CN115785849A - 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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- CN115785849A CN115785849A CN202211628826.3A CN202211628826A CN115785849A CN 115785849 A CN115785849 A CN 115785849A CN 202211628826 A CN202211628826 A CN 202211628826A CN 115785849 A CN115785849 A CN 115785849A
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- 239000000725 suspension Substances 0.000 claims abstract description 9
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
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- 238000012545 processing Methods 0.000 claims description 13
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- 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 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
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- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
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- 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
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- 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
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
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- 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
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims 1
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- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
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- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a polymer micro-nano binder and preparation and application thereof, belonging 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 meets the following requirements: a temperature of < 60 ℃, which is a non-solvent for the polymeric binder but is capable of forming a uniform and stable sol or suspension dispersion with said existing polymeric binder; a temperature > 60 ℃, which is capable of swelling or dissolving the existing polymeric binder. According to the invention, a specific solvent which does not dissolve the existing polymer adhesive but can realize good dispersion of the polymer adhesive micro-nano material through strong shearing, ultrasonic, stirring and other actions is selected, so that a polymer sol or a suspension adhesive is prepared, and the adhesive also has good dispersion capacity on solid components such as a conductive agent, active particles and the like, so that plastic electrode slurry with thixotropic rheological characteristics is prepared; further preparing the battery electrode with excellent comprehensive performance.
Description
Technical Field
The invention provides a polymer micro-nano binder and preparation and application thereof, belonging to the field of batteries.
Background
As one of the power sources, lithium ion batteries have been widely used as power sources in consumer electronics (such as mobile phones and notebook computers) to the automotive industry and stationary storage systems due to their high energy density, long life and light weight. Lithium ion batteries have attracted considerable attention due to their high energy density and have been successfully used in a variety of fields such as intelligent automobiles, information technology, mobile devices, and the like. It remains highly desirable to design next generation rechargeable batteries with higher energy density, shape-on-demand design, lower cost, and longer cycle life. For the lithium ion battery electrode active material is the key to determine the battery performance, the conventional electrode pole piece is a typical multi-component system consisting of an active substance, a conductive filler, a polymer adhesive and a metal current collector, and the performance of the conventional electrode pole piece is determined by the active material and the assembly structure of the composite pole piece. The requirements of lithium ion batteries on energy density and power density need 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 high-load electrodes are also the key for developing next-generation high-performance lithium ion batteries.
In the traditional electrode preparation, polymer adhesives such as PVDF, PLA, PVA, PAA and the like are dissolved in good solvents of the polymer adhesives, and then the polymer adhesives are blended with active materials and conductive agents to form uniform electrode slurry. In the slurry, the polymeric binder is distributed on a molecular scale and achieves a relatively uniform distribution over the surface of the other solid components, which may also be referred to as a "uniform distribution" pattern of binder. However, such a slurry based on a binder solution has the following problems: (1) In the electrode processing (heating drying and rolling) after coating, the volume shrinkage is large, and meanwhile, the polymer molecular chain can be crystallized and shrunk to cause component separation and uncontrollable aggregation or reunion, so that the internal stress of the pole piece in the drying process is overlarge, and the thick pole piece is seriously cracked. Meanwhile, the effectiveness of interfacial adhesion between the active material and the conductive agent in the electrode is weakened, and an electron transport network and an ion transport network in the electrode are damaged. If a new adhesive system or a new bonding mode can be found, the defect can be improved, and the method has obvious practical significance on the aspect of improving the performance of the electrode. (2) In the uniform dispensing mode, when the adhesive ratio is low, the content of the interfacial adhesive to which each component is dispensed is low, and the uniform dispensing manner of the solution-based adhesive may deteriorate the interfacial adhesion effect. Therefore, the development of a novel adhesive system not only needs to solve the problems of controllability and uniformity of an internal structure, but also needs to improve the mechanical strength and stability of an adhesive interface on the premise of lower adhesive loading capacity, and effectively regulate and control the rheological property of electrode slurry so as to support the innovation of an electrode processing technology.
Disclosure of Invention
Aiming at the defects, 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 strong shearing, ultrasonic, stirring and other actions from the initial state of the adhesive, thereby preparing a polymer sol or a suspension adhesive system, and the adhesive system also has good dispersion capacity on solid components such as a conductive agent, active particles and the like, thereby preparing the plastic electrode slurry with thixotropic rheological characteristic; the obtained electrode slurry is utilized to further prepare the battery electrode with low content of the bonding agent (less than or equal to 2 wt%), high loading capacity of the active material, uniform structure, excellent comprehensive performance and customized 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 meets the following requirements: at lower temperatures (< 60 ℃), it is a non-solvent for the polymeric binder, but is able to form 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 propylene 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 proportion of the mass of the polymer in the polymer micro-nano binder mixing system to the total mass of the binder mixing system.
Further, the polymer micro-nano binder is in a form comprising: at least one of a dispersion of polymer nanoparticles, a sol system of polymer nanoparticles, a dispersion of polymer microparticles, a dispersion of polymer nanoplatelets, a dispersion of polymer microflakes, a dispersion of polymer nanofibers, or a dispersion of polymer microfibers.
Further, the existing polymer binder 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), levorotatory polylactic acid (PLLA), polymethyl methacrylate (PMMA), high density Polyethylene (PE), linear Low Density Polyethylene (LLDPE), polypropylene (PP), ethylene-propylene copolymer (EPDM), polycarbonate (PC), polyvinyl 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 may include 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), dichloromethane (CH) 2 Cl 2 ) Acetone (C) 3 H 6 O), dimethylsulfoxide (DMSO), acetonitrile (ACN), toluene, carbon tetrachloride, cyclohexane, carbonates, alcohols, ketones, ethers or glycerol, 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 binder, wherein the preparation method comprises the following steps: adding the micro-nano powder of the existing polymer binder into the solvent, and shearing at a high speed (the shearing speed is more than or equal to 100 s) at the temperature of 0-60 DEG C -1 ) Or preparing a uniform and stable sol or suspension dispersion system by ultrasonic dispersion to obtain the polymer micro-nano binder, namely the polymer in the polymer micro-nano binder exists in a micro-nano size (the particle diameter is between 10 nanometers and 10 micrometers).
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 present invention is to point out: the polymer micro-nano binder is used for preparing high-quality electrode slurry, a positive plate, a negative plate, various electrochemical energy storage devices such as a lithium ion battery, a sodium ion battery, a super capacitor or a lithium metal battery and the like.
The fourth technical problem to be solved by the invention is to provide a use method of the polymer micro-nano binder, wherein the use method comprises the following steps: adding the polymer micro-nano binder into an anode or cathode active material and a conductive filler, and mechanically mixing and dispersing uniformly to obtain electrode slurry; preparing a wet electrode blank with a uniform structure and a customizable shape from the obtained electrode slurry by the conventional processing method; and heating the wet electrode blank to 100-200 ℃ to fully swell, melt and permeate the polymer micro-nano adhesive in the blank, so that the components are bonded and the solvent is volatilized, and further performing rolling treatment to prepare the electrode plate, which 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 blade coating, extrusion, injection, hot pressing and the like.
Further, in the using method, the temperature is increased to 100-200 ℃ for treatment 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 the solvent, and thus the polymer micro-nano structure is fully permeated and the component adhesion is realized.
The fifth technical problem to be solved by the invention is to provide electrode paste, which is prepared by adopting the following method: and adding the polymer micro-nano binder into the positive electrode or negative electrode 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 of positive electrode active material or negative electrode active material, 0.5 to 50 parts of conductive filler and 0.1 to 50 parts of polymer binder.
Further, the method for uniformly mixing comprises the following steps: the polymer dispersion system is premixed with an active material and a conductive filler, and then is 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 clay-like electrode slurry, and the shear yield stress of the electrode slurry is between 100 and 3000 Pa.
Further, the obtained electrode paste has plasticity.
Furthermore, the electrode slurry (electrode slurry with ceramic clay rheological characteristics) can be directly molded by an extruder, an injection machine and a hot press to obtain a blank, and then the binder is activated and dried to finally obtain the high-energy density electrode with a customizable shape.
Furthermore, the electrode paste can realize 3D printing and forming of the electrode: the electrode slurry is filled into a storage tank of a 3D printer head, and the electrode slurry is extruded out of a current collector substrate at a constant speed by the aid of pushing of the 3D printer and computer control; 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 a customized shape.
Further, the positive electrode active material includes: lithium iron phosphate, lithium manganese phosphate, lithium nickel phosphate, lithium cobalt phosphate, lithium iron manganese phosphate, lithium manganese oxide, lithium nickel oxide, lithium cobalt oxide, lithium nickel cobalt aluminate, or a sulfur carbon composite particle.
Further, the anode active material includes: artificial graphite, natural graphite, lithium titanate, silicon-carbon composite materials, tin and alloy materials 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 present invention is to provide a method for preparing an electrode, wherein the method for preparing the electrode comprises: 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 an electrode blank with a uniform structure and a customizable shape from the obtained electrode slurry by the conventional processing method; heating the electrode blank to 100-200 ℃ to fully melt and permeate the polymer micro-nano particles in the binder, thereby realizing the binding among the components and simultaneously ensuring the volatilization of the solvent, and further preparing the electrode plate; the polymer micro-nano binder is a mixed system of the existing polymer binder and a solvent, and the solvent meets the following requirements: at lower temperatures (< 60 ℃) they are non-solvents for the polymeric binder, at higher temperatures (> 60 ℃) they swell or dissolve the polymeric binder and they form a uniform sol or suspension dispersion with the polymeric binder.
Further, the solvent includes at least one of Propylene Carbonate (PC) or propylene carbonate (EC).
Further, the polymer micro-nano binder is prepared by adopting the following method: adding the existing polymer binder into the solvent, and dispersing by utilizing 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 (a polymer micro-nano dispersion system);
2) Preparing uniform electrode slurry: fully premixing a positive electrode active material or a negative electrode active material and a conductive filler, adding the polymer micro-nano adhesive into the mixture, and mixing by adopting grinding, mechanical mixing or a ball mill until uniform electrode slurry is obtained;
3) Processing electrode slurry: and (3) coating the electrode slurry on the surface of a positive electrode or a negative electrode current collector, heating to 100-200 ℃, treating for 3 min-10 h to swell or dissolve the polymer micro-nano adhesive, activating the adhesive while volatilizing the solvent, and finally drying and rolling to obtain the electrode with a uniform structure.
Further, in the battery electrode method, the ratio of each component is as follows: 20 to 98 parts of positive electrode active material or negative electrode active material, 1 to 50 parts of conductive filler and 1 to 30 parts of polymer binder.
Further, the current collector is an aluminum foil, a copper foil, an aluminum wire or a copper wire.
Further, a mortar, a ball mill or a twin-screw extruder is adopted for uniform mixing to obtain the electrode slurry.
Further, the obtained electrode is dried and then rolled to obtain the positive and negative pole pieces 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 prepared by adopting 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 (a polymer dispersion system or a polymer sol) can be used for more reasonably distributing the binder, so that the interfacial adhesion among an electrode active material, a conductive agent and a current collector is effectively strengthened, and the result stability of the whole electrode is ensured.
2) Because the polymer nano adhesive does not need to dissolve the polymer, and only needs to prepare the dispersion system through strong shearing or ultrasonic dispersion at a lower temperature, the preparation process is more efficient and energy-saving compared with the traditional solution type adhesive system.
3) According to the electrode slurry prepared by the method, the dispersed polymer micro-nano particles can be swelled, gelatinized and even dissolved by the solvent by utilizing the high-temperature activation and simultaneous drying process, so that the uncontrollable aggregation and separation of components are inhibited, the more uniform distribution of the active material and the conductive agent is realized, the homogenization degree of ions and an electron transmission network in the electrode is improved, and the internal resistance of the electrode is reduced.
3) The electrode slurry prepared by the invention realizes bonding by in-situ swelling and dissolving of polymer binder such as PVDF nano particles, and can effectively improve the stress cracking condition 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 the in-situ swelling and dissolving manner of the binder such as PVDF nano particles, and the binder can form a highly-interpenetrating framework structure in the electrode at a proper dosage, so that the bonding among the components of the electrode is effectively ensured, the stability of the whole structure of the electrode is also ensured, and the preparation of the flexible electrode can be realized at a lower binder dosage (less than 10 wt%).
5) After the composite electrode prepared by the method is used for half-cell assembly, the cycle performance and the rate capability of the cell are obviously improved.
6) The adhesive can be used for preparing plastic electrode paste with high solid content and thixotropic fluid characteristic, and realizes innovation of various processing modes of the electrode paste, including the formation processing of electrodes by using common polymer forming and processing technologies such as extrusion, calendaring, injection molding, pressing and the like.
7) The electrode slurry obtained by the invention can be coated on the surface of a positive electrode current collector or a negative electrode current collector by a traditional blade coating mode and a mouth film extrusion method, so that a uniform electrode slurry coating with the adjustable thickness of 50-5000 micrometers can be obtained.
8) The binder can realize the improvement of the electrode loading capacity (the surface loading capacity of the single surface of the active material can be increased from 20 mg/cm) 2 Lifting to 50mg/cm 2 But not cracking), rate capability promotion, circulation performance optimization simultaneously, can also be used to the processing of the novel battery of special electrode shape, establish the basis for preparing the diversified electrode of structure and battery.
Drawings
FIG. 1 is a SEM image of a composite electrode obtained in example one and comparative example two, wherein (a) is a SEM image of an electrode in example one and (b) is a SEM image of an electrode in comparative example two.
FIG. 2 shows comparative example I (a/a) 1 ) Comparative example No. (b/b) 1 ) And example one (c/c) 1 ) SEM image of the resulting composite electrode surface.
Fig. 3 (a) and (b) are representations of the bending deformation conductive stability of the composite electrode obtained in the first comparative example, the second comparative example and the first example (the first comparative example, the second comparative example and the first example are sequentially arranged from top to bottom in the drawing of a).
FIG. 4 (a) test charts of peel strength between electrodes 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 surface of the aluminum foil after the adhesive system peel test.
Fig. 5 is a rate 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 of the cycle performance test results for button half cells prepared from composite electrodes obtained in example two and example three.
Figure 7 is a digital photograph of the four extruded electrodes of the example.
FIG. 8 is a graph showing the structural evolution of PVDF nanoparticles in the fifth comparative example, the sixth comparative example and the fifth example under different drying conditions.
FIG. 9 is an SEM image of a graphite negative electrode prepared by the PVDF-PC binder system in the sixth example.
FIG. 10 is an SEM image of the distribution of PVDF-EC nano binder in the conductive agent in the seventh embodiment.
FIG. 11 is a temperature-rising rheology diagram of the PVDF-EC nano binder in example seven.
Detailed Description
Starting from the initial state of the adhesive, the invention selects a specific solvent which does not dissolve the existing polymer adhesive at low temperature but can realize good dispersion of the polymer adhesive micro-nano material through 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 a conductive agent, active particles and the like, thereby preparing the plastic electrode slurry with thixotropic rheological characteristics; and then, preparing an electrode blank with a uniform structure and a customizable shape by using the obtained electrode slurry in flexible and changeable processing modes such as blade coating, extrusion and the like, drying and shaping to obtain the high-energy-density electrode plate with excellent comprehensive performance, and the electrode plate 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 current collector or the negative electrode current collector, then the temperature is raised to 100-200 ℃; in the process of temperature rise, the system is changed from a low-viscosity dispersion system into a high-viscosity swelling or even dissolving system, and the phenomenon of gelation physical transformation occurs; the polymer in the polymer dispersion system is fully melted and permeated, so that the bonding among all components of the electrode is realized, the volatilization of a solvent is ensured, and the battery electrode with low bonding agent content, high active material loading capacity, uniform structure, excellent comprehensive performance and customized shape and high energy density is prepared.
The following examples further describe the embodiments of the present invention, but should not be construed as limiting the invention. The skilled person can reasonably design the technical solution with reference to the embodiments, and can also obtain the results of the present invention.
The first embodiment is as follows:
(1) Preparation of the polymer dispersion: adding dried and weighed polyvinylidene fluoride (PVDF) micro-nano aggregate powder into a Propylene Carbonate (PC) solvent, stirring for about 10-20 min by a high-speed stirrer, and uniformly dispersing polyvinylidene fluoride (PVDF) in the Propylene Carbonate (PC) solvent in a form of nanoparticles (100-300 nm) to obtain a nano dispersion liquid with the mass fraction of 5%.
(2) Preparation of composite electrode slurry (functional slurry): adding a certain amount of the obtained polymer dispersion liquid into weighed nickel cobalt lithium manganate (NCM) or Lithium Cobaltate (LCO) and conductive carbon black, wherein the mass ratio of an active material/a conductive filler/a polymer is 92.
(3) Preparing a composite electrode: coating the obtained uniformly mixed slurry on the surface of an aluminum foil in a certain thickness (about 500 mu m), activating and drying at 100 ℃ for 180min to ensure that the solvent is completely volatilized, fully melting and permeating polyvinylidene fluoride (PVDF) among the components of the electrode to realize effective bonding of the interfaces of the components, obtaining the required composite electrode, and obtaining the electrode plate with a specific shape by using a sheet punching machine for later use.
(4) The electrode plates are assembled and used by a 2032 button cell: the positive electrode piece 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 of 1.
The raw material ratios and activation conditions of the examples and comparative examples are shown in table 1.
Example two:
(1) Preparation of polymer dispersion: adding dried and weighed polyvinylidene fluoride (PVDF) powder into a Propylene Carbonate (PC) solvent, stirring for about 10-20 min with a high-speed stirrer, and dispersing the polyvinylidene fluoride (PVDF) in the Propylene Carbonate (PC) solvent in a nanoparticle form to obtain a nano dispersion liquid with the mass dispersion of 5%.
(2) Preparation of composite slurry (functional slurry): adding a certain amount of the obtained polymer dispersion liquid into weighed nickel cobalt lithium manganate (NCM) or Lithium Cobaltate (LCO) and conductive carbon black, wherein the mass ratio of an active material/a conductive filler/a polymer is 94.
(3) Preparing a composite electrode: coating the obtained uniformly mixed slurry on the surface of an aluminum foil in a certain thickness (about 500 mu m), activating and drying at 120 ℃ for 120min to ensure that the solvent is completely volatilized, polyvinylidene fluoride (PVDF) is fully melted and permeates among the components of the electrode to realize effective bonding of the interfaces of the components, obtaining the required composite electrode, and obtaining the electrode plate with a specific shape by using a sheet punching machine for later use.
(4) The electrode plates are assembled and used by a 2032 button cell: the positive electrode piece 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 of 1.
Example three:
(1) Preparation of polymer dispersion: adding dried and weighed polyvinylidene fluoride (PVDF) into a Propylene Carbonate (PC) solvent, stirring for about 10-20 min with a high-speed stirrer, and dispersing the polyvinylidene fluoride (PVDF) in the Propylene Carbonate (PC) solvent in a nanoparticle form to obtain a nano dispersion liquid with the mass dispersion of 5%.
(2) Preparation of composite slurry (functional slurry): adding a certain amount of the obtained polymer dispersion liquid into weighed nickel cobalt lithium manganate (NCM) or Lithium Cobaltate (LCO) and conductive carbon black, wherein the mass ratio of an active material/a conductive filler/a polymer is 93;
(3) Preparing a composite electrode: coating the obtained uniformly mixed slurry on the surface of an aluminum foil in a certain thickness (about 500 mu m), activating and drying at 140 ℃ for 60min to ensure that the solvent is completely volatilized, polyvinylidene fluoride (PVDF) is fully melted and permeates among the electrode components to realize effective bonding of the interfaces of the electrode components, obtaining a required composite electrode, and obtaining an electrode plate with a specific shape by using a sheet punching machine for later use;
(4) The electrode plates are assembled and used by a 2032 button cell: the positive electrode piece 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 of 1.
Example four:
(1) Preparation of polymer dispersion: adding dried and weighed polyvinylidene fluoride (PVDF) into a Propylene Carbonate (PC) solvent, stirring for about 10-20 min with a high-speed stirrer, and dispersing the polyvinylidene fluoride (PVDF) in the Propylene Carbonate (PC) solvent in a nanoparticle form to obtain a nano dispersion liquid with the mass dispersion of 20%.
(2) Preparation of composite slurry (functional slurry): adding a certain amount of the obtained polymer dispersion liquid into weighed nickel cobalt lithium manganate (NCM) or Lithium Cobaltate (LCO) and conductive carbon black, wherein the mass ratio of an active material/a conductive filler/a polymer is 85.
(3) Injecting PVDF nano-particle-based 'ink' into the injection tube, pushing the injection tube to the foremost end of the injection tube, simultaneously discharging gas in the ink, fixing the injection tube on a movable arm of a 3D printer after a nozzle and a piston are installed, and connecting the injection tube with a gas flow system to enable the whole injection tube to be in a closed state.
(4) The method comprises the steps of inputting a pre-designed program comprising the setting of a printing pattern and the moving speed (namely the printing speed) of a nozzle by using a control panel, adjusting air pressure, introducing gas, starting the printing program to print, and extruding ink in an injection tube at a constant speed under the pushing of constant-speed air flow.
(5) And finally, activating and drying the extruded electrode at 160 ℃ for 30min to ensure that the solvent is completely volatilized, and polyvinylidene fluoride (PVDF) is fully melted and permeates into the components of the electrode to realize effective bonding of the interfaces of the PVDF and the PVDF.
Example five:
(1) Preparation of polymer dispersion: adding dried and weighed polyvinylidene fluoride (PVDF) into a Propylene Carbonate (PC) solvent, stirring for about 10-20 min with a high-speed stirrer, and dispersing the polyvinylidene fluoride (PVDF) in the Propylene Carbonate (PC) solvent in a nanoparticle form to obtain a nano dispersion liquid with the mass dispersion of 5%.
(2) Preparation of composite slurry (functional slurry): adding a certain amount of the obtained polymer dispersion liquid into weighed nickel cobalt lithium manganate (NCM) or Lithium Cobaltate (LCO) and conductive carbon black, wherein the mass ratio of an active material/a conductive filler/a 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: and (3) coating the uniformly mixed slurry on the surface of an aluminum foil in a certain thickness (about 500 mu m), and activating at 180 ℃ for 20min to ensure that the solvent is completely volatilized to obtain the required composite electrode.
Example six:
(1) Preparation of the polymer dispersion: adding dried and weighed polyvinylidene fluoride (PVDF) into a Propylene Carbonate (PC) solvent, stirring for about 10-20 min with a high-speed stirrer, and dispersing the polyvinylidene fluoride (PVDF) in the Propylene Carbonate (PC) solvent in a nanoparticle form to obtain a nano dispersion liquid with the mass dispersion of 5%.
(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 an 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: and (3) coating the uniformly mixed slurry on the surface of the copper foil in a certain thickness (about 500 micrometers), and activating at 180 ℃ for 20min to ensure that the solvent is completely volatilized to obtain the required composite electrode.
Example seven:
(1) Preparation of the polymer dispersion: adding dried and weighed polyvinylidene fluoride (PVDF) into an Ethylene Carbonate (EC) solvent, stirring for about 10-20 min with a high-speed stirrer, and dispersing the polyvinylidene fluoride (PVDF) in the propylene carbonate (EC) solvent in a form of nanoparticles to obtain a nano dispersion liquid with the mass dispersion of 5%.
(2) Preparing conductive slurry: adding a certain amount of the polymer dispersion liquid obtained above to weighed conductive carbon black, wherein: the mass ratio of the conductive filler to the polymer is 1; and then coating the uniformly mixed conductive slurry on the surface of an aluminum foil in a certain thickness (about 500 micrometers), drying at 60 ℃ for 300min to ensure that the solvent is completely volatilized, and observing the distribution state of the PVDF nano particles in the conductive agent.
Comparative example one:
(1) Preparing a polyvinylidene fluoride solution: dissolving dried and weighed polyvinylidene fluoride (PVDF) in N, N-Dimethylformamide (DMF), stirring for 2 hours at normal temperature along with magnetic stirring to obtain a uniform polyvinylidene fluoride solution with the mass fraction of 5%;
(2) Preparing composite slurry: adding a certain amount of the obtained solution into weighed nickel cobalt lithium manganate (NCM) or Lithium Cobaltate (LCO) and conductive carbon black, wherein the mass ratio of an active material/a conductive filler/a polymer is (4);
(3) Preparing a composite electrode: coating the obtained uniformly mixed slurry on the surface of an aluminum foil in a certain thickness (about 500 micrometers), drying at 160 ℃ for 30min to ensure that the solvent is completely volatilized to obtain a required composite electrode, and obtaining an electrode slice with a specific shape by using a sheet punching machine for later use;
(4) Assembling 2032 button cells on the electrode plates for use: the positive pole piece 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.
Comparative example two:
(1) Preparing a polyvinylidene fluoride solution: dissolving dried and weighed polyvinylidene fluoride (PVDF) in N-methylpyrrolidone (NMP), stirring for 2 hours at normal temperature along with magnetic stirring to obtain a uniform polyvinylidene fluoride solution with the mass fraction of 5%;
(2) Preparing composite slurry: adding a certain amount of the obtained solution into weighed nickel cobalt lithium manganate (NCM) or Lithium Cobaltate (LCO) and conductive carbon black, wherein the mass ratio of an active material/a conductive filler/a polymer is (4);
(3) Preparing a composite electrode: coating the obtained uniformly mixed slurry on the surface of an aluminum foil in a certain thickness (about 500 micrometers), drying at 160 ℃ for 30min to ensure that the solvent is completely volatilized to obtain a required composite electrode, and obtaining an electrode slice with a specific shape by using a sheet punching machine for later use;
(4) The electrode plates are assembled and used by a 2032 button cell: the positive electrode piece 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 of 1.
Comparative example three:
(1) Preparing a polyvinylidene fluoride solution: dissolving dried and weighed polyvinylidene fluoride (PVDF) in N, N-Dimethylformamide (DMF), stirring for 2 hours at normal temperature along with magnetic stirring to obtain a uniform polyvinylidene fluoride solution with the mass fraction of 5%;
(2) Preparing composite slurry: adding a certain amount of the obtained solution into weighed nickel cobalt lithium manganate (NCM) or Lithium Cobaltate (LCO) and conductive carbon black, wherein the mass ratio of an active material/a conductive filler/a polymer is (94);
(3) Preparing a composite electrode: coating the obtained uniformly mixed slurry on the surface of an aluminum foil in a certain thickness (about 500 mu m), drying at 160 ℃ for 30min to ensure that the solvent is completely volatilized to obtain a required composite electrode, and obtaining an electrode slice with a specific shape by using a sheet punching machine for later use;
(4) The electrode plates are assembled and used by a 2032 button cell: the positive electrode piece 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 of 1.
Comparative example four:
(1) Preparing a polyvinylidene fluoride solution: dissolving dried and weighed polyvinylidene fluoride (PVDF) in N-methylpyrrolidone (NMP), stirring for 2 hours at normal temperature along with magnetic stirring to obtain a uniform polyvinylidene fluoride solution with the mass fraction of 5%;
(2) Preparing composite slurry: adding a certain amount of the obtained solution into weighed nickel cobalt lithium manganate (NCM) or Lithium Cobaltate (LCO) and conductive carbon black, wherein the mass ratio of an active material/a conductive filler/a polymer is 94;
(3) Preparing a composite electrode: coating the obtained uniformly mixed slurry on the surface of an aluminum foil in a certain thickness (about 500 mu m), drying at 160 ℃ for 30min to ensure that the solvent is completely volatilized to obtain a required composite electrode, and obtaining an electrode slice with a specific shape by using a sheet punching machine for later use;
(4) The electrode plates are assembled and used by a 2032 button cell: the positive pole piece 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.
Comparative example five:
(1) Preparation of polymer dispersion: adding dried and weighed polyvinylidene fluoride (PVDF) into a Propylene Carbonate (PC) solvent, stirring for about 10-20 min with a high-speed stirrer, and dispersing the polyvinylidene fluoride (PVDF) in the Propylene Carbonate (PC) solvent in a nanoparticle form to obtain a nano dispersion liquid with the mass dispersion of 5%.
(2) Preparation of composite slurry (functional slurry): adding a certain amount of the obtained polymer dispersion liquid into weighed nickel cobalt lithium manganate (NCM) or Lithium Cobaltate (LCO) and conductive carbon black, wherein the mass ratio of an active material/a conductive filler/a 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: and (3) coating the uniformly mixed slurry on the surface of an aluminum foil in a certain thickness (about 500 mu m), and drying at 60 ℃ for 300min to ensure that the solvent is completely volatilized to obtain the required composite electrode.
Comparative example six:
(1) Preparation of polymer dispersion: adding dried and weighed polyvinylidene fluoride (PVDF) into a Propylene Carbonate (PC) solvent, stirring for about 10-20 min with a high-speed stirrer, and dispersing the polyvinylidene fluoride (PVDF) in the Propylene Carbonate (PC) solvent in a nanoparticle form to obtain a nano dispersion liquid with the mass dispersion of 5%.
(2) Preparation of composite slurry (functional slurry): adding a certain amount of the obtained polymer dispersion liquid into weighed nickel cobalt lithium manganate (NCM) or Lithium Cobaltate (LCO) and conductive carbon black, wherein the mass ratio of an active material/a conductive filler/a 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: and (3) coating the uniformly mixed slurry on the surface of an aluminum foil in a certain thickness (about 500 mu m), and drying at 80 ℃ for 200min to ensure that the solvent is completely volatilized to obtain the required composite electrode.
TABLE 1 raw material ratios and activation conditions of examples and comparative examples
And (3) performance testing:
the microstructure of the obtained composite electrode material was observed in the present invention, and fig. 1 is a cross-sectional SEM image of the composite electrode material obtained in example one and comparative example two. From the SEM of fig. 1 (a) and 1 (b), it can be seen that the coating of the conductive filler around the active particles and the uniform dispersion of the conductive filler are more uniform in the electrode prepared by using the binder obtained in example 1, compared with the electrode prepared by using N-methylpyrrolidone (NMP), which is a commercially prepared electrode solvent.
Fig. 2 is a surface SEM image of the composite electrode materials 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 N, N-Dimethylformamide (DMF) as a solvent, and it can be seen that the composite electrode material of comparative example i has poor structural uniformity, has more exposed active materials, and has an imperfect electron transport network construction. Commercial PVDF-NMP solution binder electrodes showed significant polymerization of the conductive agent and many bare active material surfaces forming a non-uniform electron transport network, as shown in fig. 2 b. In contrast, the electrode prepared with the binder (PVDF-PC) obtained in the first embodiment of the present invention showed uniform distribution, as shown in fig. 2 c. Most of the active material surface is covered with the conductive agent. These results indicate that the binder has a very important influence on the micro-environmental structure of the active material.
The electrodes obtained in comparative example one, comparative example two and example one were tested for dry and wet flex resistance. The result is shown in fig. 3, which further indicates that the nano adhesive system obtained in the first embodiment can better bond the active particles and the conductive filler, and more effectively fix the conductive network.
According to the invention, the peel strength tests are carried out on the first comparative example, the second comparative example and the first example, the peel temperature is room temperature, the rate is 500 mu m/s, and as can be seen from figure 4, the peel strength of the first example is obviously higher than that of the first comparative example and the second comparative example, which shows 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, so that the good structural stability and integrity of the whole electrode can be realized.
The rate performance of the button cell prepared by the composite electrode obtained in the third comparative example, the fourth comparative example and the second example is tested (the test temperature is 25 ℃), and the results are shown in fig. 5, and as can be seen from fig. 5, the capacity of the second example at the current density of 0.05C to 1C is much higher than that of the third comparative example and the fourth comparative example, and the advantages of the button cell prepared by the invention can be seen; the construction of the electrode conductive network prepared by the novel adhesive obtained in the embodiment of the invention has higher efficacy, and the good coating of the active particles enables the electron transmission network and the ion transmission channel in the electrode to be more perfect, so that the reaction of the electrode in the charging and discharging process is more synergistic, more sites can participate in the reaction, and the lithium ion transmission is uniform.
The cycling performance of the button cell prepared by the composite electrode obtained in the second and third embodiments is tested, and the result is shown in fig. 6; as can be seen from fig. 6, the ultra-low binder, high loading electrode has very excellent cycling performance. The electrode structure of the dispersive type adhesive is good in uniformity, the active particles are uniformly coated by the conductive filler in a large quantity, the nano adhesive has better bonding capacity and can bear structural damage caused by deformation of the active particles, and the damage to the structure and the consumption of recombination on lithium ions in the deformation process are reduced.
FIG. 7 is a digital photograph of a fourth extruded electrode of an example; as can be seen from fig. 7: high solids, clay-like electrode slurries can be readily prepared using a dispersing binder, the slurries exhibiting typical thixotropic fluid properties. Thus, different shaped electrodes can be extruded as desired by 3D printing, as shown in fig. 7. We prepared electrode fibres of different diameters and the morphology and dimensions of the printed electrode were well maintained after drying thanks to the low stress drying of electrode pastes prepared with dispersed binders.
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 the fifth example, the fifth comparative example and the sixth comparative example. The structure of PVDF nanoparticles evolves at different temperatures. The results show that the PVDF maintains a spherical structure when the temperature is increased from 20 ℃ to 60 ℃. When the temperature was further increased to 80 ℃, the boundaries of the PVDF nanoparticles began to merge together due to the progressive gelation of the outer solvating shell. When the temperature exceeds 100 ℃, the PVDF fusion is accelerated, and finally a strong bond between the PVDF and the conductive agent is achieved. The result shows that in order to ensure the PVDF-PC system nano adhesive to exert the effect, the electrode needs to be dried at the temperature of more than 80 ℃; the PVDF dispersion type adhesive can better bond the active particles and the conductive filler, and can more effectively fix the conductive network.
The invention makes microscopic observation on the six composite electrodes of the examples, and SEM results are shown in figure 9, and the PVDF-PC dispersion type adhesive is found to be applicable to the graphite negative electrode. The conductive agent was uniformly dispersed, most of the active material surface was covered with the conductive agent, and it was observed that strong interfacial adhesion was achieved between the active material and the conductive agent. These results indicate that the dispersion type binder is also applicable to the preparation of graphite negative electrodes.
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 the dispersion of PVDF-NP; the PVDF nanoparticles are uniformly distributed around the conductive agent. FIG. 11 is a temperature rising rheology curve for a PVDF-EC dispersion, showing that the PVDF-EC dispersion undergoes a distinct gelation transition stage. The result shows that the PVDF-EC nano adhesive system can realize the adhesion among the components of the electrode through the activation of 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 all such modifications and alterations should fall within the scope of the invention.
Claims (10)
1. The polymer micro-nano binder is characterized by being a mixed system of the existing polymer binder and a solvent, wherein the solvent meets the following requirements: a temperature of < 60 ℃, which is a non-solvent for the polymeric binder but is capable of forming a uniform and stable sol or suspension dispersion with said existing polymeric binder; a temperature > 60 ℃, which is capable of swelling or dissolving the existing polymeric binder.
2. The polymer micro-nano binder as claimed in claim 1, wherein the solvent comprises at least one of propylene carbonate or propylene carbonate;
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%;
further, the polymer micro-nano binder is in a form comprising: at least one of a dispersion of polymer nanoparticles, a sol system of polymer nanoparticles, a dispersion of polymer microparticles, a dispersion of polymer nanoplatelets, a dispersion of polymer microflakes, a dispersion of polymer nanofibers, or a dispersion of polymer microfibers.
3. The polymer micro-nano binder as claimed in claim 1 or 2, wherein the existing polymer binder comprises at least one of polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyethylene oxide, polyethylene glycol, polyvinylidene fluoride, polyvinyl acetate, polytetrafluoroethylene, poly (lactic acid) with a left-hand side, polymethyl methacrylate, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, polycarbonate, polyvinyl amide, polyimide, sodium carboxymethyl cellulose, styrene butadiene rubber, polyacrylonitrile, poly (4-methacrylic acid-2, 6-tetramethylpiperidine-1-nitroxide radical, polyvinylpyrrolidone, poly (3, 4-ethylenedioxythiophene) or poly (styrenesulfonic acid);
further, the solvent comprises at least one of the following solvents in addition to propylene carbonate or propylene carbonate: dimethylacetamide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, dichloromethane, acetone, dimethyl sulfoxide, acetonitrile, toluene, carbon tetrachloride, cyclohexane, carbonates, alcohols, ketones, ethers, glycerol or deionized water.
4. The preparation method of the polymer micro-nano binder according to any one of claims 1 to 3, characterized by comprising the following steps: 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 the temperature of 0-60 ℃ to obtain the polymer micro-nano binder;
further, the shearing speed is more than or equal to 100s -1 (ii) a The time of high-speed shearing or ultrasonic dispersion is 1-30 minutes.
5. The polymer micro-nano binder of any one of claims 1 to 3 is used for preparing electrode slurry, a positive plate, a negative plate, a lithium ion battery, a sodium ion battery, a super capacitor or a lithium metal battery.
6. The use method of the polymer micro-nano binder according to any one of claims 1 to 3, characterized in that the use method comprises the following steps: adding the polymer micro-nano binder into an anode or cathode active material and a conductive filler, and mechanically mixing and dispersing uniformly to obtain electrode slurry; preparing a wet electrode blank with a uniform structure and a customizable shape from the obtained electrode slurry by the conventional processing method; heating the wet electrode blank to 100-200 ℃ to fully swell, melt and permeate the polymer micro-nano adhesive in the blank, thereby realizing the bonding of all components and the volatilization of the solvent, and further performing roll-pressing treatment to prepare an electrode plate;
further, the existing processing modes comprise blade coating, extrusion, injection or hot pressing;
further, in the using method, the temperature is increased to 100-200 ℃ for treatment for 3 min-10 h, so that the polymer micro-nano structure in the polymer micro-nano binder is swelled, gelatinized, dissolved or melted in the solvent, and thus the polymer micro-nano binder is fully permeated and the component adhesion is realized.
7. The electrode slurry is characterized by being prepared by the following method: adding the polymer micro-nano binder of any one of claims 1 to 3 into the positive or negative active material and the conductive filler, and uniformly mixing to obtain uniformly dispersed electrode slurry.
8. The electrode slurry according to claim 7, wherein the ratio of each component is as follows: 1 to 99 parts of positive electrode active material or negative electrode active material, 0.5 to 50 parts of conductive filler and 0.1 to 50 parts of polymer binder;
further, the method for uniformly mixing comprises the following steps: premixing the polymer dispersion system with an active material and a conductive filler, and then dispersing and mixing by adopting a grinding machine, a mechanical stirring machine, 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%;
further, the obtained electrode paste has plasticity;
preferably, the electrode slurry is clay-like electrode slurry, and the shear yield stress of the electrode slurry is between 100 and 3000 Pa;
further, the electrode slurry can be shaped by an extruder, an injection machine or a hot press to obtain a blank, and then the blank is activated and dried to finally obtain an electrode with a customized shape;
further, the electrode paste can realize 3D printing and forming of the electrode: the electrode slurry is filled into a storage tank of a 3D printer head, and the electrode slurry is extruded out of a current collector substrate at a constant speed by the aid of pushing of the 3D printer and computer control; then heating the printed electrode to 100-200 ℃ to realize effective bonding and shaping of each component, and finally obtaining the electrode with a customized shape;
further, the positive electrode active material includes: lithium iron phosphate, lithium manganese phosphate, lithium nickel phosphate, lithium cobalt phosphate, lithium iron manganese 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 materials, tin and alloy materials thereof;
further, the conductive filler is at least one of conductive carbon black, conductive graphite, carbon nanofiber, carbon nanotube or graphene.
9. A preparation method of an electrode is characterized by comprising the following steps: adding the polymer micro-nano binder of any one of claims 1 to 3 into a positive electrode or negative electrode active material and a conductive filler, and uniformly mixing to obtain electrode slurry; preparing an electrode blank with a uniform structure and a customizable shape from the obtained electrode slurry by the conventional processing method; heating the electrode blank to 100-200 ℃ to fully melt and permeate the polymer micro-nano particles in the binder, thereby realizing the binding of the components and ensuring the volatilization of the solvent, and further preparing the electrode plate;
further, 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 solvent, and dispersing by using a high-speed shearing machine or an ultrasonic dispersion machine to obtain a uniform polymer micro-nano binder;
2) Preparing uniform electrode slurry: fully premixing a positive electrode active material or a negative electrode active material and a conductive filler, adding the polymer micro-nano adhesive into the mixture, and mixing by adopting grinding, mechanical mixing or a ball mill until uniform electrode slurry is obtained;
3) Processing electrode slurry: coating the obtained electrode slurry on the surface of a positive electrode or negative electrode current collector, heating to 100-200 ℃, treating for 3 min-10 h to swell or dissolve the polymer micro-nano adhesive, activating the adhesive while volatilizing the solvent, and finally drying and rolling to obtain an electrode with a uniform structure;
further, in the step 2), the proportion of each component is as follows: 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, in the step 2), uniformly mixing by adopting a mortar, a ball mill or a double-screw extruder to obtain electrode slurry;
further, in the step 3), the current collector is an aluminum foil, a copper foil, an aluminum wire or a copper wire;
further, in the step 3), the obtained electrode is dried and then is subjected to rolling treatment to obtain the positive and negative pole pieces 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.
10. An electrode produced by the production method according to claim 9.
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