CN114725498A - Method for preparing PEO-MOF composite solid electrolyte based on 3D printing - Google Patents
Method for preparing PEO-MOF composite solid electrolyte based on 3D printing Download PDFInfo
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- CN114725498A CN114725498A CN202210344962.3A CN202210344962A CN114725498A CN 114725498 A CN114725498 A CN 114725498A CN 202210344962 A CN202210344962 A CN 202210344962A CN 114725498 A CN114725498 A CN 114725498A
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000010146 3D printing Methods 0.000 title claims abstract description 22
- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 239000000945 filler Substances 0.000 claims abstract description 14
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- 239000013118 MOF-74-type framework Substances 0.000 claims description 5
- 239000013207 UiO-66 Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 5
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 abstract description 14
- 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 abstract description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 30
- 238000005303 weighing Methods 0.000 description 10
- 238000007639 printing Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- -1 lithium salt anions Chemical class 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
Images
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
- H01M10/052—Li-accumulators
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a method for preparing a PEO-MOF composite solid electrolyte based on Direct Ink Writing (DIW)3D printing, which is characterized in that PEO, LiTFSI and MOF filler are mixed in acetonitrile to form slurry, and the PEO-MOF composite solid electrolyte is prepared by utilizing 3D printing. The solid electrolyte prepared by the invention has excellent electrochemical performance, and can realize the customization of the shape, thickness and function of the solid electrolyte.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a method for preparing a PEO-MOF composite solid electrolyte based on 3D printing.
Background
Industries such as portable mobile equipment and electric automobiles have increasingly large demands for energy storage devices due to rapid development. In particular, lithium ion batteries with high energy density and operating voltage dominate the energy storage device market.
The traditional lithium ion battery mainly adopts organic liquid electrolytes such as ethers, esters and the like, and has stable electrochemistryLow performance, serious interface side reaction, flammability, explosiveness, easy leakage and the like. These problems can be solved well by using a solid electrolyte having high thermal stability instead of an organic liquid electrolyte. At the same time, the solid electrolyte allows the direct use of a high theoretical specific capacity (3860mAh g)-1) The lithium metal replaces a graphite cathode to assemble a lithium metal battery, and the energy density of the battery is further improved without worrying about the trouble of lithium dendrites.
Specifically, the composite solid electrolyte consists of a polymer matrix and an inorganic filler, the introduction of the inorganic filler can improve the ionic conductivity and the mechanical strength of the polymer matrix, and decorative groups on the inorganic filler can change the local structure and increase the lithium ion concentration and the mobility, so that the selection of a proper filler is very important. The MOF is a porous crystal material formed by periodic arrangement of metal atoms and organic ligands, has an open framework structure, a rich pore structure, high surface energy and strong adsorption capacity, can capture byproducts generated in the battery circulation process, enhances the adsorption effect on lithium salt anions, and promotes the migration of lithium ions.
At present, the method for preparing the composite solid electrolyte mainly comprises coating and mould forming, has poor flexibility, and cannot realize flexible regulation and control on the shape and the thickness of the electrolyte.
Disclosure of Invention
Based on the above, a method for preparing the PEO-MOF composite solid electrolyte based on 3D printing is needed, so that the shape and thickness of the electrolyte can be flexibly regulated, and the discharge specific capacity and the rate capability can be ensured and even improved.
The invention adopts the following technical scheme:
the invention provides a method for preparing a PEO-MOF composite solid electrolyte based on 3D printing, which comprises the following steps:
adding lithium salt and PEO with the molar ratio of 1 (10-25) into acetonitrile, and uniformly stirring to obtain a mixed solution; adding an MOF filler into the mixed solution, and uniformly stirring to obtain slurry; and transferring the slurry into an injector, performing 3D printing on the substrate to form a parison with a preset shape, and performing vacuum drying to obtain the composite material.
In some of these embodiments, the lithium salt is selected from at least one of lithium bis (trifluoromethane sulfonyl) imide, lithium bis (fluorosulfonyl) imide, and lithium perchlorate.
In some of these embodiments, the molar ratio of lithium salt to PEO is preferably 1: 18.
In some of these embodiments, the MOF filler is selected from at least one of ZIF-67, ZIF-8, UIO-66, MOF-74.
In some of these embodiments, the amount of MOF filler is 5 to 10 wt% of the total amount of PEO and LiTFSI.
In some of these embodiments, the process parameters for 3D printing are: 5 to 40 psi. The process parameters of 3D printing are preferably 15-40 psi.
In some of the embodiments, the temperature of the vacuum drying is 55-65 ℃.
In some of these embodiments, the temperature of the agitation is 50 to 60 ℃.
The PEO-MOF composite solid electrolyte prepared by the method is provided.
The invention can also provide a lithium battery comprising the PEO-MOF composite solid electrolyte prepared by the method.
The beneficial effects of the invention are:
compared with the prior art, the invention firstly provides and realizes the preparation of the PEO-MOF composite solid electrolyte by utilizing 3D printing, can realize the customization of the shape and the thickness of the solid electrolyte, and can ensure and even improve the ionic conductivity, the discharge specific capacity, the multiplying power and other performances.
Drawings
FIG. 1 is an optical photograph of PEO/ZIF-67 solid electrolytes of various shapes prepared in example 1.
FIG. 2 is a graph showing rate capability tests of the circular PEO/ZIF-67 solid electrolyte and the pure PEO solid electrolyte of example 1.
FIG. 3 is a scanning electron microscope photograph of example 2 prepared PEO/ZIF-67 solid electrolytes of varying thickness.
FIG. 4 is a scanning electron microscope picture of PEO/MOF-74 solid electrolyte prepared in example 3 and a charge and discharge curve at time 1 at 0.2C.
FIG. 5 is a scanning electron microscope photograph of PEO/UIO-66 solid electrolyte prepared in example 4 and a charge-discharge curve at time 1 at 0.2C.
FIG. 6 is a scanning electron microscope photograph of PEO/ZIF-8 solid electrolyte prepared in example 5 and a charge and discharge curve at time 1 at 0.2C.
Detailed Description
The present invention is further described in detail below with reference to specific examples so that those skilled in the art can more clearly understand the present invention.
The following examples are provided only for illustrating the present invention and are not intended to limit the scope of the present invention. All other embodiments obtained by a person skilled in the art based on the specific embodiments of the present invention without any inventive step are within the scope of the present invention.
In the examples of the present invention, all the raw material components are commercially available products well known to those skilled in the art, unless otherwise specified; in the examples of the present invention, unless otherwise specified, all the technical means used are conventional means well known to those skilled in the art.
The application is directed to method steps for composite solid electrolyte product detection:
the ionic conductivity was measured by assembling a stainless steel/electrolyte/stainless steel CR2016 cell using a CHI 760e electrochemical workstation with an ac impedance frequency ranging from 10MHz to 100KHz with an amplitude of 10 mV. The calculation of the ionic conductivity (σ) is based on the following equation:
in the formula, L is the thickness of the electrolyte membrane, R is the resistance of the electrolyte, and A is the contact area (16mm) between the electrolyte and the stainless steel electrode.
Using lithium iron phosphate (LiFePO)4) The positive electrode, the printed solid electrolyte of the invention and lithium foil assembled a CR2016 solid state lithium battery. Constant current charging was carried out at 60 ℃ in a voltage range of 2.5-4.2V using LAND CT3001AAnd (5) measuring discharge.
Example 1
The embodiment provides a preparation method of a composite solid electrolyte, which comprises the following steps:
s1, weighing 0.181g of lithium bistrifluoromethanesulfonylimide LiTFSI and 0.5g of polyethylene oxide PEO (molar ratio is 1:18) and adding into 10mL of acetonitrile, and magnetically stirring for 3h at 60 ℃ to obtain a mixed solution.
S2, weighing 0.0353g of ZIF-67, adding into the mixed solution, and continuing to magnetically stir for 2 hours at the temperature of 60 ℃ to obtain slurry.
S3, adding the slurry obtained in the step S2 into a syringe, setting the pressure to be 20psi, printing on label paper according to a set three-dimensional size program, and then placing the label paper in a vacuum oven at 60 ℃ for drying for 24 hours to obtain the composite solid electrolyte.
From FIG. 1, it can be seen that there are optical photographs of various shapes of PEO/ZIF-67 solid electrolyte. The shape and thickness of the solid electrolyte can be customized by the preparation method of the embodiment.
As can be seen from fig. 2, the specific capacities of the circular PEO/ZIF-67 solid electrolyte and the pure PEO solid electrolyte were higher compared to the pure PEO solid electrolyte.
Example 2
The embodiment researches the influence of different printing pressure parameters on the shape and thickness of the composite solid electrolyte, and comprises the following steps:
s1, 0.181g of LiTFSI and 0.5g of PEO (molar ratio is 1:18) are weighed and added into 10mL of acetonitrile, and magnetic stirring is carried out for 3h at 60 ℃ to obtain a mixed solution.
S2, weighing 0.0353g of ZIF-67, adding into the mixed solution, and continuing to magnetically stir for 2 hours at the temperature of 60 ℃ to obtain slurry.
S3, adding the slurry obtained in the step S2 into an injector, setting the pressure to be 5psi, 10psi, 20psi, 30psi and 40psi respectively, printing on the substrate according to the set three-dimensional size program, and then placing the substrate in a vacuum oven at 60 ℃ for drying for 24 hours to obtain the composite solid electrolyte.
Scanning electron microscopy pictures of PEO/ZIF-67 solid electrolytes of varying thickness are shown in fig. 3.
The results of the tests of the composite solid electrolytes of different shapes prepared according to the method of this example are summarized in the following table:
influence of different printing pressure parameters (circular shape)
| Pressure of | Molding conditions | Thickness of |
| 5psi | |
15±3μm |
| 10psi | |
40±3μm |
| 20psi | Complete molding | 90±3μm |
| 30psi | Complete molding | 190±3μm |
| 40psi | Complete molding | 290±3μm |
As can be seen from the above table and the related test results, the process parameters of the 3D printing composite solid electrolyte are preferably 15-30 psi.
Example 3
The embodiment provides a preparation method of a composite solid electrolyte, which comprises the following steps:
s1, 0.181g of LiTFSI and 0.5g of PEO (molar ratio is 1:18) are weighed and added into 10mL of acetonitrile, and magnetic stirring is carried out for 3h at 60 ℃ to obtain a mixed solution.
S2, weighing 0.0353g of MOF-74, adding into the mixed solution, and continuing to magnetically stir for 2h at 60 ℃ to obtain slurry.
S3, adding the slurry obtained in the step S2 into a syringe, setting the pressure to be 20psi, printing on the label paper substrate according to a set three-dimensional size program, and then placing the label paper substrate in a vacuum oven at 60 ℃ for drying for 24 hours to obtain the composite solid electrolyte.
FIG. 4 is a scanning electron microscope picture of the prepared PEO/MOF-74 solid state electrolyte and charge and discharge curves at 0.2C time 1.
Example 4
The embodiment provides a preparation method of a composite solid electrolyte, which comprises the following steps:
s1, 0.181g of LiTFSI and 0.5g of PEO (molar ratio is 1:18) are weighed and added into 10mL of acetonitrile, and magnetic stirring is carried out for 3h at 60 ℃ to obtain a mixed solution.
S2, weighing 0.0353g of UIO-66, adding into the mixed solution, and continuing to magnetically stir for 2h at 60 ℃ to obtain slurry.
S3, adding the slurry obtained in the step S2 into a syringe, setting the pressure to be 20psi, printing on the label paper substrate according to a set three-dimensional size program, and then placing the label paper substrate in a vacuum oven at 60 ℃ for drying for 24 hours to obtain the composite solid electrolyte.
FIG. 5 is a scanning electron microscope photograph of the prepared PEO/UIO-66 solid electrolyte and a charge and discharge curve at time 1 at 0.2C.
Example 5
The embodiment provides a preparation method of a composite solid electrolyte, which comprises the following steps:
s1, 0.181g of LiTFSI and 0.5g of PEO (molar ratio is 1:18) are weighed and added into 10mL of acetonitrile, and magnetic stirring is carried out for 3h at 60 ℃ to obtain a mixed solution.
S2, weighing 0.0353g of ZIF-8, adding into the mixed solution, and continuing to magnetically stir for 2 hours at the temperature of 60 ℃ to obtain slurry.
S3, adding the slurry obtained in the step S2 into a syringe, setting the pressure to be 20psi, printing on label paper according to a set three-dimensional size program, and then placing the label paper in a vacuum oven at 60 ℃ for drying for 24 hours to obtain the composite solid electrolyte.
FIG. 5 is a scanning electron microscope picture of the prepared PEO/ZIF-8 solid electrolyte and a charge and discharge curve at time 1 at 0.2C.
Test example 6
The test researches the influence of materials with different dosage ratios on the composite solid electrolyte, and comprises the following steps:
s1, weighing LiTFSI and PEO with different molar ratios, adding the LiTFSI and the PEO into 10mL of acetonitrile, and magnetically stirring the mixture for 3 hours at the temperature of 60 ℃ to obtain a mixed solution.
S2, weighing ZIF-67 accounting for a specific percentage of the total mass of the solid, adding the ZIF-67 into the mixed solution, and continuing to magnetically stir for 2 hours at the temperature of 60 ℃ to obtain slurry.
S3, adding the slurry obtained in the step S2 into an injector, setting the pressure to be 20psi respectively, printing on a substrate according to the set three-dimensional size program setting, and then placing the substrate in a vacuum oven at 60 ℃ for drying for 24 hours to obtain the composite solid electrolyte.
The results of the tests of the composite solid electrolytes of different shapes prepared according to the method of this example are summarized in the following table:
effect of different molar ratios of LiTFSI and PEO on the Ionic conductivity
Influence of different Filler amounts
(LiTFSI and PEO in the shape of a circle in a molar ratio of 1:18)
Test example 7
The test explores the influence of different filler types on the composite solid electrolyte, and comprises the following steps:
s1, weighing LiTFSI and PEO with the molar ratio of 1:18, adding the LiTFSI and the PEO into 10mL of acetonitrile, and magnetically stirring the mixture for 3 hours at the temperature of 60 ℃ to obtain a mixed solution.
S2, weighing filler accounting for 5 wt% of the total solid content, adding the filler into the mixed solution, and continuing to magnetically stir for 2 hours at the temperature of 60 ℃ to obtain slurry.
S3, adding the slurry obtained in the step S2 into an injector, setting the pressure to be 20psi respectively, printing on a substrate according to the set three-dimensional size program setting, and then placing the substrate in a vacuum oven at 60 ℃ for drying for 24 hours to obtain the composite solid electrolyte.
The results of testing the non-filler type composite solid electrolyte prepared according to the method of this example are shown in the following table:
influence of different Filler types (circular shape)
Labeling: the prepared solid electrolyte, lithium iron phosphate and a lithium sheet are assembled into a CR2016 battery, and the CR2016 battery is tested at 0.2C.
It should be noted that the above examples are only for further illustration and description of the technical solution of the present invention, and are not intended to further limit the technical solution of the present invention, and the method of the present invention is only a preferred embodiment, and is not intended to limit the protection scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing a PEO-MOF composite solid electrolyte based on 3D printing is characterized by comprising the following steps:
adding lithium salt and PEO in a molar ratio of 1 (10-25) into an organic solvent, and uniformly stirring to obtain a mixed solution;
adding MOF filler into the mixed solution, and uniformly stirring to obtain slurry;
and transferring the slurry into an injector, performing 3D printing on the substrate to form a parison with a preset shape, and performing vacuum drying to obtain the composite material.
2. The method for preparing the PEO-MOF composite solid electrolyte based on 3D printing according to claim 1, wherein the lithium salt is at least one selected from lithium bistrifluoromethanesulfonylimide, lithium bifluorosulfonylimide and lithium perchlorate, and the organic solvent is acetonitrile.
3. The method for preparing a PEO-MOF composite solid state electrolyte based on 3D printing of claim 2, wherein the molar ratio of lithium salt to PEO is 1: 18.
4. The 3D printing-based method for preparing a PEO-MOF composite solid electrolyte according to claim 3, wherein the MOF filler is selected from at least one of ZIF-67, ZIF-8, UIO-66, MOF-74.
5. The method for preparing the PEO-MOF composite solid electrolyte based on 3D printing according to claim 4, wherein the MOF filler is used in an amount of 5-10 wt% of the total amount of PEO and lithium salt.
6. The method for preparing the PEO-MOF composite solid electrolyte based on 3D printing according to any one of the claims 1 to 5, wherein the process parameters of the 3D printing are as follows: 15 to 40 psi.
7. The method for preparing the PEO-MOF composite solid electrolyte based on 3D printing according to any one of claims 1 to 5, wherein the temperature of vacuum drying is 55-65 ℃.
8. The method for preparing the PEO-MOF composite solid electrolyte based on 3D printing according to any one of claims 1 to 5, wherein the temperature of stirring is 50-60 ℃.
9. A PEO-MOF composite solid electrolyte prepared by the method of any one of claims 1 to 8.
10. A lithium battery comprising the PEO-MOF composite solid electrolyte of claim 9.
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| US20210167376A1 (en) * | 2017-07-11 | 2021-06-03 | University College Cork - National University Of Ireland, Cork | 3d printed battery and method of making same |
| CN111886090A (en) * | 2018-02-15 | 2020-11-03 | 马里兰大学派克分院 | Ordered porous solid electrolyte structure, electrochemical device having the same, and method of manufacturing the same |
| CN108878970A (en) * | 2018-06-29 | 2018-11-23 | 华中科技大学 | A kind of composition polymer solid electrolyte, solid state lithium battery and preparation method thereof |
| CN111048829A (en) * | 2019-12-16 | 2020-04-21 | 河南科技学院 | Solid lithium ion composite electrolyte membrane and preparation method thereof |
| CN111081909A (en) * | 2019-12-26 | 2020-04-28 | 郑州大学 | Compressible quasi-solid nickel-iron battery prepared based on 3D printing technology and preparation method |
| CN111326786A (en) * | 2020-03-19 | 2020-06-23 | 珠海冠宇电池有限公司 | Composite solid electrolyte with three-dimensional penetrating structure and all-solid-state lithium ion battery |
| CN111554972A (en) * | 2020-05-11 | 2020-08-18 | 珠海冠宇电池股份有限公司 | Wire and application thereof |
| WO2021248766A1 (en) * | 2020-06-10 | 2021-12-16 | 华南理工大学 | Composite polymer solid-state electrolyte material and preparation method therefor and application thereof |
| CN112186257A (en) * | 2020-08-28 | 2021-01-05 | 西安交通大学 | Three-dimensional lithium battery preparation method based on direct-writing forming 3D printing technology |
| CN112331912A (en) * | 2020-11-09 | 2021-02-05 | 贵州梅岭电源有限公司 | Preparation method of gel electrolyte |
| CN112549528A (en) * | 2020-11-20 | 2021-03-26 | 中国地质大学（武汉） | Preparation method of optimized extrusion type 3D printing electrode |
| CN114069024A (en) * | 2021-11-15 | 2022-02-18 | 惠州亿纬锂能股份有限公司 | 3D printing solid-state battery and preparation method and application thereof |
| CN114243088A (en) * | 2021-11-25 | 2022-03-25 | 广州大学 | PEO-based composite solid electrolyte and preparation method and application thereof |
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