CN113839145A - Electrolyte diaphragm based on PVDF-HFP and ionic liquid and preparation method thereof - Google Patents
Electrolyte diaphragm based on PVDF-HFP and ionic liquid and preparation method thereof Download PDFInfo
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- CN113839145A CN113839145A CN202111095615.3A CN202111095615A CN113839145A CN 113839145 A CN113839145 A CN 113839145A CN 202111095615 A CN202111095615 A CN 202111095615A CN 113839145 A CN113839145 A CN 113839145A
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 90
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 title claims abstract description 87
- 239000003792 electrolyte Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 18
- 239000012528 membrane Substances 0.000 claims description 24
- 239000010408 film Substances 0.000 claims description 23
- 239000000839 emulsion Substances 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000007888 film coating Substances 0.000 claims description 7
- 238000009501 film coating Methods 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- -1 1-methyl-3-hexyl imidazole fluoromethylsulfonyl imide salt Chemical class 0.000 claims description 5
- 239000003729 cation exchange resin Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000003957 anion exchange resin Substances 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- OWOQXILFSFZPGY-UHFFFAOYSA-N CCN1C=CN(C)C1.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O Chemical compound CCN1C=CN(C)C1.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O OWOQXILFSFZPGY-UHFFFAOYSA-N 0.000 claims 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 14
- 229920000642 polymer Polymers 0.000 abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002800 charge carrier Substances 0.000 abstract description 3
- 239000004014 plasticizer Substances 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000011245 gel electrolyte Substances 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- YCLCFZRBVJIBMF-UHFFFAOYSA-N [Li].FC(F)(F)S(=N)C(F)(F)F Chemical group [Li].FC(F)(F)S(=N)C(F)(F)F YCLCFZRBVJIBMF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/426—Fluorocarbon polymers
-
- 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
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/497—Ionic conductivity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses an electrolyte diaphragm based on PVDF-HFP and ionic liquid, which is prepared from polyvinylidene fluoride-hexafluoropropylene powder, Li salt and ionic liquid according to a specific proportion. In the invention, Li salt and ionic liquid are mixed in polymer polyvinylidene fluoride-hexafluoropropylene, and the ionic liquid in gel is used as a plasticizer and a charge carrier, so that the obtained electrolyte diaphragm has high ionic conductivity, good thermal stability and safety, and can be used as diaphragms of various high-performance safety lithium ion batteries so as to meet the requirements of people on the high-performance safety lithium ion batteries.
Description
Technical Field
The invention relates to the technical field of lithium battery electrolyte diaphragms, in particular to an electrolyte diaphragm based on PVDF-HFP and ionic liquid and a preparation method thereof.
Background
In the research of rechargeable batteries, two key issues of concern are battery performance and its safety performance. Lithium Metal Batteries (LMBs) are lithium ion batteries in which lithium metal is the anode and are considered to be one of the most promising high performance battery systems. However, since it can react with an organic electrolyte, lithium metal as an anode causes serious problems such as non-uniform lithium deposition and formation of lithium dendrites during charge and discharge cycles, resulting in short-circuiting and safety hazards of a battery. These problems pose serious obstacles to the practical production application of LMBs. In addition, in practical production applications of lithium ion batteries, the electrolytes commonly used are composed of Li salts dissolved in aprotic molecular solvents, such as diethyl carbonate and ethylene carbonate. Although these electrolytes, which are based on carbonates, ensure a high energy density of the battery, their inflammable, volatile instability, which brings further problems in terms of safety performance of lithium ion batteries, is involved.
Disclosure of Invention
The invention aims to provide an electrolyte membrane based on PVDF-HFP and ionic liquid, aiming at the defects in the prior art. Li salt is mixed with ionic liquid in the polymer, and the ionic liquid in the gel acts as a plasticizer and a charge carrier, so that the ionic conductivity can be in a relatively high range. In application research of different polymers, the polymer prepared by taking polyvinylidene fluoride-hexafluoropropylene as a matrix has excellent mechanical property and thermal stability, and has the advantage of good compatibility with ionic liquid, and meanwhile, the ionic gel electrolyte can inhibit the formation of lithium dendrite in a lithium battery. Therefore, the method can be used for preparing the electrolyte diaphragm with higher ionic conductivity and good safety, thereby meeting the requirements of the current market on batteries.
The invention also aims to provide a preparation method of the electrolyte membrane based on PVDF-HFP and ionic liquid.
In order to achieve the above object, the present invention is realized by: the electrolyte membrane based on PVDF-HFP and ionic liquid is prepared from the following components in percentage by mass:
20-35% of polyvinylidene fluoride-hexafluoropropylene powder
60-73% of ionic liquid
5-7% of Li salt.
The ionic liquid is one of 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt, 1-methyl-3-hexyl imidazole fluoromethylsulfonyl imide salt, 1-ethyl-3-methylimidazole tetrafluoroborate and 1-n-butyl-1-methylpyrrolidine bis (trifluoromethylsulfonyl) imide salt.
The Li salt is bis (trifluoromethyl) sulfimide lithium.
The polyvinylidene fluoride-hexafluoropropylene powder is prepared from the following components in percentage by mass:
50-60% of polyvinylidene fluoride-hexafluoropropylene emulsion
3-10% of anion and cation exchange resin
30-45% of electrolyte.
The preparation method comprises the following steps:
(1) weighing the anion-cation exchange resin and the polyvinylidene fluoride-hexafluoropropylene emulsion according to the formula proportion, and mixing for 4-6 hours under the stirring action to form mixed emulsion;
(2) filtering the formed mixed emulsion to obtain viscous adsorbed polyvinylidene fluoride-hexafluoropropylene emulsion;
(3) dropwise adding electrolyte into the adsorbed polyvinylidene fluoride-hexafluoropropylene emulsion while stirring to prepare polyvinylidene fluoride-hexafluoropropylene gel;
(4) drying the polyvinylidene fluoride-hexafluoropropylene gel at 40-50 ℃;
(5) and (3) ball-milling the dried polyvinylidene fluoride-hexafluoropropylene gel by a ball mill, and screening powder below 60 microns by a sieve.
The polyvinylidene fluoride-hexafluoropropylene emulsion (PVDF-HFP emulsion) has a solid content of 25-50%.
The electrolyte is a hydrochloric acid solution with the solution concentration of 0.1 mol/L.
And (3) dropwise adding electrolyte while stirring, so that the emulsion and the electrolyte are uniformly mixed. Preferably, the stirring speed is 400-800rpm.
In the step (5), the ball milling speed is 300-400rpm, and the time is 8-20 h.
The polyvinylidene fluoride-hexafluoropropylene emulsion is prepared by dissolving polyvinylidene fluoride-hexafluoropropylene in N, N-dimethylformamide, wherein the content of the polyvinylidene fluoride-hexafluoropropylene is 25-50%.
The anion-cation exchange resin adopted by the polyvinylidene fluoride-hexafluoropropylene powder can effectively adsorb the ionic surfactant in the PVDF-HFP emulsion on the resin; the porosity can reach 80%, nanometer-scale and evenly-distributed pore channels are provided for electron circulation, the conductivity of the polymer can be greatly improved, and the cycle efficiency of the battery is effectively improved; the preparation process is simple, the material source is wide and economical, the circulation efficiency of the electrolyte is greatly improved, and the requirement of the battery on the electrolyte material is met in practical application.
The preparation method of the electrolyte membrane based on PVDF-HFP and ionic liquid comprises the following steps:
(1) weighing Li salt and ionic liquid according to the formula proportion, and dissolving the Li salt in the ionic liquid to obtain a salt-ionic liquid solution;
(2) mixing the Li salt-ionic liquid solution with polyvinylidene fluoride-hexafluoropropylene powder, and performing ultrasonic dispersion for 30-50 min to obtain a uniform co-dispersion body;
(3) coating the co-dispersion body on an aluminum foil through a film coating machine to form a thin film;
(4) drying the film at the temperature of 120-130 ℃ for 8-15 h;
(5) and (3) quickly transferring the dried film into a glove box, and removing the film in the glove box to obtain the electrolyte diaphragm based on PVDF-HFP and ionic liquid.
In the step (1), the process of dissolving the Li salt in the ionic liquid needs to be carried out in a glove box so as to avoid pollution.
In the step (2), the frequency of ultrasonic treatment is 10-30KHz, and the power is 300-600W.
Preferably, in the step (2), the ultrasonic treatment has a frequency of 20KHz and a power of 450W, and has an excellent dispersion effect and an activation promoting effect.
In the step (2), the film is dried at 125 ℃ for 12 h.
When the co-dispersion was coated, the thickness of the film was 50 μm.
The drying device is a vacuum drying oven.
According to the technical scheme, Li salt-ionic liquid solution is injected into gaps of polyvinylidene fluoride-hexafluoropropylene, then the film is coated into a 50-micrometer film through a film coating machine, and vacuum drying is carried out at 125 ℃, so that the polyvinylidene fluoride-hexafluoropropylene/ionic liquid ionic gel electrolyte diaphragm with good ionic conductivity is finally obtained. The polymer prepared by taking polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) as a matrix not only has excellent mechanical property and thermal stability, but also has the advantage of good compatibility with ionic liquid, and meanwhile, the ionic gel electrolyte can also inhibit the formation of lithium dendrites in a lithium battery, so that the cycle stability and the ionic conductivity of an electrolyte diaphragm are greatly improved. In view of good performance and simple manufacturing process, the polyvinylidene fluoride-hexafluoropropylene/ionic liquid ionic gel electrolyte membrane synthesized by the method can be widely applied to the field of battery electrolyte membranes, and has important economic and social significance for the development of lithium ion battery electrolytes.
Compared with the prior art, the invention has the following outstanding effects:
(1) because the ionic liquid is non-volatile, high in thermal stability and high in ionic conductivity, the traditional liquid electrolyte is replaced, and the safety problem of the lithium battery is solved;
(2) the Li salt is mixed within the polymer with an ionic liquid which acts as a charge carrier and plasticizer in the gel, so the ionic conductivity of the electrolyte is relatively high, typically 10 at room temperature-4-10-3Scm-1Thereby effectively improving the cycle efficiency of the battery;
(3) the preparation process is simple, the material source is wide and economic, the cycle life and the cycle efficiency of the electrode are greatly improved, the requirement of the battery on the electrolyte diaphragm is met in practical application, and the electrode can be widely applied to electric vehicle storage batteries, mobile phone batteries, watch electronics and the like.
Description of the drawings:
fig. 1 is an SEM image of PVDF-HFP and ionic liquid based electrolyte separator example 1 of the present invention;
fig. 2 is an SEM image of PVDF-HFP and ionic liquid based electrolyte separator example 2 of the present invention;
fig. 3 is an SEM image of PVDF-HFP and ionic liquid based electrolyte separator example 3 of the present invention;
fig. 4 is an SEM image of PVDF-HFP and ionic liquid based electrolyte separator example 4 of the present invention.
The specific implementation mode is as follows:
the present invention is further described below with reference to examples, which are intended to illustrate and limit the scope of the claimed invention.
The electrolyte membrane prepared by the invention can be characterized by the following method: the appearance of the prepared electrode material can be scanned by a Scanning Electron Microscope (SEM).
Example 1
The electrolyte membrane based on PVDF-HFP and ionic liquid comprises the following components of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) powder, Li salt and ionic liquid, wherein the specific mixture ratio of the components is shown in the following table:
the preparation method of the electrolyte membrane based on PVDF-HFP and ionic liquid comprises the following steps:
(1) weighing 7% of Li salt and 73% of ionic liquid, and dissolving the Li salt in the ionic liquid to obtain a Li salt-ionic liquid solution with the concentration of 0.5 mol/L;
(2) mixing the Li salt-ionic liquid solution with polyvinylidene fluoride-hexafluoropropylene powder, and performing ultrasonic dispersion treatment for 30min at the frequency of 25KHz and the power of 400W to obtain a uniform co-dispersion body;
(3) coating the co-dispersion body on an aluminum foil through a film coating machine to form a thin film;
(4) drying the film for 10h under the drying condition of 127 ℃;
(5) and (3) quickly transferring the dried film into a glove box, and removing the film in the glove box to obtain the electrolyte diaphragm based on PVDF-HFP and ionic liquid.
The electrolyte separator based on PVDF-HFP and ionic liquid prepared as described above is shown in fig. 1, and it is seen from the figure that: the electrolyte membrane has high porosity, and the porous channels can add Li+Channels for transport of Li+Migration and conduction of electricity. The battery performance test shows that the electrolyte diaphragm based on PVDF-HFP and ionic liquid has good cycling stability, and the specific discharge capacity is 118.2mAH g after the 0.1C current density is charged and discharged for 100 times-1。
Example 2
The electrolyte membrane prepared based on PVDF-HFP and ionic liquid comprises the following components of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) powder, Li salt and ionic liquid, wherein the specific mixture ratio of the components is shown in the following table:
the preparation method of the electrolyte membrane prepared based on PVDF-HFP and ionic liquid comprises the following steps:
(1) weighing 6% of Li salt and 69% of ionic liquid, and dissolving the Li salt in the ionic liquid to obtain about 0.5mol/L of Li salt-ionic liquid solution;
(2) mixing the Li salt-ionic liquid solution with polyvinylidene fluoride-hexafluoropropylene powder, and performing ultrasonic dispersion treatment for 50min at the frequency of 20KHz and the power of 450W to obtain a uniform co-dispersion body;
(3) coating the co-dispersion body on an aluminum foil through a film coating machine to form a thin film;
(4) drying the film at 120 ℃ for 18 h;
(5) and (3) quickly transferring the dried film into a glove box, and removing the film in the glove box to obtain the electrolyte diaphragm based on PVDF-HFP and ionic liquid.
The electrolyte separator based on PVDF-HFP and ionic liquid prepared is shown in fig. 2, from which it can be seen that: the electrolyte membrane has high porosity, and the porous channels can add Li+Channels for transport of Li+Migration and conduction of electricity. The battery performance test shows that the electrolyte diaphragm based on PVDF-HFP and ionic liquid has good cycling stability, and the specific discharge capacity is 125.2mAH g after the 0.1C current density charging and discharging cycle is carried out for 100 times-1。
Example 3
The electrolyte membrane prepared based on PVDF-HFP and ionic liquid comprises the following components of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) powder, Li salt and ionic liquid, wherein the specific mixture ratio of the components is shown in the following table:
the preparation method of the electrolyte membrane based on PVDF-HFP and ionic liquid comprises the following steps:
(1) weighing 6% of Li salt and 64% of ionic liquid, and dissolving the Li salt in the ionic liquid to obtain 0.5mol/L of Li salt-ionic liquid solution;
(2) mixing the Li salt-ionic liquid solution with polyvinylidene fluoride-hexafluoropropylene powder, and performing ultrasonic dispersion treatment for 40min at the frequency of 26KHz and the power of 500W to obtain a uniform co-dispersion body;
(3) coating the co-dispersion body on an aluminum foil through a film coating machine to form a thin film;
(4) drying the film at 125 deg.C for 12 h;
(5) and (3) quickly transferring the dried film into a glove box, and removing the film in the glove box to obtain the electrolyte diaphragm based on PVDF-HFP and ionic liquid.
The electrolyte separator based on PVDF-HFP and ionic liquid prepared is shown in fig. 3, from which it can be seen that: the electrolyte membrane has high porosity, and the porous channels can add Li+Channels for transport of Li+Migration and conduction of electricity. The battery performance test shows that the electrolyte diaphragm based on PVDF-HFP and ionic liquid has good cycling stability, and the specific discharge capacity is 135.2mAH g after the 0.1C current density charging and discharging cycle is carried out for 100 times-1。
Example 4:
the electrolyte membrane prepared based on PVDF-HFP and ionic liquid comprises the following components of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) powder, Li salt and ionic liquid, wherein the specific mixture ratio of the components is shown in the following table:
the preparation method of the electrolyte membrane based on PVDF-HFP and ionic liquid comprises the following steps:
(1) weighing 5% of Li salt and 60% of ionic liquid, and dissolving the Li salt in the ionic liquid to obtain 0.5mol/L of Li salt-ionic liquid solution;
(2) mixing the Li salt-ionic liquid solution with polyvinylidene fluoride-hexafluoropropylene powder, and performing ultrasonic dispersion treatment for 45min at the frequency of 18KHz and the power of 550W to obtain a uniform co-dispersion body;
(3) coating the co-dispersion body on an aluminum foil through a film coating machine to form a thin film;
(4) drying the film for 14h under the drying condition of 123 ℃;
(5) and (3) quickly transferring the dried film into a glove box, and removing the film in the glove box to obtain the electrolyte diaphragm based on PVDF-HFP and ionic liquid.
The electrolyte separator based on PVDF-HFP and ionic liquid prepared is shown in fig. 4, from which it can be seen that: the electrolyte membrane has high porosity, and the porous channels can add Li+Channels for transport of Li+Migration and conduction of electricity. The battery performance test shows that the electrolyte diaphragm based on PVDF-HFP and ionic liquid has good cycling stability, and the specific discharge capacity is 138.2mAH g after the 0.1C current density charging and discharging cycle is carried out for 100 times-1。
The above description is only a preferred embodiment of the present invention, and the scope of the present invention should not be limited thereby, and all the simple equivalent changes and modifications made in the claims and the description of the present invention are within the scope of the present invention.
Claims (10)
1. The electrolyte membrane based on PVDF-HFP and ionic liquid is characterized by being prepared from the following components in percentage by mass:
20-35% of polyvinylidene fluoride-hexafluoropropylene powder
60-73% of ionic liquid
5-7% of Li salt.
2. The PVDF-HFP and ionic liquid based electrolyte separator as claimed in claim 1, wherein the ionic liquid is one of 1-ethyl-3-methylimidazole bis-trifluoromethanesulfonimide salt, 1-methyl-3-hexyl imidazole fluoromethylsulfonyl imide salt, 1-ethyl-3-methylimidazole tetrafluoroborate salt, 1-n-butyl-1-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt.
3. The PVDF-HFP and ionic liquid based electrolyte separator according to claim 2, wherein the Li salt is lithium bis (trifluoromethyl) sulfonimide.
4. The PVDF-HFP and ionic liquid based electrolyte membrane as claimed in claim 3, wherein the polyvinylidene fluoride-hexafluoropropylene powder is made from the following components in percentage by mass:
50-60% of polyvinylidene fluoride-hexafluoropropylene emulsion
3-10% of anion and cation exchange resin
30-45% of electrolyte.
The preparation method comprises the following steps:
(1) weighing the anion-cation exchange resin and the polyvinylidene fluoride-hexafluoropropylene emulsion according to the formula proportion, and mixing for 4-6 hours under the stirring action to form mixed emulsion;
(2) filtering the formed mixed emulsion to obtain viscous adsorbed polyvinylidene fluoride-hexafluoropropylene emulsion;
(3) dropwise adding electrolyte into the adsorbed polyvinylidene fluoride-hexafluoropropylene emulsion while stirring to prepare polyvinylidene fluoride-hexafluoropropylene gel;
(4) drying the polyvinylidene fluoride-hexafluoropropylene gel at 40-50 ℃;
(5) and (3) ball-milling the dried polyvinylidene fluoride-hexafluoropropylene gel by a ball mill, and screening powder below 60 microns by a sieve.
5. The PVDF-HFP and ionic liquid based electrolyte membrane as claimed in claim 5, wherein the polyvinylidene fluoride-hexafluoropropylene emulsion has a solid content of 25-50%; the electrolyte is a hydrochloric acid solution with the solution concentration of 0.1 mol/L.
6. The method for preparing the PVDF-HFP and ionic liquid based electrolyte separator according to claim 4, comprising the steps of:
(1) weighing Li salt and ionic liquid according to the formula proportion, and dissolving the Li salt in the ionic liquid to obtain a salt-ionic liquid solution;
(2) mixing the Li salt-ionic liquid solution with polyvinylidene fluoride-hexafluoropropylene powder, and performing ultrasonic dispersion for 30-50 min to obtain a uniform co-dispersion body;
(3) coating the co-dispersion body on an aluminum foil through a film coating machine to form a thin film;
(4) drying the film at the temperature of 120-130 ℃ for 8-15 h;
(5) and (3) quickly transferring the dried film into a glove box, and removing the film in the glove box to obtain the electrolyte diaphragm based on PVDF-HFP and ionic liquid.
7. The method for preparing the PVDF-HFP and ionic liquid based electrolyte separator according to claim 6, wherein the Li salt dissolution in the ionic liquid in the step (1) is performed in a glove box.
8. The method for preparing an electrolyte membrane based on PVDF-HFP and ionic liquid as defined in claim 6, wherein in the step (2), the ultrasonic treatment frequency is 10-30KHz and the power is 300-600W.
9. The method for preparing an electrolyte membrane based on PVDF-HFP and ionic liquid according to claim 8, wherein in the step (2), the ultrasonic treatment is performed at a frequency of 20KHz and a power of 450W.
10. The method for preparing the PVDF-HFP and ionic liquid based electrolyte separator according to claim 6, wherein in the (2) step, the film is dried at 125 ℃ for 12 hours.
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