CN108666501A - A kind of preparation method for the p-aramid fiber membrane for polymer that can be used for lithium ion battery produced with method of electrostatic spinning - Google Patents
A kind of preparation method for the p-aramid fiber membrane for polymer that can be used for lithium ion battery produced with method of electrostatic spinning Download PDFInfo
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- CN108666501A CN108666501A CN201810385938.8A CN201810385938A CN108666501A CN 108666501 A CN108666501 A CN 108666501A CN 201810385938 A CN201810385938 A CN 201810385938A CN 108666501 A CN108666501 A CN 108666501A
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- aramid fiber
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- ion battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
- D01F6/905—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides of aromatic polyamides
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/4334—Polyamides
- D04H1/4342—Aromatic polyamides
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation methods for the p-aramid fiber membrane for polymer that can be used for lithium ion battery produced with method of electrostatic spinning, by adding cosolvent, after p-aramid fiber polymer or para-aramid fiber dissolving, it is added thereto inorganic nano ceramic particle to obtain mixed liquor.Through mechanical agitation and supersound process so that inorganic ceramic particle is uniformly dispersed, dispersion liquid is obtained.Electrostatic spinning is carried out using the dispersion liquid, obtains inorganic/organic hybrid films of coming into being, processing is then dried to get to the p-aramid fiber membrane for polymer that can be used for lithium ion battery produced with electrostatic spinning.Lithium ion battery separator prepared by the present invention, porosity is high, thermal shrinkage energy is good, while having high ionic conductivity, good electrochemical stability, improves the safe application performance of battery.
Description
Technical field
The present invention relates to lithium ion batteries and high molecular material production technical field, and in particular to one kind is with method of electrostatic spinning
That produces can be used for the preparation method of the p-aramid fiber membrane for polymer of lithium ion battery.
Background technology
As a kind of clean secondary energy sources, lithium ion battery because high with voltage, energy is big, memory-less effect, can be fast
The advantages that fast charge and discharge, is widely used in the fields such as portable electronic product, electric vehicle and energy-storage system, is current energy
The research hotspot of source domain.Lithium ion battery is mainly made of positive and negative anodes, diaphragm, electrolyte.Its septation is in positive and negative anodes material
Between material, because the film has the micropore of a large amount of tortuous perforations, ensure that electrolyte ion passes freely through to form charging and discharging circuit, when
When battery overcharges or temperature increases, diaphragm is separated the positive and negative anodes of battery by closed pore function, prevents short circuit.To reach
The conduction of barrier electric current prevents battery the overheat even effect of explosion.The performance of diaphragm determines internal resistance and the internal interface knot of battery
Structure, and then capacity, charge-discharge performance, cycle performance and the security performance etc. of battery are influenced, therefore the quality of diaphragm is to lithium ion
The comprehensive performance important of battery.
Electrostatic spinning is the process that polymer solution or polymer melt form fiber under the action of high-voltage electrostatic field,
Cardinal principle is so that electrically charged Polymer Solution or melt are flowed, are divided in electrostatic field and deform, then through evaporation of the solvent
Or melt is cooling and cure, and finally obtains tunica fibrosa.The fibre diameter being prepared with electrostatic spinning technique can be at hundreds of nanometers
Extremely and between micron.Electrostatic spinning technique is applicable in because of the features such as its spinning equipment is simple, the operating time is short, spinning solution dosage is few
Preparation in film direction.Prepared film has the good characteristics such as large specific surface area, porosity are high, aperture is small.These characteristics make
Obtain superfine fibre film has comparable potential application in filtering, electricity, optics, biomedicine, battery diaphragm and water process etc.
Value.
For aramid fiber, p-aramid fiber polymer is because with solvent resistant, heat-resisting, excellent with low thermal coefficient of expansion etc.
Physicochemical property and as make the top-priority new material of lithium ion battery separator.But in the production process of p-aramid fiber polymer
It undergoing phase transition, final products exist in solid particulate form, and the only a fews strong protonic acid such as be only only soluble in the concentrated sulfuric acid or benzene sulfonic acid,
It is unfavorable for post-production, this becomes the biggest obstacle that p-aramid fiber polymer material is applied to lithium ion battery separator field.
Invention content
The present invention provides a kind of p-aramid fiber membrane for polymer that can be used for lithium ion battery produced with method of electrostatic spinning
Preparation method, with overcome the deficiencies in the prior art, the present invention is being retained pair by being added after cosolvent dissolves to organic solvent
Under the premise of the excellent physicochemical property of aramid fiber polymeric compound of position, its good mobility is assigned, and porous structure is formed with ceramic particle,
In addition electrospinning process processing film forming is used, it is simple for process.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of preparation method for the p-aramid fiber membrane for polymer that can be used for lithium ion battery produced with method of electrostatic spinning,
Include the following steps：
1) after adding cosolvent A and cosolvent B into organic solvent, p-aramid fiber polymer or para-aramid fiber is added
Dissolving is added nano grade inorganic ceramic particle after forming uniform solution, obtains mixed liquor；
2) mixed liquor is stirred tentatively to disperse, then ultrasonic disperse, further disperses nano grade inorganic ceramics
Grain, obtains dispersion liquid；
3) it utilizes the dispersion liquid to implement electrostatic spinning, obtains nascent inorganic/organic hybrid films on the reception device；
4) processing is dried in inorganic/organic hybrid films, removes the residual organic solvent in composite membrane to get with electrostatic
What spinning process was produced can be used for the p-aramid fiber membrane for polymer of lithium ion battery.
Further, the cosolvent A described in step 1) is the one or two of sec-butyl alcohol potassium and potassium tert-butoxide；Described
Cosolvent B is the one or two of methanol and ethyl alcohol；The cosolvent A additions are p-aramid fiber polymer or p-aramid fiber
One times of nitrogen equivalent in fiber；Cosolvent B additions are that nitrogen is worked as in p-aramid fiber polymer or para-aramid fiber
Four times of amount.
Further, the organic solvent described in step 1) be n,N-Dimethylformamide, N, N- dimethylacetylamides,
One or both of acetone, N-Methyl pyrrolidone, tetrahydrofuran and dimethyl sulfoxide (DMSO).
Further, in step 1) quality of p-aramid fiber polymer or para-aramid fiber be p-aramid fiber polymer or
The 0.6%~9.8% of para-aramid fiber and organic solvent and cosolvent A and cosolvent B quality sums.
Further, the nano grade inorganic ceramic particle described in step 1) is zirconium dioxide, alundum (Al2O3), titanium dioxide
One or both of titanium, silica, magnesia, zinc oxide, and nano grade inorganic ceramic particle grain size is 10~130nm,
Preferably 20~98nm.
Further, in step 1) p-aramid fiber polymer or para-aramid fiber and nano grade inorganic ceramic particle matter
Amount is than being (0.75~0.85): (0.15~0.25).
Further, the ultrasonic disperse time is 15~28min in step 2).
Further, in step 3) spinning rate be 0.5~1.6mL/h, spinning nozzle between reception device at a distance from be 10
~16cm, spinning voltage are 10~18kV.
Further, drying temperature is 50~220 DEG C in step 4), and the time is 1~1.5h.
Further, the thickness for the p-aramid fiber membrane for polymer that step 4) obtains is 22~48 μm, tensile break strength
For 4.2~14.7MPa, porosity is 90~99%, and imbibition rate is 240~320%.
Compared with prior art, the present invention has technique effect beneficial below：
The present invention is simple for process using electrospinning process processing film forming, the p-aramid fiber polymer lithium of preparation from
Sub- battery diaphragm forms porous structure with ceramic particle.The structure is conducive to improve the porosity and imbibition rate of diaphragm, and ceramic
Particle can be adsorbed on during circulating battery a small amount of H caused by electrolyte decomposition2O and HF improves battery efficiency,
Extend battery cycle life, in addition the p-aramid fiber polymer lithium cell diaphragm of the invention prepared, film thickness are smaller and easy
Control, and there is lower percent thermal shrinkage, good electrochemical stability, higher porosity and imbibition rate, while machinery is strong
Degree can meet the requirement of cell assembling processes.
The solvent that the present invention uses does not have corrosivity, greatly extends the service life of equipment, is keeping contraposition virtue
On the basis of synthetic fibre physicochemical property, its good mobility is assigned.
Specific implementation mode
Embodiments of the present invention are described in further detail below：
A kind of preparation method for the p-aramid fiber membrane for polymer that can be used for lithium ion battery produced with method of electrostatic spinning,
Include the following steps：
1) after adding cosolvent A and cosolvent B into organic solvent, p-aramid fiber polymer or para-aramid fiber is added
Dissolving is added nano grade inorganic ceramic particle after forming uniform solution, obtains mixed liquor；
The cosolvent A is the one or two of sec-butyl alcohol potassium and potassium tert-butoxide；The cosolvent B be methanol and
The one or two of ethyl alcohol；The cosolvent A additions are that nitrogen is worked as in p-aramid fiber polymer or para-aramid fiber
One times of amount；Cosolvent B additions are four times of nitrogen equivalent in p-aramid fiber polymer or para-aramid fiber；Described
Organic solvent is n,N-Dimethylformamide (DMF), n,N-dimethylacetamide (DMAc), acetone, N-Methyl pyrrolidone
(NMP), one or both of tetrahydrofuran (THF), dimethyl sulfoxide (DMSO) (DMSO)；And p-aramid fiber polymer or p-aramid fiber
The quality of fiber be p-aramid fiber polymer or para-aramid fiber with organic solvent and cosolvent A and cosolvent B mass it
The 0.6%~9.8% of sum, the nano grade inorganic ceramic particle are zirconium dioxide, alundum (Al2O3), titanium dioxide, dioxy
One or both of SiClx, magnesia, zinc oxide, and nano grade inorganic ceramic particle grain size be 10~130nm, preferably 20
~98nm, and the mass ratio of p-aramid fiber polymer or para-aramid fiber and nano grade inorganic ceramic particle be (0.75~
0.85): (0.15~0.25)；
2) mixed liquor is stirred tentatively to disperse, then 15~28min of ultrasonic disperse, further disperse nanoscale without
Machine ceramic particle, obtains dispersion liquid；
3) it utilizes the dispersion liquid to implement electrostatic spinning, obtains nascent inorganic/organic hybrid films, spinning on the reception device
Rate be 0.5~1.6mL/h, spinning nozzle between reception device at a distance from be 10~16cm, spinning voltage be 10~18kV；
4) processing is dried in inorganic/organic hybrid films, removes the residual organic solvent in composite membrane, drying temperature is
50~220 DEG C, the time is 1~1.5h poly- to get the p-aramid fiber that can be used for lithium ion battery produced with electrospinning process
Object diaphragm is closed, the thickness of obtained p-aramid fiber membrane for polymer is 22~48 μm, tensile break strength is 4.2~
14.7MPa, porosity are 90~99%, and imbibition rate is 240~320%.
The present invention is described in further detail with reference to embodiment：
Embodiment 1
At room temperature, cosolvent A (sec-butyl alcohol potassium) and cosolvent B (methanol) are first added to stirring and dissolving in DMF.Then
Weigh dry p-aramid fiber polymer/fiber and nanometer ZrO2, the mass ratio of aramid fiber quality and inorganic nanoparticles is 0.75:
0.25.First p-aramid fiber polymer/fiber is added into above-mentioned solvent, is obtained after dissolving with the quality of p-aramid fiber content meter
The stoste that score is 0.6%.Again by nanometer ZrO2It is added thereto, mechanical agitation 1h is with preliminary dispersing nanoparticles.It is then ultrasonic
15min is handled, it is further that nano particle is evenly dispersed, dispersion liquid is made.
Under the conditions of 25 DEG C of temperature, humidity 30%, above-mentioned dispersion liquid is subjected to Static Spinning with the spinning rate of 0.5mL/h
Silk：The voltage applied is 10kV, and the distance between syringe needle and receiver are 10cm.It is nascent by what is obtained after the completion of electrostatic spinning
ZrO2/ p-aramid fiber composite membrane is removed from receiver, and the p-aramid fiber that can be used for lithium ion battery is obtained after 160 DEG C of drying 1h
Membrane for polymer.The diaphragm is handled into 1.5h, shrinking percentage 0.5% at 130 DEG C, membrane thicknesses are 48 μm, and porosity is
97.2%, tensile break strength 5.2MPa；The diaphragm is immersed in ethylene carbonate/carbonic acid two of 1mol/L lithium hexafluoro phosphates
In the electrolyte of methyl esters/diethyl carbonate (mass ratio 1: 1: 1), the imbibition rate of acquisition is 371.2%, ionic conductivity is
1.93mS/cm, electrochemical stability window 5.63V.
Embodiment 2
At room temperature, cosolvent A (sec-butyl alcohol potassium) and cosolvent B (ethyl alcohol) are first added to stirring and dissolving in DMAc.Then
Weigh dry p-aramid fiber polymer/fiber and nanometer Al2O3, the mass ratio of aramid fiber quality and inorganic nanoparticles is 0.75:
0.25.First p-aramid fiber polymer/fiber is added into above-mentioned solvent, is obtained after dissolving with the quality of p-aramid fiber content meter
The stoste that score is 2.44%.Again by nanometer Al2O3It is added thereto, mechanical agitation 1h is with preliminary dispersing nanoparticles.It is then ultrasonic
20min is handled, it is further that nano particle is evenly dispersed, dispersion liquid is made.
Under the conditions of 25 DEG C of temperature, humidity 30%, above-mentioned dispersion liquid is subjected to Static Spinning with the spinning rate of 0.5mL/h
Silk：The voltage applied is 11.6kV, and the distance between syringe needle and receiver are 11.2cm.It will obtain after the completion of electrostatic spinning
Nascent Al2O3/ p-aramid fiber composite membrane is removed from receiver, and the contraposition that can be used for lithium ion battery is obtained after 170 DEG C of drying 1h
Aramid fiber polymeric compound diaphragm.The diaphragm is handled into 1.5h, shrinking percentage 0.6% at 130 DEG C, membrane thicknesses are 41 μm, porosity
It is 96.7%, tensile break strength 6.6MPa；The diaphragm is immersed in ethylene carbonate/carbonic acid of 1mol/L lithium hexafluoro phosphates
In the electrolyte of dimethyl ester/diethyl carbonate (mass ratio 1: 1: 1), the imbibition rate of acquisition is 359.6%, ionic conductivity is
2.14mS/cm, electrochemical stability window 5.58V.
Embodiment 3
At room temperature, cosolvent A (potassium tert-butoxide) and cosolvent B (methanol) are first added to stirring and dissolving in acetone.Then
Weigh dry p-aramid fiber polymer/fiber and nano-TiO2, the mass ratio of aramid fiber quality and inorganic nanoparticles is 0.80:
0.20.First p-aramid fiber polymer/fiber is added into above-mentioned solvent, is obtained after dissolving with the quality of p-aramid fiber content meter
The stoste that score is 4.28%.Again by nano-TiO2It is added thereto, mechanical agitation 1h is with preliminary dispersing nanoparticles.Then surpass
Sonication 25min, further that nano particle is evenly dispersed, obtained dispersion liquid.
Under the conditions of 25 DEG C of temperature, humidity 30%, above-mentioned dispersion liquid is subjected to Static Spinning with the spinning rate of 0.5mL/h
Silk：The voltage applied is 13.2kV, and the distance between syringe needle and receiver are 12.4cm.It will obtain after the completion of electrostatic spinning
Nascent TiO2P-aramid fiber composite membrane is removed from receiver, and the contraposition virtue that can be used for lithium ion battery is obtained after 75 DEG C of drying 1h
Synthetic fibre membrane for polymer.The diaphragm is handled into 1.5h, shrinking percentage 0.3% at 130 DEG C, membrane thicknesses are 39 μm, and porosity is
97.2%, tensile break strength 7.4MPa；The diaphragm is immersed in ethylene carbonate/carbonic acid two of 1mol/L lithium hexafluoro phosphates
In the electrolyte of methyl esters/diethyl carbonate (mass ratio 1: 1: 1), the imbibition rate of acquisition is 324.8%, ionic conductivity is
2.37mS/cm, electrochemical stability window 5.64V.
Embodiment 4
At room temperature, cosolvent A (potassium tert-butoxide) and cosolvent B (ethyl alcohol) are first added to stirring and dissolving in NMP.Then
Weigh the nanometer Al of dry p-aramid fiber polymer/fiber and arbitrary molar ratio2O3With Nano-meter SiO_22, aramid fiber quality with it is inorganic
The mass ratio of nano particle is 0.80: 0.20.First p-aramid fiber polymer/fiber is added into above-mentioned solvent, after dissolving
To the stoste for being 6.12% with the mass fraction of p-aramid fiber content meter.Again by inorganic nano Al2O3With Nano-meter SiO_22It is added
In, mechanical agitation 1h is with preliminary dispersing nanoparticles.It is then ultrasonically treated 28min, it is further that nano particle is evenly dispersed,
Dispersion liquid is made.
Under the conditions of 25 DEG C of temperature, humidity 30%, above-mentioned dispersion liquid is subjected to Static Spinning with the spinning rate of 1.16mL/h
Silk：The voltage applied is 14.8kV, and the distance between syringe needle and receiver are 13.6cm.It will obtain after the completion of electrostatic spinning
Primary silicon O2/ p-aramid fiber composite membrane is removed from receiver, and pair that can be used for lithium ion battery is obtained after 220 DEG C of drying 1.4h
Position aramid fiber polymeric compound diaphragm.The diaphragm is handled into 1.5h, shrinking percentage 0.6% at 130 DEG C, membrane thicknesses are 37 μm, hole
Rate is 94.9%, tensile break strength 8.2MPa；By the diaphragm be immersed in the ethylene carbonates of 1mol/L lithium hexafluoro phosphates/
In the electrolyte of dimethyl carbonate/diethyl carbonate (mass ratio 1: 1: 1), the imbibition rate of acquisition is 301.9%, ion-conductance
Conductance is 2.51mS/cm, electrochemical stability window 5.59V.
Embodiment 5
At room temperature, first cosolvent A (the sec-butyl alcohol potassium and potassium tert-butoxide of arbitrary proportion) and cosolvent B (methanol) is added
To stirring and dissolving in THF.Then weigh the nano-MgO and nanometer of dry p-aramid fiber polymer/fiber and arbitrary molar ratio
SiO2, the mass ratio of aramid fiber quality and inorganic nanoparticles is 0.85: 0.15.First by p-aramid fiber polymer/fiber be added to
The stoste for being 7.96% with the mass fraction of p-aramid fiber content meter is obtained in above-mentioned solvent, after dissolving.Again by inorganic nano MgO
With Nano-meter SiO_22It is added thereto, mechanical agitation 1h is with preliminary dispersing nanoparticles.It is then ultrasonically treated 28min, will further be received
Rice grain is evenly dispersed, and dispersion liquid is made.
Under the conditions of 25 DEG C of temperature, humidity 30%, above-mentioned dispersion liquid is subjected to Static Spinning with the spinning rate of 1.38mL/h
Silk：The voltage applied is 16.4kV, and the distance between syringe needle and receiver are 14.8cm.It will obtain after the completion of electrostatic spinning
Nascent MgO/ p-aramid fiber composite membranes are removed from receiver, and the contraposition that can be used for lithium ion battery is obtained after 70 DEG C of drying 1.2h
Aramid fiber polymeric compound diaphragm.The diaphragm is handled into 1.5h, shrinking percentage 0.5% at 130 DEG C, membrane thicknesses are 30 μm, porosity
It is 96.4%, tensile break strength 10.4MPa；The diaphragm is immersed in ethylene carbonate/carbon of 1mol/L lithium hexafluoro phosphates
In the electrolyte of dimethyl phthalate/diethyl carbonate (mass ratio 1: 1: 1), the imbibition rate of acquisition is 289.1%, ionic conductance
Rate is 2.58mS/cm, electrochemical stability window 5.62V.
Embodiment 6
At room temperature, cosolvent A (potassium tert-butoxide) and cosolvent B (methanol and ethyl alcohol of arbitrary proportion) are first added to DMSO
Middle stirring and dissolving.The nano-MgO and nano-ZnO of dry p-aramid fiber polymer/fiber and arbitrary molar ratio are then weighed, virtue
The mass ratio of synthetic fibre quality and inorganic nanoparticles is 0.85: 0.15.First p-aramid fiber polymer/fiber is added to above-mentioned molten
The stoste for being 9.80% with the mass fraction of p-aramid fiber content meter is obtained in agent, after dissolving.Again by inorganic nano MgO and nanometer
ZnO is added thereto, and mechanical agitation 1h is with preliminary dispersing nanoparticles.It is then ultrasonically treated 28min, further by nano particle
It is evenly dispersed, dispersion liquid is made.
Under the conditions of 25 DEG C of temperature, humidity 30%, above-mentioned dispersion liquid is subjected to Static Spinning with the spinning rate of 1.6mL/h
Silk：The voltage applied is 18kV, and the distance between syringe needle and receiver are 16.0cm.It is first by what is obtained after the completion of electrostatic spinning
Raw ZnO/ p-aramid fiber composite membranes are removed from receiver, and the contraposition that can be used for lithium ion battery is obtained after 220 DEG C of drying 1.5h
Aramid fiber polymeric compound diaphragm.The diaphragm is handled into 1.5h, shrinking percentage 0.4% at 130 DEG C, membrane thicknesses are 36 μm, porosity
It is 91.2%, tensile break strength 12.9MPa；The diaphragm is immersed in ethylene carbonate/carbon of 1mol/L lithium hexafluoro phosphates
In the electrolyte of dimethyl phthalate/diethyl carbonate (mass ratio 1: 1: 1), the imbibition rate of acquisition is 274.7%, ionic conductance
Rate is 3.02mS/cm, electrochemical stability window 5.59V.
Claims (10)
1. a kind of preparation method for the p-aramid fiber membrane for polymer that can be used for lithium ion battery produced with method of electrostatic spinning,
It is characterized in that, includes the following steps：
1) after adding cosolvent A and cosolvent B into organic solvent, p-aramid fiber polymer is added or para-aramid fiber is molten
Solution is added nano grade inorganic ceramic particle after forming uniform solution, obtains mixed liquor；
2) mixed liquor is stirred tentatively to disperse, then ultrasonic disperse, further disperses nano grade inorganic ceramic particle, obtains
To dispersion liquid；
3) it utilizes the dispersion liquid to implement electrostatic spinning, obtains nascent inorganic/organic hybrid films on the reception device；
4) processing is dried in inorganic/organic hybrid films, removes the residual organic solvent in composite membrane to get with electrostatic spinning
What method was produced can be used for the p-aramid fiber membrane for polymer of lithium ion battery.
2. a kind of p-aramid fiber polymerization that can be used for lithium ion battery produced with method of electrostatic spinning according to claim 1
The preparation method of object diaphragm, which is characterized in that cosolvent A described in step 1) be sec-butyl alcohol potassium and potassium tert-butoxide one kind or
Two kinds；The cosolvent B is the one or two of methanol and ethyl alcohol；The cosolvent A additions polymerize for p-aramid fiber
One times of nitrogen equivalent in object or para-aramid fiber；Cosolvent B additions are that p-aramid fiber polymer or p-aramid fiber are fine
Four times of nitrogen equivalent in dimension.
3. a kind of p-aramid fiber polymerization that can be used for lithium ion battery produced with method of electrostatic spinning according to claim 1
The preparation method of object diaphragm, which is characterized in that the organic solvent described in step 1) is n,N-Dimethylformamide, N, N- diformazans
One or both of yl acetamide, acetone, N-Methyl pyrrolidone, tetrahydrofuran and dimethyl sulfoxide (DMSO).
4. a kind of p-aramid fiber polymerization that can be used for lithium ion battery produced with method of electrostatic spinning according to claim 1
The preparation method of object diaphragm, which is characterized in that the quality of p-aramid fiber polymer or para-aramid fiber is contraposition in step 1)
The 0.6%~9.8% of aramid fiber polymeric compound or para-aramid fiber and organic solvent and cosolvent A and cosolvent B quality sums.
5. a kind of p-aramid fiber polymerization that can be used for lithium ion battery produced with method of electrostatic spinning according to claim 1
The preparation method of object diaphragm, which is characterized in that the nano grade inorganic ceramic particle described in step 1) is zirconium dioxide, three oxidations
One or both of two aluminium, titanium dioxide, silica, magnesia, zinc oxide, and nano grade inorganic ceramic particle grain size is
10~130nm, preferably 20~98nm.
6. a kind of p-aramid fiber polymerization that can be used for lithium ion battery produced with method of electrostatic spinning according to claim 5
The preparation method of object diaphragm, which is characterized in that p-aramid fiber polymer or para-aramid fiber and nano grade inorganic in step 1)
The mass ratio of ceramic particle is (0.75~0.85): (0.15~0.25).
7. a kind of p-aramid fiber polymerization that can be used for lithium ion battery produced with method of electrostatic spinning according to claim 1
The preparation method of object diaphragm, which is characterized in that the ultrasonic disperse time is 15~28min in step 2).
8. a kind of p-aramid fiber polymerization that can be used for lithium ion battery produced with method of electrostatic spinning according to claim 1
The preparation method of object diaphragm, which is characterized in that spinning rate is 0.5~1.6mL/h in step 3), between spinning nozzle and reception device
Distance be 10~16cm, spinning voltage be 10~18kV.
9. a kind of p-aramid fiber polymerization that can be used for lithium ion battery produced with method of electrostatic spinning according to claim 1
The preparation method of object diaphragm, which is characterized in that drying temperature is 50~220 DEG C in step 4), and the time is 1~1.5h.
10. a kind of p-aramid fiber that can be used for lithium ion battery produced with method of electrostatic spinning according to claim 1 is poly-
Closing the preparation method of object diaphragm, which is characterized in that the thickness for the p-aramid fiber membrane for polymer that step 4) obtains is 22~48 μm,
Tensile break strength is 4.2~14.7MPa, and porosity is 90~99%, and imbibition rate is 240~320%.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
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| CN201810385938.8A CN108666501A (en) | 2018-04-26 | 2018-04-26 | A kind of preparation method for the p-aramid fiber membrane for polymer that can be used for lithium ion battery produced with method of electrostatic spinning |
| PCT/CN2018/115437 WO2019205589A1 (en) | 2018-04-26 | 2018-11-14 | Preparation method for para-aramid polymer separator made by electrospinning and used for lithium ion battery |
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| CN201810385938.8A CN108666501A (en) | 2018-04-26 | 2018-04-26 | A kind of preparation method for the p-aramid fiber membrane for polymer that can be used for lithium ion battery produced with method of electrostatic spinning |
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| CN108666501A true CN108666501A (en) | 2018-10-16 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110364665A (en) * | 2019-07-29 | 2019-10-22 | 四川大学 | Septum for lithium ion battery and preparation method thereof |
| WO2019205589A1 (en) * | 2018-04-26 | 2019-10-31 | 烟台泰和新材料股份有限公司 | Preparation method for para-aramid polymer separator made by electrospinning and used for lithium ion battery |
| CN110499542A (en) * | 2019-09-27 | 2019-11-26 | 中芳特纤股份有限公司 | A kind of para-aramid fiber and preparation method thereof |
| CN113206345A (en) * | 2021-04-21 | 2021-08-03 | 陕西科技大学 | Para-aramid nanofiber/inorganic nanoparticle composite coating enhanced polyolefin battery diaphragm and preparation method thereof |
| WO2022127148A1 (en) * | 2020-12-16 | 2022-06-23 | 烟台泰和新材料股份有限公司 | Modified para-aramid polymerization liquid, coating slurry, lithium battery separator and preparation method therefor |
| CN114725616A (en) * | 2022-04-15 | 2022-07-08 | 青岛科技大学 | Inorganic hybrid aramid nanofiber membrane, preparation method and application of inorganic hybrid aramid nanofiber membrane in lithium battery |
| CN115093563A (en) * | 2022-07-14 | 2022-09-23 | 中科国生(杭州)科技有限公司 | Preparation method of bio-based aromatic polyamide polymerization solution and nano composite membrane |
| CN115295961A (en) * | 2022-08-29 | 2022-11-04 | 上海恩捷新材料科技有限公司 | Para-aramid diaphragm slurry, para-aramid diaphragm, preparation method of para-aramid diaphragm and lithium battery |
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| CN114374054A (en) * | 2022-01-14 | 2022-04-19 | 惠州市赛能电池有限公司 | Silicon-containing diaphragm, preparation method thereof and lithium battery |
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| CN110364665A (en) * | 2019-07-29 | 2019-10-22 | 四川大学 | Septum for lithium ion battery and preparation method thereof |
| CN110364665B (en) * | 2019-07-29 | 2020-11-13 | 四川大学 | Diaphragm for lithium battery and preparation method thereof |
| CN110499542A (en) * | 2019-09-27 | 2019-11-26 | 中芳特纤股份有限公司 | A kind of para-aramid fiber and preparation method thereof |
| WO2022127148A1 (en) * | 2020-12-16 | 2022-06-23 | 烟台泰和新材料股份有限公司 | Modified para-aramid polymerization liquid, coating slurry, lithium battery separator and preparation method therefor |
| CN113206345A (en) * | 2021-04-21 | 2021-08-03 | 陕西科技大学 | Para-aramid nanofiber/inorganic nanoparticle composite coating enhanced polyolefin battery diaphragm and preparation method thereof |
| CN114725616A (en) * | 2022-04-15 | 2022-07-08 | 青岛科技大学 | Inorganic hybrid aramid nanofiber membrane, preparation method and application of inorganic hybrid aramid nanofiber membrane in lithium battery |
| CN115093563A (en) * | 2022-07-14 | 2022-09-23 | 中科国生(杭州)科技有限公司 | Preparation method of bio-based aromatic polyamide polymerization solution and nano composite membrane |
| CN115295961A (en) * | 2022-08-29 | 2022-11-04 | 上海恩捷新材料科技有限公司 | Para-aramid diaphragm slurry, para-aramid diaphragm, preparation method of para-aramid diaphragm and lithium battery |
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