CN112928387A - Boron-containing modified diaphragm, preparation method and application thereof, and battery containing diaphragm - Google Patents
Boron-containing modified diaphragm, preparation method and application thereof, and battery containing diaphragm Download PDFInfo
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- CN112928387A CN112928387A CN202110117225.5A CN202110117225A CN112928387A CN 112928387 A CN112928387 A CN 112928387A CN 202110117225 A CN202110117225 A CN 202110117225A CN 112928387 A CN112928387 A CN 112928387A
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- 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
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The invention discloses a boron-containing modified diaphragm, a preparation method and application thereof, and a battery containing the diaphragm. The invention adopts the irradiation in-situ grafting technology, utilizes the high specific energy of the rays generated by the radiation source, uniformly grafts the boron-containing compound on the surface and the inside of the holes of the porous diaphragm through in-situ grafting on the basis of ensuring the original basic characteristics and the appearance of the porous diaphragm as much as possible, on one hand, the transference number of lithium ions can be improved, thereby improving the energy efficiency of the lithium ion secondary battery, on the other hand, the diaphragm is modified by utilizing the irradiation grafting technology, and the invention provides a commercial prospect for modifying the diaphragm on a large scale.
Description
Technical Field
The invention relates to the field of high polymer modified materials, in particular to a boron-containing modified diaphragm, a preparation method and application thereof, and a battery containing the diaphragm.
Background
The lithium ion battery is used as a chemical power system which has high energy density, high output voltage, no memory effect, excellent cycle performance and environmental friendliness, has good economic benefit, social benefit and strategic significance, is widely applied to various fields such as mobile communication, digital products and the like, and is most likely to become the most main power system in the fields of energy storage and electric automobiles.
In a lithium ion battery, a separator mainly functions to prevent positive and negative electrodes from contacting and to allow ion conduction, and is an important component of the lithium ion battery. Up to now, the separator used in commercial lithium ion batteries is mainly polyolefin-based separator material with microporous structure, such as single-layer or multi-layer film of Polyethylene (PE), Polypropylene (PP). Although polyolefin separators can provide sufficient mechanical strength and chemical stability at normal temperature due to the characteristics of the polymer itself, these polyolefin separators still have some disadvantages. The common polyolefin diaphragm has poor wettability in the traditional liquid electrolyte, so that the liquid absorption capacity is low, and the cycle life of the lithium ion battery is influenced. In addition, the low transference number of lithium ions of the liquid electrolyte matched with the polyolefin diaphragm cannot meet the requirement of the emerging field for high-performance lithium ion batteries.
The transference number of lithium ions is an important parameter of a lithium ion secondary battery. The higher the transference number of lithium ions, the higher the energy efficiency of the lithium ion battery. The energy efficiency of the battery will be highest when the transport number of lithium ions approaches or reaches 1. This is because, inside the secondary battery, on the one hand, the migration of anions leads to the consumption of battery energy; on the other hand, since the migration speed of anions is faster than that of lithium ions, concentration gradient of electrolyte salt is generated in the charging and discharging process, concentration polarization is generated, and thus the energy efficiency of the lithium ion battery is reduced. The existing electrolyte system has low transference number of lithium ions (less than 0.3), and greatly influences the energy efficiency of the battery. In general, modification of a separator is not common, and there have been reported in a few documents in the past that a porous safety functional separator is formed by coating a uniform protective layer made of inorganic ceramic fine particles or the like on one side or both sides of a separator substrate. However, the coating method also has inevitable adverse effects such as a significant increase in the thickness of the separator, severe clogging of the porous structure, etc., and it is difficult for the current technology to modify the separator by modifying the ion transport channels on the separator.
Disclosure of Invention
In order to solve the problems, the invention adopts an irradiation in-situ grafting technology, utilizes the high specific energy of rays generated by a radiation source, uniformly grafts the boron-containing monomer on the surface and in the holes of the porous diaphragm through in-situ grafting on the basis of ensuring the original basic characteristics and appearance of the porous diaphragm as far as possible, and realizes the effective contact of ions and boron atoms through modifying on an ion transmission path, and the electron-deficient effect of the boron atoms can be used as Lewis acid to coordinate with anions, thereby limiting the movement of the anions. On one hand, the transference number of lithium ions is improved so as to improve the energy efficiency of the lithium ion secondary battery; on the other hand, the membrane is modified by utilizing the irradiation grafting technology, thereby providing a commercial prospect for modifying the membrane on a large scale.
The invention aims to overcome the defects of the prior art and provides a boron-containing modified diaphragm, a preparation method and application thereof and a battery containing the diaphragm.
One of the technical schemes of the invention is that the boron-containing modified diaphragm is prepared by introducing boron element with electron deficiency effect into the surface and holes of a diaphragm substrate by adopting an irradiation grafting technology; the boron element is derived from a group having an unsaturated bond and a boron atom in sp2A boron-containing compound that hybridizes to the covalent molecule formed.
The boron atom having an unsaturated bond group represented by sp2The boron-containing compound of the covalent molecule formed by hybridization is one or more of 4,4,5, 5-tetramethyl-2-vinyl-1, 3, 2-dioxaborolan, 2-methyl-2, 4-pentanediol vinyl borate, methyl imino diacetate vinyl borate and dibutyl vinyl borate.
The diaphragm base material is one or more of polyolefin porous polymer film polyethylene or single-layer or multi-layer composite film of polypropylene, non-woven fabric, polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl alcohol and polyimide, and blending and copolymerization polymer derived from the polymer material.
The irradiation grafting method is one of a pre-irradiation grafting method, a co-irradiation grafting method and a peroxidation method. The pre-irradiation grafting process includes irradiating the diaphragm in oxygen eliminating condition to produce stable free radical, and grafting with air eliminating monomer outside the radiation field at room temperature; the co-irradiation grafting method is a method of performing irradiation and peroxidation under the condition that the diaphragm and the monomer are in direct contact, and is characterized in that the diaphragm substrate is pre-irradiated in an oxygen atmosphere and then grafted with the monomer.
The radiation source for irradiation grafting comprises one of radioactive rays, acceleration provided radiation source and neutron source.
Further, the radioactive rays include 1 of alpha rays, beta rays and gamma rays, wherein the radioactive source of the alpha rays is241Am、239Pu and235one kind of U, the radioactive source of beta ray is3H、14C and90one of Sr and a radioactive source of gamma rays is60Co、137Cs and110sn.
Further, the source of radiation provided for acceleration comprises one of an electron accelerator electron source and a source of heavily charged particles.
Further, the neutron source includes one of an isotope neutron source, an accelerator neutron source, and a reactor neutron source.
The irradiation dose in the step (3) is 10 to 100KGy, and the irradiation dose is preferably 10 to 30KGy for the radiation resistance and the available effectiveness of the diaphragm substrate.
The second technical scheme of the invention is the application of the boron-containing modified diaphragm in the lithium ion secondary battery.
The third technical scheme of the invention is a lithium battery which comprises a positive electrode material and a negative electrode material, wherein the boron-containing modified diaphragm is arranged between the positive electrode material and the negative electrode material.
In general, a positive electrode active material of a positive electrode material may use a compound Li that reversibly stores/releases (intercalates and deintercalates) lithium ionsxMO2Or LiyM2O4(wherein M is a transition metal, x is 0. ltoreq. x.ltoreq.1, and y is 0. ltoreq. y.ltoreq.2), a lithium-containing composite oxide, a spinel-like oxide, a metal chalcogenide having a layered structure, an olivine structure, or the like.
The positive electrode active material may specifically be LiCoO2Lithium cobalt oxide, LiMn2O4Lithium manganese oxide, LiNiO, etc2Lithium nickel oxide, Li4/3Ti5/3O4Lithium titanium oxide, lithium manganese nickel composite oxide, lithium manganese nickel cobalt composite oxide and lithium manganese nickel cobalt composite oxide having LiMPO4(M ═ Fe, Mn, Ni) olivine crystal structure material.
Lithium-containing composite oxides having a layered structure or a spinel-like structure are preferably used as the positive electrode active material, and LiCoO2、LiMn2O4、LiNiO2、LiNi1/2Mn1/2O2Lithium manganese nickel composite oxide typified by the like, LiNil/3Mn1/3Co1/3O2、LiNi0.6Mn0.2Co0.2O2Lithium manganese nickel cobalt composite oxide typified by the like, or LiNi1-x-y-zCoxAlyMgzO2(wherein x is not less than 0 and not more than 1, y is not less than 0 and not more than 0.1, z is not less than 0 and not more than 0.1, and 1-x-y-z is not more than 0 and not more than 1). In addition, the lithium-containing composite oxide described above includes lithium-containing composite oxides in which a part of the constituent elements is substituted with an additive element such as Ge, Ti, Zr, Mg, Al, Mo, and Sn.
These positive electrode active materials may be used alone in 1 kind, or in combination of 2 or more kinds. For example, by using a lithium-containing composite oxide having a layered structure and a lithium-containing composite oxide having a spinel structure, both a large capacity and an improvement in safety can be achieved
For example, a conductive additive such as carbon black or acetylene black, or a binder such as polyvinylidene fluoride or polyethylene oxide is appropriately added to the above positive electrode active material to prepare a positive electrode material mixture, and the positive electrode material mixture is applied to a tape-shaped molded body having a current collecting material such as aluminum foil as a core material. However, the method for manufacturing the positive electrode is not limited to the above example.
The negative electrode material generally used for lithium ion batteries can be used in the present invention. As the negative electrode active material for the negative electrode, a compound capable of inserting and extracting lithium metal or lithium may be used. For example, alloys of aluminum, silicon, tin, or the like, oxides, carbon materials, or the like can be used as the negative electrode active material. Examples of the oxide include titanium dioxide, and examples of the carbon material include graphite, pyrolytic carbons, cokes, glassy carbons, a fired product of an organic polymer compound, mesophase carbon microbeads, and the like.
For the negative electrode constituting the nonaqueous electrolyte secondary battery, for example, a conductive additive such as carbon black or acetylene black, or a binder such as polyvinylidene fluoride or polyethylene oxide is appropriately added to the negative electrode active material to prepare a negative electrode mixture, and the negative electrode mixture is applied to a tape-shaped molded body having a current collecting material such as a copper foil as a core material. However, the method for producing the negative electrode is not limited to the above example.
In the nonaqueous electrolyte secondary battery provided by the present invention, a nonaqueous solvent (organic solvent) is used as the nonaqueous electrolyte. The nonaqueous solvent includes carbonates, ethers, and the like.
The carbonate includes cyclic carbonates and chain carbonates, and examples of the cyclic carbonates include ethylene carbonate, propylene carbonate, butylene carbonate, γ -butyrolactone, and sulfur esters (ethylene glycol sulfide, etc.). Examples of the chain carbonate include low-viscosity polar chain carbonates such as dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate, and aliphatic branched carbonates. A mixed solvent of a cyclic carbonate (particularly, ethylene carbonate) and a chain carbonate is particularly preferable. Examples of the ethers include dimethyl ether tetraethylene glycol (TEGDME), ethylene glycol dimethyl ether (DME), 1, 3-Dioxolane (DOL), and the like.
In addition to the nonaqueous solvent, chain alkyl esters such as methyl propionate, chain phosphoric acid triesters such as trimethyl phosphate, and the like; nitrile solvents such as 3-methoxypropionitrile; a nonaqueous solvent (organic solvent) such as a branched compound having an ether bond typified by a dendrimer.
In addition, fluorine-based solvents can also be used. As the fluorine-containing solvent, for example, H (CF) may be mentioned2)2OCH3、C4F9OCH3、H(CF2)2OCH2CH3、H(CF2)2OCH2CF3、H(CF2)2CH2O(CF2)2H, etc., or CF3CHFCF2OCH3、CF3CHFCF2OCH2CH3(perfluoroalkyl) alkyl ethers of isolinear structure, i.e., 2-trifluoromethylhexafluoropropyl methyl ether, 2-trifluoromethylhexafluoropropyl ethyl ether, 2-trifluoromethylhexafluoropropyl propyl ether, 3-trifluoromethyloctafluorobutyl methyl ether, 3-trifluoromethyloctafluorobutyl ethyl ether, 3-trifluoromethyloctafluorobutyl propyl ether, 4-trifluoromethyldecafluoropentyl methyl ether, 4-trifluoromethyldecafluoropentyl ethyl ether, 4-trifluoromethyldecafluoropentyl propyl ether, 5-trifluoromethyldodecafluorohexyl methyl ether, 5-trifluoromethyldodecafluorohexyl ethyl ether, 5-trifluoromethyldodecafluorohexyl propyl ether, 6-trifluoromethyltetradecafluoroheptyl methyl ether, 6-trifluoromethyltetradecafluoroheptyl ethyl ether, 6-trifluoromethyltetradecafluoroheptyl propyl ether, 7-trifluoromethyldecahexafluorooctyl methyl ether, 7-trifluoromethyl hexadecyl octyl ethyl ether, 7-trifluoromethyl decahexafluoro octyl propyl ether, and the like.
The above-mentioned iso (perfluoroalkyl) alkyl ether and the above-mentioned (perfluoroalkyl) alkyl ether having a linear structure may be used in combination.
As the electrolyte salt used in the nonaqueous electrolytic solution, lithium salts such as lithium perchlorate, organoboron lithium salt, lithium salt of fluorine-containing compound, and lithium imide salt are preferable.
Examples of such electrolyte salts include LiClO4、LiPF6、LiBF4、LiAsF6、LiSbF6、LiCF3SO3、LiCF3CO2、LiC2F4(SO3)2、LiN(C2F5SO2)2、LiC(CF3SO2)3、LiCnF2n+1SO3(n≥2)、LiN(RfOSO2)2(wherein Rf is fluoroalkyl), and the like. Among these lithium salts, fluorine-containing organic lithium salts are particularly preferred. The fluorine-containing organic lithium salt is highly anionic and easily separated into ions, and therefore is easily dissolved in the nonaqueous electrolytic solution.
The concentration of the electrolytic lithium salt in the nonaqueous electrolytic solution is, for example, preferably 0.3mol/L or more, more preferably 0.7mol/L or more, preferably 1.7mol/L or less, and more preferably 1.2mol/L or less. If the concentration of the electrolyte lithium salt is too low, the ionic conductivity is too low, and if it is too high, there is a fear that the electrolyte salt which is not completely dissolved may be precipitated.
The nonaqueous electrolytic solution may contain various additives for improving the performance of the battery using the nonaqueous electrolytic solution, and is not particularly limited.
The fourth technical scheme of the invention is a preparation method of a boron-containing modified diaphragm, which comprises the following steps:
(1) preparing the organic solution containing the boron compound: adding the boron-containing compound into the organic solvent outside the irradiation field, and stirring at the speed of 450-550r/min for 5.5-6.5h to obtain an organic solution of the boron-containing compound with the mass fraction of 10-100%; wherein when the content of the organic solvent is 0, the boron-containing compound with the mass fraction of 100 percent is obtained.
(2) Cleaning and drying the membrane substrate: cleaning the membrane substrate with acetone and drying at 55-65 deg.C for 5.5-6.5 h;
(3) adopting one of co-irradiation grafting reaction, pre-irradiation grafting reaction and peroxidation grafting reaction to carry out irradiation grafting, wherein the irradiation dose is 10-100 KGy;
(4) and (3) cleaning and drying after the irradiation grafting is finished: and (4) cleaning the modified diaphragm obtained in the step (3) with ethanol, drying at 55-65 ℃ for 5.5-6.5h, and drying to obtain the boron-containing modified diaphragm.
The co-irradiation grafting method comprises the following steps: and (3) soaking the diaphragm base material treated in the step (2) in an organic solution containing a boron compound, sealing, introducing inert gas argon to remove dissolved oxygen (inhibiting polymerization), and then carrying out co-irradiation grafting reaction by a radiation source.
The pre-irradiation grafting method comprises the following steps: pre-irradiating the diaphragm base material treated in the step (2) in an argon atmosphere, and then placing the diaphragm base material in an organic solution containing a boron compound for grafting reaction;
the peroxidation method comprises the following steps: and (3) pre-irradiating the diaphragm base material treated in the step (2) in an oxygen atmosphere, and then placing the diaphragm base material in an organic solution containing a boron compound for grafting reaction.
The boron-containing compound has an unsaturated bond group and a boron atom is represented by sp2Hybridization forms covalent molecules.
The organic solvent for dissolving the boron-containing compound is some small molecular alcohol, for example, methanol, ethanol, isopropanol, ethylpropanol, n-butanol, isobutanol, tert-butanol, etc.; or other small molecule solvents such as acetone, chloroform, ethyl acetate, etc.
The technical scheme has the following beneficial effects:
1. according to the invention, boron with an electron deficiency effect is introduced into the diaphragm substrate, and the electron deficiency effect of boron can interact with anions in the electrolyte, so that the dissociation of lithium salt is promoted, the anions are fixed, and the transference number of lithium ions is increased; the lithium ion migration number of the invention is obviously higher than that of the common polyethylene diaphragm, and the energy efficiency of the battery is effectively improved.
2. The invention can directly introduce the boron element into the porous diaphragm by the irradiation grafting method, has simple process operation, does not need additional process and is beneficial to commercial production. The radiation grafting method is a method in which active sites (radicals or ions) are generated in a polymer by high-energy radiation, and graft polymerization of a monomer is initiated by the active sites. The radiation grafting method has a significant advantage over the conventional chemical grafting method in that as a result of the interaction of the substance with radiation, active particles such as various radicals and positive and negative ions are generated, and since energy absorption is not dependent on temperature and molecular structure, the substance can be uniformly "activated" by radiation, which is also possible for substances with higher chemical stability, which is not possible with the conventional chemical grafting method.
Drawings
The invention is further illustrated by the following figures and examples.
Fig. 1 is an infrared spectrum of the modified separator and a general commercial polyolefin separator used in examples 1 to 3.
FIGS. 2a and 2b are the scanning electron micrograph and the energy spectrometer elemental analysis micrograph of the plane and the cross section of the modified polyethylene diaphragm, respectively;
FIG. 3 shows the actual borane content as determined by thermogravimetric analysis for examples 1-3.
FIGS. 4a to 4k are an AC impedance spectrum and a steady-state current chart of comparative example 1 and examples 11 to 20 in which the transference number of lithium ions was measured by the steady-state current method.
Fig. 5 is a graph comparing the rate performance of a battery using the modified separator of the present invention in example 21 with that of a battery using a general polyethylene separator in comparative example 2.
Fig. 6 is a comparison of the cycle performance of the batteries obtained in example 21 and comparative example 2.
Detailed Description
The present invention will be described in more detail by way of examples, but the scope of the present invention is not limited to these examples.
Example 1
Preparing a modified boron-containing separator: 10g of 4,4,5, 5-tetramethyl-2-vinyl-1, 3, 2-dioxaborolan is added into 90g of absolute ethyl alcohol outside a radiation field, and the mixture is stirred for 6 hours at the speed of 500r/min to obtain an ethanol solution of the borane with the mass fraction of 10%. The Polyethylene (PE) membrane was washed with acetone and dried at 60 c for 6 hours, then soaked in borane in ethanol and sealed, and the dissolved oxygen was removed by passing an inert gas of argon (inhibition of polymerization). The material is placed in a radiation field and is irradiated by gamma rays, and the irradiation dose is 10 kGy. After the irradiation is finished, the irradiated polyethylene diaphragm is washed by a large amount of ethanol to remove unreacted monomers and homopolymers. And then drying the membrane for 6 hours at the temperature of 60 ℃ to obtain the modified polyolefin membrane.
Example 2
Preparing a modified boron-containing separator: 20g of 4,4,5, 5-tetramethyl-2-vinyl-1, 3, 2-dioxaborolan is added into 80g of absolute ethyl alcohol outside a radiation field, and the mixture is stirred for 6 hours at the speed of 500r/min to obtain an ethanol solution of the borane with the mass fraction of 20%. The polyethylene membrane was washed with acetone and dried at 60 ℃ for 6 h. Then, the polyethylene diaphragm is soaked in ethanol solution of borane and sealed, and inert gas argon is introduced to remove dissolved oxygen (polymerization inhibition). The material is placed in a radiation field and is irradiated by gamma rays, and the irradiation dose is 10 kGy. After the irradiation is finished, the irradiated polyethylene diaphragm is washed by a large amount of ethanol to remove unreacted monomers and homopolymers. And then drying the membrane for 6 hours at the temperature of 60 ℃ to obtain the modified polyolefin membrane.
Example 3
Preparing a modified boron-containing separator: 30g of 4,4,5, 5-tetramethyl-2-vinyl-1, 3, 2-dioxaborolan is added into 70g of absolute ethyl alcohol outside a radiation field, and the mixture is stirred for 6 hours at the speed of 500r/min to obtain an ethanol solution of the borane with the mass fraction of 30%. The polyethylene membrane was washed with acetone and dried at 60 ℃ for 6 h. Then, the polyethylene diaphragm is soaked in ethanol solution of borane and sealed, and inert gas argon is introduced to remove dissolved oxygen (polymerization inhibition). The material is placed in a radiation field and is irradiated by gamma rays, and the irradiation dose is 10 kGy. After the irradiation is finished, the irradiated polyethylene diaphragm is washed by a large amount of ethanol to remove unreacted monomers and homopolymers. And then drying the membrane for 6 hours at the temperature of 60 ℃ to obtain the modified polyolefin membrane.
Fig. 1 is an ir spectrum of the modified polyethylene separator prepared in examples 1 to 3 and a general commercial polyethylene separator. The modified polyethylene separator showed three distinct characteristic peaks, one being 1370cm, compared to the ordinary commercial polyethylene separator-1Of (C-CH)3The stretching vibration peak of (1); one is 1310cm-1B-O stretching vibration peak of (1); one is 1150cm-1The stretching vibration peak of C-O (C-O). And at 1650cm-1The peak of C ═ C does not appear nearby, and the borane can be judged to be successfully grafted to the polyOn the ethylene separator. From the IR spectrum, it can also be seen that-CH increases with increasing borane concentration3The peak values of the stretching vibration peaks of B-O and C-O are gradually increased, and the grafted proportion is also gradually increased.
Fig. 2a and 2b are scanning electron micrographs and energy spectrometer elemental analysis photographs of the plane and the cross section of the modified polyethylene diaphragm, respectively. It can be seen from fig. 2a that the element C, O, B is uniformly distributed on the surface of the polyolefin separator, and from fig. 2b that C, O, B is uniformly distributed on the cross-section of the polyolefin separator, it can be judged that the borane was successfully grafted on the ion transport channel.
FIG. 3 shows the actual borane content as determined by thermogravimetric analysis for examples 1-3. As is evident from the results of fig. 3: compared with the original unmodified diaphragm, the diaphragm after grafting the borane begins to lose weight at about 200 ℃, and before reaching the decomposition temperature of the diaphragm, the weights of examples 1 to 3 are respectively lost by about 2.1%, 4.1% and 7.9%, which are the mass of the actual grafted borane.
Example 4
Preparing a modified boron-containing separator: 20g of 4,4,5, 5-tetramethyl-2-vinyl-1, 3, 2-dioxaborolan is added into 80g of absolute ethyl alcohol outside a radiation field, and the mixture is stirred for 6 hours at the speed of 500r/min to obtain an ethanol solution of the borane with the mass fraction of 20%. The polyethylene membrane was washed with acetone and dried at 60 ℃ for 6 h. Then, the polyethylene diaphragm is soaked in ethanol solution of borane and sealed, and inert gas argon is introduced to remove dissolved oxygen (polymerization inhibition). The material is placed in a radiation field and is irradiated by gamma rays, and the irradiation dose is 30 kGy. After the irradiation is finished, the irradiated polyethylene diaphragm is washed by a large amount of ethanol to remove unreacted monomers and homopolymers. And then drying the membrane for 6 hours at the temperature of 60 ℃ to obtain the modified polyolefin membrane.
Example 5
Preparing a modified boron-containing separator: 20g of 4,4,5, 5-tetramethyl-2-vinyl-1, 3, 2-dioxaborolan is added into 80g of absolute ethyl alcohol outside a radiation field, and the mixture is stirred for 6 hours at the speed of 500r/min to obtain an ethanol solution of the borane with the mass fraction of 20%. The polyvinylidene fluoride-hexafluoropropylene film was washed with acetone and dried at 60 ℃ for 6 h. Then, the mixture is soaked in ethanol solution of borane and sealed, and inert gas argon is introduced to remove dissolved oxygen (polymerization inhibition). The material is placed in a radiation field and is irradiated by gamma rays, and the irradiation dose is 10 kGy. After the irradiation is finished, the irradiated polyethylene diaphragm is washed by a large amount of ethanol to remove unreacted monomers and homopolymers. Then drying the film for 6 hours at the temperature of 60 ℃ to obtain the modified polyvinylidene fluoride-hexafluoropropylene film.
Example 6
Preparing a modified boron-containing separator: 20g of 2-methyl-2, 4-pentanediol vinylborate is added into 80g of absolute ethyl alcohol outside a radiation field, and the mixture is stirred at the speed of 500r/min for 6 hours to obtain an ethanol solution of boric acid ester with the mass fraction of 20%. The polyethylene membrane was washed with acetone and dried at 60 ℃ for 6 h. Then, the polyethylene diaphragm is soaked in ethanol solution of borane and sealed, and inert gas argon is introduced to remove dissolved oxygen (polymerization inhibition). The material is placed in a radiation field and is irradiated by gamma rays, and the irradiation dose is 10 kGy. After the irradiation is finished, the irradiated polyethylene diaphragm is washed by a large amount of ethanol to remove unreacted monomers and homopolymers. And then drying the membrane for 6 hours at the temperature of 60 ℃ to obtain the modified polyolefin membrane.
Example 7
Preparing a modified boron-containing separator: 20g of 4,4,5, 5-tetramethyl-2-vinyl-1, 3, 2-dioxaborolan is added into 80g of absolute ethyl alcohol outside a radiation field, and the mixture is stirred for 6 hours at the speed of 500r/min to obtain an ethanol solution of the borane with the mass fraction of 20%. The polyethylene membrane was washed with acetone and dried at 60 c for 6 hours, then soaked in a borane in ethanol and sealed, and the dissolved oxygen was removed by passing an inert gas, argon (inhibition). The material is placed in a radiation field and is irradiated by gamma rays, and the irradiation dose is 100 kGy. After the irradiation is finished, the irradiated polyethylene diaphragm is washed by a large amount of ethanol to remove unreacted monomers and homopolymers. And then drying the membrane for 6 hours at the temperature of 60 ℃ to obtain the modified polyolefin membrane.
Example 8
Preparing a modified boron-containing separator: washing the polyethylene diaphragm with acetone outside a radiation field, drying the polyethylene diaphragm for 6 hours at the temperature of 60 ℃, then putting the polyethylene diaphragm into 4,4,5, 5-tetramethyl-2-vinyl-1, 3, 2-dioxaborolane for soaking and sealing, and introducing inert gas argon to remove dissolved oxygen (polymerization inhibition). The material is placed in a radiation field and is irradiated by gamma rays, and the irradiation dose is 10 kGy. After the irradiation is finished, the irradiated polyethylene diaphragm is washed by a large amount of ethanol to remove unreacted monomers and homopolymers. And then drying the membrane for 6 hours at the temperature of 60 ℃ to obtain the modified polyolefin membrane.
Examples 1-8 the radiation grafting method used to prepare a modified boron-containing separator was co-irradiation grafting.
Example 9
Preparing a modified boron-containing separator: 20g of 4,4,5, 5-tetramethyl-2-vinyl-1, 3, 2-dioxaborolan is added into 80g of absolute ethyl alcohol outside a radiation field, and the mixture is stirred for 6 hours at the speed of 500r/min to obtain an ethanol solution of the borane with the mass fraction of 20%. The polyethylene membrane was washed clean with acetone and dried at 60 ℃ for 6 h. And then placing the polyethylene diaphragm in a radiation field under the atmosphere preserved by argon gas for pre-irradiation by utilizing gamma rays, wherein the irradiation dose is 10 kGy. And after the irradiation is finished, soaking the pre-irradiated polyethylene diaphragm in an ethanol solution of boric acid ester, and heating and reacting for 12 hours at the temperature of 60 ℃. And washing the polyethylene membrane after the grafting reaction by using a large amount of ethanol to remove unreacted monomers and homopolymers, drying at 60 ℃ for 6 hours, and drying to obtain the modified polyolefin membrane. The irradiation grafting method employed in this example was a pre-irradiation grafting method.
Example 10
Preparing a modified boron-containing separator: 20g of 2-methyl-2, 4-pentanediol vinylborate is added into 80g of absolute ethyl alcohol outside a radiation field, and the mixture is stirred at the speed of 500r/min for 6 hours to obtain an ethanol solution of boric acid ester with the mass fraction of 20%. The polyvinylidene fluoride-hexafluoropropylene is washed clean by acetone and dried for 6h at 60 ℃. And then placing the polyethylene diaphragm in a radiation field under the atmosphere of oxygen storage, and performing pre-irradiation by utilizing gamma rays, wherein the irradiation dose is 10 kGy. And after the irradiation is finished, soaking the pre-irradiated polyethylene diaphragm in an ethanol solution of boric acid ester, and heating and reacting for 12 hours at the temperature of 60 ℃. And washing the polyethylene membrane after the grafting reaction by using a large amount of ethanol to remove unreacted monomers and homopolymers, drying at 60 ℃ for 6 hours, and drying to obtain the modified polyolefin membrane. The irradiation grafting method used in this example was a peroxide method.
Example 11
A simulated cell comprised of two sheets of lithium metal with the modified polyethylene separator of example 1 between them.
Example 12
A simulated cell comprised of two sheets of lithium metal with the modified polyethylene separator of example 2 between them.
Example 13
A simulated cell comprised of two sheets of lithium metal with the modified polyethylene separator of example 3 between them.
Example 14
A simulated cell comprised of two sheets of lithium metal with the modified polyethylene separator of example 4 between them.
Example 15
A simulated cell comprised of two sheets of lithium metal with the modified polyethylene separator of example 5 between them.
Example 16
A simulated cell comprised of two sheets of lithium metal with the modified polyethylene separator prepared in example 6 between them.
Example 17
A simulated cell comprised of two sheets of lithium metal with the modified polyethylene separator prepared in example 7 between them.
Example 18
A simulated cell comprised of two sheets of lithium metal with the modified polyethylene separator prepared in example 8 between them.
Example 19
A simulated cell comprised of two sheets of lithium metal with the modified polyethylene separator of example 9 between them.
Example 20
A simulated cell comprised of two sheets of lithium metal with the modified polyethylene separator of example 10 between them.
Comparative example 1
A simulated battery comprised two lithium metal sheets with a common commercial polyethylene separator between them.
The transference numbers of lithium ions of examples 11 to 20 and comparative example 1 were tested by the steady-state current method. As shown in fig. 4a, the transference number of lithium ions of comparative example 1 was measured to be 0.17. As shown in fig. 4b to 4k, the transference numbers of lithium ions of examples 11 to 20 were measured to be 0.32, 0.55, 0.47, 0.50, 0.44, 0.51, 0.38, 0.37, 0.41, and 0.40, respectively. The test result shows that the lithium ion migration number of the diaphragm modified by the method is obviously higher than that of the common polyethylene diaphragm. The improvement of the transference number of the lithium ions can avoid the concentration polarization of electrolyte salt, prevent the formation of lithium dendrite and effectively improve the energy efficiency of the battery. Fig. 4h and 4i show the test results of examples 17 and 18, respectively, from which it can be seen that the radiation graft modified membrane method of the present invention is also applicable to higher radiation doses and higher borane concentrations. Fig. 4j and 4k are the test results of examples 19 and 20, respectively, and it can be seen from the test results that the pre-irradiation graft modification and peroxide graft modification methods of the present invention are also suitable for preparing boron-containing modified membranes.
Example 21
A battery comprising a positive electrode material and a negative electrode material with the modified polyethylene separator prepared in example 2 therebetween.
Comparative example 2
A battery includes a positive electrode material and a negative electrode material with a common commercial polyethylene separator therebetween.
The rate performance of the batteries obtained in example 21 and comparative example 2 was tested, as shown in fig. 5. The modified diaphragm obtained by the invention has the advantages that the boron-containing borane is introduced, so that the transference number of lithium ions is obviously increased, the rapid conduction of the lithium ions is realized, and the rate capability of a battery using the modified diaphragm under the conditions of large-current charge and discharge can be improved.
The batteries obtained in example 21 and comparative example 2 were tested for cycle performance as shown in fig. 6. It can be seen that the cycle performance of the battery using the modified diaphragm obtained by the invention is obviously improved compared with the cycle performance of the battery using the common diaphragm in the prior art.
Example 22
A battery comprising a positive electrode material and a negative electrode material with the modified separator prepared in example 1 therebetween.
Example 23
A battery comprising a positive electrode material and a negative electrode material with the modified separator prepared in example 3 therebetween.
Example 24
A battery comprising a positive electrode material and a negative electrode material with the modified separator prepared in example 4 therebetween.
The foregoing is for illustrative purposes only, and therefore the scope of the invention should not be limited by this description, and all modifications made within the scope of the invention and the contents of the description should be considered within the scope of the invention.
Claims (10)
1. A boron-containing modified membrane characterized by: the modified diaphragm is prepared by grafting boron with electron deficiency effect on the surface and holes of a diaphragm substrate by using an irradiation grafting technology.
2. The boron-containing modified membrane of claim 1, wherein: the boron element is derived from a group having an unsaturated bond and a boron atom in sp2A boron-containing compound that hybridizes to the covalent molecule formed.
3. Root of herbaceous plantThe boron-containing modified membrane of claim 1, wherein: said boron atom having an unsaturated bond group in sp2The boron-containing compound of the covalently formed molecule comprises one or more of 4,4,5, 5-tetramethyl-2-vinyl-1, 3, 2-dioxaborolane, 2-methyl-2, 4-pentanediol vinyl borate, methyl iminodiacetate vinyl borate, and dibutyl vinyl borate.
4. The boron-containing modified membrane of claim 1, wherein: the irradiation grafting method is one of a pre-irradiation grafting method, a co-irradiation grafting method and a peroxidation method.
5. The boron-containing modified membrane of claim 1, wherein: the irradiation dose of the irradiation grafting is 10-100 KGy.
6. Use of the boron-containing modified separator according to any one of claims 1 to 5 in a lithium ion secondary battery.
7. A battery comprises a positive electrode material and a negative electrode material, and is characterized in that: the boron-containing modified separator according to any one of claims 1 to 5 between a positive electrode material and a negative electrode material.
8. A preparation method of a boron-containing modified diaphragm is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing the organic solution containing the boron compound: adding the boron-containing compound into an organic solvent, and stirring for 5.5-6.5h at the speed of 450-550r/min to obtain an organic solution of the boron-containing compound with the mass fraction of 10-100%;
(2) cleaning and drying the membrane substrate: cleaning the membrane substrate with acetone and drying at 55-65 deg.C for 5.5-6.5 h;
(3) adopting one of a co-irradiation grafting method, a pre-irradiation grafting method and a peroxidation method to carry out irradiation grafting, wherein the irradiation dose is 10-100 KGy;
(4) and (3) cleaning and drying after the irradiation grafting is finished: and (4) cleaning the modified diaphragm obtained in the step (3) with ethanol, drying at 55-65 ℃ for 5.5-6.5h, and drying to obtain the boron-containing modified diaphragm.
9. The method of claim 8, wherein the at least one boron-containing modified membrane is prepared by:
the co-irradiation grafting method comprises the following steps: placing the diaphragm base material treated in the step (2) in an organic solution containing a boron compound, and carrying out co-irradiation by a radiation source;
the pre-irradiation grafting method comprises the following steps: pre-irradiating the diaphragm base material treated in the step (2) in an argon atmosphere, and then placing the diaphragm base material in an organic solution containing a boron compound for grafting reaction;
the peroxidation method comprises the following steps: and (3) pre-irradiating the diaphragm base material treated in the step (2) in an oxygen atmosphere, and then placing the diaphragm base material in an organic solution containing a boron compound for grafting reaction.
10. The method of producing a boron-containing modified membrane according to claim 8, wherein: the boron-containing compound has an unsaturated bond group and a boron atom is represented by sp2Hybridization forms covalent molecules.
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| CN202110117225.5A CN112928387B (en) | 2021-01-28 | 2021-01-28 | Boron-containing modified diaphragm, preparation method and application thereof, and battery containing diaphragm |
| PCT/CN2022/074331 WO2022161438A1 (en) | 2021-01-28 | 2022-01-27 | Boron-containing modified diaphragm and preparation method and application therefor, and battery including diaphragm |
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Cited By (2)
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| WO2022161438A1 (en) * | 2021-01-28 | 2022-08-04 | 厦门大学 | Boron-containing modified diaphragm and preparation method and application therefor, and battery including diaphragm |
| CN115385350A (en) * | 2022-09-05 | 2022-11-25 | 深圳大学 | Preparation method and application of hydroxylated boron alkene material |
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| CN112928387B (en) | 2022-05-03 |
| WO2022161438A1 (en) | 2022-08-04 |
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