CN107546410A - A kind of flexible composite polymeric thing dielectric film and preparation method thereof and lithium ion battery - Google Patents
A kind of flexible composite polymeric thing dielectric film and preparation method thereof and lithium ion battery Download PDFInfo
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Abstract
The invention provides a kind of flexible composite polymeric thing dielectric film and preparation method thereof and and lithium ion battery, the composite polymer electrolyte membrane using liquid electrolyte, polymer monomer, nanometer inorganic filler and light trigger as raw material by mixing, pouring into a mould, ultra-violet curing and peel off four steps and be prepared, the polymer monomer is ethoxylated trimethylolpropane triacrylate and/or propoxylation trimethylolpropane trimethacrylate, the concentration of the liquid electrolyte is 0.2 2mol/L, and the mass ratio of the polymer monomer and liquid electrolyte is 40:60‑90:10, the quality of the light trigger is 0.5% the 20% of polymer monomer quality, and the nanometer inorganic filler accounts for 1% the 80% of raw material gross mass.The composite polymer electrolyte membrane not only has higher ionic conductivity, also with good pliability and heat endurance, can arbitrarily bend, for lithium ion battery, its security can be improved, and the composite polymer electrolyte membrane preparation method is simple, suitable industrialized production.
Description
Technical field
The present invention relates to electrochemical material technical field, more particularly to a kind of flexible composite polymeric thing dielectric film and its system
Preparation Method and lithium ion battery.
Background technology
Lithium ion battery has operating voltage height, light weight, small volume, higher than energy and right as a kind of novel energy
Advantages of environment protection, turn into the preferable energy of focus development in recent years.Compared with liquid lithium ionic cell, polymer Li-ion
The ratio energy of battery is higher, profile is more frivolous, design flexibility is higher and electroless liquid is revealed, and turns into following lithium ion battery
The inexorable trend of development.
The preparation of polymer dielectric is the core technology of polymer Li-ion battery, and therefore, prepared by polymer dielectric
The development of technology, the progress of polymer Li-ion battery technology can be promoted.At present, polymer dielectric is broadly divided into：Gel
The compound polymer electrolyte of type polymer dielectric, pure solid polymer electrolyte and inorganic powder incorporation blending.Gel
Type polymer dielectric is mainly made up of several parts such as polymer, plasticizer and lithium salts, by properly selecting plasticizer
And lithium salts, the lithium ion conductivity of the system can be made to be greatly improved, still, due in large quantities using increasing in the system
Modeling agent can cause the safety problem similar to liquid electrolyte；Full solid state polymer electrolyte is only by polymer and lithium salts two parts
Composition, due to that need not add plasticizer, so as to avoid the safety problem because caused by adding plasticizer, but the system exists
Electrical conductivity at room temperature is too low, prevents their commercial applications；Composite polymer electrolyte is using polymer as monomer, is led to
The polymer dielectric that the methods of crossing blending, plasticising and incorporation inorganic powder obtains, it not only has higher at room temperature
Ionic conductivity, and there is preferable processing characteristics and shape stability, meanwhile, it is intrinsic not only to have had both polymer dielectric
Security, and due to the addition of inorganic powder, it is suppressed the growth of Li dendrite to a certain extent, therefore, be
The best electrolyte of security in polymer electrolyte, and most have a kind of polymer dielectric of application prospect.
Research on polymer dielectric has had a lot, and as patent CN 101901938A are disclosed, one kind is compound to gather
Polymer electrolyte and preparation method and application, the composite polymer electrolyte are that inorganic oxide is added in polymeric matrix
The polymer dielectric of tiny balloon or core-shell composite material.Its preparation method includes direct addition method and situ aggregation method two
Kind.Patent CN 102412378A disclose a kind of polymer dielectric barrier film, its preparation method and its application, the polymer
Electrolyte barrier film is made up of lithium salts, organic solvent, Photosensitive monomers, light trigger and Nano filling；Its preparation method is：Will
Lithium salts is added in organic solvent, and magnetic agitation obtains electrolyte solution；Light trigger, magnetic agitation are added into Photosensitive monomers
Monomer must be blended；Electrolyte solution is added into blending monomer and Nano filling, ultrasonic vibration obtain mixed liquor；Mixed liquor is coated with
On separated type material surface；The separated type material surface of mixed liquor is scribbled with ultraviolet light, that is, obtains lithium battery and is isolated with polymer
Film.Patent CN 101517814B disclose a kind of non-aqueous electrolyte, and it contains the first of one or two acryl group
Acrylate compounds；The second acrylate compounds containing three or more acryl groups；Electrolytic salt and have
Solvent.Equally, its a kind of surface upper part or the electrode fully formed with coat are also disclosed, the coat includes：(i)
The first acrylate compounds containing one or two acryl group of reduction form；And (ii) reduces containing for form
There are the second acrylate compounds of three or more acryl groups.In addition also disclose it is a kind of comprising negative electrode, anode,
The electrochemical appliance of barrier film and non-aqueous electrolyte.
Although current polymer dielectric increases in terms of ionic conductivity, it is generally existing mechanical performance
The shortcomings that poor, preparing, there is good flexible electrolyte to need further to study.
The content of the invention
It is an object of the invention to provide a kind of flexible composite polymeric thing dielectric film and preparation method thereof and lithium-ion electric
Pond, the composite polymer electrolyte not only have higher ionic conductivity, can be arbitrarily curved also with good pliability
Folding.
To use following technical scheme up to this purpose, the present invention：
On the one hand, the invention provides a kind of preparation method of flexible composite polymeric thing dielectric film, comprise the following steps：
1) mix：Liquid electrolyte, polymer monomer, light trigger and nanometer inorganic filler are mixed, mixed
Close uniform slurry；
2) pour into a mould：Step 1) the slurry is equably poured on mould, obtains wet film in uniform thickness；
3) ultra-violet curing：Step 2) the wet film is placed under uviol lamp and irradiated, until its completion of cure；
4) peel off：Wet film after solidification is stripped down from mould, obtains flexible composite polymeric thing dielectric film；
The liquid electrolyte is made up of lithium salts and organic solvent；The polymer monomer is ethoxylation trihydroxy methyl third
Alkane triacrylate and/or propoxylation trimethylolpropane trimethacrylate, the concentration of the lithium salts in organic solvent are
0.2-2mol/L, the mass ratio of the polymer monomer and liquid electrolyte is 40:60-90:10, the quality of the light trigger
For the 0.5%-20% of polymer monomer quality, the nanometer inorganic filler accounts for the 1%-80% of raw material gross mass.
Described polymer monomer is ethoxylated trimethylolpropane triacrylate (ETPTA) and the hydroxyl of propoxylation three
During the mixture of propane tri (TPPTA), ethoxylated trimethylolpropane triacrylate (ETPTA) and third
The ratio of epoxide trimethylolpropane trimethacrylate (TPPTA) is arbitrary.The polymer monomer and liquid electrolyte
Mass ratio be 40:60-90:10, such as 50:50、60:40、65:35、70:30、80:20 or 85:15.The present invention using have compared with
The trifunctional functional group polymer monomer of high activity, suitable viscosity and superior solubility power, the dielectric film of preparation have well
Pliability and relatively low shrinkage.
The lithium salts is lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), lithium perchlorate (LiClO4), hexafluoro arsenic
Sour lithium (LiAsF6), trifluoromethyl sulfonic acid lithium (LiCF3SO3), bis trifluoromethyl sulfimide lithium (Li (CF3SO2)2) or double grass N
Sour lithium borate (LiB (C2O4)2) any of or at least two mixture, when the lithium salts is mixture, in mixture
The mass ratio of each component is arbitrary.
Described organic solvent is the mixture of the carbonate-based solvent of two kinds or the above, and the carbonate-based solvent is
Ethylene carbonate (EC), propene carbonate (PC), butylene (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC),
Methyl ethyl carbonate (EMC) or methyl propyl carbonate (MPC).In the ORGANIC SOLVENT MIXTURES, the volume ratio of each component is arbitrary.
The concentration of the lithium salts in organic solvent is 0.2-2mol/L, as 0.5mol/L, 0.8mol/L, 1.0mol/L,
1.2mol/L, 1.5mol/L, 1.7mol/L or 1.9mol/L.
Described nanometer inorganic filler is nano aluminium oxide (Al2O3), nano silicon oxide (SiO2), nano-titanium oxide
(TiO2), nano zircite (ZrO2), nano magnesia (MgO) or nano ferriferrous oxide (Fe3O4) in one kind or at least two
The mixture of kind.When the nanometer inorganic filler is mixture, the mass ratio of each component is arbitrary in mixture.The nanometer
The average grain diameter of inorganic filler is 10-500nm, as 50nm, 100nm, 150nm, 200nm, 240nm, 280nm, 300nm,
350nm, 400nm or 450nm.The nanometer inorganic filler accounts for the 1%-80% of raw material gross mass, such as 5%, 10%, 15%,
25%th, 40%, 50%, 60%, 70% or 75%.Nanometer inorganic filler provided by the invention has certain parent to organic solvent
And power, therefore solvent stability can be played a part of；The addition of nanometer inorganic filler can improve the mechanical performance of dielectric film
And heat endurance；When prepared dielectric film is used in lithium ion battery, because nanometer inorganic filler can suppress lithium
The growth of dendrite, the security of lithium ion battery can be significantly improved.
The light trigger is 2- hydroxy-2-methyl -1- phenyl -1- acetone (HMPP), and the quality of the light trigger is
The 0.5%-20% of polymer monomer quality, such as 0.8%, 1%, 5%, 7%, 10%, 12%, 14%, 16% or 18%.It is described
Light trigger is in ultraviolet light starting stage initiated polymerization so that the polymerization of polymerized monomer can carry out ground thoroughly.
The step 1) is mixed into grinding, stirring, ball milling or bead mill, and raw material is mainly well mixed by its purpose, is made
Nanometer inorganic filler is evenly dispersed in composite polymer electrolyte membrane；The step 1) is entered in the glove box full of argon gas
OK.
Be carved with the groove of certain depth on the mould of the step 2), the shape of the groove depending on production needs,
Such as circle, triangle, quadrangle, the depth of the groove are 1-500 μm, such as 10 μm, 50 μm, 100 μm, 150 μm, 200 μm,
250 μm, 300 μm, 350 μm, 400 μm or 450 μm.The base material of the mould is polypropylene (PP) or polyethylene glycol terephthalic acid (TPA)
Ester (PET).
The uviol lamp of the step 3) is LED uviol lamps, and the light application time is 10-300s, as 20s, 30s, 50s,
60s, 80s, 90s, 100s, 120s, 160s, 180s, 200s, 240s or 280s.Ultra-violet curing condition, to the property of solid electrolyte
It can have a major impact, the long dielectric film over-curing of irradiation time, when can reduce the pliability of solid electrolyte membrane, and irradiate
Between too short solid electrolyte membrane then can make it that the skeleton of solid electrolyte membrane is not firm enough due to solidifying not exclusively, and then influence
The intensity of solid electrolyte membrane.
On the other hand, the invention provides a kind of composite polymer electrolyte membrane that as described above prepared by preparation method, institute
The thickness for stating composite polymer electrolyte membrane is 1-500 μm, such as 10 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μ
M, 350 μm, 400 μm or 450 μm.
Present invention also offers a kind of lithium ion battery, including：Positive electrode, negative electrode and flexible compound as described above are gathered
Polymer electrolyte membrane, the flexible composite polymeric thing dielectric film are placed between the positive electrode and negative electrode.The lithium ion
Battery replaces original electrolyte and barrier film with composite polymer electrolyte membrane, and structure is simpler, and safer.
Compared with prior art, beneficial effects of the present invention are：
(1) flexible composite polymeric thing dielectric film provided by the invention has higher ionic conductivity, and due to choosing
Polymerized monomer has higher active, suitable viscosity and excellent dissolving power, and the dielectric film has well flexible
Property and relatively low shrinkage, can be securely attached on the base material of mould；
(2) flexible composite polymeric thing dielectric film provided by the invention has well due to containing nanometer inorganic filler
Mechanicalness and heat endurance；
(3) lithium ion battery security provided by the invention containing flexible composite polymeric thing dielectric film is higher；
(4) preparation method of flexible composite polymeric thing dielectric film provided by the invention is simple, suitable industrialized production.
Brief description of the drawings
Fig. 1 is the preparation technology flow chart of flexible composite polymeric thing dielectric film provided by the invention.
Fig. 2 is the structural representation of flexible composite polymeric thing dielectric film provided by the invention.
Fig. 3 is the bending sketch map of flexible composite polymeric thing dielectric film provided by the invention.
Fig. 4 is lithium dendrite growth schematic diagram：Growth schematic diagram of a Li dendrites in liquid lithium ionic cell；B Li dendrites exist
Growth schematic diagram in composite polymer electrolyte membrane lithium ion battery provided by the invention.
Wherein, 1, nanometer inorganic filler；2, polymeric matrix；3, electrolyte；4, Li dendrite；5, lithium piece.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
As shown in figure 1, the preparation process of flexible composite polymeric thing dielectric film of the present invention includes following specific step
Suddenly：
1) mix：In the glove box full of argon gas, weigh liquid electrolyte, polymerized monomer, light respectively by charge ratio and draw
Agent and inorganic particle are sent out, is sequentially placed into container and is mixed, obtain well mixed slurry；
2) pour into a mould：Step 1) the slurry is equably poured on mould, obtains wet film in uniform thickness；
3) ultra-violet curing：Step 2) the wet film is placed under uviol lamp and irradiated, until its completion of cure；
4) peel off：Wet film after step 3) is solidified strips down from mould, obtains flexible composite polymeric thing electrolyte
Film.
The structural representation of flexible composite polymeric thing dielectric film provided by the invention is illustrated in figure 2, can be with from figure
Find out, the dielectric film is made up of inorganic filler 1, polymeric matrix 2 and electrolyte 3.
The bending sketch map of flexible composite polymeric thing dielectric film provided by the invention is illustrated in figure 3, can be with from figure
Find out, described composite polymer electrolyte membrane is still not broken through bending, and illustrates that it has good pliability.
Lithium dendrite growth schematic diagram provided by the invention is illustrated in figure 4, contrast a and b can be seen that Li dendrite 4 multiple
The growth closed in polymer dielectric film is suppressed, so that composite polymer electrolyte membrane lithium ion battery is with higher
Security.
Embodiment 1
The preparation process of flexible composite polymeric thing dielectric film is as follows：
1) mix：
A. in the glove box full of argon gas, weigh 3.0g ETPTA and 4.5g 0.2mol/L's respectively with electronic balance
LiPF6(EC:PC:BC=2:1:4 volume ratios) electrolyte, the two is mixed in beaker, magnetic agitation, obtains uniform solution A；
B. 0.15g HMPP are weighed with electronic balance to be put into above-mentioned solution, continues magnetic agitation, obtain homogeneous mixing
Liquid B；
C. with electronic balance weigh 6g particle diameters be about 100nm in mass ratio be 1:1 Al2O3/ZrO2Mixed-powder, will
It is mixed with above-mentioned mixed liquid B in zirconia ball grinding jar, with 10:1 ratio of grinding media to material adds zirconia ball, and ball grinder is sealed
It is good, removed from glove box, ball milling 1h, obtain well mixed slurry；
2) pour into a mould：Above-mentioned slurry is equably cast in being carved with using PET sheet as base material in the glove box full of argon gas
Depth is 200 μm, in the mould of a diameter of 18 μm of circular trough, obtains wet film in uniform thickness；
3) ultra-violet curing：Above-mentioned wet film is irradiated into 30s under 200W LED uviol lamps, obtains the electrolyte of completion of cure
Film；
4) peel off：The dielectric film of completion of cure is stripped down from mould, obtains flexible composite polymeric thing electrolyte
Film.
Embodiment 2
The detailed preparation process of flexible composite polymeric thing dielectric film is as follows：
1) mix：
A. in the glove box full of argon gas, 9g ETPTA and 9g 0.5mol/L LiB are weighed respectively with electronic balance
(C2O4)2(EC:PC=1:1 volume ratio) electrolyte, the two is mixed in beaker, magnetic agitation, obtains uniform solution A；
B. 0.15g HMPP are weighed with electronic balance to be put into above-mentioned solution, continues magnetic agitation, obtain homogeneous mixing
Liquid B；
C. with electronic balance weigh 6g particle diameters be about 10nm in mass ratio be 1:2:1 Al2O3/SiO2/Fe3O4Mixed powder
End, it is mixed in zirconia ball grinding jar with above-mentioned mixed liquid B, with 10:1 ratio of grinding media to material adds zirconia ball, by ball grinder
Good seal, removed from glove box, ball milling 1h, obtain well mixed slurry；
2) pour into a mould：In the glove box full of argon gas, above-mentioned slurry is equably cast in using PET sheet as base material, carved
There is depth in 100 μm, the mould of a diameter of 18 μm of circular trough, to obtain wet film in uniform thickness；
3) ultra-violet curing：Above-mentioned wet film is irradiated into 30s under 200W LED uviol lamps, obtains the electrolyte of completion of cure
Film；
4) peel off：The dielectric film of completion of cure is stripped down from mould, obtains flexible composite polymeric thing electrolyte
Film.
Embodiment 3
The detailed preparation process of flexible composite polymeric thing dielectric film is as follows：
1) mix：
A. in the glove box full of argon gas, 5g ETPTA and 4.5g 0.8mol/L Li are weighed respectively with electronic balance
(CF3SO2)2N(EC:MPC=1:5 volume ratios) electrolyte, the two is mixed in beaker, magnetic force stirs 10min, obtains homogeneous molten
Liquid A；
B. 0.75g HMPP are weighed with electronic balance to be put into above-mentioned solution, continues magnetic agitation, obtain homogeneous mixing
Liquid B；
C. the Fe that 6g particle diameters are about 100nm is weighed with electronic balance3O4Powder, by its with above-mentioned mixed liquid B in zirconia ball
Mixed in grinding jar, with 10:1 ratio of grinding media to material adds zirconia ball, and ball grinder good seal removes from glove box, ball milling 1h, obtained
To well mixed slurry；
2) pour into a mould：In the glove box full of argon gas, above-mentioned slurry is equably cast in using PET sheet as base material, carved
There is depth in 300 μm, the mould of a diameter of 18 μm of circular trough, to obtain wet film in uniform thickness；
3) ultra-violet curing：Above-mentioned wet film is irradiated into 10s under 200W LED uviol lamps, obtains the electrolyte of completion of cure
Film；
4) peel off：The dielectric film of completion of cure is stripped down from mould, obtains flexible composite polymeric thing electrolyte
Film.
Embodiment 4
The detailed preparation process of flexible composite polymeric thing dielectric film is as follows：
1) mix：
A. in the glove box full of argon gas, weigh 6g TPPTA and 4.5g 1mol/L's respectively with electronic balance
LiCF3SO3(EC:PC:EMC=1:2:1 volume ratio) electrolyte, the two is mixed in beaker, magnetic agitation, obtained homogeneous molten
Liquid A；
B. 0.3g HMPP are weighed with electronic balance to be put into above-mentioned solution, continues magnetic agitation, obtain homogeneous mixed liquor
B；
C. weigh the MgO powder that 6g particle diameters are about 50nm with electronic balance, by its with above-mentioned mixed liquid B in zirconium oxide ball milling
Mixed in tank, with 10:1 ratio of grinding media to material adds zirconia ball, and ball grinder good seal removes from glove box, ball milling 1h, obtained
Well mixed slurry；
2) pour into a mould：In the glove box full of argon gas, above-mentioned slurry is equably cast in using PET sheet as base material, carved
There is depth in 50 μm, the mould of a diameter of 18 μm of circular trough, to obtain wet film in uniform thickness；
3) ultra-violet curing：Above-mentioned wet film is irradiated into 30s under 200W LED uviol lamps, obtains the electrolyte of completion of cure
Film；
4) peel off：The dielectric film of completion of cure is stripped down from mould, obtains flexible composite polymeric thing electrolyte
Film.
Embodiment 5
The detailed preparation process of flexible composite polymeric thing dielectric film is as follows：
1) mix：
A. in the glove box full of argon gas, 10g mass ratioes are weighed respectively with electronic balance as 2:1 ETPTA and TPPTA
The LiAsF of mixture and 4.5g 1.2mol/L6(EC:PC:DEC=1:1:1 volume ratio) electrolyte, the two is mixed in beaker
Close, magnetic agitation, obtain uniform solution A；
B. 1.0g HMPP are weighed with electronic balance to be put into above-mentioned solution, continues magnetic agitation, obtain homogeneous mixed liquor
B；
C. the ZrO that 62g particle diameters are about 100nm is weighed with electronic balance2Powder, by its with above-mentioned mixed liquid B in zirconium oxide
Mixed in ball grinder, with 10:1 ratio of grinding media to material adds zirconia ball, ball grinder good seal removes from glove box, ball milling 1h,
Obtain well mixed slurry；
2) pour into a mould：In the glove box full of argon gas, above-mentioned slurry is equably cast in using PET sheet as base material, carved
There is depth in 500 μm, the mould of a diameter of 18 μm of circular trough, to obtain wet film in uniform thickness；
3) ultra-violet curing：Above-mentioned wet film is irradiated into 50s under 200W LED uviol lamps, obtains the electrolyte of completion of cure
Film；
4) peel off：The dielectric film of completion of cure is stripped down from mould, obtains flexible composite polymeric thing electrolyte
Film.
Embodiment 6
The detailed preparation process of flexible composite polymeric thing dielectric film is as follows：
1) mix：
A. in the glove box full of argon gas, weigh 25g ETPTA and 4.5g 1.8mol/L's respectively with electronic balance
LiClO4(EC:DMC=1:3 volume ratios) electrolyte, the two is mixed in beaker, magnetic agitation, obtains uniform solution A；
B. 0.15g HMPP are weighed with electronic balance to be put into above-mentioned solution, continues magnetic agitation, obtain homogeneous mixing
Liquid B；
C. the SiO that 0.3g particle diameters are 300nm is weighed with electronic balance2Powder, by its with above-mentioned mixed liquid B in zirconia ball
Mixed in grinding jar, with 10:1 ratio of grinding media to material adds zirconia ball, and ball grinder good seal removes from glove box, ball milling 1h, obtained
To well mixed slurry；
2) pour into a mould：In the glove box full of argon gas, above-mentioned slurry is equably cast in using PET sheet as base material, carved
There is depth in 1 μm, the mould of a diameter of 18 μm of circular trough, to obtain wet film in uniform thickness；
3) ultra-violet curing：Above-mentioned wet film is irradiated into 100s under 200W LED uviol lamps, obtains the electrolyte of completion of cure
Film；
4) peel off：The dielectric film of completion of cure is stripped down from mould, obtains flexible composite polymeric thing electrolyte
Film.
Embodiment 7
The detailed preparation process of flexible composite polymeric thing dielectric film is as follows：
1) mix：
A. in the glove box full of argon gas, 30g ETPTA and 4.5g 1.5mol/L matter are weighed respectively with electronic balance
Amount is than being 3:1 LiBF4And LiClO4Mixture (EC:BC=1:2 volume ratios) electrolyte, the two is mixed in beaker, magnetic force
Stirring, obtains uniform solution A；
B. 0.15g HMPP are weighed with electronic balance to be put into above-mentioned solution, continues magnetic agitation, obtain homogeneous mixing
Liquid B；
C. the TiO that 6g particle diameters are 400nm is weighed with electronic balance2Powder, by its with above-mentioned mixed liquid B in zirconium oxide ball milling
Mixed in tank, with 10:1 ratio of grinding media to material adds zirconia ball, and ball grinder good seal removes from glove box, ball milling 1h, obtained
Well mixed slurry；
2) pour into a mould：In the glove box full of argon gas, above-mentioned slurry is equably cast in using PP plates as base material, is carved with
Depth is 10 μm, in the mould of a diameter of 18 μm of circular trough, obtains wet film in uniform thickness；
3) ultra-violet curing：Above-mentioned wet film is irradiated into 200s under 200W LED uviol lamps, obtains the electrolyte of completion of cure
Film；
4) peel off：The dielectric film of completion of cure is stripped down from mould, obtains flexible composite polymeric thing electrolyte
Film.
Embodiment 8
The detailed preparation process of flexible composite polymeric thing dielectric film is as follows：
1) mix：
A. in the glove box full of argon gas, weigh 40.5g ETPTA and 4.5g 2mol/L's respectively with electronic balance
LiPF6(EC:PC=1:1 volume ratio) electrolyte, the two is mixed in beaker, magnetic agitation, obtains uniform solution A；
B. 8.1g HMPP are weighed with electronic balance to be put into above-mentioned solution, continues magnetic agitation, obtain homogeneous mixed liquor
B；
C. the Al that 3g particle diameters are 500nm is weighed with electronic balance2O3Powder, by its with above-mentioned mixed liquid B in zirconium oxide ball milling
Mixed in tank, with 10:1 ratio of grinding media to material adds zirconia ball, and ball grinder good seal removes from glove box, ball milling 1h, obtained
Well mixed slurry；
2) pour into a mould：In the glove box full of argon gas, above-mentioned slurry is equably cast in using PET sheet as base material, carved
There is depth in 150 μm, the mould of a diameter of 18 μm of circular trough, to obtain wet film in uniform thickness；
3) ultra-violet curing：Above-mentioned wet film is irradiated into 300s under 200W LED uviol lamps, obtains the electrolyte of completion of cure
Film；
4) peel off：The dielectric film of completion of cure is stripped down from mould, obtains flexible composite polymeric thing electrolyte
Film.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of preparation method of flexible composite polymeric thing dielectric film, it is characterised in that comprise the following steps：
1) mix：Liquid electrolyte, polymer monomer, light trigger and nanometer inorganic filler are mixed, it is equal to obtain mixing
Even slurry；
2) pour into a mould：Step 1) the slurry is equably poured on mould, obtains wet film in uniform thickness；
3) ultra-violet curing：Step 2) the wet film is placed under uviol lamp and irradiated, until its completion of cure；
4) peel off：Wet film after solidification is stripped down from mould, obtains flexible composite polymeric thing dielectric film；
The liquid electrolyte is made up of lithium salts and organic solvent；The polymer monomer is ethoxylated trimethylolpropane three
Acrylate and/or propoxylation trimethylolpropane trimethacrylate, the concentration of the lithium salts in organic solvent are 0.2-
2mol/L, the mass ratio of the polymer monomer and liquid electrolyte is 40:60-90:10, the quality of the light trigger is poly-
The 0.5%-20% of monomer adduct quality, the nanometer inorganic filler account for the 1%-80% of raw material gross mass.
2. preparation method according to claim 1, it is characterised in that described organic solvent is for two kinds or two or more
Carbonate-based solvent mixture, the carbonate-based solvent be ethylene carbonate, propene carbonate, butylene, carbon
Dimethyl phthalate, diethyl carbonate, methyl ethyl carbonate or methyl propyl carbonate.
3. preparation method according to claim 1 or 2, it is characterised in that the step 1) nanometer inorganic filler is nanometer
One kind in aluminum oxide, nano silicon oxide, nano-titanium oxide, nano zircite, nano magnesia or nano ferriferrous oxide or
At least two mixture；
Preferably, the average grain diameter of the nanometer inorganic filler is 10-500nm.
4. according to the preparation method described in one of claim 1-3, it is characterised in that the lithium salts is lithium hexafluoro phosphate, tetrafluoro
Lithium borate, lithium perchlorate, hexafluoroarsenate lithium, trifluoromethyl sulfonic acid lithium, bis trifluoromethyl sulfimide lithium or di-oxalate lithium borate
Any of or at least two mixture.
5. according to the preparation method described in one of claim 1-4, it is characterised in that the light trigger is 2- hydroxyl -2- first
Base -1- phenyl -1- acetone.
6. according to the preparation method described in one of claim 1-5, it is characterised in that step 1) is described be mixed into grinding, stirring,
Ball milling or bead mill；
Preferably, the step 1) is carried out in the glove box full of argon gas.
7. according to the preparation method described in one of claim 1-6, it is characterised in that be carved with a depthkeeping on the step 2) mould
The groove of degree, the base material of the mould is polypropylene or polyethyleneterephthalate.
8. according to the preparation method described in one of claim 1-7, it is characterised in that the step 3) uviol lamp is that LED is ultraviolet
Lamp, the light application time are 10-300s.
A kind of 9. composite polymer electrolyte membrane prepared by preparation method as described in one of claim 1-8, it is characterised in that institute
The thickness for stating dielectric film is 1-500 μm.
A kind of 10. lithium ion battery of the composite polymer electrolyte membrane with described in claim 9, it is characterised in that including
Positive electrode, negative electrode and described composite polymer electrolyte membrane, the composite polymer electrolyte membrane are placed in the positive electrode
Between negative electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710740126.6A CN107546410A (en) | 2017-08-25 | 2017-08-25 | A kind of flexible composite polymeric thing dielectric film and preparation method thereof and lithium ion battery |
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| CN113437359A (en) * | 2021-05-18 | 2021-09-24 | 长沙矿冶研究院有限责任公司 | Preparation method of polypropylene oxide polymer solid electrolyte film |
| CN113437359B (en) * | 2021-05-18 | 2023-04-07 | 长沙矿冶研究院有限责任公司 | Preparation method of polypropylene oxide polymer solid electrolyte film |
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