CN101260216A - PVDF-HFP base composite porous polymer membrane and preparation method thereof - Google Patents
PVDF-HFP base composite porous polymer membrane and preparation method thereof Download PDFInfo
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- CN101260216A CN101260216A CNA2008100644094A CN200810064409A CN101260216A CN 101260216 A CN101260216 A CN 101260216A CN A2008100644094 A CNA2008100644094 A CN A2008100644094A CN 200810064409 A CN200810064409 A CN 200810064409A CN 101260216 A CN101260216 A CN 101260216A
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Abstract
A PVDF-HFP group composite porous polymer membrane and a preparation method thereof relate to a composite porous polymer membrane and a preparation method thereof, and solve the problems that the prior PVDF-HFP group composite porous polymer membrane has poor interface compatibility, smaller transference number of ions, easy agglomeration of ultrafine powder filler and limited adding amount. The product is made from PVDF-HFP, sodium hexametaphosphate and ultrafine powder filler. The preparation method is as follows: (1) PVDF-HFP is dissolved in organic solvent; (2) sodium hexametaphosphate, ultrafine powder filler and distilled water are mixed and stirred; (3) the mixed solution obtained by step (2) is dripped into the mixed solution obtained by step (1) and then is evenly stirred, thereby obtaining the product through molding and drying forming. The dosage of the ultrafine powder filler occupies more than 41.7 percent of the total weight of raw materials and is evenly dispersed in the polymer matrix; meanwhile, the polymer electrolyte membrane has reinforced mechanical strength, high interface performance and excellent processability; moreover, the product has high conductivity with the transference number of ion Li+ reaching 0.85 and the electrochemical stability window as high as 5.8V.
Description
Technical field
The present invention relates to a kind of composite porous polymer membrane and preparation method thereof
Background technology
Replace organic electrolyte in the conventional serondary lithium battery with polymer dielectric, not only can realize lightweight, filming, rapid charge and the high-energy-density of battery, can also solve such as safety issues such as leakage, burning, blasts.With this polymkeric substance serondary lithium battery excellent property that gel-type PVDF-HFP ionogen is made, can satisfy the needs of equipment such as the mobile telephone little, in light weight towards volume, that the portability direction develops, portable type Communication Equipment, notebook computer.Compound by polymkeric substance and polymkeric substance, inorganics and organic softening agent can effectively be improved the room-temperature conductivity of polymer dielectric, improves the state of interface of electrode/electrolyte, and can keep certain mechanical strength.Because performance and advantage in price can also be used for electricity and cause colour developing, photoelectrochemistry, large value capacitor and sensor etc., therefore have huge consumption market, development prospect is very wide.
But there is the shortcoming that interface compatibility is bad, transference number of ions is lower in the PVDF-HFP base composite porous polymer membrane of broad research at present.Though the adding of ultrafine powder filler helps reducing the degree of crystallinity of PVDF-HFP, improve the interface performance of material, improve membranous physical strength, ionic conductivity also improves thereupon.But because currently used physics dispersing method (as ultrasonic dispersion) causes the add-on of ultrafine powder filler must be controlled in certain scope, otherwise agglomeration traits can cause the decline of dielectric film over-all properties.
Summary of the invention
The objective of the invention is bad for the interface compatibility that solves existing PVDF-HFP base composite porous polymer membrane, transference number of ions is lower, the ultrafine powder filler is easily reunited and the limited problem of add-on; And provide a kind of PVDF-HFP base composite porous polymer membrane and preparation method thereof.
PVDF-HFP base composite porous polymer membrane of the present invention is to be made by poly-(biasfluoroethylene-hexafluoropropylene) (abbreviating PVDF-HFP as), Sodium hexametaphosphate 99 and ultrafine powder filler; Wherein Sodium hexametaphosphate 99 is 0.2～0.4: 1 with the mass ratio of poly-(biasfluoroethylene-hexafluoropropylene), and the mass ratio of ultrafine powder filler and Sodium hexametaphosphate 99 is 0.5～1: 1.
PVDF-HFP base composite porous polymer electrolyte preparation method is realized by following reaction among the present invention: one, will gather (biasfluoroethylene-hexafluoropropylene) and organic solvent by 0.1～0.2: 1 mass ratio mixes, be stirred to poly-(biasfluoroethylene-hexafluoropropylene) and dissolve fully under 30～60 ℃ of conditions, organic solvent is acetone or tetrahydrofuran (THF); Two, will be stirred to evenly after Sodium hexametaphosphate 99, ultrafine powder filler and the distilled water mixing; Wherein the mass ratio of poly-(biasfluoroethylene-hexafluoropropylene) in Sodium hexametaphosphate 99 and the step 1 is 0.2～0.4: 1, the mass ratio of ultrafine powder filler and Sodium hexametaphosphate 99 is 0.5～1: 1, and the organic solvent mass ratio in distilled water and the step 1 is 0.1～0.15: 1; Three, the mixed solution that step 2 is obtained dropwise joins in the mixed solution that step 1 obtains, and is stirred to after being added dropwise to complete evenly, is poured in the mould drying and moulding under the room temperature again; Obtain the PVDF-HFP base composite porous polymer membrane.
Above-mentioned ultrafine powder filler is that particle diameter is the Al of 10～100nm
2O
3, TiO
2, ZrO
2Or SiO
2, the ultrafine powder filler can also be that particle diameter is lithium nickelate, cobalt acid lithium, polynite or the saponite of 10～100 μ m.
The present invention adopts the chemical dispersion method to improve the add-on (accounting for the raw material gross weight more than 41.7%) of ultrafine powder filler, the ultrafine powder filler (see figure 1) that in polymeric matrix, is uniformly dispersed, the structure of effective control punch, and improved the physical strength of polymer dielectric film, improve interface performance and processing characteristics simultaneously, thereby improved the specific conductivity and the Li of polymer dielectric film
+Transference number of ions etc.After tested, (specific conductivity can reach 6.5 * 10 to the specific conductivity height of product of the present invention 20 ℃ the time
-3Scm
-1), its Li
+Transference number of ions is up to 0.85, and its electrochemical stability window is up to 5.8V.
Description of drawings
Fig. 1 is the microcosmic sem photograph of product of the present invention.Fig. 2 is the XRD figure of product of the present invention.Fig. 3 is the stress strain curve figure of PVDF-HFP film.Fig. 4 is the PVDF-HFP/SiO of embodiment two
2/ Na (PO
3)
6The stress strain curve figure of film.Fig. 5 is the PVDF-HFP/Al of embodiment two
2O
3/ Na (PO
3)
6The stress strain curve figure of film.Fig. 6 is the tensile strength curve figure of the PVDF-HFP/ polynite film of embodiment five.Fig. 7 is the tensile strength curve figure of the PVDF-HFP/ saponite film of embodiment five.
Embodiment
Embodiment one: present embodiment PVDF-HFP base composite porous polymer membrane is to be made by poly-(biasfluoroethylene-hexafluoropropylene) (abbreviating PVDF-HFP as), polyvinylpyrrolidone and ultrafine powder filler; Sodium hexametaphosphate 99 is 0.2～0.4: 1 with the mass ratio of poly-(biasfluoroethylene-hexafluoropropylene), and the mass ratio of ultrafine powder filler and Sodium hexametaphosphate 99 is 0.5～1: 1.
After tested, (specific conductivity can reach 6.5 * 10 to the specific conductivity height of present embodiment product 20 ℃ the time
-3Scm
-1), its Li
+Transference number of ions is up to 0.85, and its electrochemical stability window is up to 5.8V.
Embodiment two: what present embodiment and embodiment one were different is: the ultrafine powder filler is that particle diameter is the Al of 10～100nm
2O
3, TiO
2, ZrO
2Or SiO
2Other is identical with embodiment one.
The ultrafine powder filler sees Table 1 to the influence of barrier film mechanical property in the present embodiment.
Table 1
| Barrier film | Sectional area/mm 2 | Rupture stress/kN | Tensile strength/MPa |
| PVDF-HFP | 3.996 | 0.01944 | 4.86 |
| PVDF-HFP/SiO 2/Na(PO 3) 6 | 4.367 | 0.02554 | 5.85 |
| PVDF-HFP/Al 2O 3/Na(PO 3) 6 | 5.492 | 0.03664 | 6.67 |
Embodiment three: what present embodiment and embodiment two were different is: the particle diameter of ultrafine powder filler is 15～40nm.Other is identical with embodiment two.
Embodiment four: what present embodiment and embodiment two were different is: the particle diameter of ultrafine powder filler is 20nm.Other is identical with embodiment two.
Embodiment five: what present embodiment and embodiment one were different is: the ultrafine powder filler is that particle diameter is lithium nickelate, cobalt acid lithium, polynite or the saponite of 10～100 μ m.Other is identical with embodiment one.
The ultrafine powder filler sees Table 2 to the influence of barrier film mechanical property in the present embodiment.
Table 2
| Barrier film | Sectional area/mm 2 | Rupture stress/kN | Tensile strength/MPa |
| The VDF-HFP/ polynite | 4.379 | 0.02675 | 6.11 |
| The PVDF-HFP/ saponite | 5.085 | 0.04135 | 8.13 |
Embodiment six: what present embodiment and embodiment five were different is: the particle diameter of ultrafine powder filler is 15～40 μ m.Other is identical with embodiment five.
Embodiment seven: what present embodiment and embodiment five were different is: the particle diameter of ultrafine powder filler is 20 μ m.Other is identical with embodiment five.
Embodiment eight: what present embodiment embodiment one was different is: Sodium hexametaphosphate 99 is 0.23～0.35: 1 with the mass ratio of poly-(biasfluoroethylene-hexafluoropropylene).Other is identical with embodiment one.
Embodiment nine: what present embodiment embodiment one was different is: Sodium hexametaphosphate 99 is 0.30: 1 with the mass ratio of poly-(biasfluoroethylene-hexafluoropropylene).Other is identical with embodiment one.
Embodiment ten: what present embodiment embodiment one was different is: the mass ratio of ultrafine powder filler and Sodium hexametaphosphate 99 is 0.6～0.9: 1.Other is identical with embodiment one.
Embodiment 11: what present embodiment embodiment one was different is: the mass ratio of ultrafine powder filler and Sodium hexametaphosphate 99 is 0.7: 1.Other is identical with embodiment one.
Embodiment 12: what present embodiment embodiment one was different is: the mass ratio of ultrafine powder filler and Sodium hexametaphosphate 99 is 0.8: 1.Other is identical with embodiment one.
Embodiment 13: PVDF-HFP base composite porous polymer electrolyte preparation method is realized by following reaction in the present embodiment: one, will gather (biasfluoroethylene-hexafluoropropylene) and organic solvent by 0.1～0.2: 1 mass ratio mixes, be stirred to poly-(biasfluoroethylene-hexafluoropropylene) and dissolve fully under 30～60 ℃ of conditions, organic solvent is acetone or tetrahydrofuran (THF); Two, will be stirred to evenly after Sodium hexametaphosphate 99, ultrafine powder filler and the distilled water mixing; The mass ratio of poly-(biasfluoroethylene-hexafluoropropylene) in Sodium hexametaphosphate 99 and the step 1 is 0.2～0.4: 1, and the mass ratio of ultrafine powder filler and Sodium hexametaphosphate 99 is 0.5～1: 1, and the organic solvent mass ratio in distilled water and the step 1 is 0.1～0.15: 1; Three, the mixed solution that step 2 is obtained dropwise joins in the mixed solution that step 1 obtains, and is stirred to after being added dropwise to complete evenly, is poured in the mould drying and moulding under the room temperature again; Obtain the PVDF-HFP base composite porous polymer membrane.
As seen from Figure 2, add the ultrafine powder filler (as nanometer SiO
2, Al
2O
3) after, the position of its diffraction peak is constant substantially, illustrate that obvious change does not take place the crystalline structure of composition polymer, but its diffraction peak intensity decreases, illustrate that the adding of inorganic nano material can reduce the degree of crystallinity of polymeric matrix effectively, helps the raising of barrier film ionic conductivity.
Embodiment 14: what present embodiment and embodiment 13 were different is: the ultrafine powder filler is that particle diameter is the Al of 10～100nm in the step 2
2O
3, TiO
2, ZrO
2Or SiO
2Other is identical with embodiment 13.
Embodiment 15: what present embodiment and embodiment 14 were different is: the particle diameter of ultrafine powder filler is 15～40nm.Other is identical with embodiment 14.
Embodiment 16: what present embodiment and embodiment 14 were different is: the particle diameter of ultrafine powder filler is 20nm.Other is identical with embodiment 14.
Embodiment 17: what present embodiment and embodiment 13 were different is; The ultrafine powder filler is that particle diameter is lithium nickelate, cobalt acid lithium, polynite or the saponite of 10～100 μ m.Other is identical with embodiment 13.
Embodiment 18: what present embodiment and embodiment 17 were different is: the particle diameter of ultrafine powder filler is 15～40 μ m.Other is identical with embodiment 17.
Embodiment 19: what present embodiment and embodiment 17 were different is: the particle diameter of ultrafine powder filler is 20 μ m.Other is identical with embodiment 17.
Embodiment 20: what present embodiment and embodiment 13 were different is: the mass ratio of poly-(biasfluoroethylene-hexafluoropropylene) in Sodium hexametaphosphate 99 in the step 2 and the step 1 is 0.23～0.35: 1.Other is identical with embodiment nine.
Embodiment 21: what present embodiment and embodiment 13 were different is: the mass ratio of poly-(biasfluoroethylene-hexafluoropropylene) in Sodium hexametaphosphate 99 in the step 2 and the step 1 is 0.30: 1.Other is identical with embodiment 13.
Embodiment 22; What present embodiment and embodiment 13 were different is: the mass ratio of ultrafine powder filler and Sodium hexametaphosphate 99 is 0.6～0.9: 1 in the step 2.Other is identical with embodiment nine.
Embodiment 23; What present embodiment and embodiment 13 were different is: the mass ratio of ultrafine powder filler and Sodium hexametaphosphate 99 is 0.7: 1 in the step 2.Other is identical with embodiment 13.
Embodiment 24; What present embodiment and embodiment 13 were different is: the mass ratio of ultrafine powder filler and Sodium hexametaphosphate 99 is 0.8: 1 in the step 2.Other is identical with embodiment 13.
Claims (10)
1, a kind of PVDF-HFP base composite porous polymer membrane is characterized in that the PVDF-HFP base composite porous polymer membrane is to be made by poly-(biasfluoroethylene-hexafluoropropylene), Sodium hexametaphosphate 99 and ultrafine powder filler; Wherein Sodium hexametaphosphate 99 is 0.2～0.4: 1 with the mass ratio of poly-(biasfluoroethylene-hexafluoropropylene), and the mass ratio of ultrafine powder filler and Sodium hexametaphosphate 99 is 0.5～1: 1.
2,, it is characterized in that the Sodium hexametaphosphate 99 and the mass ratio of poly-(biasfluoroethylene-hexafluoropropylene) are 0.23～0.35: 1 according to the described PVDF-HFP base composite porous polymer membrane of claim 1.
3,, it is characterized in that the Sodium hexametaphosphate 99 and the mass ratio of poly-(biasfluoroethylene-hexafluoropropylene) are 0.30: 1 according to the described PVDF-HFP base composite porous polymer membrane of claim 1.
4, according to the described PVDF-HFP base composite porous polymer membrane of claim 1, the mass ratio that it is characterized in that ultrafine powder filler and Sodium hexametaphosphate 99 is 0.6～0.9: 1.
5, according to the described PVDF-HFP base composite porous polymer membrane of claim 1, the mass ratio that it is characterized in that ultrafine powder filler and Sodium hexametaphosphate 99 is 0.7～0.8: 1.
6,, it is characterized in that the ultrafine powder filler is that particle diameter is the Al of 10～100nm according to the described PVDF-HFP base composite porous polymer membrane of claim 1
2O
3, TiO
2, ZrO
2Or SiO
2
7,, it is characterized in that the ultrafine powder filler is that particle diameter is lithium nickelate, cobalt acid lithium, polynite or the saponite of 10～100 μ m according to the described PVDF-HFP base composite porous polymer membrane of claim 1.
8, the method for preparing the described PVDF-HFP base composite porous polymer membrane of claim 1, it is characterized in that PVDF-HFP base composite porous polymer electrolyte preparation method realizes by following reaction: one, will gather (biasfluoroethylene-hexafluoropropylene) and organic solvent by 0.1～0.2: 1 mass ratio mixes, be stirred to poly-(biasfluoroethylene-hexafluoropropylene) and dissolve fully under 30～60 ℃ of conditions, organic solvent is acetone or tetrahydrofuran (THF); Two, will be stirred to evenly after Sodium hexametaphosphate 99, ultrafine powder filler and the distilled water mixing; Wherein the mass ratio of poly-(biasfluoroethylene-hexafluoropropylene) in Sodium hexametaphosphate 99 and the step 1 is 0.2～0.4: 1, the mass ratio of ultrafine powder filler and Sodium hexametaphosphate 99 is 0.5～1: 1, and the organic solvent mass ratio in distilled water and the step 1 is 0.1～0.15: 1; Three, the mixed solution that step 2 is obtained dropwise joins in the mixed solution that step 1 obtains, and is stirred to after being added dropwise to complete evenly, is poured in the mould drying and moulding under the room temperature again; Obtain the PVDF-HFP base composite porous polymer membrane.
9, the preparation method of described according to Claim 8 PVDF-HFP base composite porous polymer membrane is characterized in that the ultrafine powder filler is that particle diameter is the Al of 10～100nm in the step 2
2O
3, TiO
2, ZrO
2Or SiO
2
10, the preparation method of described according to Claim 8 PVDF-HFP base composite porous polymer membrane is characterized in that the ultrafine powder filler is that particle diameter is lithium nickelate, cobalt acid lithium, polynite or the saponite of 10～100 μ m in the step 2.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102286158A (en) * | 2011-06-23 | 2011-12-21 | 中南大学 | Method for preparing porous composite polymer electrolyte film through gas volatilization |
| CN102924732A (en) * | 2012-11-05 | 2013-02-13 | 南京大学 | Method for preparing polyvinylidene fluoride (PVDF)-hexafluoropropylene (HFP) modification membrane of high energy density through hot pressing cross linking |
| CN103903871A (en) * | 2012-12-28 | 2014-07-02 | 海洋王照明科技股份有限公司 | Electrochemical power supply diaphragm, manufacturing method thereof, electrochemical battery or capacitor |
| CN103897207A (en) * | 2012-12-28 | 2014-07-02 | 海洋王照明科技股份有限公司 | Electrochemical power source diaphragm and preparation method thereof, and electrochemical cell or capacitor |
| CN105280868A (en) * | 2015-09-30 | 2016-01-27 | 中国科学院长春应用化学研究所 | Vinylidene fluoride-hexafluoropropylene copolymer/SiO2 composite membrane, preparation method and application therefor |
| CN105390646A (en) * | 2015-11-02 | 2016-03-09 | 中国第一汽车股份有限公司 | Homogeneous fiber reinforced fluorine-containing resin based diaphragm |
| CN109576981A (en) * | 2018-11-19 | 2019-04-05 | 肇庆市华师大光电产业研究院 | A kind of MnO2The coaxial composite fiber membrane of/Ni/PVDF, preparation method and application |
| CN109728236A (en) * | 2019-01-25 | 2019-05-07 | 深圳锂硫科技有限公司 | A kind of battery two-layer separator and preparation method thereof |
| CN111180637A (en) * | 2020-01-07 | 2020-05-19 | 四川东为氢源科技有限公司 | Sodium ion battery diaphragm and preparation method and application thereof |
| CN113851704A (en) * | 2021-09-24 | 2021-12-28 | 中化学南方建设投资有限公司 | Preparation method of polymer electrolyte membrane |
| CN113904061A (en) * | 2021-12-07 | 2022-01-07 | 北京金羽新材科技有限公司 | High-safety diaphragm and preparation method and application thereof |
| CN114079124A (en) * | 2020-08-14 | 2022-02-22 | 中国科学院上海硅酸盐研究所 | Organic-inorganic composite lithium ion battery diaphragm and preparation method thereof |
| CN114188667A (en) * | 2021-11-18 | 2022-03-15 | 哈尔滨工业大学 | Composite diaphragm of rechargeable lithium ion battery and preparation method and application thereof |
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2008
- 2008-04-29 CN CNA2008100644094A patent/CN101260216A/en active Pending
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|---|---|---|---|---|
| CN102286158A (en) * | 2011-06-23 | 2011-12-21 | 中南大学 | Method for preparing porous composite polymer electrolyte film through gas volatilization |
| CN102286158B (en) * | 2011-06-23 | 2012-12-12 | 中南大学 | Method for preparing porous composite polymer electrolyte film through gas volatilization |
| CN102924732A (en) * | 2012-11-05 | 2013-02-13 | 南京大学 | Method for preparing polyvinylidene fluoride (PVDF)-hexafluoropropylene (HFP) modification membrane of high energy density through hot pressing cross linking |
| CN103903871A (en) * | 2012-12-28 | 2014-07-02 | 海洋王照明科技股份有限公司 | Electrochemical power supply diaphragm, manufacturing method thereof, electrochemical battery or capacitor |
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| CN105280868A (en) * | 2015-09-30 | 2016-01-27 | 中国科学院长春应用化学研究所 | Vinylidene fluoride-hexafluoropropylene copolymer/SiO2 composite membrane, preparation method and application therefor |
| CN105390646A (en) * | 2015-11-02 | 2016-03-09 | 中国第一汽车股份有限公司 | Homogeneous fiber reinforced fluorine-containing resin based diaphragm |
| CN109576981A (en) * | 2018-11-19 | 2019-04-05 | 肇庆市华师大光电产业研究院 | A kind of MnO2The coaxial composite fiber membrane of/Ni/PVDF, preparation method and application |
| CN109728236A (en) * | 2019-01-25 | 2019-05-07 | 深圳锂硫科技有限公司 | A kind of battery two-layer separator and preparation method thereof |
| CN111180637A (en) * | 2020-01-07 | 2020-05-19 | 四川东为氢源科技有限公司 | Sodium ion battery diaphragm and preparation method and application thereof |
| CN114079124A (en) * | 2020-08-14 | 2022-02-22 | 中国科学院上海硅酸盐研究所 | Organic-inorganic composite lithium ion battery diaphragm and preparation method thereof |
| CN113851704A (en) * | 2021-09-24 | 2021-12-28 | 中化学南方建设投资有限公司 | Preparation method of polymer electrolyte membrane |
| CN113851704B (en) * | 2021-09-24 | 2023-12-15 | 中化学南方建设投资有限公司 | Preparation method of polymer electrolyte membrane |
| CN114188667A (en) * | 2021-11-18 | 2022-03-15 | 哈尔滨工业大学 | Composite diaphragm of rechargeable lithium ion battery and preparation method and application thereof |
| CN113904061A (en) * | 2021-12-07 | 2022-01-07 | 北京金羽新材科技有限公司 | High-safety diaphragm and preparation method and application thereof |
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