SiO2/ PVDF-HFP composite cellulosic membrane and its preparation method and application
阅读说明：本技术 SiO2/PVDF-HFP复合纤维膜及其制备方法和应用 (SiO2/ PVDF-HFP composite cellulosic membrane and its preparation method and application ) 是由 龙云泽 徐源 于淼 朱建伟 王晓雄 张俊 李晓 于 2019-08-15 设计创作，主要内容包括：本发明提出SiO_2/PVDF-HFP复合纤维膜及其制备方法和应用,其制备方法包括以下步骤：制备PVDF-HFP纳米纤维膜：配制PVDF-HFP纺丝前驱液,利用静电纺丝法制得PVDF-HFP纳米纤维膜；制备SiO_2纤维膜：分别配制SiO_2前驱体溶液和配制模板高聚物溶液,将二者混合配成杂化SiO_2纺丝前驱液,利用静电纺丝法制得杂化SiO_2纳米纤维膜,对所得杂化SiO_2纳米纤维膜进行高温退火以除去模板高聚物,得SiO_2纤维膜；材料复合：以电池专用胶粘合PVDF-HFP纳米纤维膜和SiO_2纤维膜得SiO_2/PVDF-HFP复合纤维膜。该复合纤维膜具有高机械强度,高热稳定性、高孔隙率、高电解质吸液率和高锂离子电导率,将其应用于锂电池可提高电池性能,且当锂电池处于高充放电速率时,电池隔膜能够产生闭孔效应,可提高电池的安全性。(The present invention proposes SiO 2 / PVDF-HFP composite cellulosic membrane and its preparation method and application, preparation method includes the following steps: preparation PVDF-HFP nano fibrous membrane: preparing PVDF-HFP spinning precursor liquid, PVDF-HFP nano fibrous membrane is made using method of electrostatic spinning；Prepare SiO 2 Tunica fibrosa: SiO is prepared respectively 2 Precursor solution and match pallet high polymeric solution, by the two mix be made into hydridization SiO 2 Hydridization SiO is made using method of electrostatic spinning in spinning precursor liquid 2 Nano fibrous membrane, to gained hydridization SiO 2 Nano fibrous membrane carries out high annealing to remove template high polymer, obtains SiO 2 Tunica fibrosa；Material cladding: with the dedicated glue bond PVDF-HFP nano fibrous membrane of battery and SiO 2 Tunica fibrosa obtains SiO 2 / PVDF-HFP composite cellulosic membrane.The composite cellulosic membrane has high mechanical strength, high thermal stability, high porosity, polyelectrolyte imbibition rate and high-lithium ion conductivity, being applied to lithium battery can be improved battery performance, and when lithium battery is in high charge-discharge rate, battery diaphragm can generate closed pore effect, and the safety of battery can be improved.)
1. a kind of SiO2The preparation method of/PVDF-HFP composite cellulosic membrane, which comprises the following steps:
It prepares PVDF-HFP nano fibrous membrane: preparing PVDF-HFP spinning precursor liquid, PVDF-HFP spinning precursor liquid is injected quiet In electric spinning device, PVDF-HFP nano fibrous membrane is made using method of electrostatic spinning；
Prepare SiO2Tunica fibrosa: soluble silicon salt, inorganic acid are dissolved in solvent and match to obtain SiO2Precursor solution, it is poly- with pallet height Object solution, by the SiO2Precursor solution mixes with template high polymeric solution and is made into hydridization SiO2Spinning precursor liquid, by hydridization SiO2Spinning precursor liquid injects in electrostatic spinning apparatus, and hydridization SiO is made using method of electrostatic spinning2Nano fibrous membrane, it is miscellaneous to gained Change SiO2Nano fibrous membrane carries out high annealing to remove template high polymer, obtains SiO2Tunica fibrosa；
Material cladding: with the dedicated glue bond PVDF-HFP nano fibrous membrane of battery and SiO2Tunica fibrosa obtains SiO2/ PVDF-HFP is compound Tunica fibrosa.
2. SiO according to claim 12The preparation method of/PVDF-HFP composite cellulosic membrane, which is characterized in that described solvable Property silicate be one of ethyl orthosilicate, methyl orthosilicate and trimethoxy silane or a variety of；The inorganic acid is phosphorus One of acid, hydrochloric acid and oxalic acid are a variety of；The battery special glue is in PVDF base battery glue and butadiene-styrene rubber base battery glue One kind, the template high polymer be PVA (polyvinyl alcohol), PVP (polyethylene pyrrole network alkanone), CMC (sodium cellulose glycolate), One of CA (cellulose acetate), PEO (Pluronic F-127) and PAA (polyacrylic acid) or a variety of.
3. SiO according to claim 12The preparation method of/PVDF-HFP composite cellulosic membrane, which is characterized in that the electrostatic The collection of device for spinning extremely roller collector, the liquid storage mechanism that the electrostatic spinning apparatus is used to supply precursor liquid, which is equipped with, to be used In the propulsion pump for pushing spinning precursor liquid injection spinning nozzle.
4. SiO according to claim 32The preparation method of/PVDF-HFP composite cellulosic membrane, which is characterized in that the preparation PVDF-HFP nano fibrous membrane step the following steps are included:
It prepares PVDF-HFP spinning precursor liquid: acetone and DMF in the mixed solvent is added in PVDF-HFP, in 20~50 DEG C of water-bath Stirring is completely dissolved to obtain PVDF-HFP spinning precursor liquid to PVDF-HFP in heating environment, in the PVDF-HFP spinning precursor liquid The content of PVDF-HFP is 12~22wt%, and the mass ratio of the in the mixed solvent acetone and DMF are 1: 1；
Electrospinning PVDF-HFP nanofiber: PVDF-HFP spinning precursor liquid is injected in the liquid storage mechanism in electrostatic spinning apparatus, The electrostatic spinning apparatus is opened, PVDF-HFP nano fibrous membrane is deposited to obtain on roller collector, by PVDF-HFP Nanowire Dimension film is removed from roller collector；The spinning parameter of the electro-spinning process be 13~20cm of spinning distance, spinning voltage 14~ 22kV, promoting the propulsion rate of pump is 22~32 μ L/min, and roller collector revolving speed is 100~400r/min, and spinning temperature is 10~35 DEG C, humidity is 10~50%, 1~3h of spinning time.
5. SiO according to claim 42The preparation method of/PVDF-HFP composite cellulosic membrane, which is characterized in that described in configuration The bath temperature of PVDF-HFP spinning precursor liquid is 40 DEG C, and the content of PVDF-HFP is in the PVDF-HFP spinning precursor liquid 18wt%, the spinning parameter for preparing PVDF-HFP nano fibrous membrane is spinning distance 16cm, and spinning voltage 16kV promotes pushing away for pump It is 27 μ L/min into rate, roller collector revolving speed is 260r/min, and spinning temperature is 26 DEG C, humidity 37%, the spinning time 2h。
6. SiO according to claim 32The preparation method of/PVDF-HFP composite cellulosic membrane, which is characterized in that the preparation SiO2Tunica fibrosa step the following steps are included:
Prepare SiO2Precursor solution: being 1: 0.5: 0.01~1: 3: 0.1 ratio by ethyl orthosilicate, water, phosphoric acid in mass ratio Mixing, stirring to formation clear solution is at room temperature to get SiO2Precursor solution；
With pallet high polymeric solution: PVA being added to the water, is stirred in 20~60 DEG C of heating water bath environment complete to PVA Dissolve to obtain template high polymeric solution；
Prepare hydridization SiO2Spinning precursor liquid: by template high polymeric solution and SiO2Precursor solution in mass ratio 1: 4~4: 1 is mixed It closes, stirs evenly to obtain hydridization SiO2Spinning precursor liquid；
Electrospinning hydridization SiO2Nano fibrous membrane: by hydridization SiO2Spinning precursor liquid injects in the liquid storage mechanism in electrostatic spinning apparatus, The electrostatic spinning apparatus is opened, hydridization SiO is deposited to obtain on roller collector2Spinning precursor liquid, by hydridization SiO2Spinning forerunner Liquid is removed from roller collector；The spinning parameter of the electro-spinning process be 13~20cm of spinning distance, 14~22kV of spinning voltage, The propulsion rate for promoting pump is 12~22 μ L/min, and roller collector revolving speed is 100~400r/min, and spinning temperature is 10~35 DEG C, humidity is 10~50%, 3~6h of spinning time；
High annealing: by hydridization SiO2Nano fibrous membrane is heated in air atmosphere with 0.5~4 DEG C of heating rate per minute 600~1000 DEG C, kept in 600~1000 DEG C of temperature 1~5 hour to remove the PVA ingredient in hybridized film, Temperature fall Room temperature after, obtain the SiO of free from admixture2Tunica fibrosa.
7. SiO according to claim 62The preparation method of/PVDF-HFP composite cellulosic membrane, which is characterized in that the SiO2 Ethyl orthosilicate in precursor solution, water, phosphoric acid mass ratio be 1: 1: 0.02；Configure the water-bath of the template high polymeric solution Temperature is 50 DEG C, and the content of PVA is 10wt% in the template high polymeric solution；The hydridization SiO2Template in spinning precursor liquid High polymeric solution and SiO2The mass ratio of precursor solution is 1: 1；Prepare hydridization SiO2The spinning parameter of nano fibrous membrane is spinning Distance 17cm, spinning voltage 18kV, promoting the propulsion rate of pump is 14 μ L/min, and roller collector revolving speed is 260r/min, is spun Silk temperature is 25 DEG C, humidity 45%, spinning time 4h；High-temperature annealing process is by hydridization SiO2Nano fibrous membrane is in air atmosphere Be heated to 600 DEG C in enclosing with 2 DEG C of heating rate per minute, kept in 600 DEG C of temperature 2 hours to remove in hybridized film PVA ingredient after the room temperature of Temperature fall, obtains the SiO of free from admixture2Tunica fibrosa.
8. SiO according to claim 32The preparation method of/PVDF-HFP composite cellulosic membrane, which is characterized in that the material Composite steps stir the following steps are included: battery special glue is added in the mixed solution of water and alcohol according to 2% mass ratio Slurry is obtained to solution is uniform, the mass ratio of water and alcohol is 2: 3 in the mixed solution, and slurry is soaked with spray pattern SiO2Tunica fibrosa, by PVDF-HFP fiber it is smooth be layered on SiO2On tunica fibrosa, and carry out at room temperature pressing processing make its with SiO2Tunica fibrosa sufficiently bonds and obtains SiO2/ PVDF-HFP composite cellulosic membrane.
9. a kind of SiO2/ PVDF-HFP composite cellulosic membrane, which is characterized in that using described in any item of the claim 1 to 8 SiO2The preparation method of/PVDF-HFP composite cellulosic membrane is made.
10. a kind of lithium battery, which is characterized in that use SiO as claimed in claim 92/ PVDF-HFP composite cellulosic membrane is as electricity Pond diaphragm.
Technical field
The invention belongs to electrochemical technology field more particularly to SiO2/ PVDF-HFP composite cellulosic membrane and preparation method thereof And application.
Background technique
Diaphragm is given more sustained attention as the pith in lithium ion battery by various regions research and development laboratory.Electrostatic spinning The lithium battery diaphragm of technology preparation has high porosity, imbibition rate, specific surface area, uniform pore-size distribution and lesser aperture Many advantages, such as.
Chinese patent CN201710133122 " a kind of lithium battery diaphragm and preparation method thereof and the application in lithium battery " It discloses electrostatic spinning and prepares pure inorganic SiO2Nano fibrous membrane is used for lithium ion battery separator, this SiO2Nano fibrous membrane tool There are high thermal stability, high porosity, polyelectrolyte imbibition rate and high-lithium ion conductivity, the performance of lithium ion battery for preparing it Also it increases.But SiO2Nano fibrous membrane is lower as the mechanical strength of lithium battery diaphragm, and when battery is in high charge and discharge When the temperature is excessively high, there are biggish safety issues for electric rate battery, are limited its practical application.
Summary of the invention
The present invention proposes SiO2/ PVDF-HFP composite cellulosic membrane and its preparation method and application, which has High mechanical strength, high thermal stability, high porosity, polyelectrolyte imbibition rate and high-lithium ion conductivity are applied to lithium electricity Battery performance can be improved in pond, and when lithium battery is in high charge-discharge rate battery when the temperature is excessively high, battery diaphragm can be generated and be closed The safety of lithium battery can be improved in the effect of holes.
In order to achieve the above object, the present invention provides a kind of SiO2The preparation method of/PVDF-HFP composite cellulosic membrane, packet Include following steps:
It prepares PVDF-HFP nano fibrous membrane: preparing PVDF-HFP (Kynoar-hexafluoropropene) spinning precursor liquid, it will PVDF-HFP spinning precursor liquid injects in electrostatic spinning apparatus, and PVDF-HFP nano fibrous membrane is made using method of electrostatic spinning；
Prepare SiO2Tunica fibrosa: soluble silicon salt, inorganic acid are dissolved in solvent and match to obtain SiO2(silica) presoma is molten Liquid matches pallet high polymeric solution, by the SiO2Precursor solution mixes with template high polymeric solution and is made into hydridization SiO2Spinning Precursor liquid, by hydridization SiO2Spinning precursor liquid injects in electrostatic spinning apparatus, and hydridization SiO is made using method of electrostatic spinning2Nanowire Film is tieed up, to gained hydridization SiO2Nano fibrous membrane carries out high annealing to remove template high polymer, obtains SiO2Tunica fibrosa；
Material cladding: with the dedicated glue bond PVDF-HFP nano fibrous membrane of battery and SiO2Tunica fibrosa obtains SiO2/PVDF-HFP Composite cellulosic membrane.
Preferably, the soluble silicate is one in ethyl orthosilicate, methyl orthosilicate and trimethoxy silane Kind is a variety of；The inorganic acid is one of phosphoric acid, hydrochloric acid and oxalic acid or a variety of；The battery special glue is PVDF base battery One of glue and butadiene-styrene rubber base battery glue, the template high polymer are PVA (polyvinyl alcohol), PVP (polyethylene pyrrole network alkane Ketone), CMC (sodium cellulose glycolate), CA (cellulose acetate), one of PEO (Pluronic F-127) and PAA (polyacrylic acid) Or it is a variety of.
Preferably, the collection of the electrostatic spinning apparatus extremely roller collector, the electrostatic spinning apparatus are used for The liquid storage mechanism of supply precursor liquid is equipped with the propulsion pump for pushing spinning precursor liquid injection spinning nozzle.
Preferably, the preparation PVDF-HFP nano fibrous membrane step the following steps are included:
It prepares PVDF-HFP spinning precursor liquid: acetone is added in PVDF-HFP and is mixed with DMF (n,N-Dimethylformamide) In solvent, stirs in 20~50 DEG C of heating water bath environment to PVDF-HFP and is completely dissolved to obtain PVDF-HFP spinning precursor liquid, The content of PVDF-HFP is 12~22wt% in the PVDF-HFP spinning precursor liquid, the in the mixed solvent acetone and DMF's Mass ratio is 1: 1；
Electrospinning PVDF-HFP nanofiber: PVDF-HFP spinning precursor liquid is injected into the liquid storage mechanism in electrostatic spinning apparatus In, the electrostatic spinning apparatus is opened, PVDF-HFP nano fibrous membrane is deposited to obtain on roller collector, by PVDF-HFP nanometers Tunica fibrosa is removed from roller collector；The spinning parameter of the electro-spinning process be 13~20cm of spinning distance, spinning voltage 14~ 22kV, promoting the propulsion rate of pump is 22~32 μ L/min, and roller collector revolving speed is 100~400r/min, and spinning temperature is 10~35 DEG C, humidity is 10~50%, 1~3h of spinning time.
Preferably, the bath temperature for configuring the PVDF-HFP spinning precursor liquid is 40 DEG C, the PVDF-HFP spinning The content of PVDF-HFP is 18wt% in precursor liquid, and the spinning parameter for preparing PVDF-HFP nano fibrous membrane is spinning distance 16cm, spinning voltage 16kV, promoting the propulsion rate of pump is 27 μ L/min, and roller collector revolving speed is 260r/min, spinning temperature Degree is 26 DEG C, humidity 37%, spinning time 2h.
Preferably, the preparation SiO2Tunica fibrosa step the following steps are included:
Prepare SiO2Precursor solution: being 1: 0.5: 0.01~1: 3: 0.1 by ethyl orthosilicate, water, phosphoric acid in mass ratio Ratio mixing, at room temperature stirring to formed clear solution to get SiO2Precursor solution；
With pallet high polymeric solution: PVA being added to the water, is stirred in 20~60 DEG C of heating water bath environment to PVA It is completely dissolved to obtain template high polymeric solution；
Prepare hydridization SiO2Spinning precursor liquid: by template high polymeric solution and SiO2Precursor solution in mass ratio 1: 4~4: 1 mixing, stirs evenly to obtain hydridization SiO2Spinning precursor liquid；
Electrospinning hydridization SiO2Nano fibrous membrane: by hydridization SiO2Spinning precursor liquid injects the liquid storage machine in electrostatic spinning apparatus In structure, the electrostatic spinning apparatus is opened, hydridization SiO is deposited to obtain on roller collector2Spinning precursor liquid, by hydridization SiO2It spins Silk precursor liquid is removed from roller collector；The spinning parameter of the electro-spinning process is 13~20cm of spinning distance, spinning voltage 14 ~22kV, promoting the propulsion rate of pump is 12~22 μ L/min, and roller collector revolving speed is 100~400r/min, spinning temperature It is 10~35 DEG C, humidity is 10~50%.3~6h of spinning time；
High annealing: by hydridization SiO2Nano fibrous membrane is added in air atmosphere with 0.5~4 DEG C of heating rate per minute Heat to 600~1000 DEG C, kept in 600~1000 DEG C of temperature 3~6 hours to remove the PVA ingredient in hybridized film, it is natural After the room temperature of cooling, the SiO of free from admixture is obtained2Tunica fibrosa.
Preferably, the SiO2Ethyl orthosilicate in precursor solution, water, phosphoric acid mass ratio be 1: 1: 0.02；Match The bath temperature for setting the template high polymeric solution is 50 DEG C, and the content of PVA is 10wt% in the template high polymeric solution；Institute State hydridization SiO2Template high polymeric solution and SiO in spinning precursor liquid2The mass ratio of precursor solution is 1: 1；Prepare hydridization SiO2 The spinning parameter of nano fibrous membrane is spinning distance 17cm, spinning voltage 18kV, and promoting the propulsion rate of pump is 14 μ L/min, rolling Cylinder collector revolving speed is 260r/min, and spinning temperature is 25 DEG C, humidity 45%, spinning time 4h；High-temperature annealing process is will Hydridization SiO2Nano fibrous membrane is heated to 600 DEG C in air atmosphere with 2 DEG C of heating rate per minute, in 600 DEG C of temperature It is middle to be kept for 2 hours to remove the PVA ingredient in hybridized film, after the room temperature of Temperature fall, obtain the SiO of free from admixture2Tunica fibrosa.
Preferably, the Material cladding step is the following steps are included: battery special glue is added according to 2% mass ratio Stirring obtains slurry to solution is uniform in the mixed solution of water and alcohol, and the mass ratio of water and alcohol is 2 in the mixed solution: 3, slurry is soaked into SiO with spray pattern2Tunica fibrosa, by PVDF-HFP fiber it is smooth be layered on SiO2On tunica fibrosa, and in room Pressing processing is carried out under temperature makes itself and SiO2Tunica fibrosa sufficiently bonds and obtains SiO2/ PVDF-HFP composite cellulosic membrane.
The invention also discloses use above-mentioned SiO2SiO made from the preparation method of/PVDF-HFP composite cellulosic membrane2/ PVDF-HFP composite cellulosic membrane.
The invention also discloses use above-mentioned SiO2Lithium battery of/PVDF-HFP the composite cellulosic membrane as battery diaphragm.
Compared with prior art, the advantages and positive effects of the present invention are:
The present invention provides SiO2/ PVDF-HFP composite cellulosic membrane and its preparation method and application, composite cellulosic membrane tool There is high mechanical strength, high thermal stability, high porosity, polyelectrolyte imbibition rate and high-lithium ion conductivity are applied to lithium Battery performance can be improved in battery, and when lithium battery is in high charge-discharge rate, battery diaphragm can generate closed pore effect, can mention The safety of high lithium battery.Specifically:
(1) SiO of the invention2/ PVDF-HFP composite cellulosic membrane, remains SiO2The high thermal stability of tunica fibrosa, high hole Rate, polyelectrolyte imbibition rate and high-lithium ion conductivity, the lithium with high electrochemical performance can be made by being applied to lithium battery Battery.
(2) SiO of the invention2/ PVDF-HFP composite cellulosic membrane, which has, is higher than SiO2The mechanical strength of tunica fibrosa, it is more suitable Cooperation is lithium battery diaphragm.
(3) when battery be in high charge-discharge rate temperature it is excessively high when, SiO of the invention2/ PVDF-HFP composite cellulosic membrane tool There is preferable heat resistance, and closed pore effect can be generated, the safety issue of battery can be reduced, the composite cellulosic membrane is in hot conditions It is lower that there is very big application potential.
Detailed description of the invention
Fig. 1 is the SiO of embodiment 12The SiO of/PVDF-HFP composite cellulosic membrane2The SEM photograph of fiber film surface；
Fig. 2 is the SiO of embodiment 12The SEM photograph of the PVDF-HFP nanofiber film surface of/PVDF-HFP composite cellulosic membrane；
Fig. 3 is the SiO of embodiment 12/ PVDF-HFP composite cellulosic membrane and SiO2The melting experiment comparison diagram of tunica fibrosa；
Fig. 4 is that embodiment 1 is the SiO being heat-treated through 180 DEG C2The SEM photograph in/PVDF-HFP composite cellulosic membrane section；
Fig. 5 is the SiO of embodiment 12The infrared spectrogram on/PVDF-HFP composite cellulosic membrane two sides；
Fig. 6 is the SiO of embodiment 12/ PVDF-HFP composite cellulosic membrane and SiO2The mechanical strength test result of tunica fibrosa is shown It is intended to；
Fig. 7 is the SiO of embodiment 12The contact angle test result of/PVDF-HFP composite cellulosic membrane to electrolyte；
Fig. 8 is the SiO of embodiment 12Battery performance test of/PVDF-HFP the composite cellulosic membrane (SPF) as battery diaphragm As a result；
Fig. 9 is the SiO of embodiment 12/ PVDF-HFP composite cellulosic membrane (SPF) is tested as the high rate performance of battery diaphragm As a result.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects It encloses.
The embodiment of the invention provides a kind of SiO2The preparation method of/PVDF-HFP composite cellulosic membrane, comprising the following steps:
It prepares PVDF-HFP nano fibrous membrane: preparing PVDF-HFP (Kynoar-hexafluoropropene) spinning precursor liquid, it will PVDF-HFP spinning precursor liquid injects in electrostatic spinning apparatus, and PVDF-HFP nano fibrous membrane is made using method of electrostatic spinning；
Prepare SiO2Tunica fibrosa: soluble silicon salt, inorganic acid are dissolved in solvent and match to obtain SiO2(silica) presoma is molten Liquid matches pallet high polymeric solution, by the SiO2Precursor solution mixes with template high polymeric solution and is made into hydridization SiO2Spinning Precursor liquid, by hydridization SiO2Spinning precursor liquid injects in electrostatic spinning apparatus, and hydridization SiO is made using method of electrostatic spinning2Nanowire Film is tieed up, to gained hydridization SiO2Nano fibrous membrane carries out high annealing to remove template high polymer, obtains SiO2Tunica fibrosa；
Material cladding: with the dedicated glue bond PVDF-HFP nano fibrous membrane of battery and SiO2Tunica fibrosa obtains SiO2/PVDF-HFP Composite cellulosic membrane.
Above-mentioned preparation method is by PVDF-HFP nano fibrous membrane and SiO2Tunica fibrosa progress is compound to be made SiO2/PVDF- HFP composite cellulosic membrane, remains SiO2High thermal stability, high porosity, polyelectrolyte imbibition rate and the high-lithium ion of tunica fibrosa Conductivity, the lithium battery with high electrochemical performance can be made by being applied to lithium battery, and the composite cellulosic membrane has and is higher than SiO2The mechanical strength of tunica fibrosa, is more suitable as lithium battery diaphragm.PVDF has good electrochemical stability and right Lithium ion has splendid affinity, but PVDF has relatively high crystallinity, can reduce the migration velocity of lithium ion, and originally Inventing the PVDF-HFP used has the advantages that high dielectric constant, chemistry and stable electrochemical property, PVDF- compared to PVDF Fluorine atom on HFP strand makes existing Van der Waals force between its macromolecular chain, also there is hydrogen bond, can increase the machinery of PVDF-HFP Intensity.Further, since the presence of fluorine atom, lithium ion can be migrated towards the ordered arrangement direction of fluorine atom on amorphous phase region, be increased Migration velocity of the blooming to lithium ion.
Meanwhile when battery is in high charge-discharge rate, reaches hot melting temperature (160 DEG C) of PVDF-HFP tunica fibrosa, Thawing, at this temperature, SiO takes place in PVDF-HFP tunica fibrosa2Skeleton provided by tunica fibrosa does not change still, melts PVDF-HFP be filled in SiO2In the hole of tunica fibrosa, the effect of closed pore can be played, this closed pore effect combines the present invention The excellent heat resistance of composite cellulosic membrane, the safety issue of battery will be greatly reduced, the SiO2/ PVDF-HFP composite cellulosic membrane There is very big application potential under the high temperature conditions.
Specifically, the soluble silicate is one of ethyl orthosilicate, methyl orthosilicate and trimethoxy silane Or it is a variety of；The inorganic acid is one of phosphoric acid, hydrochloric acid and oxalic acid or a variety of；The battery special glue is PVDF base battery glue One of with butadiene-styrene rubber base battery glue, the template high polymer is PVA (polyvinyl alcohol), PVP (polyethylene pyrrole network alkanone), One of CMC (sodium cellulose glycolate), CA (cellulose acetate), PEO (Pluronic F-127) and PAA (polyacrylic acid) or more Kind.
Specifically, the collection of the electrostatic spinning apparatus extremely roller collector, the electrostatic spinning apparatus is for supplying The propulsion pump for pushing spinning precursor liquid injection spinning nozzle is equipped with to the liquid storage mechanism of precursor liquid.
Specifically, the preparation PVDF-HFP nano fibrous membrane step the following steps are included:
It prepares PVDF-HFP spinning precursor liquid: acetone is added in PVDF-HFP and is mixed with DMF (n,N-Dimethylformamide) In solvent, stirs in 20~50 DEG C of heating water bath environment to PVDF-HFP and is completely dissolved to obtain PVDF-HFP spinning precursor liquid, The content of PVDF-HFP is 12~22wt% in the PVDF-HFP spinning precursor liquid, the in the mixed solvent acetone and DMF's Mass ratio is 1: 1；
Electrospinning PVDF-HFP nanofiber: PVDF-HFP spinning precursor liquid is injected into the liquid storage mechanism in electrostatic spinning apparatus In, the electrostatic spinning apparatus is opened, PVDF-HFP nano fibrous membrane is deposited to obtain on roller collector, by PVDF-HFP nanometers Tunica fibrosa is removed from roller collector；The spinning parameter of the electro-spinning process be 13~20cm of spinning distance, spinning voltage 14~ 22kV, promoting the propulsion rate of pump is 22~32 μ L/min, and roller collector revolving speed is 100~400r/min, and spinning temperature is 10~35 DEG C, humidity is 10~50%, 1~3h of spinning time.
Specifically, the preparation SiO2Tunica fibrosa step the following steps are included:
Prepare SiO2Precursor solution: being 1: 0.5: 0.01~1: 3: 0.1 by ethyl orthosilicate, water, phosphoric acid in mass ratio Ratio mixing, at room temperature stirring to formed clear solution to get SiO2Precursor solution；
With pallet high polymeric solution: PVA being added to the water, is stirred in 20~60 DEG C of heating water bath environment to PVA It is completely dissolved to obtain template high polymeric solution；
Prepare hydridization SiO2Spinning precursor liquid: by template high polymeric solution and SiO2Precursor solution in mass ratio 1: 4~4: 1 mixing, stirs evenly to obtain hydridization SiO2Spinning precursor liquid；
Electrospinning hydridization SiO2Nano fibrous membrane: by hydridization SiO2Spinning precursor liquid injects the liquid storage machine in electrostatic spinning apparatus In structure, the electrostatic spinning apparatus is opened, hydridization SiO is deposited to obtain on roller collector2Spinning precursor liquid, by hydridization SiO2It spins Silk precursor liquid is removed from roller collector；The spinning parameter of the electro-spinning process is 13~20cm of spinning distance, spinning voltage 14 ~22kV, promoting the propulsion rate of pump is 12~22 μ L/min, and roller collector revolving speed is 100~400r/min, spinning temperature It is 10~35 DEG C, humidity is 10~50%, 3~6h of spinning time；
High annealing: by hydridization SiO2Nano fibrous membrane is added in air atmosphere with 0.5~4 DEG C of heating rate per minute Heat to 600~1000 DEG C, kept in 600~1000 DEG C of temperature 1~5 hour to remove the PVA ingredient in hybridized film, it is natural After the room temperature of cooling, the SiO of free from admixture is obtained2Tunica fibrosa.
It is produced provided by the embodiment of the present invention without finish fiber producing processes and its gained to become apparent to introduce in detail Product are described below in conjunction with specific embodiment.
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