CN110808410A - Solid electrolyte of lithium metal battery, preparation method and application thereof, and lithium metal battery - Google Patents
Solid electrolyte of lithium metal battery, preparation method and application thereof, and lithium metal battery Download PDFInfo
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- CN110808410A CN110808410A CN201910958441.5A CN201910958441A CN110808410A CN 110808410 A CN110808410 A CN 110808410A CN 201910958441 A CN201910958441 A CN 201910958441A CN 110808410 A CN110808410 A CN 110808410A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 104
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910001868 water Inorganic materials 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims description 38
- 239000004814 polyurethane Substances 0.000 claims description 35
- 229920002635 polyurethane Polymers 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 229910052681 coesite Inorganic materials 0.000 claims description 23
- 229910052906 cristobalite Inorganic materials 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 23
- 229910052682 stishovite Inorganic materials 0.000 claims description 23
- 229910052905 tridymite Inorganic materials 0.000 claims description 23
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 15
- 239000002033 PVDF binder Substances 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- 229920000557 Nafion® Polymers 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000004880 explosion Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 19
- 229910001416 lithium ion Inorganic materials 0.000 description 19
- 239000011244 liquid electrolyte Substances 0.000 description 13
- 239000002105 nanoparticle Substances 0.000 description 13
- 229910013872 LiPF Inorganic materials 0.000 description 12
- 101150058243 Lipf gene Proteins 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 238000005303 weighing Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- -1 polytetrafluoroethylene Polymers 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000126 substance 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
- H01M10/056—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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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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 belongs to the technical field of lithium metal batteries, and particularly relates to a solid electrolyte of a lithium metal battery, a preparation method and application thereof, and the lithium metal battery. The solid electrolyte includes: a lithium-philic agent; a hydrophobic film-forming agent; and a solvent. The preparation method comprises the following steps: 1) preparing a composite solution of a lithium-philic agent, a film-forming agent for forming a hydrophobic film and a solvent; 2) removing water from the composite liquid prepared in the step 1); 3) and (3) forming a film by using the dehydrated composite liquid obtained in the step 2), thus obtaining the solid electrolyte of the lithium metal battery. The technical scheme provided by the invention can reduce the consumption rate of lithium of the lithium metal battery, prevent liquid leakage and avoid the problem of fire or even explosion under the condition of high temperature or short circuit.
Description
Technical Field
The invention belongs to the technical field of lithium metal batteries, and particularly relates to a solid electrolyte of a lithium metal battery, a preparation method and application thereof, and the lithium metal battery.
Background
The lithium-air battery takes the metal lithium as the negative electrode and the oxygen in the air as the positive active material, the positive active material oxygen can be continuously obtained from the air and does not need to be stored in the battery structure, and the metal lithium has the height of 3861mAh g-1Specific capacity, relative standard ofHydrogen electrode potential-3.04V, 0.534gcm-3So that the theoretical specific energy of the lithium-oxygen battery can be up to 11140 Whkg-1(not noting the quality of oxygen), 6-9 times of lithium ion batteries, and is a novel green secondary battery between fuel cells and lithium ion batteries.
Currently, liquid electrolytes are researched and used for organic substances as solvents and lithium salts as solutes, and the liquid electrolytes have the following problems: 1) the overpotential rises along with the progress of charge/discharge, and at a high potential, the generated discharge intermediate promotes the reaction of by-products generated by the decomposition of the electrolyte and the metallic lithium so as to accelerate the consumption rate of the lithium; 2) the problem of liquid leakage; 3) the fire and even explosion are easy to happen under the condition of high temperature or short circuit.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a solid electrolyte of a lithium metal battery, a preparation method and application thereof and the lithium metal battery. The technical scheme provided by the invention can reduce the consumption rate of lithium of the lithium metal battery, prevent liquid leakage and avoid the problem of fire or even explosion under the condition of high temperature or short circuit.
The technical scheme provided by the invention is as follows:
a solid-state electrolyte for a lithium metal battery comprising:
a lithium-philic agent;
a hydrophobic film-forming agent;
and a solvent that is dispersible or soluble in the lithium-philic agent and is dispersible or soluble in the film-forming agent.
The solid electrolyte of the lithium metal battery provided by the technical scheme has good lithium ion conduction capability due to the addition of the lithium-philic agent.
The solid electrolyte of the lithium metal battery provided by the technical scheme has hydrophobicity, so that the lithium electrode can be prevented from being corroded by water.
The solid electrolyte of the lithium metal battery provided by the technical scheme is in a solid form, so that the leakage problem of the liquid electrolyte can be solved, and the stability of the electrolyte at high temperature and high potential can be improved, so that the problem of consumption of a metal lithium cathode caused by decomposition of the electrolyte is solved.
The solid electrolyte of the lithium metal battery provided by the technical scheme is in a solid state form, so that the corrosion of water to the lithium electrode can be avoided, the problem of metal lithium negative electrode consumption caused by electrolyte decomposition can be relieved, and the cycling stability of the lithium-air battery can be greatly improved.
Specifically, the lithium-philic agent is selected from SiO2、Co3O4Or ZnO.
Preferably, the lithium-philic agent is SiO2The lithium ion conductive electrolyte has good lithium affinity, and can be used for ensuring the effective transmission of lithium ions in the electrolyte. And Co3O4Or ZnO, SiO2The lithium ion transport vehicle has the advantages of good affinity with lithium, capability of promoting the transport of lithium ions, simple preparation, low raw material cost, rich sources and the like.
Specifically, SiO2As nanoparticles (D ═ 15 ± 5 nm).
Specifically, the film forming agent is selected from any one of Polyurethane (PU), Nafion or polyvinylidene fluoride (PVDF).
Preferably, the film-forming agent is polyurethane.
Specifically, the polyurethane is a thermoplastic polyurethane. Compared with Nafion or polyvinylidene fluoride, the polyurethane has the advantages of higher strength, larger elongation, better rebound resilience and the like, can inhibit the growth of lithium dendrites and relieve the problem of volume expansion caused by the deposition/dissolution process on the contact surface of a lithium metal electrode, and plays a certain role in protection.
Specifically, the solvent is selected from any one of N-methylpyrrolidone (NMP), N-N-Dimethylformamide (DMF) or Tetrahydrofuran (THF).
Preferably, the solvent is N-methylpyrrolidone. Compared with N-N-dimethylformamide or tetrahydrofuran, the N-dimethylformamide or tetrahydrofuran polar solvent has the advantages of strong selectivity and stability, low toxicity, high boiling point, strong dissolving power and the like, and the polyurethane has good solubility in N-methylpyrrolidone.
In the technical scheme, N-methylpyrrolidone is used for polyurethane and SiO2Has good dispersibility and is easy to realize the film forming process.
Specifically, the weight ratio of the lithium-philic agent to the film forming agent is 1: 1-5.
Based on the proportion, oxygen, water, carbon dioxide and the like can be prevented from permeating the solid electrolyte to corrode the lithium metal negative electrode, and good transmission of lithium ions in the solid electrolyte can be ensured.
Specifically, the solid electrolyte of the lithium metal battery is also immersed in a lithium battery electrolyte, and the weight percentage of the lithium battery electrolyte to the solid electrolyte of the lithium metal battery is 5-100 wt%.
Based on the technical scheme, the film formed by the film forming agent forms a main carrier of the hydrophobic solid electrolyte and is loaded with the lithium-philic agent, so that oxygen, water, carbon dioxide and a discharge intermediate can be prevented from permeating the solid electrolyte to corrode a metal lithium cathode, the lithium ions can be ensured to be well transmitted in the solid electrolyte, the lithium ions can be ensured to be well contacted with the cathode lithium by soaking part of the liquid electrolyte, the interface impedance is reduced, and the comprehensive effect of the lithium-air battery can obviously improve the cycle performance of the lithium-air battery.
Specifically, the electrolyte of the lithium battery can be 1mol/L LiPF6An EC-DMC electrolyte.
The invention also provides a preparation method of the solid electrolyte of the lithium metal battery, which is characterized by comprising the following steps:
1) preparing a composite liquid of a lithium-philic agent, a hydrophobic membrane-forming agent and a solvent, wherein the lithium-philic agent is dispersed or dissolved in the solvent, and the membrane-forming agent is dispersed or dissolved in the solvent;
2) removing water from the composite liquid prepared in the step 1);
3) and (3) forming a film by using the dehydrated composite liquid obtained in the step 2), thus obtaining the solid electrolyte of the lithium metal battery.
The solid electrolyte of the lithium metal battery prepared by the technical scheme has good lithium ion conduction capability due to the addition of the lithium-philic agent.
The solid electrolyte of the lithium metal battery prepared by the technical scheme has hydrophobicity, so that the corrosion of water to a lithium electrode can be avoided.
The solid electrolyte of the lithium metal battery prepared by the technical scheme is in a solid form, so that the leakage problem of the liquid electrolyte can be solved, and the stability of the electrolyte at high temperature and high potential can be improved, so that the consumption of a lithium metal cathode caused by the decomposition of the electrolyte is relieved.
The solid electrolyte of the lithium metal battery prepared by the technical scheme is in a solid state form, so that the corrosion of water to the lithium electrode can be avoided, the consumption of a metal lithium cathode caused by the decomposition of the electrolyte can be relieved, and the circulation stability of the lithium-air battery can be greatly improved.
Specifically, the lithium-philic agent is selected from SiO2、Co3O4Or ZnO.
Preferably, the lithium-philic agent is SiO2The lithium ion conductive electrolyte has good lithium affinity, and can be used for ensuring the effective transmission of lithium ions in the electrolyte. And Co3O4Or ZnO, SiO2The lithium ion transport vehicle has the advantages of good affinity with lithium, capability of promoting the transport of lithium ions, simple preparation, low raw material cost, rich sources and the like.
Specifically, SiO2As nanoparticles (D ═ 15 ± 5 nm).
SiO2The nano particles are connected through high molecular PU, SiO2Has better lithium affinity, and can be used for ensuring the effective transmission of lithium ions in the electrolyte.
Specifically, the film forming agent is selected from any one of Polyurethane (PU), Nafion or polyvinylidene fluoride (PVdF).
Preferably, the film-forming agent is polyurethane.
Specifically, the polyurethane is a thermoplastic polyurethane. Compared with Nafion or polyvinylidene fluoride, the polyurethane has the advantages of higher strength, larger elongation, better rebound resilience and the like, can inhibit the growth of lithium dendrites and relieve the problem of volume expansion caused by the deposition/dissolution process on the contact surface of a lithium metal electrode, and achieves a certain protection effect.
Specifically, the solvent is selected from any one of N-methylpyrrolidone (NMP), N-N-Dimethylformamide (DMF) or Tetrahydrofuran (THF).
Preferably, the solvent is N-methylpyrrolidone. Compared with N-N-dimethylformamide or tetrahydrofuran, the N-dimethylformamide or tetrahydrofuran polar solvent has the advantages of strong selectivity and stability, low toxicity, high boiling point, strong dissolving power and the like, and the polyurethane has good solubility in N-methylpyrrolidone.
The solid content of the composite liquid is 15-25%.
In the technical scheme, N-methylpyrrolidone is used for polyurethane and SiO2Has good dispersibility and is easy to realize the film forming process.
Specifically, the weight ratio of the lithium-philic agent to the film forming agent is 1: 1-5.
Based on the proportion, oxygen, water, carbon dioxide and the like can be prevented from permeating the solid electrolyte to corrode the lithium metal negative electrode, and good transmission of lithium ions in the solid electrolyte can be ensured.
Specifically, the preparation method further comprises a step 4): and immersing the solid electrolyte of the lithium metal battery into the electrolyte of the lithium battery, wherein the weight percentage of the electrolyte of the lithium battery to the solid electrolyte of the lithium metal battery is 5-100 wt%.
Based on the technical scheme, the film formed by the film forming agent forms a main carrier of the hydrophobic solid electrolyte and is loaded with the lithium-philic agent, so that oxygen, water, carbon dioxide and a discharge intermediate can be prevented from permeating the solid electrolyte to corrode a metal lithium cathode, the lithium ions can be ensured to be well transmitted in the solid electrolyte, the lithium ions can be ensured to be well contacted with the cathode lithium by soaking part of the liquid electrolyte, the interface impedance is reduced, and the comprehensive effect of the lithium-air battery can obviously improve the cycle performance of the lithium-air battery. Specifically, the electrolyte of the lithium battery can be 1mol/L LiPF6An EC-DMC electrolyte.
Specifically, the preparation method of the solid electrolyte of the lithium metal battery comprises the following steps:
the invention also provides the application of the solid electrolyte of the lithium metal battery, and the solid electrolyte is used as the solid electrolyte of the lithium metal battery.
The solid electrolyte of the lithium metal battery provided by the invention can remarkably relieve the problem of consumption of a metal lithium negative electrode caused by electrolyte decomposition.
The invention also provides a lithium metal battery, which comprises a solid electrolyte, wherein the solid electrolyte is selected from the solid electrolyte of the lithium metal battery provided by the invention.
Specifically, the lithium metal battery is a lithium-air battery.
The solid electrolyte of the lithium metal battery provided by the invention can effectively solve the problems of liquid leakage, consumption of a metal lithium negative electrode and the like when being used in a lithium-air battery.
Drawings
Fig. 1 is a charge-discharge cycle diagram of a lithium-air battery according to example 1 of the present invention.
Fig. 2 is a charge-discharge cycle diagram of a lithium-air battery of example 2 of the invention.
Fig. 3 is a charge-discharge cycle diagram of a lithium-air battery of example 3 of the invention.
Fig. 4 is a charge-discharge cycle diagram of a lithium-air battery of example 4 of the invention.
Fig. 5 is a charge-discharge cycle diagram of a lithium-air battery of example 5 of the invention.
FIG. 6 shows a solid electrolyte (a) and LiPF in a comparative example6Lithium-air battery with a/EC-DMC liquid electrolyte (b) lithium negative electrode cross-sectional view cycled 30 times.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
1) Weighing a certain amount of PU particles, slowly adding the PU particles (preventing the PU particles from being agglomerated into one block and increasing the dissolving difficulty) into the NMP solution in a magnetic stirring state, and continuously stirring for 2 hours to obtain 0.1g/mL of PU-NMP solution;
2) weighing a certain amount of SiO2The nanoparticles are slow (SiO prevention)2Nanoparticle agglomeration) is added into the PU-NMP solution, and the mixture is continuously stirred for 3 hours to obtain PU and SiO2SiO with mass ratio of 1:12-PU-NMP solution with a solid content of 20%;
3) adding a molecular sieve, and baking in an oven at 80 ℃ to remove water;
4) removing water from the SiO2Putting the PU-NMP solution into a glove box, pouring the glove box into a polytetrafluoroethylene film forming die, putting the polytetrafluoroethylene film forming die into a vacuum drying box at 45 ℃ for baking, and obtaining a PU solid electrolyte after film forming;
5) the PU solid electrolyte was put into a previously prepared LiPF containing 1mol/L before assembling the lithium-air battery6Soaking in organic solvent of EC-DMC with the immersion amount of 80 wt%.
6) The performance of the assembled lithium-air battery is tested, and the solid electrolyte and the liquid electrolyte of the common lithium battery are respectively used as the electrolytes of the lithium-air battery under the same condition and are respectively added into 1Ag-1Constant capacity at current density (1000 mAhg)-1) And performing charge and discharge cycles. The test results are shown in fig. 1, and the cycle number of the battery after using the solid electrolyte is increased from 43 times to 112 times, which is greatly improved. The common battery is LiPF with 1mol/L6CR2032 type coin cell with EC-DMC as electrolyte.
The specific test conditions were: the cycle life of the battery was evaluated by conducting a constant current charge/discharge cycle for a long time in a test container (99.9%, vacuum degree 0.1atm) of pure oxygen atmosphere using a CT2001A-5V 2mA type battery test system manufactured by blue-electron Ltd, Wuhan City, in which cutoff potentials were set to 2.0V and 4.5V, and a current density was set to 1Ag-1Setting the specific charge/discharge capacity to 1000mAhg based on the load mass of the positive electrode active material-1。
Example 2
1) Weighing a certain amount of PU particles, slowly adding the PU particles (preventing the PU particles from being agglomerated into one block and increasing the dissolving difficulty) into the NMP solution in a magnetic stirring state, and continuously stirring for 2 hours to obtain 0.1g/mL of PU-NMP solution;
2) weighing a certain amount of SiO2The nanoparticles are slow (SiO prevention)2Nanoparticle agglomeration) is added into the PU-NMP solution, and the mixture is continuously stirred for 3 hours to obtain PU and SiO2SiO with mass ratio of 1:32-PU-NMP solution with a solid content of 20%;
3) adding a molecular sieve, and baking in an oven at 80 ℃ to remove water;
4) removing water from the SiO2Putting the PU-NMP solution into a glove box, pouring the glove box into a polytetrafluoroethylene film forming die, putting the polytetrafluoroethylene film forming die into a vacuum drying box at 45 ℃ for baking, and obtaining a PU solid electrolyte after film forming;
5) the PU solid electrolyte was put into a previously prepared LiPF containing 1mol/L before assembling the lithium-air battery6Soaking in organic solvent of EC-DMC with the immersion amount of 80 wt%.
6) The performance of the assembled lithium-air battery is tested, and the solid electrolyte and the liquid electrolyte of the common lithium battery are respectively used as the electrolytes of the lithium-air battery under the same condition and are respectively added into 1Ag-1Constant capacity at current density (1000 mAhg)-1) And performing charge and discharge cycles. The test results are shown in fig. 2, and the cycle number of the battery after using the solid electrolyte is increased from 43 times to 118 times, which is greatly improved. The common battery is LiPF with 1mol/L6CR2032 type coin cell with EC-DMC as electrolyte.
The specific test conditions were: the cycle life of the battery was evaluated by conducting a constant current charge/discharge cycle for a long time in a test container (99.9%, vacuum degree 0.1atm) of pure oxygen atmosphere using a CT2001A-5V 2mA type battery test system manufactured by blue-electron Ltd, Wuhan City, in which cutoff potentials were set to 2.0V and 4.5V, and a current density was set to 1Ag-1Setting the specific charge/discharge capacity to 1000mAhg based on the load mass of the positive electrode active material-1。
Example 3
1) Weighing a certain amount of PU particles, slowly adding the PU particles (preventing the PU particles from being agglomerated into one block and increasing the dissolving difficulty) into the NMP solution in a magnetic stirring state, and continuously stirring for 2 hours to obtain 0.1g/mL of PU-NMP solution;
2) weighing a certain amount of SiO2The nanoparticles are slow (SiO prevention)2Nanoparticle agglomeration) is added into the PU-NMP solution, and the mixture is continuously stirred for 3 hours to obtain PU and SiO2SiO with mass ratio of 1:52-PU-NMP solution with a solid content of 20%;
3) adding a molecular sieve, and baking in an oven at 80 ℃ to remove water;
4) removing water from the SiO2Putting the PU-NMP solution into a glove box, pouring the glove box into a polytetrafluoroethylene film forming die, putting the polytetrafluoroethylene film forming die into a vacuum drying box at 45 ℃ for baking, and obtaining a PU solid electrolyte after film forming;
5) the PU solid electrolyte was put into a previously prepared LiPF containing 1mol/L before assembling the lithium-air battery6Soaking in organic solvent of EC-DMC with the immersion amount of 80 wt%.
6) Assembling lithium-air battery to test battery performance, the solid electrolyte and the liquid electrolyte of a common lithium battery were used as the electrolyte of the lithium-air battery under the same conditions, respectively, at 1A g-1Constant capacity at current density (1000mAh g)-1) And performing charge and discharge cycles. The test results are shown in fig. 3, and the cycle number of the battery after using the solid electrolyte is increased from 43 times to 102 times, which is greatly improved. The common battery is LiPF with 1mol/L6CR2032 type coin cell with EC-DMC as electrolyte.
The specific test conditions were: the cycle life of the battery was evaluated by conducting a constant current charge/discharge cycle for a long time in a test container (99.9%, vacuum degree 0.1atm) of pure oxygen atmosphere using a CT2001A-5V 2mA type battery test system manufactured by blue-electron Ltd, Wuhan City, in which cutoff potentials were set to 2.0V and 4.5V, and a current density was set to 1Ag-1Setting the specific charge/discharge capacity to 1000mAh g based on the load mass of the positive electrode active material-1。
Example 4
1) Weighing a certain amount of Nafion, slowly adding the Nafion into the THF solution in a magnetic stirring state, and continuously stirring for 2 hours to obtain 0.1g/mL Nafion-THF solution;
2) weighing a certain amount of ZnO nanoparticles, slowly adding the ZnO nanoparticles into the Nafion-THF solution (for preventing the ZnO nanoparticles from agglomerating), and continuously stirring for 3 hours to obtain the ZnO-Nafion-THF solution with the mass ratio of Nafion to ZnO of 1:3, wherein the solid content is 20%;
3) adding a molecular sieve, and baking in an oven at 80 ℃ to remove water;
4) putting the dehydrated ZnO-Nafion-THF solution into a glove box, pouring the solution into a polytetrafluoroethylene film forming mold, putting the polytetrafluoroethylene film forming mold into a vacuum drying oven at 45 ℃ for baking, and obtaining Nafion solid electrolyte after film forming;
5) the Nafion solid electrolyte was placed in a previously prepared LiPF containing 1mol/L prior to assembly of the lithium-air battery6Soaking in organic solvent of EC-DMC with the immersion amount of 80 wt%.
6) Assembling lithium-air battery to test battery performance, the solid electrolyte and the liquid electrolyte of a common lithium battery were used as the electrolyte of the lithium-air battery under the same conditions, respectively, at 1A g-1Constant capacity at current density (1000mAh g)-1) And performing charge and discharge cycles. The test results are shown in fig. 4, and the cycle number of the battery after using the solid electrolyte is increased from 43 times to 110 times, which is greatly improved. The common battery is LiPF with 1mol/L6CR2032 type coin cell with EC-DMC as electrolyte.
The specific test conditions were: the cycle life of the battery was evaluated by conducting a constant current charge/discharge cycle for a long time in a test container (99.9%, vacuum degree 0.1atm) of pure oxygen atmosphere using a CT2001A-5V 2mA type battery test system manufactured by blue-electron Ltd, Wuhan City, in which cutoff potentials were set to 2.0V and 4.5V, and a current density was set to 1Ag-1Setting the specific charge/discharge capacity to 1000mAh g based on the load mass of the positive electrode active material-1。
Example 5
1) Weighing a certain amount of PVdF particles, slowly adding the PVdF particles (preventing the PVdF particles from agglomerating together and increasing the dissolving difficulty) into the DMF solution in a magnetic stirring state, and continuously stirring for 2 hours to obtain 0.1g/mL of PVdF-DMF solution;
2) weighing a certain amount of Co3O4Nanoparticle slowness (prevention of Co)3O4Nano-particlesParticle agglomeration) is added into the PVdF-DMF solution, and the mixture is continuously stirred for 3 hours to obtain the PVdF and Co3O4Co in a mass ratio of 1:33O4-PVdF-DMF solution with a solid content of 20%;
3) adding a molecular sieve, and baking in an oven at 80 ℃ to remove water;
4) putting the dewatered PVdF-DMF solution into a glove box, pouring the solution into a polytetrafluoroethylene film forming die, putting the die into a vacuum drying oven at 45 ℃ for baking, and obtaining the PVdF solid electrolyte after film forming;
5) the PVdF solid electrolyte was placed in a previously prepared LiPF containing 1mol/L prior to assembly of the lithium-air battery6Soaking in organic solvent of EC-DMC with the immersion amount of 80 wt%.
6) Assembling lithium-air battery to test battery performance, the solid electrolyte and the liquid electrolyte of a common lithium battery were used as the electrolyte of the lithium-air battery under the same conditions, respectively, at 1A g-1Constant capacity at current density (1000mAh g)-1) And performing charge and discharge cycles. The test results are shown in fig. 5, and the cycle number of the battery after using the solid electrolyte is increased from 43 times to 108 times, which is greatly improved. The common battery is LiPF with 1mol/L6CR2032 type coin cell with EC-DMC as electrolyte. The specific test conditions were: the cycle life of the battery was evaluated by conducting a constant current charge/discharge cycle for a long time in a test container (99.9%, vacuum degree 0.1atm) of pure oxygen atmosphere using a CT2001A-5V 2mA type battery test system manufactured by blue-electron Ltd, Wuhan City, in which cutoff potentials were set to 2.0V and 4.5V, and a current density was set to 1Ag-1Setting the specific charge/discharge capacity to 1000mAh g based on the load mass of the positive electrode active material-1。
Comparative example 1
Testing of PU solid electrolyte (1:3) and LiPF provided in example 2 of the present invention under equivalent conditions6The lithium-air battery with the/EC-DMC liquid electrolyte has a cross-sectional view of the lithium negative electrode after 30 cycles, as shown in FIG. 6. Comparing (a) and (b) in fig. 6, it was found that the consumption rate of the lithium negative electrode was significantly slowed down after using the PU solid electrolyte.
The specific test conditions were the same as those in example 2.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A solid electrolyte for a lithium metal battery, comprising:
a lithium-philic agent;
a hydrophobic film-forming agent;
and a solvent that is dispersible or soluble in the lithium-philic agent and is dispersible or soluble in the film-forming agent.
2. The solid electrolyte for a lithium metal battery according to claim 1, characterized in that:
the lithium-philic agent is selected from SiO2、Co3O4Or ZnO;
the film forming agent is selected from any one of polyurethane, Nafion or polyvinylidene fluoride;
the solvent is selected from any one of N-methyl pyrrolidone, N-N-dimethylformamide or tetrahydrofuran.
3. The solid electrolyte for a lithium metal battery according to claim 1, characterized in that: the weight ratio of the lithium-philic agent to the film forming agent is 1: 1-5.
4. The solid electrolyte for a lithium metal battery according to any one of claims 1 to 3, characterized in that: and the lithium battery is also immersed with a lithium battery electrolyte, and the weight percentage of the lithium battery electrolyte and the solid electrolyte of the lithium metal battery is 5-100 wt%.
5. A method for preparing a solid electrolyte of a lithium metal battery, comprising the steps of:
1) preparing a composite liquid of a lithium-philic agent, a hydrophobic membrane-forming agent and a solvent, wherein the lithium-philic agent is dispersed or dissolved in the solvent, and the membrane-forming agent is dispersed or dissolved in the solvent;
2) removing water from the composite liquid prepared in the step 1);
3) and (3) forming a film by using the dehydrated composite liquid obtained in the step 2), thus obtaining the solid electrolyte of the lithium metal battery.
6. The method of preparing a solid electrolyte for a lithium metal battery according to claim 1, wherein:
the lithium-philic agent is selected from SiO2、Co3O4Or ZnO;
the film forming agent is selected from any one of polyurethane, Nafion or polyvinylidene fluoride;
the solvent is selected from any one of N-methyl pyrrolidone, N-N-dimethylformamide or tetrahydrofuran.
7. The method of preparing a solid electrolyte for a lithium metal battery according to claim 1, wherein: the weight ratio of the lithium-philic agent to the film forming agent is 1: 1-5.
8. The method for preparing a solid electrolyte for a lithium metal battery according to any one of claims 5 to 7, further comprising the step 4): and immersing the solid electrolyte of the lithium metal battery into a lithium battery electrolyte, wherein the weight percentage of the lithium battery electrolyte to the solid electrolyte of the lithium metal battery is 5-100 wt%.
9. Use of a solid-state electrolyte for a lithium metal battery according to any one of claims 1 to 4, characterized in that: as a solid electrolyte for lithium metal batteries.
10. A lithium metal battery comprising a solid state electrolyte, characterized in that: the solid electrolyte is selected from the solid electrolytes of the lithium metal batteries of any one of claims 1 to 4.
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Denomination of invention: A solid-state electrolyte for lithium metal batteries and its preparation method, application, and lithium metal batteries Granted publication date: 20220125 Pledgee: Guanggu Branch of Wuhan Rural Commercial Bank Co.,Ltd. Pledgor: WUHAN RUIKEMEI NEW ENERGY Co.,Ltd. Registration number: Y2024980018586 |