CN109065948B - All-solid-state lithium battery, solid polymer electrolyte film and preparation method thereof - Google Patents
All-solid-state lithium battery, solid polymer electrolyte film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a solid polymer electrolyte film, an all-solid-state lithium battery and a preparation method of an amino acid-starch-PEO polymer solid electrolyte, wherein the solid polymer electrolyte film comprises a polymer and a lithium salt, and the mass ratio of the polymer to the lithium salt is 1-3: 1; the polymer is a copolymer of amino acid, starch and PEO, and the lithium salt is LiClO4、LiPF6、LiBF4、LiTFSI、LiAsF6、Li B(C2O4)2(Li BOB)、Li SO2CF3(Li Tf). The solid electrolyte provided by the invention has higher thermal stability and ionic conductivity, and the multiplying power and the cycle performance of the corresponding battery are good.
Description
Technical Field
The invention relates to the technical field of all-solid-state lithium batteries, in particular to an all-solid-state lithium battery, a solid polymer electrolyte film and a preparation method thereof.
Background
Energy is a main material basis for developing national economy and improving the living standard of people, and is also an important factor directly influencing the economic development. Since the 21 st century, the problems of resource shortage, environmental pollution, greenhouse effect and the like brought by the traditional energy utilization mode are increasingly prominent, the improvement of an energy structure and the development of efficient and clean novel energy have become global consensus. Lithium ion batteries are favored because of their superior properties, such as safety, environmental protection, high specific energy, and good electrochemical properties. However, in the commercialized lithium ion battery containing the liquid organic solvent, since the liquid electrolyte slowly interacts and reacts with the electrode material and the packaging material, the solvent is easily dried, volatilized and leaked during long-term service, and the electrode material is easily corroded, which affects the battery life. In recent years, a large-capacity lithium ion battery has a serious safety accident in the auxiliary power supply of an electric automobile or an airplane, and the cause of the problem is related to the use of a combustible organic solvent in the lithium ion battery. The solid electrolyte can avoid the problems of side reaction, leakage and corrosion caused by the liquid electrolyte, thereby being expected to obviously prolong the service life, fundamentally ensuring the safety of the lithium ion battery, improving the energy density, the cyclicity and the service life and reducing the battery cost. Therefore, the selection of a proper solid electrolyte material is the core content of battery design, and the development of a solid electrolyte with excellent performance has great significance for the development of all-solid-state lithium batteries.
Disclosure of Invention
The invention mainly aims to provide an all-solid-state lithium battery, a solid polymer electrolyte film and a preparation method thereof, and aims to prepare the electrolyte film with high safety and high ionic conductivity, and apply the electrolyte film to the all-solid-state lithium battery so as to realize normal charge and discharge of the battery at room temperature.
In order to achieve the purpose, the solid polymer electrolyte film provided by the invention comprises a polymer and a lithium salt, wherein the mass ratio of the polymer to the lithium salt is 1-3: 1; the polymer is a copolymer of amino acid, starch and PEO, and the lithium salt is LiClO4、LiPF6、LiBF4、LiTFSI、LiAsF6、Li B(C2O4)2(Li BOB)、Li SO2CF3(Li Tf).
Preferably, the amino acid comprises glutamic acid or arginine.
In order to achieve the above object, the present invention provides an all solid-state lithium battery including a positive electrode, a solid electrolyte layer and a negative electrode stacked on each other, wherein the solid electrolyte layer is the solid polymer electrolyte thin film described in any one of the above.
In order to achieve the above objects, the present invention provides a method for preparing an amino acid-starch-PEO polymer solid electrolyte, comprising the steps of:
(1) synthesis of amino acid-starch polymers
Weighing starch and amino acid by using an electronic balance in an argon glove box, wherein the molar ratio of the starch monomer to the amino acid is 30-50:1, and the amino acid comprises glutamic acid or arginine; placing starch and amino acid into a single-neck flask with a vent valve, wherein the single-neck flask is connected with a condenser pipe and a three-way valve with a balloon to form a reactor; adding dimethyl sulfoxide into a flask and stirring by using a magnetic heating stirrer in an argon atmosphere; after stirring completely, adding KH560, and stirring with a magnetic heating stirrer to obtain transparent colloidal amino acid-starch polymer;
(2) synthetic amino acid-starch-PEO polymer solid electrolyte
Mixing amino acid-starch, PEO and lithium salt in an argon glove box, and stirring by using a magnetic heating stirrer at room temperature to obtain a uniform solution; and pouring the solution on a mold and heating to obtain the amino acid-starch-PEO polymer solid electrolyte.
Preferably, after the dimethyl sulfoxide is added in the step (1), stirring is carried out at the rotation speed of 300-800rmp for 10-50min at the temperature of 75-95 ℃ by an oil bath.
Preferably, after KH560 is added in the step (1), the mixture is continuously stirred at a rotating speed of 700-.
Preferably, the mass of the lithium salt in the step (2) is 25-50% of the total mass of the amino acid-starch, the PEO and the lithium salt.
Preferably, the step (2) is performed by stirring for more than 10 hours at a rotating speed of 800-.
Preferably, the step (2) is carried out on a mold for 6-12h at 40-80 ℃.
Preferably, the amino acid-starch polymer has the structure:
the technical scheme of the invention has the following beneficial effects:
(1) compared with the common electrolyte of the lithium ion battery, the amino acid-starch-PEO polymer solid electrolyte provided by the invention has higher safety performance and thermal stability.
(2) The modification of the amino acids increased the conductivity by nearly 2 orders of magnitude compared to pure PEO electrolytes.
(3) Compared with the PEO and amino acid polymer electrolyte, the amino acid-starch-PEO polymer solid electrolyte has higher conductivity in the temperature range of 25-50 ℃.
(4) The battery capacity of the all-solid-state lithium battery using the amino acid-starch-PEO polymer solid electrolyte is 4 times of that of the traditional liquid-state lithium iron phosphate battery, and the battery has good cyclicity.
(5) Silane coupling agent KH-560 (chemical formula CH)2-CH(O)CH2-O(CH2)3Si(OCH3)3) The acrylic acid modified polyurethane adhesive is an excellent adhesion promoter and is often applied to preparation of acrylic acid coatings. In the present invention, KH560 is used to crosslink amino acid-starch, thereby obtaining an amino acid-starch polymer. And the polymer is combined with PEO with extremely strong flexibility to obtain a novel polymer solid electrolyte film with high flexibility, high mechanical strength and high lithium ion conductivity.
Drawings
Fig. 1 is a preparation scheme of an amino acid-starch-PEO polymer solid electrolyte.
Detailed Description
The following examples are intended to illustrate the present invention in further detail, but are not intended to limit the scope of the invention as claimed.
Example 1
Synthesizing an amino acid-starch polymer by the following steps: weighed in an argon glove box using an electronic balance. 0.5g of starch and 0.0113g of glutamic acid are weighed into a single-neck flask with a vent valve. The single-mouth flask is connected with a condenser pipe and a three-way valve with a balloon to form a reactor, the reactor is vacuumized and filled with argon, and the process is repeated for three times. After completion, 10g of dimethyl sulfoxide (DMSO) solvent was added to the flask, heated in an oil bath for 20 minutes under Ar protection, heated at 90 ℃ with a magnetic heating stirrer, and stirred at 500 rmp; after 30 minutes complete dissolution, 0.74g KH560 was added to crosslink the starch, and the reaction was carried out with a magnetic heating stirrer at 90 ℃ under 750rmp conditions and stirred for 12 hours. After the reaction was completed, a transparent gel-like glutamic acid-starch polymer was obtained.
Synthesizing an amino acid-starch-PEO polymer solid electrolyte in the step (2): the whole process was carried out in an argon glove box. Mixing an amino acid-starch solution, polyethylene oxide (PEO) and 40 wt% lithium salt (LiTFSI); heating the stirrer by magnetic force at room temperature, stirring at 1000rmp for 12 hours to obtain a uniform solution, pouring the solution into a positive shell of a CR2025 battery, and heating at 60 ℃ for 10 hours to obtain a flexible solid electrolyte film with the thickness of about 0.8 mm: glutamic acid-starch-PEO-LiTFSI.
Scheme for preparation of amino acid-starch-PEO polymer solid electrolyte please refer to fig. 1.
Example 2
Synthesizing an amino acid-starch polymer by the following steps: weighed in an argon glove box using an electronic balance. 0.5g of starch and 0.013g of arginine were weighed. The mixture was put into a three-necked flask, 10g of DMSO solvent was added by a syringe, stirred for 40 minutes using a magnetic heating stirrer, and then 0.73gKH560 was injected to crosslink the starch. The transparent gelatinous arginine-starch polymer is obtained after the continuous stirring of a magnetic heating stirrer for 12 hours under the condition of 90 ℃ and 800 rmp.
Synthesizing an amino acid-starch-PEO polymer solid electrolyte in the step (2): the whole process was carried out in an argon glove box. Mixing amino acid-starch solution, PEO and 30 wt% lithium salt (LiBF)4) Mixing; heating the stirrer by magnetic force at room temperature, stirring at 1000rmp for 12 hours to obtain a uniform solution, pouring the solution into a positive shell of a CR2025 battery, and heating at 60 ℃ for 10 hours to obtain a flexible solid electrolyte film with the thickness of about 0.8 mm: arginine-starch-PEO-LiBF4。
Example 3
Synthesizing an amino acid-starch polymer by the following steps: weighed in an argon glove box using an electronic balance. 0.4g of starch, 0.009g of glutamic acid were weighed into a single-neck flask with a vent valve. The single-mouth flask is connected with a condenser pipe and a three-way valve with a balloon to form a reactor, the reactor is vacuumized and filled with argon, and the process is repeated for three times. After completion, 8g of dimethyl sulfoxide (DMSO) solvent was added to the flask, heated in an oil bath for 15 minutes under Ar protection, heated at 80 ℃ with a magnetic heating stirrer, and stirred at 400 rmp; after 30 minutes complete dissolution, 0.7g KH560 was added to crosslink the starch, and the reaction was carried out with a magnetic heating stirrer at 80 ℃ under 800rmp and stirred for 11 hours. After the reaction was completed, a transparent gel-like glutamic acid-starch polymer was obtained.
Synthesizing an amino acid-starch-PEO polymer solid electrolyte in the step (2): the whole process was carried out in an argon glove box. Mixing an amino acid-starch solution, polyethylene oxide (PEO) and 40 wt% lithium salt (LiTFSI); heating the stirrer by magnetic force at room temperature, stirring at 1100rmp for 11 hours to obtain a uniform solution, pouring the solution into a positive shell of a CR2025 battery, and heating at 70 ℃ for 8 hours to obtain a flexible solid electrolyte film with the thickness of about 0.9 mm: glutamic acid-starch-PEO-LiTFSI.
Example 4
Synthesizing an amino acid-starch polymer by the following steps: weighed in an argon glove box using an electronic balance. 0.6g of starch and 0.015g of arginine are weighed. The mixture was put into a three-necked flask, 15g of DMSO solvent was added by a syringe, and stirred for 40 minutes using a magnetic heating stirrer, and then 0.83gKH560 was injected to crosslink the starch. The transparent gelatinous arginine-starch polymer is obtained after the continuous stirring of a magnetic heating stirrer for 12 hours under the condition of 90 ℃ and 800 rmp.
Synthesizing an amino acid-starch-PEO polymer solid electrolyte in the step (2): the whole process was carried out in an argon glove box. Mixing amino acid-starch solution, PEO and 30 wt% lithium salt (LiBF)4) Mixing; heating the stirrer by magnetic force at room temperature, stirring at 1000rmp for 12 hours to obtain a uniform solution, pouring the solution into a positive shell of a CR2025 battery, and heating at 50 ℃ for 10 hours to obtain a flexible solid electrolyte film with the thickness of about 0.8 mm: arginine-starch-PEO-LiBF4。
The amino acid-starch-PEO polymer solid electrolyte film obtained in the above example was subjected to a fire resistance test experiment: the amino acid-starch-PEO polymer solid electrolyte membrane is made in a battery case and placed on an electric hot plate which is heated to 191 ℃, and after 20 seconds, the shape of the solid electrolyte membrane is deformed but is not burnt; when an organic electrolyte (a common electrolyte for commercial lithium ion batteries) is dropped into the battery case, the electrolyte burns immediately (<1 second) with an open flame. The results show that the prepared polymer solid electrolyte has higher safety performance and thermal stability.
The polymer solid electrolyte membrane obtained in the above example was placed between two stainless steel sheets with a diameter of 1.6cm, and packaged in a CR2025 button cell to obtain a stainless steel/electrolyte/stainless steel button cell for conductivity test. The conductivity of the electrolyte is measured by an alternating current impedance method of an electrochemical workstation, and the temperature of the battery is controlled by a high-low temperature box. All cell assembly procedures used to test electrochemical performance were performed under an argon atmosphere. The ionic conductivity can be calculated through an alternating current impedance spectrum and a calculation formula.
TABLE 1 shows the room temperature ionic conductivities of solid electrolytes of different amino acids and amino acid-starch modified polymers
As can be seen from table 1, the modification of amino acids increased conductivity by nearly 2 orders of magnitude compared to pure PEO electrolyte, while the modification of the glutamic acid-starch synthesis product further increased the conductivity of the polymer solid electrolyte. Compared with arginine, glutamic acid has a better effect on the improvement of electrolyte conductivity, and particularly, the glutamic acid-starch-PEO polymer solid electrolyte shows the highest room-temperature ionic conductivity in all conditions studied.
The polymer solid electrolyte film obtained in the above example was placed between a stainless steel sheet and a metal lithium sheet, and packaged in a CR2025 button cell to obtain a solid electrolyte cell for electrochemical stability testing. By testing the electrochemical stability of different amino acids and amino acid-starch modified polymer solid electrolytes, PEO + Glu + starch, PEO + Arg and PEO + Glu show the redox reaction of lithium, namely the deposition and dissolution peak of metal lithium appears near 0V, and particularly the PEO + Glu electrolyte shows good lithium deposition and dissolution reversibility. And the oxidation potentials of the electrolytes are basically the same and are about 5.4V, which is higher than the decomposition potential of the liquid electrolyte to 4.2V.
Based on the conductivity test results and electrochemical stability test results, studies of different temperature conductivities were also performed for PEO + Glu and PEO + Glu + starch electrolytes. The research result is as follows: the conductivity of the PEO + Glu + starch is higher within the temperature range of 25-50 ℃, and the conductivity of the PEO + Glu + starch and the conductivity of the PEO + Glu electrolyte are basically the same within the temperature range of 50-100 ℃. The Glu + starch synthetic material is more beneficial to improving the conductivity of the solid electrolyte at a lower temperature.
The all-solid-state lithium-sulfur battery prepared by the method is at 60 ℃ and 0Cyclic voltammetry was carried out at 80 ℃ and 0.1 ℃. The test result shows that: the discharge capacity of the first-circle battery is 268mAh g under the conditions of 60 ℃ and 0.1C-1And the capacity after 7 cycles is 728mAh g-1The battery cycle was good. The theoretical capacity of the traditional liquid lithium iron phosphate battery is 172mAh g-1The capacity of the lithium-sulfur battery prepared by the invention can reach 4 times of that of the battery system. Under the conditions of 80 ℃ and 0.1C, the discharge capacity of the first-circle battery is 764mAh g-1And after 4 cycles, the capacity is 772mAh g-1The battery has good cycle and the discharge capacity is further improved. The battery cycle result proves that the prepared amino acid-starch modified polymer solid electrolyte can be applied to a wide-temperature (25-80 ℃) all-solid-state lithium-sulfur battery. In addition, under the condition of room temperature, the battery shows obvious oxidation and reduction peaks, corresponding to the reaction of lithium and sulfur, and the curve after 5 circles of circulation is coincided with the 4 th circle, so that the room temperature lithium conductivity and the good electrochemical stability of the synthesized solid electrolyte are further verified.
Claims (7)
1. A preparation method of an amino acid-starch-PEO polymer solid electrolyte is characterized by comprising the following steps:
(1) synthesis of amino acid-starch polymers
Weighing starch and amino acid by using an electronic balance in an argon glove box, wherein the molar ratio of the starch monomer to the amino acid is 30-50:1, and the amino acid comprises glutamic acid or arginine; placing starch and amino acid into a single-neck flask with a vent valve, wherein the single-neck flask is connected with a condenser pipe and a three-way valve with a balloon to form a reactor; adding dimethyl sulfoxide into a flask and stirring by using a magnetic heating stirrer in an argon atmosphere; after stirring completely, adding KH560, and stirring with a magnetic heating stirrer to obtain transparent colloidal amino acid-starch polymer;
(2) synthetic amino acid-starch-PEO polymer solid electrolyte
Mixing amino acid-starch, PEO and lithium salt in an argon glove box, and stirring by using a magnetic heating stirrer at room temperature to obtain a uniform solution; and pouring the solution on a mold and heating to obtain the amino acid-starch-PEO polymer solid electrolyte.
2. The method for preparing amino acid-starch-PEO polymer solid electrolyte as claimed in claim 1, wherein after adding dimethyl sulfoxide in the step (1), stirring is carried out at the rotation speed of 300-800rmp for 10-50min at 75-95 ℃ by oil bath.
3. The method for preparing amino acid-starch-PEO polymer solid electrolyte as claimed in claim 1, wherein after KH560 is added in step (1), the mixture is continuously stirred at a rotation speed of 700-850rmp for more than 10h at 75-95 ℃.
4. The method for preparing an amino acid-starch-PEO polymer solid electrolyte as claimed in claim 1, wherein the mass of the lithium salt in the step (2) is 25-50% of the total mass of the amino acid-starch, PEO and lithium salt.
5. The method for preparing the amino acid-starch-PEO polymer solid electrolyte as claimed in claim 1, wherein the step (2) is performed by stirring at a rotation speed of 800-.
6. The method for preparing the amino acid-starch-PEO polymer solid electrolyte as claimed in claim 1, wherein the step (2) is performed by heating on a mold, particularly at 40-80 ℃ for 6-12 h.
7. The method for preparing the amino acid-starch-PEO polymer solid electrolyte according to claim 1, wherein the amino acid-starch polymer has a structure of:
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