CN111925471A - Silane modified fluoroethyl ester polymer used as lithium battery binder and preparation method thereof - Google Patents

Silane modified fluoroethyl ester polymer used as lithium battery binder and preparation method thereof Download PDF

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CN111925471A
CN111925471A CN202010817148.XA CN202010817148A CN111925471A CN 111925471 A CN111925471 A CN 111925471A CN 202010817148 A CN202010817148 A CN 202010817148A CN 111925471 A CN111925471 A CN 111925471A
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perfluorovinyl
silane
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CN111925471B (en
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张群朝
杨纪元
史明慧
蒋涛
施德安
郝同辉
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Hubei University
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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
    • C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/20—Esters containing halogen
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a preparation method of a silane modified fluoroethyl ester polymer used as a lithium battery binder, which comprises the following steps: 1) adding a perfluorovinyl ester compound, a silane compound and 80-90% of solvent into a container, stirring, heating to 60-80 ℃, dissolving an initiator in the residual solvent, then dropwise adding the initiator into the reaction liquid, and keeping the temperature to continue reacting for 10-12 hours after dropwise adding; 2) transferring the reaction solution obtained in the step 1) into a rotary evaporator, evaporating the solvent, washing the precipitate with n-hexane, and drying the precipitate to obtain the silane-modified fluoroethyl ester polymer. The polymer prepared by the method has good binding force between fluorine atoms and lithium ions, accelerates the transfer of the lithium ions, and improves the coulomb efficiency of the battery; the silane structure enhances the adhesion between the polymer and the inorganic active silicon particles, improves the cycling stability of the battery, and enables the prepared polymer to have excellent initial coulombic efficiency and electrochemical stability.

Description

Silane modified fluoroethyl ester polymer used as lithium battery binder and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a silane modified fluoroethyl ester polymer used as a lithium battery binder and a preparation method thereof.
Background
At present, graphite is the main negative active material of commercial lithium ion batteries, the theoretical specific capacity of the graphite is 370mA · h/g, and the requirement of high energy storage equipment cannot be met, while the theoretical specific capacity of a fully lithiated silicon negative electrode is 4200mA · h/g, which is more than 10 times of the capacity of graphite, and silicon elements in the nature are rich, so that the graphite has attracted extensive attention of researchers. However, the silicon active material has huge volume expansion when embedded with lithium, the expansion rate is 400%, after a plurality of charging and discharging cycles, silicon particles can be cracked and pulverized and gradually fall off from a current collector, so that the content of active substances of the electrode is reduced, the capacity of the battery is rapidly attenuated, the service life of the battery is greatly reduced, and the application of the silicon-based lithium ion battery is limited.
The binder is a key substance for maintaining the integrity of the electrode, and researchers realize the excellent electrochemical performance of the silicon-based lithium ion battery by modifying the binder. The main lithium ion battery binder in the current market is polyvinylidene fluoride (PVDF), but the binding property and the flexibility are poor, the volume change of a silicon cathode cannot be flexibly adapted, and a novel binder needs to be searched for the silicon cathode.
US20100129704a1 discloses a tri-block polymer binder containing fluoromonomers, acrylates and ethylenes for use in silicon negative electrodes, which binder in small amounts can bind the silicon particles together. The adhesive force between the silicon particles and the current collector is enhanced, the specific capacity and the cycle performance of the lithium ion battery are improved, but the multiplying power performance of the silicon cathode using the adhesive is poor.
Patent CN108987753A discloses that a polymer binder of acrylic acid is modified by a silane coupling agent, the cohesiveness of the polymer is enhanced, the first specific capacity of the battery is 1883mAh/g, the initial specific capacity is lower, and the commercial requirement cannot be met. Patent CN110247017A also discloses that the initial specific capacity of the battery is 3000mAh/g by using silane coupling agent to modify acrylic acid and carboxymethyl cellulose polymer binder, but the capacity of the battery is reduced to 1500mAh/g after 30 cycles, the capacity loss of the battery is too fast, the cycle performance is poor, and further improvement is needed.
Patent CN107863535A discloses that the composite binder of polyimide and polyaniline, which is a conductive polymer, is used for silicon cathode, and improves the cycle performance of the battery, but the battery has poor high temperature resistance, and the system temperature rises after many times of charging and discharging, so that there is a great potential safety hazard.
U.S. Pat. No. 4, 20180083268, 1 discloses functionalized graft polymer binders containing amino, carboxyl, anhydride branches. The adhesive can form chemical bonds with functionalized silicon particles and a current collector, the adhesion among electrode components is enhanced, the service life of the battery is prolonged, the capacity of the battery is still kept above 2000mAh/g after 70 times of charge-discharge cycles, and the grafted polymer is proved to be capable of improving the cycle performance of the silicon negative electrode battery.
In conclusion, the development of a high-performance binder for silicon-based lithium ion batteries to improve the capacity and the cycle stability of the batteries is the focus of lithium battery research at present.
Disclosure of Invention
Therefore, the invention provides a silane modified fluoroethyl ester polymer used as a lithium battery binder, which has the advantages of short film forming time, excellent flexibility and adhesiveness, capability of increasing the practical use capacity of a silicon-based lithium ion battery and prolonging the service life of the battery, and a preparation method thereof.
In order to achieve the purpose, the invention discloses a silane modified fluoroethyl ester polymer used as a lithium battery binder, which has a structural formula shown in a formula I.
Figure BDA0002633118620000021
In the formula I, R1Representing a carbon number of C1～C18Saturated linear or branched perfluoroalkyl, perfluoroalkoxy, or perfluorocycloalkyl groups; r2Represents oxygen or has a carbon number of C1～C18Saturated linear or branched alkyl, alkoxy or cycloalkyl; r3Representing a carbon number of C1～C4Saturated straight or branched chain alkyl; x and y are positive integers of 1-10.
The silane modified fluoroethyl ester polymer contains fluorine atoms and siloxane functionalized branched chains on side chains, enriches the structure of a polymer binder, provides more reaction contact points, is beneficial to forming a cross-linked network structure, can relieve the volume change of silicon particles in circulation when being applied as the binder of a silicon lithium battery, prevents the silicon cathode from collapsing and falling off in the circulation process, maintains the integrity of the silicon cathode, and improves the circulation stability of the silicon lithium battery.
The silane-modified fluoroethyl ester polymer of the present invention has R1Representing a carbon number of C1～C18Saturated linear or branched perfluoroalkyl, perfluoroalkoxy, or perfluorocycloalkyl groups, the polymer containing a significant number of fluorine atoms. When the polymer is used as a lithium ion battery binder, the binding force between fluorine atoms and lithium ions is strong, the electron transfer rate of the lithium ions is accelerated, and the rate capability of the battery is improved; and secondly, the silane chain in the polymer improves the flexibility of the polymer chain, enhances the cohesiveness between the polymer and inorganic particle silicon and between current collectors, maintains the integrity of the electrode and improves the cycling stability of the battery.
In the silane modified fluoroethyl polymer, the tail end of one graft structure is connected with three siloxane groups, and the siloxane groups have strong activity and can be hydrolyzed to generate a large number of hydroxyl groups when meeting water, so that the hydroxyl groups can be further crosslinked through intermolecular hydrogen bonds to form a three-dimensional network skeleton structure with strong mechanical property, the volume change of silicon particles in circulation is relieved, the collapse and falling of the silicon negative electrode in the circulation process are prevented, the hydrogen bonds can be formed with the hydroxyl groups on the surface of the silicon particles, the silicon particles are fixed on a current collector, the adhesion between the silicon particles and the current collector is enhanced, the integrity of the silicon negative electrode is maintained, and the circulation stability of a silicon-based lithium ion battery is improved.
The invention also discloses a preparation method of the silane modified fluoroethyl ester polymer used as the lithium battery binder, which comprises the following steps:
1) adding a perfluorovinyl ester compound, a silane compound and 80-90% of solvent into a container, stirring, heating to 60-80 ℃, dissolving an initiator in the residual solvent, then dropwise adding the initiator into the reaction liquid, and keeping the temperature to continue reacting for 10-12 hours after dropwise adding; the mol ratio of the perfluorovinyl ester compound to the silane compound is 0.5-5: 1; the amount of the initiator is 0.3-0.6% of the total weight of the perfluorovinyl ester compound and the silane compound;
2) transferring the reaction solution obtained in the step 1) to a rotary evaporator, evaporating the solvent, washing the precipitate, and drying the precipitate to obtain the silane-modified fluoroethyl ester polymer.
By adopting the preparation method of solution polymerization, reactants are uniformly mixed, the system heat transfer is uniform, the reaction temperature is easy to control, the reaction system is a low-viscosity system, and the phenomenon of accelerating gelation is avoided; meanwhile, the reaction process is simple to operate, and the obtained silane modified fluoroethyl ester polymer is easy to store and transport.
Preferably, the structural formula of the perfluorovinyl ester compound is shown as formula II:
Figure BDA0002633118620000041
in the formula II, R1Representing a carbon number of C1～C18Saturated linear or branched perfluoroalkyl, perfluoroalkoxy, or perfluorocycloalkyl groups.
Preferably, the perfluorovinyl ester compound is one of the following: perfluorovinyl acetate, perfluorovinyl octanoate, perfluorovinyl dodecanoate, perfluorovinyl hexadecanoate, perfluorovinyl octadecanoate, perfluorovinyl tert-valerate, perfluorovinyl tert-heptanoate, perfluorovinyl tert-decanoate, perfluorovinyl tert-butyltetradecanoate, perfluorovinyl ethoxyhexanoate, perfluorovinyl methoxynonanoate, perfluorovinyl propoxycatanoate, perfluorovinyl ethoxydodecanoate, perfluoro-2-cyclopropyldodecyl vinyl ester. Wherein, in the compounds such as the perfluoroethoxy vinyl hexanoate, the perfluoromethoxy vinyl nonanoate, the perfluoropropoxy vinyl octanoate, the perfluoroethoxy vinyl dodecanoate, the perfluoro-2-cyclopropyl vinyl dodecyl ester and the like, except for the vinyl ester structure, hydrogen atoms on other carbons are replaced by fluorine atoms. For example, vinyl perfluoroethoxyhexanoate has the structural formula shown in IV:
Figure BDA0002633118620000051
preferably, the structural formula of the silane compound is shown as III:
Figure BDA0002633118620000052
in the formula III, R2Represents oxygen or has a carbon number of C1～C18Saturated linear or branched alkyl, alkoxy or cycloalkyl; r3Representing a carbon number of C1～C4Saturated straight or branched chain alkyl.
Preferably, the silane compound is one of the following: propenyltriethoxysilane, propenyltripropoxysilane, tetradecenyltrimethoxysilane, octadecenyltrimethoxysilane, (6-methyl) tetradecenyltrimethoxysilane, (4-ethyl) propenyltriethoxysilane, vinyloxytrimethoxysilane, (2-allyloxy) ethoxytrimethoxysilane, (8-en-butoxyl) octyloxytetraoxysilane, (9-allyloxy) nonyloxytriethoxysilane, decentri-butoxysilane, dodecentripropoxysilane, and (4-cyclopropyl) ene decyltrimethoxysilane.
Preferably, the solvent is one or a mixed solution of two or more of the following: butyl formate, ethyl acetate, hexyl acetate, tert-butyl formate, isopropanol, cyclopentanone, methyl isobutyl ketone, ethylene glycol, n-butanol.
Preferably, the initiator is one of the following: azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, azobisisodecylonitrile, azobisdicyclohexylcarbonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, lauroyl peroxide, diisopropyl peroxydicarbonate, tert-butyl peroxypivalate.
The invention has the beneficial effects that:
1. the invention adopts molecular chain structure design to prepare the segmented copolymer with the silane soft segment structure being in harmony with the perfluoro alkene ester hard segment structure, the synergy between the soft and hard molecular chains enriches the structure and the function of the polymer, the hard segment fluoroethyl ester structure is used as a framework to endow the polymer with strong mechanical property and cohesiveness, the soft segment silane is used as a buffering agent to accommodate the huge volume change of silicon particles, the flexibility and the film forming property of the polymer molecular chains are improved, and the stability of the electrochemical property of the silicon-based lithium ion battery is facilitated.
2. In the silane modified fluoroethyl polymer, the tail end of one graft structure is connected with three siloxane groups, and the siloxane groups have strong activity and can be hydrolyzed to generate a large number of hydroxyl groups when meeting water, so that the hydroxyl groups can form a three-dimensional network skeleton structure with strong mechanical property through intermolecular hydrogen bond crosslinking, the volume change of silicon particles in circulation is relieved, the collapse and falling of a silicon cathode in the circulation process are prevented, the silicon particles can form hydrogen bonds with the hydroxyl groups on the surfaces of the silicon particles, the silicon particles are fixed on a current collector, the adhesion between the silicon particles and the current collector is enhanced, the integrity of the silicon cathode is maintained, and the circulation stability of a silicon-based lithium ion battery is improved.
3. According to the perfluorinated ethyl ester structure in the polymer binder, a large number of fluorine atoms are provided on a molecular side chain, and due to the strong binding capacity between the fluorine atoms and lithium ions, the transfer rate of the lithium ions is accelerated, and the rate capability of a silicon-based lithium ion battery is greatly improved; on the other hand, the perfluorinated ethyl ester structure has strong chemical corrosion resistance, so that the silane modified fluorinated ethyl ester polymer can stably exist in electrolyte when being used as a binder, and the perfluorinated ethyl ester structure has good high-temperature resistance and can improve the safety of the lithium ion battery; finally, the perfluorinated polymer has high crystallinity, and the crystallinity and the adhesiveness of the silane modified fluoroethyl ester polymer are enhanced.
4. The preparation method is simple in preparation process, convenient to operate and easy to industrialize.
Detailed Description
In order to explain technical contents, structural features, and objects and effects of the technical means in detail, the following detailed description is given with reference to specific embodiments.
Example 1
First, 21.42 g (0.05mol) of vinyl perfluorooctanoate, 20.41 g (0.1mol) of propylenetrioxysilane and 50ml of butyl formate solvent were weighed and stirred in a four-neck flask; after the temperature is raised to 60 ℃ and the mixture is stabilized, 0.1255 g (0.0008mol) of initiator azobisisobutyronitrile and 10ml of butyl formate solvent are mixed evenly and then are dripped into a four-neck flask; and after 12h of reaction, transferring the mixture to a rotary evaporator to remove the solvent, finally washing the precipitate by using n-hexane, and drying the precipitate to obtain the silane modified fluoroethyl ester polymer.
Then, the silicon negative electrode lithium ion button half cell is assembled by adopting the polymer binder: according to the mass ratio of commercial silicon particles, carbon black and a binder of 8: 1: 1, adding an N-methyl pyrrolidone solvent, uniformly mixing, coating on a copper foil current collector, drying at 100 ℃ in vacuum for 8 hours, slicing into 12mm wafers, assembling a battery in a glove box, standing at room temperature for activation for 24 hours, and then performing electrochemical tests (including tests on initial discharge capacity, initial coulombic efficiency and capacity retention rate).
Finally, the above silane-modified fluoroethyl ester-based polymer was subjected to a tensile test and a paint film tack-free time test in accordance with GB/T1040-2006 and GB/T1728-1989.
Example 2
First, 21.42 g (0.05mol) of vinyl perfluorooctanoate, 16.41 g (0.1mol) of ethyleneethoxy trimethoxysilane and 50ml of butyl formate solvent were weighed and stirred in a four-necked flask; after the temperature is raised to 65 ℃ and the mixture is stabilized, 0.1513 g (0.0009mol) of initiator azobisisobutyronitrile and 10ml of butyl formate solvent are mixed evenly and then are dripped into a four-neck flask; and after 12h of reaction, transferring the mixture to a rotary evaporator to remove the solvent, finally washing the precipitate by using n-hexane, and drying the precipitate to obtain the silane modified fluoroethyl ester polymer.
Then, the silicon negative electrode lithium ion button half cell is assembled by adopting the polymer binder: according to the mass ratio of commercial silicon particles, carbon black and a binder of 8: 1: 1, adding an N-methyl pyrrolidone solvent, uniformly mixing, coating on a copper foil current collector, drying at 100 ℃ in vacuum for 8 hours, slicing into 12mm wafers, assembling a battery in a glove box, standing at room temperature for activation for 24 hours, and then performing electrochemical tests (including tests on initial discharge capacity, initial coulombic efficiency and capacity retention rate).
Finally, the above silane-modified fluoroethyl ester-based polymer was subjected to a tensile test and a paint film tack-free time test in accordance with GB/T1040-2006 and GB/T1728-1989.
Example 3
First, 31.40 g (0.05mol) of perfluorododecanoic acid vinyl ester, 8.21 g (0.05mol) of ethyleneethoxy trimethoxysilane and 50ml of butyl formate solvent were weighed and stirred in a four-necked flask; after the temperature is raised to 70 ℃ and the mixture is stabilized, 0.1983 g (0.0012mol) of initiator azobisisobutyronitrile and 10ml of butyl formate solvent are mixed evenly and then are dripped into a four-neck flask; and after reacting for 11h, transferring the mixture to a rotary evaporator to remove the solvent, finally washing the precipitate by using n-hexane, and drying the precipitate to obtain the silane modified fluoroethyl ester polymer.
Then, the silicon negative electrode lithium ion button half cell is assembled by adopting the polymer binder: according to the mass ratio of commercial silicon particles, carbon black and a binder of 8: 1: 1, adding an N-methyl pyrrolidone solvent, uniformly mixing, coating on a copper foil current collector, drying at 100 ℃ in vacuum for 8 hours, slicing into 12mm wafers, assembling a battery in a glove box, standing at room temperature for activation for 24 hours, and then performing electrochemical tests (including tests on initial discharge capacity, initial coulombic efficiency and capacity retention rate).
Finally, the above silane-modified fluoroethyl ester-based polymer was subjected to a tensile test and a paint film tack-free time test in accordance with GB/T1040-2006 and GB/T1728-1989.
Example 4
First, a weighed amount of 31.44 g (0.05mol) of perfluorododecanoic acid vinyl ester, 16.55 g (0.05mol) of (4-ethyl) decanoic acid triethoxysilane, and 50ml of ethyl acetate solvent were added to a four-necked flask and stirred; after the temperature is raised to 70 ℃ and the mixture is stabilized, 0.1439 g (0.0007mol) of initiator dimethyl azodiisobutyrate and 10ml of ethyl acetate solvent are mixed evenly and then are dripped into a four-neck flask; and after reacting for 11h, transferring the mixture to a rotary evaporator to remove the solvent, finally washing the precipitate by using n-hexane, and drying the precipitate to obtain the silane modified fluoroethyl ester polymer.
Then, the silicon negative electrode lithium ion button half cell is assembled by adopting the polymer binder: according to the mass ratio of commercial silicon particles, carbon black and a binder of 8: 1: 1, adding an N-methyl pyrrolidone solvent, uniformly mixing, coating on a copper foil current collector, drying at 100 ℃ in vacuum for 8 hours, slicing into 12mm wafers, assembling a battery in a glove box, standing at room temperature for activation for 24 hours, and then performing electrochemical tests (including tests on initial discharge capacity, initial coulombic efficiency and capacity retention rate).
Finally, the above silane-modified fluoroethyl ester-based polymer was subjected to a tensile test and a paint film tack-free time test in accordance with GB/T1040-2006 and GB/T1728-1989.
Example 5
First, a weighed amount of 29.01 g (0.1mol) of perfluoropivalic acid vinyl ester, 16.55 g (0.05mol) of (4-ethyl) decene triethoxysilane, and 50ml of ethyl acetate solvent were put into a four-necked flask and stirred; after the temperature is raised to 70 ℃ and the mixture is stabilized, 0.1367 g (0.0006mol) of initiator dimethyl azodiisobutyrate and 10ml of ethyl acetate solvent are mixed evenly and then are dripped into a four-neck flask; and (3) after reacting for 10 hours, transferring the mixture to a rotary evaporator to remove the solvent, and finally washing the precipitate with n-hexane and drying to obtain a solid, namely the silane modified fluoroethyl ester polymer.
Then, the silicon negative electrode lithium ion button half cell is assembled by adopting the polymer binder: according to the mass ratio of commercial silicon particles, carbon black and a binder of 8: 1: 1, adding an N-methyl pyrrolidone solvent, uniformly mixing, coating on a copper foil current collector, drying at 100 ℃ in vacuum for 8 hours, slicing into 12mm wafers, assembling a battery in a glove box, standing at room temperature for activation for 24 hours, and then performing electrochemical tests (including tests on initial discharge capacity, initial coulombic efficiency and capacity retention rate).
Finally, the above silane-modified fluoroethyl ester-based polymer was subjected to a tensile test and a paint film tack-free time test in accordance with GB/T1040-2006 and GB/T1728-1989.
Example 6
First, a weighed amount of 43.51 g (0.15mol) of perfluoropivalic acid vinyl ester, 11.1 g (0.05mol) of (2-allyloxy) ethoxytrimethoxysilane and 50ml of ethyl acetate solvent were put into a four-necked flask and stirred; after the temperature is raised to 72 ℃ and the mixture is stabilized, 0.1638 g (0.0007mol) of initiator dimethyl azodiisobutyrate and 10ml of ethyl acetate solvent are mixed evenly and then are dripped into a four-neck flask; and after reacting for 11h, transferring the mixture to a rotary evaporator to remove the solvent, finally washing the precipitate by using n-hexane, and drying the precipitate to obtain the silane modified fluoroethyl ester polymer.
Then, the silicon negative electrode lithium ion button half cell is assembled by adopting the polymer binder: according to the mass ratio of commercial silicon particles, carbon black and a binder of 8: 1: 1, adding an N-methyl pyrrolidone solvent, uniformly mixing, coating on a copper foil current collector, drying at 100 ℃ in vacuum for 8 hours, slicing into 12mm wafers, assembling a battery in a glove box, standing at room temperature for activation for 24 hours, and then performing electrochemical tests (including tests on initial discharge capacity, initial coulombic efficiency and capacity retention rate).
Finally, the above silane-modified fluoroethyl ester-based polymer was subjected to a tensile test and a paint film tack-free time test in accordance with GB/T1040-2006 and GB/T1728-1989.
Example 7
First, a weighed amount of 22.87 g (0.05mol) of vinyl perfluoroethoxyhexanoate, 22.20 g (0.1mol) of (2-allyloxy) ethoxytrimethoxysilane and 50ml of an isopropyl alcohol solvent were put in a four-necked flask and stirred; after the temperature is raised to 80 ℃ and the mixture is stabilized, 0.1803 g (0.0007mol) of initiator benzoyl peroxide and 10ml of isopropyl ketone solvent are mixed evenly and then are dripped into a four-neck flask; and after reacting for 10 hours, transferring the mixture to a rotary evaporator to remove the solvent, finally washing the precipitate by using n-hexane, and drying the precipitate to obtain the silane modified fluoroethyl ester polymer.
Then, the silicon negative electrode lithium ion button half cell is assembled by adopting the polymer binder: according to the mass ratio of commercial silicon particles, carbon black and a binder of 8: 1: 1, adding an N-methyl pyrrolidone solvent, uniformly mixing, coating on a copper foil current collector, drying at 100 ℃ in vacuum for 8 hours, slicing into 12mm wafers, assembling a battery in a glove box, standing at room temperature for activation for 24 hours, and then performing electrochemical tests (including tests on initial discharge capacity, initial coulombic efficiency and capacity retention rate).
Finally, the above silane-modified fluoroethyl ester-based polymer was subjected to a tensile test and a paint film tack-free time test in accordance with GB/T1040-2006 and GB/T1728-1989.
Example 8
First, 22.81 g (0.05mol) of vinyl perfluoroethoxyhexanoate, 19.30 g (0.05mol) of alkenyltridecyltributoxysilane and 50ml of isopropyl alcohol solvent were weighed and charged into a four-necked flask and stirred; after the temperature is raised to 60 ℃ and the mixture is stabilized, 0.2105 g (0.0009mol) of initiator benzoyl peroxide and 10ml of isopropyl ketone solvent are mixed evenly and then are dripped into a four-mouth flask; and after 12h of reaction, transferring the mixture to a rotary evaporator to remove the solvent, finally washing the precipitate by using n-hexane, and drying the precipitate to obtain the silane modified fluoroethyl ester polymer.
Then, the silicon negative electrode lithium ion button half cell is assembled by adopting the polymer binder: according to the mass ratio of commercial silicon particles, carbon black and a binder of 8: 1: 1, adding an N-methyl pyrrolidone solvent, uniformly mixing, coating on a copper foil current collector, drying at 100 ℃ in vacuum for 8 hours, slicing into 12mm wafers, assembling a battery in a glove box, standing at room temperature for activation for 24 hours, and then performing electrochemical tests (including tests on initial discharge capacity, initial coulombic efficiency and capacity retention rate).
Finally, the above silane-modified fluoroethyl ester-based polymer was subjected to a tensile test and a paint film tack-free time test in accordance with GB/T1040-2006 and GB/T1728-1989.
Example 9
First, a weighed amount of 27.86 g (0.05mol) of vinyl perfluoromethyloxynonanoate, 19.34 g (0.05mol) of alkenyltridecylbutanoylsilane and 50ml of an isopropyl ketone solvent were put into a four-necked flask and stirred; after the temperature is raised to 80 ℃ and the mixture is stabilized, 0.1413 g (0.0006mol) of initiator benzoyl peroxide and 10ml of isopropyl ketone solvent are mixed evenly and then are dripped into a four-neck flask; and after reacting for 10 hours, transferring the mixture to a rotary evaporator to remove the solvent, finally washing the precipitate by using n-hexane, and drying the precipitate to obtain the silane modified fluoroethyl ester polymer.
Then, the silicon negative electrode lithium ion button half cell is assembled by adopting the polymer binder: according to the mass ratio of commercial silicon particles, carbon black and a binder of 8: 1: 1, adding an N-methyl pyrrolidone solvent, uniformly mixing, coating on a copper foil current collector, drying at 100 ℃ in vacuum for 8 hours, slicing into 12mm wafers, assembling a battery in a glove box, standing at room temperature for activation for 24 hours, and then performing electrochemical tests (including tests on initial discharge capacity, initial coulombic efficiency and capacity retention rate).
Finally, the above silane-modified fluoroethyl ester-based polymer was subjected to a tensile test and a paint film tack-free time test in accordance with GB/T1040-2006 and GB/T1728-1989.
Example 10
First, a weighed amount of 7.05 g (0.05mol) of perfluorovinyl acetate, 8.29 g (0.05mol) of vinyloxytrimethoxysilane and 50ml of cyclopentanone solvent were added to a four-necked flask and stirred; after the temperature is raised to 75 ℃ and the mixture is stabilized, 0.0912 g (0.0003mol) of initiator lauroyl peroxide and 10ml of cyclopentanone solvent are mixed evenly and then are dripped into a four-neck flask; and after reacting for 11h, transferring the mixture to a rotary evaporator to remove the solvent, finally washing the precipitate by using n-hexane, and drying the precipitate to obtain the silane modified fluoroethyl ester polymer.
Then, the silicon negative electrode lithium ion button half cell is assembled by adopting the polymer binder: according to the mass ratio of commercial silicon particles, carbon black and a binder of 8: 1: 1, adding an N-methyl pyrrolidone solvent, uniformly mixing, coating on a copper foil current collector, drying at 100 ℃ in vacuum for 8 hours, slicing into 12mm wafers, assembling a battery in a glove box, standing at room temperature for activation for 24 hours, and then performing electrochemical tests (including tests on initial discharge capacity, initial coulombic efficiency and capacity retention rate).
Finally, the above silane-modified fluoroethyl ester-based polymer was subjected to a tensile test and a paint film tack-free time test in accordance with GB/T1040-2006 and GB/T1728-1989.
Example 11
First, a weighed amount of 35 g (0.25mol) of perfluorovinyl acetate, 18.6 g (0.05mol) of octadecenyltrimethoxysilane, and 50ml of cyclopentanone solvent were added to a four-necked flask and stirred; after the temperature is raised to 80 ℃ and the mixture is stabilized, 0.1608 g (0.0004mol) of initiator lauroyl peroxide and 10ml of cyclopentanone solvent are mixed evenly and then are dripped into a four-neck flask; and after reacting for 10 hours, transferring the mixture to a rotary evaporator to remove the solvent, finally washing the precipitate by using n-hexane, and drying the precipitate to obtain the silane modified fluoroethyl ester polymer.
Then, the silicon negative electrode lithium ion button half cell is assembled by adopting the polymer binder: according to the mass ratio of commercial silicon particles, carbon black and a binder of 8: 1: 1, adding an N-methyl pyrrolidone solvent, uniformly mixing, coating on a copper foil current collector, drying at 100 ℃ in vacuum for 8 hours, slicing into 12mm wafers, assembling a battery in a glove box, standing at room temperature for activation for 24 hours, and then performing electrochemical tests (including tests on initial discharge capacity, initial coulombic efficiency and capacity retention rate).
Finally, the above silane-modified fluoroethyl ester-based polymer was subjected to a tensile test and a paint film tack-free time test in accordance with GB/T1040-2006 and GB/T1728-1989.
Example 12
First, 37.81 g (0.05mol) of vinyl perfluoroethoxydodecanoate, 18.65 g (0.05mol) of octadecenyltrimethoxysilane and 50ml of cyclopentanone solvent were weighed and stirred in a four-necked flask; after the temperature is raised to 65 ℃ and the mixture is stabilized, 0.1692 g (0.0004mol) of initiator lauroyl peroxide and 10ml of cyclopentanone solvent are mixed evenly and then are dripped into a four-neck flask; and after 12h of reaction, transferring the mixture to a rotary evaporator to remove the solvent, finally washing the precipitate by using n-hexane, and drying the precipitate to obtain the silane modified fluoroethyl ester polymer.
Then, the silicon negative electrode lithium ion button half cell is assembled by adopting the polymer binder: according to the mass ratio of commercial silicon particles, carbon black and a binder of 8: 1: 1, adding an N-methyl pyrrolidone solvent, uniformly mixing, coating on a copper foil current collector, drying at 100 ℃ in vacuum for 8 hours, slicing into 12mm wafers, assembling a battery in a glove box, standing at room temperature for activation for 24 hours, and then performing electrochemical tests (including tests on initial discharge capacity, initial coulombic efficiency and capacity retention rate).
Finally, the above silane-modified fluoroethyl ester-based polymer was subjected to a tensile test and a paint film tack-free time test in accordance with GB/T1040-2006 and GB/T1728-1989.
Example 13
First, 37.83 g (0.05mol) of vinyl perfluoroethoxydodecanoate, 12.91 g (0.05mol) of (4-cyclopropyl) decene trimethoxysilane and 50ml of n-butanol solvent were weighed and added to a four-necked flask and stirred; after the temperature is raised to 70 ℃ and the mixture is stabilized, 0.1521 g (0.0009mol) of initiator tert-butyl peroxypivalate and 10ml of n-butanol solvent are mixed evenly and then are dripped into a four-mouth flask; and after reacting for 11h, transferring the mixture to a rotary evaporator to remove the solvent, finally washing the precipitate by using n-hexane, and drying the precipitate to obtain the silane modified fluoroethyl ester polymer.
Then, the silicon negative electrode lithium ion button half cell is assembled by adopting the polymer binder: according to the mass ratio of commercial silicon particles, carbon black and a binder of 8: 1: 1, adding an N-methyl pyrrolidone solvent, uniformly mixing, coating on a copper foil current collector, drying at 100 ℃ in vacuum for 8 hours, slicing into 12mm wafers, assembling a battery in a glove box, standing at room temperature for activation for 24 hours, and then performing electrochemical tests (including tests on initial discharge capacity, initial coulombic efficiency and capacity retention rate).
Finally, the above silane-modified fluoroethyl ester-based polymer was subjected to a tensile test and a paint film tack-free time test in accordance with GB/T1040-2006 and GB/T1728-1989.
Example 14
First, 30.16 g (0.05mol) of vinyl perfluoro-2-cyclopropyldodecanoate, 12.92 g (0.05mol) of (4-cyclopropyl) decene trimethoxysilane and 50ml of n-butanol solvent were weighed and added to a four-necked flask and stirred; after the temperature is raised to 75 ℃ and the mixture is stabilized, 0.1720 g (0.0010mol) of initiator tert-butyl peroxypivalate and 10ml of n-butanol solvent are mixed evenly and then are dripped into a four-neck flask; and after reacting for 11h, transferring the mixture to a rotary evaporator to remove the solvent, finally washing the precipitate by using n-hexane, and drying the precipitate to obtain the silane modified fluoroethyl ester polymer.
Then, the silicon negative electrode lithium ion button half cell is assembled by adopting the polymer binder: according to the mass ratio of commercial silicon particles, carbon black and a binder of 8: 1: 1, adding an N-methyl pyrrolidone solvent, uniformly mixing, coating on a copper foil current collector, drying at 100 ℃ in vacuum for 8 hours, slicing into 12mm wafers, assembling a battery in a glove box, standing at room temperature for activation for 24 hours, and then performing electrochemical tests (including tests on initial discharge capacity, initial coulombic efficiency and capacity retention rate).
Finally, the above silane-modified fluoroethyl ester-based polymer was subjected to a tensile test and a paint film tack-free time test in accordance with GB/T1040-2006 and GB/T1728-1989.
Example 15
First, a weighed amount of 24.08 g (0.04mol) of vinyl perfluoro-2-cyclopropyldodecanoate, 7.72 g (0.02mol) of alkenyltridecyltributoxysilane and 50ml of n-butanol solvent were put in a four-necked flask and stirred; after the temperature is raised to 80 ℃ and the mixture is stabilized, 0.1908 g (0.0011mol) of initiator tert-butyl peroxypivalate and 10ml of n-butanol solvent are mixed evenly and then are dripped into a four-mouth flask; and after reacting for 10 hours, transferring the mixture to a rotary evaporator to remove the solvent, finally washing the precipitate by using n-hexane, and drying the precipitate to obtain the silane modified fluoroethyl ester polymer.
Then, the silicon negative electrode lithium ion button half cell is assembled by adopting the polymer binder: according to the mass ratio of commercial silicon particles, carbon black and a binder of 8: 1: 1, adding an N-methyl pyrrolidone solvent, uniformly mixing, coating on a copper foil current collector, drying at 100 ℃ in vacuum for 8 hours, slicing into 12mm wafers, assembling a battery in a glove box, standing at room temperature for activation for 24 hours, and then performing electrochemical tests (including tests on initial discharge capacity, initial coulombic efficiency and capacity retention rate).
Finally, the above silane-modified fluoroethyl ester-based polymer was subjected to a tensile test and a paint film tack-free time test in accordance with GB/T1040-2006 and GB/T1728-1989.
Example 16
Polyvinylidene fluoride (PVDF) is used as a silicon-based lithium ion battery binder, a silicon negative button half cell is assembled according to the method of example 1, and electrochemical test is carried out after activation for 24 hours at room temperature; tensile testing and determination of the surface dry time of the paint film of polyvinylidene fluoride (PVDF) were carried out according to GB/T1040-2006 and GB/T1728-1989.
The battery performance tests of examples 1 to 16, as well as the tensile test and the paint film tack-free time measurement of the silane-modified fluoroethyl ester-based polymer binder, are shown in Table 1. The specific test method for various battery performances is as follows:
1) initial discharge capacity: the lithium/Celgard 2500 diaphragm/silicon button cell is assembled by taking metal lithium as an anode and silicon particles as a cathode, and is subjected to constant current analysis on a Xinwei cell cycle workstation, wherein the test voltage range is 0.01-2V, and the charge-discharge rate is 0.1C.
2) Initial coulombic efficiency: is the ratio of the initial charge-discharge capacity to the initial discharge capacity.
3) Capacity retention ratio: and (2) assembling a Li/diaphragm/silicon button cell by using metal lithium as a positive electrode and silicon particles as a negative electrode, performing constant current analysis on a cell cycle workstation, testing the voltage range of 0.01-2V, the charge-discharge multiplying power of 01C, and cycling for 200 weeks to obtain the ratio of the cell capacity to the initial capacity.
The surface dry time test method of the polymer comprises the following steps: when the surface of the paint film is touched with a finger, if the paint film feels a little sticky, but no paint is stuck on the finger, the surface is dry, and the time is recorded.
The breaking elongation test method of the polymer comprises the following steps: the ratio of the stretched length of the polymeric form after stretching under force to the length before stretching.
Table 1 examples 1-16 test data
Figure BDA0002633118620000171
As can be seen from Table 1, the silane modified fluoroethyl ester polymer binder is used for the negative electrode of a silicon-based lithium ion battery, the initial discharge capacity is more than 2857mAh/g and can reach 2857mAh/g to the maximum, the initial coulomb rate is up to 91%, the capacity retention rate is 80% after the battery is cycled for 200 circles, and the electrochemical performance is superior to that of PVDF, so that the silane modified fluoroethyl ester polymer binder used for the silicon-based lithium ion battery has excellent initial coulomb efficiency and electrochemical stability. The polymer binder has good binding force between fluorine atoms and lithium ions, so that the transfer of the lithium ions is accelerated, and the coulomb efficiency of the battery is improved; the silane compound enhances the adhesion between the polymer and the inorganic active silicon particles, maintains the integrity of the electrode, and improves the cycling stability of the battery.
The surface drying time of the silane modified fluoroethyl ester polymer binder is within 9h, the film forming time is shorter than that of PVDF, the maximum elongation at break is 201.76%, and the elongation at break is much higher than that of a PVDF film by 87.9%, so that the polymer binder has excellent film forming performance and flexibility. The silane chain in the molecular chain enhances the flexibility of the polymer, lowers the glass transition temperature of the polymer, promotes the film formation of an electrode coating and is beneficial to the preparation of electrodes.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or terminal that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or terminal. Without further limitation, an element defined by the phrases "comprising … …" or "comprising … …" does not exclude the presence of additional elements in a process, method, article, or terminal that comprises the element. Further, herein, "greater than," "less than," "more than," and the like are understood to exclude the present numbers; the terms "above", "below", "within" and the like are to be understood as including the number.
It should be noted that, although the above embodiments have been described herein, the invention is not limited thereto. Therefore, based on the innovative concepts of the present invention, the technical solutions of the present invention can be directly or indirectly applied to other related technical fields by making changes and modifications to the embodiments described herein or by using equivalent structures or equivalent processes performed in the present specification, and are included in the scope of the present invention.

Claims (8)

1. The silane modified fluoroethyl ester polymer used as the lithium battery binder is characterized in that the structural formula is shown as a formula I.
Figure FDA0002633118610000011
In the formula I, R1Representing a carbon number of C1～C18Saturated linear or branched perfluoroalkyl, perfluoroalkoxy, or perfluorocycloalkyl groups; r2Represents oxygen or has a carbon number of C1～C18Saturated linear or branched alkyl, alkoxy or cycloalkyl; r3Representing a carbon number of C1～C4Saturated straight or branched chain alkyl; x and y are positive integers of 1-10.
2. The method for preparing a silane-modified fluoroethyl ester-based polymer for a lithium battery binder according to claim 1, comprising the steps of:
1) adding a perfluorovinyl ester compound, a silane compound and 80-90% of solvent into a container, stirring, heating to 60-80 ℃, dissolving an initiator in the residual solvent, then dropwise adding the initiator into the reaction liquid, and keeping the temperature to continue reacting for 10-12 hours after dropwise adding; the mol ratio of the perfluorovinyl ester compound to the silane compound is 0.5-5: 1; the amount of the initiator is 0.3-0.6% of the total weight of the perfluorovinyl ester compound and the silane compound;
2) transferring the reaction solution obtained in the step 1) to a rotary evaporator, evaporating the solvent, washing the precipitate, and drying the precipitate to obtain the silane-modified fluoroethyl ester polymer.
3. The method for preparing a silane-modified fluoroethyl ester polymer for a lithium battery binder according to claim 2, wherein the structural formula of the perfluorovinyl ester compound is represented by formula II:
Figure FDA0002633118610000012
in the formula II, R1Representing a carbon number of C1～C18Saturated linear or branched perfluoroalkyl, perfluoroalkoxy, or perfluorocycloalkyl groups.
4. The method for preparing a silane-modified fluoroethyl ester-based polymer for a lithium battery binder according to claim 2 or 3, wherein the perfluorovinyl ester-based compound is one of the following: perfluorovinyl acetate, perfluorovinyl octanoate, perfluorovinyl dodecanoate, perfluorovinyl hexadecanoate, perfluorovinyl octadecanoate, perfluorovinyl tert-valerate, perfluorovinyl tert-heptanoate, perfluorovinyl tert-decanoate, perfluorovinyl tert-butyltetradecanoate, perfluorovinyl ethoxyhexanoate, perfluorovinyl methoxynonanoate, perfluorovinyl propoxycatanoate, perfluorovinyl ethoxydodecanoate, perfluoro-2-cyclopropyldodecyl vinyl ester.
5. The method of claim 2, wherein the silane compound has a formula of III:
Figure FDA0002633118610000021
in the formula III, R2Represents oxygen or has a carbon number of C1～C18Saturated linear or branched alkyl, alkoxy or cycloalkyl; r3Representing a carbon number of C1～C4Saturated straight or branched chain alkyl.
6. The method for preparing a silane-modified fluoroethyl ester-based polymer for a lithium battery binder according to claim 5 or 6, wherein the silane compound is one of the following: propenyltriethoxysilane, propenyltripropoxysilane, tetradecenyltrimethoxysilane, octadecenyltrimethoxysilane, (6-methyl) tetradecenyltrimethoxysilane, (4-ethyl) propenyltriethoxysilane, vinyloxytrimethoxysilane, (2-allyloxy) ethoxytrimethoxysilane, (8-en-butoxyl) octyloxytetraoxysilane, (9-allyloxy) nonyloxytriethoxysilane, decentri-butoxysilane, dodecentripropoxysilane, and (4-cyclopropyl) ene decyltrimethoxysilane.
7. The method for preparing a silane-modified fluoroethyl ester-based polymer for a lithium battery binder according to claim 2, wherein the solvent is one or a mixed solution of two or more of: butyl formate, ethyl acetate, hexyl acetate, tert-butyl formate, isopropanol, cyclopentanone, methyl isobutyl ketone, ethylene glycol, n-butanol.
8. The method of claim 2, wherein the initiator is one of the following: azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, azobisisodecylonitrile, azobisdicyclohexylcarbonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, lauroyl peroxide, diisopropyl peroxydicarbonate, tert-butyl peroxypivalate.
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