide (NCM) or Lithium Cobalt Oxide (LCO) and conductive carbon black, wherein the mass ratio of active materials to conductive fillers to polymers is 92:4:4, and adding the raw materials into a ceramic mortar for mixing for 10 minutes to obtain uniform slurry;
(3) Preparing a composite electrode: coating the uniformly mixed slurry on the surface of an aluminum foil with a certain thickness (about 500 mu m), drying for 30min at 160 ℃ to ensure that the solvent is completely volatilized, obtaining a required composite electrode, and obtaining an electrode sheet with a specific shape for standby by using a sheet punching machine;
(4) Electrode plate was assembled with 2032 button cell: the positive electrode plate is the composite electrode, the negative electrode is made of lithium metal, the diaphragm is a Celgard commercial diaphragm, and the electrolyte is an EC/EMC/DMC (volume ratio is 1:1:1) solution of 1MLiPF 6.
Comparative example three:
(1) Preparing polyvinylidene fluoride solution: dissolving the dried and weighed polyvinylidene fluoride (PVDF) in N, N-Dimethylformamide (DMF), and stirring for 2 hours at normal temperature with magnetic stirring to obtain a uniform polyvinylidene fluoride solution with the mass fraction of 5%;
(2) Preparation of composite slurry: adding a certain amount of the obtained solution into weighed lithium nickel cobalt manganese oxide (NCM) or Lithium Cobalt Oxide (LCO) and conductive carbon black, wherein the mass ratio of active material to conductive filler to polymer is 94:5:1, and adding the raw materials into a ceramic mortar for mixing for 10 minutes to obtain uniform slurry;
(3) Preparing a composite electrode: coating the uniformly mixed slurry on the surface of an aluminum foil with a certain thickness (about 500 mu m), drying for 30min at 160 ℃ to ensure that the solvent is completely volatilized, obtaining a required composite electrode, and obtaining an electrode sheet with a specific shape for standby by using a sheet punching machine;
(4) Electrode plate was assembled with 2032 button cell: the positive electrode plate is the composite electrode, the negative electrode is made of lithium metal, the diaphragm is a Celgard commercial diaphragm, and the electrolyte is an EC/EMC/DMC (volume ratio is 1:1:1) solution of 1MLiPF 6.
Comparative example four:
(1) Preparing polyvinylidene fluoride solution: dissolving the dried and weighed polyvinylidene fluoride (PVDF) in N-methyl pyrrolidone (NMP), and stirring for 2 hours at normal temperature with magnetic stirring to obtain a uniform polyvinylidene fluoride solution with the mass fraction of 5%;
(2) Preparation of composite slurry: adding a certain amount of the obtained solution into weighed lithium nickel cobalt manganese oxide (NCM) or Lithium Cobalt Oxide (LCO) and conductive carbon black, wherein the mass ratio of active material to conductive filler to polymer is 94:5:1, and adding the raw materials into a ceramic mortar for mixing for 10 minutes to obtain uniform slurry;
(3) Preparing a composite electrode: coating the uniformly mixed slurry on the surface of an aluminum foil with a certain thickness (about 500 mu m), drying for 30min at 160 ℃ to ensure that the solvent is completely volatilized, obtaining a required composite electrode, and obtaining an electrode sheet with a specific shape for standby by using a sheet punching machine;
(4) Electrode plate was assembled with 2032 button cell: the positive electrode plate is the composite electrode, the negative electrode is made of lithium metal, the diaphragm is a Celgard commercial diaphragm, and the electrolyte is an EC/EMC/DMC (volume ratio is 1:1:1) solution of 1MLiPF 6.
Comparative example five:
(1) Preparing a polymer dispersion: the dried and weighed polyvinylidene fluoride (PVDF) is added into Propylene Carbonate (PC) solvent, and the polyvinylidene fluoride (PVDF) is dispersed in the solvent Propylene Carbonate (PC) in the form of nano particles along with the stirring of a high-speed stirrer for about 10 to 20 minutes, so that nano dispersion liquid with the mass dispersion of 5% is obtained.
(2) Preparation of composite slurry (functional slurry): a certain amount of the polymer dispersion liquid is added into weighed nickel cobalt lithium manganate (NCM) or Lithium Cobalt Oxide (LCO) and conductive carbon black, and the mass ratio of active material/conductive filler/polymer is 80:10:10, adding the raw materials into a ceramic mortar, and mixing for 20 minutes to obtain uniform slurry;
(3) Preparing a composite electrode: the evenly mixed slurry is coated on the surface of aluminum foil with a certain thickness (about 500 mu m), and is dried for 300min at 60 ℃ to ensure that the solvent is completely volatilized, thus obtaining the required composite electrode.
Comparative example six:
(1) Preparing a polymer dispersion: the dried and weighed polyvinylidene fluoride (PVDF) is added into Propylene Carbonate (PC) solvent, and the polyvinylidene fluoride (PVDF) is dispersed in the solvent Propylene Carbonate (PC) in the form of nano particles along with the stirring of a high-speed stirrer for about 10 to 20 minutes, so that nano dispersion liquid with the mass dispersion of 5% is obtained.
(2) Preparation of composite slurry (functional slurry): a certain amount of the polymer dispersion liquid is added into weighed nickel cobalt lithium manganate (NCM) or Lithium Cobalt Oxide (LCO) and conductive carbon black, and the mass ratio of active material/conductive filler/polymer is 80:10:10, adding the raw materials into a ceramic mortar, and mixing for 20 minutes to obtain uniform slurry;
(3) Preparing a composite electrode: the evenly mixed slurry is coated on the surface of aluminum foil with a certain thickness (about 500 mu m), and is dried for 200min at 80 ℃ to ensure that the solvent is completely volatilized, thus obtaining the required composite electrode.
Table 1 raw material ratios and activation conditions of examples and comparative examples
Performance test:
In the present invention, the microstructure of the obtained composite electrode material was observed, and fig. 1 is a cross-sectional SEM image of the composite electrode material obtained in example one and comparative example two. From fig. 1 (a) and 1 (b) SEM, it can be seen that the electrode prepared by using the binder obtained in example 1 is more uniform in the coating of the conductive filler around the active particles and in the uniform dispersion of the conductive filler, compared to the electrode prepared by using N-methylpyrrolidone (NMP), which is an electrode solvent already commercially prepared.
Fig. 2 is a surface SEM image of the composite electrode material obtained in comparative example one, comparative example two and example one. Fig. 2 (a) is a surface SEM image of a composite electrode prepared by using solvent N, N-Dimethylformamide (DMF), and it can be seen that the composite electrode material of comparative example one has poor structural uniformity, has more exposed active material, and has imperfect electron transport network construction. The electrodes of the commercial PVDF-NMP solution binders showed significant polymerization of the conductive agent and many bare active material surfaces, forming a heterogeneous electron transport network, as shown in fig. 2 b. In contrast, the electrode prepared with the binder (PVDF-PC) obtained in example one of the present invention showed a uniform distribution, as shown in FIG. 2 c. Most of the active material surface is covered with a conductive agent. These results indicate that the binder has a very important impact on the active material microenvironment structure.
The dry and wet bending resistance of the electrodes obtained in comparative example one, comparative example two and example one was tested. The results are shown in fig. 3, and further demonstrate that the nano-adhesive system obtained in the first embodiment can better adhere active particles and conductive fillers, and more effectively fix the conductive network.
According to the invention, the peel strength test is carried out on the first comparative example, the second comparative example and the first comparative example, the peel temperature is room temperature, the speed is 500 mu m/s, and as can be seen from fig. 4, the peel strength of the first comparative example is obviously higher than that of the first comparative example and the second comparative example, so that the novel nano adhesive obtained in the first example can better bond active particles and conductive fillers, and can better interact with a current collector, and the overall good structural stability and integrity of the electrode can be realized.
The invention tests the multiplying power performance of button cell prepared by the composite electrode obtained in the third, fourth and second examples (the testing temperature is 25 ℃), the result is shown in fig. 5, and as can be seen from fig. 5, the capacity of the second example is far higher than that of the third and fourth examples under the current density of 0.05 to 1C, and the advantages of the battery prepared by the invention can be seen; the electrode conductive network prepared by the novel adhesive has more efficacy, and the good coating of the active particles ensures that the electron transmission network and the ion transmission channel in the electrode are more perfect, the electrode has more synergistic reaction in the charge and discharge process, more sites capable of participating in the reaction and uniform lithium ion transmission.
The invention tests the cycle performance of button cells prepared by the composite electrode obtained in the second and third embodiments, and the results are shown in fig. 6; as can be seen from fig. 6, this ultra-low binder, high loading electrode has very good cycling performance. The dispersion adhesive electrode has good structural uniformity, active particles are uniformly coated by conductive fillers in a large amount, the nano adhesive has better adhesive capacity, and can bear structural damage caused by active particle deformation, so that the damage of the structure and the consumption of recombination to lithium ions in the deformation process are reduced.
FIG. 7 is a digital photograph of a four-extrusion electrode according to an embodiment; as can be seen from fig. 7: high solids electrode slurries like clays can be readily prepared using dispersion binders, and the slurries exhibit typical thixotropic fluid properties. Thus, electrodes of different shapes can be extruded as desired by 3D printing, as shown in fig. 7. We prepared electrode fibers of different diameters, the morphology and size of the printed electrode being well preserved after drying, which benefits from low stress drying of the electrode slurry prepared with the dispersed binder.
In the invention, the microstructure of the composite electrode material obtained at different activation and drying temperatures is observed, and fig. 8 is a surface SEM image of the composite electrode material obtained in example five, comparative example five and comparative example six. Structural evolution of PVDF nanoparticles at different temperatures. The results show that PVDF retains a spherical structure when the temperature is increased from 20 ℃ to 60 ℃. As the temperature is further raised to 80 ℃, the boundaries of PVDF nanoparticles begin to merge together, as the outer solvated shell gradually gels. When the temperature exceeds 100 ℃, PVDF fusion is intensified, and strong adhesion between PVDF and the conductive agent is finally realized. The result shows that the PVDF-PC system nano adhesive is required to play a role, and the electrode is required to be dried at the temperature of more than 80 ℃; the PVDF dispersion type adhesive can better adhere the active particles and the conductive filler, and is more effective in fixing the conductive network.
Microscopic observation was made on the composite electrode of example six according to the present invention, and the SEM results thereof are shown in fig. 9, which shows that PVDF-PC dispersion type adhesive is equally applicable to graphite negative electrode. The conductive agent is uniformly dispersed, most of the surface of the active material is covered with the conductive agent, and it can be observed that strong interfacial adhesion between the active material and the conductive agent is achieved. These results indicate that the dispersed binder is also applicable to the preparation of graphite anodes.
According to the invention, the microstructure of the adhesive-conductive agent composite material obtained in the seventh embodiment is observed, and as shown in fig. 10, the solvent EC can also realize dispersion of PVDF-NP; the PVDF nanoparticles are uniformly distributed around the conductive agent. FIG. 11 is a graph of the temperature ramp up rheology of a PVDF-EC dispersion, which shows that the PVDF-EC dispersion undergoes a significant gel transition stage. The results show that the PVDF-EC nanoadhesive system can also achieve bonding between the electrode components by activation at temperature.
It will be understood by those skilled in the art that various modifications may be made to the above-described embodiments without departing from the spirit and scope of the claims, and that all such modifications and changes are intended to be within the scope of the present invention.
Claims (17)
1. The polymer micro-nano binder is characterized in that the polymer micro-nano binder is a mixed system of the existing polymer binder and a solvent, and the solvent satisfies the following conditions: a temperature of < 60 ℃, which is a non-solvent for the polymer binder but which is capable of forming a uniform stable sol or suspension dispersion with the existing polymer binder; a temperature > 60 ℃, which is capable of swelling or dissolving the existing polymeric binder; the solvent comprises at least one of propylene carbonate or ethylene carbonate; the existing polymer binder is polyvinylidene fluoride; the drying temperature of the binder is higher than 80 ℃ when the binder is used.
2. The polymer micro-nano binder according to claim 1, wherein the particle diameter of the polymer micro-nano binder is 10 nanometers to 10 micrometers;
the mass fraction of the polymer micro-nano binder is 1% -70%;
the polymer micro-nano binder comprises the following forms: at least one of a dispersion of polymer nanoparticles, a sol system of polymer nanoparticles, a dispersion of polymer microparticles, a dispersion of polymer nanoflakes, a dispersion of polymer microflakes, a dispersion of polymer nanofibers, or a dispersion of polymer microfibers.
3. The polymer micro-nano binder according to claim 2, wherein the mass fraction of the polymer micro-nano binder is 5% -40%.
4. A polymer micro-nano binder according to any one of claims 1-3, wherein,
The solvent comprises at least one of the following solvents in addition to propylene carbonate or ethylene carbonate: n, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, methylene chloride, dimethylsulfoxide, acetonitrile, toluene, carbon tetrachloride, cyclohexane, alcohols, ketones, ethers or deionized water.
5. The polymeric micro-nano binder of claim 4, wherein the solvent further comprises at least one of the following solvents: acetone or glycerol.
6. The method for preparing the polymer micro-nano adhesive according to any one of claims 1 to 4, wherein the preparation method is as follows: adding the existing polymer binder into the solvent, and preparing a uniform and stable sol or suspension dispersion system by high-speed shearing or ultrasonic dispersion at 0-60 ℃ to obtain the polymer micro-nano binder.
7. The method for preparing the polymer micro-nano adhesive according to claim 6, wherein the shearing speed is not less than 100 s -1; the time of high-speed shearing or ultrasonic dispersing is 1-30 minutes.
8. The polymer micro-nano binder according to any one of claims 1-4, which is used for preparing electrode slurry, positive electrode sheet, negative electrode sheet, lithium ion battery, sodium ion battery, super capacitor or lithium metal battery.
9. The method of using a polymer micro-nano binder according to any one of claims 1-4, wherein the method of using is: firstly, adding the polymer micro-nano binder into an anode or cathode active material and a conductive filler, and uniformly mixing and dispersing the mixture by a machine to obtain electrode slurry; the obtained electrode slurry is used for preparing a wet electrode blank with uniform structure and customizable shape by the existing processing mode; the wet electrode blank is heated to 100-200 ℃ to enable the polymer micro-nano binder in the blank to be fully swelled, melted and permeated, so that the bonding among the components is realized, the volatilization of the solvent is realized, and then the electrode plate is manufactured by rolling treatment.
10. The method of claim 9, wherein the existing processing means comprises knife coating, extrusion, injection or hot pressing; in the using method, the temperature is raised to 100-200 ℃ to treat 3 min-10 h, so that the polymer micro-nano structure in the polymer micro-nano binder is swelled, gelled, dissolved or melted in a solvent, and the polymer micro-nano binder is fully permeated and component bonding is realized.
11. The electrode paste is characterized by being prepared by the following steps: the polymer micro-nano binder according to any one of claims 1-4 is added into an anode or cathode active material and a conductive filler, and uniformly mixed to obtain uniformly dispersed electrode slurry.
12. An electrode slurry according to claim 11, wherein the proportions of the components are: 1-99 parts of positive electrode active material or negative electrode active material, 0.5-50 parts of conductive filler and 0.1-50 parts of polymer binder;
the method for uniformly mixing comprises the following steps: premixing the polymer dispersion system, active materials and conductive fillers, and then adopting grinding, mechanical stirring, a single screw extruder, a double screw extruder or a ball mill to carry out dispersion mixing;
the mass fraction of the solid content of the electrode slurry is 20% -80%;
The resulting electrode slurry has plasticity.
13. The electrode slurry of claim 12, wherein the electrode slurry is a clay-like electrode slurry having a shear yield stress of between 100 and 3000 Pa;
The electrode slurry can be molded by an extruder, an injection machine or a hot press to obtain a blank, and then activated and dried to finally obtain the electrode with customizable shape;
The electrode paste can realize 3D printing and forming of the electrode: the electrode paste is filled into a storage tank of a 3D printer head, and the electrode paste is extruded onto a current collector matrix at a constant speed by utilizing the pushing of the 3D printer and the control of a computer; then heating the printed electrode to 100-200 ℃ to realize effective bonding and shaping of each component, and finally obtaining the electrode with customized shape;
The positive electrode active material includes: lithium iron phosphate, lithium manganese phosphate, lithium nickel phosphate, lithium cobalt phosphate, lithium manganese iron phosphate, lithium manganate, lithium nickelate, lithium cobaltate, lithium nickelate manganate, lithium nickelate aluminate or sulfur carbon composite particles;
the negative electrode active material includes: artificial graphite, natural graphite, lithium titanate, silicon-carbon composite material, tin and alloy materials thereof;
The conductive filler is at least one of conductive carbon black, conductive graphite, carbon nanofiber, carbon nanotube or graphene.
14. A method for preparing an electrode, comprising the steps of: adding the polymer micro-nano binder of any one of claims 1-4 into an anode or cathode active material and a conductive filler, and uniformly mixing to obtain electrode slurry; preparing electrode blanks with uniform structures and customizable shapes from the electrode slurry in the existing processing mode; the temperature of the electrode blank is raised to 100-200 ℃ to enable the polymer micro-nano particles in the binder to be fully melted and permeated, so that the bonding between the components is realized, the volatilization of the solvent is ensured, and the electrode plate is further manufactured.
15. The method for preparing an electrode according to claim 14, comprising the steps of:
1) Preparing a polymer micro-nano binder: adding the weighed existing polymer binder into a solvent, and dispersing by using a high-speed shearing machine or an ultrasonic dispersing machine to obtain a uniform polymer micro-nano binder;
2) Preparing uniform electrode slurry: fully premixing an anode active material or a cathode active material and a conductive filler, adding the polymer micro-nano binder into the mixture, and mixing the mixture by adopting grinding, mechanical mixing or a ball mill until uniform electrode slurry is obtained;
3) Electrode slurry processing: and (3) coating the obtained electrode slurry on the surface of a positive electrode or negative electrode current collector, heating to 100-200 ℃ for 3 min-10 h to swell or dissolve the polymer micro-nano binder, realizing the activation of the binder while volatilizing the solvent, and finally drying and rolling to obtain the electrode with uniform structure.
16. The method for preparing an electrode according to claim 15, wherein in step 2), the ratio of each component is: 20-98 parts of positive electrode active material or negative electrode active material, 1-50 parts of conductive filler and 1-30 parts of polymer binder;
In the step 2), uniformly mixing by adopting a mortar, a ball mill or a double-screw extruder to obtain electrode slurry;
In the step 3), the current collector is aluminum foil, copper foil, aluminum wire or copper wire;
In the step 3), the electrode is obtained by drying the electrode slurry and then rolling the electrode slurry, wherein the rolling temperature is 50-300 ℃, the pressure is 1-200 MPa, and the rolling time is 1 second-15 minutes.
17. An electrode characterized in that the electrode is manufactured by the manufacturing method according to any one of claims 14 to 16.
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