CN115775916A - Polymer solid electrolyte with high lithium ion conductivity at room temperature - Google Patents
Polymer solid electrolyte with high lithium ion conductivity at room temperature Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 75
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 45
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 50
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 230000005496 eutectics Effects 0.000 claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 7
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 7
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 7
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 6
- 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 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- 238000003892 spreading Methods 0.000 claims description 3
- 230000007480 spreading Effects 0.000 claims description 3
- RWGSUPSHDHVNAX-UHFFFAOYSA-N 2,2-dihydroxyethyl prop-2-enoate Chemical compound OC(O)COC(=O)C=C RWGSUPSHDHVNAX-UHFFFAOYSA-N 0.000 claims description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims 1
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 claims 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 description 21
- 238000003756 stirring Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- ZXOYISJKORDHJT-UHFFFAOYSA-N 4-methyl-1,3-dioxolan-2-one;hydrofluoride Chemical compound F.CC1COC(=O)O1 ZXOYISJKORDHJT-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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 discloses a polymer solid electrolyte with high lithium ion conductivity at room temperature, which is prepared by adding a negative electrode protection additive, a polymer monomer, a cross-linking agent and a photoinitiator into a deep eutectic electrolyte and then adopting ultraviolet polymerization; the deep eutectic electrolyte is prepared from N-methylacetamide and lithium salt; the polymer monomer is a monomer which is difficult to dissolve in the electrolyte and a monomer which is easy to dissolve in the electrolyte. The polymer electrolyte for the all-solid-state battery provided by the invention has the advantages of high conductivity, simple preparation method, good flexibility and easiness in processing, solves the problem of low room-temperature ionic conductivity of the polymer solid electrolyte, has good stability for a lithium metal cathode, and can be applied to a lithium metal battery with high energy density and high safety.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a polymer solid electrolyte with high lithium ion conductivity at room temperature.
Background
At present, secondary batteries represented by lithium ion batteries are widely applied to the fields of consumer electronics, electric automobiles, large-scale energy storage and the like, however, commercial organic carbonate electrolytes have potential safety hazards such as easy volatilization, high flammability and the like, so that the safety of the batteries cannot be guaranteed. Therefore, the solid electrolyte is a reliable solution to the above challenges, wherein the polymer solid electrolyte has the advantages of flexibility, easy processing, and non-flammability, and greatly improves the safety performance of the battery. However, the room temperature ionic conductivity of solid polymer electrolytes composed of polymers such as polyethylene oxide and polyvinylidene fluoride and lithium salt is generally less than 10 -5 S cm -1 And the electrolyte can normally work only at high temperature, which is not beneficial to the practical application of the polymer electrolyte.
In order to improve the room temperature lithium ion conductivity of the polymer solid electrolyte, lithium ion conductor type inorganic nanoparticles are generally required to be mixed to reduce the crystallinity of the polymer and provide an additional lithium ion transmission path, but excessive inorganic fillers are easy to agglomerate in the polymer, so that a lithium ion transmission channel is affected, a large amount of organic solvent is often required to be introduced to uniformly disperse the inorganic fillers, and the solvent is difficult to completely remove in the subsequent drying process, so that a series of problems of interface impedance increase, cycle life reduction, safety deterioration and the like in the battery cycle process are caused. In addition to the introduction of the inorganic filler, the introduction of the plasticizer with a high dielectric constant can also promote the dissociation of the lithium salt, however, the introduction of the plasticizer not only affects the thermal stability of the polymer electrolyte, but also reduces the mechanical strength of the polymer electrolyte membrane, and still has a safety hazard. At present, the problems of low lithium ion conductivity, low mechanical strength and narrow electrochemical window of the polymer solid electrolyte are still huge challenges for restricting the development of the polymer-based all-solid-state battery.
Disclosure of Invention
In order to solve the technical problems, the invention provides a polymer solid electrolyte with high lithium ion conductivity at room temperature and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a polymer solid electrolyte is prepared by adding a negative electrode protection additive, a polymer monomer, a cross-linking agent and a photoinitiator into a deep eutectic electrolyte and then adopting ultraviolet polymerization;
the deep eutectic electrolyte is prepared from N-methylacetamide, lithium salt and a negative electrode protection additive;
the polymer monomer is a monomer which is difficult to dissolve in the electrolyte and a monomer which is easy to dissolve in the electrolyte.
Further, in the deep eutectic electrolyte, the lithium salt is at least one of lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethyl) sulfonyl imide or lithium nitrate, the molar ratio of N-methylacetamide to the lithium salt is 4.
In one embodiment of the invention, the lithium salt is lithium bis (fluorosulfonyl) imide, the negative electrode protection additive is fluoropropylene carbonate, and the addition amount is 5wt%.
Further, the monomer which is difficult to dissolve in the electrolyte is acrylamide, the monomer which is easy to dissolve in the electrolyte is at least one of N, N-dimethylacrylamide, dihydroxyethyl acrylate or hydroxyethyl methacrylate, the total concentration range of the polymer monomer in the deep eutectic electrolyte is 1.5-6mol/L, and the molar ratio of the difficult to dissolve monomer to the easy to dissolve monomer is 1-5: 1.
in one embodiment of the invention, the monomer easily soluble in the electrolyte is N, N-dimethylacrylamide, the total concentration of the polymer monomer in the deep eutectic electrolyte is 3mol/L, and the molar ratio of the difficult soluble monomer to the easy soluble monomer is 4.
Further, the crosslinking agent was N, N' -methylenebisacrylamide in an amount of 0.1mol% (compared to the total concentration of the polymer monomers).
Further, the photoinitiator was photoinitiator 2959, which was used in an amount of 0.05mol% (compared to the total concentration of polymer monomers).
The preparation method of the polymer solid electrolyte comprises the following steps:
and 4, adding a cross-linking agent and a photoinitiator into the uniform solution obtained in the step 4, uniformly mixing, spreading on a plane, and standing under ultraviolet illumination to obtain the polymer solid electrolyte.
The polymer solid electrolyte is applied to the preparation of lithium batteries.
The invention utilizes the solubility difference of different monomers in the electrolyte to form a macroscopically uniform polymer solid electrolyte membrane with a flexible phase and a rigid phase through random copolymerization. The electrolyte membrane has the advantages of good compatibility with lithium metal, wide electrochemical window, good self-repairing capability, difficult combustion and the like. In addition, the polymer solid electrolyte has high lithium ion conductivity, so that the polymer solid electrolyte can normally work at-10-60 ℃, and is expected to realize a polymer all-solid-state battery with wide temperature range and high stability.
The room temperature lithium ion conductivity of the polymer solid electrolyte membrane provided by the invention is 2.01mS cm -1 The lithium ion conductivity is up to 0.2mS cm at-10 DEG C -1 Has a wide electrochemical window (0-4.75V vs Li/Li) + ) At least 400% of tensile deformation can be realized, the contact interface of the electrolyte membrane and the metal lithium cathode has good stability, the growth of lithium dendrite is effectively inhibited, and the polymer all-solid-state battery with wide temperature range work, high rate performance and long cycle life is realized.
Drawings
FIG. 1 is a schematic view of a polymer solid electrolyte membrane having a phase separation structure prepared according to the present invention.
FIG. 2 (a) is an electrochemical window of the polymer solid electrolyte membrane prepared in example 1; FIG. 2 (b) is an electrochemical impedance profile within-10 to 70 ℃ and corresponding ionic conductivity data of the polymer solid electrolyte membrane prepared in example 1; FIG. 2 (c) is a graph showing the current density of 0.1mA cm of the polymer solid electrolyte membrane prepared in example 1 -2 Lower lithium symmetric battery cycle characteristics.
FIG. 3 is a graph showing a comparison of the cycle at room temperature (25 ℃ C.) at 0.2C of an all-solid battery assembled with two polymer solid electrolyte membranes prepared in example 2.
FIG. 4 (a) is a long cycle diagram of an all-solid battery assembled with the polymer solid electrolyte membrane prepared in example 3 at room temperature (25 ℃ C.) at 1C; FIG. 4 (b) is a long cycle diagram at room temperature (25 ℃) of an all-solid-state battery assembled with the polymer solid electrolyte membrane prepared in example 3 at 0.5 ℃; FIG. 4 (C) is a long cycle diagram at room temperature (25 ℃) at 0.2 ℃ for an all-solid battery assembled with the polymer solid electrolyte membrane prepared in example 3; fig. 4 (d) is a graph showing rate performance test at room temperature (25 ℃) of an all-solid battery assembled with the polymer solid electrolyte membrane prepared in example 3.
FIG. 5 (a) is a charge/discharge diagram at 0.1C rate of an all-solid-state battery at low temperature (-10 ℃,0 ℃, 25 ℃) assembled with the polymer solid electrolyte membrane prepared in example 4; fig. 5 (b) is a cycle diagram of a high-temperature (60 ℃) all-solid-state battery assembled with the polymer solid electrolyte membrane prepared in example 4 at 1C rate.
Detailed Description
The invention is described in further detail below with reference to the figures and the examples, but the invention should not be construed as being limited thereto. Modifications or substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and scope of the invention. The experimental methods and reagents of the formulations not specified in the examples are in accordance with the conventional conditions in the art.
Example 1
Step 1: respectively weighing solid N-methylacetamide and lithium bis (fluorosulfonyl) imide according to a molar ratio of 4;
step 2: weighing the deep eutectic electrolyte and the fluoropropylene carbonate according to the mass ratio of 95 to 5, and magnetically stirring for 6 hours to obtain a uniform electrolyte;
and 3, step 3: adding acrylamide (AAm) and N, N-dimethylacrylamide (DMAAm) into the electrolyte in the step 2 according to the concentration of 2.4mol/L and 0.6mol/L respectively, and magnetically stirring for 10min to obtain a macroscopically uniform solution;
and 4, step 4: and (3) adding a photoinitiator 2959 with the concentration of 0.05mol% and a cross-linking agent N, N' -Methylene Bisacrylamide (MBAA) with the concentration of 0.1mol% into the solution obtained in the step (3), stirring the mixture by magnetic force for 5min, uniformly mixing the mixture, spreading the mixture in a container, and standing the mixture for 5min under ultraviolet illumination to obtain the polymer solid electrolyte film.
Cutting a polymer solid electrolyte membrane with the diameter of 16mm to assemble a button cell of stainless steel and lithium at 1mV s -1 The electrolyte membrane electrochemical window was tested at sweep speed. As shown in FIG. 2 (a), the polymer solid electrolyte membrane is at 0-4.75V vs Li/Li + No obvious oxidation reduction peak exists in the voltage range, and the electrolyte membrane has a wider electrochemical window. FIG. 2 (b) is a graph showing electrochemical impedance spectroscopy test of a stainless steel symmetrical cell assembled using the polymer solid electrolyte membrane at a temperature ranging from-10 to 70 ℃ and an impedance of 3.5. Omega. Cm at room temperature 2 The room-temperature conductivity is calculated to be 2.01mS cm -1 The room temperature conductivity of the polymer solid electrolyte is far higher than that of the polymer electrolyte commonly used at present. FIG. 2 (c) is a button type lithium metal symmetrical battery assembled using the polymer solid electrolyte, which is subjected to a cycle performance test at room temperature after being left for 6 hours at 0.1mA cm -2 Current density of 0.1mAh cm -2 Has stable circulation for more than 1100h under the surface loading, and proves that the polymer solid electrolyte has good compatibility with lithium metal.
Example 2
Step 1: respectively weighing solid N-methylacetamide and lithium bis (fluorosulfonyl) imide according to a molar ratio of 4;
and 2, step: weighing the deep eutectic electrolyte and the propylene carbonate fluoride according to the mass ratio of 95;
and step 3: adding acrylamide and hydroxyethyl methacrylate into the electrolyte in the step 2 according to the concentration of 2.4mol/L and 0.6mol/L respectively, and magnetically stirring for 10min to obtain a macroscopically uniform solution;
and 4, step 4: adding 0.05mol% of photoinitiator 2959 and 0.1mol% of cross-linking agent MBAA into the solution obtained in the step 3, stirring uniformly for 5min by magnetic force to obtain a polymer precursor solution, dripping 50 mu L of the solution onto a commercial NCM pole piece with the diameter of 12mm, and standing for 5min under ultraviolet illumination to obtain the polymer-containing positive pole piece.
In order to further examine the influence of the easily soluble monomer on the electrolyte, N-dimethylacrylamide was selected as the easily soluble monomer for comparative experiments. The method comprises the following specific steps:
and 5: adding acrylamide and N, N-dimethylacrylamide into the electrolyte in the step 2 according to the concentration of 2.4mol/L and 0.6mol/L respectively, and magnetically stirring for 10min to obtain a macroscopically uniform solution;
and 6: adding 0.05mol% of photoinitiator 2959 and 0.1mol% of cross-linking agent MBAA into the solution obtained in the step 5, stirring uniformly for 5min by magnetic force to obtain a polymer precursor solution, dripping 50 mu L of the solution on a commercial NCM pole piece with the diameter of 12mm, and standing for 5min under ultraviolet illumination to obtain the polymer-containing positive pole piece.
The button type all-solid-state battery is assembled by directly using positive plates containing different monomers (hydroxyethyl methacrylate and N, N-dimethylacrylamide) and polymers and lithium metal, and after standing for 6 hours, the battery is subjected to cycle test at room temperature within the voltage range of 2.7-4.4V. Compared with the cycle chart of the battery assembled by using the pole piece obtained in the step 4 in the step 3 (a) under 0.2C, the cycle performance of the battery assembled by using the pole piece obtained in the step 6 in the step 3 (b) under 0.2C is greatly improved.
Example 3
Step 1: respectively weighing solid N-methylacetamide and lithium bis (fluorosulfonyl) imide according to a molar ratio of 4;
and 2, step: weighing the deep eutectic electrolyte and the propylene carbonate fluoride according to the mass ratio of 95;
and 3, step 3: adding acrylamide and N, N-dimethylacrylamide into the electrolyte in the step 2 according to the concentration of 2.4mol/L and 0.6mol/L respectively, and magnetically stirring for 10min to obtain a macroscopically uniform solution;
and 4, step 4: adding 0.05mol% of photoinitiator 2959 and 0.1mol% of cross-linking agent MBAA into the solution obtained in the step 3, magnetically stirring for 5min, uniformly mixing to obtain a polymer precursor solution, dropwise adding 50 mu L of the solution onto a lithium iron phosphate pole piece with the diameter of 12mm, and standing for 5min under ultraviolet illumination to obtain the polymer-containing positive pole piece.
And (3) directly assembling the lithium iron phosphate pole piece containing the polymer and lithium metal into a button type all-solid-state battery, standing for 6 hours, and testing the battery at room temperature. As shown in fig. 4, the cells all exhibited good cycling stability at 1,0.5,0.2c, fig. 4 (d) is a rate performance test of a polymer all solid-state battery, and all solid-state lithium batteries with lithium iron phosphate as the positive electrode had capacities of 174,170,159,153,140, and 102mAh g at 0.1,0.2,0.5,1,2,5c rates, respectively -1 And excellent rate performance is shown.
Example 4
Example 4 differed from example 3 only in the test temperature.
The rest is the same as embodiment 2 and will not be described again.
As shown in figure 5, the polymer all-solid-state battery prepared by the invention can adapt to different working temperatures, can maintain higher capacity even at the low temperature of minus 10 ℃, and has wide application prospect.
Claims (10)
1. A polymer solid electrolyte characterized by: the electrolyte is prepared by adding a negative electrode protection additive, a polymer monomer, a cross-linking agent and a photoinitiator into a deep eutectic electrolyte and then adopting ultraviolet polymerization;
the deep eutectic electrolyte is prepared from N-methylacetamide and lithium salt;
the polymer monomer is a monomer which is difficult to dissolve in the electrolyte and a monomer which is easy to dissolve in the electrolyte.
2. The polymer solid electrolyte according to claim 1, characterized in that: in the deep eutectic electrolyte, the lithium salt is at least one of lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethyl) sulfonyl imide or lithium nitrate, and the molar ratio of N-methylacetamide to the lithium salt is (4).
3. The polymer solid electrolyte according to claim 1, characterized in that: the negative electrode protection additive is at least one of fluoroethylene carbonate, lithium dioxalate borate or lithium difluorooxalate borate, and the addition amount of the negative electrode protection additive is 1-5wt% of the deep eutectic electrolyte.
4. The polymer electrolyte of claim 1, wherein: the monomer which is difficult to dissolve in the electrolyte is acrylamide, and the monomer which is easy to dissolve in the electrolyte is at least one of N, N-dimethylacrylamide, dihydroxyethyl acrylate or hydroxyethyl methacrylate.
5. The polymer solid electrolyte according to claim 1, characterized in that: the concentration of the polymer monomer in the deep eutectic electrolyte is 1.5-6mol/L, and the molar ratio of the monomer which is difficult to dissolve in the electrolyte to the monomer which is easy to dissolve in the electrolyte is 1-5: 1.
6. the polymer solid electrolyte according to claim 1, characterized in that: the cross-linking agent is N, N' -methylene-bisacrylamide, and the dosage of the cross-linking agent is 0.1mol percent of the concentration of the polymer monomer.
7. The polymer solid electrolyte according to claim 1, characterized in that: the photoinitiator was photoinitiator 2959, which was used in an amount of 0.05mol% of the polymer monomer concentration.
8. The method for producing a polymer solid electrolyte according to claim 1, wherein: the method comprises the following steps:
step 1, mixing N-methylacetamide and lithium salt to obtain a deep eutectic electrolyte;
step 2, adding a negative electrode protection additive into the deep eutectic electrolyte obtained in the step 1 to obtain a uniform electrolyte;
step 3, dispersing a polymer monomer in the electrolyte obtained in the step 2 to obtain a uniform solution;
and 4, adding a cross-linking agent and a photoinitiator into the uniform solution obtained in the step 4, uniformly mixing, spreading on a plane, and standing under ultraviolet illumination to obtain the polymer solid electrolyte.
9. Use of the polymer solid electrolyte of claim 1 for the preparation of a lithium battery.
10. Use according to claim 9, characterized in that: the lithium battery is an all-solid-state lithium battery.
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| CN116864797A (en) * | 2023-07-20 | 2023-10-10 | 安徽创速新能源科技有限公司 | Ultrathin solid polymer electrolyte membrane and preparation method and application thereof |
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| CN115775916B (en) | 2024-04-09 |
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