CN115732770B - Flexible self-healing electrolyte membrane, preparation method thereof and battery - Google Patents
Flexible self-healing electrolyte membrane, preparation method thereof and battery Download PDFInfo
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- CN115732770B CN115732770B CN202211561928.8A CN202211561928A CN115732770B CN 115732770 B CN115732770 B CN 115732770B CN 202211561928 A CN202211561928 A CN 202211561928A CN 115732770 B CN115732770 B CN 115732770B
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- electrolyte membrane
- zinc
- healing
- gum
- maleic
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- 239000012528 membrane Substances 0.000 title claims abstract description 55
- 239000003792 electrolyte Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 150000003751 zinc Chemical class 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000007731 hot pressing Methods 0.000 claims abstract description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 238000004806 packaging method and process Methods 0.000 claims description 7
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 6
- -1 zinc trifluoromethane acetate Chemical compound 0.000 claims description 4
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 claims description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000007784 solid electrolyte Substances 0.000 description 20
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000004621 scanning probe microscopy Methods 0.000 description 1
- 235000008113 selfheal Nutrition 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- VCQWRGCXUWPSGY-UHFFFAOYSA-L zinc;2,2,2-trifluoroacetate Chemical compound [Zn+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F VCQWRGCXUWPSGY-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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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- Secondary Cells (AREA)
- Primary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The invention provides a flexible self-healing electrolyte membrane, a preparation method thereof and a battery, wherein the method comprises the following steps: adding the maleic gum into an organic solvent, stirring until the maleic gum is dissolved, adding the zinc salt, continuously stirring to obtain a uniform suspension, pouring the uniform suspension into a container, and drying to obtain the flexible self-healing electrolyte membrane. The electrolyte membrane prepared by the method has uniform texture, porous morphology, good conductivity (the conductivity can reach 0.8-1.6X10 ‑4 S cm‑1 under the environment of 60 degrees), and flexible and self-healing properties (the electrolyte membrane can be recovered by hot pressing after being sheared). The zinc-MnO 2 full cell assembled by using the film shows good energy density (the mass specific capacity is 50 mAh g ‑1 under the current density of 0.1A g ‑1) and cycle performance. The electrolyte membrane prepared by the invention has the advantages of simple preparation method, self-healing flexibility, stable performance, safe use and the like.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a flexible self-healing electrolyte membrane, a preparation method thereof and a battery.
Background
At present, the disadvantages of high cost, low safety, lack of lithium resources and the like of the lithium ion battery prompt researchers to search for other energy storage systems for replacing the lithium ion battery. Recently, the water-based zinc ion battery has attracted wide attention due to the advantages of green safety, outstanding theoretical capacity, low raw material cost and the like.
The current zinc ion battery system has the biggest disadvantages of poor cycle reversibility of a metallic zinc anode, which is manifested by serious growth of zinc dendrites in an aqueous electrolyte and unstable electrochemical performance. After research, researchers find that the solid electrolyte composed of the chemically inert material with high mechanical strength can be used for replacing the water-based liquid electrolyte to relieve the instability of the performance of the metallic zinc anode.
However, achieving a solid zinc ion electrolyte with high conductivity remains challenging due to the high charge density limitations of Zn 2+. The prior research work of the solid electrolyte of the zinc ion battery is mainly focused on development of poly (ethylene oxide) (PEO) and different zinc salt systems, but the solid electrolyte of the system has lower ionic conductivity (about 10 -7 S/cm), poor contact with an electrode and poor mechanical property, and cannot deform such as bending, stretching, torsion and the like, so that the solid electrolyte is insufficient for meeting the application of the solid zinc ion battery. Therefore, the development of novel high conductivity and high stability zinc ion solid state electrolytes to meet zinc ion battery applications is an extremely important research development direction.
Disclosure of Invention
The embodiment of the invention provides a preparation method of a flexible self-healing electrolyte membrane, which comprises the following steps:
adding the maleic gum into an organic solvent, stirring until the maleic gum is dissolved, adding the zinc salt, continuously stirring to obtain a uniform suspension, pouring the uniform suspension into a container, and drying to obtain the flexible self-healing electrolyte membrane.
Preferably, the mass ratio of the maleic gum to the zinc salt is 1:1-1:3, a step of;
Preferably, the optimal mass ratio of the maleic gum to the zinc triflate is 1:2. the conductivity of the solid electrolyte membrane prepared from the above-mentioned mixture ratio of the maleic gum and zinc trifluoromethane sulfonate is optimal.
Preferably, the mass/volume ratio of the maleic gum to the organic solvent is 1:15-1:50g/ml.
Preferably, the zinc salt comprises zinc triflate or zinc triflate.
Preferably, the container comprises a glass vessel; the temperature of the drying step is room temperature, and the time is 5-8 hours;
Preferably, the organic solvent comprises chloroform;
Preferably, the maleic gum is added into the organic solvent and stirred until the maleic gum is dissolved for 1 to 2 hours; the time for continuously stirring the zinc salt is 10 to 12 hours.
Preferably, the maleic gum is a trans isomer of rubber and the main component is a trans polymer of isoamylene.
The invention also provides a flexible self-healing electrolyte membrane, which is characterized in that the flexible self-healing electrolyte membrane is prepared by adopting any one of the methods.
The invention also provides a preparation method of the zinc-MnO 2 full battery, which comprises the following steps:
Firstly placing a negative electrode shell, placing a zinc negative electrode on the negative electrode shell, placing the flexible self-healing electrolyte membrane on the zinc negative electrode, then placing a MnO 2 positive plate above the electrolyte membrane, covering a gasket, a spring piece and the positive electrode shell, and packaging by a battery packaging machine to obtain the zinc-MnO 2 full battery.
The invention also provides a flexible self-healing electrolyte membrane, which is characterized in that the electrolyte membrane takes the maleic gum as a matrix and zinc salt as a salt body, and the mass ratio of the maleic gum to the zinc salt is 1: 1-1:3.
Preferably, the zinc salt comprises zinc triflate or zinc triflate;
Preferably, the electrolyte membrane is in a porous morphology, and the conductivity can reach 0.8-1.6x10 -4S cm-1 under the 60-DEG environment.
The invention also provides a zinc-MnO 2 battery which is characterized by comprising the electrolyte membrane of any one of the above.
Preferably, the battery further comprises: and the zinc cathode and the MnO 2 positive plate are respectively arranged on two sides of the electrolyte membrane.
The invention aims to improve the poor electrochemical and mechanical stability of a zinc ion battery, applies the gum maleate to the preparation of a zinc ion solid electrolyte membrane for the first time, and provides a preparation method of a flexible self-healing all-solid zinc ion electrolyte membrane. The full-solid zinc-MnO 2 full battery assembled by the film shows good energy density (the mass specific capacity is more than 50mAh g -1 under the current density of 0.1Ag -1) and cycle performance. The electrolyte membrane prepared by the invention has the advantages of simple preparation method, flexibility, self-healing, safe use and the like.
Drawings
The features and advantages of the present invention will be more clearly understood by reference to the accompanying drawings, which are illustrative and should not be construed as limiting the invention in any way, in which:
FIG. 1 (a) is a physical view of an all-solid electrolyte membrane; (b) electron scanning microscopy of all solid electrolyte membranes.
Fig. 2 is a graph of the conductivity of all-solid electrolyte membranes prepared according to the present invention at various temperatures.
Fig. 3 is a graph for testing the self-healing performance of the all-solid electrolyte membrane.
FIG. 4 is a graph showing the cycling stability of a Zn-MnO 2 full cell.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The invention takes the gum maleate and the zinc trifluoromethane sulfonate or the zinc trifluoromethane acetate as raw materials, and the chloroform as the solvent, and prepares the flexible self-healing all-solid zinc ion electrolyte at normal temperature. Wherein, in chloroform solvent, the maleic gum and zinc trifluoromethane sulfonate or zinc trifluoromethane acetate are crosslinked, and can be combined and dried into a flexible self-healing electrolyte membrane at normal temperature.
Example 1:
(1) 1.0g of maleic gum is added into 20ml of chloroform solvent and stirred for 1h, and then 1.5g of zinc trifluoromethane sulfonate is added and stirred for 10-12 h continuously, so as to obtain uniform suspension.
(2) Pouring the suspension obtained in the step 1 into a glassware, and drying for 5-8 hours at normal temperature to obtain the self-healing solid electrolyte membrane.
(3) The solid electrolyte membrane measured a conductivity of 0.8 x 10 -4S cm-1 under a 60 degree environment. The testing method comprises the following steps: and placing the gasket on a negative electrode shell of the button cell, adding the prepared electrolyte membrane, placing the other gasket above the membrane, adding the elastic sheet, packaging the gasket into the button cell by a packaging machine, measuring the resistance of the button cell by using an alternating current impedance method, and calculating to obtain the conductivity of the button cell.
Example 2:
(1) 1.0g of maleic gum is added into 20ml of chloroform solvent and stirred for 2 hours, and then 2.0g of zinc trifluoromethane sulfonate is added and stirred for 10 to 12 hours continuously, thus obtaining uniform suspension.
(2) Pouring the suspension obtained in the step 1 into a glassware, and drying for 5-8 hours at normal temperature to obtain the bendable self-healing solid electrolyte membrane, wherein the solid electrolyte membrane can be observed under a scanning electron microscope, and the surface of the electrolyte membrane presents a porous morphology, as shown in the figure 1 (b).
(3) The solid electrolyte membrane measured a conductivity of 1.6 x 10 -4S cm-1 in a 60 degree environment and increased with increasing temperature, and the conductivity reached 3.2 x 10 -4S cm-1 in an 80 degree environment, see fig. 2.
(4) When the obtained solid electrolyte membrane (fig. 3 (a)) is sheared (fig. 3 (b)), the cracks can self-heal into a complete solid electrolyte membrane after hot pressing (fig. 3 (c)).
(5) Sequentially stacking a zinc cathode, a solid electrolyte membrane and a MnO 2 anode into a battery mould for pressurizing and packaging. The mass specific capacity of the obtained battery cell was 50mAh g -1 (calculated based on the positive electrode active material) at a current density of 0.1Ag -1, and the battery cell was circulated for 200 cycles, see fig. 4.
Example 3:
(1) 1.0g of maleic gum is added into 20ml of chloroform solvent and stirred for 1h, and then 2.5 g of zinc trifluoromethane acetate is added and stirred for 10-12 h continuously, so as to obtain uniform suspension.
(2) Pouring the suspension obtained in the step 1 into a glassware, and drying for 5-8 hours at normal temperature to obtain the self-healing solid electrolyte membrane.
(3) The conductivity was measured to be 1.2 x 10 -4S cm-1.
Example 4:
(1) 1.0g of maleic gum is added into 30ml of chloroform solvent and stirred for 1h, and then 3g of zinc trifluoroacetate is added and stirred for 10-12 h continuously, thus obtaining uniform suspension.
(2) Pouring the suspension obtained in the step 1 into a glassware, and drying for 5-8 hours at normal temperature to obtain the self-healing solid electrolyte membrane.
The above-described embodiments illustrate only the principle of the invention and its efficacy, but are not intended to limit the invention, as various modifications and variations can be made by those skilled in the art without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (12)
1. A method for preparing a flexible self-healing electrolyte membrane, the method comprising the steps of:
adding maleic gum into an organic solvent, stirring until the maleic gum is dissolved, adding zinc salt, continuously stirring to obtain uniform suspension, pouring the suspension into a container, and drying to obtain the flexible self-healing electrolyte membrane;
Wherein the mass ratio of the maleic gum to the zinc salt is 1:1-1:3, a step of;
the zinc salt comprises zinc trifluoromethane sulfonate or zinc trifluoromethane acetate;
The mass/volume ratio of the maleic gum to the organic solvent is 1:15-1:50g/ml.
2. The method of claim 1, wherein the container comprises a glass vessel; the temperature of the drying step is room temperature and the time is 5-8 hours.
3. The method of claim 1, wherein the organic solvent comprises chloroform.
4. The process according to claim 1, wherein the maleic gum is added to the organic solvent and stirred until dissolved for 1 to 2 hours; the time for continuously stirring the zinc salt is 10 to 12 hours.
5. The process of claim 1 wherein the maleic gum is the trans isomer of rubber and the major component is the trans polymer of isoamylene.
6. A flexible self-healing electrolyte membrane prepared by the method of any one of claims 1 to 5.
7. A method for preparing a zinc-MnO 2 full cell, which is characterized by comprising the following steps:
Firstly placing a negative electrode shell, placing a zinc negative electrode on the negative electrode shell, placing the flexible self-healing electrolyte membrane of claim 6 on the zinc negative electrode, then placing a MnO 2 positive plate above the electrolyte membrane, covering a gasket, a spring plate and the positive electrode shell, and packaging by a battery packaging machine to obtain the zinc-MnO 2 full battery.
8. The flexible self-healing electrolyte membrane is characterized in that the electrolyte membrane takes maleic gum as a matrix and zinc salt as a salt body, and the mass ratio of the maleic gum to the zinc salt is 1:1-1:3, a step of; the zinc salt comprises zinc triflate or zinc triflate.
9. The electrolyte membrane according to claim 8, wherein the electrolyte membrane has a porous morphology and a conductivity of 0.8 to 1.6 x 10 -4S cm-1 at 60 degrees.
10. The electrolyte membrane according to claim 8, wherein the electrolyte membrane has a flexible and self-healing property, i.e., the electrolyte membrane is recoverable by hot pressing after being sheared.
11. A zinc-MnO 2 battery comprising the electrolyte membrane of any one of claims 8-10.
12. The battery of claim 11, wherein the battery further comprises: and the zinc cathode and the MnO 2 positive plate are respectively arranged on two sides of the electrolyte membrane.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211561928.8A CN115732770B (en) | 2022-12-07 | 2022-12-07 | Flexible self-healing electrolyte membrane, preparation method thereof and battery |
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| CN202211561928.8A CN115732770B (en) | 2022-12-07 | 2022-12-07 | Flexible self-healing electrolyte membrane, preparation method thereof and battery |
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| CN115732770B true CN115732770B (en) | 2024-07-19 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104810549A (en) * | 2015-04-20 | 2015-07-29 | 江苏科技大学 | Method for preparing porous gel polymer electrolyte doped with composite nanoparticles |
| CN109860647A (en) * | 2018-12-19 | 2019-06-07 | 苏州柔能纳米科技有限公司 | Alkaline flexible electrolyte film of zinc-manganese battery and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6733920B2 (en) * | 2001-04-19 | 2004-05-11 | Zinc Matrix Power, Inc. | Recombinant separator |
| US11094929B2 (en) * | 2019-05-06 | 2021-08-17 | City University Of Hong Kong | Energy storage device, an electrode for an energy storage device, and a method of fabricating the electrode |
| US20220200054A1 (en) * | 2020-12-18 | 2022-06-23 | Phillips 66 Company | Ex situ electrolyte additives for batteries |
| CN113437360A (en) * | 2021-05-20 | 2021-09-24 | 上海大学 | Novel gel electrolyte for zinc battery and preparation method thereof |
| CN115172868A (en) * | 2022-07-06 | 2022-10-11 | 北京理工大学 | Self-healing gel polymer electrolyte and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104810549A (en) * | 2015-04-20 | 2015-07-29 | 江苏科技大学 | Method for preparing porous gel polymer electrolyte doped with composite nanoparticles |
| CN109860647A (en) * | 2018-12-19 | 2019-06-07 | 苏州柔能纳米科技有限公司 | Alkaline flexible electrolyte film of zinc-manganese battery and preparation method thereof |
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