CN114335695A - In-situ generated silicon dioxide composite solid polymer electrolyte and application thereof in lithium battery - Google Patents
In-situ generated silicon dioxide composite solid polymer electrolyte and application thereof in lithium battery Download PDFInfo
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Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a silicon dioxide composite solid polymer electrolyte generated in situ and application thereof in a lithium battery. The invention mixes the inorganic filler into the polyethylene oxide by the method of in-situ generation to lead the SiO2More uniform distribution in PEO matrix, and SiO in the material2The nanospheres and lithium salt interact with the PEO matrix chain to disturb the order of chain segments in the polymer matrix, thereby reducing the crystallinity of the PEO matrix chain, and the interaction generated among the polymer, the lithium salt and the inorganic filler increases a lithium ion transmission channel, thereby improving the ionic conductivity of the PEO matrix chain; and are interlaced and deposited into the in-situ SiO of the non-woven fabric fiber structure after solvent evaporation2The composite solid polymer electrolyte has high porosity, can further improve the electrochemical performance and the mechanical property, and is applied to new energy automobiles, portable electronic equipment, communication equipment and intelligent equipmentPlays more and more important roles in the fields of standby, energy storage and the like.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a silicon dioxide composite solid polymer electrolyte generated in situ and application thereof in a lithium battery.
Background
The electrolyte of the commercial lithium ion battery has considerable potential safety hazards of easy leakage, easy volatilization, easy flammability and easy explosion, and the like, and liquid electrolyte is replaced by solid electrolyte, so that the adjustment of an industrial structure and the conversion of energy to green are promoted. Compared with commercial lithium batteries, the solid-state lithium battery well solves the safety problem of organic electrolyte, has the advantages of high energy density, long cycle life and the like, and is one of the hotspots in the research field of the current lithium battery.
The all-solid electrolytes in solid-state lithium batteries fall into two broad categories, inorganic all-solid electrolytes and all-Solid Polymer Electrolytes (SPE). Among them, the inorganic all-solid electrolyte has good chemical stability and mechanical strength, and high room temperature ionic conductivity, but its brittleness is large, resulting in poor processability. The all-solid-State Polymer Electrolyte (SPE) has lower ionic conductivity, but is easier to form and more suitable for large-scale production, so the SPE has better development prospect.
Addition of titanium dioxide (TiO) to PEO-salt systems2) Silicon dioxide (SiO)2) And the inorganic particles are used for forming the composite polymer electrolyte, and the method is an effective way for improving the room-temperature ionic conductivity of the composite polymer electrolyte. But adopts an in-situ compounding method to prepare TiO2The composite polymer electrolyte can effectively improve the ionic conductivity of the polymer electrolyte, but because of TiO2The reaction rate is high in the generation process, and partial particles are agglomerated to influence the electrochemical performance of the polymer electrolyte. The influence of the inorganic particles on the conductivity of the composite polymer electrolyte system depends not only on the type of the particles themselves but also on the particle size, particle shape, and distribution thereof in the electrolyte system. Therefore, the improvement of all-solid-state polymer electrolysis is made by controlling the particle size, particle shape and distribution of inorganic particles in the electrolyte systemThe ion conductivity of the electrolyte is the most effective scheme at present, for example, the patent "a solid polymer electrolyte and a preparation method thereof" (CN105680092A) provides a preparation method of a solid polymer electrolyte of a lithium ion battery doped with modified mesoporous silica, but the addition mode used by the modified mesoporous silica has its own limitations, such as: the inorganic nanoparticles added by the stirring mode in the water bath have high surface energy, are easy to agglomerate, have hydrophilic and oleophobic surfaces, and are difficult to disperse uniformly in an organic medium, thereby reducing the modification effect of the inorganic nanoparticles on the polymer electrolyte.
Disclosure of Invention
In order to solve the problems of low ionic conductivity, unstable interface contact and the like of the conventional solid polymer electrolyte, the invention aims to provide the in-situ generated silicon dioxide composite solid polymer electrolyte and application thereof in a lithium battery. The invention mixes the inorganic filler into the polyethylene oxide by the method of in-situ generation to lead the SiO2More uniform distribution in PEO matrix, and SiO in the material2The interaction of the nanospheres and lithium salt with the PEO matrix chain disturbs the order of the chain segments in the polymer matrix, thereby reducing its crystallinity, and the interaction between the polymer, lithium salt and inorganic filler increases the lithium ion transport channels, thereby increasing the in situ SiO2Ionic conductivity of the composite solid polymer electrolyte (i.e., the in situ generated silica composite solid polymer electrolyte). In addition, the in-situ SiO of the non-woven fabric fiber structure is formed by staggered deposition after solvent evaporation2The composite solid polymer electrolyte has high porosity, and can further improve the electrochemical performance and the mechanical performance of the composite solid polymer electrolyte.
The electrostatic spinning technology is a process that under the action of a high-voltage electric field, precursor solution is sprayed from a capillary tip, and is interlaced and deposited into non-woven fabric fibers after solvent evaporation. The electrostatic spinning nanofiber has higher specific surface area and porosity, an electrolyte membrane prepared by the electrostatic spinning technology can provide an ion transmission channel, the ionic conductivity is effectively improved, and the electrode and diaphragm material with a highly flexible and foldable layered structure prepared by the technology is a novel high-performance energy storage material with a very promising prospect.
The invention adopts a method of combining in-situ synthesis and electrostatic spinning technology to generate SiO in situ on the surface of a PEO matrix2And then combined with lithium salt to prepare in-situ SiO2Composite solid polymer electrolyte prepared by reacting in-situ SiO2Characterization of the composite solid polymer electrolyte, such as measuring ionic conductivity by an impedance method, measuring an electrochemical stability window by a voltammetry method, measuring a lithium ion migration number by a steady-state current method, and the like, is performed to meet the purpose of commercialization of the solid lithium battery, and plays an increasingly important role in the fields of new energy automobiles, portable electronic equipment, communication equipment, intelligent equipment, energy storage, and the like.
The purpose of the invention can be realized by the following technical scheme:
the first purpose of the invention is to provide an in-situ generated SiO2A method of making a composite solid polymer electrolyte comprising the steps of:
(1) solution preparation: uniformly mixing PEO with a first organic solvent to obtain a PEO solution; uniformly mixing ammonia water and alcohol or uniformly mixing ammonia water and deionized water to obtain an ammonia precursor solution;
(2) first SiO2Preparation of nanosphere solution: adjusting deionized water to be alkaline, heating in water bath, adding tetraethoxysilane, uniformly mixing and diluting to obtain first SiO2A nanosphere solution;
(3) second SiO2Preparation of nanosphere solution: adding the PEO solution prepared in the step (1), the ammonia precursor solution and the first SiO prepared in the step (2) into a second organic solvent in sequence2Mixing the nanosphere solution uniformly, adding ethyl orthosilicate to obtain second SiO2A nanosphere solution;
(4) preparing an electrostatic spinning solution: the second SiO obtained in the step (3)2Uniformly mixing the nanosphere solution with lithium salt, and drying in a vacuum oven to remove the organic solvent to obtain an electrostatic spinning solution;
(5) in-situ SiO2Preparation of composite solid polymer electrolyte: electrostatically directly spraying the electrostatic spinning solution prepared in the step (4) to a receiver to obtain the in-situ SiO with the nanofiber structure2A composite solid polymer electrolyte.
In one embodiment of the present invention, in step (1), the first organic solvent is selected from one or more of diethyl ether, ethanol, acetonitrile, tetrahydrofuran, malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, nonanedionitrile or decanedionitrile;
the dosage ratio of the ammonia water to the alcohol is (3.2 mL: 34.8mL) - (4.8 mL: 23.2 mL);
the dosage ratio of the ammonia water to the deionized water is (3.2 mL: 34.8mL) - (4.8 mL: 23.2 mL);
the ratio of the amount of PEO to the first organic solvent was (0.56 mL: 14.4mL) - (0.84 mL: 9.6 mL).
In one embodiment of the present invention, in the step (2), the amount ratio of the ethyl orthosilicate to the deionized water is (1.68 mL: 36mL) - (2.52 mL: 24 mL).
In one embodiment of the present invention, in step (3), the second organic solvent is selected from one or more of diethyl ether, ethanol, acetonitrile, tetrahydrofuran, malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, nonanedionitrile or decanedionitrile;
a second organic solvent, an ammonia precursor solution, a first SiO2The dosage ratio of the nanosphere solution to the tetraethoxysilane is 25-50 mL: 8-12 mL: 0.08-0.60 mL: 0.2776-0.4164 g.
In one embodiment of the present invention, in the step (4), the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonyl imide, lithium dioxalate borate, lithium difluorooxalate borate, lithium trifluoromethanesulfonate or lithium bistrifluoromethylsulfonyl imide;
second SiO2The molar ratio of the nanosphere solution to the lithium salt is (4: 1) - (16: 1).
In one embodiment of the invention, in the step (4), the drying temperature is 35-80 ℃ and the drying time is 5-24h during the drying process.
In one embodiment of the present invention, in the step (5), in the electrospinning process, the receiver is one of a metal mesh receiver, a spindle receiver, a cage-type rotor receiver, a disk receiver, an X-Y moving stage receiver, a strip-type electrode receiver, a ring-type electrode receiver, a sheet-type electrode receiver, a flat plate receiver, a turntable receiver, a patterned receiver, a water bath receiver, or a double-spindle receiver.
In one embodiment of the present invention, in the step (5), during the electrospinning process, the electrospinning parameters are: the moving speed of the nozzle is 0.01-100mm/s, the moving distance is 1-8000mm, the pushing speed of the needle tube is 0.001-80mm/min, the spinning temperature is 20-80 ℃, the negative voltage is 1-80kV, and the positive voltage is 1-100 kV.
It is a second object of the present invention to provide an in situ formed SiO prepared by the above method2A composite solid polymer electrolyte.
The third purpose of the invention is to provide the in-situ generated SiO2The application of the composite solid polymer electrolyte in preparing a solid lithium battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention uses the in-situ generation method to prepare SiO2Incorporation into polyethylene oxide to form SiO2More uniform distribution in PEO matrix, and SiO in the material2The nanospheres and lithium salt interact with the PEO matrix chain, disturbing the order of the segments in the polymer matrix, thereby reducing its crystallinity, and the polymer, lithium salt and SiO2The generated interaction increases the lithium ion transmission channel, thereby improving the in-situ SiO2Ionic conductivity of the composite solid polymer electrolyte. In addition, the electrolyte membrane which is subjected to solvent evaporation and then is deposited into a non-woven fabric fiber structure in a staggered mode has high porosity, and in-situ SiO (silicon dioxide) can be further improved2The electrochemical performance and the mechanical performance of the composite solid polymer electrolyte play more and more important roles in the fields of new energy automobiles, portable electronic equipment, communication equipment, intelligent equipment, energy storage and the like.
(2) The technical scheme provided by the invention can obtain the ionic conductivity with excellent ionic conductivity in a short time through a simple process flowAnd certain electrochemical and thermal stability of in situ SiO2A composite solid polymer electrolyte. The invention uses the in-situ SiO2The composite solid polymer electrolyte is used for battery assembly and test, and the in-situ SiO of the electrode material is realized2The composite solid polymer electrolyte is subjected to charge-discharge circulation for a long time, and the fact that the composite solid polymer electrolyte can be applied to a solid lithium battery is proved.
(3) The invention provides two ammonia precursor solution preparation methods, wherein the in-situ SiO is prepared by electrostatic spinning of spinning solution prepared from ammonia water and alcohol ammonia precursor solution2The composite solid polymer electrolyte membrane is prepared by electrostatic spinning of the spinning solution prepared by using ammonia water and deionized water2The composite solid polymer electrolyte membrane has good film forming property and mechanical property, and is beneficial to the assembly of a battery later.
Drawings
FIG. 1 is a schematic diagram of a lithium ion button cell assembled with an in situ generated silica composite solid polymer electrolyte prepared by example 1;
FIG. 2 is a schematic view of an in-situ formed silica composite solid polymer electrolyte membrane prepared in example 1 of the present invention;
FIG. 3 is a schematic view of an in-situ formed silica composite solid polymer electrolyte membrane prepared in example 2 of the present invention;
FIG. 4 is a plot of the AC impedance of a test of a lithium ion button cell assembled with an in situ generated silica composite solid polymer electrolyte prepared by example 1;
fig. 5 is a linear sweep voltammogram of a lithium ion coin cell test assembled with in situ generated silica composite solid polymer electrolyte prepared by example 1.
Detailed Description
The invention provides an in-situ generated SiO2A method of making a composite solid polymer electrolyte comprising the steps of:
(1) solution preparation: uniformly mixing PEO with a first organic solvent to obtain a PEO solution; uniformly mixing ammonia water and alcohol or uniformly mixing ammonia water and deionized water to obtain an ammonia precursor solution;
(2) first SiO2Preparation of nanosphere solution: adjusting deionized water to be alkaline, heating in water bath, adding tetraethoxysilane, uniformly mixing and diluting to obtain first SiO2A nanosphere solution;
(3) second SiO2Preparation of nanosphere solution: adding the PEO solution prepared in the step (1), the ammonia precursor solution and the first SiO prepared in the step (2) into a second organic solvent in sequence2Mixing the nanosphere solution uniformly, adding ethyl orthosilicate to obtain second SiO2A nanosphere solution;
(4) preparing an electrostatic spinning solution: the second SiO obtained in the step (3)2Uniformly mixing the nanosphere solution with lithium salt, and drying in a vacuum oven to remove the organic solvent to obtain an electrostatic spinning solution;
(5) in-situ SiO2Preparation of composite solid polymer electrolyte: electrostatically directly spraying the electrostatic spinning solution prepared in the step (4) to a receiver to obtain the in-situ SiO with the nanofiber structure2A composite solid polymer electrolyte.
In one embodiment of the present invention, in step (1), the first organic solvent is selected from one or more of diethyl ether, ethanol, acetonitrile, tetrahydrofuran, malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, nonanedionitrile or decanedionitrile;
the dosage ratio of the ammonia water to the alcohol is (3.2 mL: 34.8mL) - (4.8 mL: 23.2 mL);
the dosage ratio of the ammonia water to the deionized water is (3.2 mL: 34.8mL) - (4.8 mL: 23.2 mL);
the ratio of the amount of PEO to the first organic solvent was (0.56 mL: 14.4mL) - (0.84 mL: 9.6 mL).
In one embodiment of the present invention, in the step (2), the amount ratio of the ethyl orthosilicate to the deionized water is (1.68 mL: 36mL) - (2.52 mL: 24 mL).
In one embodiment of the present invention, in step (3), the second organic solvent is selected from one or more of diethyl ether, ethanol, acetonitrile, tetrahydrofuran, malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, nonanedionitrile or decanedionitrile;
a second organic solvent, an ammonia precursor solution, a first SiO2The dosage ratio of the nanosphere solution to the tetraethoxysilane is 25-50 mL: 8-12 mL: 0.08-0.60 mL: 0.2776-0.4164 g.
In one embodiment of the present invention, in the step (4), the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonyl imide, lithium dioxalate borate, lithium difluorooxalate borate, lithium trifluoromethanesulfonate or lithium bistrifluoromethylsulfonyl imide;
second SiO2The molar ratio of the nanosphere solution to the lithium salt is (4: 1) - (16: 1).
In one embodiment of the invention, in the step (4), the drying temperature is 35-80 ℃ and the drying time is 5-24h during the drying process.
In one embodiment of the present invention, in the step (5), in the electrospinning process, the receiver is one of a metal mesh receiver, a spindle receiver, a cage-type rotor receiver, a disk receiver, an X-Y moving stage receiver, a strip-type electrode receiver, a ring-type electrode receiver, a sheet-type electrode receiver, a flat plate receiver, a turntable receiver, a patterned receiver, a water bath receiver, or a double-spindle receiver.
In one embodiment of the present invention, in the step (5), during the electrospinning process, the electrospinning parameters are: the moving speed of the nozzle is 0.01-100mm/s, the moving distance is 1-8000mm, the pushing speed of the needle tube is 0.001-80mm/min, the spinning temperature is 20-80 ℃, the negative voltage is 1-80kV, and the positive voltage is 1-100 kV.
The invention provides an in-situ generated SiO prepared by the method2A composite solid polymer electrolyte.
The invention provides an in-situ generated SiO2The application of the composite solid polymer electrolyte in preparing a solid lithium battery.
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
The present embodiment provides an in-situ SiO2The preparation method of the composite solid polymer electrolyte comprises the following specific steps:
(1) 30mL of deionized water was added to a 100mL beaker. The pH of the deionized water was adjusted to 10.8 with ammonia. Magnetic stirring is carried out while water bath heating is carried out at the temperature of 60 ℃, 2.1g of tetraethoxysilane is dropwise added into the solution, and then stirring is continuously carried out for 24 hours to obtain monodisperse SiO with the particle size of 12nm2Nanosphere seed solution. Magnetic stirring parameters: 600 rpm.
(2) 4mL of ammonia water and 29mL of absolute ethyl alcohol are mixed and stirred uniformly to prepare an ammonia precursor solution. Mixing 0.6g of seed solution with 30mL of deionized water, and uniformly stirring to obtain first SiO2A nanosphere solution. Magnetic stirring parameters: 400 rpm.
(3) 0.6994g of PEO were dissolved in 25mL of acetonitrile to prepare a PEO solution. The PEO solution was added to 25mL of absolute ethanol, followed by 10mL of ammonia precursor solution and 0.2mL of the first SiO2The nanosphere solution was stirred at room temperature for 3 h. Magnetic stirring parameters: 400 rpm.
(4) Dropwise adding 0.347g of ethyl orthosilicate into the solution obtained in the step (3), stirring the solution without stopping the stirring in the dropwise adding process, and then continuously stirring the solution for 12 hours to obtain second SiO with the particle size of 45nm2A nanosphere solution. Magnetic stirring parameters: 500 rpm.
(5) Adding LiClO to the solution obtained in the step (4)4(molar ratio PEO: LiClO)4When the ratio is 8: 1) and magnetically stirring for 5 hours, and then putting the mixture into a vacuum oven at 45 ℃ for evaporation for 6 hours to obtain the electrostatic spinning solution.
(6) Carrying out electrostatic spinning on the electrostatic spinning solution under electrostatic high pressure to a grid receiver, and preparing the in-situ SiO with the grid structure by adjusting the parameters of electrostatic spinning equipment2Composite solid polymer electrolyte, in-situ SiO of grid structure2And (3) drying the composite solid polymer electrolyte for 24 hours in vacuum. The parameters of electrospinning were as follows: the moving speed of the nozzle is 50mm/s, the moving distance is 80mm, the pushing speed of the needle tube is 0.120mm/min, the spinning temperature is 40 ℃, the negative voltage is 2.5kV, and the positive voltage is 14.25 kV.
Using the above-preparedIn-situ SiO2The composite solid polymer electrolyte was subjected to battery assembly (shown in fig. 1 after battery assembly) and testing, specifically as follows:
prepared in-situ SiO2The composite solid polymer electrolyte punching sheet is in a circular shape with the diameter of 19mm, is arranged between two stainless steel electrodes (SS) and is assembled into SS/in-situ SiO2The composite solid polymer electrolyte/SS simulates a battery for detection.
Wherein the preparation process of the test sample is carried out in a glove box, and the oxygen content and the water content of the glove box are both lower than 0.1 ppm. The frequency range of the alternating current impedance test from high frequency to low frequency in the conductivity performance test process is 1MHz to 0.01Hz, the test temperature range of the test sample is 20-60 ℃, the impedance data test is carried out at intervals of 5 ℃, and the test sample is tested after the test temperature is kept for 1 hour before the impedance test. And when the heating temperature reaches 60 ℃, completing the test, cooling the test sample to 30 ℃, then performing impedance test again, performing temperature rise test again every 10 ℃, and keeping the test temperature interval and the test interval consistent. In-situ SiO prepared by AC impedance testing2Impedance value of composite solid polymer electrolyte, and in-situ SiO prepared by calculating impedance value2Ionic conductivity of the composite solid polymer electrolyte.
The analysis result shows that the in-situ SiO2The ionic conductivity of the composite solid polymer electrolyte increases with increasing temperature, and the in-situ SiO2The composite solid polymer electrolyte has good thermal stability. In situ SiO at 60 deg.C, as shown in FIG. 42The impedance of the composite solid polymer electrolyte is far lower than that of the SiO generated in situ2Impedance of the composite solid polymer electrolyte is calculated according to the formula of ionic conductivity, wherein sigma is L/(R)bS) calculation, in-situ generation of SiO2The ionic conductivity of the composite solid polymer electrolyte is 9.35 multiplied by 10-4S/cm, ex situ generation of SiO2The ionic conductivity of the composite solid polymer electrolyte is 1.42 multiplied by 10- 5S/cm, demonstrating the SiO produced by the in situ generation method2Nanosphere ratio mechanical mixed doped SiO2Nanosphere pairThe polymer electrolyte has obvious modification effect, great improvement on ionic conductivity and in-situ SiO2The low impedance and high ionic conductivity of the composite solid polymer electrolyte laterally reflects the in situ SiO2The composite solid polymer electrolyte has the characteristics of high porosity, easy lithium ion migration, good effect of reducing PEO crystallinity and the like. In the ion conductivity calculation formula, L is the thickness (cm) of the electrolyte membrane, and S is the area (cm) of the stainless steel electrode2)，RbThe bulk impedance (Ω) and σ are the ionic conductivity (S/cm).
The reaction of the electrolyte in the battery can be predicted and analyzed according to the change of current and voltage by adopting Linear Sweep Voltammetry (LSV), and the electrochemical stability window of the polymer electrolyte can be determined. In a glove box in argon atmosphere, a polymer electrolyte wafer with the diameter of 19mm is assembled into a lithium wafer/in-situ SiO2And (3) compounding the solid polymer electrolyte/stainless steel sheet sandwich type half-blocking button cell, and then placing the assembled button cell in a blowing drying oven at 80 ℃ for standing for 12 hours. Test scan rate set point is 5mVs-1The voltage range is selected to be 0-6V, the standing time is 2s, and the test temperature is normal temperature.
The test results are shown in FIG. 5, from which it can be found that the samples are at 1-5.2V (vs. Li/Li)+) The curve in the voltage interval is smooth and the current hardly fluctuates, indicating that almost no electrochemical reaction occurs in this interval, and the in-situ SiO2The composite solid polymer electrolyte has certain electrochemical stability. However, when the voltage exceeds 5.2V (vs. Li/Li)+) There is a significant increase in current. This increase in current can be attributed to in situ SiO2Electrochemical reactions taking place within the composite solid polymer electrolyte. The results show that this in situ SiO2The composite solid polymer electrolyte can stably operate in a high-voltage all-solid-state lithium battery.
Example 2
The present embodiment provides an in-situ SiO2A composite solid polymer electrolyte was prepared by substantially the same procedure as in example 1, except that the ammonia precursor solution was prepared from ammoniaAnd uniformly mixing water and deionized water, wherein the dosage ratio of ammonia water to deionized water is 4 mL: 29 mL.
Analysis of FIGS. 2 and 3, i.e., in situ SiO prepared by examples 1 and 22Composite solid polymer electrolytes it has been found that in situ SiO prepared by electrospinning a dope prepared using an ammonia precursor solution of aqueous ammonia and deionized water2The composite solid polymer electrolyte is flocculent, has poor mechanical property and is not beneficial to the installation of a subsequent battery; and in-situ SiO prepared by electrostatic spinning of spinning solution prepared from ammonia water and ammonia precursor solution of absolute ethyl alcohol2The composite solid polymer electrolyte has good film forming property and good mechanical property, and is beneficial to the assembly of batteries.
Examples 3 to 12
In-situ SiO2A method of preparing a composite solid polymer electrolyte, the steps of which are substantially the same as in example 1, except as indicated in the following table. Wherein the lithium salt corresponds to the lithium perchlorate in example 1; the first organic solvent corresponds to acetonitrile in example 1; the second organic solvent corresponds to ethanol in example 1; first SiO2Nanosphere solution (mL) first SiO2The addition amount of the nanosphere solution is detailed in table 1 below;
TABLE 1 summary of the conditions in examples 3-12
Examples 13 to 17
In-situ SiO2The preparation method of the composite solid polymer electrolyte basically comprises the same steps as the embodiment 1, and is different in parameters of the electrostatic spinning process, and is detailed in the following table 2, wherein the moving speed in the table 2 is the moving speed of the nozzle in mm/s, the moving distance is the moving distance of the nozzle in mm, the pushing speed of the needle tube is in mm/min, the spinning temperature is in ℃, the negative voltage is in kV, and the positive voltage is in kV;
TABLE 2 Electrostatic spinning parameter Table in Electrostatic spinning Processes in examples 13 to 17
| Examples | Speed of movement | Distance of movement | Pushing speed of needle tube | Spinning temperature | Negative voltage | Positive voltage |
| 13 | 50 | 80 | 0.120 | 40 | 2.5 | 14 |
| 14 | 40 | 120 | 0.150 | 45 | 2.5 | 16 |
| 15 | 30 | 100 | 0.100 | 40 | 2.5 | 11 |
| 16 | 40 | 80 | 0.120 | 35 | 2.0 | 14 |
| 17 | 50 | 120 | 0.100 | 40 | 2.5 | 16 |
| 18 | 0.01 | 1 | 0.001 | 20 | 1 | 1 |
| 19 | 100 | 8000 | 80 | 80 | 80 | 100 |
Example 20
In-situ SiO2A method for preparing a composite solid polymer electrolyte, which has substantially the same procedure as in example 1, except that the mass ratio of PEO to Li was 4: 1.
example 21
In-situ SiO2A method for preparing a composite solid polymer electrolyte, which has substantially the same procedure as in example 1, except that the mass ratio of PEO to Li was 16: 1.
the above examples are only a few specific cases, but the in-situ SiO of the present invention can be used within the following ranges of conditions2Preparation method of composite solid polymer electrolyte to prepare in-situ SiO2A composite solid polymer electrolyte;
(1) the dosage ratio of the ammonia water to the alcohol is (3.2 mL: 34.8mL) - (4.8 mL: 23.2 mL);
(2) the dosage ratio of the ammonia water to the deionized water is (3.2 mL: 34.8mL) - (4.8 mL: 23.2 mL);
(3) the dosage ratio of PEO to the first organic solvent was (0.56 mL: 14.4mL) - (0.84 mL: 9.6 mL);
(4) the dosage ratio of the ethyl orthosilicate to the deionized water is (1.68 mL: 36mL) - (2.52 mL: 24 mL);
(5) a second organic solvent, an ammonia precursor solution, a first SiO2The dosage ratio of the nanosphere solution to the tetraethoxysilane is 25-50 mL: 8-12 mL: 0.08-0.60 mL: 0.2776-0.4164 g.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. In-situ generation of SiO2A method for producing a composite solid polymer electrolyte, characterized in that,the method comprises the following steps:
(1) solution preparation: uniformly mixing PEO with a first organic solvent to obtain a PEO solution; uniformly mixing ammonia water and alcohol or uniformly mixing ammonia water and deionized water to obtain an ammonia precursor solution;
(2) first SiO2Preparation of nanosphere solution: adjusting deionized water to be alkaline, heating in water bath, adding tetraethoxysilane, uniformly mixing and diluting to obtain first SiO2A nanosphere solution;
(3) second SiO2Preparation of nanosphere solution: adding the PEO solution prepared in the step (1), the ammonia precursor solution and the first SiO prepared in the step (2) into a second organic solvent in sequence2Mixing the nanosphere solution uniformly, adding ethyl orthosilicate to obtain second SiO2A nanosphere solution;
(4) preparing an electrostatic spinning solution: the second SiO obtained in the step (3)2Uniformly mixing the nanosphere solution with lithium salt, and drying in a vacuum oven to remove the organic solvent to obtain an electrostatic spinning solution;
(5) in-situ SiO2Preparation of composite solid polymer electrolyte: electrostatically directly spraying the electrostatic spinning solution prepared in the step (4) to a receiver to obtain the in-situ SiO with the nanofiber structure2A composite solid polymer electrolyte.
2. An in situ generated SiO as defined in claim 12The preparation method of the composite solid polymer electrolyte is characterized in that in the step (1), the first organic solvent is selected from one or more of diethyl ether, ethanol, acetonitrile, tetrahydrofuran, malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, nonadinitrile or sebaconitrile;
the dosage ratio of the ammonia water to the alcohol is (3.2 mL: 34.8mL) - (4.8 mL: 23.2 mL);
the dosage ratio of the ammonia water to the deionized water is (3.2 mL: 34.8mL) - (4.8 mL: 23.2 mL);
the ratio of the amount of PEO to the first organic solvent was (0.56 mL: 14.4mL) - (0.84 mL: 9.6 mL).
3. According to the rightIn situ generation of SiO according to claim 12The preparation method of the composite solid polymer electrolyte is characterized in that in the step (2), the dosage ratio of the ethyl orthosilicate to the deionized water is (1.68 mL: 36mL) - (2.52 mL: 24 mL).
4. An in situ generated SiO as defined in claim 12The preparation method of the composite solid polymer electrolyte is characterized in that in the step (3), the second organic solvent is one or more selected from diethyl ether, ethanol, acetonitrile, tetrahydrofuran, malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, nonanedionitrile or decanedionitrile;
a second organic solvent, an ammonia precursor solution, a first SiO2The dosage ratio of the nanosphere solution to the tetraethoxysilane is 25-50 mL: 8-12 mL: 0.08-0.60 mL: 0.2776-0.4164 g.
5. An in situ generated SiO as defined in claim 12The preparation method of the composite solid polymer electrolyte is characterized in that in the step (4), the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bistrifluoromethylsulfonyl imide, lithium difluorosulfonyl imide, lithium dioxalate borate, lithium difluorooxalate borate, lithium trifluoromethanesulfonate and lithium bistrifluoromethylsulfonyl imide;
second SiO2The molar ratio of the nanosphere solution to the lithium salt is (4: 1) - (16: 1).
6. An in situ generated SiO as defined in claim 12The preparation method of the composite solid polymer electrolyte is characterized in that in the step (4), the drying temperature is 35-80 ℃ in the drying process, and the drying time is 5-24 h.
7. An in situ generated SiO as defined in claim 12The preparation method of the composite solid polymer electrolyte is characterized in that in the step (5), in the electrostatic spinning process, the receivers are metal grid receivers, rotating shaft receivers and cage-shaped rotorsA receiver, a disk receiver, an X-Y mobile station receiver, a strip electrode receiver, a ring electrode receiver, a sheet electrode receiver, a plate receiver, a turntable receiver, a patterned receiver, a water bath receiver, or a dual spindle receiver.
8. An in situ generated SiO as defined in claim 12The preparation method of the composite solid polymer electrolyte is characterized in that in the step (5), in the electrostatic spinning process, electrostatic spinning parameters are as follows: the moving speed of the nozzle is 0.01-100mm/s, the moving distance is 1-8000mm, the pushing speed of the needle tube is 0.001-80mm/min, the spinning temperature is 20-80 ℃, the negative voltage is 1-80kV, and the positive voltage is 1-100 kV.
9. An in situ formed SiO prepared by the process of any of claims 1-82A composite solid polymer electrolyte.
10. The in situ generated SiO of claim 92The application of the composite solid polymer electrolyte in preparing a solid lithium battery.
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