CN117996178A - Preparation method of deep eutectic solvent-based polymer solid electrolyte for lithium battery - Google Patents
Preparation method of deep eutectic solvent-based polymer solid electrolyte for lithium battery Download PDFInfo
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- 230000005496 eutectics Effects 0.000 title claims abstract description 68
- 239000002904 solvent Substances 0.000 title claims abstract description 68
- 229920000642 polymer Polymers 0.000 title claims abstract description 49
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 29
- 229910001416 lithium ion Inorganic materials 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 230000008014 freezing Effects 0.000 claims description 18
- 238000007710 freezing Methods 0.000 claims description 18
- 238000010257 thawing Methods 0.000 claims description 14
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 235000019743 Choline chloride Nutrition 0.000 claims description 4
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 4
- 229960003178 choline chloride Drugs 0.000 claims description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000002787 reinforcement Effects 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000733 Li alloy Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000010408 film Substances 0.000 claims 1
- 239000010409 thin film Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 5
- 229920000620 organic polymer Polymers 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 abstract description 5
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 2
- 159000000002 lithium salts Chemical class 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 239000011259 mixed solution Substances 0.000 abstract 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 239000000370 acceptor Substances 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000007614 solvation Methods 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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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
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
Abstract
The invention belongs to the field of polymer electrolytes, and relates to a preparation method and application of a deep eutectic solvent-based polymer solid electrolyte. The invention comprises the following steps: stirring and mixing a lithium salt hydrogen bond acceptor and a hydrogen bond donor to clear and transparent liquid under the heating of an oil bath to obtain a Deep Eutectic Solvent (DES); adding the organic polymer reinforcing phase into the deep eutectic solvent, and continuously heating and stirring to obtain a transparent mixed solution; pouring the mixed solution into a polytetrafluoroethylene mould, and standing for a certain time at room temperature to obtain eutectic polymer electrolyte; the whole process is carried out in a glove box filled with nitrogen, and the water and oxygen content is below 0.2 ppm. When the polymer electrolyte is applied to a lithium battery, the polymer cross-linked network can endow the electrolyte with good mechanical property, and the inter-polymer hydrogen bonds can promote migration of Li + while endowing the electrolyte with excellent self-healing property, so that the electrolyte circulation stability is improved.
Description
Technical Field
The invention belongs to the field of polymer electrolytes, and particularly relates to a preparation method of a deep eutectic solvent-based polymer solid electrolyte and application of the deep eutectic solvent-based polymer solid electrolyte in a lithium ion battery.
Background
With the progress of human production and life and the development of scientific technology, new energy automobiles, intelligent wearable equipment, portable electronic products and novel sensors are emerging, so that a great deal of energy demands are induced. However, fossil fuels, which are currently used in large quantities, cause problems of environmental pollution and exhaustion of energy, and although renewable energy sources such as solar energy, wind energy, tidal energy, and geothermal energy supply us with electric energy, reliable energy storage devices are urgently needed to balance supply due to their limitations in natural conditions such as climate and geography. The lithium metal has an ultrahigh theoretical specific capacity (3830 mAh g -1) and a lower oxidation-reduction potential (-3.04V vs. Li +/Li), so that the lithium ion battery becomes the head plate in a plurality of energy storage devices. However, the lithium ion battery in commercial use at present uses liquid organic electrolyte, so that potential risks such as electrolyte leakage, thermal runaway, even fire explosion and the like are caused. Meanwhile, since lithium metal has high reactivity, liquid electrolyte is easy to react with the lithium metal to generate an unstable SEI layer, so that a lithium ion tip is deposited, dendrite is formed, and a separator is pierced to cause short circuit of the battery. Therefore, developing a solid electrolyte with high safety and high stability for lithium ion batteries is a key to improving the electrochemical performance of lithium ion batteries.
The deep eutectic solvent is formed by hydrogen bond interaction of a hydrogen bond acceptor and a hydrogen bond donor, has low vapor pressure, good thermal stability and chemical stability and incombustibility, and has a melting point which is obviously lower than an ideal mixture value. This makes its solvated structure different from conventional water or organic solvents, and its ordered solvated structure favors better coordination with Li +, thus allowing DES-based electrolytes with a wider electrochemical window and more stable cycling performance.
The organic polymer electrolyte fixes the electrolyte solution in a polymer network through hydrogen bond interaction, has considerable ionic conductivity and migration number, excellent mechanical strength and thermal stability, can better inhibit the growth of Li + dendrite, and is widely focused and researched in the fields of energy conversion and energy storage. The polymer electrolyte based on the deep eutectic solvent has the advantages of high cost efficiency, simple synthesis, excellent biocompatibility and excellent thermal stability and electrochemical stability. The preparation of deep eutectic solvent polymer electrolyte lithium ion batteries with high ionic conductivity by blending different solvation structures and viscosities has great potential.
Disclosure of Invention
Aiming at the technical defects of leakage, thermal runaway, potential explosion risk and the like of an organic electrolyte of the existing lithium ion battery, the invention aims to provide a solid lithium ion polymer electrolyte which is based on a deep eutectic solvent and does not contain free water molecules, a preparation method thereof and the solid lithium ion polymer electrolyte which is used for the lithium ion battery electrolyte. The deep eutectic solvent-based polymer solid electrolyte adopts a lithium salt-based deep eutectic solvent ion conductive phase without water, and the ion conductive phase is dispersed in a polymer network of an organic polymer reinforcing phase, so that the polymer electrolyte is endowed with excellent conductivity and mechanical strength, and a stable solid electrolyte with an adjustable solvation structure is constructed.
Specifically, the invention is realized by the following scheme:
a deep eutectic solvent-based polymer solid electrolyte comprising an organic polymer reinforcement phase and an ion conducting phase, the organic polymer reinforcement phase being at least one of polyvinyl alcohol, polyacrylamide and polyacrylic acid; the ion conducting phase is a lithium-based deep eutectic solvent and consists of a hydrogen bond donor and a hydrogen bond acceptor; the hydrogen bond donor is at least one of ethylene glycol, choline chloride, glycerol and urea; the hydrogen bond acceptor is at least one of lithium chloride, lithium triflate, lithium bis (fluorosulfonyl) imide and lithium bis (trifluoromethanesulfonyl) imide.
In order to realize the scheme, the preparation method of the deep eutectic solvent-based polymer solid electrolyte is characterized by comprising the following steps of:
(1) Mixing a hydrogen bond acceptor and a hydrogen bond donor in a certain proportion, and heating for a period of time at a certain temperature to obtain a lithium-based deep eutectic solvent;
(2) Adding a certain amount of polymer reinforcing phase into the deep eutectic solvent, continuously heating and mixing for a period of time, pouring into a polytetrafluoroethylene mould, and repeatedly freezing and thawing to obtain the deep eutectic solvent-based polymer solid electrolyte;
the whole process is carried out in a glove box filled with argon, and the water and oxygen content is below 0.2 ppm.
The preparation method of the deep eutectic solvent-based polymer solid electrolyte in the technical scheme comprises the steps that the hydrogen bond donor is at least one selected from ethylene glycol, choline chloride, glycerol and urea; the hydrogen bond acceptor is at least one of lithium chloride, lithium triflate, lithium bis (fluorosulfonyl) imide and lithium bis (trifluoromethanesulfonyl) imide. The ratio of the amounts of hydrogen bond acceptors to hydrogen bond donor materials is 1:1 to 1:6. As a further improvement of the invention, the preferred hydrogen bond donor is ethylene glycol, the hydrogen bond acceptor is lithium chloride, and the ratio of the two substances is 1:4.
Further, in the step (1), the heating temperature is 80-100 ℃, and the heating reaction time is 1-4 hours. Preferably, the heating temperature is 100 ℃, and the heating reaction time is 2h.
The preparation method of the deep eutectic solvent-based polymer solid electrolyte in the technical scheme comprises the step of preparing a polymer reinforced phase from at least one of polyvinyl alcohol, polyacrylamide and polyacrylic acid. The addition amount of the polymer reinforcing phase is 5-10wt% of the total mass fraction. As a further improvement of the present invention, the preferred polymer reinforcement phase is polyvinyl alcohol added in an amount of 10wt% of the total mass fraction.
Further, in the step (2), the heating temperature is 80-140 ℃, the heating time is 2-5 h, the freezing and thawing temperature is minus 30-minus 10 ℃, the freezing and thawing times are 1-3, and the freezing time is 12-24 h. Preferably, the heating temperature is 120 ℃, the heating time is 4 hours, the freezing and thawing temperature is minus 20 ℃, the freezing and thawing times are 3 times, and the freezing time is 12 hours.
According to the technical scheme, the deep eutectic solvent-based polymer solid electrolyte is prepared by the preparation method, and the film thickness of the deep eutectic solvent-based polymer solid electrolyte is 0.2-1 mm.
A further object of the invention is: the lithium ion solid-state battery based on the deep eutectic solvent polymer electrolyte comprises an electrolyte, a positive electrode and a negative electrode, and is characterized in that the electrolyte is obtained by adopting the preparation method in the technical scheme.
Preferably, the positive electrode is at least one of lithium iron phosphate, lithium manganate, lithium cobaltate and nickel cobalt manganese ternary materials; the negative electrode is at least one of metal lithium, graphite, lithium alloy, lithium titanate and silicon negative electrode.
Preferably, the lithium ion solid-state battery is one or more of button battery, soft package battery and cylindrical battery.
In general, compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) The invention uses the lithium-based deep eutectic solvent without water to replace the traditional aqueous electrolyte, and has low saturated vapor pressure, incombustibility, high thermal stability, wide electrochemical stability window and excellent freezing resistance. By preparing the solvation structure of Li +, the deep eutectic solvent electrolyte with rapid ion transmission capability is obtained, the problems of hydrogen evolution reaction caused by free water, self corrosion of a zinc cathode and dissolution of a positive electrode material in the charge and discharge process can be well inhibited, and reversible deposition and stripping of lithium ions are realized.
(2) The invention introduces the polymer reinforcing phase into the deep eutectic solvent electrolyte with solvation structure, and obtains the deep eutectic polymer electrolyte film with excellent ionic conductivity and mechanical strength through proper proportion regulation, replaces the combination of the traditional diaphragm and electrolyte, and simplifies the battery structure. The hydrogen bond interaction between the polymer reinforced phase molecular chains forms a network structure, and the electrolyte is endowed with excellent self-healing performance, so that further expansion of cracks generated by bending deformation in the use process of the lithium ion battery is inhibited, and the safety problem caused by short circuit of the polymer electrolyte at the cracks is effectively avoided. Meanwhile, the polymer electrolyte with certain mechanical properties can effectively inhibit dendrite growth and improve the cycle life of the battery.
(3) The deep eutectic solvent-based polymer solid electrolyte prepared by the method has a large number of hydrogen bonds, so that solvent molecules are fixed in a polymer network, thereby inhibiting the decomposition of the solvent molecules on the surface of an electrode, and meanwhile, the existence of the hydrogen bonds endows the solid electrolyte and the electrode material with good adhesiveness, thereby being beneficial to the migration and stable deposition stripping of Li +.
Drawings
For further explanation of the technical solutions in the embodiments of the present invention, the following description will briefly describe the drawings in the embodiments, and it is apparent that the following drawings represent only some embodiments of the present invention and are not intended to limit the present invention.
FIG. 1 is a schematic diagram of a polymer electrolyte according to example 1 of the present invention;
fig. 2 is a schematic view showing the internal structure of the polymer electrolyte in example 1 of the present invention.
Detailed Description
The invention relates to a preparation method of a deep eutectic solvent-based polymer solid electrolyte and application of the solid electrolyte in a lithium ion battery, and aims and technical schemes of the invention are fully and specifically described below by combining with examples. It is apparent that the described embodiments are only a part of the present invention, and are merely for explaining the present invention, not limiting the present invention.
Example 1
The preparation of the deep eutectic solvent polymer electrolyte is carried out in the embodiment, and the deep eutectic solvent polymer electrolyte is used for a lithium ion battery, and the specific steps are as follows:
(1) Preparing a lithium-based deep eutectic solvent: under an argon atmosphere having both water and oxygen contents of less than 0.01ppm, the ratio of the amounts of the substances was 1:4, stirring the lithium chloride and the ethylene glycol for 2 hours at the temperature of 100 ℃, uniformly mixing, and cooling to room temperature to obtain uniform and transparent liquid, thus obtaining the lithium-based deep eutectic solvent;
(2) Preparing a deep eutectic solvent-based polymer solid electrolyte: adding 10wt% of polyvinyl alcohol organic matter reinforcing phase into the lithium-based deep eutectic solvent, heating for 4 hours at 120 ℃, pouring into a polytetrafluoroethylene die, freezing for 12 hours at-20 ℃, thawing for 12 hours at room temperature, and circularly freezing and thawing for three times to obtain the deep eutectic solvent-based polymer solid electrolyte with the thickness of 0.3 mm;
(3) Preparing a polymer-based solid-state lithium ion battery: cutting the metal lithium sheet and the lithium iron phosphate positive electrode sheet into wafers with the diameter of 14mm by using a punching machine respectively; cutting the deep eutectic solvent-based polymer solid electrolyte into electrolyte membranes with the diameters of 16 mm; button cell model CR2032 was used according to: the negative electrode shell, the elastic sheet, the gasket, the metal lithium sheet, the polymer electrolyte membrane, the lithium iron phosphate positive electrode sheet and the positive electrode shell are assembled into the lithium ion battery in a sequential glove box.
Example 2
The preparation of the deep eutectic solvent polymer electrolyte is carried out in the embodiment, and the deep eutectic solvent polymer electrolyte is used for a lithium ion battery, and the specific steps are as follows:
(1) Preparing a lithium-based deep eutectic solvent: under an argon atmosphere having both water and oxygen contents of less than 0.01ppm, the ratio of the amounts of the substances was 1:4, stirring the lithium bistrifluoromethane sulfonyl imide and ethylene glycol for 2 hours at the temperature of 100 ℃, uniformly mixing, and cooling to room temperature to obtain uniform and transparent liquid, thus obtaining the lithium-based deep eutectic solvent;
(2) Preparing a deep eutectic solvent-based polymer solid electrolyte: adding 10wt% of polyvinyl alcohol organic matter reinforcing phase into the lithium-based deep eutectic solvent, heating for 4 hours at 120 ℃, pouring into a polytetrafluoroethylene die, freezing for 12 hours at-20 ℃, thawing for 12 hours at room temperature, and circularly freezing and thawing for three times to obtain the deep eutectic solvent-based polymer solid electrolyte with the thickness of 0.3 mm;
(3) Preparing a polymer-based solid-state lithium ion battery: cutting the metal lithium sheet and the lithium iron phosphate positive electrode sheet into wafers with the diameter of 14mm by using a punching machine respectively; cutting the deep eutectic solvent-based polymer solid electrolyte into electrolyte membranes with the diameters of 16 mm; button cell model CR2032 was used according to: the negative electrode shell, the elastic sheet, the gasket, the metal lithium sheet, the polymer electrolyte membrane, the lithium iron phosphate positive electrode sheet and the positive electrode shell are assembled into the lithium ion battery in a sequential glove box.
Example 3
The preparation of the deep eutectic solvent polymer electrolyte is carried out in the embodiment, and the deep eutectic solvent polymer electrolyte is used for a lithium ion battery, and the specific steps are as follows:
(1) Preparing a lithium-based deep eutectic solvent: under an argon atmosphere having both water and oxygen contents of less than 0.01ppm, the ratio of the amounts of the substances was 1:4, stirring the lithium bistrifluoromethane sulfonyl imide and choline chloride for 2 hours at the temperature of 100 ℃, uniformly mixing, and cooling to room temperature to obtain uniform and transparent liquid, thus obtaining the lithium-based deep eutectic solvent;
(2) Preparing a deep eutectic solvent-based polymer solid electrolyte: adding 10wt% of polyvinyl alcohol organic matter reinforcing phase into the lithium-based deep eutectic solvent, heating for 4 hours at 120 ℃, pouring into a polytetrafluoroethylene die, freezing for 12 hours at-20 ℃, thawing for 12 hours at room temperature, and circularly freezing and thawing for three times to obtain the deep eutectic solvent-based polymer solid electrolyte with the thickness of 0.3 mm;
(3) Preparing a polymer-based solid-state lithium ion battery: cutting the metal lithium sheet and the lithium manganate positive electrode sheet into wafers with the diameter of 14mm by using a punching machine respectively; cutting the deep eutectic solvent-based polymer solid electrolyte into electrolyte membranes with the diameters of 16 mm; button cell model CR2032 was used according to: the negative electrode shell, the elastic sheet, the gasket, the metal lithium sheet, the polymer electrolyte membrane, the lithium manganate positive electrode sheet and the positive electrode shell are assembled into the lithium ion battery in a sequential glove box.
Claims (9)
1. A method for preparing a deep eutectic solvent-based polymer solid electrolyte, comprising the steps of:
(1) Mixing a hydrogen bond acceptor and a hydrogen bond donor in a certain proportion, and heating for a period of time at a certain temperature to obtain a lithium-based deep eutectic solvent;
(2) Adding a certain amount of polymer reinforcing phase into the deep eutectic solvent, continuously heating and mixing for a period of time, pouring into a polytetrafluoroethylene mould, and repeatedly freezing and thawing to obtain the deep eutectic solvent-based polymer solid electrolyte;
The whole process is carried out in a glove box filled with argon, and the water and oxygen content is below 0.2 ppm.
2. The method of preparing a deep eutectic solvent based polymer solid electrolyte according to claim 1, wherein the hydrogen bond donor is at least one selected from the group consisting of ethylene glycol, choline chloride, glycerol, and urea; the hydrogen bond acceptor is at least one of lithium chloride, lithium triflate, lithium bis (fluorosulfonyl) imide and lithium bis (trifluoromethanesulfonyl) imide; the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1-1:6.
3. The method for preparing a deep eutectic solvent-based polymer solid electrolyte according to claim 1, wherein the heating temperature in the step (1) is 80-100 ℃, and the heating time is 1-4 hours.
4. The method of preparing a deep eutectic solvent based polymer solid electrolyte of claim 1, wherein the polymer reinforcement phase is at least one of polyvinyl alcohol, polyacrylamide, and polyacrylic acid; the addition amount of the polymer reinforcing phase is 5-10wt% of the total mass fraction.
5. The method for preparing a deep eutectic solvent-based polymer solid electrolyte according to claim 1, wherein in the step (2), the heating temperature is 80-140 ℃, the heating time is 2-5 h, the freezing and thawing temperature is minus 30-minus 10 ℃, the freezing and thawing times are 1-3, and the freezing time is 12-24 h.
6. The deep eutectic solvent-based polymer solid electrolyte is characterized in that the deep eutectic solvent-based polymer solid electrolyte is a thin film type electrolyte with a film thickness of 0.2-1 mm, and is prepared by the preparation method of any one of claims 1-5.
7. A lithium ion solid state battery based on a deep eutectic solvent polymer electrolyte comprising an electrolyte, a positive electrode, a negative electrode, wherein the electrolyte is prepared by the preparation method of claim 6.
8. The deep eutectic solvent polymer electrolyte based lithium ion solid state battery of claim 7 wherein the positive electrode is at least one of lithium iron phosphate, lithium manganate, lithium cobaltate, nickel cobalt manganese ternary material; the negative electrode is at least one of metal lithium, graphite, lithium alloy, lithium titanate and silicon negative electrode.
9. The deep eutectic solvent polymer electrolyte based lithium ion solid state battery of claim 7, wherein the lithium ion battery is one or more of a button cell battery, a pouch cell battery, and a cylindrical cell battery.
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