CN117832604A - Solid polymer electrolyte membrane and preparation method thereof - Google Patents
Solid polymer electrolyte membrane and preparation method thereof Download PDFInfo
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- CN117832604A CN117832604A CN202311782259.1A CN202311782259A CN117832604A CN 117832604 A CN117832604 A CN 117832604A CN 202311782259 A CN202311782259 A CN 202311782259A CN 117832604 A CN117832604 A CN 117832604A
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- electrolyte membrane
- polyacrylic acid
- solid polymer
- polymer electrolyte
- polyethylene oxide
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- 239000012528 membrane Substances 0.000 title claims abstract description 40
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000007787 solid Substances 0.000 title claims abstract description 17
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 32
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 29
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 230000003472 neutralizing effect Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000005266 casting Methods 0.000 claims description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000009489 vacuum treatment Methods 0.000 claims description 3
- 239000000084 colloidal system Substances 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000007784 solid electrolyte Substances 0.000 abstract description 19
- 238000002156 mixing Methods 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000243 solution Substances 0.000 description 20
- 238000012360 testing method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Conductive Materials (AREA)
Abstract
The invention discloses a solid polymer electrolyte membrane and a preparation method thereof, wherein polyacrylic acid and polyethylene oxide are blended to prepare a high-performance polymer composite solid electrolyte membrane, and the solid polymer electrolyte membrane prepared by blending PEO and PAA by adopting the preparation method can reduce the crystallinity of polyethylene oxide PEO and can improve the upper limit of an electrochemical window to 4.8V; and has good interface compatibility with the battery anode and the metal lithium cathode.
Description
Technical Field
The invention belongs to the technical field of electrolyte membranes, and particularly relates to a solid polymer electrolyte membrane and a preparation method thereof.
Background
The lithium ion battery is the most advanced energy storage technology in the prior art, and has the advantages of high energy density, high voltage, environmental protection and the like. However, with the progress of society and science, people put higher demands on specific energy and safety performance of lithium ion batteries. Commercial lithium ion batteries often use liquid electrolytes with organic carbonates as the main solvent, and have narrow electrochemical windows and potential safety hazards such as leakage, combustion, and even explosion. The polymer solid electrolyte can obviously improve the safety of the lithium ion battery and has the advantages of light weight, good processability, good interface compatibility and the like.
Polyethylene oxide (PEO) solid state electrolytes are the most classical solid state polymer electrolytes with higher dielectric constants (epsilon=8), stronger Li + The dissolution ability and excellent thermoplasticity ensure that the thermoplastic material is manufactured into different shapes so as to meet the differential requirements of special application fields. However, the ethylene oxide solid electrolyte also has the following problems: (1) PEO system has high crystallinity and low ion conductivity at room temperature (10) -7 ～10 -8 S/cm); (2) Electrochemical window is narrow<4.0V), and is difficult to match with a high-voltage system.
The invention patent in China with application number 202010201848.6 discloses a solid polymer electrolyte and a preparation method thereof, wherein the solid polymer electrolyte is formed by carrying out free radical crosslinking reaction on polyethylene oxide, an auxiliary reagent and a photoinitiator under the condition of light irradiation, so that the electrolyte with a 3D space network structure is formed, the crystallinity of the polyethylene oxide is reduced, the amorphous area of the polyethylene oxide is increased, the transmission of lithium ions is accelerated, and the room temperature conductivity of the electrolyte is improved. However, light irradiation is needed in the preparation process, the preparation environment requirement is high, and the preparation cost is high.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a solid polymer electrolyte membrane and a preparation method thereof.
The invention adopts the following specific technical scheme:
a solid polymer electrolyte membrane made from the following raw materials: polyethylene oxide, polyacrylic acid, an alkaline neutralizer and lithium salt.
Preferably, the weight ratio of polyacrylic acid to polyethylene oxide is 0.02-0.07:1.
preferably, the alkaline neutralizer is selected from one or more of ammonia water, sodium hydroxide, lithium hydroxide or potassium hydroxide;
preferably, the molar ratio of the alkaline neutralizing agent to the polyacrylic acid is 0.25-0.75:1.
preferably, the lithium salt is selected from lithium bis (trifluoromethanesulfonyl) imide (LiTFSi), lithium hexafluorophosphate (LiPF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) One of the following;
preferably, the molar ratio of lithium salt to polyethylene oxide is from 16 to 18:1.
correspondingly, the invention also provides a preparation method of the solid polymer electrolyte membrane, which comprises the following steps:
s1, adding polyacrylic acid into ultrapure water, and slowly stirring until the polyacrylic acid is uniformly dispersed to form a pale yellow solution;
s2, adding the alkaline neutralizer into the pale yellow solution obtained in the step S1, and stirring for 1-2 h;
s3, adding polyethylene oxide into the solution obtained in the step S2, and stirring until a colloidal solution which is uniformly dispersed and has no floccules is formed;
s4, adding lithium salt into the colloid solution obtained in the step S3, stirring for 3-5 hours to obtain a precursor solution, and performing ultrasonic dispersion on the precursor solution for 15-30 min;
s5, pouring the precursor solution subjected to ultrasonic treatment into a die for casting, and vacuumizing after leveling to remove bubbles generated in the casting process;
s6, placing the solution subjected to vacuum treatment and the mold in an oven to slowly dry at a low temperature of 30-40 ℃ and slowly remove most of water; then the temperature is increased to 55 ℃ to 60 ℃ and the drying is continued for 8h to 12h;
s7, vacuum drying treatment is carried out, residual moisture is removed, and an electrolyte membrane sample is obtained.
Preferably, the preparation method further comprises the step of placing the electrolyte membrane sample in an environment with the water oxygen content lower than 50PPm and standing for 24-72 h. The electrolyte membrane is further removed from water, so that the electrolyte membrane has certain mechanical properties.
Preferably, the slow stirring rate in the step S1 is 250 revolutions per minute, and the weight ratio of the polyacrylic acid to the ultrapure water is as follows: 1:25-30.
Preferably, the stirring rate in step S2 is 400 revolutions per minute; the stirring speed in the step S3 is 450 revolutions per minute; the stirring rate in step S4 was 450 rpm.
Preferably, the vacuum is applied to-0.08 MPa to 0MPa in step S5 for 10min to remove bubbles generated during the casting process.
Preferably, in the step S6, the mixture is slowly dried for 8-12 hours at a low temperature of 30-40 ℃ to slowly remove most of water; step S7, vacuum drying treatment is to vacuum dry at 60 ℃ for 48-72 h.
The beneficial effects of the invention are as follows:
polyacrylic acid (PAA) is a high polymer material with excellent comprehensive performance, high temperature resistance and a melting point of about 300 ℃, the difference between the melting point and polyethylene oxide is large, and the purposes of reducing the crystallinity of the polyethylene oxide and improving the ionic conductivity can be realized by blending the two materials. However, the two have larger melting point difference, so that the phase separation is easy to occur in direct blending. In order to better fuse polyacrylic acid and polyethylene oxide, the rheological property of the mixture is improved, and the mixture is convenient for later pouring and film forming. After a large number of experiments, the invention discovers that PAA-X (X=NH) with better rheological property can be formed by adding a certain proportion of alkaline neutralizer into polyacrylic acid and utilizing the alkaline neutralizer to promote the molecular chain development of the polyacrylic acid 4 One or more of Li, na and K ions) and PAA, and then selecting a proper blending proportion, and blending the mixture with PEO can solve the problem that the direct blending is easy to generate phase separation.
The solid polymer electrolyte membrane prepared by blending PEO and PAA by adopting the preparation method can reduce the crystallinity of polyethylene oxide PEO and can improve the upper limit of an electrochemical window to 4.8V; and has good interface compatibility with the battery anode and the metal lithium cathode.
Drawings
FIG. 1 is a photograph of solid electrolyte membrane of example 2, comparative example 4, comparative example 5
FIG. 2 is the LSV test results of example 2;
FIG. 3 shows the ionic conductivity results of examples 1-3 and comparative example 3;
FIG. 4 is a first charge-discharge curve of examples 1-3 and comparative example 3;
FIG. 5 is a cycle performance curve of examples 1-3 and comparative example 3.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
A method for preparing a polymer composite solid electrolyte membrane, comprising the steps of:
(1) 0.7g of PAA was added to ultra pure water and stirred slowly at 250 rpm until the polyacrylic acid was dispersed uniformly to form a pale yellow solution. Wherein the mass of ultrapure water is 25/1 in terms of the ultrapure water/PEO mass ratio);
(2) 0.340g of ammonia water was added to the solution obtained in step 1, and the mixed solution was stirred at 400 rpm for 1 hour.
(3) 13.300g PEO is added into the solution in the step 2 and stirred for 2 hours at 450 r/min to form a colloidal solution which is uniformly dispersed and has no floccules;
(4) 4.800g of lithium bistrifluoromethane sulfonyl imide (LiTFSI) is added into the solution in the step 3, the solution is stirred for 3 hours at 450 r/min to obtain a precursor solution, the solution is subjected to ultrasonic dispersion for 15min, the dissolution is accelerated, and most of bubbles are removed;
(5) Pouring the solution obtained in the step 4 into a die for casting, and vacuumizing to-0.08 MPa after leveling for 10min so as to remove bubbles generated in the casting process;
(6) The solution after the vacuum treatment and the mould are placed in a blast oven to be slowly dried for 10 hours at the low temperature of 35 ℃ to slowly remove most of water; the temperature was then raised to 55℃and drying was continued for 12h.
(7) The electrolyte membrane was vacuum dried at 60 ℃ for 48 hours to remove residual moisture in the electrolyte material.
(8) Placing the sample in an environment with the water oxygen content lower than 10PPm, standing for 72h, and cutting the electrolyte membrane into small discs with the diameter of 18mm for later use.
Examples 2 to 3
The raw materials for preparing the solid electrolyte membranes described in examples 2 and 3 are shown in table 1; the preparation method and the test method of the solid electrolyte membrane described in examples 2 and 3 are the same as in example 1.
Table 1: example composition of solid electrolyte film
| Sample numbering | Example 1 | Example 2 | Example 3 |
| PEO | 13.300g | 13.300g | 13.300g |
| PAA | 0.700g | 0.700g | 0.700g |
| NH.H 2 O | 0.340g | 0.680g | 1.020g |
| LiTFSI | 4.800g | 4.800g | 4.800g |
Comparative examples 1 to 5
The raw materials for preparing the solid electrolyte membranes described in comparative examples 1 to 5 are described in table 2; comparative example the method for preparing and testing a solid electrolyte membrane was conducted with reference to example 1, except that the preparation step containing a certain component was removed accordingly if that component was not present.
Table 2 comparative examples 1 to 5 composition of solid electrolyte membranes
| Sample numbering | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| PEO | 13.300g | 13.300g | 13.300g | 13.300g | 13.300g |
| PAA | 0 | 0.140g | 0.700g | 0.700g | 1.340g |
| NH.H 2 O | 0 | 0 | 0 | 1.35g | 0 |
| LiTFSI | 4.800g | 4.800g | 4.800g | 4.800g | 4.800g |
From the external appearance, the solid electrolyte membranes prepared in the above examples and comparative examples were inferior in film forming property and better in all of the other examples (Table 3).
The solid electrolyte membranes of examples 1-3 and comparative examples 1-3 (good film forming properties) were tested as follows:
(1) And (3) putting a stainless Steel Sheet (SS), a solid electrolyte membrane, the stainless Steel Sheet (SS), a gasket and an elastic sheet into the positive electrode shell, covering the negative electrode shell, placing the positive electrode shell on a hydraulic press for pressure maintaining, taking out, placing the positive electrode shell in a 60 ℃ oven for 12 hours, and taking out to obtain the SS/composite solid electrolyte/SS button cell. EIS test of SS/composite solid electrolyte/SS button cell at electrochemical workstation with test frequency range of 10 6 Hz-10 -1 Hz. The LSV test results showed that: the solid electrolyte membrane test ranges of examples 1-3 are 2-6V and fig. 2 is the LSV test results of example 2.
(2) Weighing LiFePO4, acetylene black and polyvinylidene fluoride PVDF in a mass ratio of 8:1:1, mixing, adding N-methylpyrrolidone (NMP), and stirring, wherein 1g of acetylene black corresponds to 30-60ml of NMP, so as to obtain uniform slurry; pouring the uniform slurry on aluminum foil, vacuum drying at 110deg.C for 12 hr, and cutting into round pieces with diameter of 12mm to obtain LiFePO 4 And a positive pole piece.
And sequentially placing the LiFePO4 anode, the solid electrolyte, the lithium sheet, the gasket and the elastic sheet into an anode shell, finally covering a cathode shell, placing the anode shell on a hydraulic press, maintaining the pressure, taking out the anode shell, and placing the anode shell at 60 ℃ for 12h for heat curing to obtain the solid-state battery.
The solid-state battery was subjected to constant current charge-discharge test and cycle performance test, and the battery was charged to 3.8V, discharged to 2.8V, and the rate was 0.1C (1c=170 mAg -1 ). The results are shown in Table 3 and FIGS. 3-5.
Table 3 film Forming Properties, ion conductivity, and highest Voltage Window for examples 1-3 and comparative examples 1-5
According to the invention, through a large number of experiments, the addition amounts of polyacrylic acid and an alkaline neutralizer are optimized, and a preparation process adapting to the formula is developed according to the optimized formula; finally, the polymer solid electrolyte membrane with high voltage resistance and high ionic conductivity is prepared.
From the physical diagram of fig. 1, it can be seen that the film forming property of the electrolyte film can be judged simply by observing the surface of the physical film. Wherein the polymer film with good film forming property has smooth surface and uniform polymer film as in example 2. The polymer surface of comparative example 5 showed a remarkable phase separation phenomenon. From a combination of Table 1, table 2, table 3 and FIG. 1, it can be determined that the weight ratio of polyacrylic acid to polyethylene oxide is 0.02-0.07:1 can prepare electrolyte membranes with good performances. An excessive amount of polyacrylic acid, such as comparative example 5, causes a remarkable phase separation phenomenon. Too little, as in comparative example 2, has no significant effect on enhancing ion conductance.
As can be seen from table 3 and fig. 2 to 5, in examples 1 to 3 in which the alkaline neutralizing agent was added, the electrolyte membrane had a higher voltage window than in comparative example 3 in which the alkaline neutralizing agent was not added, and as shown in fig. 2, the highest voltage window of example 2 was 4.8V. As shown in Table 3, examples 1-3 with the alkaline neutralizing agent added have better ionic conductivity than comparative example 3 without the alkaline neutralizing agent added. The electrolyte membrane of examples 1 to 3 was used to assemble a battery, and the capacity and cycle performance of the battery were both superior to those of example 3 in which no neutralizing agent was added. This benefits from the addition of the alkaline neutralizing agent, which promotes better fusion of the polyacrylic acid with the polyethylene oxide, reducing the crystallinity of the polyethylene oxide. When the alkali neutralizing agent is excessively added, as in comparative example 4 (fig. 1), the film forming property of the electrolyte film is deteriorated. Thus, the suitable molar ratio of alkaline neutralizing agent to polyacrylic acid is from 0.25 to 0.75:1.
while the embodiments have been described above, other variations and modifications will occur to those skilled in the art once the basic inventive concepts are known, and it is therefore intended that the foregoing description and drawings illustrate only embodiments of the invention and not limit the scope of the invention, and it is therefore intended that the invention not be limited to the specific embodiments described, but that the invention may be practiced with their equivalent structures or with their equivalent processes or with their use directly or indirectly in other related fields.
Claims (10)
1. A solid polymer electrolyte membrane characterized by being made from the following raw materials: polyethylene oxide, polyacrylic acid, an alkaline neutralizer and lithium salt.
2. The solid polymer electrolyte membrane of claim 1 wherein the weight ratio of polyacrylic acid to polyethylene oxide is from 0.02 to 0.07:1.
3. the solid polymer electrolyte membrane according to claim 1, wherein the alkaline neutralizing agent is selected from one or more of ammonia water, sodium hydroxide, lithium hydroxide or potassium hydroxide; and/or the molar ratio of the alkaline neutralizer to the polyacrylic acid is 0.25-0.75:1.
4. the solid polymer electrolyte membrane according to claim 1, wherein the lithium salt is selected from one of lithium bistrifluoromethane sulfonyl imide, lithium hexafluorophosphate, lithium tetrafluoroborate; and/or the molar ratio of the lithium salt to polyethylene oxide is 16-18:1.
5. a method for producing the solid polymer electrolyte membrane according to claim 1 or 2 or 3, comprising the steps of:
s1, adding polyacrylic acid into ultrapure water, and slowly stirring until the polyacrylic acid is uniformly dispersed to form a pale yellow solution;
s2, adding the alkaline neutralizer into the pale yellow solution obtained in the step S1, and stirring for 1-2 h;
s3, adding polyethylene oxide into the solution obtained in the step S2, and stirring until a colloidal solution which is uniformly dispersed and has no floccules is formed;
s4, adding lithium salt into the colloid solution obtained in the step S3, stirring for 3-5 hours to obtain a precursor solution, and performing ultrasonic dispersion on the precursor solution for 15-30 min;
s5, pouring the precursor solution subjected to ultrasonic treatment into a die for casting, and vacuumizing after leveling to remove bubbles generated in the casting process;
s6, placing the solution subjected to vacuum treatment and the mold in an oven to slowly dry at a low temperature of 30-40 ℃ and slowly remove most of water; then the temperature is increased to 55 ℃ to 60 ℃ and the drying is continued for 8h to 12h;
s7, vacuum drying treatment is carried out, residual moisture is removed, and an electrolyte membrane sample is obtained.
6. The method of claim 5, further comprising placing the electrolyte membrane sample in an environment having a water oxygen content of less than 50PPm, and allowing the electrolyte membrane sample to stand for 24 hours to 72 hours.
7. The method according to claim 5 or 6, wherein the slow stirring rate in step S1 is 250 rpm, and the weight ratio of the polyacrylic acid to the ultrapure water is: 1:25-30.
8. The method according to claim 5 or 6, wherein the stirring rate in step S2 is 400 rpm; the stirring speed in the step S3 is 450 revolutions per minute; the stirring rate in step S4 was 450 rpm.
9. The method according to claim 5 or 6, wherein the vacuum is applied to-0.08 MPa-0MPa in step S5 for 10min to remove bubbles generated during the casting process.
10. The preparation method according to claim 5 or 6, wherein in step S6, the water is slowly removed by slow drying at 30 ℃ to 40 ℃ for 8 hours to 12 hours; step S7, vacuum drying treatment is to vacuum dry at 60 ℃ for 48-72 h.
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