CN103147224B - Polyvinylidene fluoride composite cellulosic membrane and preparation method thereof and application - Google Patents
Polyvinylidene fluoride composite cellulosic membrane and preparation method thereof and application Download PDFInfo
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- CN103147224B CN103147224B CN201310056528.6A CN201310056528A CN103147224B CN 103147224 B CN103147224 B CN 103147224B CN 201310056528 A CN201310056528 A CN 201310056528A CN 103147224 B CN103147224 B CN 103147224B
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Abstract
The invention provides a kind of polyvinylidene fluoride composite cellulosic membrane, comprise polyvinylidene fluoride layer, thickness is 5 ~ 120 μm, the diameter of fiber is between 80 ~ 1500nm, described polyvinylidene fluoride layer comprises the composition of following mass percent: the Kynoar of 15 ~ 95%, the modifier of 5 ~ 85%, described modifier comprises polymer and/or inorganic oxide.Preparation method provided by the invention is simple, raw materials used and equipment is cheap, obtained composite cellulosic membrane has that porosity is high, membrane flux is high, mechanical strength is good, Heat stability is good, thickness are even and the advantage such as controlled, be applied to lithium ion battery and can improve ionic conductivity, improve its high rate during charging-discharging, demonstrate good chemical property and cycle performance.
Description
Technical field
The present invention relates to power battery diaphragm technical field, particularly relate to a kind of polyvinylidene fluoride composite cellulosic membrane and preparation method thereof and application.
Background technology
Many remarkable advantages such as lithium (Li) ion battery has that energy density is high, operating voltage is high, self discharge is little, has extended cycle life, memory-less effect, belong to new generation of green high-energy battery.Lithium ion battery has been widely used in the fields such as notebook computer, multiple portable power tool, weapon, creates huge economic benefit.And at present, all multiple enterprises and scientific research institutions just can be applied to efficient, safe, the cheap new type power lithium ion battery in the field such as battery-operated motor cycle and electric automobile at active development, have very tempting industrial prospect.
Barrier film is the critical component of lithium ion battery, and playing isolation both positive and negative polarity electronic conductance and allow electrolyte ion freely pass through thus realize the important function of ionic conduction, is the important decisive factor of the performances such as battery capacity, cycle performance and security performance.Conventional lithium ion battery separator preparation method is dry method and wet method etc.Although the industrialization of this kind of barrier film is produced, also there are some obvious defects, especially in the electrokinetic cell requiring high current charge-discharge.As, dry method tension is difficult to the aperture and the porosity that control barrier film, and extensibility can not be too high, otherwise easily causes septal perforator when stretching, and therefore membrane thicknesses is restricted, and that can not do is very thin, therefore mainly for the production of mid and low-end products; Wet method i.e. thermally induced phase separation, wet method can control aperture and the porosity of barrier film preferably, but this method output is lower, and after using solvent, may produce and pollute, and cost is higher to environment.
Therefore, be extremely necessary that the new diaphragm material of exploitation and relevant technology of preparing are to improve the combination property of barrier film, promote that its heavy industrialization is applied, and reduce costs.
Summary of the invention
For solving problems of the prior art, inventor against expectation finds, electrospinning process is applied to the preparation of lithium ion battery separator, preparation method is simple, raw materials used and equipment is cheap, by the composite cellulosic membrane obtained by the synergy of Kynoar and modifier, there is porosity high, membrane flux is high, mechanical strength is good, Heat stability is good, even and the advantage such as controlled of thickness, thus improve the ionic conductivity of lithium ion battery, improve its high rate during charging-discharging, demonstrate good chemical property and cycle performance, thus realize the present invention, in addition, by replacing electrostatic spinning, the compound of multilayer composite fiber film can be realized, the comprehensive advantage of multiple material coordinative role can be played, there is good lyophily.
An aspect, the invention provides a kind of polyvinylidene fluoride composite cellulosic membrane, comprise polyvinylidene fluoride layer, thickness is 5 ~ 120 μm, the diameter of fiber is between 80 ~ 1500nm, described polyvinylidene fluoride layer comprises the composition of following mass percent: the Kynoar of 15 ~ 95%, the modifier of 5 ~ 85%, and described modifier comprises polymer and/or inorganic oxide.
As a further improvement on the present invention, described polymer is selected from one or more in polyacrylonitrile, polyvinylpyrrolidone, polymethyl methacrylate, polyimides, poly(ethylene oxide), polyvinyl alcohol, polyvinyl butyral resin and Kynoar-hexafluoropropylene copolymer.
As a further improvement on the present invention, described inorganic compound is selected from one or more in silica, aluminium oxide, boron oxide, magnesia, titanium dioxide and zinc oxide.
As a further improvement on the present invention, polyvinylidene fluoride composite cellulosic membrane provided by the invention also comprises the first polymer fibres layers and the second polymer fibres layers, and described first polymer fibres layers is by described polyvinylidene fluoride layer and described second polymer fibres layers phase compound; Described first polymer fibres layers is made up of the mixture of polymer or polymer and Kynoar, and thickness is 3 ~ 80 μm; It is 3 ~ 80 μm that described second polymer fibres layers forms thickness by the mixture of polymer or polymer and Kynoar; The comprehensive advantage of multiple material coordinative role can be played by the compound of the first polymer fibres layers, polyvinylidene fluoride layer and the second polymer fibres layers, there is good lyophily.In addition, also can according to actual needs, by the first polymer fibres layers and the second polymer fibres layers more fibrage of compound again.
As a further improvement on the present invention, in the mixture of described polymer and Kynoar, the mass ratio of polymer and Kynoar is 0.1 ~ 10:1.
On the other hand, the present invention also provides the preparation method of polyvinylidene fluoride composite cellulosic membrane, comprises the steps:
A) preparation of polyvinylidene fluoride layer electrostatic spinning solution: the Kynoar getting 15 ~ 95 parts by weight, the modifier of 5 ~ 85 parts by weight, described modifier comprises polymer and/or inorganic oxide, dissolve and obtain polyvinylidene fluoride layer electrostatic spinning solution in a solvent, described solvent is selected from water, methyl alcohol, ethanol, ethylene glycol, acetone, N, one or more in dinethylformamide, DMA and oxolane;
B) preparation of polyvinylidene fluoride layer: under certain spinning condition, is spun into polyvinylidene fluoride layer by described polyvinylidene fluoride layer electrostatic spinning solution; Described spinning condition is voltage 4 ~ 60kV, temperature 10 ~ 90 DEG C, and the distance of gathering-device distance spinning appts is 3 ~ 50cm.
Electrospinning process is applied to the preparation of polyvinylidene fluoride composite cellulosic membrane, preparation method is simple, raw materials used and equipment is cheap, obtained composite cellulosic membrane has that porosity is high, membrane flux is high, mechanical strength is good, Heat stability is good, thickness are even and the advantage such as controlled, be applied to lithium ion battery and can improve ionic conductivity, improve its high rate during charging-discharging, demonstrate good chemical property and cycle performance.
Alternately the basic process of electrostatic spinning is: the electrostatic spinning solution that preparation is suitable, by the one of above-mentioned electrostatic spinning solution, two or more, pour into respectively in spray silk container used, pass through gauge tap, each moment is selected to be communicated with one of them spinning nozzle, carries out the spinning of certain solution.Under certain spinning condition, first a kind of electrostatic spinning solution is spun into tunica fibrosa, and then pass through gauge tap, select to be communicated with another spinning nozzle, the basis of the tunica fibrosa obtained is carried out the spinning of another kind of solution, obtain second layer composite cellulosic membrane, according to similar method, third layer and more multi-layered composite cellulosic membrane can be obtained.By by change the concentration of solution, spinning voltage, receiving range and spinning time can obtain the multilayer composite fiber membrane sample of different thicknesses, different-shape and different-thickness.
Composite cellulosic membrane can modulation obtain the membrane material of the significant advantage that one-component tunica fibrosa does not have by the compound of various raw material.Even but composite membrane, be also difficult to the demand simultaneously meeting high-end barrier film, as high mechanical properties, high thermal stability, high porosity, good lyophily performance etc.The situation of normal appearance is, a certain composite cellulosic membrane is particularly outstanding in the performance in some, but poor-performing in other respects.Therefore, the gathering into folds from level to level of the composite cellulosic membrane some with different advantage, the multilayer composite fiber film obtained, can possess the advantage of each layer simultaneously, thus becomes the very outstanding novel film materials of combination property.
As a further improvement on the present invention, preparation method provided by the invention also comprises the steps:
C) preparation of the first polymer fibres layers electrostatic spinning solution and the second polymer fibres layers electrostatic spinning solution: obtain the first polymer fibres layers electrostatic spinning solution in a solvent by the mixture dissolving of polymer or polymer and Kynoar, the second polymer fibres layers electrostatic spinning solution is obtained in a solvent by the mixture dissolving of polymer or polymer and Kynoar, described solvent is selected from water, methyl alcohol, ethanol, ethylene glycol, acetone, N, one or more in dinethylformamide, DMA and oxolane;
D) described first polymer fibres layers electrostatic spinning solution is spun into the first polymer fibres layers in the one side of polyvinylidene fluoride layer, described second polymer fibres layers electrostatic spinning solution is spun into the second polymer fibres layers at the another side of polyvinylidene fluoride layer, described first polymer fibres layers, by described polyvinylidene fluoride layer and described second polymer fibres layers phase compound, obtains polyvinylidene fluoride composite cellulosic membrane.
As a further improvement on the present invention, described polymer is selected from one or more in polyacrylonitrile, polyvinylpyrrolidone, polymethyl methacrylate, polyimides, poly(ethylene oxide), polyvinyl alcohol, polyvinyl butyral resin and Kynoar-hexafluoropropylene copolymer.
As a further improvement on the present invention, described inorganic compound is selected from one or more in silica, aluminium oxide, boron oxide, magnesia, titanium dioxide and zinc oxide.
Correspondingly, the present invention also provides polyvinylidene fluoride composite cellulosic membrane preparing the application in lithium ion battery separator.
Compared with prior art, the invention has the beneficial effects as follows: preparation electrospinning process being applied to lithium ion battery separator, preparation method is simple, raw materials used and equipment is cheap, and obtained composite cellulosic membrane has that porosity is high, membrane flux is high, mechanical strength is good, Heat stability is good, thickness are even and the advantage such as controlled.Polyvinylidene fluoride composite cellulosic membrane provided by the invention is applied to lithium ion battery, can improve ionic conductivity, improves its high rate during charging-discharging, demonstrates good chemical property and cycle performance, thus realizes the present invention; In addition, by replacing electrostatic spinning, the compound of multilayer composite fiber film can be realized, the comprehensive advantage of multiple material coordinative role can be played, there is good lyophily.
Accompanying drawing explanation
Fig. 1 is the present invention's alternately electrostatic spinning apparatus schematic diagram used.
Fig. 2 is the SEM photo of one deck PVDF tunica fibrosa that the embodiment of the present invention 1 obtains.
Fig. 3 is the SEM photo of one deck PVDF-PAN composite cellulosic membrane that the embodiment of the present invention 2 obtains.
Fig. 4 is the SEM photo of one deck PVDF-PMMA composite cellulosic membrane that the embodiment of the present invention 3 obtains.
Fig. 5 is the SEM photo of one deck PVDF-PVP composite cellulosic membrane that the embodiment of the present invention 4 obtains.
Fig. 6 is one deck PVDF-Al that the embodiment of the present invention 5 obtains
2o
3the SEM photo of composite cellulosic membrane.
Fig. 7 is one deck PVDF-SiO that the embodiment of the present invention 6 obtains
2the SEM photo of composite cellulosic membrane.
Fig. 8 is the PAN/PVDF-Al that the embodiment of the present invention 7 obtains
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3the SEM photo of composite cellulosic membrane.
Fig. 9 is the PVDF-PMMA/PVDF-B that the embodiment of the present invention 8 obtains
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3the SEM photo of composite cellulosic membrane.
Figure 10 is the PVDF-PMMA/PVDF-Al that the embodiment of the present invention 9 obtains
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3the SEM photo of/PVDF-PMMA composite cellulosic membrane.
Figure 11 is the PAN/PVDF-B that the embodiment of the present invention 10 obtains
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3the SEM photo of/PAN composite cellulosic membrane.
Figure 12 is the PVDF-HFP/PVDF-B that the embodiment of the present invention 11 obtains
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3the SEM figure of/PVDF-HFP composite cellulosic membrane.
Figure 13 is the cycle performance resolution chart of the obtained tunica fibrosa of the embodiment of the present invention 1 and example 3 and business PP/PE/PP composite diaphragm, and wherein 13-a refers to specific discharge capacity; 13-b refers to coulombic efficiency.
Figure 14 is the PVDF-HFP/PVDF-B that the embodiment of the present invention 11 obtains
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3the charge and discharge cycles curve of/PVDF-HFP composite cellulosic membrane.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in further details.
embodiment 1
1.5gPVDF is dissolved in the mixed solvent of 8mLDMF and 2mL acetone, stirs 20 hours under 60 ° of C water bath condition, obtain 15%PVDF spinning solution.Spinning solution is poured in the container be connected with spinning nozzle, carry out electrostatic spinning.Spinning condition is: spinning voltage is 20kV, and spinning nozzle syringe needle internal diameter is 0.45mm, and the distance between syringe needle and gathering-device is 15cm, and adopt aluminium sheet to collect fiber, spinning process carries out 1h, obtains PVDF tunica fibrosa.As shown in Figure 2, product has fiber morphology to SEM photo, and fiber exists node, and fibre diameter thickness is uneven, and average diameter is 195nm.Average diameter of the present invention refers to the population mean of fibre diameter, measurement be the position of non-protruding in fiber.
embodiment 2
0.8gPVDF and 0.4gPAN is dissolved in 10mLDMF solvent, stirs 20 hours under 60 ° of C water bath condition, obtain 8%PVDF-4%PAN mixed solution.Mixed solution is poured in the container be connected with spinning nozzle, carry out electrostatic spinning.Spinning condition is: spinning voltage is 20kV, and spinning nozzle syringe needle internal diameter is 0.45mm, and the distance between syringe needle and gathering-device is 15cm, and adopt aluminium sheet to collect fiber, spinning process carries out 1h, obtains PVDF-PAN composite cellulosic membrane.As shown in Figure 3, product has fiber morphology to SEM photo, and fiber exists node, and average fibre diameter is 452nm.
embodiment 3
1.6gPVDF and 0.4gPMMA is dissolved in 7.5mLDMF and 2.5mL acetone solvent, stirs 20 hours under 60 ° of C water bath condition, obtain 16%PVDF-4%PMMA mixed solution.Mixed solution is poured in the container be connected with spinning nozzle, carry out electrostatic spinning.Spinning condition is: spinning voltage is 15kV, and spinning nozzle syringe needle internal diameter is 0.45mm, and the distance between syringe needle and gathering-device is 15cm, and adopt aluminium sheet to collect fiber, spinning process carries out 1h, obtains PVDF-PMMA composite cellulosic membrane.As shown in Figure 4, product has fiber morphology to SEM photo, and average fibre diameter is 728nm.
embodiment 4
1.5gPVDF and 0.5gPVP is dissolved in 10mLDMF solvent, stirs 20 hours under 70 ° of C water bath condition, obtain 15%PVDF-5%PVP mixed solution.Mixed solution is poured in the container be connected with spinning nozzle, carry out electrostatic spinning.Spinning condition is: spinning voltage is 25kV, and spinning nozzle syringe needle internal diameter is 0.8mm, and the distance between syringe needle and gathering-device is 15cm, and adopt graphite paper to collect fiber, spinning process carries out 1h, obtains PVDF-PVP composite cellulosic membrane.As shown in Figure 5, product has fiber morphology to SEM photo, there is adhesion between fiber, and average fibre diameter is 1007nm.
embodiment 5
By 1.6gPVDF and 0.4gAl
2o
3nano-powder dissolves and is scattered in 8mLDMF and 2mL acetone solvent, stirs 20 hours, obtain 16%PVDF-4%Al under 60 ° of C water bath condition
2o
3mixed liquor.Mixed liquor is poured in the container be connected with spinning nozzle, carry out electrostatic spinning.Spinning condition is: spinning voltage is 10kV, and spinning nozzle syringe needle internal diameter is 1.2mm, and the distance between syringe needle and gathering-device is 15cm, and adopt aluminium sheet to collect fiber, spinning process carries out 1h, obtains PVDF-Al
2o
3composite cellulosic membrane.As shown in Figure 6, product has fiber morphology to SEM photo, and average fibre diameter is 504nm.
embodiment 6
By 1.6gPVDF and 0.4gSiO
2nano-powder dissolves and is scattered in 8mLDMF and 2mL acetone solvent, stirs 20 hours, obtain 16%PVDF-4%SiO under 60 ° of C water bath condition
2mixed liquor.Mixed liquor is poured in the container be connected with spinning nozzle, carry out electrostatic spinning.Spinning condition is: spinning voltage is 10kV, and spinning nozzle syringe needle internal diameter is 1.2mm, and the distance between syringe needle and gathering-device is 18cm, and adopt aluminium sheet to collect fiber, spinning process carries out 1h, obtains PVDF-SiO
2composite cellulosic membrane.As shown in Figure 7, product has fiber morphology to SEM photo, and fiber surface exists some particles, and average fibre diameter is 302nm.
embodiment 7
By 1.6gPVDF and 0.4gAl
2o
3nano-powder dissolves and is scattered in 8mLDMF and 2mL acetone solvent, stirs 20 hours, obtain 16%PVDF-4%Al under 60 ° of C water bath condition
2o
3mixed liquor.0.8gPAN is dissolved in 10mLDMF solvent, stirs 20 hours under 60 ° of C water bath condition, obtain 5.3%PAN spinning solution.By 16%PVDF-4%Al
2o
3mixed liquor and 5.3%PAN solution are poured in the container be connected with spinning nozzle 2 with spinning nozzle 1 respectively.By gauge tap conducting spinning nozzle 1, first by 16%PVDF-4%Al
2o
3mixed liquor is spun into composite fiber membrane, and spinning condition is: spinning voltage is 10kV, and spinning nozzle syringe needle internal diameter is 1.2mm, and the distance between syringe needle and gathering-device is 18cm, and adopt aluminium sheet to collect fiber, spinning process carries out 0.5h.Then, spinning nozzle 1 is cut off, conducting spinning nozzle 2,5.3%PAN solution spun is become second layer tunica fibrosa, and spinning condition is: spinning voltage is 15kV, and spinning nozzle syringe needle internal diameter is 0.45mm, distance between syringe needle and gathering-device is 15cm, and spinning process carries out 0.5h, obtains PAN/PVDF-Al
2o
3composite cellulosic membrane.As shown in Figure 8, viewed be the fibrolaminar microscopic appearance of PAN to SEM photo, has fiber morphology, and average fibre diameter is 87nm.
embodiment 8
1.6gPVDF and 0.4gPMMA is dissolved in 7.5mLDMF and 2.5mL acetone solvent, stirs 20 hours under 60 ° of C water bath condition, obtain 16%PVDF-4%PMMA mixed solution.By 1.5gPVDF and 50mgB
2o
3be dissolved in 9mLDMF and 1mL acetone solvent, stir 15 hours under 80 ° of C water bath condition, obtain 15%PVDF-0.5%B
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3mixed solution.By 16%PVDF-4%PMMA mixed solution and 15%PVDF-0.5%B
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3mixed solution is poured in the container be connected with spinning nozzle 2 with spinning nozzle 1 respectively.By gauge tap conducting spinning nozzle 1, first 16%PVDF-4%PMMA mixed solution is spun into composite fiber membrane, spinning condition is: spinning voltage is 15kV, spinning nozzle syringe needle internal diameter is 0.45mm, distance between syringe needle and gathering-device is 15cm, adopt aluminium sheet to collect fiber, spinning process carries out 0.5h.Then, cut off spinning nozzle 1, conducting spinning nozzle 2, by 15%PVDF-0.5%B
2o
3mixed solution is spun into second layer tunica fibrosa, and spinning condition is: spinning voltage is 15kV, and spinning nozzle syringe needle internal diameter is 0.45mm, and the distance between syringe needle and gathering-device is 15cm, and spinning process carries out 0.5h, obtains PVDF-PMMA/PVDF-B
2o
3composite cellulosic membrane.As shown in Figure 9, viewed be PVDF-B to SEM photo
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3the microscopic appearance of composite fibre layer, has fiber morphology, and average fibre diameter is 276nm.
embodiment 9
1.25gPVDF and 0.75gPMMA is dissolved in 8mLDMF and 2mL acetone solvent, stirs 20 hours under 60 ° of C water bath condition, obtain 12.5%PVDF-7.5%PMMA mixed solution.By 1.7gPVDF and 0.2gAl
2o
3nano-powder dissolves and is scattered in 10mLDMF solvent, stirs 20 hours, obtain 17%PVDF-2%Al under 60 ° of C water bath condition
2o
3mixed liquor.By 12.5%PVDF-7.5%PMMA mixed solution and 17%PVDF-2%Al
2o
3mixed liquor is poured in the container be connected with spinning nozzle 2 with spinning nozzle 1 respectively.By gauge tap conducting spinning nozzle 1, first 12.5%PVDF-7.5%PMMA mixed solution is spun into composite fiber membrane, spinning condition is: spinning voltage is 15kV, spinning nozzle syringe needle internal diameter is 0.45mm, distance between syringe needle and gathering-device is 15cm, adopt aluminium sheet to collect fiber, spinning process carries out 0.5h.Then, cut off spinning nozzle 1, conducting spinning nozzle 2, by 17%PVDF-2%Al
2o
3mixed liquor is spun into second layer tunica fibrosa, and spinning condition is: spinning voltage is 10kV, and spinning nozzle syringe needle internal diameter is 1.2mm, and the distance between syringe needle and gathering-device is 15cm, and spinning process carries out 0.5h.Finally, cut off spinning nozzle 2, conducting spinning nozzle 1 again, 12.5%PVDF-7.5%PMMA mixed solution is spun into third layer composite fiber membrane, spinning condition is: spinning voltage is 15kV, and spinning nozzle syringe needle internal diameter is 0.45mm, and the distance between syringe needle and gathering-device is 15cm, spinning process carries out 0.5h, finally obtains PVDF-PMMA/PVDF-Al
2o
3/ PVDF-PMMA composite cellulosic membrane.As shown in Figure 10, viewed be the microscopic appearance of PVDF-PMMA composite fibre layer to SEM photo, has fiber morphology, and fiber thickness is comparatively even, and average diameter is 512nm.
embodiment 10
0.8gPAN is dissolved in 10mLDMF solvent, stirs 20 hours under 60 ° of C water bath condition, obtain 8%PAN solution.By 1.5gPVDF and 50mgB
2o
3be dissolved in 9mLDMF and 1mL acetone solvent, stir 15 hours under 80 ° of C water bath condition, obtain 15%PVDF-0.5%B
2o
3mixed solution.By 8%PAN solution and 15%PVDF-0.5%B
2o
3mixed solution is poured in the container be connected with spinning nozzle 2 with spinning nozzle 1 respectively.By gauge tap conducting spinning nozzle 1, first 8%PAN solution spun is become composite fiber membrane, spinning condition is: spinning voltage is 20kV, spinning nozzle syringe needle internal diameter is 0.45mm, distance between syringe needle and gathering-device is 15cm, and adopt aluminium sheet to collect fiber, spinning process carries out 0.5h.Then, cut off spinning nozzle 1, conducting spinning nozzle 2, by 15%PVDF-0.5%B
2o
3mixed solution is spun into second layer tunica fibrosa, and spinning condition is: spinning voltage is 15kV, and spinning nozzle syringe needle internal diameter is 0.45mm, and the distance between syringe needle and gathering-device is 15cm, and spinning process carries out 0.5h.Finally, cut off spinning nozzle 2, conducting spinning nozzle 1 again, 8%PAN solution spun is become third layer composite fiber membrane, spinning condition is: spinning voltage is 20kV, and spinning nozzle syringe needle internal diameter is 0.45mm, and the distance between syringe needle and gathering-device is 15cm, spinning process carries out 0.5h, finally obtains PAN/PVDF-B
2o
3/ PAN composite cellulosic membrane.As shown in figure 11, viewed be the microscopic appearance of PAN composite fibre layer to SEM photo, has fiber morphology, and fiber thickness is very even, and average diameter is 552nm.
embodiment 11
2gPVDF-HFP is dissolved in the mixed solvent of DMF and 2mL acetone of 8mL, stirs 20 hours under the water bath condition of 60 ° of C, obtain 20%PVDF-HFP solution.By the B of PVDF and 0.18g of 1.8g
2o
3be dissolved in the mixed solvent of 8mLDMF and 2ml ethanol, stir 15 hours under 80 ° of C water bath condition, obtain 18%PVDF-1.8%B
2o
3mixed solution.By 20%PVDF-HFP solution and 18%PVDF-1.8%B
2o
3mixed solution is poured in the container be connected with spinning nozzle 2 with spinning nozzle 1 respectively.By gauge tap conducting spinning nozzle 1, first 20%PVDF-HFP solution spun is become composite fiber membrane, spinning condition is: spinning voltage is 20kV, spinning nozzle syringe needle internal diameter is 0.45mm, distance between syringe needle and gathering-device is 15cm, and adopt aluminium sheet to collect fiber, spinning process carries out 0.5h.Then, cut off spinning nozzle 1, conducting spinning nozzle 2, by 18%PVDF-1.8%B
2o
3mixed solution is spun into second layer tunica fibrosa, and spinning condition is: spinning voltage is 15kV, and spinning nozzle syringe needle internal diameter is 0.45mm, and the distance between syringe needle and gathering-device is 15cm, and spinning process carries out 0.5h.Finally, cut off spinning nozzle 2, conducting spinning nozzle 1 again, 20%PVDF-HFP solution spun is become third layer composite fiber membrane, spinning condition is: spinning voltage is 20kV, and spinning nozzle syringe needle internal diameter is 0.45mm, and the distance between syringe needle and gathering-device is 15cm, spinning process carries out 0.5h, finally obtains PVDF-HFP/PVDF-B
2o
3/ PVDF-HFP composite fibre membrane sample.As shown in figure 12, viewed be the microscopic appearance of PVDF-HFP composite fibre layer to SEM photo, and have fiber morphology, average fibre diameter is 443nm.
embodiment 12
The tunica fibrosa obtain embodiment 1 and example 3 and business PP/PE/PP composite diaphragm are assembled into CR2032 type button cell as barrier film, and carry out cycle performance test, result as shown in figure 13.As can be seen from Figure 13, adopt the battery of PVDF tunica fibrosa and the assembling of PVDF-PMMA composite cellulosic membrane, its specific discharge capacity is all higher than business PP/PE/PP barrier film.Adopt the battery of PVDF-PMMA composite cellulosic membrane assembling, experiencing 40 rear specific capacities of circulation is 116mAh/g, and compare to initial specific capacities (122mAh/g), have dropped 6mAh/g, rate of descent is 4.9%; And under the same conditions, business PP/PE/PP composite diaphragm is assembled into the battery of specific capacity, experiencing 40 rear specific capacities of circulation is 91mAh/g, and compare to initial specific capacities (96mAh/g), have dropped 5mAh/g, rate of descent is 5.2%.In addition, after 40 charge and discharge cycles, the contrast of the coulombic efficiency of battery, can find out, the cycle efficieny adding VDF-PMMA composite cellulosic membrane is more stable and close to 100%, reach the level of business PP/PE/PP composite diaphragm.
embodiment 13
By PVDF-HFP/PVDF-B obtained for embodiment 11
2o
3/ PVDF-HFP composite cellulosic membrane is assembled into CR2032 type button cell, carries out the test of charge and discharge cycles curve, and result as shown in figure 14.As can be seen from Figure 14, under the circulation of different rate charge-discharges, PVDF-HFP/PVDF-B
2o
3/ PVDF-HFP composite cellulosic membrane all shows excellent charge-discharge performance, and coulombic efficiency is near 98%.Its specific discharge capacity when 0.5C can reach 127mAh/g in addition, and show higher specific discharge capacity, its combination property is comparatively excellent.
Above content is in conjunction with concrete preferred embodiment further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.
Claims (7)
1. a polyvinylidene fluoride composite cellulosic membrane, comprise polyvinylidene fluoride layer, thickness is 5 ~ 120 μm, the diameter of fiber is between 80 ~ 1500nm, described polyvinylidene fluoride layer comprises the composition of following mass percent: the Kynoar of 15 ~ 95% and the polymer modifiers of 5 ~ 85%, or the Kynoar of 15 ~ 95% and 5 ~ 85% inorganic oxide modifier, it is characterized in that: also comprise the first polymer fibres layers and the second polymer fibres layers, described first polymer fibres layers is by described polyvinylidene fluoride layer and described second polymer fibres layers phase compound, described first polymer fibres layers is made up of the mixture of polymer and Kynoar, and thickness is 3 ~ 80 μm, described second polymer fibres layers forms thickness by the mixture of polymer and Kynoar, is 3 ~ 80 μm, and described polyvinylidene fluoride composite cellulosic membrane is for the preparation of lithium ion battery separator.
2. polyvinylidene fluoride composite cellulosic membrane according to claim 1, is characterized in that: in described polymer modifiers, polymer is selected from one or more in polyacrylonitrile, polyvinylpyrrolidone, polymethyl methacrylate, polyimides, poly(ethylene oxide), polyvinyl alcohol, polyvinyl butyral resin and Kynoar-hexafluoropropylene copolymer.
3. polyvinylidene fluoride composite cellulosic membrane according to claim 1, is characterized in that: described inorganic oxide modifier be selected from silica, aluminium oxide, boron oxide, magnesia, titanium dioxide and zinc oxide one or more.
4. polyvinylidene fluoride composite cellulosic membrane according to claim 1, is characterized in that: in the mixture of described polymer and Kynoar, and the mass ratio of polymer and Kynoar is 0.1 ~ 10:1.
5. the preparation method of polyvinylidene fluoride composite cellulosic membrane according to claim 1, is characterized in that: comprise the steps:
The preparation of polyvinylidene fluoride layer electrostatic spinning solution: the Kynoar getting 15 ~ 95 parts by weight, the modifier of 5 ~ 85 parts by weight, described modifier is polymer modifiers or inorganic oxide modifier, dissolve and obtain polyvinylidene fluoride layer electrostatic spinning solution in a solvent, described solvent is selected from water, methyl alcohol, ethanol, ethylene glycol, acetone, N, one or more in dinethylformamide, DMA and oxolane;
The preparation of polyvinylidene fluoride layer: under certain spinning condition, is spun into polyvinylidene fluoride layer by described polyvinylidene fluoride layer electrostatic spinning solution; Described spinning condition is voltage 4 ~ 60kV, temperature 10 ~ 90 DEG C, and the distance of gathering-device distance spinning appts is 3 ~ 50cm;
Comprise further: the preparation of the first polymer fibres layers electrostatic spinning solution and the second polymer fibres layers electrostatic spinning solution: obtain the first polymer fibres layers electrostatic spinning solution in a solvent by the mixture dissolving of polymer and Kynoar, the second polymer fibres layers electrostatic spinning solution is obtained in a solvent by the mixture dissolving of polymer and Kynoar, described solvent is selected from water, methyl alcohol, ethanol, ethylene glycol, acetone, N, one or more in dinethylformamide, DMA and oxolane;
Described first polymer fibres layers electrostatic spinning solution is spun into the first polymer fibres layers in the one side of polyvinylidene fluoride layer, described second polymer fibres layers electrostatic spinning solution is spun into the second polymer fibres layers at the another side of polyvinylidene fluoride layer, described first polymer fibres layers, by described polyvinylidene fluoride layer and described second polymer fibres layers phase compound, obtains polyvinylidene fluoride composite cellulosic membrane.
6. the preparation method of polyvinylidene fluoride composite cellulosic membrane according to claim 5, is characterized in that: in described polymer modifiers, polymer is selected from one or more in polyacrylonitrile, polyvinylpyrrolidone, polymethyl methacrylate, polyimides, poly(ethylene oxide), polyvinyl alcohol, polyvinyl butyral resin and Kynoar-hexafluoropropylene copolymer.
7. the preparation method of polyvinylidene fluoride composite cellulosic membrane according to claim 5, is characterized in that: described inorganic oxide modifier be selected from silica, aluminium oxide, boron oxide, magnesia, titanium dioxide and zinc oxide one or more.
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