CN109004155A - A kind of preparation method of aramid fiber composite diaphragm for lithium battery - Google Patents
A kind of preparation method of aramid fiber composite diaphragm for lithium battery Download PDFInfo
- Publication number
- CN109004155A CN109004155A CN201810835751.3A CN201810835751A CN109004155A CN 109004155 A CN109004155 A CN 109004155A CN 201810835751 A CN201810835751 A CN 201810835751A CN 109004155 A CN109004155 A CN 109004155A
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- Prior art keywords
- pmia
- lithium
- dimethylacetamide
- spinning
- preparation
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 17
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 46
- 238000009987 spinning Methods 0.000 claims abstract description 39
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000012046 mixed solvent Substances 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000012530 fluid Substances 0.000 claims abstract description 13
- 239000000835 fiber Substances 0.000 claims abstract description 11
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 7
- 239000000460 chlorine Substances 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 claims abstract 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- -1 N, N- dimethylacetamide Amine Chemical class 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 229920002994 synthetic fiber Polymers 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000001523 electrospinning Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 43
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 239000004760 aramid Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000002121 nanofiber Substances 0.000 description 5
- 229940113088 dimethylacetamide Drugs 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005213 imbibition Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229920003367 Teijinconex Polymers 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004765 teijinconex Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- 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
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
- D06B3/10—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fabrics
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Cell Separators (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a kind of preparation methods of aramid fiber composite diaphragm for lithium battery, comprising the following steps: (1) chlorination lithium powder is added in n,N-dimethylacetamide under room temperature, is made into n,N-dimethylacetamide/lithium chloride mixed solvent；(2) dried PMIA is added to n,N-dimethylacetamide/lithium chloride in the mixed solvent, compound concentration is the PMIA spinning solution of 15-25wt%, and wherein the concentration of Chlorine in Solution lithium is 1-3wt%；(3) prepared PMIA spinning solution is subjected to electrostatic spinning, the processed PET non-woven fabrics base material for the treatment of fluid receives；(4) tunica fibrosa obtained after the completion of spinning is immersed into 40 DEG C of ethanol solutions and stands 1-3min, dry, mechanical roll-in obtains PMIA/PET composite diaphragm.The present invention adjusts electrospinning processes parameter in which can be convenient, and effectively changes the key properties such as porosity, fibre diameter, aperture, the thickness of film to adapt to the actual needs in applying, to obtain the lithium ion battery separator of high porosity, high liquid absorption amount.
Description
Technical field
The present invention relates to a kind of preparation methods of composite diaphragm for lithium battery, belong to chemical technology field.
Background technique
It is polyethylene (PE), polypropylene (PP) microporous barrier that lithium ion battery separator is most commonly used at present.Due to both
Polyolefins membrane surface can be lower, poor with electrolyte compatibility, assemble electrolyte in resulting battery/diaphragm interface resistance compared with
Height, and battery performance is finally influenced, and (polyethylene is about 140 DEG C, and polypropylene is about 160 since polyolefine material fusing point is lower
DEG C), high temperature thermal dimensional stability is poor, and high temperature electric current barrier property can be poor, causes in high current, high power power battery charge and discharge item
Under part, internal temperature of battery can be increased sharply, so that there is a situation where short circuits for inside battery, when accordingly acting as power battery diaphragm
Have security risk.Electrostatic spinning is film pore-forming new technology more concerned in recent years.By electrostatic spinning technique, it is special to spray
High molecular polymer form nano fibrous membrane, this spining technology can prepare high porosity, high thermal stability, lyophily
Good and relatively uniform distribution of fiber diameters nano fiber diaphragm.
Summary of the invention
In order to overcome, existing lithium battery diaphragm temperature tolerance is lower, limits high rate discharge for lithium ion battery and circulation
The deficiency of performance, the present invention provide a kind of good security, are conducive to improve the use of lithium ion battery under extreme conditions, mention
The preparation method of the aramid fiber composite diaphragm for lithium battery of the safety of high power lithium-ion battery.
For achieving the above object, present invention employs following technical solutions:
A kind of preparation method of aramid fiber composite diaphragm for lithium battery, comprising the following steps:
(1) n,N-dimethylacetamide/lithium chloride mixed solvent preparation: under nitrogen protection, by chlorination lithium powder under room temperature
It is added in n,N-dimethylacetamide, with magnetic stirrer 10min to being completely dissolved, is made into N, N- dimethylacetamide
Amine/lithium chloride mixed solvent；
(2) preparation of PMIA spinning solution: by dried meta-aramid (PMIA) fiber be added to n,N-dimethylacetamide/
Lithium chloride in the mixed solvent, with oil bath pan at 80 DEG C heating stirring 10h, until PMIA fiber is completely dissolved, PMIA spinning is molten
Liquid is prepared and is completed；The PMIA spinning solution that PMIA concentration is 15-25wt% is prepared, wherein the concentration of Chlorine in Solution lithium is 1-
3wt%；
(3) prepared PMIA spinning solution is subjected to electrostatic spinning, the processed PET non-woven fabrics base material for the treatment of fluid receives, institute
State the condition of electrostatic spinning are as follows: 25-40 DEG C of temperature, voltage 20-40KV, positive and negative electrode spacing 10-20cm, solution flow velocity are 0.8-
6mL/h, the revolving speed 200-600rpm of reception device；
(4) tunica fibrosa obtained after the completion of spinning is immersed into 40 DEG C of ethanol solutions and stands 1-3min, dry, mechanical roll-in obtains virtue
Synthetic fibre composite diaphragm for lithium battery: PMIA/PET composite diaphragm.
Further, in the step (1), the n,N-dimethylacetamide uses preceding dry by 4A molecular sieve, steaming
Evaporate purification.
Further, in the step (2), the meta-aramid fibers (PMIA) are using preceding in 120 DEG C of vacuum drying ovens
Dry 2h-4h.
Further, in the step (3), the treatment fluid is the modified acroleic acid adhesive of concentration 0.5-1wt%.
Further, it in the step (4), after the completion of spinning and the tunica fibrosa that ethanol solution obtains will be impregnated is segmented
Heat up drying, is first warming up to 80 DEG C, after keeping the temperature 15min, then is warming up to 120 DEG C, keeps the temperature 20min.
Meta-aramid fibers (PMIA) are a kind of high-performance fibers, and decomposition temperature is up to 500 DEG C, height prepared therefrom
Performance fibers, which have been obtained, to be widely applied.PMIA is that be connected with each other the line style that meta position phenyl is constituted by amide group big
Molecule, in the crystal of PMIA, hydrogen bond such as clathrate are arranged in two planes, so as to form three-dimensional structure, hydrogen bond
Strong effect makes PMIA have many advantages, such as heat resistance, anti-flammability, chemical stability and mechanical performance outstanding.Lithium ion power
The safe operation of battery needs diaphragm to have higher intensity, thermal stability.The present invention relates to lithium ion battery aramid fibers
(PMIA) preparation method of nano fiber non-woven fabric composite diaphragm is prepared using high-voltage electrostatic spinning method, with PET non-woven fabrics
As substrate, non-woven fabrics nano fiber diaphragm is prepared.The diaphragm has porosity height, imbibition liquid-keeping property strong, compared with high heat stability
Property, it can satisfy the security performance requirement of high capacity, high power lithium ion power battery.
Beneficial effects of the present invention are mainly manifested in: the preparation process that the present invention uses is relative to traditional stretching membrane process
More simple, the method for the present invention adjusts electrospinning processes ginseng to prepare lithium ion battery composite nano fiber diaphragm in which can be convenient
Number, changes the key properties such as porosity, fibre diameter, aperture, thickness of film effectively to adapt to the actual needs in applying, from
And obtain the lithium ion battery separator of high porosity, high liquid absorption amount.By electrostatic spinning technique, special high molecular polymerization is sprayed
Object forms nanofiber composite diaphragm to improve diaphragm thermal stability.
Specific embodiment
Below with reference to embodiment, invention is further described in detail.
Embodiment 1:
A kind of preparation method of aramid fiber composite diaphragm for lithium battery, comprising the following steps:
(1) n,N-dimethylacetamide/lithium chloride mixed solvent preparation: n,N-dimethylacetamide is dry by 4A molecular sieve
It is dry, distillation purification；Under nitrogen protection, chlorination lithium powder is added in n,N-dimethylacetamide under room temperature, is stirred with magnetic force
Device stirring 10min is mixed to being completely dissolved, is made into n,N-dimethylacetamide/lithium chloride mixed solvent；
(2) preparation of PMIA spinning solution: dried PMIA is added to N, N- by the PMIA dry 2h of 120 DEG C of vacuum drying ovens
Dimethyl acetamide/lithium chloride in the mixed solvent, with oil bath pan at 80 DEG C heating stirring 10h, until PMIA fiber is completely molten
Solution, PMIA spinning solution are prepared and are completed；The PMIA spinning solution that PMIA concentration is 15wt% is prepared, wherein Chlorine in Solution lithium
Concentration be 1wt%；
(3) prepared PMIA spinning solution is subjected to electrostatic spinning, the processed PET non-woven fabrics base material for the treatment of fluid receives, institute
State the condition of electrostatic spinning are as follows: 25 DEG C of temperature, voltage 20KV, positive and negative electrode spacing 10cm, solution flow velocity are 0.8mL/h, are received
The revolving speed 200rpm of device；Treatment fluid is the modified acroleic acid adhesive of concentration 0.5wt%；
(4) tunica fibrosa obtained after the completion of spinning is immersed into 40 DEG C of ethanol solutions and stands 1min；Tunica fibrosa temperature-gradient method is dry, first
80 DEG C are warming up to, after keeping the temperature 15min, then is warming up to 120 DEG C, keeps the temperature 20min；Mechanical roll-in obtain PMIA/PET it is compound every
Film.
Embodiment 2:
A kind of preparation method of aramid fiber composite diaphragm for lithium battery, comprising the following steps:
(1) n,N-dimethylacetamide/lithium chloride mixed solvent preparation: n,N-dimethylacetamide is dry by 4A molecular sieve
It is dry, distillation purification；Under nitrogen protection, chlorination lithium powder is added in n,N-dimethylacetamide under room temperature, is stirred with magnetic force
Device stirring 10min is mixed to being completely dissolved, is made into n,N-dimethylacetamide/lithium chloride mixed solvent；
(2) preparation of PMIA spinning solution: dried PMIA is added to N, N- by the PMIA dry 3h of 120 DEG C of vacuum drying ovens
Dimethyl acetamide/lithium chloride in the mixed solvent, with oil bath pan at 80 DEG C heating stirring 10h, until PMIA fiber is completely molten
Solution, PMIA spinning solution are prepared and are completed；The PMIA spinning solution that PMIA concentration is 17wt% is prepared, wherein Chlorine in Solution lithium
Concentration be 2wt%；
(3) prepared PMIA spinning solution is subjected to electrostatic spinning, the processed PET non-woven fabrics base material for the treatment of fluid receives, institute
State the condition of electrostatic spinning are as follows: 30 DEG C of temperature, voltage 30KV, positive and negative electrode spacing 15cm, solution flow velocity are 3mL/h, receive dress
The revolving speed 300rpm set；Treatment fluid is the modified acroleic acid adhesive of concentration 0.8wt%；
(4) tunica fibrosa obtained after the completion of spinning is immersed into 40 DEG C of ethanol solutions and stands 2min；Tunica fibrosa temperature-gradient method is dry, first
80 DEG C are warming up to, after keeping the temperature 15min, then is warming up to 120 DEG C, keeps the temperature 20min；Mechanical roll-in obtain PMIA/PET it is compound every
Film.
Embodiment 3:
A kind of preparation method of aramid fiber composite diaphragm for lithium battery, comprising the following steps:
(1) n,N-dimethylacetamide/lithium chloride mixed solvent preparation: n,N-dimethylacetamide is dry by 4A molecular sieve
It is dry, distillation purification；Under nitrogen protection, chlorination lithium powder is added in n,N-dimethylacetamide under room temperature, is stirred with magnetic force
Device stirring 10min is mixed to being completely dissolved, is made into n,N-dimethylacetamide/lithium chloride mixed solvent；
(2) preparation of PMIA spinning solution: dried PMIA is added to N, N- by the PMIA dry 4h of 120 DEG C of vacuum drying ovens
Dimethyl acetamide/lithium chloride in the mixed solvent, with oil bath pan at 80 DEG C heating stirring 10h, until PMIA fiber is completely molten
Solution, PMIA spinning solution are prepared and are completed；The PMIA spinning solution that PMIA concentration is 19wt% is prepared, wherein Chlorine in Solution lithium
Concentration be 3wt%；
(3) prepared PMIA spinning solution is subjected to electrostatic spinning, the processed PET non-woven fabrics base material for the treatment of fluid receives, institute
State the condition of electrostatic spinning are as follows: 40 DEG C of temperature, voltage 40KV, positive and negative electrode spacing 20cm, solution flow velocity are 6mL/h, receive dress
The revolving speed 600rpm set；Treatment fluid is the modified acroleic acid adhesive of concentration 1wt%；
(4) tunica fibrosa obtained after the completion of spinning is immersed into 40 DEG C of ethanol solutions and stands 3min；Tunica fibrosa temperature-gradient method is dry, first
80 DEG C are warming up to, after keeping the temperature 15min, then is warming up to 120 DEG C, keeps the temperature 20min；Mechanical roll-in obtain PMIA/PET it is compound every
Film.
Embodiment 4:
A kind of preparation method of aramid fiber composite diaphragm for lithium battery, comprising the following steps:
(1) n,N-dimethylacetamide/lithium chloride mixed solvent preparation: n,N-dimethylacetamide is dry by 4A molecular sieve
It is dry, distillation purification；Under nitrogen protection, chlorination lithium powder is added in n,N-dimethylacetamide under room temperature, is stirred with magnetic force
Device stirring 10min is mixed to being completely dissolved, is made into n,N-dimethylacetamide/lithium chloride mixed solvent；
(2) preparation of PMIA spinning solution: dried PMIA is added to N, N- by the PMIA dry 3h of 120 DEG C of vacuum drying ovens
Dimethyl acetamide/lithium chloride in the mixed solvent, with oil bath pan at 80 DEG C heating stirring 10h, until PMIA fiber is completely molten
Solution, PMIA spinning solution are prepared and are completed；The PMIA spinning solution that PMIA concentration is 18wt% is prepared, wherein Chlorine in Solution lithium
Concentration be 2wt%；
(3) prepared PMIA spinning solution is subjected to electrostatic spinning, the processed PET non-woven fabrics base material for the treatment of fluid receives, institute
State the condition of electrostatic spinning are as follows: 25 ± 2 DEG C of temperature environment, ambient humidity < 45%RH, voltage 30KV, positive and negative electrode spacing 15-
17cm, solution flow velocity are 2.80mL/h, the revolving speed 400rpm of reception device；Treatment fluid is the modified acroleic acid glue of concentration 0.8wt%
Glutinous agent；
(4) tunica fibrosa obtained after the completion of spinning is immersed into 40 DEG C of ethanol solutions and stands 2min；Tunica fibrosa temperature-gradient method is dry, first
80 DEG C are warming up to, after keeping the temperature 15min, then is warming up to 120 DEG C, keeps the temperature 20min；Mechanical roll-in obtain PMIA/PET it is compound every
Film.
Embodiment 5:
Such as embodiment 4, dried PMIA is added to n,N-dimethylacetamide/lithium chloride mixed solvent in step (2)
In, it is configured to the PMIA spinning solution that PMIA concentration is 21wt%.Other steps are identical.
Embodiment 6:
Such as embodiment 4, dried PMIA is added to n,N-dimethylacetamide/lithium chloride mixed solvent in step (2)
In, it is configured to the PMIA spinning solution that PMIA concentration is 23wt%.Other steps are identical.
Embodiment 7:
Such as embodiment 4, dried PMIA is added to n,N-dimethylacetamide/lithium chloride mixed solvent in step (2)
In, it is configured to the PMIA spinning solution that PMIA concentration is 25wt%.Other steps are identical.
The PET non-woven fabrics (25 μm) used in above-described embodiment originates from Mitsubishi paper company；Meta-aramid
(PMIA) trade mark: Teijinconex, Teijin Ltd.
The present invention has carried out thickness, imbibition to the PMIA/PET composite diaphragm that the electrostatic spinning in above-described embodiment obtains
The measurement of rate, porosity, percent thermal shrinkage and air penetrability fundamental performance parameter, referring to table 1, obtaining best spinning condition is PMIA
Concentration is 21wt%-23wt%.
The performance parameter table of 1 PMIA/PET composite diaphragm of table:
The test method of the fundamental performance parameter of PMIA/PET composite diaphragm are as follows:
1, the nano fibrous membrane that quality after post treatment is m the test of imbibition rate: is impregnated into 1M LiPF6/EC/DMC/DEC
2h in (EC/DMC/DEC=1/1/1, mass ratio) electrolyte solution, blots the electrolyte electronics of film surface with filter paper after taking-up
Balance weighing and calculating obtains composite membrane and impregnates (Δ m), then the matter before being impregnated with Δ m divided by film of poor quality before and after electrolyte solution
M is measured, electrolyte imbibition rate K=Δ m/m × 100% of film is obtained.Whole operation process is completed in vacuum glove box.
2, the test of puncture strength: using puncture needle Φ=1.0mm, tip R=0.5mm, with (100 ± 10) mm/min progress
The test of puncture force.
3, the test of porosity: film is impregnated into 2h in n-butanol, the positive fourth of film surface absorption is blotted in taking-up with filter paper
Alcohol, impregnated with electronic balance weighing film it is of poor quality before and after n-butanol, then with the body of the density divided by n-butanol and film of poor quality
Product.
4, the test of air penetrability: (Jinan blue streak mechanical & electrical technology is limited for test on air penetrability tester (model TQD-G1)
Company)
In order to study the thermal stability of diaphragm, to Celgard diaphragm and PMIA/PET composite diaphragm respectively 120 DEG C, 180 DEG C,
250 DEG C of progress vacuum drying ovens test 2h.PMIA/PET composite diaphragm is compared with the percent thermal shrinkage of Celgard diaphragm, referring to table 2.
As can be seen from Table 2, Celgard (2320) diaphragm is at 120 DEG C, longitudinal percent thermal shrinkage 2.5%；PMIA/PET composite diaphragm exists
There was only about 2.0% percent thermal shrinkage at 250 DEG C.
The test method of percent thermal shrinkage: it cuts the mm of 100mm × 100 sample 5 and opens, at different temperatures in vacuum drying oven
2h is managed, its longitudinal size is then surveyed.Percent thermal shrinkage: Δ L=(L-L0)/L × 100%, L are longitudinal length before heating, and L0 is heating
Preceding longitudinal length, unit mm.
2 PMIA/PET composite diaphragm of table is compared with the percent thermal shrinkage of Celgard diaphragm
Claims (5)
1. a kind of preparation method of aramid fiber composite diaphragm for lithium battery, it is characterised in that: the following steps are included:
(1) n,N-dimethylacetamide/lithium chloride mixed solvent preparation: under nitrogen protection, by chlorination lithium powder under room temperature
It is added in n,N-dimethylacetamide, with magnetic stirrer 10min to being completely dissolved, is made into N, N- dimethylacetamide
Amine/lithium chloride mixed solvent；
(2) dried PMIA the preparation of PMIA spinning solution: is added to n,N-dimethylacetamide/lithium chloride mixed solvent
In, compound concentration is the PMIA spinning solution of 15-25wt%, and wherein the concentration of Chlorine in Solution lithium is 1-3wt%；Finally use oil bath
Pot heating stirring 10h at 80 DEG C, until PMIA fiber is completely dissolved, PMIA spinning solution is prepared and is completed；
(3) prepared PMIA spinning solution is subjected to electrostatic spinning, the processed PET non-woven fabrics base material for the treatment of fluid receives, institute
State the condition of electrostatic spinning are as follows: 25-40 DEG C of temperature, voltage 20-40KV, positive and negative electrode spacing 10-20cm, solution flow velocity are 0.8-
6mL/h, the revolving speed 200-600rpm of reception device；
(4) tunica fibrosa obtained after the completion of spinning is immersed into 40 DEG C of ethanol solutions and stands 1-3min, dry, mechanical roll-in obtains virtue
Synthetic fibre composite diaphragm for lithium battery: PMIA/PET composite diaphragm.
2. the preparation method of aramid fiber composite diaphragm for lithium battery according to claim 1, it is characterised in that: the step (1)
In, the n,N-dimethylacetamide uses preceding dry by 4A molecular sieve, distillation purification.
3. the preparation method of aramid fiber composite diaphragm for lithium battery according to claim 1, it is characterised in that: the step (2)
In, the PMIA uses preceding 2h-4h dry in 120 DEG C of vacuum drying ovens.
4. the preparation method of aramid fiber composite diaphragm for lithium battery according to claim 1, it is characterised in that: the step (3)
In, the treatment fluid is the modified acroleic acid adhesive of concentration 0.5-1wt%.
5. the preparation method of aramid fiber composite diaphragm for lithium battery according to claim 1, it is characterised in that: the step (4)
In, after the completion of spinning and the tunica fibrosa that ethanol solution obtains will be impregnated to carry out temperature-gradient method dry, is first warming up to 80 DEG C, heat preservation
After 15min, then 120 DEG C are warming up to, keep the temperature 20min.
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