CN116742107B - Composite solid electrolyte membrane for lithium metal negative electrode and preparation method thereof - Google Patents
Composite solid electrolyte membrane for lithium metal negative electrode and preparation method thereof Download PDFInfo
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 239000012528 membrane Substances 0.000 title claims abstract description 46
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002033 PVDF binder Substances 0.000 claims abstract description 39
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 39
- 229920000642 polymer Polymers 0.000 claims abstract description 37
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 31
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011858 nanopowder Substances 0.000 claims abstract description 15
- 239000012266 salt solution Substances 0.000 claims abstract description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 13
- 239000003292 glue Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 14
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 3
- 229910010941 LiFSI Inorganic materials 0.000 claims description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 3
- 229910020056 Mg3N2 Inorganic materials 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 239000011777 magnesium Substances 0.000 description 12
- 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 description 9
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 8
- -1 magnesium nitride Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004222 uncontrolled growth Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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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
-
- 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
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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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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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
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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
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
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- 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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Abstract
The invention relates to the technical field of solid-state lithium batteries, in particular to a solid-state electrolyte for a lithium metal negative electrode and a preparation method thereof. The invention provides a composite solid electrolyte membrane, which comprises lithium salt, PVDF-based polymer and Mg 3 N 2 A nano powder. The method for preparing the composite solid electrolyte membrane comprises the following steps: step 1, preparing a lithium salt solution and a PVDF-based polymer glue solution by using DMF and acetone as solvents respectively, and then mixing the lithium salt solution and the PVDF-based polymer glue solution to obtain a mixed solution; step 2, adding Mg into the mixed solution obtained in the step 1 3 N 2 The nano powder is uniformly dispersed by ultrasonic to obtain slurry; and 3, stirring the slurry obtained in the step 2 while heating, pouring the slurry into a mold, and drying to obtain the composite solid electrolyte membrane. The composite solid electrolyte membrane provided by the invention has higher ionic conductivity, better stability to lithium metal negative electrode, simple and easy preparation method and easy operation, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of solid lithium batteries, in particular to a composite solid electrolyte membrane for a lithium metal negative electrode and a preparation method thereof.
Background
Compared with the conventional negative electrode materials such as graphite, the lithium metal negative electrode has higher specific capacity (3860 mAh g -1 ) And lower electrode potential (-3.040V), show great potential for the next generation of energy storage devices. Currently, in liquid batteries, practical application of lithium metal cathodes is affected by their high chemical reactivity with the electrolyte and the poor cycle life and safety properties resulting from uncontrolled growth of lithium dendrites during repeated deposition/delithiation.
Compared with a liquid battery, the solid battery has specific advantages in indexes such as energy density, service life, application range, safety and the like, and is a research and development hot spot worldwide. The use of solid polymer electrolytes instead of highly active and flammable liquid electrolytes is a very promising strategy and polymer solid electrolytes are the current route of higher technical suitability. But the ionic conductivity is relatively poor, and a higher working temperature is generally required, so that the requirements of practical application are far from met.
The composite solid electrolyte has both mechanical performance and electrochemical performance. In the selection of composite solid electrolyte polymer substrates, polyvinylidene fluoride (PVDF) -based polymers are often selected as substrates that have strongly polar electron withdrawing groups (-C-F), a higher dielectric constant and a lower glass transition temperature, which facilitate dissociation of lithium salts, and thus have relatively high lithium ion conductivities, as in chinese patent applications CN114203948A (under examination) and CN114204118A (under examination). However, although PVDF-based polymer is used as a substrate, the lithium ion conductivity of the composite solid electrolyte is still low, and the requirement of high lithium ion conductivity of the composite solid electrolyte membrane in practical application cannot be met. In addition, the PVDF-based solid electrolyte is prepared by a solution method, the solvent which is commonly used is N, N-Dimethylformamide (DMF), but DMF has higher boiling point, is not easy to dry at a lower temperature (below 100 ℃), the composite solid electrolyte membrane can be damaged due to drying at a higher temperature (above 100 ℃), and the stability of the electrolyte to a lithium metal anode can be reduced due to excessive free DMF when the electrolyte is difficult to dry.
Disclosure of Invention
In order to solve the problems of low ionic conductivity and poor stability to a lithium metal electrode of the composite solid electrolyte, the invention prepares the composite solid electrolyte membrane by using a proper amount of DMF and acetone as solvents and doping magnesium nitride, thereby improving the ionic conductivity of the composite solid electrolyte membrane and the stability to a lithium metal negative electrode. In order to achieve the technical effects, the specific technical scheme is as follows:
a composite solid electrolyte membrane for lithium metal negative electrode comprises lithium salt, PVDF-based polymer and Mg 3 N 2 A nano powder.
In particular, the lithium salt is selected from LiFSI, liTFSI and LiClO 4 At least one of them.
Specific LiFSI, liTFSI and LiClO 4 Respectively refers to lithium triflimide, lithium bistrifluoromethylsulfonimide and lithium perchlorate;
specifically, the thickness of the composite solid electrolyte membrane is 10-200 mu m;
more specifically, the thickness of the composite solid electrolyte membrane is controlled by controlling the use amount of the slurry and the size of the casting mold; the thickness of the composite solid electrolyte membrane can be designed according to the requirement;
specifically, the solute in the PVDF-based polymer glue solution is a PVDF-based polymer;
more specifically, the PVDF-based polymer is PVDF or one of the crosslinked derivatives of PVDF, including PVDF-HFP and P (VDF-TrFE).
Specifically, PVDF-HFP refers to polyvinylidene fluoride-hexafluoropropylene, and P (VDF-TrFE) refers to polyvinylidene fluoride-tetrafluoroethylene.
The invention also provides a preparation method of the composite solid electrolyte membrane, which comprises the following steps:
step 1, preparing a lithium salt solution and a PVDF-based polymer glue solution by using DMF and acetone as solvents respectively, and then mixing the lithium salt solution and the PVDF-based polymer glue solution to obtain a mixed solution;
step 2, adding Mg into the mixed solution obtained in the step 1 3 N 2 The nano powder is uniformly dispersed by ultrasonic to obtain slurry;
and 3, stirring the slurry obtained in the step 2 while heating, pouring the slurry into a mold, and drying to obtain the composite solid electrolyte membrane for the lithium metal cathode.
Specifically, the molar ratio of DMF added by the lithium salt solution prepared in the step 1 to lithium salt (calculated by Li) is 2.5-6:1, and the content of PVDF-based polymer in the PVDF-based polymer glue solution in the step 1 is 10-15 wt%.
Specifically, the mass ratio of the lithium salt to the PVDF-based polymer in the mixed solution in the step 1 is 0.5-1.5:1.
Specifically, the Mg added in step 2 3 N 2 The mass ratio of the nano powder to the PVDF-based polymer added in the step 1 is 0.1-0.15.
Specifically, the Mg 3 N 2 The size of the nano powder is 50-100 nm.
Specifically, the heating temperature in the step 3 is 60-70 ℃, the stirring speed is 700-1000 rpm, and the stirring time while heating is 10-15 h.
Specifically, the mold in the step 3 is a glass or polytetrafluoroethylene mold.
Specifically, the temperature of the drying in the step 3 is 45-75 ℃, and the drying time is 20-30 hours.
The composite solid electrolyte membrane provided by the invention can destroy a polymer chain segment in the solid electrolyte membrane by doping nano magnesium nitride, so that the polymerization degree of the polymer chain segment is reduced, and the ion conductivity of the prepared solid electrolyte can be improved; in addition, when the nano magnesium nitride contacts with the lithium metal cathode in electrochemical circulation, li with high ion conductivity and high stability can be formed in situ 3 N, thereby again improving the ionic conductivity of the composite solid electrolyte membrane and the stability to the lithium metal negative electrode;
in the preparation process, a very small amount of DMF is firstly adopted to dissolve lithium salt to form lithium salt solution, and the DMF has solvation effect on the lithium salt and forms coordination with lithium ions in the lithium salt, so that the ion conductivity of the composite solid electrolyte membrane can be improved; and simultaneously, the PVDF-based polymer glue solution is prepared by dissolving the PVDF-based polymer by taking acetone with a low boiling point as a solvent, so that the stability of the prepared composite solid electrolyte can be improved.
Compared with the prior art, the invention has the following beneficial effects:
(1) The solid electrolyte membrane provided by the invention contains a proper amount of DMF and lithium salt to form a coordination structure, and is doped with a proper amount of magnesium nitride, so that the prepared composite solid electrolyte membrane has better stability on a lithium metal negative electrode and higher ionic conductivity;
(2) The preparation method of the invention prepares the composite solid electrolyte membrane by adding a small amount of DMF solvent to treat lithium salt to form lithium salt solution, then matching with low boiling point acetone solvent and doped magnesium nitride, and has the advantages of simple preparation method, easy operation, short drying time and relatively high preparation efficiency, and is suitable for large-scale industrial production.
Drawings
Fig. 1 is an ac impedance diagram at room temperature of the composite solid electrolyte membrane prepared in comparative example 1 and the composite solid electrolyte membrane prepared in example 1;
FIG. 2 is a test result of stability of the composite solid electrolyte membrane prepared in example 1 to a lithium metal electrode;
fig. 3 is a test result of stability of the composite solid electrolyte membrane prepared in comparative example 1 to a lithium metal electrode;
fig. 4 is a test result of the stability of the composite solid electrolyte membrane prepared in comparative example 2 to a lithium metal electrode.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. It should be noted that this example is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
Example 1
(1) Weighing and mixing 0.85g of DMF and 0.8g of lithium salt LiTFSI, and carrying out ultrasonic treatment for 15 minutes to obtain a lithium salt solution; and weighing 0.8g of polymer PVDF-HFP and 5.9g of acetone, mixing, carrying out ultrasonic treatment for 15 minutes, and mixing and stirring for 3 hours at 50 ℃ to obtain PVDF-based polymer glue solution; mixing a lithium salt solution and a PVDF-based polymer glue solution to obtain a mixed solution;
(2) 0.1g of Mg was added to the mixture 3 N 2 Carrying out ultrasonic treatment on the nano powder (80 nm) for 15 minutes to ensure that the nano powder is uniformly dispersed to obtain slurry;
(3) And stirring the slurry at 65 ℃ for 12 hours at 800rpm, pouring the slurry into a clean glass mold, rapidly transferring the glass mold into a vacuum drying oven, and drying the glass mold at 60 ℃ for 24 hours to obtain the composite solid electrolyte membrane.
In this example, the molar ratio of DMF to LiTFSI is 4.2:1, the PVDF-HFP content in the PVDF-based polymer dope is 12wt%, and the mass ratio of LiTFSI added to lithium salt solution to PVDF-HFP added to the PVDF-based polymer dope is 1:1, mg added 3 N 2 The mass ratio to PVDF-HFP was 0.12:1.
Example 2
In this example, the molar ratio of DMF to LiTFSI was 6:1 as compared to example 1. Other features are the same as in example 1.
Example 3
In this example the molar ratio of DMF to LiTFSI was 2.5:1 compared to example 1. Other features are the same as in example 1.
Example 4
In this example, the PVDF-HFP content of the PVDF-based polymer dope was 10% by weight, as compared with example 1. Other features are the same as in example 1.
Example 5
In this example, the PVDF-HFP content of the PVDF-based polymer dope was 15wt% as compared with example 1. Other features are the same as in example 1.
Example 6
In comparison with example 1, the mass ratio of LiTFSI added to the lithium salt solution and PVDF-HFP added to the PVDF-based polymer dope in this example was 1.5. Other features are the same as in example 1.
Example 7
In comparison with example 1, the mass ratio of LiTFSI added to the lithium salt solution and PVDF-HFP added to the PVDF-based polymer dope in this example was 0.5. Other features are the same as in example 1.
Example 8
In comparison with example 1, mg added in this example 3 N 2 The mass ratio of the nano powder to PVDF-HFP was 0.1. Other features are the same as in example 1.
Example 9
In comparison with example 1, mg added in this example 3 N 2 The mass ratio of the nano powder to PVDF-HFP was 0.15. Other features are the same as in example 1.
Comparative example 1
Comparative example 1 differs from example 1 in that no Mg was added in comparative example 1 3 N 2 A nano powder. Other features are the same as in example 1.
Comparative example 2
Comparative example 2 differs from example 1 in that the molar ratio of DMF and LiTFSI is 6.5:1. Other features are the same as in example 1.
Test results
Fig. 1 is an ac impedance diagram at room temperature of the composite solid electrolyte films prepared in comparative example 1, comparative example 2 and example 1. The ionic conductivities of example 1, comparative example 1 and comparative example 2 were calculated to be 1.04×10, respectively -3 S cm -1 、4.07×10 -4 S cm -1 1.19X10 -3 S cm -1 (σ=l/r·s, σ is the ion conductivity, L is the thickness of the thin film, R is the impedance plot x-axis intercept, S is the effective contact area of the thin film). The results showed that the composite solid electrolyte membranes prepared in comparative example 2 and example 1 were higher in ionic conductivity.
Fig. 2 to 4 are stability tests of the composite solid electrolyte membranes prepared in example 1, comparative example 1 and comparative example 2 to lithium metal electrodes. The testing method comprises the following steps: the prepared composite solid electrolyte is clamped between two lithium electrodes to be assembled into a lithium symmetric battery (Li|SPE|Li), and the batteries are tested in a battery test system respectively0.1mA cm -2 、0.15mA cm -2 、0.2mA cm -2 、0.25mA cm -2 Cycle performance at current density. The results of fig. 2 to 4 show that the composite solid electrolyte membrane obtained in example 1 can stably operate under the above current, the voltage range is always lower than 0.2V, and the stability to lithium metal electrodes is better. Comparative example 1 since the resulting composite solid electrolyte membrane was undoped Mg 3 N 2 The nano powder can not resist dendrite growth, and the current is increased to 0.15mA cm -2 And then the short circuit is punctured by the lithium dendrite, and the stability of the lithium metal electrode is poor. Since the composite solid electrolyte membrane obtained in comparative example 2 contains excessive free DMF, uneven side reaction with lithium metal can occur, which leads to an increase in interfacial resistance, and the side reaction is more remarkable under current, which finally leads to disconnection of the electrolyte from contact with the electrode, and the stability to the lithium metal electrode is also poor.
Claims (9)
1. A composite solid electrolyte membrane for a lithium metal anode is characterized by comprising lithium salt, PVDF-based polymer and Mg 3 N 2 A nano powder;
the preparation method of the composite solid electrolyte membrane comprises the following steps:
step 1, preparing a lithium salt solution by using DMF as a solvent, preparing PVDF-based polymer glue solution by using acetone as a solvent, and then mixing the lithium salt solution and the PVDF-based polymer glue solution to obtain a mixed solution;
step 2, adding Mg into the mixed solution obtained in the step 1 3 N 2 The nano powder is uniformly dispersed by ultrasonic to obtain slurry;
step 3, stirring the slurry obtained in the step 2 while heating, pouring the slurry into a mold, and drying to obtain the composite solid electrolyte membrane;
wherein, the molar ratio of DMF added by the lithium salt solution prepared in the step 1 to lithium salt calculated by Li is 2.5-6:1.
2. The composite solid electrolyte membrane for a lithium metal anode according to claim 1, wherein the Mg 3 N 2 Particle size of nanopowder50-100 nm.
3. The composite solid electrolyte membrane for a lithium metal anode of claim 1 wherein the PVDF-based polymer is PVDF or one of the cross-linked derivatives of PVDF including PVDF-HFP and P (VDF-TrFE).
4. The composite solid electrolyte membrane for a lithium metal anode according to claim 1, wherein the lithium salt is selected from the group consisting of LiFSI, liTFSI and LiClO 4 At least one of them.
5. The composite solid electrolyte membrane for a lithium metal anode according to claim 1, wherein the PVDF-based polymer in the PVDF-based polymer dope in step 1 is 10 to 15wt%.
6. The composite solid electrolyte membrane of claim 1 wherein the mass ratio of lithium salt to PVDF-based polymer in step 1 is 0.5 to 1.5:1.
7. the composite solid electrolyte membrane according to claim 1, wherein the mass ratio of the Mg3N2 nanopowder added in step 2 to the PVDF-based polymer added in step 1 is 0.1 to 0.15.
8. The composite solid electrolyte membrane according to claim 1, wherein the heating temperature in step 3 is 60 to 70 ℃ and the stirring speed is 700 to 1000rpm.
9. The composite solid electrolyte membrane according to claim 1, wherein the temperature of the drying in step 3 is 45 to 75 ℃.
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