CN105261722B - It is orientated modified fibre homogeneity enhancing fluorine resin base barrier film - Google Patents
It is orientated modified fibre homogeneity enhancing fluorine resin base barrier film Download PDFInfo
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- CN105261722B CN105261722B CN201510730415.9A CN201510730415A CN105261722B CN 105261722 B CN105261722 B CN 105261722B CN 201510730415 A CN201510730415 A CN 201510730415A CN 105261722 B CN105261722 B CN 105261722B
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- fluorine resin
- barrier film
- pvdf
- reinforcing fiber
- hfp
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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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
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- 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
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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Reinforced Plastic Materials (AREA)
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Abstract
The present invention relates to one kind orientation modified fibre homogeneity enhancing fluorine resin base barrier film, it is characterised in that the composite diaphragm includes following components：A）：Matrix, B）：Reinforcing fiber；Wherein component A）With component B）Including fluorine resin and reinforcing fiber, the adding proportion mass ratio of fluorine resin and reinforcing fiber is 99 ~ 90/1 ~ 10；It is characterized in that described reinforcing fiber is selected from glass fibre, polyester fiber, PI fibers one or more.It uses the homo-fibers of orientation fibre modification to strengthen the mechanical strength of barrier film, and the barrier film mechanical property is strengthened, particularly suitable for power battery diaphragm field.
Description
Technical field
The present invention relates to one kind orientation modified fibre homogeneity enhancing fluorine resin base barrier film, led for power battery diaphragm
Domain.
Background technology
The fluorine resin base composite diaphragm such as PVDF, PCTFE, PTFE is convenient due to preparing, electrochemical performance, in power
Battery diaphragm field causes very big attention, but the mechanical property of this kind of barrier film is unsatisfactory, and its tensile strength does not surpass typically
20MPa is crossed, limits its application industrially.
Above-mentioned composite diaphragm can be prepared by techniques such as phase inversion method, the tape castings, in order to improve the power of composite diaphragm
Performance is learned, more using inorganic nano-particle, such as Al2O3, SiO2, BaTiO3Etc. composite mixed, but because inorganic nano-particle is easy
The characteristics of reunion, the mechanical property of barrier film can not be effectively improved, or even new stress concentration can be brought, come not to mode separation strapping
Necessary mechanical property loss.
The content of the invention
It is an object of the invention to provide one kind orientation modified fibre homogeneity enhancing fluorine resin base barrier film, it uses orientation
The homo-fibers of fibre modification strengthen the mechanical strength of barrier film, and the barrier film mechanical property strengthened, particularly suitable for dynamic
Power battery diaphragm field.
To achieve these goals, the technical proposal of the invention is realized in this way, and one kind orientation modified fibre homogeneity increases
Strong fluorine resin base barrier film, it is characterised in that including：
A）Matrix；
B）Reinforcing fiber；
Wherein A）With B）Contained material all includes a certain proportion of fluorine resin, and content is generally 90 ~ 99（Quality percentage
Than）, selected from Kynoar（PVDF）, poly- trifluoro-ethylene（PCTFE）, polytetrafluoroethylene (PTFE)（PTFE）, vinylidene-hexafluoro third
Alkene copolymer（PVDF-HFP）, trifluoro-ethylene-hexafluoropropylene copolymer（PCTFE-HFP）, tetrafluoroethene hexafluoropropylene copolymer
（PTFE-HFP）, polyhexafluoropropylene（PHFP）, vinylidene-trifluoro-ethylene copolymer（PVDF-CTFE）, vinylidene-tetrafluoro
Ethylene copolymer（PVDF-TFE）, trifluoro-ethylene-TFE copolymer（PCTFE-TFE）, vinylidene-trifluoro-ethylene-four
PVF terpolymer（PVDF-CTFE-TFE）Or vinylidene-trifluoro-ethylene-hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)（PVDF-
CTFE-TFE-HFP）One or more in multiple copolymer, especially, the copolymer selected from PVDF or PVDF and HFP
Or blend.
A）, especially B）In contain a certain amount of reinforcing fiber, content is generally 1 ~ 10（Mass percent）, selected from glass
The one or more of glass fiber, polyester fiber, PI fibers etc., silk particle diameter are 0.1 μm ~ 10 μm, also including other unaccounted tools
There is the fiber of humidification, such as PP fibers, asbestos fibre etc.；
In order that the enhancing component in reinforcing fiber is significantly orientated, reinforcing fiber is prepared using spinning technique more, preferentially adopted
Prepared with electrostatic spinning process, specifically, with certain solvent, such as acetone, NMP, DMF etc., after dissolving fluorine resin, then by one
Quantitative organic or inorganic fiber is scattered in previous solu, under 15 ~ 30kV, electrostatic spinning, silk dress is connect using high speed runner
Collection is put, then dry out solvent, that is, obtain fibrofelt, connecing silk device using high speed runner collects, and can make reinforcing fiber height
Orientation, so as to improve fibre strength, the string diameter of the reinforcing fiber of acquisition is between 0.1 ~ 10 μm.
For tetrafluoroethene system, because dissolving is difficult, preferentially using commercial polytetrafluoroethylene fibre（Such as teflon）Directly
Connect as reinforcing fiber, equally, teflon can be further enhanced using fiber.
Composite diaphragm uses phase inversion method, and either prepared by the tape casting or czochralski method, and specifically, the former two is obtained foregoing
To fibrofelt be laid on substrate, then certain density fluorine resin solution is poured on substrate, casting film-forming, dry
Solvent is settled out barrier film, the composite diaphragm that further drying to homo-fibers strengthens using phase inversion method；And the latter is
Obtained fibrofelt is impregnated in fluorine resin solution, fully after infiltration, drying is extracted out and obtains being orientated the increasing of modified fibre homogeneity
Strong fluorine resin base barrier film.
For tetrafluoroethene system, because dissolving is difficult, prepare orientation modified fibre homogeneity enhancing fluorine resin base every
It is preferential that above-mentioned solution is replaced using ptfe emulsion during film, it can contain a certain amount of and reinforcing fiber institute in the emulsion
The same fiber of fibre-bearing, so as to improve barrier film intensity after hardening.
The positive effect of the present invention is strengthened using homo-fibers, fine in particular by the homogeneity of inorganic nano-particle enhancing
Dimension enhancing can improve the mechanical property of PVDF base barrier films, and still, we are had found by studying, and the intensity of homo-fibers can lead to
The modification for crossing nanofiber is significantly improved, and in the absence of nanofiber dispersion it is irregular the problem of, research is found, this be because
To be significantly improved by drawing process, nanofiber dispersion, and it is orientated significantly, passes through prepared by method of electrostatic spinning
PVDF/ is orientated fiber composite fiber, and monofilament has the mechanical property higher than fibers such as PVDF/ ceramics, so as to obtain mechanical property
Fluorine resin base barrier film that can be higher.Therefore, the PVDF/ prepared by techniques such as electrostatic spinnings is orientated the fluorine resin bases such as fiber
Fiber be used to strengthen the fluorine resin base barrier film such as PVDF, further improved because the reinforcing fiber intensity obtains, Er Qiezhu
Body and resin base homogeneity, and resin base have a perfect compatibility performance, and enhancing effect is notable and lasting.Enter one using mechanical property
The orientation modified fibre homogeneity enhancing fluorine resin base barrier film that step improves, the mechanical property of the barrier film, stretching can be effectively improved
Strength test results show that mechanical property can improve 40% or so.And then promote the application of type barrier film industrially.
Brief description of the drawings
Fig. 1：Homo-fibers strengthen composite diaphragm schematic diagram, and 1 is reinforcing fiber B）, 2 be matrix A）.
Fig. 2：Pure homo-fibers reinforced resin base barrier film stress strain curve, the tensile strength of the barrier film is 27MPa.
Fig. 3：The resin base barrier film stress strain curve of PET reinforcing fiber homogeneity enhancing, the tensile strength of the barrier film are reachable
To 38.6MPa.
Embodiment
The present invention will be further described in conjunction with the accompanying drawings and embodiments, in following instantiations, gives a large amount of
Concrete details is in order to the more deep understanding present invention.It will be apparent, however, to one skilled in the art that
The present invention can be carried out without one or more of these details.
Embodiment 1
PVDF is that the fiberglass reinforced fiber homogeneity of substrate strengthens composite diaphragm and its preparation：1）Electrostatic spinning prepares nanometer and increased
Strong PVDF fibers, solvent acetone/DMF=3/7（v/v）, after PVDF dissolves, add 5% glass fibre（1μm）, disperse equal
After even, voltage 18KV collects distance 30cm, runner diameter 20cm, rotating speed 300r/min, spinning speed 2ml/h, and drying arrives
The PVDF fibrofelts of fiberglass reinforced, 1 ~ 3 μm of string diameter；2）Prepared by barrier film, foregoing fibrofelt is laid in into glass surface, is by concentration
8% PVDF solution（Solvent is DMF）Fibrofelt surface is laid in by curtain coating, then dried, that is, it is the same of substrate that PVDF, which is made,
The fibre-reinforced barrier film of matter；Compared to the PVDF barrier films strengthened without fibrofelt, intensity brings up to 41MPa from 19MPa；
Embodiment 2
PTFE is the barrier film and its preparation that the homo-fibers of substrate strengthen：1）Teflon fiber felt, 10 μm of string diameter；2）Barrier film
Prepare：10% is added into PTFE emulsion（Mass ratio）PI fibers（100nm）, after being uniformly dispersed, foregoing fibrofelt is impregnated in
3min in the emulsion, after infiltration, take out, vacuum drying, that is, obtain the barrier film that the homo-fibers that PTFE is substrate strengthen；Phase
Than bringing up to 40MPa from 17MPa in the PTFE barrier films strengthened without fibrofelt, intensity；
Embodiment 3
PVDF-HFP is the barrier film and its preparation that the PET reinforcing fiber homogeneity of substrate strengthens：1）It is prepared by electrostatic spinning
PET strengthens PVDF-HFP fibers, solvent acetone/DMF=8/2（v/v）, after dissolving, add 1% PET（200nm）,
After scattered 3h, electrostatic spinning, condition is voltage 23KV, collects distance 30cm, runner diameter 20cm, rotating speed 300r/min, spinning
Speed 2ml/h, the PVDF-HFP fibrofelts that drying to PET strengthens, 3 ~ 7 μm of string diameter；2）Prepared by barrier film, by foregoing fibrofelt
Glass surface is laid in, by the PVDF-HFP solution that concentration is 12%（Solvent is acetone）Fibrofelt surface is laid in by curtain coating,
Then dry, that is, the barrier film that the homo-fibers that PVDF-HFP is substrate strengthen is made；Strengthen compared to without PET reinforcing fiber mats
PVDF-HFP barrier films, intensity brings up to 38.6MPa from 27MPa（Such as Fig. 2, shown in Fig. 3）；
Embodiment 4
PVDF-HFP is the barrier film and its preparation that the PP/PI fibers homogeneity of substrate strengthens：1）Electrostatic spinning prepares PVDF-
HFP fibers, solvent acetone/DMF=8/2（v/v）, after dissolving, add 2% PP fibers（200nm）It is fine with the PI of homogenous quantities
Dimension（300nm）, after disperseing 4h, electrostatic spinning, condition is voltage 23KV, collects distance 30cm, runner diameter 20cm, rotating speed
300r/min, spinning speed 2ml/h, drying to the fibre-reinforced PVDF-HFP fibrofelts of PP/PI, 3 ~ 7 μm of string diameter；2）Every
Film preparation, foregoing fibrofelt is laid in glass surface, by the PVDF-HFP solution that concentration is 12%（Solvent is acetone）Pass through stream
Yangjing is laid on fibrofelt surface, then dries, that is, the barrier film that the reinforcing fiber that PVDF-HFP is substrate strengthens is made；Compared to not
The PVDF-HFP barrier films strengthened with the fibrofelt, intensity bring up to 35Mpa from 12MPa.
Claims (3)
1. one kind orientation modified fibre homogeneity enhancing fluorine resin base barrier film, it is characterised in that the barrier film includes following components：
A）：Matrix,
B）：Reinforcing fiber；
Wherein described component A）With component B）Include fluorine resin, the component B）In fluorine resin and reinforcing fiber matter
Amount is than being 99 ~ 90：1~10；
One or more of the described reinforcing fiber in glass fibre, polyester fiber and PI fibers；Wherein, first using spinning
Silk method the fluorine resin and reinforcing fiber is made the fluorine resin base fibrofelt of orientation modified fibre enhancing, then using same
The solution of kind fluorine resin casting film-forming on the fibrofelt, is dried, and then the barrier film is made afterwards.
A kind of 2. orientation modified fibre homogeneity enhancing fluorine resin base barrier film according to claim 1, wherein described fluorine-containing
Resin is selected from Kynoar（PVDF）, poly- trifluoro-ethylene（PCTFE）, polytetrafluoroethylene (PTFE)（PTFE）, vinylidene-hexafluoro third
Alkene copolymer（PVDF-HFP）, trifluoro-ethylene-hexafluoropropylene copolymer（PCTFE-HFP）, tetrafluoraoethylene-hexafluoropropylene copolymer
（PTFE-HFP）, polyhexafluoropropylene（PHFP）, vinylidene-trifluoro-ethylene copolymer（PVDF-CTFE）, vinylidene-tetrafluoro
Ethylene copolymer（PVDF-TFE）, trifluoro-ethylene-TFE copolymer（PCTFE-TFE）, vinylidene-trifluoro-ethylene-four
PVF terpolymer（PVDF-CTFE-TFE）Or vinylidene-trifluoro-ethylene-hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)（PVDF-
CTFE-TFE-HFP）One or more in multiple copolymer.
A kind of 3. orientation modified fibre homogeneity enhancing fluorine resin base barrier film according to claim 1, wherein the enhancing
The string diameter of fiber is 0.1 ~ 10 μm.
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| CN106099013B (en) * | 2016-07-18 | 2019-03-12 | 四川理工学院 | A kind of preparation method of polyimide foraminous diaphragm |
| CN109585751A (en) * | 2018-10-30 | 2019-04-05 | 东莞理工学院 | A kind of high strength fibre structure lithium electric separator and its preparation method and application |
| CN112830688B (en) * | 2021-04-16 | 2022-08-09 | 巨石集团有限公司 | Impregnating compound for glass fiber and preparation and application thereof |
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