CN110120550A - Polymer dielectric film and preparation method thereof and lithium ion battery - Google Patents
Polymer dielectric film and preparation method thereof and lithium ion battery Download PDFInfo
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- CN110120550A CN110120550A CN201810123371.7A CN201810123371A CN110120550A CN 110120550 A CN110120550 A CN 110120550A CN 201810123371 A CN201810123371 A CN 201810123371A CN 110120550 A CN110120550 A CN 110120550A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
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Abstract
The present invention relates to field of lithium ion battery, and in particular to polymer dielectric film and preparation method thereof and lithium ion battery.The polymer dielectric film includes the polyelectrolyte floor in nonwoven layer and nonwoven layer surface, the lithium salts that the polyelectrolyte floor contains polymeric matrix and is scattered in the polymeric matrix, the polymeric matrix contain the cross-linked structure provided by crosslinking agent, the copolymer chain structure and inorganic nano-particle that are provided by cross-linkable copolymers.Polymer dielectric film provided by the invention has compared with high ion conductivity, crystallinity is lower, flexibility is suitable, with and preparation method thereof process is simple, cost is lower.
Description
Technical field
The present invention relates to field of lithium ion battery, and in particular to polymer dielectric film and preparation method thereof and lithium-ion electric
Pond.
Background technique
Lithium ion battery currently on the market is mostly using liquid electrolyte as conductive materials, but in use, liquid
Electrolyte is volatile, inflammable and explosive, leads to many safety problems；And it easily grows Li dendrite, limits lithium metal as negative
The application of pole in the battery.Therefore, it has been proposed that substituting liquid electrolyte with solid polymer electrolyte (SPE).Solid-state is poly-
Polymer electrolyte membrane not only plays a part of ionic conduction, can also prevent the contact of positive and negative electrode.It, can again because its plasticity is strong
Film of different shapes is made according to different needs, flexibility is good, can bear pressure of the electrode in charge and discharge process, high temperature
Stability is good, greatly improves the safety of lithium battery.
CN105591154A discloses a kind of polycarbonate-based full solid state polymer electrolyte, full solid state polymer electrolysis
Matter includes polycarbonate-based macromolecule, lithium salts and porous support materials, wherein porous support materials are cellulose non-woven film, glass
One of glass fiber, polyethylene terephthalate film, polyimides nonwoven film are a variety of.Although relative to polyoxyethylene
For alkene, use polycarbonate-based macromolecule and using porous support materials as supporter under can obtain ionic conductivity it is higher and
The better full solid state polymer electrolyte of mechanical performance.However, inorganic particulate in polycarbonate-based macromolecule dispersibility compared with
Difference is easy to reunite, and the electrical property and security performance to entire full solid state polymer electrolyte all have an impact.
Summary of the invention
The purpose of the present invention is to provide a kind of novel non-woven fabric compounded polymer dielectric films and preparation method thereof
And lithium ion battery, which has compared with high ion conductivity, crystallinity is lower, flexibility is suitable and its system
Preparation Method process is simple, cost is lower.
To achieve the goals above, one aspect of the present invention provides a kind of polymer dielectric film, the polymer dielectric film
Including the polyelectrolyte floor in nonwoven layer and nonwoven layer surface, the polyelectrolyte floor contains polymeric matrix
With the lithium salts being scattered in the polymeric matrix, the polymeric matrix contains the cross-linked structure provided by crosslinking agent, by can
The copolymer chain structure and inorganic nano-particle that cross-linked copolymer provides；
Wherein, the cross-linkable copolymers contain structural unit shown in structural unit shown in formula (1), formula (2) and appoint
Structural unit shown in the formula (3) of choosing,
Formula (1):Formula (2):Formula (3):
Wherein, R is the alkyl of H or C1-C4, and L is the alkylidene or-R of C0-C41-O-R2, R1For the alkylidene of C0-C4,
R2For the alkylidene of C0-C4；
The crosslinking agent is one of acrylic ester cross-linking agent containing at least two esters of acrylic acid groups or more
Kind, the esters of acrylic acid group is group shown in formula (4) :-O-C (O)-C (R ')=CH2, R ' is the alkyl of H or C1-C4.
Second aspect of the present invention provides a kind of preparation method of polymer dielectric film, this method comprises:
(1) the electrolysis chylema containing cross-linkable copolymers, lithium salts, crosslinking agent, inorganic nano-particle and photoinitiator is provided
Material；
(2) electrolyte slurry is coated on non-woven fabrics simultaneously drying and forming-film, is then consolidated under ultraviolet light
Change crosslinking to form polyelectrolyte floor on non-woven fabrics；
Wherein, the cross-linkable copolymers contain structural unit shown in structural unit shown in formula (1), formula (2) and appoint
Structural unit shown in the formula (3) of choosing,
Formula (1):Formula (2):Formula (3):
Wherein, R is the alkyl of H or C1-C4, and L is the alkylidene or-R of C0-C41-O-R2, R1For the alkylidene of C0-C4,
R2For the alkylidene of C0-C4；
The crosslinking agent is one of acrylic ester cross-linking agent containing at least two esters of acrylic acid groups or more
Kind, the esters of acrylic acid group is group shown in formula (4) :-O-C (O)-C (R ')=CH2, R ' is the alkyl of H or C1-C4.
Third aspect present invention provides the polymer dielectric film as made from the method for second aspect.
Fourth aspect present invention provides the lithium ion battery including above-mentioned polymer dielectric film.
Polymer dielectric film provided by the invention has compared with high ion conductivity, crystallinity is lower, flexibility is suitable, with
And preparation method thereof process is simple, cost is lower.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
One aspect of the present invention provides a kind of polymer dielectric film, which includes nonwoven layer and nonwoven
Polyelectrolyte floor in cloth layer surface, the polyelectrolyte floor contain polymeric matrix and are scattered in the polymer
Lithium salts in matrix, the polymeric matrix contain the cross-linked structure provided by crosslinking agent, are total to by what cross-linkable copolymers provided
Polymers chain structure and inorganic nano-particle；
Wherein, the cross-linkable copolymers contain structural unit shown in structural unit shown in formula (1), formula (2) and appoint
Structural unit shown in the formula (3) of choosing,
Formula (1):Formula (2):Formula (3):
Wherein, R is the alkyl of H or C1-C4, and L is the alkylidene or-R of C0-C41-O-R2, R1For the alkylidene of C0-C4,
R2For the alkylidene of C0-C4；
The crosslinking agent is one of acrylic ester cross-linking agent containing at least two esters of acrylic acid groups or more
Kind, the esters of acrylic acid group is group shown in formula (4) :-O-C (O)-C (R ')=CH2, R ' is the alkyl of H or C1-C4.
According to the present invention, polymeric matrix of the invention has tridimensional network, by the effect of crosslinking agent and initiation,
So that can be mutually bonded between structure in the polymeric matrix.
In particular, in the case where containing structural unit shown in formula (3) for cross-linkable copolymers, pair of the crosslinking agent
The double bond of structural unit shown in the formula (3) of key and the cross-linkable copolymers can be caused mutually polymerization, such as this
Multiple double bonds of molecule cross-link agent can structural unit shown in multiple formulas (3) with a cross-linkable copolymers double bond, or
Multiple formulas (3) of the double bond of structural unit shown in formula (3) with multiple cross-linkable copolymers or a cross-linkable copolymers
Shown in the double bond of structural unit can be bonded with the double bond of multiple crosslinking agents, and inorganic nano-particle is tightly wrapped up and winds it
In.
Certainly, highly preferred mode is that the inorganic nano-particle is by silane coupler modified inorganic nano
Particle, for this purpose, silane coupler modified group can be bonded with crosslinking agent and cross-linkable copolymers, so that inorganic receive
Rice corpuscles is preferably acted on component of polymer.
Certainly, when the cross-linkable copolymers contain structural unit shown in formula (3), the inorganic nano-particle be by
The silane coupler modified inorganic nano-particle period of the day from 11 p.m. to 1 a.m, the polyelectrolyte floor of formation are more advantageous to and nonwoven layer phase interaction
With, can especially be bonded, certainly also include other intermolecular interactions.
In the present invention, the specific example of the alkyl of C1-C4 can be for example methyl, ethyl, n-propyl, isopropyl, just
Butyl, isobutyl group, sec-butyl or tert-butyl.
The specific example of the alkylidene of C0-C4 for example can be the alkylidene ,-CH of C02-、-CH2CH2-、-
CH2CH2CH2-、-CH(CH3)CH2-、-CH2CH(CH3)-、-CH2CH2CH2CH2Etc..Wherein, the alkylidene of the C0 refers to and does not deposit
Or be connecting key, i.e. the group on the group both sides will be directly connected to.
Preferably, R H, methyl or ethyl, L are the alkylidene ,-CH of C02-、-CH2CH2-、-CH2CH2CH2-、-O-、-O-
CH2-、-O-CH2CH2-、-CH2-O-、-CH2-O-CH2-、-CH2-O-CH2CH2-、-CH2CH2-O-、-CH2CH2-O-CH2Or-
CH2CH2-O-CH2CH2-；R ' is H, methyl or ethyl.
According to the present invention, in the cross-linkable copolymers, structural unit shown in formula (1), structural unit shown in formula (2)
It can be changed in a wider range with the molar ratio of structural unit shown in optional formula (3), it is preferable that tied shown in formula (1)
The molar ratio of structural unit shown in structure unit and formula (2) is 100:0.5-25, preferably 100:1-21, more preferably 100:1-
15, it is still more preferably 100:1-8.Containing structural unit shown in formula (3), it is preferable that described cross-linking
In copolymer, the molar ratio of structural unit shown in formula (1), structural unit shown in structural unit and formula (3) shown in formula (2)
For 100:0.5-25:0.5-20, preferably 100:1-21:0.5-15, more preferably 100:1-15:1-10, still more preferably
For 100:1-8:1-6.In most preferred embodiments, the structural unit of the cross-linkable copolymers is tied as shown in formula (1)
Structural unit shown in structural unit shown in structure unit, formula (2) and formula (3) is constituted.And the cross-linkable copolymers are preferably
The structural unit shown in formula (1), structural unit shown in structural unit and formula (3) shown in formula (2) are constituted linear random
Copolymer.
According to the present invention, the weight average molecular weight of the cross-linkable copolymers can change in a wider range, it is preferable that institute
The weight average molecular weight for stating cross-linkable copolymers is 5,000-5,000,000g/mol, preferably 50,000-1,000,000g/mol,
More preferably 50,000-500,000g/mol are still more preferably 50,000-95,000g/mol, for example, 60,000-95,
000g/mol。
According to the present invention, the crosslinking agent is in the acrylic ester cross-linking agent containing at least two esters of acrylic acid groups
It is one or more, the esters of acrylic acid group of group shown in the formula (4) can be acrylate group, methacrylate
Group etc..The crosslinking agent used in the present invention is small molecule crosslinking agent, it is preferable that the crosslinking agent is dimethacrylate second
Diol ester, ethylene glycol diacrylate, dimethacrylate, diethylene glycol diacrylate, triethylene glycol two
Methacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethylacrylate, tetraethylene glycol diacrylate, two
Methacrylic acid -1,3- propylene glycol ester, dimethacrylate -1,2- propylene glycol ester, diacrylate -1,3- propylene glycol ester, dipropyl
Olefin(e) acid -1,2- propylene glycol ester, dimethacrylate -1,4- butanediol ester, dimethacrylate -1,3 butylene glycol ester, two propylene
Acid -1,4- butanediol ester, diacrylate -1,3 butylene glycol ester, pentaerythritol diacrylate, pentaerythritol triacrylate and
One of pentaerythritol tetraacrylate is a variety of, more preferably triethylene glycol dimethacrylate, triethylene glycol dipropyl
One of olefin(e) acid ester, pentaerythritol triacrylate and pentaerythritol tetraacrylate are a variety of.
In accordance with the present invention it is preferred that the inorganic nano-particle is inorganic oxide nanoparticles, rare-earth oxidation ceramics are received
One of rice corpuscles and poly- nitrine phosphine compound are a variety of, preferably SiO2、MgO、CaO、CeO2、ZnO、SnO2、Al2O3、
TiO2、ZrO2、SrO、BaO、B2O3、Ga2O3、In2O3、GeO2、Nb2O5、SiC、MgS、CaS、SrS、BaS、B2S3、Al2S3、Ga2S3、
In2S3、SiS2、GeS2、SnS2、CeS2、NbS2、Li7La3Zr2O12、SrBi4Ti4O15And BaSO4One of or it is a variety of.This is inorganic
Nanoparticle can be the forms such as nano particle, nano wire, nanometer rods, nanotube.For nano particle, granularity is for example
It can be 10nm-2 μm.For nano wire, diameter for example can be 10nm-1 μm, and length for example can be 500nm-20
μm.For nanometer rods, diameter for example can be 10nm-1 μm, and length for example can be 50nm-5 μm.For nanotube
For, diameter for example can be 10nm-1 μm, and length for example can be 100nm-1 μm.
As described above, it is preferable that the inorganic nano-particle is by silane coupler modified.The silane coupling agent can be with
With multiple choices, it is preferable that the silane coupling agent is mercaptopropyl trimethoxysilane, mercaptopropyltriethoxysilane, ammonia
Propyl-triethoxysilicane, 3- glycidyloxypropyl trimethoxy silane, 3- glycidylpropyl triethoxysilicane
Alkane, 3- acryloxypropyl trimethoxy silane, 3- methyl allyl acyloxypropyl trimethoxysilane, 3- acryloxypropyl three
Ethoxysilane, 3- methacryloxypropyl triethoxysilane, 3- acryloxypropyl methyl dimethoxysilane, 3- first
Base acryloxypropyl methyl dimethoxysilane, 3- acryloxypropyl ethyl diethoxy silane, 3- methacryloxypropyl
Ethyl diethoxy silane, 3- acryloxypropyl dimethylethoxysilane, 3- methacryloxypropyl dimethyl
Ethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilanis and allyl three
One of Ethoxysilane is a variety of, preferably 3- acryloxypropyl trimethoxy silane, 3- methacryloxypropyl
Trimethoxy silane, 3- acryloxypropyl triethoxysilane, 3- methacryloxypropyl triethoxysilane, 3- propylene
Monomethacryloxypropyl methyl dimethoxysilane, 3- methacryloxymethyl dimethoxysilane, 3- acryloxypropyl ethyl two
Ethoxysilane, 3- methacryloxypropyl ethyl diethoxy silane, 3- acryloxypropyl dimethylethoxysilane
With one of 3- methacryloxypropyl dimethylethoxysilane or a variety of.
Wherein, in the case where containing unsaturated double-bond for silane coupling agent, the unsaturated double-bond can with crosslinking agent,
Cross-linkable copolymers are preferably bonded, and can also preferably act on nonwoven layer, with 3- acryloxypropyl trimethoxy silicon
For the modified inorganic nano-particle of alkane, structure is as follows:
Wherein, although only having the silane coupling agent of two molecules on upper structural formula inorganic nano-particle it should be appreciated that
, the silane coupling agent of a molecule can be had on the inorganic nano-particle, it can also be with the silane of more than two molecules
Coupling agent, there is no particular limitation to this by the present invention.
According to the present invention, the content for the cross-linked structure unit that the crosslinking agent provides depends on required polymeric matrix
The degree of cross linking, it is preferable that in the polymeric matrix, the content of the cross-linked structure is 5-30 weight %, preferably 10-25 weight
Measure %, more preferably 15-22 weight %, for example, 18.5-21.5 weight %.Thus, it is preferable that the copolymer chain structure
Content is 55-90 weight %, preferably 60-80 weight %, more preferably 65-78 weight %, for example, 68-76 weight %.It is excellent
Selection of land, the content of the inorganic nano-particle are 1-20 weight %, preferably 2-15 weight %, more preferably 3-12 weight %,
For example, 3.5-11.5 weight %.
According to the present invention, also containing the lithium salts being scattered in polymeric matrix in the polyelectrolyte floor, wherein institute
Stating lithium salts can be the lithium salts that polymer dielectric usually contains, it is preferable that the lithium salts is LiClO4、LiPF6、LiBF4、
LiBOB (dioxalic acid lithium borate), LiN (SO2CF3)2、LiCF3SO3With LiN (SO2CF2CF3)2One of or it is a variety of.
Preferably, the polymeric matrix shown in formula (1) in terms of structural unit and the lithium salts in terms of Li rub
You are than being 5-20:1, preferably 8-20:1, more preferably 10-15:1.
According to the present invention, the thickness of the nonwoven layer and polyelectrolyte floor can change in a wider range, excellent
Selection of land, the nonwoven layer with a thickness of 1-100 μm (preferably 30-80 μm), the polyelectrolyte floor with a thickness of 20-
150 μm (preferably 50-100 μm).
Wherein, the non-woven fabrics that the nonwoven layer uses can have multiple choices, such as the nonwoven layer is poly- pair
Ethylene terephthalate, polyimides, polyetherimide, aramid fiber 1313, poly(p-phenylene terephthalamide), poly- isophthalic diformazan
Acyl m-phenylene diamine (MPD), poly(p-benzamide), polyhenylene benzo double thiazole, polybenzoxazoles, polybenzimidazoles, copolyether ketone and polyphenyl
One of azoles or the non-woven fabrics of a variety of formation.
Second aspect of the present invention provides a kind of preparation method of polymer dielectric film, this method comprises:
(1) the electrolysis chylema containing cross-linkable copolymers, lithium salts, crosslinking agent, inorganic nano-particle and photoinitiator is provided
Material；
(2) electrolyte slurry is coated on non-woven fabrics simultaneously drying and forming-film, is then consolidated under ultraviolet light
Change crosslinking to form polyelectrolyte floor on non-woven fabrics；
Wherein, the cross-linkable copolymers contain structural unit shown in structural unit shown in formula (1), formula (2) and appoint
Structural unit shown in the formula (3) of choosing,
Formula (1):Formula (2):Formula (3):
Wherein, R is the alkyl of H or C1-C4, and L is the alkylidene or-R of C0-C41-O-R2, R1For the alkylidene of C0-C4,
R2For the alkylidene of C0-C4；
The crosslinking agent is one of acrylic ester cross-linking agent containing at least two esters of acrylic acid groups or more
Kind, the esters of acrylic acid group is group shown in formula (4) :-O-C (O)-C (R ')=CH2, R ' is the alkyl of H or C1-C4.
According to the present invention, the group of above-mentioned cross-linkable copolymers and type selection, the group of crosslinking agent and type selection, nothing
The type of machine nanoparticle selects and the type of non-woven fabrics selects as described above, and details are not described herein by the present invention.
According to the present invention, the method that the cross-linkable copolymers can be this field routine is made, and is also possible to commercially available product
According to the present invention, there is no particular limitation to this by the present invention.
According to the present invention, silane coupler modified inorganic nano-particle can be adopted and be made with the conventional methods in the field
It is standby, such as preparation method may include: that in organic solvent, inorganic nano-particle is mixed with the silane coupling agent
(such as ultrasonic disperse 20-40min) is then heated (such as heating 10-24h at 90-120 DEG C).Wherein, this has
Solvent for example can be one of ethyl alcohol, methanol, propyl alcohol, propylene glycol, ethylene glycol and isopropanol or a variety of.Relative to 100
The inorganic nano-particle of parts by weight, the dosage of the organic solvent for example can be 500-5000 parts by weight.Wherein, relative to 100
The inorganic nano-particle of parts by weight, the dosage of the silane coupling agent are 5-20 parts by weight.
The dosage of the cross-linkable copolymers, crosslinking agent and inorganic nano-particle can be according to the polymer being outlined above
Content respectively shared is selected in matrix, it is preferable that with the cross-linkable copolymers, crosslinking agent and inorganic nano-particle
On the basis of total weight, the contents of the cross-linkable copolymers is 55-90 weight %, preferably 60-80 weight %, more preferably
65-78 weight %, for example, 18.5-21.5 weight %.Preferably, the content of the crosslinking agent is 5-30 weight %, preferably
10-25 weight %, more preferably 15-22 weight %, for example, 68-76 weight %.Preferably, the inorganic nano-particle contains
Amount is 1-20 weight %, preferably 2-15 weight %, more preferably 3-12 weight %, for example, 3.5-11.5 weight %.
According to the present invention, the selection of the lithium salts is as described in above, and details are not described herein by the present invention.The lithium salts
Dosage can be selected according to the description of lithium salt content in above polymer dielectric, it is preferable that tie shown in formula (1)
The cross-linkable copolymers of structure unit meter and the molar ratio of the lithium salts in terms of Li are 5-20:1, preferably 8-20:1, more
Preferably 10-15:1.
In accordance with the present invention it is preferred that the photoinitiator is 2- hydroxy-2-methyl propiophenone, (2,4,6- trimethylbenzene first
Acyl group) phosphinic acid ethyl ester, 4- dimethylaminobenzoic acid ethyl ester, 1- hydroxycyclohexyl phenyl ketone, benzoin dimethylether, o-benzoyl
One of methyl benzoate and 4- chlorobenzophenone are a variety of.The dosage of the photoinitiator can become in a wider range
It is dynamic, it is preferable that on the basis of the total weight of the cross-linkable copolymers, crosslinking agent and inorganic nano-particle, the photoinitiator
Dosage be 2-15 weight %, preferably 4-10 weight %, more preferably 5-8 weight %.
According to the present invention, as long as the organic solvent that the electrolyte slurry uses can fully disperse or dissolve step
(1) raw material, preferably n,N-Dimethylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone, tetrahydro furan
It mutters, one of chloroform, methylene chloride and acetonitrile or a variety of, wherein the dosage of the organic solvent can be in a wider range
It changes, it is preferable that relative to the total weight of the cross-linkable copolymers of 10g, crosslinking agent and inorganic nano-particle, the organic solvent
Dosage be 20-100g, preferably 30-80g, more preferably 35-60g.
According to the present invention, in step (1), preferably first cross-linkable copolymers is dissolved in organic solvent, add lithium salts
And it is sufficiently mixed (such as mixing 10-30h), inorganic nano-particle (such as mixing 10-30h) is then added, friendship is eventually adding
Connection agent and photoinitiator are mixed (such as mixing 1-4h), to obtain the electrolyte slurry.
According to the present invention, electrolyte slurry is coated on non-woven fabrics in step (2), it can be using the side such as blade coating, roller coating
Formula, and it is dry (such as drying 0.5-10h at 40-70 DEG C), half dry film not being completely dried can be formed on non-woven fabrics；Then
Again under ultraviolet light, so that photoinitiator cause the free radical of polymerization, so that above-mentioned raw materials crosslink polymerization,
Obtain the polyelectrolyte floor of tridimensional network described above.Wherein it is preferred in step (2), the crosslinking
The cured time is 30s-15min, preferably 2-10min.The ultraviolet light can use the ultraviolet irradiation of this field routine
Mode carries out, and there is no particular limitation to this by the present invention.
According to the present invention, by the above method, polyelectrolyte floor can be formed on non-woven fabrics, this method can be with
Resulting polymers dielectric film is dried after being included in solidification crosslinking to remove remaining solvent and moisture etc., such as
Dry 8-20h at 40-80 DEG C.
Third aspect present invention provides the polymer dielectric film as made from the method for second aspect.
The polymer dielectric film made from the above method of the invention can be polymer electrolytic as described above
Plasma membrane is such, provided of course that polymer dielectric film prepared by the above method belongs to this aspect.
Above method process of the invention is simple, cost is lower, and resulting polymer dielectric has leads compared with macroion
Electric rate, compared with low-crystallinity, suitable flexibility.Specifically, resulting polymer dielectric is reachable in 30 DEG C of ionic conductivity
To 3.5 × 10-6S/cm or more, preferably 2.1 × 10-5S/cm or more, more preferably 5.0 × 10-5S/cm to 9.5 × 10-5S/
Cm, particularly preferably 7.5 × 10-5S/cm to 9 × 10-5S/cm；It can reach 4.0 × 10 in 60 DEG C of ionic conductivities-5S/cm with
On, preferably 3.0 × 10-4S/cm or more, more preferably 5.0 × 10-4S/cm to 9.9 × 10-4S/cm, particularly preferably 9 ×
10-4S/cm to 9.8 × 10-4S/cm；Tensile strength is 20MPa or more, preferably 25MPa or more, especially 27-30MPa.
Fourth aspect present invention provides the lithium ion battery including above-mentioned polymer dielectric film.
The lithium ion battery can be the all-solid lithium-ion battery of the conventional configurations of this field, as long as including of the invention
Polymer dielectric film.
The present invention will be described in detail by way of examples below.
In following example:
Cross-linkable copolymers 1# is purchased from the bright copolymer at chemical company, is structural unit, formula as shown in formula (1)
(2) structural unit (R=H, L=-CH shown in structural unit and formula shown in (3)2-O-CH2) composition random copolymer,
In, structural unit shown in formula (1), structural unit shown in structural unit and formula (3) shown in formula (2) molar ratio be 93:
6:1, weight average molecular weight 50,000g/mol.
Cross-linkable copolymers 2# is purchased from the bright copolymer at chemical company, is structural unit, formula as shown in formula (1)
(2) structural unit (R=H, L=-CH shown in structural unit and formula shown in (3)2-O-CH2) composition random copolymer,
In, structural unit shown in formula (1), structural unit shown in structural unit and formula (3) shown in formula (2) molar ratio be 90:
5:5, weight average molecular weight 70,000g/mol.
Cross-linkable copolymers 3# is purchased from the bright copolymer at chemical company, is structural unit, formula as shown in formula (1)
(2) structural unit (R=H, L=-CH shown in structural unit and formula shown in (3)2-O-CH2) composition random copolymer,
In, structural unit shown in formula (1), structural unit shown in structural unit and formula (3) shown in formula (2) molar ratio be 93:
6:1, weight average molecular weight 95,000g/mol.
Cross-linkable copolymers 4# is purchased from the bright copolymer at chemical company, is structural unit, formula as shown in formula (1)
(2) structural unit (R=H, L=-CH shown in structural unit and formula shown in (3)2-O-CH2) composition random copolymer,
In, structural unit shown in formula (1), structural unit shown in structural unit and formula (3) shown in formula (2) molar ratio be 93:
6:1, weight average molecular weight 200,000g/mol.
Cross-linkable copolymers 5# is purchased from the bright copolymer at chemical company, is structural unit, formula as shown in formula (1)
(2) structural unit (R=H, L=-CH shown in structural unit and formula shown in (3)2-O-CH2) composition random copolymer,
In, structural unit shown in formula (1), structural unit shown in structural unit and formula (3) shown in formula (2) molar ratio be 93:
6:1, weight average molecular weight 40,000g/mol.
Copolymer 6# is purchased from the bright copolymer at chemical company, for the structural unit as shown in formula (1) and formula (2) institute
The random copolymer of the structural unit composition shown, wherein structural unit shown in structural unit shown in formula (1) and formula (2)
Molar ratio is 93:6, weight average molecular weight 50,000g/mol.
PET non-woven fabrics is purchased from the Shandong Tai Peng Group Co., Ltd XL-50 trade mark.
PEO: the product of Aladdin IndustrialCo., weight average molecular weight 50,000g/mol are commercially available from.
Preparation example 1
This preparation example is for illustrating silane coupler modified inorganic nano-particle.
The TiO for being 1:2 by mass ratio2Nanometer rods (diameter 150nm, 1 μm of length) and vinyltrimethoxysilane are added
To ethyl alcohol (ethyl alcohol and TiO2Nanometer rods dosage mass ratio is 5:1) in, then ultrasonic disperse 30min, and reacted at 100 DEG C
12h, to obtain silane coupler modified inorganic nano-particle C1.
Preparation example 2
This preparation example is for illustrating silane coupler modified inorganic nano-particle.
By nanometer Al2O3(being purchased from SUMITOMO CHEMICAL company, partial size is the particle of 300nm) is at hydrochloric acid (concentration 0.1mol/L)
In be surface-treated so that nanometer Al2O3It is upper hydroxyl, then according to mass ratio 1:3 by the nanometer after the surface treatment
Al2O3Isopropanol (isopropanol and nanometer Al are added to 3- methacryloxypropyl ethyl diethoxy silane2O3Dosage matter
Amount is than being 4:1) in, then ultrasonic disperse 35min, and 10h is reacted at 110 DEG C, to obtain silane coupler modified nothing
Machine nanoparticle C2.
Preparation example 3
This preparation example is for illustrating silane coupler modified inorganic nano-particle.
According to method shown in preparation example 2, the difference is that, using nanometer Li7La3Zr2O12(it is purchased from Switzerland Bu Qi company, is
Particle of the partial size by 250nm) replace nanometer Al2O3, to obtain silane coupler modified inorganic nano-particle C3.
Embodiment 1
The present embodiment is for illustrating polymer dielectric film and preparation method thereof of the invention.
(1) 10g cross-linkable copolymers 1# is added to stirring and dissolving in the N,N-dimethylformamide of 56g；LiN is added
(SO2CF3)2(its dosage makes, and the molar ratio of structural unit shown in formula (1) and Li element is 14:1), stirring and dissolving was for 24 hours；And
Inorganic nano-particle C1 (in terms of dry weight, dosage 1g) is added afterwards, is dispersed with stirring for 24 hours, 2.8g pentaerythrite four is then added
The 2- hydroxy-2-methyl Propafenone of acrylate and 0.8g, and 2h is stirred, obtain electrolyte slurry.
(2) electrolyte slurry is coated on the PET non-woven fabrics of 50 μ m-thicks, after toasting 1h at 60 DEG C, obtains leather hard
Composite polymeric film；
(3) by half dry film ultraviolet light 5min, then 60 DEG C of dry 12h under vacuum conditions, obtain electrostrictive polymer
Plasma membrane S1 is solved, is made of the polyelectrolyte floor in nonwoven layer and nonwoven layer, the thickness of the polyelectrolyte floor
It is 80 μm.
Embodiment 2
The present embodiment is for illustrating polymer dielectric film and preparation method thereof of the invention.
(1) 10g cross-linkable copolymers 2# is added to stirring and dissolving in the DMAC N,N' dimethyl acetamide of 80g；LiN is added
(SO2CF2CF3)2(its dosage makes, and the molar ratio of structural unit shown in formula (1) and Li element is 10:1) stirring and dissolving 20h；
Inorganic nano-particle C1 (in terms of dry weight, dosage 1.8g) then is added, is dispersed with stirring 20h, tri- second two of 3.5g is then added
The 4- dimethylaminobenzoic acid ethyl ester of alcohol dimethylacrylate and 1g, and 1.5h is stirred, obtain electrolyte slurry.
(2) electrolyte slurry is coated on the PET non-woven fabrics of 50 μ m-thicks, after toasting 1h at 60 DEG C, obtains leather hard
Composite polymeric film；
(3) by half dry film ultraviolet light 4min, then 60 DEG C of dry 12h under vacuum conditions, obtain electrostrictive polymer
Plasma membrane S2 is solved, is made of the polyelectrolyte floor in nonwoven layer and nonwoven layer, the thickness of the polyelectrolyte floor
It is 80 μm.
Embodiment 3
The present embodiment is for illustrating polymer dielectric film and preparation method thereof of the invention.
According to method described in embodiment 1, the difference is that, the dosage of pentaerythritol tetraacrylate is 1g, to obtain
Polymer dielectric film S3 is made of the polyelectrolyte floor in nonwoven layer and nonwoven layer, the polymer dielectric
Layer with a thickness of 80 μm.
Embodiment 4
The present embodiment is for illustrating polymer dielectric film and preparation method thereof of the invention.
According to method described in embodiment 1, the difference is that, the dosage of pentaerythritol tetraacrylate is 4.5g, thus
It to polymer dielectric film S4, is made of the polyelectrolyte floor in nonwoven layer and nonwoven layer, the polymer electrolytic
Matter layer with a thickness of 80 μm.
Embodiment 5
The present embodiment is for illustrating polymer dielectric film and preparation method thereof of the invention.
According to method described in embodiment 1, the difference is that, LiN (SO2CF3)2Dosage make, structure shown in formula (1)
The molar ratio of unit and Li element is 5:1, so that polymer dielectric film S5 is obtained, by nonwoven layer and nonwoven layer
Polyelectrolyte floor constitute, the polyelectrolyte floor with a thickness of 80 μm.
Embodiment 6
The present embodiment is for illustrating polymer dielectric film and preparation method thereof of the invention.
According to method described in embodiment 1, the difference is that, LiN (SO2CF3)2Dosage make, structure shown in formula (1)
The molar ratio of unit and Li element is 20:1, so that polymer dielectric film S6 is obtained, by nonwoven layer and nonwoven layer
Polyelectrolyte floor constitute, the polyelectrolyte floor with a thickness of 80 μm.
Embodiment 7
The present embodiment is for illustrating polymer dielectric film and preparation method thereof of the invention.
According to method described in embodiment 1, the difference is that, cross-linkable copolymers 1# is replaced using cross-linkable copolymers 3#,
To obtain polymer dielectric film S7, it is made of the polyelectrolyte floor in nonwoven layer and nonwoven layer, the polymerization
Object electrolyte layer with a thickness of 80 μm.
Embodiment 8
The present embodiment is for illustrating polymer dielectric film and preparation method thereof of the invention.
According to method described in embodiment 1, the difference is that, cross-linkable copolymers 1# is replaced using cross-linkable copolymers 4#,
To obtain polymer dielectric film S8, it is made of the polyelectrolyte floor in nonwoven layer and nonwoven layer, the polymerization
Object electrolyte layer with a thickness of 80 μm.
Embodiment 9
The present embodiment is for illustrating polymer dielectric film and preparation method thereof of the invention.
According to method described in embodiment 1, the difference is that, cross-linkable copolymers 1# is replaced using cross-linkable copolymers 5#,
To obtain polymer dielectric film S9, it is made of the polyelectrolyte floor in nonwoven layer and nonwoven layer, the polymerization
Object electrolyte layer with a thickness of 80 μm.
Embodiment 10
The present embodiment is for illustrating polymer dielectric film and preparation method thereof of the invention.
According to method described in embodiment 1, the difference is that, cross-linkable copolymers 1# is replaced using copolymer 6#, thus
It to polymer dielectric film S10, is made of the polyelectrolyte floor in nonwoven layer and nonwoven layer, the polymer electrolytic
Matter layer with a thickness of 80 μm.
Embodiment 11-13
The present embodiment is for illustrating polymer dielectric film and preparation method thereof of the invention.
According to method described in embodiment 1, the difference is that, in which:
Embodiment 11: inorganic nano-particle C1 is replaced using the inorganic nano-particle C2 of equivalent, so that electrostrictive polymer be made
Plasma membrane S11 is solved, is made of the polyelectrolyte floor in nonwoven layer and nonwoven layer, the thickness of the polyelectrolyte floor
It is 80 μm；
Embodiment 12: inorganic nano-particle C1 is replaced using the inorganic nano-particle C3 of equivalent, so that electrostrictive polymer be made
Plasma membrane S12 is solved, is made of the polyelectrolyte floor in nonwoven layer and nonwoven layer, the thickness of the polyelectrolyte floor
It is 80 μm；
Embodiment 13: using equivalent without coupling agent modified TiO2Nanometer rods replace inorganic nano-particle C1, thus
Polymer dielectric film S13 is made, is made of the polyelectrolyte floor in nonwoven layer and nonwoven layer, the electrostrictive polymer
Solve matter layer with a thickness of 80 μm.
Comparative example 1
According to method described in embodiment 1, unlike, using etc. the PEO of weight replace cross-linkable copolymers 1#, thus
Polymer dielectric film DS1 is obtained, is made of the polyelectrolyte floor in nonwoven layer and nonwoven layer, the electrostrictive polymer
Solve matter layer with a thickness of 80 μm.
Test case 1
Respectively to the ionic conductivity of above-mentioned polymer dielectric film and untreated PET non-woven fabrics, tensile strength, disconnected
It splits extensibility, crystallinity and glass transformation temperature to be measured, the results are shown in Table 1, in which:
Ionic conductivity is obtained by surveying the AC impedance derivation of equation of film, and detailed process includes: after drying film
It is cut into the disk of 19mm diameter with mold, places in glove box and places 8h.With stainless steel/dielectric film, (effective area is
2cm2)/stainless steel structure, in glove box (O2﹤ 1ppm, H2O ﹤ 1ppm) in prepare button cell.The button cell prepared is put
It is tested in insulating box, Range of measuring temp is 20-90 DEG C, and ac impedance measurement frequency range is 10-5- 1Hz, amplitude
100mV, before testing impedance, sample constant temperature 1h under preset temperature.Then ac impedance technology is utilized, using Shanghai Chen Hua instrument
The CHI660B type electrochemical workstation of company, measures the conductivity of dielectric film, and test frequency range is 1-100kHz, disturbance
Signal is 5mV.The intersection point of the nyquist plot (Nyquist plot) and real axis that measure is the sheet of polymer dielectric film
Bulk resistor (Rb), then calculate the conductivityσ of polymer dielectric film according to the following formula: σ=l/ (ARb), l are polymer electrolytic
The thickness of plasma membrane；A is the contact area of polymer dielectric film and electrode.
The test process of tensile strength includes: the elongate in shape that film is cut into 1 × 5cm in advance, keeps sample dry before testing
It is dry, thickness of sample is measured, sample both ends are clamped, using universal testing machine, is slowly drawn according to certain speed (15mm/min)
It stretches to fracture, the Mechanical Data of sample under software records.
Crystallinity: using the differential scanning calorimeter (DSC, METTLER, DSC823e) for being furnished with cryogenic system (FT100),
It is corrected using indium reference substance, example weight 3-10mg, for temperature range from -85 DEG C~130 DEG C, the rate of heat addition is 5 DEG C/min, cold
But rate is 2 DEG C/min.The crystallinity of polymer dielectric film sample is recorded respectively.
Table 1
Can be seen that the resulting polymer dielectric film of the present invention by the result of table 1 has compared with high ion conductivity, knot
Brilliant degree is lower, flexibility is suitable, and polymer dielectric film performance particularly preferably is more excellent, and preparation method process
Simply, cost is lower.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (22)
1. a kind of polymer dielectric film, which is characterized in that the polymer dielectric film includes nonwoven layer and nonwoven layer table
Polyelectrolyte floor on face, the polyelectrolyte floor contain polymeric matrix and are scattered in the polymeric matrix
Lithium salts, the polymeric matrix contain by crosslinking agent provide cross-linked structure, by cross-linkable copolymers provide copolymer chain
Structure and inorganic nano-particle；
Wherein, the cross-linkable copolymers contain structural unit shown in structural unit shown in formula (1), formula (2) and optional
Structural unit shown in formula (3),
Formula (1):Formula (2):Formula (3):
Wherein, R is the alkyl of H or C1-C4, and L is the alkylidene or-R of C0-C41-O-R2, R1For the alkylidene of C0-C4, R2For
The alkylidene of C0-C4；
The crosslinking agent is one of acrylic ester cross-linking agent containing at least two esters of acrylic acid groups or a variety of, institute
Stating esters of acrylic acid group is group shown in formula (4) :-O-C (O)-C (R ')=CH2, R ' is the alkyl of H or C1-C4.
2. polymer dielectric film according to claim 1, wherein R H, methyl or ethyl, L be C0 alkylidene ,-
CH2-、-CH2CH2-、-CH2CH2CH2-、-O-、-O-CH2-、-O-CH2CH2-、-CH2-O-、-CH2-O-CH2-、-CH2-O-
CH2CH2-、-CH2CH2-O-、-CH2CH2-O-CH2Or-CH2CH2-O-CH2CH2-；R ' is H, methyl or ethyl.
3. polymer dielectric film according to claim 1 or 2, wherein in the cross-linkable copolymers, shown in formula (1)
Structural unit and formula (2) shown in structural unit molar ratio be 100:0.5-25, preferably 100:1-21, more preferably
100:1-15 is still more preferably 100:1-8；
Containing structural unit shown in formula (3), in the cross-linkable copolymers, structural unit shown in formula (1),
The molar ratio of structural unit shown in structural unit shown in formula (2) and formula (3) is 100:0.5-25:0.5-20, preferably
100:1-21:0.5-15, more preferably 100:1-15:1-10 are still more preferably 100:1-8:1-6；
Preferably, the weight average molecular weight of the cross-linkable copolymers is 5,000-5,000,000g/mol, preferably 50,000-1,
000,000g/mol, more preferably 50,000-500,000g/mol are still more preferably 50,000-95,000g/mol.
4. polymer dielectric film described in any one of -3 according to claim 1, wherein in the polymeric matrix, institute
The content for stating copolymer chain structure is 55-90 weight %, preferably 60-80 weight %, more preferably 65-78 weight %；It is described
The content of cross-linked structure is 5-30 weight %, preferably 10-25 weight %, more preferably 15-22 weight %；
Preferably, the crosslinking agent is ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethyl propylene
Olefin(e) acid ester, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol
Dimethylacrylate, tetraethylene glycol diacrylate, dimethacrylate -1,3- propylene glycol ester, dimethacrylate -1,2-
Propylene glycol ester, diacrylate -1,3- propylene glycol ester, diacrylate -1,2- propylene glycol ester, dimethacrylate -1,4- butanediol
Ester, dimethacrylate -1,3 butylene glycol ester, diacrylate -1,4- butanediol ester, diacrylate -1,3 butylene glycol ester, season penta
One of tetrol diacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate are a variety of, more preferably
Triethylene glycol dimethacrylate, triethylene glycol diacrylate, pentaerythritol triacrylate and pentaerythrite tetrapropylene
One of acid esters is a variety of.
5. polymer dielectric film described in any one of -3 according to claim 1, wherein the inorganic nano-particle contains
Amount is 1-20 weight %, preferably 2-15 weight %, more preferably 3-12 weight %.
6. polymer dielectric film according to claim 5, wherein the inorganic nano-particle is SiO2、MgO、CaO、
CeO2、ZnO、SnO2、Al2O3、TiO2、ZrO2、SrO、BaO、B2O3、Ga2O3、In2O3、GeO2、Nb2O5、SiC、MgS、CaS、SrS、
BaS、B2S3、Al2S3、Ga2S3、In2S3、SiS2、GeS2、SnS2、CeS2、NbS2、Li7La3Zr2O12、SrBi4Ti4O15And BaSO4In
It is one or more.
7. polymer dielectric film according to claim 6, wherein the inorganic nano-particle changes by silane coupling agent
Property, the silane coupling agent be mercaptopropyl trimethoxysilane, mercaptopropyltriethoxysilane, aminopropyl triethoxysilane,
3- glycidyloxypropyl trimethoxy silane, 3- glycidylpropyl triethoxysilane, 3- acryloxypropyl
Trimethoxy silane, 3- methyl allyl acyloxypropyl trimethoxysilane, 3- acryloxypropyl triethoxysilane, 3- methyl
Acryloxypropyl triethoxysilane, 3- acryloxypropyl methyl dimethoxysilane, 3- methacryloxypropyl first
Base dimethoxysilane, 3- acryloxypropyl ethyl diethoxy silane, 3- methacryloxypropyl ethyl diethoxy
Silane, 3- acryloxypropyl dimethylethoxysilane, 3- methacryloxypropyl dimethylethoxysilane, vinyl
One in trimethoxy silane, vinyltriethoxysilane, allyltrimethoxysilanis and allyltriethoxysilane
Kind is a variety of.
8. polymer dielectric film described in any one of -3 according to claim 1, wherein the nonwoven layer is poly- to benzene
Naphthalate, polyimides, polyetherimide, aramid fiber 1313, poly(p-phenylene terephthalamide), it is poly- between phenyl-diformyl
M-phenylene diamine (MPD), poly(p-benzamide), polyhenylene benzo double thiazole, polybenzoxazoles, polybenzimidazoles, copolyether ketone and polyphenyl azoles
One of or a variety of formation non-woven fabrics.
9. polymer dielectric film described in any one of -3 according to claim 1, wherein the nonwoven layer with a thickness of
1-100 μm, the polyelectrolyte floor with a thickness of 20-150 μm.
10. polymer dielectric film described in any one of -3 according to claim 1, wherein the lithium salts is LiClO4、
LiPF6、LiBF4、LiBOB、LiN(SO2CF3)2、LiCF3SO3With LiN (SO2CF2CF3)2One of or it is a variety of；
Preferably, the molar ratio of the polymeric matrix shown in formula (1) in terms of structural unit and the lithium salts in terms of Li
For 5-20:1, preferably 8-20:1, more preferably 10-15:1.
11. a kind of preparation method of polymer dielectric film, which is characterized in that this method comprises:
(1) electrolyte slurry containing cross-linkable copolymers, lithium salts, crosslinking agent, inorganic nano-particle and photoinitiator is provided；
(2) electrolyte slurry is coated on non-woven fabrics simultaneously drying and forming-film, solidification friendship is then carried out under ultraviolet light
Connection on non-woven fabrics to form polyelectrolyte floor；
Wherein, the cross-linkable copolymers contain structural unit shown in structural unit shown in formula (1), formula (2) and optional
Structural unit shown in formula (3),
Formula (1):Formula (2):Formula (3):
Wherein, R is the alkyl of H or C1-C4, and L is the alkylidene or-R of C0-C41-O-R2, R1For the alkylidene of C0-C4, R2For
The alkylidene of C0-C4；
The crosslinking agent is one of acrylic ester cross-linking agent containing at least two esters of acrylic acid groups or a variety of, institute
Stating esters of acrylic acid group is group shown in formula (4) :-O-C (O)-C (R ')=CH2, R ' is the alkyl of H or C1-C4.
12. according to the method for claim 11, wherein R H, methyl or ethyl, L are the alkylidene ,-CH of C02-、-
CH2CH2-、-CH2CH2CH2-、-O-、-O-CH2-、-O-CH2CH2-、-CH2-O-、-CH2-O-CH2-、-CH2-O-CH2CH2-、-
CH2CH2-O-、-CH2CH2-O-CH2Or-CH2CH2-O-CH2CH2-；R ' is H, methyl or ethyl；
Preferably, in the cross-linkable copolymers, mole of structural unit shown in structural unit shown in formula (1) and formula (2)
Than being still more preferably 100:1-8 for 100:0.5-25, preferably 100:1-21, more preferably 100:1-15；Containing formula
(3) in the case where structural unit shown in, in the cross-linkable copolymers, structural unit shown in formula (1), shown in formula (2)
The molar ratio of structural unit shown in structural unit and formula (3) is 100:0.5-25:0.5-20, preferably 100:1-21:0.5-
15, more preferably 100:1-15:1-10 are still more preferably 100:1-8:1-6；
Preferably, the weight average molecular weight of the cross-linkable copolymers is 5,000-5,000,000g/mol, preferably 50,000-1,
000,000g/mol, more preferably 50,000-500,000g/mol are still more preferably 50,000-95,000g/mol；
The crosslinking agent be ethylene glycol dimethacrylate, ethylene glycol diacrylate, dimethacrylate,
Diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethyl propylene
Olefin(e) acid ester, tetraethylene glycol diacrylate, dimethacrylate -1,3- propylene glycol ester, dimethacrylate -1,2- propylene glycol
Ester, diacrylate -1,3- propylene glycol ester, diacrylate -1,2- propylene glycol ester, dimethacrylate -1,4- butanediol ester, diformazan
Base acrylic acid -1,3 butylene glycol ester, diacrylate -1,4- butanediol ester, diacrylate -1,3 butylene glycol ester, pentaerythrite two
One of acrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate are a variety of, more preferably three second two
In alcohol dimethylacrylate, triethylene glycol diacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate
It is one or more.
13. according to the method for claim 11, wherein the inorganic nano-particle is SiO2、MgO、CaO、CeO2、ZnO、
SnO2、Al2O3、TiO2、ZrO2、SrO、BaO、B2O3、Ga2O3、In2O3、GeO2、Nb2O5、SiC、MgS、CaS、SrS、BaS、B2S3、
Al2S3、Ga2S3、In2S3、SiS2、GeS2、SnS2、CeS2、NbS2、Li7La3Zr2O12、SrBi4Ti4O15And BaSO4One of or
It is a variety of.
14. according to the method for claim 13, wherein the inorganic nano-particle is described by silane coupler modified
Silane coupling agent is 3 mercaptopropyl trimethoxysilanes, mercaptopropyltriethoxysilane, aminopropyl triethoxysilane, 3- shrink
Glyceryl oxygroup propyl trimethoxy silicane, 3- glycidylpropyl triethoxysilane, 3- acryloxypropyl trimethoxy
Base silane, 3- methyl allyl acyloxypropyl trimethoxysilane, 3- acryloxypropyl triethoxysilane, 3- methacryl
Oxygen propyl group triethoxysilane, 3- acryloxypropyl methyl dimethoxysilane, 3- methacryloxypropyl methyl dimethoxy
Oxysilane, 3- acryloxypropyl ethyl diethoxy silane, 3- methacryloxypropyl ethyl diethoxy silane, 3-
Acryloxypropyl dimethylethoxysilane, 3- methacryloxypropyl dimethylethoxysilane, vinyl trimethoxy
One of base silane, vinyltriethoxysilane, allyltrimethoxysilanis and allyltriethoxysilane are more
Kind.
15. according to the method for claim 11, wherein with the cross-linkable copolymers, crosslinking agent and inorganic nano-particle
Total weight on the basis of, the contents of the cross-linkable copolymers is 55-90 weight %, preferably 60-80 weight %, more preferably
65-78 weight %；The content of the crosslinking agent is 5-30 weight %, preferably 10-25 weight %, more preferably 15-22 weight
Measure %；The content of the inorganic nano-particle is 1-20 weight %, preferably 2-15 weight %, more preferably 3-12 weight %.
16. according to the method for claim 11, wherein the photoinitiator be 2- hydroxy-2-methyl propiophenone, (2,4,
6- trimethylbenzoyl) phosphinic acid ethyl ester, 4- dimethylaminobenzoic acid ethyl ester, 1- hydroxycyclohexyl phenyl ketone, styrax pair
One of methyl ether, methyl o-benzoylbenzoate and 4- chlorobenzophenone are a variety of；
Preferably, on the basis of the total weight of the cross-linkable copolymers, crosslinking agent and inorganic nano-particle, the photoinitiator
Dosage be 2-15 weight %, preferably 4-10 weight %, more preferably 5-8 weight %.
17. according to the method for claim 11, wherein the organic solvent that the electrolyte slurry uses is N, N- dimethyl
One of formamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, tetrahydrofuran, chloroform, methylene chloride and acetonitrile or
It is a variety of；
Preferably, the total weight relative to the cross-linkable copolymers of 10g, crosslinking agent and inorganic nano-particle, the organic solvent
Dosage be 20-100g, preferably 30-80g, more preferably 35-60g.
18. according to the method for claim 11, wherein the time of the crosslinking curing is 30s-15min, preferably 2-
10min。
19. according to the method for claim 11, wherein the non-woven fabrics is polyethylene terephthalate, polyamides Asia
Amine, aramid fiber 1313, poly(p-phenylene terephthalamide), poly, gathers to benzoyl at polyetherimide
One of amine, polyhenylene benzo double thiazole, polybenzoxazoles, polybenzimidazoles, copolyether ketone and polyphenyl azoles or a variety of formation
Non-woven fabrics.
20. according to the method for claim 19, wherein the non-woven fabrics with a thickness of 1-100 μm, the polymer electrolytic
Matter layer with a thickness of 20-150 μm.
21. polymer dielectric film made from the method as described in any one of claim 11-20.
22. including the lithium ion battery of polymer dielectric film described in any one of claim 1-10 and 21.
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| US20030124432A1 (en) * | 2001-11-07 | 2003-07-03 | Katsuhito Miura | Electrolyte composition and battery |
| JP2006024440A (en) * | 2004-07-08 | 2006-01-26 | Daiso Co Ltd | Battery using crosslinked polymer electrolyte |
| CN102306832A (en) * | 2011-08-12 | 2012-01-04 | 上海交通大学 | PEM (polymer electrolyte membrane) containing lithium ions and manufacturing method thereof |
| CN102529247A (en) * | 2012-01-19 | 2012-07-04 | 苏州大学 | Inorganic/organic composite porous lithium battery diaphragm and preparation method thereof |
| CN103500845A (en) * | 2013-10-08 | 2014-01-08 | 中南大学 | Cross-linked polymer-based all-solid-state electrolyte material and application of cross-linked polyoxyethylene ether |
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