CN115863738A - Secondary lithium battery using composite quasi-solid electrolyte membrane and preparation method thereof - Google Patents
Secondary lithium battery using composite quasi-solid electrolyte membrane and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the electrolyte of lithium battery, has disclosed a secondary lithium battery using compound quasi solid electrolyte membrane and its preparation method, said compound quasi solid electrolyte membrane includes compound electrolyte and compound diaphragm; the composite diaphragm is a polyacrylonitrile diaphragm containing lithium lanthanum titanium oxygen inorganic ceramic particles; the composite electrolyte comprises an anhydrous electrolyte and tetra-isoamyl tetraacrylate, wherein the anhydrous electrolyte consists of an organic solvent and lithium salt; the composite quasi-solid electrolyte membrane is a network-shaped fiber membrane. The composite electrolyte and the composite diaphragm form a rigid-flexible combined composite quasi-solid electrolyte membrane, interface compatibility of the battery is enhanced, leakage of the electrolyte can be avoided, interface side reaction caused by contact of the electrolyte and an electrode of the lithium battery can be reduced, instability of the lithium battery is relieved, and accordingly circulation stability of the lithium battery is improved, and discharge specific capacity and circulation efficiency of the lithium battery are improved.
Description
Technical Field
The present invention relates to an electrolyte for a lithium battery, and more particularly, to a secondary lithium battery using a composite quasi-solid electrolyte membrane and a method for preparing the same.
Background
With the progress of science and technology, the popularization rate of personal intelligent devices is higher and higher, and meanwhile, rechargeable secondary lithium batteries applied to the intelligent devices are also widely applied.
In the secondary lithium battery in the prior art, electrolyte is used as an ion conducting medium, so that the electrolyte is easy to volatilize and leak in the recycling process of the battery, potential safety hazards exist, and the service life of the battery is further shortened. In order to increase energy density, when lithium metal is used as a negative electrode, the liquid electrolyte used also easily causes growth of lithium dendrites, and a phenomenon occurs in which lithium dendrites penetrate through a separator to short-circuit. The solid polymer electrolyte has good safety performance, but is not beneficial to the conduction of lithium ions, so that the secondary lithium battery using the solid polymer electrolyte has low specific discharge capacity and poor charging and discharging efficiency.
Disclosure of Invention
In view of the above problems, a first object of the present invention is to provide a secondary lithium battery using a composite quasi-solid electrolyte membrane, which is a network-like fibrous membrane, has good interface compatibility, and has good cycle performance and rate capability.
Another object of the present invention is to provide a method for preparing a secondary lithium battery in which an in-situ polymerized composite quasi-solid electrolyte membrane is formed.
In order to achieve the purpose, the invention adopts the following technical scheme:
a secondary lithium battery using a composite quasi-solid electrolyte membrane, the composite quasi-solid electrolyte membrane comprising a composite electrolyte and a composite separator;
the composite diaphragm is a polyacrylonitrile diaphragm containing lithium lanthanum titanium oxygen inorganic ceramic particles;
the composite electrolyte comprises a non-aqueous electrolyte and tetra-iso-amyl tetraacrylate, wherein the non-aqueous electrolyte consists of an organic solvent and lithium salt;
the composite quasi-solid electrolyte membrane is a network-shaped fiber membrane.
Specifically, the raw materials of the composite diaphragm consist of lithium lanthanum titanium oxide inorganic ceramic particles, polyacrylonitrile powder and N, N-dimethylformamide;
the mass ratio of the lithium lanthanum titanium oxide inorganic ceramic particles to the polyacrylonitrile powder is 1:5, and the mass ratio of the polyacrylonitrile powder to the N, N-dimethylformamide is 1;
the mass percentages of the tetra-isoamyl tetraacrylate and the anhydrous electrolyte in the composite electrolyte are respectively 5% and 95%.
Preferably, the lithium salt includes LiPF 6 、LiBOB、LiFSI、LiTFSI、LiSbF 6 、LiA1O 2 And LiAlCl 4 At least one of (a).
Preferably, the organic solvent is fluoroethylene carbonate and/or ethylene carbonate.
Preferably, the concentration of the lithium salt in the nonaqueous electrolyte solution is 0.1 to 5M.
Further, the present invention provides a method for preparing a secondary lithium battery using the composite quasi-solid electrolyte membrane, comprising the steps of:
s1) weighing N, N-dimethylformamide, lithium lanthanum titanium oxide inorganic ceramic particles and polyacrylonitrile powder according to mass percentage, adding the lithium lanthanum titanium oxide inorganic ceramic particles into the N, N-dimethylformamide, ultrasonically dispersing for 1h, then placing the mixture in a magnetic stirrer at room temperature, stirring for 8h to completely disperse the inorganic ceramic particles in the N, N-dimethylformamide, then adding polyacrylonitrile powder, and stirring for 12h at room temperature to prepare a diaphragm precursor solution for electrostatic spinning;
s2) putting the diaphragm precursor solution into electrostatic spinning equipment for spinning, taking down a thin film formed by spinning from a receiver after spinning is finished, and then putting the thin film into a vacuum drying oven for vacuum drying to obtain a PAN-LLTO nanofiber film;
s3) weighing the tetra-isoamyl tetraacrylate and the anhydrous electrolyte according to the mass percentage, adding the tetra-isoamyl tetraacrylate into a glass bottle in a glove box filled with argon atmosphere, then adding the anhydrous electrolyte, adding a proper amount of azodiisobutyronitrile initiator, and continuously stirring at normal temperature to prepare an electrolyte precursor solution;
and S4) cutting the PAN-LLTO nanofiber film into round pieces, assembling the round pieces into a button cell by taking the PAN-LLTO nanofiber film as a diaphragm, injecting an electrolyte precursor solution, standing, and then placing in an oven for thermal polymerization reaction to obtain the lithium battery containing the composite quasi-solid electrolyte membrane.
Specifically, in step S2), the applied voltage is 24kV, the solution advancing speed is 1mL/h, the rotating speed of the roller is 300rpm/min, the distance between the spraying device and the receiver is 18cm, the ambient temperature is 25 +/-5 ℃, and the ambient humidity is 45 +/-5%.
Preferably, in step S2), the temperature for vacuum drying is 80 ℃, and the time for vacuum drying is 24h.
Preferably, in step S3), the amount of the azobisisobutyronitrile initiator added is 0.5% by mass of the pentaerythritol tetraacrylate, and the continuous stirring time is 1 hour.
Preferably, in step S4), the standing time is 3h, the thermal polymerization temperature is 60 ℃, and the thermal polymerization time is 12h.
The technical scheme of the invention has the beneficial effects that: according to the secondary lithium battery using the composite quasi-solid electrolyte membrane, the composite electrolyte and the composite diaphragm form the rigid-flexible combined composite quasi-solid electrolyte membrane, so that the interface compatibility of the battery is enhanced, the leakage of the electrolyte can be avoided, the interface side reaction caused by the contact of the electrolyte of the lithium battery and an electrode can be reduced, the instability of the lithium battery is relieved, the cycling stability of the lithium battery is improved, and the discharge specific capacity and the cycling efficiency of the lithium battery are improved.
Furthermore, the preparation method of the secondary lithium battery adopts an in-situ polymerization mode to polymerize in the battery to form the composite quasi-solid electrolyte membrane, so that the lithium battery has excellent interface stability and rate capability and better charge-discharge efficiency.
Drawings
FIG. 1 is an electron microscopic scan of a composite quasi-solid electrolyte membrane of example 1 of the invention;
FIG. 2 is a charge-discharge curve of the NCM811 battery of example 1 of the present invention;
fig. 3 is a rate performance graph of the NCM811 battery of example 1 of the invention;
FIG. 4 shows the current density of the lithium symmetric battery of example 1 of the present invention at 0.5mA/cm 2 (part a in the figure) and a current density of 0.2mA/cm 2 Polarization voltage curve (part b of the figure);
FIG. 5 is a graph of log ionic conductivity versus temperature for a lithium battery of example 1 of the present invention and a lithium battery of comparative example 1;
FIG. 6 is a graph of rate performance of the NCM811 battery of comparative example 1 of the present invention;
fig. 7 is a graph of rate performance for the NCM811 battery of comparative example 2 and the NCM811 battery of comparative example 3 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
In the description herein, references to the description of the terms "embodiment," "example," 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 do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
A secondary lithium battery using a composite quasi-solid electrolyte membrane, the composite quasi-solid electrolyte membrane comprising a composite electrolyte and a composite separator;
the composite diaphragm is a polyacrylonitrile diaphragm containing lithium lanthanum titanium oxide inorganic ceramic particles;
the composite electrolyte comprises an anhydrous electrolyte and tetra-isoamyl tetraacrylate, wherein the anhydrous electrolyte consists of an organic solvent and lithium salt;
the composite quasi-solid electrolyte membrane is a network-shaped fiber membrane.
According to the secondary lithium battery using the composite quasi-solid electrolyte membrane, the composite electrolyte and the composite diaphragm form the rigid-flexible combined composite quasi-solid electrolyte membrane, so that the interface compatibility of the battery is enhanced, the leakage of the electrolyte can be avoided, the interface side reaction caused by the contact of the electrolyte of the lithium battery and an electrode can be reduced, the instability of the lithium battery is relieved, the cycling stability of the lithium battery is improved, and the discharge specific capacity and the cycling efficiency of the lithium battery are improved.
Specifically, the raw materials of the composite diaphragm consist of lithium lanthanum titanium oxide inorganic ceramic particles, polyacrylonitrile powder and N, N-dimethylformamide;
the mass ratio of the lithium lanthanum titanium oxide inorganic ceramic particles to the polyacrylonitrile powder is 1:5, and the mass ratio of the polyacrylonitrile powder to the N, N-dimethylformamide is 1;
the mass percentages of the tetra-isoamyl tetraacrylate and the anhydrous electrolyte in the composite electrolyte are respectively 5% and 95%.
The introduction of the Lithium Lanthanum Titanium Oxygen (LLTO) fast ion conductor into the Polyacrylonitrile (PAN) diaphragm can not only improve the ionic conductivity of the composite quasi-solid electrolyte membrane at room temperature, but also improve the mechanical strength, thermal stability and electrochemical performance of the composite quasi-solid electrolyte membrane.
The isoprene tetraacrylate which is a monomer does not generate side reaction with lithium salt, and a fiber membrane formed by polymerizing the isoprene tetraacrylate can promote the effective dissociation of the lithium salt, thereby being beneficial to the transmission of lithium ions.
Preferably, the lithium salt includes LiPF 6 、LiBOB、LiFSI、LiTFSI、LiSbF 6 、LiA1O 2 And LiAlCl 4 At least one of (1).
Lithium ions are provided by dissociation of the above lithium salt in the electrolytic solution.
Preferably, the organic solvent is fluoroethylene carbonate and/or ethylene carbonate.
The electrolyte is formed by dissolving a lithium salt in an organic solvent, preferably fluoroethylene carbonate and/or ethylene carbonate.
Preferably, the concentration of the lithium salt in the nonaqueous electrolyte is 0.1 to 5M.
The higher the lithium salt concentration, the higher the conductivity of lithium ions in the electrolyte; when the concentration of the lithium salt is less than 0.1M, too few lithium ions result in insufficient conductivity of the electrolyte, and when the concentration of the lithium salt is more than 5M, lithium dendrites are easily formed.
Further, the present invention provides a method for preparing a secondary lithium battery using the composite quasi-solid electrolyte membrane, comprising the steps of:
s1) weighing N, N-dimethylformamide, lithium lanthanum titanium oxide inorganic ceramic particles and polyacrylonitrile powder according to mass percentage, adding the lithium lanthanum titanium oxide inorganic ceramic particles into the N, N-dimethylformamide, ultrasonically dispersing for 1h, then placing the mixture in a magnetic stirrer at room temperature, stirring for 8h to completely disperse the inorganic ceramic particles in the N, N-dimethylformamide, then adding polyacrylonitrile powder, and stirring for 12h at room temperature to prepare a diaphragm precursor solution for electrostatic spinning;
s2) putting the diaphragm precursor solution into electrostatic spinning equipment for spinning, taking down a thin film formed by spinning from a receiver after the spinning is finished, and then putting the thin film into a vacuum drying oven for vacuum drying to obtain a PAN-LLTO nanofiber membrane;
s3) weighing the tetra-isoamyl tetraacrylate and the anhydrous electrolyte according to the mass percentage, adding the tetra-isoamyl tetraacrylate into a glass bottle in a glove box filled with argon atmosphere, then adding the anhydrous electrolyte, adding a proper amount of azodiisobutyronitrile initiator, and continuously stirring at normal temperature to prepare an electrolyte precursor solution;
and S4) cutting the PAN-LLTO nanofiber film into round pieces, assembling the round pieces into a button cell by taking the PAN-LLTO nanofiber film as a diaphragm, injecting an electrolyte precursor solution, standing, and then placing in an oven for thermal polymerization reaction to obtain the lithium battery containing the composite quasi-solid electrolyte membrane.
The composite quasi-solid electrolyte membrane prepared by the in-situ polymerization process can inhibit the lithium ions from generating side reaction at the interface part to generate Li 2 O, liF or Li 2 CO 3 And the like, thereby reducing unnecessary consumption of lithium ions, avoiding reduction of coulomb efficiency due to consumption of the lithium ions, further improving the cycling stability of the lithium battery, and preparing the lithium battery with high discharge specific capacity and high cycling efficiency.
Specifically, in step S2), the applied voltage is 24kV, the solution advancing speed is 1mL/h, the rotating speed of the roller is 300rpm/min, the distance between the spraying device and the receiver is 18cm, the ambient temperature is 25 +/-5 ℃, and the ambient humidity is 45 +/-5%.
The fibrous PAN-LLTO nanomembranes were formed by electrospinning.
Preferably, in step S2), the temperature for vacuum drying is 80 ℃, and the time for vacuum drying is 24h.
The N, N-dimethylformamide contained in the PAN-LLTO nanofiber membrane was completely removed by vacuum drying.
Preferably, in step S3), the amount of the azobisisobutyronitrile initiator added is 0.5% by mass of the pentaerythritol tetraacrylate, and the continuous stirring time is 1 hour.
The azobisisobutyronitrile and the isoamyl tetraacrylate were uniformly distributed in the organic solvent by continuous stirring for 1 hour.
Preferably, in step S4), the standing time is 3h, the thermal polymerization temperature is 60 ℃, and the thermal polymerization time is 12h.
The electrolyte precursor solution fully wets the electrode and the PAN-LLTO nanofiber thin film through standing for 3 hours, so that the distribution uniformity of the fiber film generated by polymerization is improved, the distribution uniformity of the anhydrous electrolyte in the composite quasi-solid electrolyte film is improved, and the cycle performance and the charging efficiency of the secondary lithium battery are improved.
Example 1 and comparative examples 1-2
Example 1
1. A secondary lithium battery of example 1 was prepared as follows:
s1) weighing N, N-dimethylformamide, lithium lanthanum titanium oxide inorganic ceramic particles and polyacrylonitrile powder according to the mass percentage, adding the lithium lanthanum titanium oxide inorganic ceramic particles into the N, N-dimethylformamide, ultrasonically dispersing for 1h, then placing the mixture in a magnetic stirrer at room temperature, stirring for 8h to completely disperse the inorganic ceramic particles in the N, N-dimethylformamide, then adding the polyacrylonitrile powder, and stirring for 12h at room temperature to prepare a diaphragm precursor solution for electrostatic spinning;
s2) putting the diaphragm precursor solution into electrostatic spinning equipment for spinning, taking down a thin film formed by spinning from a receiver after spinning is finished, and then putting the thin film into a vacuum drying oven for vacuum drying to obtain a PAN-LLTO nanofiber film;
s3) weighing the tetra-isoamyl tetraacrylate and the anhydrous electrolyte according to the mass percentage, adding the tetra-isoamyl tetraacrylate into a glass bottle in a glove box filled with argon atmosphere, then adding the anhydrous electrolyte, adding a proper amount of azodiisobutyronitrile initiator, and continuously stirring at normal temperature to prepare an electrolyte precursor solution;
s4) cutting the PAN-LLTO nanofiber thin film into round pieces, assembling a button NCM811 battery by taking the PAN-LLTO nanofiber thin film as a diaphragm, injecting electrolyte precursor solution, standing, and then placing in a drying oven for thermal polymerization reaction to obtain the lithium battery containing the composite quasi-solid electrolyte film;
the adding amount of the lithium lanthanum titanium oxide inorganic ceramic particles is 20 percent of the mass of the polyacrylonitrile powder, and the mass ratio of the N, N-dimethylformamide to the polyacrylonitrile powder is 10;
according to the mass percentage, the mass percentages of the tetra-isoamyl tetraacrylate and the anhydrous electrolyte are respectively 5% and 95%;
the organic solvent is fluoroethylene carbonate; liPF in anhydrous electrolyte 6 The concentration of lithium salt is 1M;
in the step S2), the applied voltage is 24kV, the solution propelling speed is 1mL/h, the rotating speed of a roller is 300rpm/min, the distance between an injection device and a receiver is 18cm, the ambient temperature is 25 +/-5 ℃, and the ambient humidity is 45 +/-5%;
in the step S2), the temperature of vacuum drying is 80 ℃, and the time of vacuum drying is 24h.
In the step S3), the adding amount of the azodiisobutyronitrile initiator is 0.5 percent of the mass of the pentaerythritol tetraacrylate, and the continuous stirring time is 1h;
in the step S4), the standing time is 3h, the thermal polymerization temperature is 60 ℃, and the thermal polymerization time is 12h.
2. SEM scanning analysis was performed on the composite quasi-solid electrolyte membrane obtained in example 1, and the scanning electron micrograph thereof is shown in FIG. 1; as can be seen from fig. 1, the composite quasi-solid electrolyte membrane of example 1 is in a network shape, and the network-shaped fiber membranes are filled with the anhydrous electrolyte, which is helpful for uniform transmission of lithium ions in the anhydrous electrolyte.
3. The charge-discharge curve of the NCM811 battery of example 1 was tested at a voltage of 3.0-4.5V at an ambient temperature of 30 deg.c, and the test results are shown in fig. 2; as can be seen from FIG. 2, the first-turn coulombic efficiency of the NCM811 battery of example 1 can reach 91.58%, and the specific discharge capacity is 234.8mAh/g.
4. The NCM811 battery of example 1 was subjected to a rate capability test of 0.5C, 1C, 2C, 3C, 4C, 5C, 6C, 7C, and 8C, and the test results are shown in fig. 3, where the specific discharge capacities were 198.3mAh/g, 189.6mAh/g, and 180.8mAh/g at 0.5C, 1C, and 2C rates, respectively, the specific discharge capacity after 140 cycles was 158.6mAh/g at 1C rate, and the capacity retention rate was 81.59%. Even under 5C multiplying power, the specific discharge capacity can reach 166.3mAh/g. It can be seen that the NCM811 battery of example 1 exhibited higher specific discharge capacity at both high and low rates.
5. Replacing the positive electrode of the NCM811 battery obtained in example 1 with a lithium sheet to constitute a Li | GPE-PAN-20% 2 And 0.5mA/cm 2 The current density of the current measurement device is tested, and the test result is as followsAs shown in fig. 4. As can be seen from graph a in FIG. 4, when the current density was 0.2mA/cm 2 In this case, the Li | GPE-PAN-20% LLTO Lily symmetric battery of example 1 can be stably cycled for 300h. As can be seen from graph b in FIG. 4, when the current density was 0.5mA/cm 2 While, the Li | GPE-PAN-20% LLTO a Lisymmetric battery of example 1 can be cycled for 550h stably. The results showed that GPE-PAN-20% LLTO of example 1 had excellent cycle stability to a lithium metal negative electrode.
Comparative example 1
1. The procedure for preparing the lithium secondary battery of comparative example 1 is the same as that of example 1, except that: the LLTO lithium lanthanum titanium oxide inorganic ceramic particles were not added in step S1) of comparative example 1.
2. The logarithm of the ionic conductivity and the temperature variation tendency of the lithium NCM811 battery of example 1 and the lithium NCM811 battery of comparative example 1 were measured, respectively, and the comparison result with that of example 1 is shown in fig. 5, and it can be seen from fig. 5 that the ionic conductivity of comparative example 1 is significantly lower than that of example, indicating that the addition of the LLTO lithium lanthanum titanium oxide inorganic ceramic particles can effectively improve the ionic conductivity of the lithium battery.
3. The NCM811 cell of comparative example 1 was tested for rate capability of 0.5C, 1C, 2C, 3C, 4C, 5C, 6C, 7C and 8C, with the results shown in fig. 6. Comparing fig. 3 and fig. 6, it can be found that: under the same conditions, the NCM811 battery of comparative example 1 was significantly inferior in both specific discharge capacity and coulombic efficiency to the NCM811 battery of example 1.
Comparative examples 2 and 3
1. The preparation procedure of the NCM811 secondary lithium battery of comparative example 2 includes steps S1) and S2) which are the same as those of example 1, excluding steps S3 and S4), and the electrolyte in the NCM811 battery of comparative example 2 is a non-aqueous electrolyte solution.
2. The separator of the NCM811 secondary lithium battery of comparative example 3 is a polyacrylonitrile separator, and the electrolyte in the NCM811 battery of comparative example 3 is a nonaqueous electrolytic solution.
3. The NCM811 batteries of comparative example 2 and comparative example 3 were tested for rate capability of 0.5C, 1C, 2C, 3C, 4C, 5C, 6C, 7C, and 8C, and the results of the tests are shown in fig. 7, with NCM811 PAN-LLTO | Li in fig. 7 identifying the data of comparative example 2 and NCM811 PAN | Li identifying the data of comparative example 3. Comparing fig. 3 and fig. 7, it can be found that: under the same conditions, the specific discharge capacity and the coulombic efficiency of the NCM811 battery of comparative example 2 and the NCM811 battery of comparative example 3 were significantly inferior to those of the NCM811 battery of example 1.
In summary, in the secondary lithium battery using the composite quasi-solid electrolyte membrane in the above embodiments, the composite electrolyte and the composite diaphragm form a rigid-flexible composite quasi-solid electrolyte membrane, so that the interface compatibility of the battery is enhanced, the leakage of the electrolyte can be avoided, the interface side reaction caused by the contact between the electrolyte and the electrode of the lithium battery can be reduced, and the instability of the lithium battery is alleviated, thereby improving the cycling stability of the lithium battery, and further improving the discharge specific capacity and the cycling efficiency of the lithium battery.
Furthermore, the preparation method of the secondary lithium battery provided by the invention adopts an in-situ polymerization mode to polymerize in the battery to form the composite quasi-solid electrolyte membrane, so that the lithium battery has excellent interface stability and rate capability, and better charge and discharge efficiency.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (10)
1. A secondary lithium battery using a composite quasi-solid electrolyte membrane, characterized in that the composite quasi-solid electrolyte membrane comprises a composite electrolyte and a composite separator;
the composite diaphragm is a polyacrylonitrile diaphragm containing lithium lanthanum titanium oxygen inorganic ceramic particles;
the composite electrolyte comprises an anhydrous electrolyte and tetra-isoamyl tetraacrylate, wherein the anhydrous electrolyte consists of an organic solvent and lithium salt;
the composite quasi-solid electrolyte membrane is a network-shaped fiber membrane.
2. The lithium secondary battery using the composite quasi-solid electrolyte membrane according to claim 1, wherein the raw material of the composite separator is composed of lithium lanthanum titanium oxide inorganic ceramic particles, polyacrylonitrile powder, and N, N-dimethylformamide;
the mass ratio of the lithium lanthanum titanium oxide inorganic ceramic particles to the polyacrylonitrile powder is 1:5, and the mass ratio of the polyacrylonitrile powder to the N, N-dimethylformamide is 1;
the mass percentages of the tetra-isoamyl tetraacrylate and the anhydrous electrolyte in the composite electrolyte are respectively 5% and 95%.
3. The lithium secondary battery using the composite quasi-solid electrolyte membrane according to claim 1, wherein the lithium salt includes LiPF 6 、LiBOB、LiFSI、LiTFSI、LiSbF 6 、LiA1O 2 And LiAlCl 4 At least one of (1).
4. The lithium secondary battery using a composite quasi-solid electrolyte membrane according to claim 1, wherein the organic solvent is fluoroethylene carbonate and/or vinylene carbonate.
5. The lithium secondary battery using the composite quasi-solid electrolyte membrane according to claim 1, wherein the concentration of the lithium salt in the nonaqueous electrolyte solution is 0.1 to 5M.
6. A method for manufacturing a lithium secondary battery using the composite quasi-solid electrolyte membrane according to any one of claims 1 to 5, comprising the steps of:
s1) weighing N, N-dimethylformamide, lithium lanthanum titanium oxide inorganic ceramic particles and polyacrylonitrile powder according to the mass percentage, adding the lithium lanthanum titanium oxide inorganic ceramic particles into the N, N-dimethylformamide, ultrasonically dispersing for 1h, then placing the mixture in a magnetic stirrer at room temperature, stirring for 8h to completely disperse the inorganic ceramic particles in the N, N-dimethylformamide, then adding the polyacrylonitrile powder, and stirring for 12h at room temperature to prepare a diaphragm precursor solution for electrostatic spinning;
s2) putting the diaphragm precursor solution into electrostatic spinning equipment for spinning, taking down a thin film formed by spinning from a receiver after spinning is finished, and then putting the thin film into a vacuum drying oven for vacuum drying to obtain a PAN-LLTO nanofiber film;
s3) weighing the tetra-iso-amyl acrylate and the anhydrous electrolyte according to the mass percentage, adding the tetra-iso-amyl acrylate into a glass bottle in a glove box filled with argon atmosphere, then adding the anhydrous electrolyte, adding a proper amount of azobisisobutyronitrile initiator, and continuously stirring at normal temperature to prepare an electrolyte precursor solution;
and S4) cutting the PAN-LLTO nanofiber film into round pieces, assembling the round pieces into a button cell by taking the PAN-LLTO nanofiber film as a diaphragm, injecting an electrolyte precursor solution, standing, and then placing in an oven for thermal polymerization reaction to obtain the lithium battery containing the composite quasi-solid electrolyte membrane.
7. The method of manufacturing a lithium secondary battery as claimed in claim 6, wherein the voltage applied in step S2) is 24kV, the advancing speed of the solution is 1mL/h, the rotation speed of the drum is 300rpm/min, the distance between the spray device and the receiver is 18cm, the ambient temperature is 25 ± 5 ℃, and the ambient humidity is 45 ± 5%.
8. The method of claim 6, wherein the temperature of the vacuum drying is 80 ℃ and the time of the vacuum drying is 24 hours in the step S2).
9. The method of claim 6, wherein in the step S3), the amount of the azobisisobutyronitrile initiator is 0.5% by mass of the pentaerythritol tetraacrylate, and the continuous stirring time is 1 hour.
10. The method of claim 6, wherein the standing time is 3 hours, the thermal polymerization temperature is 60 ℃, and the thermal polymerization time is 12 hours in the step S4).
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