CN113193227A - Preparation method and application of solid electrolyte polymer modified by gas-phase permeation method - Google Patents
Preparation method and application of solid electrolyte polymer modified by gas-phase permeation method Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 87
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000945 filler Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000011261 inert gas Substances 0.000 claims abstract description 12
- 239000012707 chemical precursor Substances 0.000 claims abstract description 11
- 230000008021 deposition Effects 0.000 claims abstract description 3
- -1 alkyl compound Chemical class 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 15
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical group 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- 230000008595 infiltration Effects 0.000 claims 7
- 238000001764 infiltration Methods 0.000 claims 7
- 239000012528 membrane Substances 0.000 abstract description 29
- 238000002156 mixing Methods 0.000 abstract description 13
- 229910052744 lithium Inorganic materials 0.000 abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005275 alloying Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 25
- 239000012071 phase Substances 0.000 description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 238000003825 pressing Methods 0.000 description 15
- 239000002002 slurry Substances 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000002033 PVDF binder Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000011267 electrode slurry Substances 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011787 zinc oxide Substances 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- 229920006255 plastic film Polymers 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000000231 atomic layer deposition Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 2
- 238000007792 addition Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Classifications
-
- 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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- H01M2300/0085—Immobilising or gelification of 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
- 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
Abstract
The invention discloses a preparation method and application of a solid electrolyte polymer modified by a gas-phase permeation method. The preparation method comprises the following steps: and placing the solid electrolyte polymer in a sample barrel in a reaction cavity of deposition equipment, preheating while stirring, and then alternately introducing a gas-phase chemical precursor source and inert gas to perform gas-phase permeation circulation so as to grow uniform nano-filler in the polymer, thereby obtaining the modified solid electrolyte polymer. The invention directly grows the filler in the polymer by a gas-phase permeation method, compared with physical mixing, the filler has smaller size and stronger chemical interaction with the polymer, increases the dispersion uniformity of the filler, and can better improve the ionic conductivity and lithium ion migration number of the electrolyte; in addition, a small particle size and uniformly dispersed filler may be present on the surface of the solid electrolyte membrane to reduce the interfacial resistance to lithium by alloying with lithium metal.
Description
Technical Field
The invention relates to a preparation method and application of a solid electrolyte polymer modified by a gas-phase permeation method, belonging to the technical field of energy materials.
Background
Polymer solid-state electrolytes are among the most promising solid-state electrolytes due to their advantages of high flexibility, low cost and easy integration. However, their practical applications are limited by low ionic conductivity, lower lithium ion transport number, smaller electrochemical window and larger interfacial resistance.
The preparation of the composite polymer solid electrolyte by incorporating the inorganic filler into the polymer matrix can reduce the crystallinity of the polymer and improve the ionic conductivity. In addition, the filler can adsorb anions, improve the transference number of lithium ions and increase the mechanical strength. However, the most commonly used method for preparing a composite polymer solid electrolyte is to physically mix a filler with an electrolyte, and the interaction force between the filler and the polymer incorporated in this manner is weak, and agglomeration occurs to degrade the surface properties thereof, resulting in poor dispersion uniformity, thereby limiting the improvement in ionic conductivity and lithium ion transference number.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the practical application of polymer solid electrolytes is limited by the problems of low ionic conductivity, low transference number of lithium ions, small electrochemical window and large interface resistance.
In order to solve the technical problems, the invention provides a preparation method of a solid electrolyte polymer modified by a gas phase permeation method, which is characterized in that the solid electrolyte polymer is placed in a sample barrel in a reaction cavity of deposition equipment, is preheated under stirring, and then is alternately introduced with a gas phase chemical precursor source and inert gas to carry out gas phase permeation circulation, so that uniform nano-filler grows in the polymer, and the modified solid electrolyte polymer is obtained.
Preferably, the chemical precursor source comprises a metal alkyl compound and deionized water, and the nanofiller is a metal oxide.
Preferably, the gas phase permeation cycle is that a metal alkyl compound, inert gas, deionized water and inert gas are alternately introduced; the molar ratio of the metal alkyl compound and the deionized water which are introduced in each gas phase permeation circulation is 0.25-2: 1, and the introduction amount of the metal alkyl compound in each gas phase permeation circulation is 0.5-2% of the mass ratio of the metal element in the metal alkyl compound to the solid electrolyte polymer.
Preferably, the number of gas phase permeation cycles is 5-20.
Preferably, the mass fraction of the nano filler in the modified solid electrolyte polymer is 1-20%.
Preferably, the solid electrolyte polymer is at least one of polyethylene oxide, polyethylene glycol, polyacrylonitrile and polymethacrylate.
Preferably, the metal alkyl compound is at least one of diethyl zinc and trimethyl aluminum.
The invention also provides application of the solid electrolyte polymer prepared by the preparation method of the solid electrolyte polymer modified by the gas-phase permeation method in batteries.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention directly grows the filler in the polymer by a gas-phase permeation method, compared with physical mixing, the filler has smaller size and stronger chemical interaction with the polymer, increases the dispersion uniformity of the filler, and can better improve the ionic conductivity and lithium ion migration number of the electrolyte; in addition, a small-particle-size and uniformly dispersed filler may be present on the surface of the solid electrolyte membrane, reducing the interfacial resistance to lithium by alloying with lithium metal; meanwhile, the electrochemical stability of the modified polymer solid electrolyte is improved to a certain extent;
2. the gas phase permeation method of the invention has low difficulty in growing the filler, can grow one or more fillers, and is suitable for commercial large-scale production.
Drawings
FIG. 1 is a graph comparing the cycle performance at 50 ℃ of the cells of example 1, comparative example 1 and comparative example 2;
FIG. 2 is a graph comparing rate performance at 50 ℃ for the cells of example 1, comparative example 1, and comparative example 2;
FIG. 3 is a graph comparing the cycle performance at 50 ℃ of the batteries of example 1 and example 2;
fig. 4 is a graph comparing the cycle performance at 50 c of the batteries of example 1 and example 3.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Example 1
Preparation of a solid electrolyte polymer modified by a vapor phase permeation method:
the gas-phase permeation method can be realized by an atomic layer deposition device, polyethylene oxide (PEO) powder is placed in a sample barrel to be heated and preheated, and is mechanically stirred or vibrated for 1-2 hours at the same time, then, according to the proportion that the mass ratio of zinc in diethyl zinc to a solid electrolyte polymer is 1% and the molar ratio of diethyl zinc to deionized water is 0.75:1, diethyl zinc is alternately introduced into a chemical precursor source, so that the polyethylene oxide absorbs the diethyl zinc; introducing inert gas high-purity argon for purging; then, introducing deionized water serving as a chemical precursor source to generate zinc oxide nano-particles in the polymer; and finally, introducing high-purity argon for purging, and obtaining the modified solid electrolyte polymer after 10 cycles of gas-phase permeation circulation, wherein the mass fraction of Zn in the material is measured to be 6 wt%, and the mass fraction of corresponding ZnO is 7.48 wt%.
Preparing a battery:
1) preparation of composite polymer solid electrolyte membrane
Step 1: mixing the modified solid electrolyte polymer prepared in the above manner with lithium salt (LiTFSI) according to the mass ratio of 2.8:1, adding acetonitrile, stirring for 24h to obtain uniform slurry, and uniformly coating the slurry on a Polytetrafluoroethylene (PTFE) substrate.
Step 2: and drying the coated slurry in a 60 ℃ oven, and performing cold pressing and slitting to obtain the composite polymer solid electrolyte membrane.
2) Preparation of positive plate
Step 1: mixing a high-nickel ternary positive electrode NCM811, a binding agent polyvinylidene fluoride (PVDF) and a conductive agent Super P according to a mass ratio of 8:1:1, adding N-methylpyrrolidone (NMP), and uniformly stirring under the action of a vacuum stirrer to obtain positive electrode slurry; uniformly coating the positive electrode slurry on an aluminum foil with the thickness of 20 mu m;
step 2: and drying the coated pole piece in a 60 ℃ oven, and performing cold pressing and slitting to obtain the positive pole piece.
3) Assembly of a battery
And sequentially stacking the positive plate, the composite polymer solid electrolyte membrane and the lithium metal plate to enable the composite polymer solid electrolyte membrane to be positioned between the positive plate and the negative plate, winding the composite polymer solid electrolyte membrane into a square bare cell, filling the square bare cell into an aluminum-plastic film, baking the square bare cell at 60 ℃ to remove water, sealing the cell, and performing the working procedures of standing, hot cold pressing, formation, clamping, capacity grading and the like to obtain the finished battery.
Example 2
Preparation of a solid electrolyte polymer modified by a vapor phase permeation method:
the gas-phase permeation method can be realized by an atomic layer deposition device, polyethylene oxide (PEO) powder is placed in a sample barrel to be heated and preheated, and is mechanically stirred or vibrated for 1-2 hours at the same time, then, according to the proportion that the mass ratio of zinc in diethyl zinc to a solid electrolyte polymer is 1% and the molar ratio of diethyl zinc to deionized water is 0.75:1, diethyl zinc is alternately introduced into a chemical precursor source, so that the polyethylene oxide absorbs the diethyl zinc; introducing inert gas high-purity argon for purging; introducing deionized water serving as a chemical precursor source to generate zinc oxide nano-particles in the polymer; then introducing inert gas high-purity argon for purging; after 5 cycles of the above gas phase permeation cycle, a modified solid electrolyte polymer was obtained, in which the mass fraction of Zn was measured to be 2.7 wt%, and the mass fraction of the corresponding ZnO was 3.6 wt%.
Preparing a battery:
1) preparation of composite polymer solid electrolyte membrane
Step 1: mixing the modified solid electrolyte polymer prepared in the above manner with lithium salt (LiTFSI) according to the mass ratio of 2.8:1, adding acetonitrile, stirring for 24h to obtain uniform slurry, and uniformly coating the slurry on a Polytetrafluoroethylene (PTFE) substrate.
Step 2: and drying the coated slurry in a 60 ℃ oven, and performing cold pressing and slitting to obtain the composite polymer solid electrolyte membrane.
2) Preparation of positive plate
Step 1: mixing a high-nickel ternary positive electrode NCM811, a binding agent polyvinylidene fluoride (PVDF) and a conductive agent Super P according to a mass ratio of 8:1:1, adding N-methylpyrrolidone (NMP), and uniformly stirring under the action of a vacuum stirrer to obtain positive electrode slurry; uniformly coating the positive electrode slurry on an aluminum foil with the thickness of 20 mu m;
step 2: and drying the coated pole piece in a 60 ℃ oven, and performing cold pressing and slitting to obtain the positive pole piece.
3) Assembly of a battery
And sequentially stacking the positive plate, the composite polymer solid electrolyte membrane and the lithium metal plate to enable the composite polymer solid electrolyte membrane to be positioned between the positive plate and the negative plate, winding the composite polymer solid electrolyte membrane into a square bare cell, filling the square bare cell into an aluminum-plastic film, baking the square bare cell at 60 ℃ to remove water, sealing the cell, and performing the working procedures of standing, hot cold pressing, formation, clamping, capacity grading and the like to obtain the finished battery.
Example 3
Preparation of a solid electrolyte polymer modified by a vapor phase permeation method:
the gas-phase permeation method can be realized by an atomic layer deposition device, polyethylene oxide (PEO) powder is placed in a sample barrel to be heated and preheated, and is mechanically stirred or vibrated for 1-2 hours, then, according to the proportion that the mass ratio of zinc in diethyl zinc to a solid electrolyte polymer is 1% and the molar ratio of diethyl zinc to deionized water is 0.5-1: 1, diethyl zinc is alternately introduced into a chemical precursor source, so that the polyethylene oxide adsorbs the diethyl zinc; introducing inert gas high-purity argon for purging; introducing deionized water serving as a chemical precursor source to generate zinc oxide nano-particles in the polymer; then introducing inert gas high-purity argon for purging; after 15 cycles of the gas phase permeation cycle, the modified solid electrolyte polymer is obtained, wherein the mass fraction of Zn in the material is 11 wt%, and the mass fraction of corresponding ZnO is 13.7 wt%.
Preparing a battery:
1) preparation of composite polymer solid electrolyte membrane
Step 1: mixing the modified solid electrolyte polymer prepared in the above manner with lithium salt (LiTFSI) according to the mass ratio of 2.8:1, adding acetonitrile, stirring for 24h to obtain uniform slurry, and uniformly coating the slurry on a Polytetrafluoroethylene (PTFE) substrate.
Step 2: and drying the coated slurry in a 60 ℃ oven, and performing cold pressing and slitting to obtain the composite polymer solid electrolyte membrane.
2) Preparation of positive plate
Step 1: mixing a high-nickel ternary positive electrode NCM811, a binding agent polyvinylidene fluoride (PVDF) and a conductive agent Super P according to a mass ratio of 8:1:1, adding N-methylpyrrolidone (NMP), and uniformly stirring under the action of a vacuum stirrer to obtain positive electrode slurry; uniformly coating the positive electrode slurry on an aluminum foil with the thickness of 20 mu m;
step 2: and drying the coated pole piece in a 60 ℃ oven, and performing cold pressing and slitting to obtain the positive pole piece.
3) Assembly of a battery
And sequentially stacking the positive plate, the composite polymer solid electrolyte membrane and the lithium metal plate to enable the composite polymer solid electrolyte membrane to be positioned between the positive plate and the negative plate, winding the composite polymer solid electrolyte membrane into a square bare cell, filling the square bare cell into an aluminum-plastic film, baking the square bare cell at 60 ℃ to remove water, sealing the cell, and performing the working procedures of standing, hot cold pressing, formation, clamping, capacity grading and the like to obtain the finished battery.
Comparative example 1
Batteries were prepared with unmodified polymers:
1) preparation of polymer solid electrolyte membrane
Step 1: mixing polyethylene oxide and lithium salt (LiTFSI) according to the mass ratio of 2.8:1, adding acetonitrile, stirring for 24 hours to obtain uniform slurry, and uniformly coating the slurry on a Polytetrafluoroethylene (PTFE) substrate.
Step 2: and drying the coated slurry in a 60 ℃ oven, and performing cold pressing and slitting to obtain the polymer solid electrolyte membrane.
2) Preparation of positive plate
Step 1: mixing a high-nickel ternary positive electrode NCM811, a binding agent polyvinylidene fluoride (PVDF) and a conductive agent Super P according to a mass ratio of 8:1:1, adding N-methylpyrrolidone (NMP), and uniformly stirring under the action of a vacuum stirrer to obtain positive electrode slurry; uniformly coating the positive electrode slurry on an aluminum foil with the thickness of 20 mu m;
step 2: and drying the coated pole piece in a 60 ℃ oven, and performing cold pressing and slitting to obtain the positive pole piece.
3) Assembly of a battery
And sequentially stacking the positive plate, the polymer solid electrolyte membrane and the lithium metal plate to enable the composite polymer solid electrolyte membrane to be positioned between the positive plate and the negative plate, winding the composite polymer solid electrolyte membrane into a square bare cell, filling the square bare cell into an aluminum-plastic membrane, baking the square bare cell at 60 ℃ to remove water, sealing the aluminium-plastic membrane, and performing the working procedures of standing, hot cold pressing, formation, clamping, capacity grading and the like to obtain the finished battery.
Comparative example 2
Preparation of batteries from polymers physically mixed with fillers
1) Preparation of polymer solid electrolyte membrane with physically mixed filler
Step 1: fully stirring ZnO and polyethylene oxide according to the mass ratio of 7.5:92.5, uniformly mixing to obtain a polymer of a physical mixed filler, mixing a polymeric material of the physical mixed filler and lithium salt (LiTFSI) according to the mass ratio of 2.8:1, adding acetonitrile, stirring for 24 hours to obtain uniform slurry, and uniformly coating the slurry on a Polytetrafluoroethylene (PTFE) substrate.
Step 2: and drying the coated slurry in a 60 ℃ oven, and performing cold pressing and slitting to obtain the composite polymer solid electrolyte membrane.
2) Preparation of positive plate
Step 1: mixing a high-nickel ternary positive electrode NCM811, a binding agent polyvinylidene fluoride (PVDF) and a conductive agent Super P according to a mass ratio of 8:1:1, adding N-methylpyrrolidone (NMP), and uniformly stirring under the action of a vacuum stirrer to obtain positive electrode slurry; uniformly coating the positive electrode slurry on an aluminum foil with the thickness of 20 mu m;
step 2: and drying the coated pole piece in a 60 ℃ oven, and performing cold pressing and slitting to obtain the positive pole piece.
3) Assembly of a battery
And sequentially stacking the positive plate, the composite polymer solid electrolyte membrane and the lithium metal plate to enable the composite polymer solid electrolyte membrane to be positioned between the positive plate and the negative plate, winding the composite polymer solid electrolyte membrane into a square bare cell, filling the square bare cell into an aluminum-plastic film, baking the square bare cell at 60 ℃ to remove water, sealing the cell, and performing the working procedures of standing, hot cold pressing, formation, clamping, capacity grading and the like to obtain the finished battery.
And (3) performance testing:
the batteries of the example 1 and the comparative examples 1-2 are respectively subjected to a cycle performance test and a rate performance test to obtain a cycle charge-discharge performance comparison graph shown in fig. 1 and a rate performance comparison graph shown in fig. 2, and as can be seen from fig. 1, the battery of the example 1 has higher initial capacity and capacity retention rate than the batteries of the comparative examples 1 and 2; as can be seen from fig. 2, at a high rate of 0.5C, the discharge capacity of the battery of example 1 is significantly higher than that of the batteries of comparative examples 1 and 2, and the charge-discharge rate performance of the battery of example 1 is better, which indicates that the solid electrolyte polymer modified by the gas phase permeation method according to the present invention can better improve the ionic conductivity and lithium ion transference number of the electrolyte and reduce the interfacial resistance to lithium metal; the cyclic charge and discharge performance of the battery of example 1 and the battery of example 2 and example 3 were compared and tested to obtain a comparison graph of cyclic charge and discharge performance as shown in fig. 3 and fig. 4, which shows that when the content of zinc oxide in the composite polymer is reduced, the initial capacity of the battery is reduced and the capacity retention rate is improved, and when the content of zinc oxide in the composite polymer is increased, the initial capacity of the battery is improved and the capacity retention rate is reduced.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way and substantially, it should be noted that those skilled in the art may make several modifications and additions without departing from the scope of the present invention, which should also be construed as a protection scope of the present invention.
Claims (8)
1. A preparation method of a solid electrolyte polymer modified by a vapor infiltration method is characterized in that the solid electrolyte polymer is placed in a sample barrel in a reaction cavity of deposition equipment, is preheated under stirring, and then is alternately introduced with a vapor chemical precursor source and inert gas to carry out vapor infiltration circulation, so that uniform nano-filler grows in the polymer, and the modified solid electrolyte polymer is obtained.
2. A method of preparing a solid electrolyte polymer modified by vapor infiltration according to claim 1, wherein the chemical precursor source comprises a metal alkyl compound and deionized water, and the nanofiller is a metal oxide.
3. The method of claim 2, wherein the gas permeation cycle is a cycle of alternately introducing a metal alkyl compound, an inert gas, deionized water and an inert gas; the molar ratio of the metal alkyl compound and the deionized water which are introduced in each gas phase permeation circulation is 0.25-2: 1, and the introduction amount of the metal alkyl compound in each gas phase permeation circulation is 0.5-2% of the mass ratio of the metal element in the metal alkyl compound to the solid electrolyte polymer.
4. The method of claim 3, wherein the number of gas phase permeation cycles is 5 to 20.
5. The method for preparing a solid electrolyte polymer modified by a vapor infiltration method according to claim 1, wherein the modified solid electrolyte polymer contains 1 to 20% by mass of the nanofiller.
6. The method for preparing a solid electrolyte polymer modified by a vapor infiltration method according to claim 1, wherein the solid electrolyte polymer is at least one of polyethylene oxide, polyethylene glycol, polyacrylonitrile and polymethacrylate.
7. The method of preparing a solid electrolyte polymer modified by a vapor infiltration method according to claim 2, wherein the metal alkyl compound is at least one of diethylzinc and trimethylaluminum.
8. Use of the solid electrolyte polymer prepared by the method for preparing a solid electrolyte polymer modified by a vapor infiltration method according to any one of claims 1 to 7 in a battery.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107749491A (en) * | 2017-09-28 | 2018-03-02 | 柔电（武汉）科技有限公司 | flexible all-solid-state battery and preparation method thereof |
| WO2020130822A1 (en) * | 2018-12-19 | 2020-06-25 | Nederlandse Organisatie Voor Toegepast- Natuurwetenschappelijk Onderzoek Tno | Hybrid solid state electrolyte |
| WO2021048555A1 (en) * | 2019-09-10 | 2021-03-18 | Nexeon Limited | Electroactive materials for use in metal-ion batteries |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107749491A (en) * | 2017-09-28 | 2018-03-02 | 柔电（武汉）科技有限公司 | flexible all-solid-state battery and preparation method thereof |
| WO2020130822A1 (en) * | 2018-12-19 | 2020-06-25 | Nederlandse Organisatie Voor Toegepast- Natuurwetenschappelijk Onderzoek Tno | Hybrid solid state electrolyte |
| WO2021048555A1 (en) * | 2019-09-10 | 2021-03-18 | Nexeon Limited | Electroactive materials for use in metal-ion batteries |
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