CN112239519B - Lithium carbonate-containing ionic copolymer and preparation method thereof - Google Patents

Lithium carbonate-containing ionic copolymer and preparation method thereof Download PDF

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CN112239519B
CN112239519B CN202011066294.XA CN202011066294A CN112239519B CN 112239519 B CN112239519 B CN 112239519B CN 202011066294 A CN202011066294 A CN 202011066294A CN 112239519 B CN112239519 B CN 112239519B
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lithium carbonate
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景浩
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Fluorogold Shanghai New Materials Co ltd
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Abstract

A contains lithium carbonate ionic copolymer and its preparation method, said contains lithium carbonate ionic copolymer including polyvinylidene fluoride constitutional unit, acrylate constitutional unit and vinyl lithium carbonate constitutional unit; the preparation method comprises the following steps: and (2) respectively adding a vinylidene fluoride monomer, an acrylate monomer, a vinyl lithium carbonate monomer and an initiator into a reaction device, and carrying out one-step copolymerization by using a polymerization reaction method to obtain the product. The invention reserves the advantageous structure of polyvinylidene fluoride, ensures that the copolymer has enough mechanical strength and thermal stability, overcomes the defects of the existing PVDF as the polymer lithium ion battery material by introducing a lithium ion high-efficiency transmission structural unit, a polar group and a large number of ultrastable structural units, optimizes the transmission efficiency of lithium ions, improves the ionic conductivity of the lithium battery, reduces the polarization of the battery in the charging process, improves the charge and discharge performance of the battery, and provides a new material and a new method for further development and application of the lithium battery.

Description

Lithium carbonate-containing ionic copolymer and preparation method thereof
Technical Field
The invention relates to a lithium ion polymer and a preparation method thereof, in particular to a lithium carbonate-containing ion copolymer and a preparation method thereof, belonging to the technical field of production and manufacturing of lithium ion polymer batteries.
Background
The polymer lithium ion battery has the characteristics of small volume, light weight, high energy density, small self-discharge, no memory effect, good safety performance, capability of being made into any shape and the like, is the most advanced rechargeable battery at present, and is researched and developed vigorously by main scientific and technological strong countries in the world at present.
Lithium polymer batteries are mainly composed of a positive electrode, a negative electrode, separator paper, and the like, and in lithium polymer batteries developed at present, polymer materials are mainly applied to the positive electrode and an electrolyte.
The high molecular material polyvinylidene fluoride (PVDF) is a homopolymer of VDF, and is a thermoplastic fluorine-containing polymer, and the repeating unit of the molecular chain is-CH2-CF2The PVDF fluororesin has the characteristics of both fluorine-containing resin and general resin due to the special molecular structure, has good chemical stability and thermal stability, and has excellent electrochemical performance which is widely applied to lithium batteries as a positive electrode material, a binder, a negative electrode material, a battery diaphragm and the like.
Since the operation process of the lithium battery can be regarded as the "reciprocating motion" of lithium ions between two electrodes, along with the cyclic intercalation and deintercalation of the lithium ions, the polymer used in the lithium battery has higher requirements on the conductivity, lithium ion mobility and electrochemical stability of the material.
However, because polyvinylidene fluoride is a crystalline polymer, the crystallinity is between 60% and 80%, the dielectric constant and the ohmic resistance are high, and the crystal melting temperature is about 140 ℃, under the normal use temperature of the battery, the PVDF polymer is purely used as a battery material, and the crystalline unit of the PVDF polymer can obstruct the transmission of ions in the electrolytic liquid, thereby greatly reducing the transmission efficiency of the ions and seriously influencing the charge and discharge performance of the lithium battery.
In addition, the stronger acting force among the PVDF molecules enables the internal free volume of the polymer to be smaller, so that the number of internal ion transfer channels is reduced;
more seriously, the smaller internal free volume of PVDF polymer can reduce the adsorption capacity of the electrolyte and reduce the "back-and-forth" mobility of lithium ions.
At present, aiming at the defects of PVDF in lithium batteries, the prior art mainly introduces a conductive agent containing a lithium sulfonate component in a blending mode to improve the ion transmission performance of materials, such as:
the invention patent application (application number: 201611173765.0) provides a single ion gel polymer electrolyte and a preparation method thereof;
the invention patent application (application number: 201611145093.2) provides a lithium single-ion conductive solid polymer electrolyte, and the like.
However, although the addition of a conductive agent is effective in improving the electrochemical performance of the material, it reduces the compatibility of PVDF with other materials, weakens the adhesive force of the polymer material itself and the durability of the adhesive force, and causes problems such as easy partial or complete peeling of the electrode binder layer from the current collector, deterioration of load characteristics, and capacity deterioration.
In addition, there is also a related art that introduces a lithium sulfonate structure into the PVDF structure by way of copolymerization to improve ion conduction performance, such as:
the invention provides a manufacturing process of an electrolyte membrane special for a solid lithium ion battery (application number: 02138204.2).
However, the copolymer obtained in this way has lower chemical stability and other properties than those of the corresponding PVDF homopolymer because of the introduction of a large number of carbon-hydrogen bonds (C-H) in the copolymerization process and the stability of the copolymer is not as high as that of the carbon-fluorine bonds (C-F) in the PVDF structure.
Therefore, the chemical structure of the PVDF homopolymer is optimized so as to obtain the vinylidene fluoride multipolymer with more excellent performance, the lithium ion mobility of the PVDF copolymer is effectively improved, and the method has important significance for the development and application of lithium ion batteries.
Disclosure of Invention
In order to overcome the defects of the related technology, the invention provides a lithium carbonate-containing ionic copolymer and a preparation method thereof, aiming at:
the structural advantages of PVDF are retained, meanwhile, a structural unit (lithium carbonate structural unit) with high ion transmission efficiency is introduced into the structure in a copolymerization mode, a high-speed lithium ion transmission channel can be constructed in the material, the purposes of optimizing the transmission efficiency of PVDF ions and improving the ionic conductivity of the lithium battery are finally achieved, the polarization of the battery in the charging process can be reduced, the charging and discharging performance of the battery is improved, and an important polymer material is provided for further research and application of the lithium battery;
in addition, the acrylate structural unit can effectively regulate and control the molecular weight and molecular weight distribution of the polymer;
in addition, by introducing a large number of polar groups (ester bonds and carbonic acid bonds) into the copolymer structure, the physicochemical properties (viscosity, solubility, crystallinity and the like) of the copolymer can be effectively controlled by adjusting the proportion of the polar units.
In order to achieve the above object, the present invention provides a lithium carbonate-containing ionic copolymer, comprising:
the copolymer consists of three compound structural units, namely a polyvinylidene fluoride structural unit (A) consisting of x molar parts of vinylidene fluoride monomers, an acrylate structural unit (B) consisting of y molar parts of acrylate monomers and a vinyl lithium carbonate structural unit (C) consisting of z molar parts of vinyl lithium carbonate monomers; and is
The copolymer has the following structural general formula:
Figure GDA0003486040120000031
among the acrylate structural units, it:
r is H or CH3，m≥0；
Among the vinyl lithium carbonate structural units, it:
n≥1；
the respective mole fractions of the polyvinylidene fluoride structural unit, the acrylate structural unit and the vinyl lithium carbonate structural unit are respectively as follows:
x/(x+y+z)＝0.55～0.85，y/(x+y+z)＝0.05～0.15，z/(x+y+z)＝0.05～0.25。
further, the method comprises the following steps:
among the vinyl lithium carbonate structural units, it:
n is any one of 1, 2 and 3;
the respective mole fractions of the polyvinylidene fluoride structural unit, the acrylate structural unit and the vinyl lithium carbonate structural unit are respectively as follows:
x/(x+y+z)＝0.60～0.80，y/(x+y+z)＝0.10～0.15，z/(x+y+z)＝0.10～0.20。
further, the invention also provides a preparation method of the lithium carbonate-containing ionic copolymer, which comprises the following steps:
in a reaction device, adding a vinylidene fluoride monomer, an acrylate monomer, a vinyl lithium carbonate monomer and an initiator according to respective mole fractions of a polyvinylidene fluoride structural unit, an acrylate structural unit and a vinyl lithium carbonate structural unit, and copolymerizing by adopting a polymerization reaction method to prepare the lithium carbonate ion-containing copolymer, wherein the reaction formula is as follows:
Figure GDA0003486040120000041
further, in the above preparation method:
the reaction device is a high-pressure reaction kettle;
in the step of respectively adding the vinylidene fluoride monomer, the acrylate monomer, the vinyl lithium carbonate monomer and the initiator, the method specifically comprises the following steps:
adding an acrylate monomer, a vinyl lithium carbonate monomer and an initiator into the high-pressure reaction kettle, repeatedly evacuating to remove oxygen, then filling vinylidene fluoride monomer gas in a nitrogen atmosphere, and keeping the pressure in the high-pressure reaction kettle between 1.25 and 1.85 MPa;
the step of preparing the lithium carbonate-containing ionic copolymer by copolymerization through a polymerization reaction method specifically comprises the following steps:
slowly heating the materials in the high-pressure reaction kettle to 75-135 ℃, reacting for 12-36 hours by a polymerization reaction method under mechanical stirring, cooling to room temperature, releasing unreacted gas to obtain a lithium carbonate-containing ionic copolymer emulsion, demulsifying the emulsion by using an ethanol solution to obtain a broken emulsion, washing the broken emulsion to remove an emulsifier and unreacted vinylidene fluoride monomer, acrylate monomer and vinyl lithium carbonate monomer, and drying to obtain the lithium carbonate-containing ionic copolymer.
Further:
the initiator is one of benzoyl peroxide, azo compounds or persulfate;
the polymerization reaction method is any one of emulsion polymerization, suspension polymerization or aqueous solution polymerization.
And further:
the emulsion polymerization method further comprises an emulsifier, wherein the emulsifier is ammonium perfluorooctanoate.
And further:
the aqueous phase solution polymerization method further comprises a dispersion medium, wherein the dispersion medium is trifluorotrichloroethane.
Further, the method comprises the following steps:
and after the emulsion is demulsified by an ethanol solution to obtain a demulsified emulsion, dissolving the demulsified solution in an organic solvent to wait for the subsequent washing and drying operation steps, wherein the organic solvent is one or a mixture of more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, ethanol, isopropanol, dimethyl sulfoxide or ethyl acetate.
Compared with the prior art, the invention has the beneficial effects and remarkable progress that:
(1) the lithium carbonate-containing ionic copolymer provided by the invention introduces a vinyl lithium carbonate conducting unit into a PVDF structure in a copolymerization mode, and provides a new method for applying a PVDF material to the field of lithium batteries.
(2) The lithium carbonate-containing ionic copolymer provided by the invention contains a lithium carbonate structure, adopts a one-step copolymerization process, and is simple, convenient and effective.
(3) The comonomer vinyl lithium carbonate in the lithium carbonate-containing ionic copolymer provided by the invention has a self-emulsifying function, and the use of an emulsifier is avoided in the emulsion polymerization process.
(4) The lithium carbonate-containing ionic copolymer provided by the invention does not need subsequent alkali treatment and transformation, and can ensure that the main chain of the PVDF copolymer is not degraded under an alkaline condition.
(5) The acrylate structural unit in the lithium carbonate-containing ionic copolymer provided by the invention has the functions of regulating and controlling the molecular weight and molecular weight distribution of the polymer and improving the mechanical property of the PVDF copolymer.
(6) The lithium carbonate ion-containing copolymer provided by the invention has the advantages of a PVDF structure, and simultaneously, a large number of polar groups (ester bonds and carbonate bonds) are introduced, so that the physicochemical properties of the copolymer, such as the viscosity, the solubility, the crystallinity and the like of the copolymer, can be effectively regulated and controlled.
(7) The lithium carbonate structure unit in the lithium carbonate-containing ionic copolymer provided by the invention is connected with the controllable chain segment, so that the crystallinity and the ionic conductivity of the copolymer can be effectively controlled.
Detailed Description
In order to make the objects, technical solutions, advantages and significant progress of the present invention clearer, the following will clearly and completely describe embodiments and examples provided by the present invention, and obviously, all the described embodiments and examples are only part of the embodiments and examples of the present invention, but not all of them;
all other embodiments or examples, which can be derived by a person skilled in the art from the embodiments presented herein without making any inventive step, are within the scope of the claimed invention.
It should be noted that:
the terms "first," "second," "again," and the like in the description and in the claims of the present invention are used for distinguishing between different objects and not for describing a particular order;
furthermore, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to the listed steps or elements, but may alternatively include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus;
in addition, in the description and claims of the present invention:
the copolymer consists of three compound structural units, namely a polyvinylidene fluoride structural unit (A) consisting of x molar parts of vinylidene fluoride monomers, an acrylic ester structural unit (B) consisting of y molar parts of acrylic ester monomers and a vinyl lithium carbonate structural unit (C) consisting of z molar parts of vinyl lithium carbonate monomers; and is
The copolymer has the following structural general formula:
Figure GDA0003486040120000061
further, in the above structural formula:
x, y and z are respectively the respective mole fractions of a polyvinylidene fluoride structural unit, an acrylate structural unit and a vinyl lithium carbonate structural unit; and is
The polyvinylidene fluoride structural unit, the acrylate structural unit and the vinyl lithium carbonate structural unit respectively account for the following mole fractions in the structure of the lithium carbonate-containing ionic copolymer:
x/(x + y + z), y/(x + y + z), and z/(x + y + z).
It should also be noted that:
the following specific embodiments and examples may be combined with each other, and the same or similar concepts or processes may not be repeated in some embodiments and examples; and is
The reaction apparatus, monomer compounds, initiators, emulsifiers, demulsifiers, organic solvents, and the like, referred to in the following examples and examples, are commercially available.
The technical solution of the present invention will be described in detail below with specific examples and examples.
Example one
This example provides a lithium carbonate-containing ionic copolymer.
The lithium carbonate-containing ionic copolymer provided in this embodiment includes:
the copolymer consists of three compound structural units, namely a polyvinylidene fluoride structural unit (A) consisting of x molar parts of vinylidene fluoride monomers, an acrylate structural unit (B) consisting of y molar parts of acrylate monomers and a vinyl lithium carbonate structural unit (C) consisting of z molar parts of vinyl lithium carbonate monomers; and is
The copolymer has the following structural general formula:
Figure GDA0003486040120000071
wherein:
among the acrylate structural units, it:
r is H or CH3，m≥0；
Vinyl lithium carbonate structural unit, which:
n≥1；
the respective mole fractions of the polyvinylidene fluoride structural unit, the acrylate structural unit and the vinyl lithium carbonate structural unit are respectively as follows:
x/(x+y+z)＝0.55～0.85，y/(x+y+z)＝0.05～0.15，z/(x+y+z)＝0.05～0.25。
as a preferred technical solution, further:
among the vinyl lithium carbonate structural units, it:
n is any one of 1, 2 and 3;
the respective mole fractions of the polyvinylidene fluoride structural unit, the acrylate structural unit and the vinyl lithium carbonate structural unit are respectively as follows:
x/(x+y+z)＝0.60～0.80，y/(x+y+z)＝0.10～0.15，z/(x+y+z)＝0.10～0.20。
from the above description and the general structural formulae, it can be found that:
firstly, the lithium carbonate ion-containing copolymer provided by this embodiment retains the structural advantages of PVDF, and introduces a structural unit (lithium carbonate structural unit) with high ion transmission efficiency into the structure by means of copolymerization, so as to construct a high-speed lithium ion transmission channel in the material, and finally achieve the purposes of optimizing the transmission efficiency of PVDF ions and improving the ionic conductivity of the lithium battery, and reduce the polarization of the battery in the charging process, thereby improving the charging and discharging performance of the battery, and providing an important polymer material for further research and application of the lithium battery; in addition, the acrylate structural unit can effectively regulate and control the molecular weight and molecular weight distribution of the polymer; in addition, by introducing a large number of polar groups (ester bonds and carbonate bonds) into the copolymer structure, the physicochemical properties (viscosity, solubility, crystallinity, and the like) of the copolymer can be effectively controlled by adjusting the proportion of the polar units.
Next, the lithium carbonate ion-containing copolymer provided in this embodiment regulates and controls the acrylate monomer, the vinyl lithium carbonate, and the vinylidene fluoride monomer CH2＝CF2The feeding ratio of the gas monomer adopts the multiple CH addition according to the pressure change of the reaction kettle in the feeding process2＝CF2Of gaseous monomersFeeding in a mode;
thirdly, the lithium carbonate-containing ionic copolymer provided by the embodiment can effectively regulate and control the molecular weight and molecular weight distribution of the copolymer by regulating and controlling the chain segment length of the acrylate structural unit in the copolymer structure, so that the mechanical property of the PVDF copolymer is improved;
in addition, the crystallinity of the copolymer is further controlled by controlling the chain segment length of the alkyl linking group in the vinyl lithium carbonate, the crystalline melting temperature of the PVDF is reduced, and the problems of low ion transmission efficiency, poor charge and discharge capacity, poor load characteristics and the like when the PVDF is used alone as a binder at present are solved;
example two
This example provides a method for preparing a lithium carbonate-containing ionic copolymer.
The preparation method of the lithium carbonate-containing ionic copolymer provided by the embodiment includes the following steps:
in a reaction device, adding a vinylidene fluoride monomer, an acrylate monomer, a vinyl lithium carbonate monomer and an initiator according to respective mole fractions of a polyvinylidene fluoride structural unit, an acrylate structural unit and a vinyl lithium carbonate structural unit, and copolymerizing by adopting a polymerization reaction method to prepare the lithium carbonate ion-containing copolymer, wherein the reaction formula is as follows:
Figure GDA0003486040120000081
further, in the above preparation method:
the reaction device is a high-pressure reaction kettle;
in the step of respectively adding the vinylidene fluoride monomer, the acrylate monomer, the vinyl lithium carbonate monomer and the initiator, the method specifically comprises the following steps:
adding an acrylate monomer, a vinyl lithium carbonate monomer and an initiator into the high-pressure reaction kettle, repeatedly evacuating to remove oxygen, then filling vinylidene fluoride monomer gas in a nitrogen atmosphere, and keeping the pressure in the high-pressure reaction kettle between 1.25 and 1.85 MPa;
the step of preparing the lithium carbonate-containing ionic copolymer by copolymerization through a polymerization reaction method specifically comprises the following steps:
slowly heating the materials in the high-pressure reaction kettle to 75-135 ℃, reacting for 12-36 hours by a polymerization reaction method under mechanical stirring, cooling to room temperature, releasing unreacted gas to obtain a lithium carbonate-containing ionic copolymer emulsion, demulsifying the emulsion by using an ethanol solution to obtain a broken emulsion, washing the broken emulsion to remove an emulsifier and unreacted vinylidene fluoride monomer, acrylate monomer and vinyl lithium carbonate monomer, and drying to obtain the lithium carbonate-containing ionic copolymer.
In this embodiment:
the initiator can be one of benzoyl peroxide, azo compounds or persulfate;
the polymerization method may be any of emulsion polymerization, suspension polymerization, or aqueous solution polymerization.
In the preparation process by using an emulsion polymerization method, an emulsifier can be further included, and the emulsifier is ammonium perfluorooctanoate.
In the preparation process by using the aqueous phase solution polymerization method, the aqueous phase solution polymerization method also comprises a dispersion medium, and the dispersion medium can be trifluorotrichloroethane.
In addition, after the emulsion is demulsified by the ethanol solution to obtain a demulsified emulsion, the demulsified solution can be dissolved in an organic solvent to wait for the subsequent washing and drying operation steps;
the organic solvent may be one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, ethanol, isopropanol, dimethylsulfoxide, or ethyl acetate.
From the above description, it can be found that:
first, in the preparation method of the lithium carbonate-containing ionic copolymer provided in this embodiment, the polymerization method is adopted to copolymerize the monomers including the vinylidene fluoride, the acrylate and the vinyl lithium carbonate into a whole in one step, and the subsequent process of alkali treatment is not required, so that the medium-grade quality of the copolymer is avoidedPotential skeleton structure (-CH)2CF2-) chemical degradation;
secondly, in the preparation method of the lithium carbonate-containing ionic copolymer provided by this embodiment, since the vinyl lithium carbonate in the comonomer has a self-emulsifying function, an emulsifier may not be used or may be used less in the process of performing a polymerization reaction, which not only ensures production, but also reduces production cost and reduces waste discharge, and thus, the preparation method has great popularization and application values.
In addition, the method for preparing the lithium carbonate-containing ionic copolymer provided in this embodiment may:
by regulating and controlling acrylate monomer, vinyl lithium carbonate and vinylidene fluoride monomer CH2＝CF2The feeding ratio of the gas monomer adopts the multiple CH addition according to the pressure change of the reaction kettle in the feeding process2＝CF2Feeding in a gas monomer mode;
by regulating and controlling the chain segment length of the acrylate structural unit in the copolymer structure, the molecular weight and molecular weight distribution of the copolymer can be effectively regulated and controlled, and the mechanical property of the PVDF copolymer is improved;
the crystallinity of the copolymer is further regulated and controlled by regulating and controlling the chain segment length of an alkyl linking group in the vinyl lithium carbonate, the crystallization melting temperature of PVDF is reduced, and the problems of low ion transmission efficiency, poor charge and discharge capacity, poor load characteristics and the like when the PVDF is singly used as a binder at present are solved;
when emulsion polymerization is adopted, ammonium Perfluorooctanoate (PFOA) is adopted as an emulsifier of a reaction system. In addition, the vinyl lithium carbonate monomer has a self-emulsifying function, and can also be subjected to emulsion polymerization without adding an emulsifier.
From the above description, it can be seen that the lithium carbonate-containing ionic copolymer and the preparation method thereof provided by this embodiment have at least the following advantages:
1) the lithium carbonate-containing ionic copolymer provided in this embodiment introduces a vinyl lithium carbonate conducting unit into the PVDF structure by means of copolymerization, and provides a new method for applying the PVDF material to the field of lithium batteries.
2) The lithium carbonate-containing ionic copolymer provided by the embodiment contains a lithium carbonate structure, and a one-step copolymerization process is adopted, so that the method is simple, convenient and effective.
3) The comonomer vinyl lithium carbonate in the lithium carbonate-containing ionic copolymer provided in this example has a self-emulsifying function, and the use of an emulsifier is avoided during the emulsion polymerization process.
4) The lithium carbonate-containing ionic copolymer provided by the embodiment does not need to be subjected to subsequent alkali treatment and transformation, and can ensure that the main chain of the PVDF copolymer is not degraded under an alkaline condition.
5) The acrylate structural unit in the lithium carbonate-containing ionic copolymer provided by the embodiment has the functions of regulating and controlling the molecular weight and molecular weight distribution of the polymer and improving the mechanical property of the PVDF copolymer.
6) The lithium carbonate-containing ionic copolymer provided by the embodiment can introduce a large amount of polar groups (ester bonds and carbonate bonds) while retaining the structural advantages of PVDF, and can effectively regulate and control the physical and chemical properties of the copolymer, such as the viscosity, solubility, crystallinity and the like of the copolymer.
7) In the lithium carbonate-containing ionic copolymer provided in this embodiment, the lithium carbonate structural unit is connected to the controllable segment, so that the crystallinity and the ionic conductivity of the copolymer can be effectively controlled.
In summary, it can be seen that:
the lithium carbonate-containing ionic copolymer and the preparation method thereof provided by the invention are novel and creative and have extremely high popularization and application values.
To further assist understanding of the technical solutions of the present invention, the technical solutions of the present invention are described in more detail below by providing several specific implementation examples.
Examples 1, 1,
Adding CH with the structural formula into a high-pressure reaction kettle which can endure 10MPa2＝CH-COO(CH2)2-CH3And the structural formula is CH2＝CH-C2H4-COOLi+Repeatedly evacuating to remove oxygen, then filling into a mixture with a structural formula of CH in a nitrogen atmosphere2＝CF2Vinylidene fluoride gas of (a);
wherein:
is represented by the structural formula CH2＝CF2The polyvinylidene fluoride structural unit formed by the vinylidene fluoride gas has a structural formula of CH2＝CH-COO(CH2)2-CH3Acrylate structural unit composed of acrylate monomer (A), and acrylate structural unit having a structural formula of CH2＝CH-C2H4-COOLi+The mol fraction ratio of the vinyl lithium carbonate structural unit formed by the vinyl lithium carbonate monomer is as follows:
vinylidene fluoride structural units, acrylate structural units and vinyl lithium carbonate structural units are 0.55: 0.05;
keeping the pressure of the reaction kettle between 1.25MPa, slowly heating to 100 ℃, adding ammonium perfluorooctanoate as an emulsifier under mechanical stirring, and carrying out polymerization reaction for 24 hours by adopting an emulsion polymerization method;
after the reaction is finished, cooling the feed liquid to room temperature, releasing unreacted gas to obtain uniform copolymer emulsion, demulsifying the emulsion by using an ethanol solution, washing, removing an emulsifier, unreacted vinylidene fluoride monomer, acrylate monomer and vinyl lithium carbonate monomer, and drying to obtain the target product lithium carbonate ion-containing copolymer.
Examples 2,
The operation process and method of the present example are substantially the same as those of example 1, except that:
the added acrylate monomer has the structural formula: CH (CH)2＝CH-COO(CH2)3-CH3；
The structural formula of the added vinyl lithium carbonate monomer is as follows: CH (CH)2＝CH-C3H6-COOLi+；
Further:
is represented by the structural formula CH2＝CF2The polyvinylidene fluoride structural unit formed by the vinylidene fluoride gas has a structural formula of CH2＝CH-COO(CH2)3-CH3Acrylate structural unit composed of acrylate monomer (A), and acrylate structural unit having a structural formula of CH2＝CH-C3H6-COOLi+The mol part ratio of the vinyl lithium carbonate structural unit formed by the vinyl lithium carbonate monomer is as follows:
vinylidene fluoride structural units, acrylate structural units and vinyl lithium carbonate structural units are 0.85: 0.15: 0.25;
the pressure of the reaction kettle is kept at 1.50MPa, and the materials are slowly heated and kept at about 95 ℃;
in addition, the emulsion polymerization method is still adopted in the polymerization reaction, but no emulsifier is added, and the vinyl lithium carbonate structural unit is used as the emulsifier to carry out the polymerization reaction.
Examples 3,
The operation process and method of the present example are substantially the same as those of example 1, except that:
the initiator adopts azo compound;
the added acrylate monomer has the structural formula: CH (CH)2＝C-CH3-COO(CH2)3-CH3；
The structural formula of the added vinyl lithium carbonate monomer is as follows: CH (CH)2＝CH-(C2H4)2-COOLi+；
Further:
is represented by the structural formula CH2＝CF2The polyvinylidene fluoride structural unit formed by the vinylidene fluoride gas has a structural formula of CH2＝C-CH3-COO(CH2)3-CH3And an acrylate structural unit composed of an acrylate monomer of the formula2＝CH-(C2H4)2-COOLi+The mol fraction ratio of the vinyl lithium carbonate structural unit formed by the vinyl lithium carbonate monomer is as follows:
vinylidene fluoride structural units, acrylate structural units and vinyl lithium carbonate structural units are 0.60: 0.10;
the pressure of the reaction kettle is kept at 1.85MPa, and the materials are slowly heated and kept at about 75 ℃;
in addition, the polymerization reaction adopts a suspension polymerization method and does not add an emulsifier.
Examples 4,
The operation process and method of the present example are substantially the same as those of example 3, except that:
the added acrylate monomer has the structural formula: CH (CH)2＝C-CH3-COO(CH2)2-CH3；
The structural formula of the added vinyl lithium carbonate monomer is as follows: CH (CH)2＝CH-C5H10-COOLi+；
Further:
is represented by the structural formula CH2＝CF2The polyvinylidene fluoride structural unit formed by the vinylidene fluoride gas has a structural formula of CH2＝C-CH3-COO(CH2)2-CH3Acrylate structural unit composed of acrylate monomer (A), and acrylate structural unit having a structural formula of CH2＝CH-C5H10-COOLi+The mol fraction ratio of the vinyl lithium carbonate structural unit formed by the vinyl lithium carbonate monomer is as follows:
vinylidene fluoride structural unit, acrylic ester structural unit and vinyl lithium carbonate structural unit are 0.80: 0.15: 0.20;
the pressure of the reaction kettle is kept at 1.60MPa, and the materials are slowly heated and kept at about 135 ℃.
Examples 5,
The operation process and method of the present example are substantially the same as those of example 1, except that:
the initiator adopts sulfate;
the added acrylate monomer has the structural formula: CH (CH)2＝C-CH3-COO(CH2)4-CH3；
The structural formula of the added vinyl lithium carbonate monomer is as follows: CH (CH)2＝CH-(C2H4)3-COOLi+；
Further:
is represented by the structural formula CH2＝CF2The polyvinylidene fluoride structural unit formed by the vinylidene fluoride gas has a structural formula of CH2＝C-CH3-COO(CH2)4-CH3Acrylate structural unit composed of acrylate monomer (A), and acrylate structural unit having a structural formula of CH2＝CH-(C2H4)3-COOLi+The mol fraction ratio of the vinyl lithium carbonate structural unit formed by the vinyl lithium carbonate monomer is as follows:
vinylidene fluoride structural units, acrylate structural units and vinyl lithium carbonate structural units are 0.58: 0.08;
the pressure of the reaction kettle is kept at 1.75MPa, and the materials are slowly heated and kept at about 85 ℃;
in addition, the polymerization reaction adopts an aqueous phase solution polymerization method, and the emulsifier is not added, but the trichlorotrifluoroethane is added as a dispersion medium to carry out polymerization reaction to obtain copolymer emulsion;
and demulsifying the emulsion by using an ethanol solution, dissolving the emulsion in one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, ethanol, isopropanol, dimethyl sulfoxide and ethyl acetate for storage, washing when necessary, removing an emulsifier, an organic solvent and unreacted structural units, and drying to obtain the target product copolymer.
Examples 6,
The operation process and method of the present example are substantially the same as those of example 5, except that:
the structural formula of the added vinyl lithium carbonate monomer is as follows: CH (CH)2＝CH-C2H4-COOLi+；
Further:
is represented by the structural formula CH2＝CF2The polyvinylidene fluoride structural unit formed by the vinylidene fluoride gas has a structural formula of CH2＝C-CH3-COO(CH2)4-CH3Acrylate structural unit composed of acrylate monomer (A), and acrylate structural unit having a structural formula of CH2＝CH-C2H4-COOLi+The mol fraction ratio of the vinyl lithium carbonate structural unit formed by the vinyl lithium carbonate monomer is as follows:
vinylidene fluoride structural unit, acrylate structural unit and vinyl lithium carbonate structural unit are 0.83: 0.13: 0.23;
in addition, the pressure in the reactor was maintained at 1.55MPa, and the batch was slowly heated and maintained at about 105 ℃.
The following are specifically mentioned:
the above examples are only partial implementation examples provided for illustrating the technical solution of the present invention, and for the vinyl lithium carbonate structural unit, in addition to the monomers of the specific structural formula exemplified in the above examples, the structural formula of the monomers is as follows: CH (CH)2＝CR-COO(CH2)m-CH3；
The various monomers with n ≧ 1, especially the various monomers with n being 1, 2, 3, the related products obtained after copolymerization, also have the same or similar functions and effects as the products obtained in the above examples, and the copolymerization methods and control conditions are also the same or similar to the methods and conditions listed in the above examples and are included in the ranges listed in the above examples, therefore, the description is omitted and only the summary description is made;
EXAMPLES 1 to 6 molecular weight and distribution, ion conductivity and crystallinity were measured
[ molecular weight and distribution ] in this experiment, the weight average relative molecular mass and the relative molecular mass distribution of the copolymer were measured by PL-220 type high temperature gel permeation chromatograph. In the experiment, N-dimethylformamide is taken as a solvent, and the measurement is carried out at 160 ℃. And processing data by adopting a universal correction method with narrow-distribution vinylidene fluoride as a standard sample.
[ CRYSTALLINE ] this experiment was carried out by using DSC2910, manufactured by TA, USA, and testing under nitrogen atmosphere according to GB/T19466.3-2004. The sample is heated from room temperature to 150 ℃ at the speed of 10 ℃/min, is kept at the constant temperature for 5min and then is naturally cooled to the room temperature. The DSC curve was then recorded by temperature increasing scanning at a rate of 10 deg.C/min (room temperature to 150 deg.C).
Xi＝(ΔHf/293)*100％
In the formula: Δ Hf is the enthalpy of fusion of the sample polymer, in units of J.g-1. 293 is the enthalpy of fusion at 100% crystallinity of polyethylene, in J.g-1
[ ionic conductivity ] the copolymer is hot-pressed into a membrane at 150 ℃, a two-electrode method is adopted to test the membrane resistance R of the membrane after the propylene carbonate swells, an instrument is used as an electrochemical workstation AutolabPGSTA302, the frequency interval is 106Hz-10Hz, and the conductivity is calculated through a calculation formula sigma L/RS.
L is the thickness (cm) of the swollen membrane, R is the resistance (Ω) of the swollen membrane, σ is the conductivity (S/cm) of the swollen sample, and S is the area (cm) of the test portion of the swollen sample2)。
The test results are shown in table 1.
TABLE 1
Molecular weight Crystallinity (%) Ion conductivity (S/cm)
Example 1 300000 32 1.9×10-7
Example 2 330000 28 5.8×10-4
Example 3 310000 26 3.9×10-4
Example 4 410000 35 2.1×10-4
Example 5 400000 38 0.6×10-4
Example 6 340000 27 0.2×10-4
The test results are as follows: examples 1-6 molecular weight 310000--7-5.8×10-4. The results prove that the polymeric material provided by the invention has better stability, crystallinity and ionic conductivity.
In the course of the description of the above description:
the descriptions of the terms "present embodiment," "present example," "further," "even further," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention;
in this specification, the schematic representations of the terms used above are not necessarily for the same embodiment or example, and the particular features, structures, materials, or characteristics described, etc., may be combined or brought together in any suitable manner in any one or more embodiments or examples;
furthermore, those of ordinary skill in the art may combine or combine features of different embodiments or examples and features of different embodiments or examples described in this specification without undue conflict.
Finally, it should be noted that:
although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made on the technical solutions described in the foregoing embodiments, or some or all of the technical features of the embodiments can be equivalently replaced, and the corresponding technical solutions do not depart from the technical solutions of the embodiments of the present invention.

Claims (9)

1. A lithium carbonate-containing ionic copolymer comprising:
the copolymer consists of three compound structural units, namely a polyvinylidene fluoride structural unit (A) consisting of x molar parts of vinylidene fluoride monomers, an acrylic ester structural unit (B) consisting of y molar parts of acrylic ester monomers and a vinyl lithium carbonate structural unit (C) consisting of z molar parts of vinyl lithium carbonate monomers; and is
The copolymer has the following structural general formula:
Figure FDA0003486040110000011
among the acrylate structural units, the following:
r is H or CH3，m≥0；
Among the vinyl lithium carbonate structural units, it:
n≥1；
the respective mole fractions of the polyvinylidene fluoride structural unit, the acrylic ester structural unit and the vinyl lithium carbonate structural unit are respectively as follows:
x/(x+y+z)＝0.55～0.85，y/(x+y+z)＝0.05～0.15，z/(x+y+z)＝0.05～0.25。
2. the lithium carbonate-containing ionic copolymer of claim 1, wherein:
among the vinyl lithium carbonate structural units, it:
n is any one of 1, 2 and 3;
the respective mole fractions of the polyvinylidene fluoride structural unit, the acrylate structural unit and the vinyl lithium carbonate structural unit are respectively as follows:
x/(x+y+z)＝0.60～0.80，y/(x+y+z)＝0.10～0.15，z/(x+y+z)＝0.10～0.20。
3. a method for preparing the lithium carbonate-containing ionic copolymer according to claim 1 or 2, comprising the steps of:
in a reaction device, adding a vinylidene fluoride monomer, an acrylate monomer, a vinyl lithium carbonate monomer and an initiator according to respective mole fractions of a polyvinylidene fluoride structural unit, an acrylate structural unit and a vinyl lithium carbonate structural unit, and copolymerizing by adopting a polymerization reaction method to prepare the lithium carbonate ion-containing copolymer, wherein the reaction formula is as follows:
Figure FDA0003486040110000021
4. the method of preparing a lithium carbonate-containing ionic copolymer according to claim 3, wherein:
the reaction device is a high-pressure reaction kettle;
in the step of respectively adding the vinylidene fluoride monomer, the acrylate monomer, the vinyl lithium carbonate monomer and the initiator, the method specifically comprises the following steps:
firstly, adding an acrylate monomer, a vinyl lithium carbonate monomer and an initiator into the high-pressure reaction kettle, repeatedly evacuating to remove oxygen, then filling vinylidene fluoride monomer gas into the high-pressure reaction kettle in a nitrogen atmosphere, and keeping the pressure in the high-pressure reaction kettle between 1.25 and 1.85 MPa;
the step of preparing the lithium carbonate-containing ionic copolymer by copolymerization through a polymerization reaction method specifically comprises the following steps:
slowly heating the materials in the high-pressure reaction kettle to 75-135 ℃, reacting for 12-36 hours by a polymerization reaction method under mechanical stirring, cooling to room temperature, releasing unreacted gas to obtain a lithium carbonate-containing ionic copolymer emulsion, demulsifying the emulsion by using an ethanol solution to obtain a broken emulsion, washing the broken emulsion to remove an emulsifier and unreacted vinylidene fluoride monomer, acrylate monomer and vinyl lithium carbonate monomer, and drying to obtain the lithium carbonate-containing ionic copolymer.
5. The method of preparing a lithium carbonate-containing ionic copolymer according to claim 4, wherein: the initiator is one of benzoyl peroxide, azo compounds or persulfate.
6. The method of preparing a lithium carbonate-containing ionic copolymer according to claim 4, wherein: the polymerization reaction method is any one of emulsion polymerization, suspension polymerization or aqueous solution polymerization.
7. The method of preparing a lithium carbonate-containing ionic copolymer according to claim 6, wherein: the emulsion polymerization method further comprises an emulsifier, wherein the emulsifier is ammonium perfluorooctanoate.
8. The method of preparing a lithium carbonate-containing ionic copolymer according to claim 6, wherein: the aqueous phase solution polymerization method further comprises a dispersion medium, wherein the dispersion medium is trifluorotrichloroethane.
9. The method of preparing a lithium carbonate-containing ionic copolymer according to claim 4, wherein:
and after the emulsion is demulsified by an ethanol solution to obtain a demulsified emulsion, dissolving the demulsified solution in an organic solvent to wait for the subsequent washing and drying operation steps, wherein the organic solvent is one or a mixture of more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, ethanol, isopropanol, dimethyl sulfoxide or ethyl acetate.
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