CN114989344B - Vinylidene fluoride copolymer, preparation method thereof and application thereof in lithium ion battery - Google Patents
Vinylidene fluoride copolymer, preparation method thereof and application thereof in lithium ion battery Download PDFInfo
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- CN114989344B CN114989344B CN202210670281.6A CN202210670281A CN114989344B CN 114989344 B CN114989344 B CN 114989344B CN 202210670281 A CN202210670281 A CN 202210670281A CN 114989344 B CN114989344 B CN 114989344B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
- C08F214/225—Vinylidene fluoride with non-fluorinated comonomers
- C08F214/227—Vinylidene fluoride with non-fluorinated comonomers with non-fluorinated vinyl ethers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a vinylidene fluoride copolymer, a preparation method thereof and application thereof in a lithium ion battery, wherein the vinylidene fluoride copolymer comprises the following comonomer components: (a) vinylidene fluoride; (b) The added amount of the allyl-containing pyranose derivative accounts for 0.2 to 12 percent of the mass of the vinylidene fluoride; (c) The addition amount of the unsaturated carboxylic acid accounts for 0.1-8% of the mass of the vinylidene fluoride. The vinylidene fluoride copolymer is prepared by using a nanoparticle dispersion liquid in the polymerization process, and has ultrahigh molecular weight and excellent bonding strength; and the method is favorable for reducing the distribution proportion of large particles of more than 150 mu m and improving the solubility of the product in polar solvents, so that the method is particularly suitable for being used as a binder and applied to electrodes of lithium ion batteries.
Description
Technical Field
The present invention relates to a vinylidene fluoride copolymer and a method for the preparation thereof, to a composition for forming an electrode from the vinylidene fluoride copolymer, and to the use of the vinylidene fluoride copolymer as a binder in an electrode composition and to the use of the electrode-forming composition as an electrode in a lithium ion battery.
Background
Polyvinylidene fluoride (PVDF) is a fluorine-containing polymer obtained by homopolymerizing vinylidene fluoride or copolymerizing it with a small amount of other monomers. Among fluoropolymers, polyvinylidene fluoride is the second largest class of fluorine-containing polymers next to Polytetrafluoroethylene (PTFE). Polyvinylidene fluoride has excellent chemical stability, corrosion resistance, weather resistance, high temperature resistance, ultraviolet radiation resistance, piezoelectricity, dielectric property, adhesiveness and other special properties, and is widely applied to the fields of fluorocarbon coating, lithium battery binder and diaphragm, solar back plate, hollow fiber membrane, petrochemical products and the like.
In recent years, along with the popularity of electric automobiles, not only is the demand of lithium batteries rapidly increased, but also the performance of lithium batteries is gradually increased, and lithium battery technologies represented by high capacitance, high energy density and long service life become the main development direction, and in the process, lithium battery materials play a crucial role, and PVDF is one of key materials. Currently, PVDF occupies more than 90% of the positive electrode binder of lithium batteries. In the positive electrode composition of the lithium battery, PVDF is used as a binder to bond components such as conductive substances, active electrode materials and the like on a current collector, so that how to ensure that the positive electrode materials are bonded more compactly and more efficiently under the condition that the adding amount of PVDF is as small as possible, and meanwhile, the PVDF is durable and does not flake off, and the improvement of the quality of PVDF products such as molecular weight, bonding strength, particle size distribution and the like is important.
The patent CN104725544B takes modified acrylic esters as comonomers to prepare a high-cohesiveness vinylidene fluoride copolymer which is used as a lithium ion battery binder, wherein the weight average molecular weight of the copolymer is 30-120 ten thousand g/mol, the molecular weight distribution index is 1.6-5, and the cohesive strength is 1-10N/m. Patent 105754027B discloses a vinylidene fluoride polymer suitable for a lithium battery binder, wherein the weight average molecular weight of the polymer is 30-250 ten thousand g/mol, the molecular weight distribution index is 1.6-5, and the binding strength is more than 2.0N/m. These proprietary techniques all help to improve the product properties of PVDF, especially the molecular weight and bond strength of the polymer; however, it is necessary to enhance polymerization stability and particle size control, especially to prevent coalescence of droplets during polymerization to form large particle products of 150 μm or more, which leads to destabilization of the polymerization system to obtain no product, and to difficulty in dissolution of the large particle products, which affects uniformity of homogenization and coating in the downstream electrode preparation process.
Patent CN110114375a prepares a vinylidene fluoride polymer in an aqueous suspension medium containing at least one polysaccharide derivative for improved control of the reaction, in particular for reducing the deviation of the reaction temperature from a set temperature. However, the technique of this patent does not guarantee a sufficient stability of the suspension system, and in particular the large particle distribution above 150 μm may be more; furthermore, the polysaccharide derivatives used in this patent do not participate in the polymerization reaction themselves and have very limited impact on molecular weight and bond strength.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a vinylidene fluoride copolymer, which is prepared by copolymerizing a pyranose derivative containing an allyl group with vinylidene fluoride and an unsaturated carboxylic acid as a comonomer, and which has an ultrahigh molecular weight and a suitable solution viscosity.
Another object of the present invention is to provide a method for preparing the above vinylidene fluoride copolymer, wherein the stability of the polymerization system is enhanced by adding a nanoparticle dispersion liquid during the preparation process, and the coalescence of droplets is prevented to produce a large amount of coarse particle products, thereby effectively reducing the distribution ratio of large particles of more than 150 μm.
It is still another object of the present invention to provide an electrode composition comprising the above-mentioned vinylidene fluoride copolymer, wherein the use of the vinylidene fluoride copolymer as a binder in the electrode composition, since the above-mentioned vinylidene fluoride copolymer contains a large amount of pyran ring and hydroxyl polar groups while having an extremely low large particle distribution ratio, it is easily dissolved in a polar solvent such as N-methylpyrrolidone (NMP), solving the problem of the solubility of PVDF, thereby improving the uniformity of the electrode preparation homogenate and coating process; the vinylidene fluoride copolymer has excellent bonding strength, so that the formed electrode composition is more compact and efficient in bonding, does not peel off for a long time, and is durable.
A final object of the invention is the use of the above-described electrode-forming composition as an electrode in a lithium ion battery.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
in one aspect, the present invention provides a vinylidene fluoride copolymer having the following comonomer composition:
(a) Vinylidene fluoride;
(b) The allyl-containing pyranose derivative accounts for 0.2-12% of the mass of the vinylidene fluoride, and preferably 0.2-4%;
(c) The unsaturated carboxylic acid is added in an amount of 0.1 to 8% by mass, preferably 0.1 to 2% by mass, based on the vinylidene fluoride.
In the invention, the allyl-containing pyranose derivative is selected from compounds with the following two spatial conformations of alpha and beta, and the structures of the compounds are respectively shown as a formula (1 a) and a formula (1 b):
wherein R is 1 、R 2 、R 3 、R 4 、R 5 One of which is allyl and the other four are each independently selected from a hydrogen atom, a hydrocarbon group or a hydrocarbon group containing at least one hydroxyl group, wherein the hydrocarbon group is preferably a C1-C12 hydrocarbon group;
preferably, the allyl-containing pyranose derivative contains at least 3, preferably 4 hydroxyl groups;
more preferably, the allyl-containing pyranose derivative is selected from allyl-alpha-D-glucopyranoside and/or allyl-beta-D-glucopyranoside, and the structures are respectively shown in the following formula (2) and formula (3):
in theory, it is within the scope of the present invention to provide allyl-containing pyranose derivatives that meet the above structural characteristics. In particular, in a preferred embodiment, the allyl-containing pyranose derivative is selected from allyl- α -D-glucopyranoside or allyl- β -D-glucopyranoside, which have the same formula but slightly differ in molecular conformation, and are substantially equivalent in terms of implementation effect and are not significantly different. The addition amount is 0.2-12% of vinylidene fluoride mass, preferably 0.2-4%.
In the present invention, the allyl-containing pyranose derivative is one of the key comonomers, and the experiment of the present invention shows that the allyl-containing pyranose derivative has a special molecular structure and an effect of improving the performance of the vinylidene fluoride copolymer. The allyl-containing pyranose derivative shown in formula 1 is a monosaccharide, belongs to a small molecular compound, and is polymerized into a vinylidene fluoride polymer chain as a comonomer, so that the solubility of the product in a polar solvent can be improved, and the bonding strength of the electrode composition can be improved. The pyranose derivative adopted by the invention firstly has an allyl structure, can slowly participate in polymerization reaction as a copolymerization monomer, is relatively uniformly distributed in a polyvinylidene fluoride molecular chain skeleton, and properly adjusts the crystallinity of the copolymer. Secondly, the pyran ring structure with polyhydroxy is a carbon-oxygen hexacyclic ring formed by one oxygen heteroatom and five carbon atoms, has stable space conformation and shows very strong polarity and adhesiveness, so that on one hand, the polyvinylidene fluoride copolymer is endowed with good solubility in polar solvents, the problem of the solubility of polyvinylidene fluoride in a practical application link is improved, and the pyran ring structure is embodied in the invention, and is rapidly and uniformly dissolved in an N-methylpyrrolidone (NMP) solvent within 1 hour; on the other hand, the polyvinylidene fluoride copolymer containing pyran ring repeating units has obviously improved bonding strength, which is important to the technology of the invention, and the polyvinylidene fluoride with high bonding strength is used as a bonding agent, so that the electrode material composition can be bonded more compactly and more efficiently when being applied to a lithium ion battery, the efficiency of fully releasing an active electrode material is facilitated, the electrode material is prevented from cracking, and the service life of the battery is prolonged.
In the present invention, the unsaturated carboxylic acid is a carboxylic acid compound having a polymerizable carbon-carbon double bond, and is selected from any one or a combination of at least two of acrylic acid, crotonic acid, maleic acid, itaconic acid, and cinnamic acid, preferably itaconic acid.
In the preparation process of vinylidene fluoride polymer, the addition of acrylic acid comonomer to improve the product properties is a well known technical solution in the prior art. However, the present invention is different in that the unsaturated carboxylic acid contains not only acrylic acid but also one or more selected from crotonic acid, maleic acid, itaconic acid, cinnamic acid, of which itaconic acid is preferred. Experiments show that itaconic acid has more obvious effect in improving the performance of vinylidene fluoride polymer products, and is a preferable scheme of the invention. The unsaturated carboxylic acid is added in an amount of 0.1 to 8% by mass, preferably 0.1 to 2% by mass, based on the vinylidene fluoride.
In the present invention, the comonomer, optionally including other fluorovinyl monomers; preferably, the addition amount of the other fluorine-containing vinyl monomer is 0 to 3.8% by mass of vinylidene fluoride.
Wherein the fluorine-containing vinyl monomer comprises any one or a combination of at least two of trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoromethyl vinyl ether and perfluoropropyl vinyl ether.
In the invention, the vinylidene fluoride copolymer is prepared by polymerization reaction of a comonomer with water as a dispersion medium, and meanwhile, a nanoparticle dispersion liquid is added into the water. Experiments show that the comonomer composed of the invention can control the stability of a polymerization system by adding a nanoparticle dispersion liquid in the polymerization process, and greatly reduce the large particle distribution ratio of more than 150 mu m.
Preferably, the nanoparticle dispersion has a nanoparticle size of 2-200nm, preferably 5-50nm; the solids content is 5-50wt%, preferably 10-35wt%;
preferably, the nanoparticle dispersion is an aqueous dispersion of inorganic oxide nanoparticles; more preferably, the inorganic oxide nanoparticles are selected from any one or a combination of at least two of nano silica, nano titania, nano alumina, nano zinc oxide, nano zirconia, preferably nano silica;
preferably, the nanoparticle dispersion is an aqueous dispersion of nanosilica, e.g. winningW1714。
Preferably, the nanoparticle dispersion is added in an amount of 0.3-3% by mass of the comonomer (a) vinylidene fluoride.
The weight average molecular weight of the vinylidene fluoride copolymer is 100-260 ten thousand g/mol measured by Gel Permeation Chromatograph (GPC), and the molecular weight distribution index is 1.9-4.2.
The vinylidene fluoride copolymer of the invention has a solution viscosity of 6500-14000mPa.s of N-methylpyrrolidone (NMP) with a mass fraction of 7.2% as measured by a digital viscometer.
According to the vinylidene fluoride copolymer disclosed by the invention, the particle size distribution ratio of the vinylidene fluoride copolymer, which is measured by an electric vibrating screen, is less than 3.0%, wherein the particle size of the vinylidene fluoride copolymer is more than or equal to 150 mu m.
On the one hand, the invention also provides a preparation method of the vinylidene fluoride copolymer, which is prepared by polymerization reaction of a comonomer with water as a dispersion medium, and particularly adopts a suspension polymerization method, and is characterized in that a nanoparticle dispersion liquid is added into the water, and the preparation method comprises the following steps: and mixing vinylidene fluoride, a pyranose derivative containing allyl, unsaturated carboxylic acid and water, and simultaneously adding nanoparticle dispersion liquid to perform suspension polymerization reaction to prepare the vinylidene fluoride copolymer.
In the present invention, the water is added in an amount of 100 to 450% by mass, preferably 100 to 260% by mass, based on the comonomer (a) vinylidene fluoride.
In the invention, the allyl-containing pyranose derivative and the unsaturated carboxylic acid two comonomers are fed in a batch-wise and intermittent manner, preferably in the form of an aqueous solution with the concentration of 5-30 wt%; the feeding mode can make the allyl-containing pyranose derivative and unsaturated carboxylic acid play a role as far as possible and uniformly distribute into the vinylidene fluoride polymer chain;
preferably, the charging modes adopted by the allyl-containing pyranose derivative and the unsaturated carboxylic acid two comonomers are specifically as follows: the first feeding is that 10-30% of monomer mass is added before the reaction starts, the residual monomer is added into the reaction system for 3-5 times at intervals of 30-60min, preferably 50min after the reaction starts, and preferably, the allyl-containing pyranose derivative and unsaturated carboxylic acid added each time are 5-35% of the total mass of the monomers respectively; preferably, the residual monomer is added into the reaction system in 3-5 times of equal mass after the polymerization reaction starts; preferably, the suspension polymerization is continued for 1 to 3 hours after the last addition.
In the present invention, the suspension polymerization is carried out at a temperature of 45 to 120℃and preferably 45 to 90 ℃.
In the invention, the suspension polymerization reaction is carried out under the reaction pressure of 5-15MpaA; in the invention, the reaction pressure is controlled by the passing amount of the vinylidene fluoride, the vinylidene fluoride monomer adopts a continuous feeding mode, a certain amount (for example, 20-80% of the total mass of the vinylidene fluoride) of vinylidene fluoride is firstly passed on to the bottom before the reaction starts, the vinylidene fluoride monomer is continuously passed into the system in the reaction process, and the reaction pressure is maintained at 5-15 Mpa.
In the invention, the suspension polymerization reaction comprises the operation of introducing nitrogen and deoxidizing before the reaction, so that the oxygen content is less than or equal to 10ppm.
In the invention, the suspension polymerization method is characterized in that a nanoparticle dispersion liquid is added into water to stabilize a polymerization reaction system, prevent droplets from coalescing to form large particles or even blocks, and lead to the failure of smooth polymerization process and finally failure of obtaining products; on the other hand, the particle size of the product is more uniform, the distribution is more concentrated, and particularly, the distribution proportion of large particles with the particle size of more than 150 mu m is greatly reduced, thereby being beneficial to the rapid dissolution of the product in the electrode manufacturing link.
In addition, as with other suspension polymerization methods, the preparation raw material of the invention also comprises a dispersing agent, and the dispersing agent is not particularly required, and is of a common type, such as any one or a combination of at least two selected from polyethylene glycol, polyvinyl alcohol, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl methyl cellulose, hydroxyethyl ethyl cellulose, hydroxypropyl methyl cellulose and carboxymethyl cellulose, preferably polyethylene glycol;
preferably, the dispersant is added in an amount of 0.06 to 0.38% by mass based on the mass of the comonomer (a).
In the invention, the suspension polymerization reaction is carried out, the preparation raw material also comprises a chain transfer agent, and the specific requirement is not met, and common types are selected from any one or at least two of dimethyl carbonate, diethyl carbonate, methylethyl carbonate, ethyl acetate, methyl acetate, ethyl propionate, ethanol, n-propanol, isopropanol, acetone, diethyl ether and methyl tertiary butyl ether, preferably diethyl carbonate;
preferably, the chain transfer agent is added in an amount of 0.15 to 0.55% by mass based on the mass of the comonomer (a) vinylidene fluoride.
In the present invention, the suspension polymerization reaction, the preparation raw material further comprises an initiator, and the specific is not particularly required, and common types are, for example, any one or a combination of at least two selected from methyl ethyl ketone peroxide, dibenzoyl peroxide, t-butyl benzoyl peroxide, t-butyl peroxymaleate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, t-amyl peroxypivalate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, diethyl peroxydicarbonate, dicyclohexyl peroxydicarbonate and di-2-ethylhexyl peroxydicarbonate, preferably diisopropyl peroxydicarbonate;
preferably, the initiator is added in an amount of 0.06 to 0.55% by mass based on the mass of the comonomer (a) vinylidene fluoride.
In the present invention, other fluorine-containing vinyl monomers are optionally added during the preparation process.
In the present invention, after the suspension polymerization reaction is completed, the post-treatment processes of recovering unreacted monomers, washing, filtering, drying, etc. are also included, and are not particularly required for the conventional operation in the field, for example, the post-treatment methods adopted in some examples are specifically: stopping polymerization after the pressure is reduced to the atmospheric pressure, recovering unreacted monomers, washing with deionized water until the conductivity of the washing liquid is reduced to below 1 mu S/cm, and finally obtaining a copolymer product through filtration and drying.
In another aspect, the present invention provides an electrode-forming composition comprising the above-described vinylidene fluoride copolymer, in addition to an additive imparting electrical conductivity, a powder electrode material.
Preferably, the invention provides a composition for forming an electrode, which comprises the following components in percentage by mass:
1-6% of vinylidene fluoride copolymer;
1-7% of an additive imparting electrical conductivity;
87-98% of powder electrode material.
Preferably, the additive imparting electrical conductivity is selected from any one or a combination of at least two of carbon black, graphite, aluminum powder, nickel powder, preferably carbon black.
Preferably, the powder electrode material is selected from lithium cobaltate (LiCoO) 2 ) Lithium manganate (LiMn) 2 O 4 ) Lithium nickelate (LiNiO) 2 ) Lithium iron phosphate (LiFePO) 4 ) Any one or a combination of at least two of these.
The electrode-forming composition of the present invention can be used to prepare an electrode material by:
and dissolving the vinylidene fluoride copolymer in a polar organic solvent, adding an additive which gives electric conductivity and a powder electrode material, uniformly mixing to obtain slurry, degassing the slurry for 5-45min by a vacuum deaeration machine, uniformly coating the slurry on an aluminum foil by a bar coater, and finally placing the aluminum foil in a vacuum oven for vacuum drying to remove the solvent to obtain the electrode material.
Preferably, the vacuum drying is carried out at a drying temperature of 60-135 ℃ for 2-10 hours.
Generally, the polar organic solvent mainly comprises acetone, cyclohexanone, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, tetramethyl urea, hexamethylphosphoramide, trimethyl phosphate, triethyl phosphate and the like, and the existing polyvinylidene fluoride is dissolved by the polar organic solvent to have a problem of solubility, while the vinylidene fluoride copolymer has good solubility; preferably, the polar organic solvent used for dissolving the vinylidene fluoride copolymer in the present invention is selected from any one or a combination of at least two of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, dioxane, preferably N-methylpyrrolidone;
the mass concentration of the vinylidene fluoride copolymer dissolved in the polar organic solvent is 2-12%.
In preparing electrode materials, polyvinylidene fluoride is usually required to be formulated into a solution for use, and even if a good solvent of strong polarity is selected, solubility problems such as long dissolution time and even non-uniform dissolution are encountered. The vinylidene fluoride copolymer of the invention not only contains a pyran ring repeating unit with strong polarity, but also has a large number of polar groups such as hydroxyl, carboxyl and the like, and the particle size of the product is uniform, especially the content of large particles which are more than or equal to 150 mu m is extremely low, so that the vinylidene fluoride copolymer shows remarkably improved solubility in polar solvents.
In the invention, the product solubility is measured by preparing a solution of N-methyl pyrrolidone (NMP) and using a 1-hour solubility index, and the vinylidene fluoride copolymer disclosed by the invention can be rapidly dissolved, and the obtained solution is clear and transparent and does not contain gel or solid particles.
In the present invention, in the electrode-forming composition, the vinylidene fluoride copolymer has a use as a binder. The adhesive strength of the vinylidene fluoride copolymers of the invention was >10N/m as determined by the ISO 4624-2016 adhesion pull-off test.
In the present invention, the electrode material prepared from the electrode-forming composition has application as an electrode in a lithium ion battery.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
the invention prepares the vinylidene fluoride copolymer by copolymerizing vinylidene fluoride, a pyranose derivative containing allyl and unsaturated carboxylic acid and using a nanoparticle dispersion liquid in the polymerization process, thereby not only having ultrahigh molecular weight and excellent bonding strength; and is beneficial to reducing the distribution proportion of large particles above 150 mu m and improving the solubility of the product in polar solvents.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to illustrate the present invention further, but are not to be construed as limiting the present invention.
The main raw material source information adopted in the embodiment of the invention is as follows, and other raw materials are obtained through common commercial purchase unless specified otherwise:
vinylidene fluoride: purchased from Shandong China Shenzhou New Material Co., ltd;
itaconic acid, allyl- α -D-glucopyranoside, allyl- β -D-glucopyranoside: purchased from Shanghai Ala Biochemical technologies Co., ltd;
nano silica dispersion: purchased from winning Industrial group, product brandW1714, the size of the nanometer particles is 4-80nm; the solids content was 14% by weight.
The specific test conditions and analysis methods adopted by the main performance indexes of the embodiment of the invention are as follows:
(1) Weight average molecular weight and molecular weight distribution index
Samples were dissolved in N-methylpyrrolidone (NMP) to prepare a 0.1% mass fraction solution, and tested by Gel Permeation Chromatography (GPC) under the following conditions:
0.01mol/L lithium bromide-N-methylpyrrolidone (NMP) solution of the eluent;
a differential refractive RI detector;
polystyrene standard;
the temperature is 40 ℃;
the flow rate is 1.0mL/min;
the sample injection amount is 100 mu L.
(2) Viscosity of solution
The sample was formulated as a 7.2wt% solution of N-methylpyrrolidone (NMP) at 25℃with a digital viscometer 3 # The rotors were tested for solution viscosity.
(3) Particle size distribution
Measuring particle size distribution of sample by using Leachi AS200Digitca electric vibrating screen, weighing about 100g sample, pouring into screen, setting amplitude to 1.0mm, intensity 70%, vibrating for 5min, weighing sample mass of upper layer and lower layer of 150 μm screen, and recording AS m respectively 1 And m 2 The particle size distribution ratio of the particles with the size of more than or equal to 150 mu m is calculated according to the following formula:
(4) Bond strength
The adhesive strength of the samples after preparation of the electrodes was determined in accordance with ISO 4624-2016 (adhesion pull-off test). The electrode preparation process is as follows: a sample of 0.8g PVDF was dissolved in 25g N-methylpyrrolidone (NMP) and 0.85g conductive carbon black and 31.7g lithium iron phosphate (LiFePO) 4 ) And (3) after fully and uniformly mixing, putting the slurry into a vacuum deaeration machine for deaeration treatment for 15min, taking out the slurry, uniformly coating the slurry on an aluminum foil through a bar coater, and finally putting the aluminum foil into a vacuum oven and drying the aluminum foil at 80 ℃ for 8 hours to obtain the electrode slice. And analyzing the bonding strength of the electrode material on the electrode plates by using a tensile machine measuring instrument, and measuring the numerical values of 5 electrode plates to obtain an average value, namely the final bonding strength.
(5) Solubility for 1 hour
15g of the sample and 485g N-methylpyrrolidone (NMP) were weighed accurately, added to a 1000mL beaker, and placed in a polytetrafluoroethylene stirrer with a length of 2cm, the beaker was placed on a magnetic stirrer, stirring was started and timed, and after 1 hour the solubility of the sample was observed, wherein the temperature was controlled to 30℃and the stirring speed was 400r/min.
Example 1
The preparation of the vinylidene fluoride copolymer comprises the following raw materials in parts by weight:
comonomer(s): vinylidene fluoride 4.8Kg, allyl- α -D-glucopyranoside 576g (formulated as an aqueous solution with a concentration of 30 wt%), itaconic acid 4.8g (formulated as an aqueous solution with a concentration of 5 wt.);
win woundW1714 silica dispersion 144g;
deionized water 5Kg;
2.88g of dispersing agent polyvinyl alcohol;
7.2g of chain transfer agent ethyl acetate;
initiator t-butyl peroxypivalate 26.4g.
The method comprises the following steps: 5Kg of the mixture was charged into a 15L autoclaveIonized water, 144g win woundW1714 silica dispersion and 2.88g polyvinyl alcohol, stirring is started, the rotation speed is controlled at 600r/min, nitrogen is introduced to remove oxygen so that the oxygen content is less than or equal to 10ppm, then 1.44Kg vinylidene fluoride (30% added here), 7.2g ethyl acetate, 576g allyl-alpha-D-glucopyranoside aqueous solution (172.8 g, 30% added here) and 9.6g itaconic acid aqueous solution (0.48 g, 10% added here) are added;
heating the system to 50 ℃, continuously introducing vinylidene fluoride monomer to maintain the reaction pressure at 8MPaA, adding 26.4g of tert-butyl peroxypivalate to initiate polymerization, intermittently and batchwise adding the residual allyl-alpha-D-glucopyranoside aqueous solution and the residual itaconic acid aqueous solution in the polymerization process, wherein the allyl-alpha-D-glucopyranoside aqueous solution is added into the reaction system in 5 times at intervals of 50 minutes after the reaction starts, and the itaconic acid aqueous solution is added into the reaction system in 3 times at intervals of 50 minutes after the reaction starts;
and after the last addition of the comonomer, continuing to react for 3 hours, reducing the pressure in the kettle to the atmospheric pressure through degassing, stopping polymerization, recovering unreacted monomers, adding 4.8Kg of total reacted vinylidene fluoride, repeatedly washing the polymer slurry in the kettle with deionized water until the conductivity of the washing liquid is reduced to below 1 mu S/cm, and finally filtering and drying to obtain a finished vinylidene fluoride copolymer product.
Electrode material was prepared using the vinylidene fluoride copolymer of this example:
an electrode-forming composition comprising: 0.8g of vinylidene fluoride copolymer; 0.85g of carbon black as an additive imparting electrical conductivity; powder electrode material lithium iron phosphate (LiFePO 4 )31.7g。
Dissolving vinylidene fluoride copolymer in polar organic solvent N-methyl pyrrolidone (NMP) with mass concentration of 3.1%, and adding carbon black and powder electrode material lithium iron phosphate (LiFePO) 4 ) Uniformly mixing to obtain slurry, degassing the slurry by a vacuum deaeration machine for 15min, and uniformly coating the slurry by a bar coaterAnd (3) spreading the electrode material on an aluminum foil, and finally, placing the aluminum foil in a vacuum oven, and drying the aluminum foil at 80 ℃ in vacuum for 8 hours to remove the solvent to obtain the electrode material. Example 2
The preparation of the vinylidene fluoride copolymer comprises the following raw materials in parts by weight:
comonomer(s): vinylidene fluoride 4.6Kg, allyl- β -D-glucopyranoside 9.2g (formulated as an aqueous solution with a concentration of 5 wt%), acrylic acid 368g (formulated as an aqueous solution with a concentration of 30 wt.);
win wound13.8g of W1714 silica dispersion;
6Kg of deionized water;
17.48g of dispersant hydroxymethyl cellulose;
25.3g of chain transfer agent isopropanol;
2.76g of benzoyl tert-butyl peroxide as an initiator.
The method comprises the following steps: 6Kg deionized water and 13.8g winning wound are added into a 15L high-pressure reaction kettleThe dispersion of W1714 silica and 17.48g of hydroxymethyl cellulose are stirred at 600r/min, nitrogen is introduced to remove oxygen so that the oxygen content is less than or equal to 10ppm, then 2.76Kg of vinylidene fluoride (60% added here), 25.3g of isopropanol, 18.4g of allyl-beta-D-glucopyranoside aqueous solution (0.92 g, 10% added here) and 368g of acrylic acid aqueous solution (110.4 g, 30% added here) are added;
heating the system to 70 ℃, continuously introducing vinylidene fluoride monomer to maintain the reaction pressure at 13MPaA, adding 2.76g of benzoyl tert-butyl peroxide to initiate polymerization, intermittently and batchwise adding the residual allyl-beta-D-glucopyranoside aqueous solution and the residual acrylic acid aqueous solution in the polymerization process, wherein the allyl-beta-D-glucopyranoside aqueous solution is added into the reaction system in 3 times of equal amount every 50min after the reaction starts, and the acrylic acid aqueous solution is added into the reaction system in 5 times of equal amount every 50min after the reaction starts;
and after the last addition of the comonomer, continuing to react for 1 hour, reducing the pressure in the kettle to the atmospheric pressure through degassing, stopping polymerization, recovering unreacted monomers, adding 4.6Kg of total reacted vinylidene fluoride, repeatedly washing the polymer slurry in the kettle with deionized water until the conductivity of the washing liquid is reduced to below 1 mu S/cm, and finally filtering and drying to obtain a finished vinylidene fluoride copolymer product.
Electrode materials were prepared using the vinylidene fluoride copolymer of this example according to the procedure of example 1.
Example 3
The preparation of the vinylidene fluoride copolymer comprises the following raw materials in parts by weight:
comonomer(s): vinylidene fluoride 5Kg, allyl- β -D-glucopyranoside 100g (formulated as 15wt% strength aqueous solution), itaconic acid 50g (formulated as 15wt% strength aqueous solution);
win woundW1714 silica dispersion 100g;
deionized water 5.8Kg;
10g of dispersant polyethylene glycol;
12.5g of chain transfer agent diethyl carbonate;
the initiator diisopropyl peroxydicarbonate 12.5g.
The method comprises the following steps: 5.8Kg deionized water and 100g winning wound are added into a 15L high-pressure reaction kettleW1714 silica dispersion and 10g polyethylene glycol, stirring is started, the rotation speed is controlled at 600r/min, nitrogen is introduced to remove oxygen so that the oxygen content is less than or equal to 10ppm, then 2.5Kg of vinylidene fluoride (50% added here), 12.5g of diethyl carbonate, 133.3g of allyl-beta-D-glucopyranoside aqueous solution (20 g added here, 20%) and 66.7g of itaconic acid aqueous solution (10 g added here, 20%) are added;
heating the system to 60 ℃, continuously introducing vinylidene fluoride monomer to maintain the reaction pressure at 12MPaA, adding 12.5g of diisopropyl peroxydicarbonate to initiate polymerization, intermittently and batchwise adding the residual allyl-beta-D-glucopyranoside aqueous solution and the residual itaconic acid aqueous solution in the polymerization process, wherein the allyl-beta-D-glucopyranoside aqueous solution is added into the reaction system in 4 times at intervals of 50 minutes after the reaction starts, and the itaconic acid aqueous solution is added into the reaction system in 4 times at intervals of 50 minutes after the reaction starts;
and after the last addition of the comonomer, continuing to react for 2 hours, reducing the pressure in the kettle to the atmospheric pressure through degassing, stopping polymerization, recovering unreacted monomers, adding 5Kg of total reacted vinylidene fluoride, repeatedly washing the polymer slurry in the kettle with deionized water until the conductivity of the washing liquid is reduced to below 1 mu S/cm, and finally filtering and drying to obtain a finished vinylidene fluoride copolymer.
Electrode materials were prepared using the vinylidene fluoride copolymer of this example according to the procedure of example 1.
Example 4
A vinylidene fluoride copolymer was prepared as in example 3, except that: the unsaturated carboxylic acid is replaced by itaconic acid with equal mass of acrylic acid, and other conditions are unchanged.
Electrode materials were prepared using the vinylidene fluoride copolymer of this example according to the procedure of example 1.
Example 5
A vinylidene fluoride copolymer was prepared as in example 3, except that: the allyl-beta-D-glucopyranoside is replaced by the allyl-alpha-D-glucopyranoside with equal mass, and other conditions are unchanged.
Electrode materials were prepared using the vinylidene fluoride copolymer of this example according to the procedure of example 1.
Example 6
A vinylidene fluoride copolymer was prepared as in example 3, except that: the total amount of the allyl-beta-D-glucopyranoside aqueous solution is changed from 667g to 500g, and other conditions are unchanged.
Electrode materials were prepared using the vinylidene fluoride copolymer of this example according to the procedure of example 1.
Example 7
A vinylidene fluoride copolymer was prepared as in example 3, except that: will win the creationThe amount of the W1714 silica dispersion was changed from 100g to 75g, and the other conditions were unchanged. Electrode materials were prepared using the vinylidene fluoride copolymer of this example according to the procedure of example 1.
Example 8
A vinylidene fluoride copolymer was prepared as in example 3, except that: the total amount of the allyl-beta-D-glucopyranoside aqueous solution is changed from 667g to 500g, and meanwhile, the winning is createdThe amount of the W1714 silica dispersion was changed from 100g to 75g, and the other conditions were unchanged.
Electrode materials were prepared using the vinylidene fluoride copolymer of this example according to the procedure of example 1.
Comparative example 1
A vinylidene fluoride copolymer was prepared as in example 3, except that: the allyl-beta-D-glucopyranoside is replaced by the same amount of deionized water, and other conditions are unchanged.
Electrode materials were prepared using the vinylidene fluoride copolymer of this comparative example according to the method of example 1.
Comparative example 2
A vinylidene fluoride copolymer was prepared as in example 3, except that: the allyl-beta-D-glucopyranoside is replaced by equal amount of hydroxypropyl methylcellulose, and other conditions are unchanged.
Electrode materials were prepared using the vinylidene fluoride copolymer of this comparative example according to the method of example 1.
Comparative example 3
A vinylidene fluoride copolymer was prepared as in example 3, except that: will win the creationW1714 silica dispersionThe liquid was replaced with an equal amount of deionized water, and the other conditions were unchanged.
Electrode materials were prepared using the vinylidene fluoride copolymer of this comparative example according to the method of example 1.
The vinylidene fluoride polymers and electrode materials obtained in each of the examples and comparative examples were analyzed according to the performance test method of the present invention, and the results are shown in table 1.
Table 1 results of product performance tests in examples and comparative examples
As can be seen from the experimental results in Table 1, the examples 1 to 8 according to the present invention have a larger weight average molecular weight, a higher solution viscosity, a larger adhesive strength, and a smaller particle size distribution ratio of 150 μm or more, and a better solubility in 1 hour, as compared with the comparative examples.
In addition, comparison of examples 3 and 4 shows that the experimental effect of itaconic acid is superior to that of acrylic acid; comparison of examples 3 and 5 shows that the experimental effect of using allyl-alpha-D-glucopyranoside is equivalent to that of allyl-beta-D-glucopyranoside; by comparing examples 3 and 6 with examples 7 and 8, the increase of the amount of allyl-beta-D-glucopyranoside is beneficial to increase the weight average molecular weight, the solution viscosity and the bonding strength of the finished product; by comparing examples 3 and 7 with comparative examples 6 and 8, the use amount of the silica dispersion liquid is increased, which is beneficial to increasing the weight average molecular weight, the solution viscosity and the bonding strength of the finished product, and particularly can reduce the particle size distribution proportion of more than or equal to 150 mu m; by comparing examples 3 and 8, it is demonstrated that when the amount of allyl-beta-D-glucopyranoside and silica dispersion are simultaneously increased, the weight average molecular weight, solution viscosity and bonding strength of the final product can be increased, and the particle size distribution ratio of 150 μm or more can be reduced.
Therefore, the technology of the invention can obviously improve the performance of the polyvinylidene fluoride product, so that the obtained vinylidene fluoride copolymer is particularly suitable for being used as a binder and applied to the electrode of a lithium ion battery.
Claims (37)
1. A vinylidene fluoride copolymer characterized by the following comonomer composition:
(a) Vinylidene fluoride;
(b) An allyl-containing pyranose derivative having at least 3 hydroxyl groups in an amount of 0.2 to 12% by mass relative to vinylidene fluoride;
(c) Unsaturated carboxylic acid, the addition amount of which accounts for 0.1-8% of the mass of the vinylidene fluoride;
the vinylidene fluoride copolymer is prepared by polymerization reaction of a comonomer with water as a dispersion medium, and meanwhile, a nanoparticle dispersion liquid is added into the water.
2. The vinylidene fluoride copolymer according to claim 1, wherein the allyl group-containing pyranose derivative is added in an amount of 0.2 to 4% by mass relative to the vinylidene fluoride.
3. The vinylidene fluoride copolymer according to claim 1, wherein the unsaturated carboxylic acid is added in an amount of 0.1 to 2% by mass based on the vinylidene fluoride.
4. Vinylidene fluoride copolymer according to claim 1, characterized in that the allyl group-containing pyranose derivative is selected from compounds having the following two spatial conformations, a and β, of the formula (1 a) and (1 b), respectively:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 One of which is allyl and the other four are each independently selected from a hydrogen atom, a hydrocarbyl group or a hydrocarbyl group containing at least one hydroxyl group.
5. Vinylidene fluoride copolymer according to claim 4, characterized in that the hydrocarbon radical is a C1-C12 hydrocarbon radical.
6. Vinylidene fluoride copolymer according to claim 1, characterized in that the allyl-containing pyranose derivative contains at least 4 hydroxyl groups.
7. The vinylidene fluoride copolymer according to claim 4, wherein the allyl group-containing pyranose derivative is selected from allyl- α -D-glucopyranoside and/or allyl- β -D-glucopyranoside, and has the structure represented by the following formula (2) and formula (3), respectively:
8. the vinylidene fluoride copolymer of claim 1, wherein the unsaturated carboxylic acid is a carboxylic acid compound having a polymerizable carbon-carbon double bond.
9. The vinylidene fluoride copolymer of claim 8, wherein the unsaturated carboxylic acid is selected from any one or a combination of at least two of acrylic acid, crotonic acid, maleic acid, itaconic acid, cinnamic acid.
10. Vinylidene fluoride copolymer according to claim 1, characterized in that the comonomer, optionally further comprising other fluorovinyl monomers.
11. Vinylidene fluoride copolymer according to claim 1, characterized in that the nanoparticle dispersion has a nanoparticle size of 2-200nm and a solids content of 5-50wt%.
12. Vinylidene fluoride copolymer according to claim 11, characterized in that the nanoparticle dispersion has a nanoparticle size of 5-50nm.
13. Vinylidene fluoride copolymer according to claim 11, characterized in that the nanoparticle dispersion has a solid content of 10-35% by weight.
14. Vinylidene fluoride copolymer according to claim 1, characterized in that the nanoparticle dispersion is an aqueous dispersion of inorganic oxide nanoparticles.
15. The vinylidene fluoride copolymer of claim 14, wherein the inorganic oxide nanoparticles are selected from any one or a combination of at least two of nanosilica, nanosilica.
16. Vinylidene fluoride copolymer according to claim 1, characterized in that the nanoparticle dispersion is an aqueous dispersion of nanosilica.
17. The vinylidene fluoride copolymer of claim 16, wherein the nanoparticle dispersion is winningW1714。
18. Vinylidene fluoride copolymer according to claim 1, characterized in that the nanoparticle dispersion is added in an amount of 0.3-3% by mass of the comonomer (a).
19. The vinylidene fluoride copolymer of claim 1 having a weight average molecular weight of 100 to 260 ten thousand g/mol and a molecular weight distribution index of 1.9 to 4.2;
the vinylidene fluoride copolymer has the mass fraction of 7.2 percent and the viscosity of the N-methyl pyrrolidone solution of 6500-14000mPa.s measured by a digital viscometer;
the particle size of the vinylidene fluoride copolymer is more than or equal to 150 mu m, and the particle size distribution proportion is less than 3.0%.
20. A process for the preparation of a vinylidene fluoride copolymer according to any of claims 1 to 19, characterized in that the steps comprise: and mixing vinylidene fluoride, a pyranose derivative containing allyl, unsaturated carboxylic acid and water, and simultaneously adding nanoparticle dispersion liquid to perform suspension polymerization reaction to prepare the vinylidene fluoride copolymer.
21. The method of claim 20, wherein the suspension polymerization reaction is performed, and the preparation raw materials comprise a dispersant, a chain transfer agent, and an initiator.
22. The preparation method according to claim 20, wherein the dispersant is added in an amount of 0.06 to 0.38% by mass of the comonomer (a) as vinylidene fluoride; the addition amount of the chain transfer agent accounts for 0.15 to 0.55 percent of the mass of the vinylidene fluoride of the comonomer (a); the addition amount of the initiator accounts for 0.06-0.55% of the mass of the vinylidene fluoride of the comonomer (a).
23. The preparation method according to claim 20, wherein the water is added in an amount of 100-450% by mass of the comonomer (a) as vinylidene fluoride; and/or
The allyl-containing pyranose derivative and the unsaturated carboxylic acid two comonomers adopt a batch-wise and intermittent feeding mode; and/or
The suspension polymerization reaction is carried out at the reaction temperature of 45-120 ℃; and/or
The suspension polymerization reaction is carried out, and the reaction pressure is 5-15MpaA; controlling the reaction pressure through the inlet amount of vinylidene fluoride; and/or
The suspension polymerization reaction comprises the operation of introducing nitrogen to remove oxygen before the reaction, so that the oxygen content is less than or equal to 10ppm.
24. The process according to claim 23, wherein the water is added in an amount of 100 to 260% by mass of the comonomer (a) as vinylidene fluoride.
25. The process according to claim 23, wherein the allyl-containing pyranose derivative, unsaturated carboxylic acid is fed in the form of an aqueous solution having a concentration of 5 to 30 wt%.
26. The preparation method according to claim 23, wherein the allyl-containing pyranose derivative and the unsaturated carboxylic acid are fed in the following manner: the first feeding is to add 10-30% of monomer mass before the reaction, and 3-5 times of residual monomer is added into the reaction system every 30-60min after the reaction.
27. The method according to claim 26, wherein the remaining monomers are added to the reaction system 3 to 5 times at 50 minute intervals after the start of the reaction.
28. The process according to claim 26, wherein each of the allyl group-containing pyranose derivative and the unsaturated carboxylic acid is 5 to 35% of the total mass of each monomer.
29. The method according to claim 26, wherein the remaining monomers are added to the reaction system 3 to 5 times by equal mass after the start of the polymerization reaction.
30. The process of claim 26, wherein the suspension polymerization is continued for 1-3 hours after the last addition.
31. The process of claim 23, wherein the suspension polymerization is carried out at a temperature of 45-90 ℃.
32. An electrode-forming composition comprising the vinylidene fluoride copolymer of any one of claims 1-19 or prepared by the process of any one of claims 20-31.
33. The composition of claim 32, wherein the composition comprises, by mass:
1-6% of vinylidene fluoride copolymer;
1-7% of an additive imparting electrical conductivity;
87-98% of powder electrode material.
34. The composition of claim 33, wherein the electrical conductivity imparting additive is selected from any one or a combination of at least two of carbon black, graphite, aluminum powder, nickel powder.
35. The composition of claim 33, wherein the powder electrode material is selected from any one or a combination of at least two of lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate.
36. Use of a vinylidene fluoride copolymer as claimed in any one of claims 1 to 19 or prepared by a process as claimed in any one of claims 20 to 31 as a binder in an electrode.
37. Use of the electrode-forming composition of any one of claims 32-35 as an electrode in a lithium ion battery.
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