CN111564664A - Method for preparing battery polymer electrolyte film by using polyethylene glycol and paper pulp as matrix gel method - Google Patents
Method for preparing battery polymer electrolyte film by using polyethylene glycol and paper pulp as matrix gel method Download PDFInfo
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- CN111564664A CN111564664A CN202010416589.9A CN202010416589A CN111564664A CN 111564664 A CN111564664 A CN 111564664A CN 202010416589 A CN202010416589 A CN 202010416589A CN 111564664 A CN111564664 A CN 111564664A
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- 239000002202 Polyethylene glycol Substances 0.000 title claims abstract description 80
- 229920001223 polyethylene glycol Polymers 0.000 title claims abstract description 77
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 58
- 229920001131 Pulp (paper) Polymers 0.000 title claims abstract description 47
- 239000011159 matrix material Substances 0.000 title claims abstract description 19
- 230000001815 facial effect Effects 0.000 claims description 44
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 33
- 239000011521 glass Substances 0.000 claims description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 229920002678 cellulose Polymers 0.000 claims description 18
- 239000001913 cellulose Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- 238000005266 casting Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 229960000583 acetic acid Drugs 0.000 claims description 9
- 239000012362 glacial acetic acid Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000007790 scraping Methods 0.000 claims description 4
- 230000002195 synergetic effect Effects 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 2
- 239000003755 preservative agent Substances 0.000 claims description 2
- 230000002335 preservative effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000007796 conventional method Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 62
- 210000001519 tissue Anatomy 0.000 description 36
- 238000012360 testing method Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000007605 air drying Methods 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 210000001724 microfibril Anatomy 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention relates to a method for preparing a polymer electrolyte film by using polyethylene glycol and paper pulp as a matrix gel method, which relates to a method for preparing a battery polymer electrolyte film and solves the problems of high cost, high safety and the like of the conventional method for preparing the battery polymer electrolyte film‑3S·cm‑1And greatly saves the production cost, and has the characteristics of short period, simple operation, safety and the likeAnd is very suitable for preparing polymer electrolyte films on a large scale. The invention is applied to the field of battery polymer electrolyte films.
Description
Technical Field
The present invention relates to a method of preparing a battery polymer electrolyte membrane.
Background
The gel method is a relatively simple and cheap method for preparing the polymer electrolyte film of the battery, and the additiveThe polyethylene glycol is widely applied to chemical research, pharmaceutical industry, cosmetic industry, food industry and the like, is widely applied with the rapid development of scientific technology and the increasing attention and concern of environmental pollution in various countries around the world, the demand for renewable and degradable materials is increased, natural cellulose is a good material, has low price and wide source, and can be used as a sustainable development resource to develop and research by combining the advantages of the two, the paper pulp takes facial tissue purchased in the market as a raw material, the cellulose in the paper pulp is extracted, and the paper pulp and the battery polymer electrolyte film prepared by the polyethylene glycol through a gel method reach 2.28 × 10-3S·cm-1The polymer electrolyte film starts to decompose at 110 ℃ and the complete decomposition temperature is 800 ℃, so that good thermal stability is obtained.
Disclosure of Invention
The invention aims to solve the problems of high cost, safety and the like of the battery polymer electrolyte film prepared by the existing method, and provides a method for preparing the battery polymer electrolyte film by using a gel method with polyethylene glycol and paper pulp as matrixes.
The method for preparing the battery polymer electrolyte film by using the polyethylene glycol and paper pulp as the matrix gel method is carried out according to the following steps:
firstly, pretreating face tissues for later use by pretreating the pulp;
secondly, preparation of paper pulp
Adding a certain amount of polyethylene glycol into the pretreatment liquid of the facial tissue obtained in the step one, placing a beaker on a magnetic stirrer, and stirring for a certain time to obtain paper pulp for later use;
preparation of polymer electrolyte film
Pouring the paper pulp obtained in the step two into a weighing bottle, adding a certain amount of lithium hydroxide, stirring for 1.5-2 hours to obtain a casting solution, casting the obtained casting solution on a clean glass plate, uniformly and flatly coating the clean glass plate on the surface of glass by using a scraper, putting the glass plate into a blast drying oven, and drying for 4-5 hours at a certain temperature;
fourthly, heat treatment of the polymer electrolyte film
And (3) taking out the glass plate in the third step, putting the glass plate into a vacuum drying oven, continuously drying the glass plate for a certain time at a certain temperature, taking out the glass plate, and scraping the film to finish the preparation of the polymer electrolyte film by using the polyethylene glycol and paper pulp as matrix gel method.
Wherein the dosage of the facial tissue in the step one is 0.41-0.49 g.
Wherein the dosage of the polyethylene glycol in the step two is 0.5-5 g, and the stirring time is 3-4 h.
Wherein the mass ratio of the lithium hydroxide added in the step three to the pulp mass is 5:1, and the temperature of the air drying oven is set to be 60 ℃.
Wherein, the temperature of the drying oven in the fourth step is 120 ℃, and the drying time is 1.5-2 h.
The invention has the following beneficial effects:
the invention adopts a gel method to prepare the battery polymer electrolyte film, focuses on the consideration of the influence of the process conditions and the raw material ratio in the gel method on the preparation of the battery polymer electrolyte film, including the influence of the dosage of polyethylene glycol and facial tissue on the conductivity and the thermal stability of the film, the invention uses the polyethylene glycol and paper pulp as the matrix to prepare the battery polymer electrolyte film by the gel method, the optimal mass ratio of the facial tissue to the polyethylene glycol is 41: 100, the conductivity reaches the highest at the moment, and the value is 2.28 × 10-3S·cm-1It opens up a new way for obtaining polymer electrolyte film with high performance and low cost.
The invention prepares the battery polymer electrolyte film by using polyethylene glycol and paper pulp as a matrix gel method, glacial acetic acid is added during the pretreatment of the paper pulp, and the mass ratio of the glacial acetic acid to the facial tissue is 1: 41-1: and 49, carboxyl in a proper amount of glacial acetic acid is a strong electron-withdrawing group, so that hydrogen bonds among cellulose molecules in the facial tissue are effectively destroyed, and then rigid insoluble microfibrils are formed, the effect of effectively dissolving cellulose is achieved, and better stability is provided for subsequent film forming. The invention can prepare the solid electrolyte membrane with self-support and mechanical strength without using any binder, thus the lithium ion migration process is not hindered by the binder, high conductivity can be ensured, and the solid electrolyte membrane has good compatibility with the electrode, and simultaneously, the process is simple and easy to operate.
The invention prepares the battery polymer electrolyte film by a gel method with polyethylene glycol and paper pulp as matrixes, wherein the mass ratio of the added polyethylene glycol to the facial tissue is 50: 41-500: 41, the polyethylene glycol can change the interaction of each component in the membrane casting solution, the viscosity of the system is improved, when the polyethylene glycol is too little, the viscosity of the system is not enough, and the membrane cannot be formed, when the polyethylene glycol is too much, the viscosity value of the system is linearly increased along with the increase of the concentration of the polyethylene glycol, so that the gelation speed is reduced, the subsequent membrane forming effect is insufficient, and the impedance of the prepared polymer electrolyte membrane is increased, so that the conductivity is reduced. The polyethylene glycol acts as a film-forming agent, and has a synergistic effect with the pulp to form a polymer electrolyte film with low crystallinity.
The invention adopts the gel method to prepare the battery polymer electrolyte film, not only greatly saves the production cost, but also has the characteristics of high speed, simple operation, safety and the like, and is very suitable for preparing the polymer electrolyte film on a large scale.
The invention adopts the anhydrous glacial acetic acid as the solvent, can well dissolve the cellulose in the facial tissue to obtain the slurry, and the polymer electrolyte film obtained by subsequent preparation is uniform in texture and white, thereby providing a simple and convenient method for dissolving and extracting the cellulose.
Drawings
FIG. 1 is a film appearance diagram of a battery polymer electrolyte film prepared by a gel method using polyethylene glycol and paper pulp as matrixes.
FIG. 2 is an infrared spectrum of a battery polymer electrolyte film prepared by a gel method using polyethylene glycol and paper pulp as matrixes.
FIG. 3 is a thermogravimetric plot of a gel method for preparing a polymer electrolyte film of a battery by using polyethylene glycol and paper pulp as matrixes.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
One of the specific implementation modes is as follows: the method for preparing the battery polymer electrolyte film by using the polyethylene glycol and paper pulp as the matrix gel method is carried out according to the following steps:
firstly, pretreating face tissues for later use by pretreating the pulp;
secondly, preparation of paper pulp
Adding a certain amount of polyethylene glycol into the pretreatment liquid of the facial tissue obtained in the step one, placing a beaker on a magnetic stirrer, and stirring for a certain time to obtain paper pulp for later use;
preparation of polymer electrolyte film
Pouring the paper pulp obtained in the step two into a weighing bottle, adding a certain amount of lithium hydroxide, stirring for 1.5-2 hours to obtain a casting solution, casting the obtained casting solution on a clean glass plate, uniformly and flatly coating the clean glass plate on the surface of glass by using a scraper, putting the glass plate into a blast drying oven, and drying for 4-5 hours at a certain temperature;
fourthly, heat treatment of the polymer electrolyte film
And (3) taking out the glass plate in the third step, putting the glass plate into a vacuum drying oven, continuously drying the glass plate for a certain time at a certain temperature, taking out the glass plate, and scraping the film to finish the preparation of the polymer electrolyte film by using the polyethylene glycol and paper pulp as matrix gel method.
Wherein the dosage of the facial tissue in the step one is 0.41-0.49 g.
Wherein the dosage of the polyethylene glycol in the step two is 0.5-5 g, and the stirring time is 3-4 h.
Wherein the mass ratio of the lithium hydroxide added in the step three to the pulp mass is 5:1, and the temperature of the air drying oven is set to be 60 ℃.
Wherein, the temperature of the vacuum drying oven in the fourth step is 120 ℃, and the drying time is 1.5-2 h.
The invention adopts a gel method, prepares the battery polymer electrolyte film by using a polyethylene glycol and paper pulp as matrix gel method, and mainly inspects the influence of the process conditions in the gel method on the preparation of the battery polymer electrolyte film, including the influence of the dosage of the polyethylene glycol and the facial tissue on the conductivity and the thermal stability of the film-3S·cm-1It opens up a new way for obtaining polymer electrolyte film with high performance and low cost.
The invention uses the gel method and uses the polyethylene glycol and the paper pulp as the matrix to prepare the battery polymer electrolyte film, thereby not only greatly saving the production cost, but also having the characteristics of high speed, simple operation, safety and the like, and being very suitable for preparing the polymer electrolyte film on a large scale.
The invention uses the anhydrous glacial acetic acid as the solvent, can well dissolve the cellulose in the facial tissue to obtain the slurry, and the polymer electrolyte film obtained by subsequent preparation is uniform in texture and white, thereby providing a simple and convenient method for dissolving and extracting the cellulose.
The second embodiment is as follows: the first embodiment differs from the first embodiment in that: the dosage of the polyethylene glycol in the second step is 0.5 g. The rest is the same as in one of the embodiments.
The third concrete implementation mode: the implementation differs from the first or second embodiment in that: the dosage of the polyethylene glycol in the second step is 2 g. The others are the same as in the first or second embodiment.
The fourth concrete implementation mode: the present embodiment is different from one of the first to third embodiments in that: the dosage of the polyethylene glycol in the second step is 3 g. The rest is the same as one of the first to third embodiments.
The fifth concrete implementation mode: the present embodiment differs from one of the first to fourth embodiments in that: the dosage of the polyethylene glycol in the second step is 4 g. The rest is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: the dosage of the polyethylene glycol in the second step is 5 g. The rest is the same as one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: and (3) under the premise of determining the dosage of the polyethylene glycol to be 1g, the dosage of the facial tissue in the step one is 0.43 g. The rest is the same as one of the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: and (3) under the premise of determining the dosage of the polyethylene glycol to be 1g, the dosage of the facial tissue in the step one is 0.45 g. The rest is the same as one of the first to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: and (3) under the premise of determining the dosage of the polyethylene glycol to be 1g, the dosage of the facial tissue in the step one is 0.47 g. The rest is the same as the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: and (3) under the premise of determining the dosage of the polyethylene glycol to be 1g, the dosage of the facial tissue in the step one is 0.49 g. The rest is the same as one of the first to ninth embodiments.
The beneficial effects of the invention are verified by the following tests:
first, pretreatment of paper pulp
Taking one layer of the facial tissue, cutting the facial tissue into pieces, putting the cut facial tissue into a dry beaker, adding 10ml of glacial acetic acid, putting the beaker into a rotor, covering the rotor with a preservative film, and standing for 24 hours.
Secondly, preparation of paper pulp
Adding a certain amount of polyethylene glycol into the pretreatment liquid of the facial tissue obtained in the step one, placing the beaker on a magnetic stirrer, and stirring for a certain time;
preparation of polymer electrolyte film
Pouring the paper pulp obtained in the step two into a weighing bottle, adding a certain amount of lithium hydroxide, stirring for 1.5-2 hours to obtain a casting solution, casting the obtained casting solution on a clean glass plate, uniformly and flatly coating the clean glass plate on the surface of glass by using a scraper, putting the glass plate into a blast drying oven, and drying for 4-5 hours at a certain temperature;
fourthly, heat treatment of the polymer electrolyte film
And (3) taking out the glass plate in the third step, putting the glass plate into a vacuum drying oven, continuously drying the glass plate for a certain time at a certain temperature, taking out the glass plate, and scraping the film to finish the preparation of the polymer electrolyte film by using the polyethylene glycol and paper pulp as matrix gel method.
Wherein the dosage of the facial tissue in the step one is 0.41-0.49 g.
Wherein the dosage of the polyethylene glycol in the step two is 0.5-5 g, and the stirring time is 3-4 h.
Wherein the mass ratio of the lithium hydroxide added in the step three to the pulp mass is 5:1, and the temperature of the air drying oven is set to be 60 ℃.
Wherein, the temperature of the vacuum drying oven in the fourth step is 120 ℃, and the drying time is 1.5-2 h.
The appearance of the polymer electrolyte membrane prepared by the gel method using polyethylene glycol and paper pulp as the matrix in the test is shown in figure 1, and the figure 1 shows that the prepared polymer electrolyte membrane is uniform in texture and white. The glacial acetic acid solvent of the paper pulp has the functions of dissolution, protonation and pore-forming, and has low boiling point, is easy to volatilize and does not remain. The lithium hydroxide and the cellulose form hydrogen bonds with a synergistic effect, and the lithium hydroxide and the cellulose have the effect of improving the lithium ion conductivity in the polymer electrolyte.
By analyzing the usage amount of the polyethylene glycol and the facial tissue in the test, the influence of different parameters on the conductivity of the polymer electrolyte thin film is examined, and the method specifically comprises the following steps:
1) influence of polyethylene glycol addition on conductivity of polymer electrolyte film
And (3) changing the addition of the polyethylene glycol in the second step of the test, keeping other parameters unchanged, preparing the polymer electrolyte film according to the test method, and inspecting the influence of the addition of the polyethylene glycol on the conductivity of the polymer electrolyte film. And respectively clamping the scraped films in the middle of a positive and negative electrode shell of the battery, clamping the four tested clamps on the positive and negative electrode shells in different surfaces and different edges, and testing on an electrochemical workstation. The calculation formula of the conductivity is shown as the following formula:
σ＝d/(Rb×A)
wherein σ represents the conductivity of the electrolyte thin film and has a unit of S · cm-1，RbRepresents the measured resistance of the electrolyte film in Ω; a represents the area of the electrode in cm2(ii) a d represents the thickness of the electrolyte thin film in cm. 1.5386cm are taken in the experiment A2The results are shown in table 1 below.
Table 1:
table 1 shows the measured conductivity of the polymer electrolyte membranes prepared with 0.5g, 1g, 2g, 3g, 4g and 5g of polyethylene glycol, respectively, and it can be seen that the conductivity of the membranes initially increases with the addition of polyethylene glycol, and when 1g of polyethylene glycol is added, the conductivity of the membranes is at a maximum and reaches 2.28 × 10-3S·cm-1When the mass of the added polyethylene glycol is more than 1g, the conductivity of the film is reduced along with the increase of the polyethylene glycol, the polyethylene glycol is used as a film forming agent, the viscosity of the system can be improved, so that the stability of the film forming system is improved, and the natural logarithm value of the viscosity value of the film forming agent is linearly increased along with the increase of the concentration of the polyethylene glycol; after the polyethylene glycol is added, the gelation speed is reduced along with the increase of the viscosity of the casting solution, so that the cellulose in paper pulp cannot be combined quickly in the film gelation process, and the polyethylene glycol in the film is too much to play a role of electric conduction, so that the electric conductivity is increased. Therefore, the invention selects 1g of polyethylene glycol as the optimal polyethylene glycol addition.
2) Effect of facial tissue addition on Polymer electrolyte Membrane conductivity
After the optimal polyethylene glycol addition amount is determined to be 1g, the quality of the facial tissue and other parameter conditions are unchanged in the paper pulp pretreatment in the first test step, then the polymer electrolyte film is prepared according to the test method, the influence of the addition amount of the facial tissue on the conductivity of the polymer electrolyte film is examined, and the results are shown in the following table 2.
Table 2:
table 2 shows conductivity tables of the polymer electrolyte films prepared by adding the facial tissues in amounts of 0.41g, 0.43g, 0.45g, 0.47g and 0.49g, respectively, and it can be seen from Table 2 that the conductivity gradually decreases with the increase of the facial tissue mass, wherein the resistance is 9.234 Ω at the minimum and the conductivity is 2.28 × 10 Ω at the maximum when the facial tissue mass is 0.41g-3S·cm-1This is because the amount of cellulose in the facial tissue is too large, the cellulose cannot be sufficiently dissolved by glacial acetic acid, the pulp resistance increases, and the conductivity gradually decreases, so that the addition of 0.41g of the facial tissue mass was selected as the optimum facial tissue addition amount for the test.
Combining the influence of the addition of polyethylene glycol and facial tissue on the conductivity of a polymer electrolyte thin film, selecting the mass ratio of the facial tissue to the polyethylene glycol as 41: 100 was used as the optimum addition ratio for the test.
FIG. 2 is an infrared spectrum image of a battery polymer electrolyte film prepared by a gel method with polyethylene glycol and paper pulp as matrixes, and 3441cm can be seen from the image-1Corresponding to the stretching vibration of-OH of polyethylene glycol, 2875cm-1Corresponding to-CH of polyethylene glycol3，1110cm-1Symmetric contraction vibration of-C-O-C-corresponding to polyethylene glycol, 962cm-1In-plane deformation vibration-CH of-C-O-C-corresponding to polyethylene glycol2C-H stretching vibration of-medium, 830cm-1Corresponding to-CH of polyethylene glycol2CH2O-in-plane deformation vibration. As can be seen, 1705cm in the figure-1The C ═ O stretching vibration in cellulose is correspondingly weakened, and the C ═ O stretching vibration in the cellulose in the infrared spectrum of the polyethylene glycol-pulp film is weakened, which indicates that the cellulose is the main group of the filmOne of them. Meanwhile, the carbonyl C ═ O in the cellulose and the hydroxyl in the polyethylene glycol are compatible with each other, so that block compatibility of lithium ion transmission can be formed, and carbon in the carbonyl is an electron-withdrawing atom and repels lithium ions; the oxygen in the polyethylene glycol has nucleophilicity and attractive ions, and the staggered arrangement of the two functional groups in the matrix can not only destroy the ordered arrangement of hydrogen bonds in the paper pulp and reduce the crystallinity, but also can promote lithium ions to migrate between the two functional groups and improve the conductivity of the polymer electrolyte.
Fig. 3 is a thermogravimetric curve image of a battery polymer electrolyte film prepared by a gel method using polyethylene glycol and paper pulp as matrixes, and it can be seen from the thermogravimetric curve image that the polymer electrolyte film starts to decompose at 110 ℃ and has a complete decomposition temperature of 800 ℃, and therefore, the polymer electrolyte film has good thermal stability and is suitable for being used as an electrolyte diaphragm.
Claims (5)
1. The method for preparing the battery polymer electrolyte film by using the polyethylene glycol and paper pulp as matrix gel method is characterized in that the method for preparing the battery polymer electrolyte film by using the polyethylene glycol and paper pulp as matrix gel method is carried out according to the following steps:
first, pretreatment of paper pulp
Pretreating facial tissue for later use;
secondly, preparation of paper pulp
Adding a certain amount of polyethylene glycol into the pretreatment liquid of the facial tissue obtained in the step one, placing a beaker on a magnetic stirrer, and stirring for a certain time to obtain paper pulp for later use;
preparation of polymer electrolyte film
Pouring the paper pulp obtained in the step two into a weighing bottle, adding a certain amount of lithium hydroxide, stirring for 1.5-2 hours to obtain a casting solution, casting the obtained casting solution on a clean glass plate, uniformly and flatly coating the clean glass plate on the surface of glass by using a scraper, putting the glass plate into a blast drying oven, and drying for 4-5 hours at a certain temperature;
fourthly, heat treatment of the polymer electrolyte film
Taking out the glass plate in the third step, putting the glass plate into a vacuum drying oven, continuously drying the glass plate for a certain time at a certain temperature, taking out the glass plate, and scraping the film to finish the preparation of the polymer electrolyte film by using the polyethylene glycol and paper pulp as matrix gel method;
wherein the dosage of the facial tissue in the step one is 0.41-0.49 g;
wherein the dosage of the polyethylene glycol in the step two is 0.5-5 g, and the stirring time is 3-4 h;
wherein, the mass ratio of the lithium hydroxide added in the step three to the pulp mass is 5:1, and the temperature of the blast drying oven is 60 ℃;
wherein, the temperature of the vacuum drying oven in the fourth step is 120 ℃, and the drying time is 1.5-2 h.
2. The method for preparing a polymer electrolyte membrane for a battery by using a gel method with polyethylene glycol and paper pulp as matrixes in the step one, wherein the facial tissues are commercially available facial tissues, and the cellulose in the facial tissues is extracted by treating the facial tissues with pulp.
3. The method for preparing a battery polymer electrolyte film by using polyethylene glycol and paper pulp as a matrix gel method according to claim 1, wherein the pretreatment step in the first step is as follows: taking one layer of the facial tissue, cutting the facial tissue into pieces, putting the cut facial tissue into a dry beaker, adding 10ml of glacial acetic acid, putting the beaker into a rotor, covering the rotor with a preservative film, and standing for 24 hours.
4. The method for preparing a polymer electrolyte membrane for a battery according to claim 1, wherein the polyethylene glycol in the second step acts as a film-forming agent, and has a synergistic effect with the pulp to form a polymer electrolyte membrane with low crystallinity.
5. The method for preparing a battery polymer electrolyte film by using polyethylene glycol and paper pulp as a matrix gel method according to claim 1, wherein the lithium hydroxide in the step three is a main component of the finally prepared battery polymer electrolyte, and has a synergistic effect of forming hydrogen bonds with cellulose, thereby playing a role of improving the conductivity of lithium ions in the polymer electrolyte.
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| CN106099182A (en) * | 2016-08-05 | 2016-11-09 | 宁波高智科技咨询服务有限公司 | A kind of lithium battery bacterial cellulose gel method for preparing polymer electrolytes |
| CN107808980A (en) * | 2017-09-22 | 2018-03-16 | 哈尔滨理工大学 | A kind of preparation method of the papery lithium ion battery solid electrolyte of high conductivity |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106099182A (en) * | 2016-08-05 | 2016-11-09 | 宁波高智科技咨询服务有限公司 | A kind of lithium battery bacterial cellulose gel method for preparing polymer electrolytes |
| CN107808980A (en) * | 2017-09-22 | 2018-03-16 | 哈尔滨理工大学 | A kind of preparation method of the papery lithium ion battery solid electrolyte of high conductivity |
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| CN112421105A (en) * | 2020-11-19 | 2021-02-26 | 浙江南都电源动力股份有限公司 | Solid composite electrolyte membrane preparation process and solid composite electrolyte membrane |
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Application publication date: 20200821 |