CN114597501A - Polymer electrolyte, preparation method thereof and application thereof in solid-state lithium battery with wide temperature range and high rate - Google Patents
Polymer electrolyte, preparation method thereof and application thereof in solid-state lithium battery with wide temperature range and high rate Download PDFInfo
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 57
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- -1 polypropylene carbonate Polymers 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002033 PVDF binder Substances 0.000 claims description 10
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 9
- 238000007710 freezing Methods 0.000 claims description 8
- 230000008014 freezing Effects 0.000 claims description 8
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 238000001035 drying Methods 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
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229920000193 polymethacrylate Polymers 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical group FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910015013 LiAsF Inorganic materials 0.000 claims description 2
- 229910013075 LiBF Inorganic materials 0.000 claims description 2
- 229910013553 LiNO Inorganic materials 0.000 claims description 2
- 229910013872 LiPF Inorganic materials 0.000 claims description 2
- 101150058243 Lipf gene Proteins 0.000 claims description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 2
- 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
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 7
- 239000006256 anode slurry Substances 0.000 description 6
- 238000004108 freeze drying Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 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
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000011076 safety test Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 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
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/0566—Liquid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a polymer electrolyte, a preparation method thereof and application thereof in a solid-state lithium battery with a wide temperature region and high multiplying power, belonging to the technical field of solid-state batteries. The polymer electrolyte consists of a polymer framework, lithium salt and a small amount of limited-domain solvent, and has the characteristics of high ionic conductivity, high thermal stability and stable electrolyte/electrode interface. The solid lithium metal battery assembled by the polymer electrolyte can keep high capacity under wide temperature range (-10-100 ℃) and high multiplying power (1-50 ℃ C.). The preparation method of the invention is compatible with the existing process, can effectively simplify the production matching process of the solid-state lithium metal battery, obviously improves the battery performance, and further realizes the recovery and reutilization of the solvent in the electrolyte preparation process, thereby having better application prospect.
Description
The technical field is as follows:
the invention relates to the technical field of solid-state batteries, in particular to a polymer electrolyte, a preparation method thereof and application thereof in a solid-state lithium metal battery with a wide temperature range and high multiplying power.
Background art:
at present, the commercialized lithium battery usually adopts volatile and flammable organic liquid electrolyte, which easily causes potential safety hazards such as battery fire and explosion, and the adoption of polymer electrolyte instead of liquid electrolyte is an effective method for improving the safety of the battery. At present, documents report various polymer electrolyte systems, such as polyethylene oxide, polycarbonate, polymethacrylate and the like, however, although the above electrolyte systems exhibit certain application potential, application scenarios are generally limited, such as a battery cannot work at low temperature or higher temperature, and an assembled battery usually only works at low rate, and cannot meet the application requirements of quick charge and quick discharge of the battery. Therefore, it is of great importance to develop a high-performance solid electrolyte and a solid battery which can be charged and discharged in a wide temperature range and at a high rate.
The invention content is as follows:
in order to solve the defects in the prior art, the invention aims to provide a polymer electrolyte, a preparation method thereof and application thereof in a solid-state lithium battery with a wide temperature range and high multiplying power. The polymer electrolyte has the characteristics of high ionic conductivity, high thermal stability and stable electrolyte/electrode interface, can be applied to solid lithium metal batteries, can exert high capacity in a low-temperature (-10 ℃) and high-temperature (100 ℃) interval, and can realize quick charge and quick discharge of the solid lithium metal batteries.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a polymer electrolyte, comprising the steps of:
(1) dissolving a polymer and a lithium salt in a solvent according to a proportion, and uniformly stirring to obtain a mixed solution;
(2) freezing the mixed solution obtained in the step (1) in a low-temperature environment, and removing the solid solvent through a vacuum freeze drying device after the solvent is completely solidified to obtain the polymer electrolyte; the solvent captured in the cold trap of the vacuum freeze drying device is heated and melted, and can be recycled.
In the step (1), the polymer is at least one of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polyethylene oxide (PEO), polypropylene oxide (PPO), Polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), Polymethacrylate (PMMA) and polypropylene carbonate (PPC).
In the step (1), the lithium salt is bis (trifluoromethylsulfonyl) imide Lithium (LiTFSI), bis (fluorosulfonyl) imide Lithium (LiFSI), or lithium perchlorate (LiClO)4) Lithium hexafluorophosphate (LiPF)6) Lithium chloride (LiCl), lithium nitrate (LiNO)3) Lithium tetrafluoroborate (LiBF)4) And lithium hexafluoroarsenate (LiAsF)6) At least one of (1).
In the step (1), the solvent is at least one of dimethyl sulfoxide, sulfolane, water, N-methylpyrrolidone, benzene, tert-butanol, cyclohexane, acetic acid and N, N-dimethylformamide.
In the step (1), the weight of the lithium salt is 10 wt.% to 60 wt.% of the total weight of the polymer and the lithium salt; the weight of the solvent is 5-100 times of the weight of the polymer.
In the step (2), the vacuum freeze-drying device comprises a drying chamber, a vacuum pump and a cold trap. Preferably, the vacuum freeze-drying device is a freeze-dryer.
In the step (1), the stirring time is 12-48 hours; in the step (2), the freezing temperature is-50-0 ℃, and the heat preservation time is 1-48 hours; the drying time in the vacuum freeze drying device is 12-60 hours.
The polymer electrolyte prepared by the invention is applied to a solid lithium metal battery under the condition of a wide temperature range, wherein the wide temperature range is-10-100 ℃, and the quick charge and quick discharge is charge and discharge under the multiplying power of 1-50 ℃.
The design principle of the invention is as follows:
in the process of preparing the polymer electrolyte by the freeze-drying method, free solvent molecules are sublimated and removed, residual trace solvent is confined in a polymer framework, and the electrochemical/chemical activity of the confined trace solvent is fully inhibited, so that a stable electrolyte/electrode interface is constructed, and the polymer electrolyte can be used for a high-voltage solid-state lithium metal battery. In addition, the polymer, the lithium salt and the trace solvent form a rapid lithium ion transmission channel in the polymer electrolyte, so that the solid-state battery assembled by the polymer electrolyte has high capacity performance in a wide temperature range from low temperature to high temperature. The ternary structure of the lithium salt anions, the solvent and the polymer skeleton can effectively inhibit the migration of the lithium salt anions, thereby obviously improving the migration number of the lithium ions and further realizing the high-rate performance of fast charge and fast discharge of the solid-state lithium metal battery. In addition, the process of preparing the polymer electrolyte by adopting a freeze drying method (liquid-solid-gas-solid-liquid conversion of the solvent) can realize the high-efficiency recovery and reutilization of the solvent.
The invention has the following advantages and beneficial effects:
1. the method has the characteristics of low cost and environmental protection.
2. The polymer electrolyte provided by the invention has the characteristics of high thermal stability, high ionic conductivity and wide electrochemical stability window.
3. The polymer electrolyte prepared by the method provided by the invention is used for a solid lithium metal battery and shows higher capacity in a wide temperature range (-10-100 ℃).
4. The polymer electrolyte prepared by the method provided by the invention is used for the solid lithium metal battery, and the quick charge and quick discharge of the battery can be realized.
5. The preparation process of the polymer electrolyte provided by the invention can realize the recycling of the organic solvent in the preparation process, and solves the problems of high cost, difficult recycling and great pollution caused by using a volatile organic solvent in the production process of the conventional polymer electrolyte.
Description of the drawings:
FIG. 1 is a schematic diagram of a polymer electrolyte preparation process and solvent recovery.
Fig. 2 is an electrochemical impedance of the polymer thin film prepared according to example 1.
Fig. 3 is a charge and discharge curve at 100 c of the solid-state battery prepared according to example 5.
Fig. 4 is a charge and discharge curve at-10 c for a solid-state battery prepared according to example 5.
Fig. 5 is a charge and discharge curve at 25 ℃ of the solid-state battery prepared according to example 7.
Fig. 6 is a safety test of the pouch battery prepared according to example 6.
The specific implementation mode is as follows:
the respective steps for preparing the polymer electrolyte and the solid-state lithium metal battery of the present invention are exemplarily described below.
Example 1:
this example is the preparation of a polymer electrolyte, the procedure is as follows:
PVDF-HFP with a molecular weight of 40 ten thousand and LiTFSI are dissolved in a dimethyl sulfoxide solvent, and are stirred for 24 hours to obtain a uniform solution. Wherein the mass fraction of PVDF-HFP in the solution is 7.9 wt.%, and the weight of LiTFSI is 40 wt.% of the total mass of LiTFSI and PVDF-HFP. And then, transferring the uniform solution onto a polytetrafluoroethylene substrate, freezing the substrate for 24 hours at the temperature of-18 ℃, and taking out the substrate after freeze-drying the substrate for 48 hours in a freeze-dryer to obtain the polymer electrolyte.
FIG. 1 is a schematic diagram of the polymer electrolyte preparation and solvent recovery process.
Example 2:
this example is the preparation of a polymer electrolyte, the procedure is as follows:
PVDF and LiTFSI with molecular weight of 50 ten thousand are dissolved in N-methyl pyrrolidone solvent and stirred for 24 hours to obtain a uniform solution. Wherein, the mass fraction of PVDF in the solution is 7.9 wt.%, and the weight of LiTFSI is 40 wt.% of the total mass of LiTFSI and PVDF. And then, transferring the uniform solution onto a polytetrafluoroethylene substrate, freezing the substrate for 24 hours at the temperature of-30 ℃, and taking out the substrate after freeze drying for 48 hours in a freeze dryer to obtain the polymer electrolyte.
Example 3:
this example is the preparation of a polymer electrolyte, the procedure is as follows:
PAN and LiFSI with the molecular weight of 15 ten thousand are dissolved in a dimethyl sulfoxide solvent, and stirred for 24 hours to obtain a uniform solution. Wherein, the mass fraction of PAN in the solution is 5 wt.%, and the weight of LiFSI is 30 wt.% of the total mass of LiFSI and PAN. And then, transferring the uniform solution onto a polytetrafluoroethylene substrate, freezing the substrate for 24 hours at the temperature of-18 ℃, and taking out the substrate after freeze-drying the substrate for 48 hours in a freeze-dryer to obtain the polymer electrolyte.
Example 4:
this example is the preparation of a polymer electrolyte, the procedure is as follows:
PVDF-HFP, LiTFSI and LiFSI with the molecular weight of 50 ten thousand are dissolved in a dimethyl sulfoxide solvent, and are stirred for 24 hours to obtain a uniform solution. Wherein, PVDF-HFP accounts for 8 wt.% of the solution, and LiTFSI and LiFSI respectively account for 20 wt.% of the total mass of lithium salt and PVDF-HFP. And then, transferring the uniform solution onto a polytetrafluoroethylene substrate, freezing the substrate for 24 hours at the temperature of 18 ℃ below zero, and taking the substrate out after the substrate is frozen and dried in a freeze dryer for 48 hours to obtain the polymer electrolyte.
Example 5:
the present embodiment is a method for preparing a high performance lithium metal battery operating at a wide temperature range (-10 to 100 ℃), and the method comprises the following steps:
lithium iron phosphate, polyvinylidene fluoride and conductive carbon black are mixed according to the mass ratio of 8: 1: 1, uniformly mixing the materials in N-methyl pyrrolidone to obtain anode slurry, and coating the anode slurry on one side of the carbon-coated aluminum foil. Vacuum drying at 60 deg.C, and removing N-methyl pyrrolidone to obtain positive electrode.
And cutting the obtained composite anode into an anode electrode plate, wherein a lithium plate is adopted as a cathode. The polymer electrolyte of example 1 was sandwiched between a positive electrode tab and a negative electrode tab and packed into a 2025 battery case, which was packed into a coin cell for testing.
Example 6
The present embodiment is a method for preparing a high performance lithium metal battery operating at a wide temperature range (-10 to 100 ℃), and the method comprises the following steps:
lithium iron phosphate, polyvinylidene fluoride and conductive carbon black are mixed according to the mass ratio of 8: 1: 1, uniformly mixing the materials in N-methyl pyrrolidone to obtain anode slurry, and coating the anode slurry on one side of the carbon-coated aluminum foil. Vacuum drying at 60 deg.C, and removing N-methyl pyrrolidone to obtain positive electrode.
And cutting the obtained positive electrode into a positive electrode plate, wherein the negative electrode adopts lithium foil. The polymer electrolyte in example 1 was sandwiched between a positive electrode sheet and a negative electrode sheet to perform aluminum-plastic packaging, and a pouch cell was obtained and tested.
Example 7
The present embodiment is a method for preparing a high performance lithium metal battery operating at a wide temperature range (-10 to 100 ℃), and the method comprises the following steps:
NCM811, polyvinylidene fluoride and conductive carbon black in a mass ratio of 8: 1: 1, uniformly mixing the materials in N-methyl pyrrolidone to obtain anode slurry, and coating the anode slurry on one side of the carbon-coated aluminum foil. Vacuum drying at 60 deg.C, and removing N-methyl pyrrolidone to obtain positive electrode.
And cutting the obtained composite anode into an anode electrode plate, wherein a lithium plate is adopted as a cathode. The polymer electrolyte of example 1 was sandwiched between a positive electrode tab and a negative electrode tab and packed into a 2025 battery case, which was packed into a coin cell for testing.
The following are performance tests on the samples prepared for each example:
1. and (3) ion conductivity test:
the polymer electrolyte prepared in example 1 was punched by a sheet punch to obtain a polymer electrolyte wafer, and the thickness of the sample was about 80 μm and the diameter of the film was 19 mm. The ionic conductivity of the sample of example 1 was tested by the following specific test methods: and adding stainless steel sheets at two ends of the sample to form a battery test, wherein the diameter of the stainless steel sheet is 12 mm, the test frequency range is 0.1Hz-1MHz (electrochemical workstation), and an impedance diagram of the stainless steel sheet at the temperature of-10-80 ℃ is shown in figure 2. And finally, calculating the ionic conductivity of the sample according to parameters such as electrochemical impedance, the thickness of the sample, the area of the electrode and the like. The sample of example 1 had an ionic conductivity of 2.43mS/cm, measured at 80 ℃; an ionic conductivity of 0.353mS/cm measured at 25 ℃; the ionic conductivity measured at-10 ℃ was 0.0317 mS/cm. Therefore, the polymer electrolyte has high ionic conductivity in a wide temperature range (-10-80 ℃).
2. And (3) charge and discharge test:
the lithium metal battery prepared in example 5 was tested at 100 ℃. The charge cut-off voltage was 3.9V, and the discharge cut-off voltage was 2.5V. The charging and discharging current is set to be 1-50C. As shown in fig. 3, a charge and discharge graph at 100 c for the lithium metal battery prepared according to example 5. As can be seen from the figure, the discharge specific capacity of the lithium metal battery containing the polymer electrolyte is respectively as high as 141.6mAh/g and 102.2mAh/g under 30C and 50C. Thus, such solid-state lithium metal batteries have a fast charge and fast discharge capability.
The lithium metal battery prepared in example 5 was tested at-10 ℃. The charge cut-off voltage was 4.2V, and the discharge cut-off voltage was 2.5V. The charge and discharge currents were set at 0.05C and 0.1C. As shown in fig. 4, a charge and discharge graph at-10 c for the lithium metal battery prepared according to example 5. As can be seen from the figure, the lithium metal battery containing the polymer electrolyte has discharge specific capacities of 135mAh/g and 109.2mAh/g at 0.05C and 0.1C, respectively. Therefore, the solid-state lithium metal battery has high charge and discharge capacity at low temperature.
The lithium metal battery prepared in example 7 was tested at 25 ℃. The charge cut-off voltage was 4.3V, and the discharge cut-off voltage was 3.0V. The charge and discharge current was set to 0.2C. As shown in fig. 5, a charge and discharge graph of the lithium metal battery prepared according to example 4 at room temperature. As can be seen from the figure, the lithium metal battery containing the polymer electrolyte has the discharge specific capacity of 167.7 mAh/g. Thus, the polymer electrolyte is suitable for a high-voltage solid-state lithium metal battery.
3. And (3) testing the safety of the soft package battery:
the safety test of the soft package battery prepared in example 6 is carried out, and the specific test method is as follows: use scissors destructively to cut this laminate polymer battery, light the LED lamp plate again. As shown in fig. 6, the soft package battery can still supply power to the LED lamp panel normally under the condition of several times of cutting. Therefore, the soft package battery containing the polymer electrolyte has high safety.
The foregoing is only a preferred embodiment of the present invention and it should be noted that the above examples are illustrative in nature and are not to be construed as limiting the present invention and that several modifications and variations may be made without departing from the principles of the present invention and these modifications and variations are also to be considered as within the scope of the present invention.
Claims (10)
1. A method for preparing a polymer electrolyte, characterized by: the method comprises the following steps:
(1) dissolving a polymer and a lithium salt in a solvent according to a proportion, and uniformly stirring to obtain a mixed solution;
(2) and (2) freezing the mixed solution obtained in the step (1) in a low-temperature environment, and removing the solid solvent through a vacuum freeze drying device after the solvent in the mixed solution is completely solidified, so as to obtain the polymer electrolyte.
2. The method for producing a polymer electrolyte according to claim 1, characterized in that: in the step (2), the solid solvent captured in the cold trap of the vacuum freeze-drying device can be heated and melted for recycling.
3. The method for producing a polymer electrolyte according to claim 1, characterized in that: in the step (1), the polymer is at least one of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polyethylene oxide (PEO), polypropylene oxide (PPO), Polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), Polymethacrylate (PMMA) and polypropylene carbonate (PPC).
4. The method for producing a polymer electrolyte according to claim 1, characterized in that: in the step (1), the lithium salt is bis (trifluoromethylsulfonyl) imide Lithium (LiTFSI), bis (fluorosulfonyl) imide Lithium (LiFSI), or lithium perchlorate (LiClO)4) Lithium hexafluorophosphate (LiPF)6) Lithium chloride (LiCl), lithium nitrate (LiNO)3) Lithium tetrafluoroborate (LiBF)4) And lithium hexafluoroarsenate (LiAsF)6) At least one of (1).
5. The method for producing a polymer electrolyte according to claim 1, characterized in that: in the step (1), the solvent is at least one of dimethyl sulfoxide, sulfolane, water, N-methylpyrrolidone, benzene, tert-butyl alcohol, cyclohexane, acetic acid and N, N-dimethylformamide.
6. The method for producing a polymer electrolyte according to claim 1, characterized in that: in the step (1), the weight of the lithium salt is 10 wt.% to 60 wt.% of the total weight of the polymer and the lithium salt; the weight of the solvent is 5-100 times of the weight of the polymer.
7. The method for producing a polymer electrolyte according to claim 1, characterized in that: in the step (2), the vacuum freeze drying device comprises a drying chamber, a vacuum pump and a cold trap.
8. The method for producing a polymer electrolyte according to claim 1, characterized in that: in the step (1), the stirring time is 12-48 hours; in the step (2), the freezing temperature is-50-0 ℃, and the heat preservation time is 1-48 hours; the drying time in a vacuum freeze drying device is 12-60 hours.
9. A polymer electrolyte prepared by the method of any one of claims 1 to 8.
10. Use of a polymer electrolyte according to claim 9 in a solid state lithium metal battery, characterized in that: the polymer electrolyte is applied to a solid lithium metal battery under the conditions of a wide temperature range and a quick charge and quick discharge working condition, wherein the wide temperature range is-10-100 ℃, and the quick charge and quick discharge working condition is charge and discharge under the multiplying power of 1-50 ℃.
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| JPH1180296A (en) * | 1997-09-11 | 1999-03-26 | Matsushita Electric Ind Co Ltd | Gel form polymer electrolyte |
| JP2012025863A (en) * | 2010-07-23 | 2012-02-09 | Mitsui Chemicals Inc | Polyelectrolyte particle, method of producing the polyelectrolyte particle, and solid polyelectrolyte |
| CN104952634A (en) * | 2015-06-05 | 2015-09-30 | 北京大学 | Ionic liquid-lithium salt gel polymer electrolyte and preparation and application thereof |
| CN110690497A (en) * | 2019-11-01 | 2020-01-14 | 中国科学院金属研究所 | Polymer electrolyte film, preparation method thereof and application thereof in all-solid-state lithium battery |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1180296A (en) * | 1997-09-11 | 1999-03-26 | Matsushita Electric Ind Co Ltd | Gel form polymer electrolyte |
| JP2012025863A (en) * | 2010-07-23 | 2012-02-09 | Mitsui Chemicals Inc | Polyelectrolyte particle, method of producing the polyelectrolyte particle, and solid polyelectrolyte |
| CN104952634A (en) * | 2015-06-05 | 2015-09-30 | 北京大学 | Ionic liquid-lithium salt gel polymer electrolyte and preparation and application thereof |
| CN110690497A (en) * | 2019-11-01 | 2020-01-14 | 中国科学院金属研究所 | Polymer electrolyte film, preparation method thereof and application thereof in all-solid-state lithium battery |
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