CN102299284A - Active composite porous membrane for lithium ion battery, and preparation method thereof - Google Patents
Active composite porous membrane for lithium ion battery, and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an active composite porous membrane for a lithium ion battery, and a preparation method thereof. The membrane is prepared through combination of a porous polymer support skeleton and a cross-linked polyether/silicone rubber gel matrix. The preparation method comprises: adopting a flat porous polymer membrane as a support skeleton, dissolving polyether macromonomer containing terminal double bonds and cross-linkable silicone rubber containing double bonds in an organic solvent to prepare a precursor dipping solution; then immersing the porous polymer support skeleton in the precursor dipping solution to fully absorb the precursor dipping solution; carrying out two steps of thermal cross-linking treatment and coagulation bath curing after removing the porous polymer support skeleton; then washing and drying to obtain the active composite porous membrane for the lithium ion battery. With the present invention, the membrane has good mechanical strength; the porous structure of the membrane is provided for improving the electrolyte absorption rate and the conductivity of the membrane; the active gel matrix is provided for stabilizingt the electrolyte; the method is especially applicable for preparing the power lithium ion battery and the polymer lithium ion battery.
Description
Technical field
The present invention relates to lithium ion battery separator material field, particularly a kind of active compound porous barrier film that is applicable to power lithium-ion battery and polymer Li-ion battery and preparation method thereof.
Technical background
Lithium rechargeable battery, compare with the batteries such as alkali/manganese cell, lead/sour battery and nickel/hydrogen of present use, have advantages such as high-energy-density, high voltage, little, in light weight, the memoryless property of volume, become one of main energy sources of modern communication electronic product.In recent years, its application in the electrokinetic cell field is also developing rapidly, and is wide before the lithium ion battery market development space empty.Barrier film is as the important component part of lithium ion battery, and it mainly acts on is that positive and negative electrode with battery separates, and prevents directly contact and being short-circuited of the two poles of the earth; Barrier film itself is nonconducting, but can allow electrolyte ion to pass through.In addition, diaphragm material also must have favorable mechanical performance, chemical stability and electrochemical stability, and keeps necessary electrolyte at its microcellular structure, in the repeated charge process electrolyte is kept the height wettability.
At present, commercial polymer micro battery diaphragm one class is polyethylene (PE), high density polyethylene (HDPE) (HDPE) or polypropylene (PP) barrier film, the barrier film of producing with Celgard company is representative, its preparation method sees patent US2007221567 for details, US2008118827, though can provide the good mechanical performance at normal temperatures, but it is poor with the affinity of lithium-ion battery electrolytes that the problem of such barrier film is a material itself, cause electrolyte poor to the wetability of barrier film, make electrolyte be difficult to fully enter micropore inside, be unfavorable for the lithium ion migration, cause various problems such as internal resistance of cell increase and large current density difficulty, also influence the cycle performance of battery simultaneously.Another kind of is U.S. Bellcore company disclosed a kind of barrier film in the US5296318 patent, this barrier film is formed by vinylidene and hexafluoropropylene copolymerization, its preparation method is to be dissolved in copolymer and a certain proportion of plasticizer in the organic solvent altogether, with organic solvent this plasticizer is extracted again after making film, make barrier film with certain micropore.Not only preparation technology is miscellaneous for this class porous septum, and product percent of pass is low, and the mechanical performance deficiency.
Deficiency at above-mentioned barrier film, patent US 4550064 discloses another kind of barrier film, and it is made up of two-layer, and matrix is capillary polypropylene barrier film or glass fibre, surface-coated one deck imidazoline, a large amount of hydrophilic radical in surface has improved the interfacial property of positive pole/barrier film.Patent CN 1481036 discloses a kind of nothing extraction composition polymer lithium ion battery separator and preparation method thereof, its manufacture method is for filling material dissolves resulting mixture in solvent of matrix, with impregnation mixture, be coated with or be sprayed on the back bone network, remove and to desolvate, promptly.Patent CN101420019 discloses a kind of coating process of jelly polymer battery separator, adopt one or more coating techniques in intaglio plate coating, reverse roll coating, sloping flow coat cloth or the extrusion coated, be coated on the solution that is transported to spreader on the supporter equably, then, solidified coating gets the final finished barrier film.Patent US 20030446380 discloses a kind of preparation method of battery diaphragm, and this method is utilized the volatile difference of mixed solvent, forms on microporous barrier and contains the gel coating layer of micropore, thereby prepare a kind of compound battery diaphragm.Though these barrier film manufacture methods are improved the performance of commercialization barrier film, still have many deficiencies.For example, they also reckon without the stability problem (power that depends on adhesion between packed layer or coating layer and the matrix) of composite construction, and simple coating procedure can not guarantee the strong bonded between packed layer and matrix; Or unresolved packed layer densification is unfavorable for that Electolyte-absorptive also may stop up the problem in duct; The barrier film that does not more solve packed layer or coating layer poor mechanical property and may cause pierces through problem.
Be different from said method, it is easy that the present invention has provided technology, applied widely, active compound porous barrier film of the lithium ion battery of function admirable and preparation method thereof.The compound porous barrier film of this kind activity is by the polyalcohol stephanoporate support frame with crosslinked polyethers/the silicon rubber gel-type vehicle is compound forms.The mechanism of crosslinking of polyethers/silicon rubber gel-type vehicle as shown in Figure 1.
Be different from existing lithium ion battery separator and preparation method thereof, the compound porous barrier film of activity disclosed by the invention is owing to the existence of polyalcohol stephanoporate support frame has good mechanical intensity; The chemical crosslinking structure has guaranteed that crosslinked polyethers/silicon rubber gel active matrix combines with support frame firmly; Crosslinked polyethers/the loose structure of silicon rubber gel active matrix helps improving the electrolyte absorptivity and the conductivity of barrier film, also helps the stabilisation of barrier film to electrolyte.In addition, the active compound porous barrier film manufacture method of lithium ion battery disclosed by the invention, also have membrane configuration and performance controllability by force, low cost of manufacture, easily realize serialization production and clean advantage such as production.From disclosed document, do not find at present and active compound porous barrier film of lithium ion battery or the identical bibliographical information of its preparation method of being used for disclosed by the invention.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of structure and performance long-term stability are provided, both had the good mechanical performance, possess active compound porous barrier film of lithium ion battery of good electric chemical property and preparation method thereof again.
The compound porous barrier film of this kind activity is by the polyalcohol stephanoporate support frame and crosslinked polyethers/the silicon rubber gel-type vehicle is compound forms, wherein the mass content of polyalcohol stephanoporate support frame is 50～90%, the mass content of crosslinked polyethers/silicon rubber gel-type vehicle is 10～50%, the thickness of active compound porous barrier film is 10 μ m～100 μ m, volumetric porosity is 10-60%, described polyalcohol stephanoporate support frame is a polyethylene, polypropylene, Kynoar, Kynoar is hexafluoropropylene altogether, PETG, PTT, polybutylene terephthalate (PBT), polyimides, Polyetherimide, polysulfones, polyether sulfone, polyamide, polyphenylene oxide, plate porous membrane or nonwoven fabrics that any one polymer in the polyphenylene sulfide is prepared; Described crosslinked polyethers/silicon rubber gel-type vehicle causes crosslinked product with the precursor that contains two key crosslinkable silicon rubber compositions through free radical catalyst for being selected from the big monomer of terminal double bond polyethers of a kind of or its composition in terminal double bond type poly(ethylene oxide), PPOX or the ethylene oxide/propylene oxide copolymer at least.
The preparation method of the compound porous barrier film of this kind activity is as follows:
Method one
1) with mass fraction is two key crosslinkable silicon rubber that contain of 10～30%, mass fraction is 10～20% the big monomer of terminal double bond polyethers, mass fraction is that to be dissolved in mass fraction be that the back that stirs forms the precursor dipping solution in 50～80% the organic solvent for 0.1～3% free radical catalyst;
2) the polyalcohol stephanoporate support frame is immersed in abundant absorption precursor dipping solution in the precursor dipping solution, and scrapes off the maceration extract of surperficial excessive adsorption by slit;
3) to introduce temperature be in 70～120 ℃ of environment to the polyalcohol stephanoporate support frame that will be absorbed with the precursor dipping solution, realizes the big monomer of terminal double bond polyethers and contain the crosslinked of two key crosslinkable silicon rubber;
4) the above-mentioned polyalcohol stephanoporate support frame that is absorbed with crosslinked polyethers/silicon rubber is immersed in the coagulating bath, by the exchange between organic solvent and the non-solvent dipping filler is solidified, form the crosslinked polyethers/silicon rubber gel-type vehicle of porous type, obtain the compound porous barrier film of hygrometric state;
5) the compound porous barrier film of hygrometric state is obtained the described active compound porous barrier film that is used for lithium ion battery after cleaning, drying.
Method two
1) with mass fraction is two key crosslinkable silicon rubber that contain of 10～30%, mass fraction is 10～20% the big monomer of terminal double bond polyethers, mass fraction is that to be dissolved in mass fraction be that the back that stirs forms the precursor dipping solution in 50～80% the organic solvent for 0.1～3% free radical catalyst;
2) the polyalcohol stephanoporate support frame is immersed in abundant absorption precursor dipping solution in the precursor dipping solution, and scrapes off the maceration extract of surperficial excessive adsorption by slit;
3) the polyalcohol stephanoporate support frame that will be absorbed with the precursor dipping solution is immersed in the coagulating bath, makes the dipping filler solidify to form loose structure by the exchange between organic solvent and the non-solvent, obtains the compound porous barrier film of hygrometric state;
4) the compound porous barrier film of hygrometric state being introduced temperature is in 70～120 ℃ of environment, realizes the big monomer of terminal double bond polyethers and contains the crosslinked of two key crosslinkable silicon rubber, forms the compound porous barrier film that has crosslinked polyethers/silicon rubber gel-type vehicle;
5) above-mentioned porous septum is obtained the described active compound porous barrier film that is used for lithium ion battery after cleaning, drying.
Described polyalcohol stephanoporate support frame, thickness are 10 μ m～100 μ m, and average pore size is 1 μ m～50 μ m, and volumetric porosity is 30%～80%.
Described crosslinkable silicon rubber is one or more the mixture in methyl vinyl silicone rubber precursor, methyl phenyl vinyl silicone rubber precursor, methyl ethylene trifluoro propyl silicon rubber precursor, the silicone-nitrile rubber precursor.The number-average molecular weight of silicon rubber precursor should be between 10000～100000Da.
Described polyether monomer is one or more the mixture in poly(ethylene oxide) methacrylate, PPOX methacrylate or the polyethylene oxide/propylene oxide methacrylate, and the number of monomers average molecular weight is 500～5000Da.
Described free radical catalyst is any in benzoyl peroxide, cumyl peroxide, di-t-butyl peroxide, the peroxidized t-butyl perbenzoate.
Described organic solvent is N, N '-dimethyl formamide, N, the mixture of any one or a few in N '-dimethylacetylamide, 1-N-2-methyl pyrrolidone, the dimethyl sulfoxide (DMSO).
The active compound porous barrier film of lithium ion battery disclosed by the invention is owing to adopt polyethylene, polypropylene, Kynoar, Kynoar hexafluoropropylene, PETG, PTT, polybutylene terephthalate (PBT), polyimides, Polyetherimide altogether, perforated membrane that polysulfones, polyether sulfone, polyamide, polyphenylene oxide, polyphenylene sulfide are prepared or nonwoven fabrics are as support frame, so possess excellent mechanical property, can satisfy the requirement of strength of processing such as coiling in the cell preparation process, cutting.
Again, the active compound porous barrier film of lithium ion battery disclosed by the invention, the preparation method of the polyalcohol stephanoporate support frame that adopts has multiple, and wherein nonwoven fabrics is the supporting piece that props up of the easiest acquisition, and with low cost, and support strength is big.
Again, the active compound porous barrier film of lithium ion battery disclosed by the invention, since on the polyalcohol stephanoporate support frame compound crosslinked polyethers/silicon rubber gel active matrix be the chemical crosslinking structure, can form network-like overall structure on the inside, duct and the polyalcohol stephanoporate support frame surface of polyalcohol stephanoporate support frame, make framework film and crosslinked polyethers/silicon rubber gel active matrix form very firm composite construction.
Again, the active compound porous barrier film of lithium ion battery disclosed by the invention, owing to contain crosslinked polyethers/silicon rubber gel active matrix with polyether segment, increase barrier film to the absorbability of electrolyte and by the wetting ability of electrolyte, helped lithium ion migration, the high current charge-discharge of battery and the long-term stability of battery performance therein.
Again, the active compound porous barrier film of lithium ion battery disclosed by the invention, since contain the silicone rubber component of high tenacity and chemical crosslinking in compound crosslinked polyethers/silicon rubber gel active matrix, so improved the high and low temperature resistance of crosslinked polyethers/silicon rubber gel active matrix.
Again, the active compound porous barrier film of lithium ion battery disclosed by the invention, since contain the silicone rubber component of high tenacity and chemical crosslinking in compound crosslinked polyethers/silicon rubber gel active matrix, so improved the anti-performance that pierces through of barrier film, improved rate of finished products and the fail safe of using this barrier film assembled battery.
Again, the active compound porous barrier film of lithium ion battery disclosed in this invention in preparation process, uses the solution phase inversion, make compound crosslinked polyethers/silicon rubber gel active matrix form loose structure, help improving absorptivity ability and the retention of active component to electrolyte.
Again, the active compound porous barrier film of lithium ion battery disclosed in this invention can adopt the production technology of different order, as required to satisfy the production requirement of different product.
Again, the active compound porous barrier film of lithium ion battery disclosed in this invention is drawn materials extensively, easy and simple to handle, the efficient height changes less technological parameter and can obtain diversified pore structure, the controllable degree height of membrane structure is produced good reproducibility, is easy to realize serialization production.
Description of drawings
Fig. 1 is the mechanism of crosslinking schematic diagram of crosslinked polyethers/silicon rubber gel-type vehicle, and wherein, R-R is a peroxide vulcanizing agent, and R ' is a polyether segment;
Fig. 2 is an active compound porous barrier film electron scanning micrograph among the embodiment 1;
Fig. 3 is an active compound porous barrier film electron scanning micrograph among the embodiment 2;
Fig. 4 is an active compound porous barrier film electron scanning micrograph among the embodiment 3;
Fig. 5 is an active compound porous barrier film electron scanning micrograph among the embodiment 4;
Fig. 6 is an active compound porous barrier film electron scanning micrograph among the embodiment 5;
Fig. 7 is an active compound porous barrier film electron scanning micrograph among the embodiment 6;
Fig. 8 is an active compound porous barrier film electron scanning micrograph among the embodiment 7;
Fig. 9 is an active compound porous barrier film electron scanning micrograph among the embodiment 8;
Figure 10 is an active compound porous barrier film electron scanning micrograph among the embodiment 9.
Embodiment
The active compound porous barrier film of a kind of lithium ion battery, this kind barrier film is by the polyalcohol stephanoporate support frame and crosslinked polyethers/the silicon rubber gel-type vehicle is compound forms, wherein the mass content of polyalcohol stephanoporate support frame is 50～90%, the mass content of crosslinked polyethers/silicon rubber gel-type vehicle is 10～50%, the thickness of active compound porous barrier film is 10 μ m～100 μ m, volumetric porosity is 10-60%, described polyalcohol stephanoporate support frame is a polyethylene, polypropylene, Kynoar, Kynoar is hexafluoropropylene altogether, PETG, PTT, polybutylene terephthalate (PBT), polyimides, Polyetherimide, polysulfones, polyether sulfone, polyamide, polyphenylene oxide, plate porous membrane or nonwoven fabrics that any one polymer in the polyphenylene sulfide is prepared; Described crosslinked polyethers/silicon rubber gel-type vehicle causes crosslinked product with the precursor that contains two key crosslinkable silicon rubber compositions through free radical catalyst for being selected from the big monomer of terminal double bond polyethers of a kind of or its composition in terminal double bond type poly(ethylene oxide), PPOX or the ethylene oxide/propylene oxide copolymer at least.
The preparation method of the active compound porous barrier film of this kind lithium ion battery is as follows:
Method one
1) with mass fraction is two key crosslinkable silicon rubber that contain of 10～30%, mass fraction is 10～20% the big monomer of terminal double bond polyethers, mass fraction is that to be dissolved in mass fraction be that the back that stirs forms the precursor dipping solution in 50～80% the organic solvent for 0.1～3% free radical catalyst;
2) the polyalcohol stephanoporate support frame is immersed in abundant absorption precursor dipping solution in the precursor dipping solution, and scrapes off the maceration extract of surperficial excessive adsorption by slit;
3) to introduce temperature be in 70～120 ℃ of environment to the polyalcohol stephanoporate support frame that will be absorbed with the precursor dipping solution, realizes the big monomer of terminal double bond polyethers and contain the crosslinked of two key crosslinkable silicon rubber;
4) the above-mentioned polyalcohol stephanoporate support frame that is absorbed with crosslinked polyethers/silicon rubber is immersed in the coagulating bath, by the exchange between organic solvent and the non-solvent dipping filler is solidified, form the crosslinked polyethers/silicon rubber gel-type vehicle of porous type, obtain the compound porous barrier film of hygrometric state;
5) the compound porous barrier film of hygrometric state is obtained the described active compound porous barrier film that is used for lithium ion battery after cleaning, drying.
Method two
1) with mass fraction is two key crosslinkable silicon rubber that contain of 10～30%, mass fraction is 10～20% the big monomer of terminal double bond polyethers, mass fraction is that to be dissolved in mass fraction be that the back that stirs forms the precursor dipping solution in 50～80% the organic solvent for 0.1～3% free radical catalyst;
2) the polyalcohol stephanoporate support frame is immersed in abundant absorption precursor dipping solution in the precursor dipping solution, and scrapes off the maceration extract of surperficial excessive adsorption by slit;
3) the polyalcohol stephanoporate support frame that will be absorbed with the precursor dipping solution is immersed in the coagulating bath, makes the dipping filler solidify to form loose structure by the exchange between organic solvent and the non-solvent, obtains the compound porous barrier film of hygrometric state;
4) the compound porous barrier film of hygrometric state being introduced temperature is in 70～120 ℃ of environment, realizes the big monomer of terminal double bond polyethers and contains the crosslinked of two key crosslinkable silicon rubber, forms the compound porous barrier film that has crosslinked polyethers/silicon rubber gel-type vehicle;
5) above-mentioned porous septum is obtained the described active compound porous barrier film that is used for lithium ion battery after cleaning, drying.
Described polyalcohol stephanoporate support frame, thickness are 10 μ m～100 μ m, and average pore size is 1 μ m～50 μ m, and volumetric porosity is 30%～80%.
Described crosslinkable silicon rubber is one or more the mixture in methyl vinyl silicone rubber precursor, methyl phenyl vinyl silicone rubber precursor, methyl ethylene trifluoro propyl silicon rubber precursor, the silicone-nitrile rubber precursor.The number-average molecular weight of silicon rubber precursor should be between 10000～100000Da.
Described polyether monomer is one or more the mixture in poly(ethylene oxide) methacrylate, PPOX methacrylate or the polyethylene oxide/propylene oxide methacrylate, and the number of monomers average molecular weight is 500～5000Da.
Described free radical catalyst is any one in benzoyl peroxide, cumyl peroxide, di-t-butyl peroxide, the peroxidized t-butyl perbenzoate.
Described organic solvent is N, N '-dimethyl formamide, N, the mixture of any one or a few in N '-dimethylacetylamide, 1-N-2-methyl pyrrolidone, the dimethyl sulfoxide (DMSO).
Further specify the present invention below by embodiment.
Embodiment 1
(1) polyethylene porous membrane of choosing a volume is as the polyalcohol stephanoporate support frame, and its average pore size is 1 μ m, and volumetric porosity is 30%, and thickness is 20 μ m.
(2) with mass fraction be 10% methyl vinyl silicone rubber precursor, mass fraction is 10% poly(ethylene oxide) methacrylic acid methyl, mass fraction is that to be dissolved in mass fraction be 79.9% solvent N for 0.1% free radical catalyst benzoyl peroxide, in N '-dimethyl formamide, stir and form homogeneous precursor dipping solution.
(3) polyethylene polymer porous support frame being walked film 30cm with the 1cm/s speed of walking about continuously in the precursor dipping solution, make it fully absorb the precursor dipping solution, is the maceration extract that the slit of 25 μ m scrapes off surperficial excessive adsorption through width then.
(4) the polyethylene polymer porous support frame that will contain the precursor dipping solution is introduced temperature with the 1cm/s speed of walking about continuously to be that 70 ℃, length are that the passage of 200cm carries out two keys of gel-type vehicle monomer crosslinked.
(5) to introduce temperature be in 40 ℃ of coagulating baths to the polyethylene polymer porous support frame film that will contain the cross-linked gel matrix solution, walks film 300cm under 1cm/s speed, realizes the curing of gel-type vehicle and form micropore obtaining the compound porous barrier film of hygrometric state.
(6) the compound porous barrier film of hygrometric state is walked film 200cm with the speed of 1cm/s in clean coagulating bath and clean, the compound porous barrier film of the hygrometric state of collection obtains active compound porous barrier film after 40 ℃ of vacuum drying oven dryings.
(7) mass fraction of polyalcohol stephanoporate support frame film in the compound porous barrier film of activity is 90%, and the mass fraction of crosslinked polyethers/silicon rubber gel active matrix is 10%, and the volumetric porosity of barrier film is 25%, and the micropore average pore size is 0.1 micron.
Annotate: film parametric measurement method disclosed in this invention is as follows:
The thickness of film: measure with micrometer caliper; The porosity of film and aperture: mercury injection apparatus test; The mass fraction of polyalcohol stephanoporate support frame film is in the active compound porous barrier film:
Crosslinked polyethers/silicon rubber gel active matrix mass fraction is:
Test condition is identical with embodiment 1, and the structure and the performance of every implementation condition and gained lithium ion battery active membrane are as follows:
(1) choose a volume PETG nonwoven fabrics as the polyalcohol stephanoporate support frame, its average pore size is 50 μ m, and volumetric porosity is 80%, and thickness is 50 μ m.
(2) with mass fraction be 20% methyl phenyl vinyl silicone rubber precursor, mass fraction is 20% PPOX methyl methacrylate, mass fraction be 3% free radical catalyst cumyl peroxide to be dissolved in mass fraction be 57% solvent 1-N-2-methyl pyrrolidone, stir and form homogeneous precursor dipping solution.
(3) polyethylene terephthalate polymer porous support frame is walked film 30cm with the 1cm/s speed of walking about continuously in the precursor dipping solution, making it fully absorb the precursor dipping solution, is the maceration extract that the slit of 55 μ m scrapes off surperficial excessive adsorption through width then.
(4) the polyethylene terephthalate polymer porous support frame that will contain the precursor dipping solution is introduced temperature with the 1cm/s speed of walking about continuously to be that 120 ℃, length are that the passage of 200cm carries out two keys of gel-type vehicle monomer crosslinked.
(5) to introduce temperature be in 40 ℃ of coagulating baths to the polyethylene terephthalate polymer porous support frame film that will contain the cross-linked gel matrix solution, under 1cm/s speed, walk film 300cm, realize the curing of gel-type vehicle and form micropore obtaining the compound porous barrier film of hygrometric state.
(6) the compound porous barrier film of hygrometric state is walked film 200cm with the speed of 1cm/ in clean coagulating bath and clean, the compound porous barrier film of the hygrometric state of collection obtains active compound porous barrier film after 40 ℃ of vacuum drying oven dryings.
(7) mass fraction of polyalcohol stephanoporate support frame film in the compound porous barrier film of activity is 50%, and the mass fraction of crosslinked polyethers/silicon rubber gel active matrix is 50%, and the volumetric porosity of barrier film is 45%, and the micropore average pore size is 5.0 microns.
Embodiment 3
Test condition is identical with embodiment 1, and the structure and the performance of every implementation condition and gained lithium ion battery active membrane are as follows:
(1) choose a volume polypropylene porous film as the polyalcohol stephanoporate support frame, its average pore size is 2 μ m, and volumetric porosity is 30%, and thickness is 10 μ m.
(2) with mass fraction be 30% methyl ethylene trifluoro propyl silicon rubber precursor, mass fraction is 10% polyethylene oxide/propylene oxide methyl methacrylate, mass fraction is that to be dissolved in mass fraction be 59% solvent N for 1% free radical catalyst di-t-butyl peroxide, in N '-dimethylacetylamide, stir and form homogeneous precursor dipping solution.
(3) polyacrylic polymer porous support frame being walked film 30cm with the 1cm/s speed of walking about continuously in the precursor dipping solution, make it fully absorb the precursor dipping solution, is the maceration extract that the slit of 15 μ m scrapes off surperficial excessive adsorption through width then.
(4) the polypropylene hole on framework that will contain the precursor dipping solution is introduced temperature with the 1cm/s speed of walking about continuously to be that 90 ℃, length are that the passage of 200cm carries out two keys of gel-type vehicle monomer crosslinked.
(5) to introduce temperature be in 40 ℃ of coagulating baths to the polyacrylic polymer porous support frame film that contains the cross-linked gel matrix solution, walks film 300cm under 1cm/s speed, realizes the curing of gel-type vehicle and form micropore obtaining the compound porous barrier film of hygrometric state.
(6) the compound porous barrier film of hygrometric state is walked walk film 200cm with the speed of 1cm/ and clean in clean coagulating bath, the compound porous barrier film of the hygrometric state of collection obtains active compound porous barrier film after 40 ℃ of vacuum drying oven dryings.
(7) mass fraction of polyalcohol stephanoporate support frame film in the compound porous barrier film of activity is 70%, and the mass fraction of crosslinked polyethers/silicon rubber gel active matrix is 30%, and the volumetric porosity of barrier film is 10%, and the micropore average pore size is 0.3 micron.
Embodiment 4
Test condition is identical with embodiment 1, and the structure and the performance of every implementation condition and gained lithium ion battery active membrane are as follows:
(1) choose a volume polyvinylidene fluoride porous film as the polyalcohol stephanoporate support frame, its average pore size is 1 μ m, and volumetric porosity is 80%, and thickness is 100 μ m.
(2) with mass fraction be 10% silicone-nitrile rubber precursor, mass fraction is 20% poly(ethylene oxide) methacrylate, mass fraction is that to be dissolved in mass fraction be in 69% the solvent dimethyl sulfoxide (DMSO), to stir and form homogeneous precursor dipping solution for 1% free radical catalyst peroxidized t-butyl perbenzoate.
(3) polyvinylidene fluoride polymer porous support frame being walked film 30cm with the 2cm/s speed of walking about continuously in the precursor dipping solution, make it fully absorb the precursor dipping solution, is the maceration extract that the slit of 105 μ m scrapes off surperficial excessive adsorption through width then.
(4) the partial fluorine ethylene polymer porous support frame that will contain the precursor dipping solution is introduced temperature with the 2cm/s speed of walking about continuously to be that 100 ℃, length are that the passage of 300cm carries out two keys of gel-type vehicle monomer crosslinked.
(5) to introduce temperature be in 40 ℃ of coagulating baths to the polyvinylidene fluoride polymer porous support frame film that contains the cross-linked gel matrix solution, walks film 300cm under 2cm/s speed, realizes the curing of gel-type vehicle and form micropore obtaining the compound porous barrier film of hygrometric state.
(6) the compound porous barrier film of hygrometric state is walked walk film 200cm with the speed of 2cm/ and clean in clean coagulating bath, the compound porous barrier film of the hygrometric state of collection obtains active compound porous barrier film after 40 ℃ of vacuum drying oven dryings.
(7) mass fraction of polyalcohol stephanoporate support frame film in the compound porous barrier film of activity is 70%, and the mass fraction of crosslinked polyethers/silicon rubber gel active matrix is 30%, and the volumetric porosity of barrier film is 60%, and the micropore average pore size is 0.3 micron.
Embodiment 5
Test condition is identical with embodiment 1, and the structure and the performance of every implementation condition and gained lithium ion battery active membrane are as follows:
(1) the hexafluoropropylene perforated membrane is as the polyalcohol stephanoporate support frame altogether to choose a volume Kynoar, and its average pore size is 5 μ m, and volumetric porosity is 60%, and thickness is 100 μ m.
(2) with mass fraction be 27% silicone-nitrile rubber precursor, mass fraction is 20% PPOX methacrylate, mass fraction is that to be dissolved in mass fraction be mixed solvent (dimethyl sulfoxide (DMSO)/N of 50% for 3% free radical catalyst peroxidized t-butyl perbenzoate, N '-dimethylacetylamide, volume ratio is 1: 1) in, stir and form homogeneous precursor dipping solution.
(3) Kynoar is total to hexafluoropropylene polyalcohol stephanoporate support frame and in the precursor dipping solution, walks film 30cm with the 2cm/s speed of walking about continuously, making it fully absorb the precursor dipping solution, is the maceration extract that the slit of 105 μ m scrapes off surperficial excessive adsorption through width then.
(4) Kynoar that will contain the precursor dipping solution altogether hexafluoropropylene polyalcohol stephanoporate support frame introduce temperature with the 2cm/s speed of walking about continuously to be that 100 ℃, length are that the passage of 300cm carries out two keys of gel-type vehicle monomer crosslinked.
(5) Kynoar that contains the cross-linked gel matrix solution altogether hexafluoropropylene polyalcohol stephanoporate support frame film to introduce temperature be in 40 ℃ of coagulating baths, under 2cm/s speed, walk film 300cm, realize the curing of gel-type vehicle and form micropore obtaining the compound porous barrier film of hygrometric state.
(6) the compound porous barrier film of hygrometric state is walked walk film 200cm with the speed of 2cm/ and clean in clean coagulating bath, the compound porous barrier film of the hygrometric state of collection obtains active compound porous barrier film after 40 ℃ of vacuum drying oven dryings.
(7) mass fraction of polyalcohol stephanoporate support frame film in the compound porous barrier film of activity is 70%, and the mass fraction of crosslinked polyethers/silicon rubber gel active matrix is 30%, and the volumetric porosity of barrier film is 50%, and the micropore average pore size is 0.8 micron.
Embodiment 6
Test condition is identical with embodiment 1, and the structure and the performance of every implementation condition and gained lithium ion battery active membrane are as follows:
(1) choose a volume polyimide porous membrane as the polyalcohol stephanoporate support frame, its average pore size is 1 μ m, and volumetric porosity is 40%, and thickness is 30 μ m.
(2)) with mass fraction be 20% silicone-nitrile rubber precursor, mass fraction is 20% polyethylene oxide/propylene oxide methyl methacrylate, mass fraction is that to be dissolved in mass fraction be 58% solvent N for 2% free radical catalyst benzoyl peroxide, in N '-dimethylacetylamide, stir and form homogeneous precursor dipping solution.
(3) polyimide polymer porous support frame being walked film 30cm with the 1cm/s speed of walking about continuously in the precursor dipping solution, make it fully absorb the precursor dipping solution, is the maceration extract that the slit of 35 μ m scrapes off surperficial excessive adsorption through width then.
(4) to introduce temperature be in 40 ℃ of coagulating baths to the polyimide polymer porous support frame film that will contain the precursor dipping solution, walks film 300cm under 1cm/s speed, realizes the curing of maceration extract and form micropore obtaining the compound porous barrier film of hygrometric state.
(5) the compound porous barrier film of hygrometric state being introduced temperature with the 1cm/s speed of walking about continuously, to be that 120 ℃, length are that the passage of 200cm carries out two keys of gel-type vehicle monomer crosslinked.
(6) barrier film is walked film 200cm with the speed of 1cm/ in clean coagulating bath and clean, the compound porous barrier film of the hygrometric state of collection obtains active compound porous barrier film after 40 ℃ of vacuum drying oven dryings.
(7) mass fraction of polyalcohol stephanoporate support frame film in the compound porous barrier film of activity is 80%, and the mass fraction of crosslinked polyethers/silicon rubber gel active matrix is 20%, and the volumetric porosity of barrier film is 25%, and the micropore average pore size is 0.2 micron.
Embodiment 7
Test condition is identical with embodiment 1, and the structure and the performance of every implementation condition and gained lithium ion battery active membrane are as follows:
(1) choose a volume polybutylene terephthalate (PBT) nonwoven fabrics as the polyalcohol stephanoporate support frame, its average pore size is 30 μ m, and volumetric porosity is 60%, and thickness is 50 μ m.
(2)) with mass fraction be 30% methyl phenyl vinyl silicone rubber precursor, mass fraction is 10% poly(ethylene oxide) methyl methacrylate, mass fraction is that to be dissolved in mass fraction be 58% solvent N for 2% free radical catalyst benzoyl peroxide, in N '-dimethyl formamide, stir and form homogeneous precursor dipping solution.
(3) polybutylene terephthalate (PBT) polyalcohol stephanoporate support frame is walked film 30cm with the 1cm/s speed of walking about continuously in the precursor dipping solution, making it fully absorb the precursor dipping solution, is the maceration extract that the slit of 55 μ m scrapes off surperficial excessive adsorption through width then.
(4) to introduce temperature be in 40 ℃ of coagulating baths to the polybutylene terephthalate (PBT) polyalcohol stephanoporate support frame film that will contain the precursor dipping solution, walks film 300cm under 1cm/s speed, realizes the curing of maceration extract and form micropore obtaining the compound porous barrier film of hygrometric state.
(5) the compound porous barrier film of hygrometric state being introduced temperature with the 1cm/s speed of walking about continuously, to be that 120 ℃, length are that the passage of 200cm carries out two keys of gel-type vehicle monomer crosslinked.
(6) barrier film is walked film 200cm with the speed of 1cm/ in clean coagulating bath and clean, the compound porous barrier film of the hygrometric state of collection obtains active compound porous barrier film after 40 ℃ of vacuum drying oven dryings.
(7) mass fraction of polyalcohol stephanoporate support frame film in the compound porous barrier film of activity is 60%, and the mass fraction of crosslinked polyethers/silicon rubber gel active matrix is 40%, and the volumetric porosity of barrier film is 40%, and the micropore average pore size is 0.5 micron.
Embodiment 8
Test condition is identical with embodiment 1, and the structure and the performance of every implementation condition and gained lithium ion battery active membrane are as follows:
(1) choose a volume polyphenylene oxide perforated membrane as the polyalcohol stephanoporate support frame, its average pore size is 10 μ m, and volumetric porosity is 50%, and thickness is 30 μ m.
(2)) with mass fraction be 30% methyl phenyl vinyl silicone rubber precursor, mass fraction is 10% poly(ethylene oxide) methyl methacrylate, mass fraction is that to be dissolved in mass fraction be in 58% the solvent 1-N-2-methyl pyrrolidone, to stir and form homogeneous precursor dipping solution for 2% free radical catalyst benzoyl peroxide.
(3) polyphenylene ether polymer porous support frame being walked film 30cm with the 1cm/s speed of walking about continuously in the precursor dipping solution, make it fully absorb the precursor dipping solution, is the maceration extract that the slit of 35 μ m scrapes off surperficial excessive adsorption through width then.
(4) to introduce temperature be in 40 ℃ of coagulating baths to the polyphenylene ether polymer porous support frame film that will contain the precursor dipping solution, walks film 300cm under 1cm/s speed, realizes the curing of maceration extract and form micropore obtaining the compound porous barrier film of hygrometric state.
(5) the compound porous barrier film of hygrometric state being introduced temperature with the 1cm/s speed of walking about continuously, to be that 110 ℃, length are that the passage of 200cm carries out two keys of gel-type vehicle monomer crosslinked.
(6) barrier film is walked film 200cm with the speed of 1cm/ in clean coagulating bath and clean, the compound porous barrier film of the hygrometric state of collection obtains active compound porous barrier film after 40 ℃ of vacuum drying oven dryings.
(7) mass fraction of polyalcohol stephanoporate support frame film in the compound porous barrier film of activity is 70%, and the mass fraction of crosslinked polyethers/silicon rubber gel active matrix is 30%, and the volumetric porosity of barrier film is 35%, and the micropore average pore size is 0.5 micron.
Embodiment 9
Test condition is identical with embodiment 1, and the structure and the performance of every implementation condition and gained lithium ion battery active membrane are as follows:
(1) choose a volume polyether sulfone perforated membrane as the polyalcohol stephanoporate support frame, its average pore size is 2 μ m, and volumetric porosity is 60%, and thickness is 50 μ m.
(2) with mass fraction be 30% methyl phenyl vinyl silicone rubber precursor, mass fraction is 10% PPOX methyl methacrylate, mass fraction is that to be dissolved in mass fraction be 59% solvent N for 1% free radical catalyst benzoyl peroxide, in N '-dimethyl formamide, stir and form homogeneous precursor dipping solution.
(3) polyether sulfone polymer porous support frame being walked film 30cm with the 1cm/s speed of walking about continuously in the precursor dipping solution, make it fully absorb the precursor dipping solution, is the maceration extract that the slit of 55 μ m scrapes off surperficial excessive adsorption through width then.
(4) to introduce temperature be in 40 ℃ of coagulating baths to the polyether sulfone polymer porous support frame film that will contain the precursor dipping solution, walks film 300cm under 1cm/s speed, realizes the curing of maceration extract and form micropore obtaining the compound porous barrier film of hygrometric state.
(5) the compound porous barrier film of hygrometric state being introduced temperature with the 1cm/s speed of walking about continuously, to be that 100 ℃, length are that the passage of 200cm carries out two keys of gel-type vehicle monomer crosslinked.
(6) barrier film is walked film 200cm with the speed of 1cm/ in clean coagulating bath and clean, the compound porous barrier film of the hygrometric state of collection obtains active compound porous barrier film after 40 ℃ of vacuum drying oven dryings.
(7) mass fraction of polyalcohol stephanoporate support frame film in the compound porous barrier film of activity is 70%, and the mass fraction of crosslinked polyethers/silicon rubber gel active matrix is 30%, and the volumetric porosity of barrier film is 45%, and the micropore average pore size is 0.8 micron.
Adopt following method to measure the hot strength of the battery diaphragm that embodiment 1-9 makes, pierce through intensity and ionic conductivity respectively, measurement result is as shown in table 1.
Hot strength: the hot strength of film obtains from load-deformation curve, adopts the load-deformation curve of AG-1 electronic tensile machine test membrane sample, the length 50mm of membrane sample, width 20mm, rate of extension 50mm/min.Its mean value is got in each membrane sample test 10 times.
Pierce through intensity: the self-contained battery barrier film, used diameter be 1 millimeter, bent at its tip radius be 0.5 millimeter pin with the speed motion of 2 cels, pierce through maximum, force in the battery diaphragm process and count and pierce through intensity.
Conductivity at room temperature: the compound porous barrier film of dried active is soaked in the lithium-ion electrolyte obtained polymer dielectric film in 24 hours, electrolyte consists of the lithium hexafluoro phosphate (LiPF of 1M
6) being dissolved in dimethyl carbonate (DMC), in diethyl carbonate (DEC) and ethylene carbonate (EC) mixed solvent, the mass ratio of mixed solvent is 1: 1: 1.The conductivity of polymer dielectric film adopts AC impedence method to measure, polymer dielectric film is clipped between two stainless steel electrodes, adopt Solartron SI1287 electrochemical interface instrument in conjunction with S11255B frequency response instrument, the test of HP2192a analyzer, test frequency 0.01Hz～200kHz.Stainless steel electrode in two electrode systems is as work electrode with to electrode, and the impedance spectrogram is generally a circular arc and the rectilinear(-al) that constant slope is arranged, and calculates the resistance R of polymer dielectric according to the crossing point of real axis on high frequency region circular arc and the impedance spectrogram
b, calculate the conductivity of polymer dielectric film again by following formula:
σ is ionic conductivity (S/cm) in the formula, and L is dielectric film thickness (cm), R
bBe this volume resistance of dielectric film (Ω) that A is the area (cm of dielectric film
-2).
Table 1
Claims (10)
1. active compound porous barrier film that is used for lithium ion battery, it is characterized in that, by the polyalcohol stephanoporate support frame and crosslinked polyethers/the silicon rubber gel-type vehicle is compound forms, wherein the mass content of polyalcohol stephanoporate support frame is 50～90%, the mass content of crosslinked polyethers/silicon rubber gel-type vehicle is 10～50%, the thickness of active compound porous barrier film is 10 μ m～100 μ m, volumetric porosity is 10-60%, described polyalcohol stephanoporate support frame is a polyethylene, polypropylene, Kynoar, Kynoar is hexafluoropropylene altogether, PETG, PTT, polybutylene terephthalate (PBT), polyimides, Polyetherimide, polysulfones, polyether sulfone, polyamide, polyphenylene oxide, plate porous membrane or nonwoven fabrics that any one polymer in the polyphenylene sulfide is prepared; Described crosslinked polyethers/silicon rubber gel-type vehicle causes crosslinked product with the precursor that contains two key crosslinkable silicon rubber compositions through free radical catalyst for being selected from the big monomer of terminal double bond polyethers of a kind of or its composition in terminal double bond type poly(ethylene oxide), PPOX or the ethylene oxide/propylene oxide copolymer at least.
2. the compound porous barrier film of activity according to claim 1, it is characterized in that, described crosslinked polyethers/silicon rubber gel-type vehicle is the chemical crosslinking structure, crosslinked polyethers/silicon rubber gel-type vehicle is filled in the polyalcohol stephanoporate support frame and covers the skeleton surface fully, and containing the aperture in the crosslinked matrix is the perforation micropore of 0.1 μ m～5 μ m.
3. the compound porous barrier film of activity according to claim 1, it is characterized in that, described polyalcohol stephanoporate support frame be thickness between 10 μ m～100 μ m, average pore size between 1 μ m～50 μ m, plate porous membrane or the nonwoven fabrics of volumetric porosity between 30%～80%.
4. the compound porous barrier film of activity according to claim 1, it is characterized in that, it is described that to contain two key crosslinkable silicon rubber be one or more mixture in methyl vinyl silicone rubber precursor, methyl phenyl vinyl silicone rubber precursor, methyl ethylene trifluoro propyl silicon rubber precursor, the silicone-nitrile rubber precursor, its number-average molecular weight is between 10000～100000Da, and chemical structure of general formula is as follows:
R=-CH
3,-C
6H
5,-CH
2CH
2CF
3Or-CH
2CH
2CN, x=10～1000 wherein, y=10～1000, z=10～1000.
5. the compound porous barrier film of activity according to claim 1, it is characterized in that, the big monomer of described terminal double bond polyethers is one or more the mixture in poly(ethylene oxide) methacrylate, PPOX methacrylate or the polyethylene oxide/propylene oxide methacrylate, the number of monomers average molecular weight is 500～5000Da, and chemical structure of general formula is as follows:
Wherein, a=0～200, b=0～100.
6. the method for preparing the active compound porous barrier film of the described lithium ion battery of claim 1 is characterized in that realizing by following step successively:
1) with mass fraction is two key crosslinkable silicon rubber that contain of 10～30%, mass fraction is 10～20% the big monomer of terminal double bond polyethers, mass fraction is that to be dissolved in mass fraction be that the back that stirs forms the precursor dipping solution in 50～80% the organic solvent for 0.1～3% free radical catalyst;
2) the polyalcohol stephanoporate support frame is immersed in abundant absorption precursor dipping solution in the precursor dipping solution, and scrapes off the maceration extract of surperficial excessive adsorption by slit;
3) to introduce temperature be in 70～120 ℃ of environment to the polyalcohol stephanoporate support frame that will be absorbed with the precursor dipping solution, realizes the big monomer of terminal double bond polyethers and contain the crosslinked of two key crosslinkable silicon rubber;
4) the above-mentioned polyalcohol stephanoporate support frame that is absorbed with crosslinked polyethers/silicon rubber is immersed in the coagulating bath, by the exchange between organic solvent and the non-solvent dipping filler is solidified, form the crosslinked polyethers/silicon rubber gel-type vehicle of porous type, obtain the compound porous barrier film of hygrometric state;
5) the compound porous barrier film of hygrometric state is obtained the described active compound porous barrier film that is used for lithium ion battery after cleaning, drying.
7. the method for preparing the active compound porous barrier film of the described lithium ion battery of claim 1 is characterized in that realizing by following step successively:
1) with mass fraction is two key crosslinkable silicon rubber that contain of 10～30%, mass fraction is 10～20% the big monomer of terminal double bond polyethers, mass fraction is that to be dissolved in mass fraction be that the back that stirs forms the precursor dipping solution in 50～80% the organic solvent for 0.1～3% free radical catalyst;
2) the polyalcohol stephanoporate support frame is immersed in abundant absorption precursor dipping solution in the precursor dipping solution, and scrapes off the maceration extract of surperficial excessive adsorption by slit;
3) the polyalcohol stephanoporate support frame that will be absorbed with the precursor dipping solution is immersed in the coagulating bath, makes the dipping filler solidify to form loose structure by the exchange between organic solvent and the non-solvent, obtains the compound porous barrier film of hygrometric state;
4) the compound porous barrier film of hygrometric state being introduced temperature is in 70～120 ℃ of environment, realizes the big monomer of terminal double bond polyethers and contains the crosslinked of two key crosslinkable silicon rubber, forms the compound porous barrier film that has crosslinked polyethers/silicon rubber gel-type vehicle;
5) above-mentioned compound porous barrier film is obtained the described active compound porous barrier film that is used for lithium ion battery after cleaning, drying.
8. according to claim 6 or the 7 described methods that prepare the active compound porous barrier film of lithium ion battery, it is characterized in that described free radical catalyst is any one in benzoyl peroxide, cumyl peroxide, di-t-butyl peroxide, the peroxidized t-butyl perbenzoate.
9. according to claim 6 or the 7 described methods that prepare the active compound porous barrier film of lithium ion battery, it is characterized in that, described organic solvent is N, N '-dimethyl formamide, N, any one in N '-dimethylacetylamide, 1-N-2-methyl pyrrolidone or the dimethyl sulfoxide (DMSO) or multiple mixture.
10. according to claim 6 or the 7 described methods that prepare the active compound porous barrier film of lithium ion battery, it is characterized in that, can adopt continuous filming technology, the winding speed control dipping by telomerized polymer porous support frame, curing, crosslinked, clean and processing time in dry each stage.
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