CN104610567A - Preparation method for PVDF/PAN (polyvinylidene fluoride/polyacrylonitrile) polymer electrolyte membrane based on nonwoven fabric support - Google Patents
Preparation method for PVDF/PAN (polyvinylidene fluoride/polyacrylonitrile) polymer electrolyte membrane based on nonwoven fabric support Download PDFInfo
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Abstract
The invention discloses a preparation method for a PVDF/PAN (polyvinylidene fluoride/polyacrylonitrile) polymer electrolyte membrane based on nonwoven fabric support, and belongs to the technical field of membranes. The method comprises the following specific steps: weighing a certain amount of nano SiO2 into a solvent and ultrasonically processing to enable the nano SiO2 to be uniformly dispersed in the solvent; adding polyvinylpyrrolidone (PVP), glacial acetic acid and PVDF/PAN with different mass ratio into the solvent and mixing uniformly to obtain clear membrane casting liquor; applying the membrane casting liquor to a nonwoven fabric dipped in the solvent in a blade-coating manner, feeding the coated nonwoven fabric into a sodium bicarbonate aqueous solution, removing the solvent, producing a chemical reaction, and drying; dipping a prepared polymer in electrolytic liquor and activating to obtain the electrolyte membrane. The prepared electrolyte membrane is good in mechanical property; pore ducts in the formed electrolyte membrane are uniform, relatively large in pore size and relatively high in porosity, so that a large amount of the electrolytic liquor can be absorbed and the ionic conductivity can be improved. The process is simple, low in cost and suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of polymer dielectric film, be specifically related to a kind of preparation of battery electrolyte barrier film, belong to technical field of membrane.
Technical background
Lithium ion battery has the advantages such as operating voltage is high, specific energy is large, specific power is high, pollution-free, is therefore widely used.Barrier film is a key component of lithium ion battery, rises and prevents positive and negative electrode short circuit, provide the effect of ion transportation passage.There is a lot of shortcoming in current commercial barrier film, such as porosity is low, bad mechanical strength, and ionogen pick up is low, thus affect the security of lithium cell, and in addition, the stuctures and properties of film also has a huge impact the performance of battery.
Polymer electrolyte diaphragm is the critical material of lithium ion battery, the performance of film and the chemical property of structure to battery have a great impact, and therefore prepare uniform pore diameter and the polymer electrolyte diaphragm that porosity is high, ionic conductivity is high is one of emphasis of Study on Li-ion batteries.Preparing the most general method of polymer dielectric film is phase inversion process, this method is simple to operate, cost is lower, be applicable to industrialization scale operation, but this traditional method might not obtain good film properties and membrane structure, based on this reason, many scholars both domestic and external improve this method, comprise addO-on therapy in film-casting liquid and coagulation bath.The chemical reaction between the sodium bicarbonate in glacial acetic acid and coagulation bath is added in film-casting liquid
improve traditional phase inversion process, this is a kind of novel phase inversion process, the CO produced by chemical reaction
2bubble carrys out the homogenizing degree in controlling diaphragm aperture, and improves porosity, thus strengthens electrolytic solution pick up, improves ionic conductivity.
The physical strength of polymer dielectric film is an important factor of relation cell safety and performance.The cost that the existing disclosed method improving physical strength has is higher, some complicated operations, and what have adds inorganic particle, but improves physical strength aspect limited use.In order to overcome these difficulties, directly using non-woven fabrics as supporter, this method is simple and convenient and cost is low, greatly improve mechanical property and the chemical stability of polymeric film on the one hand, on the other hand, be solidificated in the polymer-based film on non-woven fabrics, surface is in many micropores state, be conducive to the absorption of electrolytic solution, more liquid electrolyte can be sucked, make whole system have higher ionic conductivity.
Summary of the invention
The object of the invention is, for in existing electrolytic membrane of lithium-ion battery, or have that pick up is low or specific conductivity is low or the problem such as bad mechanical strength or complicated operation, preparation is a kind of with low cost, preparation technology is simple, physical strength is high, and ionic conductivity is high, porosity is high and the polymer dielectric film of even aperture distribution.
In order to achieve the above object, the present invention is in conjunction with the advantage of PVDF and PAN, make it blended according to a certain percentage, improve the physical strength of film using non-woven fabrics as supporting layer, adopt phase inversion process, particularly introduce chemical reaction and prepare polymer electrolyte diaphragm, the polymeric film section obtained is asymmetric, have very high porosity, pick up can reach 246.5%, and ionic conductivity can reach 3.32 × 10
-3s/cm, electrochemical stability window reaches 5.0V.
Concrete technical scheme of the present invention is as follows:
Based on a preparation method for the PVDF/PAN polymer dielectric film that non-woven fabrics supports, it is characterized in that, comprise the following steps:
(1) preparation of film-casting liquid
By a certain amount of Nano-meter SiO_2
2join in solvent, ultrasonic agitation 30min, make it in a solvent dispersed, then 2wt.% glacial acetic acid, 6wt.% polyvinylpyrrolidone, 12wt.%PVDF and PAN blend films material (PVDF/PAN of different mass ratio) is added successively, it is made to dissolve completely in 60 DEG C, system after dissolving is stirred half an hour, then deaeration, obtains the film-casting liquid clarified;
(2) preparation of polymeric film
By the film-casting liquid curtain coating of step (1) to the non-woven fabrics one end being soaked with solvent, then with glass slicker, the film-casting liquid arranged is pushed into the non-woven fabrics the other end, the non-woven fabrics scribbling film liquid is immersed in the sodium bicarbonate aqueous solution of 2%, remove the solvent in film, and with glacial acetic acid generation chemical reaction, soak to take out after 2 hours and put into pure water and soak, take out and dry;
(3) preparation of polymer dielectric film
The polymeric film that step (2) is obtained is dipped into electrolytic solution LiPF
6middle activation, obtains the polymer electrolyte diaphragm for battery.
Nano-meter SiO_2 in step (1)
2massfraction is 0.5%-1.5%, preferred Nano-meter SiO_2
2massfraction is 1%.
Solvent in step (1) is DMF (DMF), N,N-dimethylacetamide (DMAc) or N-Methyl pyrrolidone (NMP), preferred N,N-dimethylacetamide (DMAc).
In preferred steps (1), in PVDF and PAN mixture, preferably PVDF/PAN mass ratio is 85/15-70/30.Advantage of the present invention:
Compared with prior art, the present invention has the features such as technique is simple, with low cost; Combined with phase inversion process by chemical reaction, utilize the CO that chemical reaction produces
2control the uniformity coefficient in aperture, and improve the porosity of polymeric film, the polymer dielectric film of preparation has good imbibition ability, higher ionic conductivity, using non-woven fabrics as supporting layer, has stronger mechanical property, ensures the safety of inside battery.
Accompanying drawing explanation
Fig. 1 is the electronic scanning Electronic Speculum figure of PVDF/PAN (70/30, w/w) the polymeric film section adopting phase inversion process to prepare;
Fig. 2 is the electronic scanning Electronic Speculum figure of the polymeric film section of case study on implementation 4 of the present invention preparation;
Fig. 3 is the stress strain curve figure of the polymeric film of embodiment 4;
Fig. 4 is the electrochemical stability windows of the polymer dielectric film of case study on implementation 4.
Fig. 5 is the Li/ dielectric film/LiFePO of the polymer dielectric film of case study on implementation 4
4charging and discharging curve.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.But the present invention is not limited to following examples.
Wherein polyvinylidene difluoride (PVDF) (PVDF), polyacrylonitrile (PAN), purchased from An get film company; Glacial acetic acid, N,N-dimethylacetamide (DMA
c), sodium bicarbonate (NaHCO
3), polyvinylpyrrolidone (PVP) is purchased from Tianjin good fortune chemical reagent factory in morning; Nano-meter SiO_2
2, step female chemical reagent factory purchased from Shanghai.
Embodiment 1
The first step, commercially available PVDF and PAN to be placed in vacuum drying oven about 60 DEG C dry, dry 12 hours, then with mass percent for joining preparation liquid, PVDF and PAN blend films material: glacial acetic acid: Nano-meter SiO_2
2: polyvinylpyrrolidone: N,N-dimethylacetamide=12%:4%:1%:6%:77% takes, the mass ratio of PVDF and the PAN described in this implementation method is 85/15.
Second step, is placed in beaker by N,N-dimethylacetamide, by Nano-meter SiO_2
2join in beaker, ultrasonic agitation 30min is to Nano-meter SiO_2
2in a solvent dispersed, again glacial acetic acid, polyvinylpyrrolidone are added in above-mentioned beaker successively and be stirred to evenly, by mass ratio be again 85/15 PVDF and PAN add in beaker, in 60 DEG C of vacuum drying ovens, heating 24 is little of dissolving completely, replace after the solution stirring of dissolving, standing and defoaming 2 hours, obtains film-casting liquid.
3rd step, non-woven fabrics is immersed in solvent N, in N-N,N-DIMETHYLACETAMIDE, take out after 10min, smooth for non-woven fabrics is pasted onto on cleaning panes, the beaker that film-casting liquid is housed is pressed close to non-woven fabrics, make the slow curtain coating of film-casting liquid to non-woven fabrics one end, make it be in one line, then with glass slicker, the stock liquid arranged slowly is pushed into the non-woven fabrics the other end, obtain the polymeric film intermediate that non-woven fabrics supports.
4th step, immerses the polymeric film intermediate made in the sodium bicarbonate aqueous solution of 2%, removes the N,N-DIMETHYLACETAMIDE in film, and with glacial acetic acid generation chemical reaction, soaks taking-up after 2 hours and puts into pure water and soak, dry and obtain polymeric film.
5th step, is immersed in electrolytic solution hexafluoro phosphorus lithium (LiPF by polymeric film
6) 1h, take out and obtain polymer dielectric film.
Embodiment 2
The first step, commercially available PVDF and PAN is placed on about 60 DEG C dryings in vacuum drying oven, then dry 12 hours be mould material with mass percent: glacial acetic acid: Nano-meter SiO_2
2: polyvinylpyrrolidone: N,N-dimethylacetamide=12%:4%:1%:6%:77% takes, the mass ratio of PVDF and the PAN described in this implementation method is 80/20.
Second step, is placed in beaker by N,N-dimethylacetamide, by Nano-meter SiO_2
2join in beaker, ultrasonic agitation 30min is to Nano-meter SiO_2
2in a solvent dispersed, again glacial acetic acid, polyvinylpyrrolidone are added in above-mentioned beaker successively and be stirred to evenly, by mass ratio be again 80/20 PVDF and PAN add in beaker, in 60 DEG C of vacuum drying ovens, heating 24 is little of dissolving completely, replace after the solution stirring of dissolving, standing and defoaming 2 hours, obtains film-casting liquid.
3rd step, non-woven fabrics is immersed in solvent N, in N-N,N-DIMETHYLACETAMIDE, take out after 10min, smooth for non-woven fabrics is pasted onto on cleaning panes, the beaker that film-casting liquid is housed is pressed close to non-woven fabrics, make the slow curtain coating of film-casting liquid to non-woven fabrics one end, make it be in one line, then with glass slicker, the stock liquid arranged slowly is pushed into the non-woven fabrics the other end, obtain the polymeric film intermediate that non-woven fabrics supports.
4th step, immerses the polymeric film intermediate made in the sodium bicarbonate aqueous solution of 2%, removes the N,N-DIMETHYLACETAMIDE in film, and with glacial acetic acid generation chemical reaction, soaks taking-up after 2 hours and puts into pure water and soak, dry and obtain polymeric film.
5th step, is immersed in electrolytic solution hexafluoro phosphorus lithium (LiPF by polymeric film
6) 1h, take out and obtain polymer dielectric film.
Embodiment 3
The first step, commercially available PVDF and PAN is placed on about 60 DEG C dryings in vacuum drying oven, then dry 12 hours be mould material with mass percent: glacial acetic acid: Nano-meter SiO_2
2: polyvinylpyrrolidone: N,N-dimethylacetamide=12%:4%:1%:6%:77% takes, the mass ratio of PVDF and the PAN described in this implementation method is 75/25.
Second step, is placed in beaker by N,N-dimethylacetamide, by Nano-meter SiO_2
2join in beaker, ultrasonic agitation 30min is to Nano-meter SiO_2
2in a solvent dispersed, again glacial acetic acid, polyvinylpyrrolidone are added in above-mentioned beaker successively and be stirred to evenly, by mass ratio be again 75/25 PVDF and PAN add in beaker, in 60 DEG C of vacuum drying ovens, heating 24 is little of dissolving completely, replace after the solution stirring of dissolving, standing and defoaming 2 hours, obtains film-casting liquid.
3rd step, non-woven fabrics is immersed in solvent N, in N-N,N-DIMETHYLACETAMIDE, take out after 10min, smooth for non-woven fabrics is pasted onto on cleaning panes, the beaker that film-casting liquid is housed is pressed close to non-woven fabrics, make the slow curtain coating of film-casting liquid to non-woven fabrics one end, make it be in one line, then with glass slicker, the stock liquid arranged slowly is pushed into the non-woven fabrics the other end, obtain the polymeric film intermediate that non-woven fabrics supports.
4th step, immerses the polymeric film intermediate made in the sodium bicarbonate aqueous solution of 2%, removes the N,N-DIMETHYLACETAMIDE in film, and with glacial acetic acid generation chemical reaction, soaks taking-up after 2 hours and puts into pure water and soak, dry and obtain polymeric film.
5th step, is immersed in electrolytic solution hexafluoro phosphorus lithium (LiPF by polymeric film
6) 1h, take out and obtain polymer dielectric film.
Embodiment 4
The first step, commercially available PVDF and PAN is placed on about 60 DEG C dryings in vacuum drying oven, then dry 12 hours be mould material with mass percent: glacial acetic acid: Nano-meter SiO_2
2: polyvinylpyrrolidone: N,N-dimethylacetamide=12%:4%:1%:6%:77% takes, the mass ratio of PVDF and the PAN described in this implementation method is 70/30.
Second step, is placed in beaker by N,N-dimethylacetamide, by Nano-meter SiO_2
2join in beaker, ultrasonic agitation 30min is to Nano-meter SiO_2
2in a solvent dispersed, again glacial acetic acid, polyvinylpyrrolidone are added in above-mentioned beaker successively and be stirred to evenly, by mass ratio be again 70/30 PVDF and PAN add in beaker, in 60 DEG C of vacuum drying ovens, heating 24 is little of dissolving completely, replace after the solution stirring of dissolving, standing and defoaming 2 hours, obtains film-casting liquid.
3rd step, non-woven fabrics is immersed in solvent N, in N-N,N-DIMETHYLACETAMIDE, take out after 10min, smooth for non-woven fabrics is pasted onto on cleaning panes, the beaker that film-casting liquid is housed is pressed close to non-woven fabrics, make the slow curtain coating of film-casting liquid to non-woven fabrics one end, make it be in one line, then with glass slicker, the stock liquid arranged slowly is pushed into the non-woven fabrics the other end, obtain the polymeric film intermediate that non-woven fabrics supports.
4th step, immerses the polymeric film intermediate made in the sodium bicarbonate aqueous solution of 2%, removes the N,N-DIMETHYLACETAMIDE in film, and with glacial acetic acid generation chemical reaction, soaks taking-up after 2 hours and puts into pure water and soak, dry and obtain polymeric film.
5th step, is immersed in electrolytic solution hexafluoro phosphorus lithium (LiPF by polymeric film
6) middle 1h, take out and obtain polymer dielectric film.
Analyze case study on implementation 4, the electronic scanning Electronic Speculum figure of the section adopting phase inversion process to prepare is shown in Fig. 1; The electronic scanning Electronic Speculum figure that the chemical reaction that the present invention adopts and phase inversion process combine the polymeric film section of preparation is shown in Fig. 2, pass through scanning electronic microscope observation, the film that embodiment 4 obtains compare with general phase inversion process aperture become even, the comparatively large and porosity in aperture uprises, section is interpenetrating(polymer)networks model, be conducive to the absorption of electrolytic solution, porosity reaches 72.9%, and pick up reaches 246.5%; Adopt Zwick/RoellBL-GRS500N type electronics tensilometer, under draw speed is 10mm/min, detect the polymeric film that case study on implementation 4 is obtained, stress strain curve is shown in Fig. 3, and known tensile strength is 18.93MPa.
25 DEG C time, adopt Shanghai Chen Hua instrument company CHI660B electrochemical workstation to measure the polymer dielectric film of case study on implementation 4 preparation, then according to formula
(d: the thickness of polymer dielectric film, unit: cm; A: the area of polymer dielectric film, unit: cm
2; R
b: the bulk resistance of dielectric film, unit: Ω; σ: ionic conductivity, unit: S/cm) calculate the known polymer dielectric film ionic conductivity prepared by case study on implementation 4 and reach 3.32 × 10
-3s/cm, electrochemical stability windows reaches 5.0V, and loading capacity reaches 152mAh/g.
Claims (5)
1., based on a preparation method for the PVDF/PAN polymer dielectric film of non-woven fabrics support, it is characterized in that, comprise the following steps:
(1) preparation of film-casting liquid
By a certain amount of Nano-meter SiO_2
2join in solvent, ultrasonic agitation 30min, make it in a solvent dispersed, then 2wt.% glacial acetic acid, 6wt.% polyvinylpyrrolidone, 12wt.%PVDF and PAN blend films material is added successively, it is made to dissolve completely in 60 DEG C, system after dissolving is stirred half an hour, then deaeration, obtains the film-casting liquid clarified;
(2) preparation of polymeric film
By the film-casting liquid curtain coating of step (1) to the non-woven fabrics one end being soaked with solvent, then with glass slicker, the film-casting liquid arranged is pushed into the non-woven fabrics the other end, the non-woven fabrics scribbling film liquid is immersed in the sodium bicarbonate aqueous solution of 2%, remove the solvent in film, and with glacial acetic acid generation chemical reaction, soak to take out after 2 hours and put into pure water and soak, take out and dry;
(3) preparation of polymer dielectric film
The polymeric film that step (2) is obtained is dipped into electrolytic solution LiPF
6middle activation, obtains the polymer electrolyte diaphragm for battery.
2. according to the method for claim 1, it is characterized in that, the Nano-meter SiO_2 in step (1)
2massfraction is 1%.
3. according to the method for claim 1, it is characterized in that, the solvent in step (1) is N,N-dimethylacetamide (DMA
c).
4. according to the method for claim 1, it is characterized in that, in step (1), in PVDF and PAN mixture, PVDF/PAN mass ratio is 85/15-70/30.
5. according to the PVDF/PAN polymer dielectric film supported based on non-woven fabrics that the either method of claim 1-4 prepares.
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| CN108400365A (en) * | 2018-03-01 | 2018-08-14 | 犀望新能源科技（昆山）有限公司 | zinc-bromine flow battery |
| CN112652797A (en) * | 2019-10-11 | 2021-04-13 | 中国科学院大连化学物理研究所 | Porous ion-conducting membrane with pore size in gradient distribution, preparation and application |
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| CN108400365A (en) * | 2018-03-01 | 2018-08-14 | 犀望新能源科技（昆山）有限公司 | zinc-bromine flow battery |
| CN112652797A (en) * | 2019-10-11 | 2021-04-13 | 中国科学院大连化学物理研究所 | Porous ion-conducting membrane with pore size in gradient distribution, preparation and application |
| CN112652797B (en) * | 2019-10-11 | 2022-03-08 | 中国科学院大连化学物理研究所 | Porous ion-conducting membrane with pore size in gradient distribution, preparation and application |
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