CN116864793A - Preparation method of polymer composite electrolyte membrane for flexible solid-state battery - Google Patents
Preparation method of polymer composite electrolyte membrane for flexible solid-state battery Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 239000012528 membrane Substances 0.000 title claims abstract description 50
- 229920000642 polymer Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 55
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 45
- 239000007788 liquid Substances 0.000 claims description 25
- 238000001523 electrospinning Methods 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 20
- 238000009987 spinning Methods 0.000 claims description 18
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 13
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 8
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000007731 hot pressing Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 230000000087 stabilizing effect Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 14
- 230000005012 migration Effects 0.000 abstract description 9
- 238000013508 migration Methods 0.000 abstract description 9
- 239000007784 solid electrolyte Substances 0.000 abstract description 7
- 239000007774 positive electrode material Substances 0.000 abstract description 6
- 229910012851 LiCoO 2 Inorganic materials 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 5
- 229910010707 LiFePO 4 Inorganic materials 0.000 abstract description 4
- 239000000919 ceramic Substances 0.000 abstract description 4
- 239000013384 organic framework Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 19
- 239000013310 covalent-organic framework Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000022131 cell cycle Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The application discloses a preparation method of a polymer composite electrolyte membrane for a flexible solid-state battery, and belongs to the field of solid-state lithium batteries. The application uses the electrospun membrane of polyacrylonitrile as a substrate to grow a conjugated organic framework in situ to obtain the in situ composite electrolyte, which is applicable to the solid electrolyte of the solid lithium battery. The migration number of lithium ions of the electrolyte is up to 0.89, which can be comparable with that of ceramic-based electrolyte, and the electrolyte can stably run for 1000 hours in a lithium symmetric battery without changing overpotential, has high-voltage and low-voltage stability, and can be matched with LiFePO 4 、LiCoO 2 Positive electrode materials such as NCM811, and the like, and are excellent in long-cycle stability and rate performance.
Description
Technical Field
The application belongs to the technical field of preparation of composite solid electrolyte, and particularly relates to a preparation method of a polymer composite electrolyte membrane for a flexible solid battery.
Background
In all-solid-state batteries, the key core component solid-state electrolyte can inhibit dendrite growth and can greatly improve the safety performance of the battery, and is the biggest technical challenge currently being overcome by researchers. The solid electrolyte may be classified into an inorganic ceramic-based electrolyte, an organic polymer-based electrolyte, and a composite solid electrolyte.
Covalent Organic Framework (COF) materials are used as solid electrolytes, which have ion conductivities and lithium ion transport numbers comparable to inorganic ceramic electrolytes. And the COF mainly comprises light elements such as C, N, O, the defect of low weight and energy density of the inorganic ceramic electrolyte is perfectly solved, in addition, the raw materials of some COF electrolytes are low in price, the preparation method is simple, and huge economic benefits can be brought. However, the COF material is mostly composed of rigid segments, so that the preparation of ultrathin flexible electrolyte by using the COF material is a great difficulty in the academic world, and in addition, the electrochemical window of the COF electrolyte is narrow, so that the COF material cannot be matched with high-nickel ternary or other positive electrode materials.
PAN is the main raw material for electrospinning. In addition, the absorption and thermal shrinkage of PAN are much better than those of commercial PP and PE separators, and the concept of a safe battery is better met. However, the crystallinity of PAN is high, especially when the PAN is applied to a lithium metal battery, the interface passivation phenomenon of cyano groups with strong polarity and lithium metal electrodes in PAN is serious, which means that the interface resistance of PAN is continuously increased after the PAN contacts lithium metal, the normal operation of the battery is affected, and the PAN electrolyte is unstable under low pressure, which is an important factor for limiting the application of the PAN solid electrolyte to the lithium metal battery.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the application and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the application and in the title of the application, which may not be used to limit the scope of the application.
As one aspect of the present application, there is provided a method for producing a polymer composite electrolyte membrane for a flexible solid-state battery, characterized by: and weighing Polyacrylonitrile (PAN), adding the Polyacrylonitrile (PAN) into an N, N-Dimethylformamide (DMF) solution while stirring, and preparing the PAN electrospun substrate by using high-voltage electrospinning. And respectively dissolving piperazine and cyanuric chloride in dioxane to be marked as liquid A and liquid B, uniformly spraying the liquid A on a PAN substrate, and uniformly spraying the liquid B on the substrate after the solvent is completely volatilized. Repeating the above operation to obtain PAN-NCS composite membrane precursor, washing PAN-NCS composite membrane precursor with deionized water, placing into aqueous solution containing lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), soaking overnight, oven drying, and hot pressing to polymerize NCS to obtain polymer composite electrolyte membrane for flexible solid state battery.
As a preferable scheme of the preparation method of the polymer composite electrolyte membrane for a flexible solid-state battery according to the present application: the preparation of the electrospinning liquid, a pipette is used for measuring 15mL of the solution of LDMF and placing the solution into a 100mL silk mouth bottle, 1.5g of Polyacrylonitrile (PAN) is weighed and added into the DMF solution while stirring, stirring is carried out at 50 ℃ overnight, after the spinning liquid is cooled to room temperature, a 10mL syringe is used for extracting the spinning liquid from the silk mouth bottle, and after bubbles in the syringe are removed, each device is connected with the electrospinning device.
As a preferable scheme of the preparation method of the polymer composite electrolyte membrane for a flexible solid-state battery according to the present application: the synthesis of the high-voltage electrospinning PAN substrate sets the electrospinning capacity as 10mL and the pushing speed as 15uL min -1 The distance between the needle and the roller is 12cm, the moving distance of the propelling pump is 20cm, and the rotating speed of the roller is 300r min -1 And regulating the pressure indication of the high-voltage power supply and stabilizing at 13kV.
As a preferable scheme of the preparation method of the polymer composite electrolyte membrane for a flexible solid-state battery according to the present application: the piperazine and the cyanuric chloride are respectively dissolved in dioxane and marked as liquid A and liquid B, wherein 0.738g of piperazine and 0.517g of cyanuric chloride are respectively dissolved in 40mL of dioxane and marked as liquid A and liquid B.
As a preferable scheme of the preparation method of the polymer composite electrolyte membrane for a flexible solid-state battery according to the present application: the hot pressing condition is that the hot pressing is carried out for 5 hours at 70 ℃ under 2000 kg.
The application has the beneficial effects that: the application provides a preparation method of a polymer composite electrolyte membrane for a flexible solid-state battery. The in-situ composite electrolyte prepared by the application has higher proportion of the covalent organic framework, and is controllable and good in uniformity. The problems of poor flexibility and high-voltage stability of the covalent organic framework and the problems of poor low-voltage stability of PAN, low migration number of lithium ions and the like are solved. The lithium symmetric battery assembled by using the in-situ composite electrolyte and lithium metal has the lithium ion migration number reaching 0.89, and can be compared favorably with the ceramic-based electrolyte. At 0.2mAh cm -2 The overpotential was only 15mV, and after 600 hours of cycling, it was also increased to only 25mV, and the steady operation was continued until the overpotential was unchanged for 1000 hours. Has high pressure and low pressure stability and can be matched with LiFePO 4 、LiCoO 2 Positive electrode materials such as NCM811 are excellent in long-cycle stability and rate capability, and can be subjected to a stability cycle of 100 cycles at a high current density (NCM 811, 1C), and the capacity retention rate is 86.9%.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the description of the embodiments will be briefly described below. Wherein:
fig. 1 is a schematic view of a polymer composite electrolyte membrane for a flexible solid-state battery prepared in example 1.
Fig. 2 shows the surface scanning electron microscope analysis of the electrolyte of example 1 and comparative example 1.
FIG. 3 shows a cross-sectional scanning electron microscope analysis of the electrolyte of example 1 and comparative example 1.
Fig. 4 is an infrared spectrum analysis of example 1, comparative example 1 and comparative example 2.
Fig. 5 is a linear sweep voltammogram of example 1, comparative example 1, and comparative example 2.
FIG. 6 is a potentiostatic polarization curve and impedance diagrams before and after potentiostatic polarization of example 1.
Fig. 7 is a graph of lithium ion migration number versus for example 1, comparative example 1, and comparative example 2.
Fig. 8 is a cycle chart of lithium-symmetric batteries of example 1, comparative example 1 and comparative example 2.
Fig. 9 is a cycle performance chart of the assembled battery of example 1, comparative example 1 and NCM 811.
Fig. 10 is a cycle performance chart of the assembled battery of example 1 and NCM 811.
FIG. 11 shows example 1 and LiFePO 4 、LiCoO 2 Cycling performance graph of assembled battery.
Detailed Description
In order that the above-recited objects, features and advantages of the present application will become more apparent, a more particular description of the application will be rendered by reference to specific embodiments thereof.
Example 1:
preparation of PAN electrospun substrate: a pipette gun measures 15mL of DMF solution in a 100mL screw flask, 1.5g of Polyacrylonitrile (PAN) was weighed and added to the DMF solution with stirring, and stirred overnight at 50 ℃. After the spinning solution is cooled to room temperature, a 10mL syringe is taken to draw the spinning solution out of a silk mouth bottle, after bubbles in the syringe are removed, each device of electrospinning is connected, the syringe is fixed on a propelling pump, a 20G needle with the inner diameter of 0.6mm is used, and oilpaper is fixed on a roller to serve as a receiving device. The electrospinning capacity is set to be 10mL, and the push speed is set to be 15uL min -1 The distance between the needle and the roller is 12cm, the moving distance of the propelling pump is 20cm, and the rotating speed of the roller is 300r min -1 . And regulating the pressure indication of the high-voltage power supply, and stabilizing at 13kV. After the electrospinning is finished, the high-voltage power supply is turned off, the spinning film loaded on the roller oiled paper is disassembled, and the middle uniform part is cut and placed on the polytetrafluoroethylene plate.
Preparation of in situ polyelectrolyte membranes: 0.738g of piperazine and 0.517g of cyanuric chloride are respectively dissolved in 40mL of dioxane and marked as A solution and B solution, 2mL of A solution is taken to be evenly sprayed on a PAN membrane, and after the solvent is completely volatilized, 2mL of B solution is taken to be evenly sprayed on the membrane. Repeating the above operation to obtain the PAN-NCS composite membrane precursor. Washing excessive HCl from the PAN-NCS composite membrane precursor by deionized water, placing the PAN-NCS composite membrane precursor into an aqueous solution containing lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), soaking the PAN-NCS composite membrane precursor overnight, and hot-pressing the PAN-NCS composite membrane precursor at 70 ℃ for 5 hours under 2000kg to further polymerize NCS, thereby obtaining the in-situ flexible composite electrolyte. The NCS ratio in the composite electrolyte was found to be 70% by weighing the mass before and after in-situ polymerization.
A method of preparing a polymer composite electrolyte membrane for a flexible solid state battery is shown in fig. 1. Fig. 2 (a) and (b) are scanning electron microscopy images before in-situ polymerization, and fig. 2 (c) and (d) are scanning electron microscopy images after in-situ polymerization, and it can be seen that the surface of the composite electrolyte membrane is not porous fiber-like before in-situ polymerization, and the surface of the composite electrolyte membrane is filled with rich NCS, and the appearance of NCS is presented. Further observing the microscopic morphology of the cross section of the composite electrolyte, as shown in fig. 3, before in-situ polymerization, the thickness of the electrospun membrane is 27 μm, no other substances exist among fiber pore channels, and after in-situ polymerization is carried out in the fibers of the electrospun membrane to prepare the composite electrolyte, the thickness of the membrane becomes 76.5 μm, and the existence of NCS phase can be obviously seen among the fiber pore channels, which indicates successful polymerization of NCS in the electrospun membrane and successful preparation of the composite electrolyte membrane.
FIG. 4 analyzes the infrared spectrum of the composite electrolyte and shows that the successful preparation of the in situ composite electrolyte, but not the simple physical mixing, PAN exists in the composite electrolyte phase rather than on the surface, and cyano groups can no longer react with metallic lithium. Meanwhile, the existence of PAN widens the voltage window of the composite electrolyte, ensures that NCS cannot be decomposed under high pressure, and prevents irreversible charge and discharge of the solid electrolyte. Figure 5 tests the electrochemical window of the composite electrolyte, and the in-situ polymerized composite electrolyte effectively combines the low-voltage and high-voltage stability of NCS and PAN, on the one hand because NCS limits the surface passivation reaction of PAN with lithium metal, and on the other hand because PAN takes over the lithium ion transport channel at high pressure, preventing decomposition of NCS. Fig. 6 is a potentiostatic polarization curve and impedance diagrams before and after potentiostatic polarization of the composite electrolyte, and lithium ion migration number of the composite electrolyte can be up to 0.89, which is comparable to that of a ceramic-based electrolyte, and the cycle life of the battery can be remarkably improved by an ultra-high lithium ion migration number, and the lithium ion migration numbers of example 1, comparative example 1 and comparative example 2 are compared with fig. 7.
By testing the stability of the composite electrolyte to lithium metal by assembling a lithium symmetric battery, fig. 8 shows that the overpotential and cycling stability of the in-situ composite electrolyte are both significantly improved compared to the pure PAN electrolyte, while having lower overpotential and lower interfacial impedance compared to the pure NCS solid state electrolyte sheet. The in-situ composite electrolyte has better affinity to lithium metal and better cycle stability. This aspect is because the characteristics of both hardness and softness reduce the interfacial resistance between the solid-state components during the battery assembly process, and the plating and stripping surfaces of lithium are smoother and more uniform; on the other hand, the service life of the battery is effectively ensured due to the ultrahigh migration number of lithium ions.
The NCM811 was first used as the positive electrode to test its long cycle stability and rate capability, as shown in FIGS. 9 (a-b), the in-situ composite electrolyte was 126.7mAhg after 200 cycles at a current density of 0.5C -1 Is a capacity of 85%. This is not achieved when PAN and NCS are present alone. Further testing the rate capability, as shown in FIG. 9 (C-e), it was found that the in-situ composite electrolyte still has a very high specific charge-discharge capacity at high rate, and the specific capacity at 1C is 141.4mAhg -1 And the capacity is not reduced suddenly when the temperature is restored to 0.2C, which shows that the in-situ composite electrolyte and the battery are not irreversibly influenced under high-rate and high-current conditions. The cycling stability of the composite electrolyte at 1C was investigated, and as shown in FIG. 10, after cycling at 1C for 100 cycles, the specific capacity was still 100mAhg -1 The capacity retention was 86.9%. The lithium ion intercalation and deintercalation method shows that under high-rate and high-current conditions, the structure of the electrolyte cannot be damaged, and the lithium ion intercalation and deintercalation method has good reversibility.
To verify that the in-situ composite electrolyte can be matched to a variety of positive electrode materials, we used as electrolyte an in-situ composite electrolyte, liFePO 4 And LiCoO 2 As the positive electrode materials, respectively, the battery was assembled. As shown in FIG. 11, in LiFePO 4 As a positive electrode, the specific capacity was 144.7mAhg after 300 cycles of 0,5C -1 The capacity retention rate is as high as 95%. By LiCoO 2 When used as the positive electrode, the specific capacity is still 117.9mAhg after 130 circles of circulation -1 The capacity retention rate is as high as 99%. The in-situ composite electrolyte can be matched with various positive electrode materials, and can meet the charge and discharge requirements under different voltages and different environments.
Comparative example 1:
a pipette gun measures 15mL of DMF solution in a 100mL screw flask, 1.5g of Polyacrylonitrile (PAN) was weighed and added to the DMF solution with stirring, and stirred overnight at 50 ℃. After the spinning solution is cooled to room temperature, a 10mL syringe is taken to draw the spinning solution out of a silk mouth bottle, after bubbles in the syringe are removed, each device of electrospinning is connected, the syringe is fixed on a propelling pump, a 20G needle with the inner diameter of 0.6mm is used, and oilpaper is fixed on a roller to serve as a receiving device. The electrospinning capacity is set to be 10mL, and the push speed is set to be 15uL min -1 The distance between the needle and the roller is 12cm, the moving distance of the propelling pump is 20cm, and the rotating speed of the roller is 300r min -1 . And regulating the pressure indication of the high-voltage power supply, and stabilizing the pressure indication near 13kV. After the electrospinning was completed, the high-voltage power supply was turned off, the spinning film carried on the roll oilpaper was removed, the middle uniform portion was cut and placed on a surface dish, the spinning film was sufficiently soaked with 1M LiTFSI in DMF, excess solvent was removed after 24 hours, and hot-pressed with a hot press at 70 ℃ under 2000kg for 5 hours. The electrolyte membrane SPE is obtained.
Comparative example 1 scanning electron microscope analysis of electrolyte membrane SPE as in fig. 2 (a-b), cross section scanning electron microscope as in fig. 3 (a-b), infrared spectrum as in SPE curve of fig. 4, electrochemical window test as in SPE curve of fig. 5, lithium ion migration number as in SPE curve of fig. 7, lithium symmetric cell cycle curve as in SPE curve of fig. 8, and NCM811 cell cycle curve as in fig. 9.
Comparative example 2:
0.738g of piperazine was dissolved in 40mL of dioxane, and stirred until it was completely dissolved, designated as solution A; 0.517g of cyanuric chloride is weighed and dissolved in 40mL of dioxane, and the mixture is stirred in an ice water bath until the cyanuric chloride is completely dissolved, and the mixture is marked as liquid B. The solution A was added dropwise to the solution B with a constant pressure dropping funnel, followed by reaction for 2 hours, taking care that the whole process was carried out in an ice-water bath. 2mL of triethylamine was removed and added to the above mixture, and after the reaction was continued in an ice-water bath for 2 hours, the temperature was raised to 70℃and the reaction was continued overnight. After the reaction was completed, cooling to room temperature, suction filtration was performed, and the precipitate was collected, and after 3 times of washing with ethanol and water alternately, the obtained powder was thoroughly dried in a vacuum oven (maintained at 60 ℃ for 12 hours). Finally, the collected dry powder was ground thoroughly for use, designated NCS.
Comparative example 2 electrolyte NCS has an infrared spectrum as the NCS curve of fig. 4, an electrochemical window test as the NCS curve of fig. 5, a lithium ion transfer number as the NCS curve of fig. 7, and a lithium symmetric cell cycle curve as the NCS curve of fig. 8.
Comparative example 3:
a pipette gun was used to measure 15mL of the solution in a 100mL jar, 1.5g of Polyacrylonitrile (PAN) was weighed and added to the DMF solution with stirring, and the mixture was stirred overnight at 50 ℃. After the spinning solution is cooled to room temperature, a 10mL syringe is taken to draw the spinning solution out of a silk mouth bottle, after bubbles in the syringe are removed, each device of electrospinning is connected, the syringe is fixed on a propelling pump, a 20G needle with the inner diameter of 0.6mm is used, and oilpaper is fixed on a roller to serve as a receiving device. The electrospinning capacity is set to be 10mL, and the push speed is set to be 15uL min -1 The distance between the needle and the roller is 12cm, the moving distance of the propelling pump is 20cm, and the rotating speed of the roller is 300r min -1 . And regulating the pressure indication of the high-voltage power supply, and stabilizing the pressure indication near 13kV. After the electrospinning was completed, the high-voltage power supply was turned off, the spinning film carried on the roll oilpaper was removed, the middle uniform portion was cut and placed on a surface dish, the spinning film was sufficiently soaked with 1M LiTFSI in DMF, excess solvent was removed after 24 hours, and hot-pressed with a hot press at 70 ℃ under 2000kg for 5 hours. The electrolyte membrane SPE is obtained.
0.738g of piperazine was dissolved in 40mL of dioxane, and stirred until it was completely dissolved, designated as solution A; 0.517g of cyanuric chloride is weighed and dissolved in 40mL of dioxane, and the mixture is stirred in an ice water bath until the cyanuric chloride is completely dissolved, and the mixture is marked as liquid B. Mixing the solution A and the solution B in a hydrothermal kettle, putting the mixture into an electrolyte membrane SPE, heating to 70 ℃, and reacting overnight.
The hydrothermal method is found to cause the phenomenon of COF particle agglomeration in the solution, and the COF particles growing on the PAN film are few, so that an electrolyte film with uniform PAN and NCS composition cannot be obtained.
Comparative example 4:
a pipette gun measures 15mL of DMF solution in a 100mL screw flask, 1.5g of Polyacrylonitrile (PAN) was weighed and added to the DMF solution with stirring, and stirred overnight at 50 ℃. After the spinning solution is cooled to room temperature, a 10mL syringe is taken to draw the spinning solution out of a silk mouth bottle, after bubbles in the syringe are removed, each device of electrospinning is connected, the syringe is fixed on a propelling pump, a 20G needle with the inner diameter of 0.6mm is used, and oilpaper is fixed on a roller to serve as a receiving device. The electrospinning capacity is set to be 10mL, and the push speed is set to be 15uL min -1 The distance between the needle and the roller is 12cm, the moving distance of the propelling pump is 20cm, and the rotating speed of the roller is 300r min -1 . And regulating the pressure indication of the high-voltage power supply, and stabilizing the pressure indication near 13kV. After the electrospinning was completed, the high-voltage power supply was turned off, the spinning film carried on the roll oilpaper was removed, the middle uniform portion was cut and placed on a surface dish, the spinning film was sufficiently soaked with 1M LiTFSI in DMF, excess solvent was removed after 24 hours, and hot-pressed with a hot press at 70 ℃ under 2000kg for 5 hours. The electrolyte membrane SPE is obtained.
0.738g of piperazine was dissolved in 40mL of dioxane, and stirred until it was completely dissolved, designated as solution A; 0.517g of cyanuric chloride is weighed and dissolved in 40mL of dioxane, and the mixture is stirred in an ice water bath until the cyanuric chloride is completely dissolved, and the mixture is marked as liquid B. The electrolyte membrane SPE was immersed directly in the a solution, followed by the B solution.
The method of directly immersing the PAN film into the raw material liquid causes a large amount of COF particles to be generated in the solution without growing on the PAN film or immersing the pores of the PAN film, and thus an electrolyte film in which PAN and NCS are uniformly compounded cannot be obtained.
It should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the same, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present application may be modified or substituted without departing from the spirit and scope of the technical solution of the present application, which is intended to be covered in the scope of the claims of the present application.
Claims (9)
1. A method for preparing a polymer composite electrolyte membrane for a flexible solid-state battery, characterized by: and (3) weighing polyacrylonitrile, adding the polyacrylonitrile into an N, N-dimethylformamide solution while stirring, preparing a PAN electrospun substrate by using high-voltage spinning, respectively dissolving piperazine and cyanuric chloride into dioxane to be respectively marked as liquid A and liquid B, uniformly spraying the liquid A on the PAN electrospun substrate, uniformly spraying the liquid B on the PAN electrospun substrate after the solvent is completely volatilized, repeating the operation of spraying the liquid A and the liquid B to obtain a PAN-NCS composite membrane precursor, washing the PAN-NCS composite membrane precursor, placing the PAN-NCS composite membrane precursor into an aqueous solution containing lithium bis (trifluoromethanesulfonyl) imide, soaking overnight, drying and hot-pressing to obtain the polymer composite electrolyte membrane for the flexible solid-state battery.
2. The method for producing a polymer composite electrolyte membrane for a flexible solid-state battery according to claim 1, characterized in that: the polyacrylonitrile is weighed and added into the N, N-dimethylformamide solution while stirring, wherein the mass fraction of the polyacrylonitrile is 10-15%.
3. The method for producing a polymer composite electrolyte membrane for a flexible solid-state battery according to claim 1 or 2, characterized in that: the PAN electrospun substrate is prepared by high-voltage electrospinning, wherein the electrospinning capacity is set to be 10mL, and the push speed is set to be 15uL min -1 The distance between the needle and the roller is 12cm, the moving distance of the propelling pump is 20cm, and the rotating speed of the roller is 300r min -1 And regulating the pressure indication of the high-voltage power supply and stabilizing at 13kV.
4. The method for producing a polymer composite electrolyte membrane for a flexible solid-state battery according to claim 3, characterized in that: the piperazine and the cyanuric chloride are respectively dissolved in dioxane and respectively marked as liquid A and liquid B, wherein 0.738g of piperazine and 0.517g of cyanuric chloride are respectively dissolved in 40mL of dioxane and respectively marked as liquid A and liquid B.
5. The method for producing a polymer composite electrolyte membrane for a flexible solid-state battery according to claim 1 or 2, characterized in that: the hot pressing is carried out under the conditions of 70 ℃ and 2000kg for 5 hours.
6. The method for producing a polymer composite electrolyte membrane for a flexible solid-state battery according to claim 4, characterized in that: the solution A is uniformly sprayed on the PAN electro-spinning substrate, and 2mL of solution A is uniformly sprayed on the PAN electro-spinning substrate.
7. The method for producing a polymer composite electrolyte membrane for a flexible solid-state battery according to claim 4, characterized in that: and uniformly spraying the solution B on the PAN electrospun substrate, wherein 2mL of the solution B is uniformly sprayed on the PAN electrospun substrate.
8. The method for producing a polymer composite electrolyte membrane for a flexible solid-state battery according to claim 1 or 2, characterized in that: the PAN-NCS composite membrane precursor is washed with deionized water.
9. The use of the product of the preparation method of claim 1 in flexible solid-state lithium batteries.
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