CN103668780B - Polymer film, gel polymer electrolyte and polymer Li-ion battery and preparation method thereof - Google Patents
Polymer film, gel polymer electrolyte and polymer Li-ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of polymer film, prepared by following steps: S1, by AN monomer and BuMA monomer copolymerization, obtain the different copolymer A a of component, Ab; S2, Aa, Ab are mixed with mixed liquid B a, Bb respectively; S3, Ba, Bb are carried out electrostatic spinning as spray source simultaneously; In electrostatic spinning process, the flow velocity of Ba increases with constant amplitude and/or reduces, and the flow velocity of Bb then reduces with identical constant amplitude and/or increases, and makes the overall flow rate of Ba and Bb be definite value; Spinning terminates after annealing process, obtains polymer film after drying.The present invention also provides a kind of gel polymer electrolyte and polymer Li-ion battery and preparation method thereof.Polymer film provided by the invention, its concentration of component gradually changes, and mechanical property, porosity, pick up are high, good thermal stability; Adopt the ionic conductivity of the gel polymer electrolyte of this polymer film high, high voltage withstanding, adopt the polymer Li-ion battery of this gel polymer electrolyte, security is high, charge-discharge performance is good.
Description
Technical field
The present invention relates to field of lithium ion battery, in particular, the present invention relates to a kind of polymer film gel polymer electrolyte and polymer Li-ion battery and preparation method thereof.
Background technology
Due to full solid state polymer electrolyte room-temperature conductivity up to the present, can't 10 be reached
– 3the level of S/cm, therefore can't obtain practical application in general lithium ion battery and large-scale lithium ion battery.In this context, as the compromise product of liquid electrolyte and full solid state polymer electrolyte, gel polymer electrolyte (GPE) is created.Gel polymer electrolyte is the gel state system formed by polymeric matrix and electrolyte.
Polymer matrix material is divided into two classes: a class is as not easily swelling by electrolyte in polyacrylonitrile (PAN), polystyrene (PS), is referred to as hard phase; Another kind of as polymethyl methacrylate (PMMA), polyethylene glycol oxide (PEO), butyl polyacrylate (PBuA), polyvinyl acetate (PVA) etc. can by electrolyte swelling or dissolve, be referred to as soft phase.Be used alone any one hard mutually or softly all can not meet requirement as good gel polymer electrolyte as polymeric matrix.Such as, CN group in PAN is easily reduced, and can be subject to serious passivation when lithium electrode contacts with the polymer dielectric taking PAN as base material affects cycle performance, and PAN imbibition power is bad, solvent can occur in storing process separate out, this use for lithium ion battery is very disadvantageous.There is the shortcomings such as shock resistance is low, shaping poor mobile performance in PMMA base GPE, can not be used alone in matrix material.PEO has solubility in organic solvent, makes the mechanical property of this gel polymer electrolyte too poor, is difficult to the gel polymer electrolyte film obtaining independent support.
Utilize the method for combined polymerization to be combined by above-mentioned swelling from electrolyte or that dissolution properties is different unit (mutually hard and soft phase), contribute to improving the mechanical property as GPE material and chemical property simultaneously.Scientist has done large quantity research to PAN and copolymer thereof as GPE matrix, stable for the both positive and negative polarity of lithium ion battery can be bonded together by P (AN-co-MMA) (copolymer of acrylonitrile and methyl methacrylate), there is acceptable electrical conductivity, high electrochemical stability, but its mechanical property poor (fracture strength 4.88MPa), is difficult to application.P (AN-co-BuA) (copolymer of acrylonitrile and butyl acrylate) comparatively P (AN-co-MMA) heat endurance improves (heat decomposition temperature 290 DEG C), mechanical strength improves (fracture strength 16MPa), and flexible moderate (elongation at break 65%), electrochemical window widen that (decomposition voltage is 6.6Vvs.Li
+/ Li), but its mechanical strength and flexibility still await further optimization.
The polymer matrices of desirable gel polymer electrolyte not only will make copolymer itself containing multiple composition of different nature, and the polymer film obtained should be also microporous barrier, and porosity is high, and aperture is little and gas cell distribution is narrow.Experimental result display porosity should be about 80%, and aperture should <1 μm, and this ensures that gel polymer electrolyte has the fundamental of good electrical chemical property.Microporous barrier is prepared usually by the following method: phase separation method and method of electrostatic spinning etc.Phase separation method is prepared in the process of microporous barrier to be needed to use a large amount of organic solvent, and the hole obtained can not be mutually through, affects the raising of gel polymer electrolyte ionic conductivity.Disclose in CN201010516552 and adopt method of electrostatic spinning to prepare PVDF, PMMA and Nano-meter SiO_2
2composite micro porous film, it improves the ionic conductivity (2.55 × 10 of gel polymer electrolyte to a certain extent
-3s/cm), maintain certain mechanical property (fracture strength is 6.71MPa), but still await further raising.
Summary of the invention
The invention solves in prior art the gel polymer electrolyte adopting various polymer film matrix to obtain and there is the still poor technical problem of ionic conductivity and mechanical property and flexibility, a kind of hard phase is provided to have both mutually with soft, there is good chemical property, heat endurance is very good, mechanical strength is high, the polymer film of the composition gradient change that pick up is high, it can be used as the good polymeric matrix of gel polymer electrolyte, thus provide a kind of ionic conductivity high further, high voltage withstanding, security improves greatly, the gel polymer electrolyte of stable electrochemical property, finally obtain a kind of security greatly to improve, charge-discharge performance is good, the generation of Li dendrite can be suppressed, without leakage polymer Li-ion battery.
Particularly, technical scheme of the present invention is:
A kind of polymer film, described polymer film is prepared by following steps:
S1, acrylonitrile monemer and butylmethacrylate monomer are carried out copolymerization, obtain component different copolymer A a and copolymer A b respectively, acrylonitrile unit unit wherein in copolymer A a is 91:9 ~ 70:30 with the molar percentage of butyl methacrylate construction unit, and the acrylonitrile unit unit in copolymer A b is 66:34 ~ 43:57 with the molar percentage of butyl methacrylate construction unit;
S2, copolymer A a, nanoparticle dispersion are formed mixed liquid B a in organic solvent, copolymer A b, nanoparticle dispersion are formed mixed liquid B b in organic solvent;
S3, using mixed liquid B a, mixed liquid B b as spray source, adopt two shower nozzles to carry out electrostatic spinning simultaneously; In electrostatic spinning process, the flow velocity of mixed liquid B a, Bb is 0.4 ~ 5mL/min, and the flow velocity of mixed liquid B a increases with constant amplitude and/or reduces, the flow velocity of mixed liquid B b then reduces with identical constant amplitude and/or increases, and makes the overall flow rate of mixed liquid B a and mixed liquid B b be definite value; After spinning terminates, annealing in process, obtains described polymer film after drying.
A kind of gel polymer electrolyte, described gel polymer electrolyte is formed by swelling after polymer film Electolyte-absorptive, and described polymer film is polymer film provided by the invention.
A kind of polymer Li-ion battery, this lithium ion battery comprises positive pole, negative pole, barrier film and gel polymer electrolyte, described gel polymer electrolyte is between positive pole and negative pole, and described gel polymer electrolyte is gel polymer electrolyte provided by the invention.
The preparation method of described polymer Li-ion battery, comprise and first polymer film, barrier film and polymer film are separated positive pole and negative pole in three stacked modes of putting, then overall stacked or be wound into pole piece, in pole piece, inject electrolyte, after sealing, obtain described polymer Li-ion battery.
Polymer film provided by the invention, it is formed by electrostatic spinning, therefore the polymer film obtained has completely mutually through hole and large specific area, effective passage can be provided for the transmission of lithium ion, be particularly suitable for the matrix of micropore gel polymer electrolyte, greatly can improve the ionic conductivity of gel polymer electrolyte.Simultaneously, polymer film provided by the invention, it adopts two spray sources to carry out spinning simultaneously when electrostatic spinning, and the P (AN-co-BuMA) (i.e. the copolymer of acrylonitrile and butyl methacrylate) adopting component different in two spray sources, control the flow velocity in two spray sources simultaneously, hard phase in the polymer film finally obtained and soft phase component concentration are gradually changed, its mechanical property, porosity and pick up are all improved significantly compared to PVDF and P (AN-co-MMA), have good heat endurance and chemical property simultaneously.Adopt the gel polymer electrolyte of polymer film provided by the invention, its ionic conductivity be high, high voltage withstanding, security improves greatly, stable electrochemical property.And adopting the polymer Li-ion battery of this gel polymer electrolyte, its security improves greatly, charge-discharge performance good, can suppress generation, the no leakage of Li dendrite.
Accompanying drawing explanation
Fig. 1 is the copolymer A a1's that obtains of embodiment 1
1h-NMR spectrogram.
Fig. 2 is the DSC curve of the copolymer A b3 that embodiment 3 obtains.
Fig. 3 is the thermogravimetric curve of the polymer film Ca2 that embodiment 2 obtains.
Fig. 4 is the SEM figure of the enlargement ratio 2000 times of the polymer film Ca2 that embodiment 2 obtains.
Detailed description of the invention
The invention provides a kind of polymer film, described polymer film is prepared by following steps:
S1, acrylonitrile (AN) monomer and butyl methacrylate (BuMA) monomer are carried out copolymerization, obtain component different copolymer A a and copolymer A b respectively, acrylonitrile (AN) construction unit wherein in copolymer A a and the molar percentage of butyl methacrylate (BuMA) construction unit are 91:9 ~ 70:30, and acrylonitrile (AN) construction unit in copolymer A b and the molar percentage of butyl methacrylate (BuMA) construction unit are 66:34 ~ 43:57;
S2, copolymer A a, nanoparticle dispersion are formed mixed liquid B a in organic solvent, copolymer A b, nanoparticle dispersion are formed mixed liquid B b in organic solvent;
S3, using mixed liquid B a, mixed liquid B b as spray source, adopt two shower nozzles to carry out electrostatic spinning simultaneously; In electrostatic spinning process, the flow velocity of mixed liquid B a, Bb is 0.4 ~ 5mL/min, and the flow velocity of mixed liquid B a increases with constant amplitude and/or reduces, the flow velocity of mixed liquid B b then reduces with identical constant amplitude and/or increases, and makes the overall flow rate of mixed liquid B a and mixed liquid B b be definite value; After spinning terminates, annealing in process, obtains described polymer film after drying.
Polymer film provided by the invention, it is formed by electrostatic spinning, the electrospinning cortina (i.e. polymer film) obtained has completely mutually through hole and large specific area, effective passage can be provided for the transmission of lithium ion, be particularly suitable for the matrix of micropore gel polymer electrolyte, greatly can improve the ionic conductivity of gel polymer electrolyte.
Simultaneously, polymer film provided by the invention, it adopts two spray sources to carry out spinning simultaneously when electrostatic spinning, and the P (AN-co-BuMA) adopting component different in two spray sources, control the flow velocity in two spray sources simultaneously, hard phase in the polymer film finally obtained and soft phase component concentration are gradually changed, its mechanical property, porosity and pick up are all improved significantly compared to PVDF and P (AN-co-MMA), have good heat endurance and chemical property simultaneously.
Particularly, first by the compounding design of the high-molecular copolymer matrix to formation polymer film in the present invention, the P (AN-co-BuMA) of different composition has been prepared with aqueous precipitation polymerization, then by designing with the structure of method of electrostatic spinning to film, prepare the microporous membrane that hard phase and soft phase composition concentration gradually change, be described polymer film, its heat endurance is very good, and heat decomposition temperature is up to 300 DEG C; Mechanical strength is further enhanced compared to PVDF and P (AN-co-MMA), and porosity is up to 72%, and pick up is up to 480%.
In polymer film provided by the invention, the polymer adopted is P (AN-co-BuMA), and wherein AN construction unit is rigid polymer, and its vitrification point (Tg) is 90 DEG C, can provide enough mechanical strengths, and it have the advantages such as chemical stability is high, nonflammable; In addition in AN construction unit containing promising strong polar group-CN, higher electrical conductivity Sum decomposition voltage can be provided, but itself and compatibility of electrolyte are poor, are referred to as hard phase; BuMA construction unit is flexible polymer, and Tg is 24 DEG C, can provide enough flexibilities; Contain ester group in BuMA construction unit simultaneously, good with carbonate-based solvent compatibility in electrolyte, a large amount of electrolyte can be absorbed, have good interface stability, be referred to as soft phase.The present invention prepares in the copolymer of polymer film employing, by optimizing the ratio of AN construction unit and BuMA construction unit in copolymer, P (AN-co-BuMA) copolymer can be made to have suitable intensity and flexibility, is convenient to processing.
Particularly, in the present invention, in step S1, the step that AN monomer and BuMA monomer carry out copolymerization is comprised: AN monomer is mixed in proportion with BuMA monomer, adds NaHSO
3after be filled with inert atmosphere, then add initator K
2s
2o
8carry out polymerisation, wash purification after reaction terminating and obtain copolymer.In the present invention, the polymerisation of described AN monomer and BuMA monomer is carried out under the initiation of redox system, wherein adopted NaHSO
3be reducibility initator, and K
2s
2o
8it is then oxidative initiator.
According to method of the present invention, in the mixed system of two kinds of monomers, add NaHSO
3after, can by containing NaHSO
3whole system be first placed in ice-water bath cooling after be filled with inert atmosphere again, and start magnetic agitation.This is because AN monomer boiling point low (77.4 ~ 79 DEG C), volatile, be directly filled with the gas of inert atmosphere if do not lower the temperature, the monomer of volatilization can be discharged along with gas, reduces reaction conversion ratio.Therefore, before being filled with inert atmosphere, first whole system system can be cooled to ﹣ 18 ~ 0 DEG C.After being filled with inert atmosphere a period of time, then add K
2s
2o
8, now get final product raised temperature, namely polymerisation starts to carry out.Whole polymerisation is carried out under inert atmosphere protection.K is added again after being filled with inert atmosphere a period of time
2s
2o
8reason mainly in order to by thorough for air in reactor emptying, make to be full of inert atmosphere gases in reactor.Generally, filling the inert atmosphere time is 20-30min.In the present invention, the gas that described inert atmosphere adopts can be nitrogen or inert gas, and described inert gas is the gas that group 0 element is corresponding.
When preparing copolymer, the total mol concentration of described AN monomer and BuMA monomer is 3 ~ 10mol/L, is preferably 4.5 ~ 9.6mol/L.With the integral molar quantity of AN monomer and BuMA monomer for benchmark, NaHSO
3consumption accounts for 1 × 10 of this integral molar quantity
-5~ 1 × 10
-2, K
2s
2o
8account for 1 × 10 of monomer integral molar quantity
-5~ 1 × 10
-2, and NaHSO
3with K
2s
2o
8mol ratio be (5 ~ 15): 1.
The condition of polymerisation comprises: reaction temperature is 40 ~ 100 DEG C, and the described reaction time is 2 ~ 10h.Under preferable case, reaction temperature is 60 ~ 80 DEG C, and the reaction time is 4 ~ 6h.Whole polymerisation is all carried out under stirring, and speed of agitator is preferably 600 ~ 1500 revs/min, is more preferably 900 ~ 1300 revs/min.
Polymerisation is washed product system after stopping.Wherein washing can adopt hot deionized water to carry out, and washing times is 3 ~ 5 times.The temperature of hot deionized water is 40 ~ 100 DEG C, is preferably 60 ~ 80 DEG C.Filter after washing, and adopt dissolving precipitated method to purify 2 times.Dissolution precipitation ratio juris is: be first scattered in solvent by the product system entirety containing copolymer p (AN-co-BuMA), copolymer p (AN-co-BuMA) is dissolved in solvent and forms solution, then dropwise is added in precipitating agent, the consumption of precipitating agent is 5-10 times of solvent volume, solvent and precipitating agent dissolve each other and copolymer p (AN-co-BuMA) is insoluble to precipitating agent, therefore copolymer p (AN-co-BuMA) is precipitated out from precipitating agent, gets this precipitation after filtration; Wherein solvent is dimethyl sulfoxide (DMSO) (DMSO), or N ' dinethylformamide (DMF), and precipitating agent is deionized water or ice ethanol.Then at being deposited in 80 DEG C, vacuumize is to constant weight, can obtain corresponding copolymer.
In the present invention, during preparation copolymer A a and Ab, the raw material adopted and reaction controlling condition all identical, and obtain the rate of charge of different component by means of only control two kinds of reaction monomers.Particularly, during preparation copolymer A a, the mol ratio of AN monomer and BuMA monomer is 99:1 ~ 87:13, and the AN construction unit in the copolymer A a that correspondence obtains and the molar percentage of BuMA construction unit are 91:9 ~ 70:30.Under preferable case, during preparation copolymer A a, the mol ratio of AN monomer and BuMA monomer is 98:2 ~ 90:10, and the AN construction unit in the copolymer A a that correspondence obtains and the molar percentage of BuMA construction unit are 91:9 ~ 74:26.
During preparation copolymer A b, the mol ratio of AN monomer and BuMA monomer is 85:15 ~ 70:30, and the AN construction unit in the copolymer A b that correspondence obtains and the molar percentage of BuMA construction unit are 66:34 ~ 43:57.Under preferable case, during preparation copolymer A b, the mol ratio of AN monomer and BuMA monomer is 85:15 ~ 75:25, and the AN construction unit in the copolymer A b that correspondence obtains and the molar percentage of BuMA construction unit are 66:34 ~ 47:53.In general, in copolymer A a, the content of AN construction unit is higher than copolymer A b, and the content of BuMA construction unit is lower than copolymer A b, and namely in copolymer A a, hard phase content is higher than copolymer A b, and soft phase content is lower than copolymer A b.
After adopting method copolymerization provided by the invention, the molecular weight of the copolymer after obtaining is 500000 ~ 2000000g/mol, and namely the molecular weight of copolymer A a, Ab is all within the scope of this.
According to the present invention, after obtaining copolymer A a, the Ab of different component respectively, then it is mixed with mixed liquor respectively, for follow-up electrostatic spinning.Particularly, copolymer A a, nanoparticle dispersion are formed mixed liquid B a in organic solvent, copolymer A b, nanoparticle dispersion are formed mixed liquid B b in organic solvent.Under preferable case, can first by nanoparticle dispersion in organic solvent, form dispersion liquid, and then add copolymer and open magnetic agitation and make copolymer be sufficiently uniformly dissolved dispersion.Also shorten the dissolution time of copolymer by the heating that heats up, such as, under 80 DEG C of magnetic agitation, copolymer fully can be dissolved in dispersion liquid.
In the present invention, do not have particular/special requirement for the kind of the nano particle adopted in mixed liquid B a, Bb, organic solvent and materials, it can adopt nano particle, the organic solvent of identical type, same amount, also can be different.Be but no matter be in mixed liquid B a or mixed liquid B b with should be noted that, with the quality of copolymer (Aa or Ab) for benchmark, the consumption of nano particle is 1 ~ 25wt%, is preferably 5 ~ 20wt%.With the quality of organic solvent for benchmark, the consumption of copolymer (Aa or Ab) is 3 ~ 15wt%, is preferably 5 ~ 10wt%.
Described nano particle is selected from titanium dioxide (rutile, anatase or other various crystalline form), Al
2o
3, SiO
2, CuO, MgO, LiAlO
2, ZrO
2, CNT (CNTs), BN, SiC, Si
3n
4, WC, BC, AlN, Fe
2o
3, BaTiO
3, MoS
2, α – V
2o
5, PbTiO
3, TiB
2, CaSiO
3, molecular sieve ZSM – 5, clay, any one in kaolin.The particle diameter of described nano particle is preferably 1 ~ 200nm.
Described organic solvent can select N ' dinethylformamide (DMF), N ' N-dimethylacetylamide (DMAc) and dimethyl sulfoxide (DMSO) (DMSO), and it can be used alone, or above with the combination of arbitrary proportion both adopting.
According to the present invention, after copolymer is mixed with mixed liquor, can start to carry out electrostatic spinning.For gel polymer electrolyte, the film of single composition is still not enough to the requirement meeting gel polymer electrolyte film diversification.Therefore, the present inventor surprisingly finds the film adopting the change of composition concentration gradient, make film composition that is middle or hard phase on one side relatively many, enough mechanical strengths are provided, the composition of both sides or the soft phase of another side is relatively many, ensures the sympathy with electrolyte, and the change of the concentration in gradient of membrane component, ensure that mutually hard and soft phase can not be separated, film (i.e. polymer film) mechanical strength, porosity and the pick up that obtain after spinning can be made to complete improve further.Therefore, in the present invention, in electrostatic spinning process, adopt mixed liquid B a, Bb respectively as spray source simultaneously, namely adopt two shower nozzles to carry out spinning simultaneously.Under preferable case, the internal diameter of two shower nozzles is 0.2 ~ 1mm, and the condition of electrostatic spinning comprises: voltage is 5 ~ 20KV, is preferably 7 ~ 15KV; Receiving range is 6 ~ 15cm, is preferably 9 ~ 13cm; Shower nozzle translational speed is 5 ~ 6mm/s.
In electrostatic spinning process, the flow velocity of mixed liquid B a, Bb is 0.4 ~ 5mL/min, is preferably 0.7 ~ 2.5mL/min; And the flow velocity of mixed liquid B a increases with constant amplitude and/or reduces, the flow velocity of mixed liquid B b then reduces with identical constant amplitude and/or increases, and ensures that the overall flow rate of mixed liquid B a and mixed liquid B b is definite value.
Particularly, described constant amplitude refers at interval of the increase of certain hour flow velocity and/or reduces by 0.01 ~ 0.5mL/min, and wherein interval time is 0.5 ~ 60min, is preferably 1 ~ 10min.
As a kind of preferred embodiment of the present invention, if think, spinning obtains middle hard relatively many, the soft phase contents of the phase content polymer film that the soft phase content in both sides is relatively many, hard phase content is relatively few relatively less, in electrostatic spinning process, first the flow velocity of mixed liquid B a can first be increased rear reduction, the flow velocity of mixed liquid B b then first reduces to increase afterwards accordingly, namely in the polymer film obtained from centre to both sides, content reduces hard phase (i.e. AN construction unit) gradually, and soft phase (i.e. BuMA construction unit) content increases gradually.
And if expect that on one side hard relatively many, the soft phase contents of phase content are relatively few, and the hard phase content of another side relatively less, polymer film that soft phase content is relatively many, in electrostatic spinning process, the flow control in spray source can carry out as follows: the flow velocity of mixed liquid B a increases successively, and the flow velocity of mixed liquid B b then reduces successively; Or the flow velocity of mixed liquid B a reduces successively, the flow velocity of mixed liquid B b then increases successively.The polymer film now obtained, to another side, content reduces hard phase (i.e. AN construction unit) gradually, and soft phase (i.e. BuMA construction unit) content increases gradually.
The total time of electrostatic spinning can carry out corresponding selection according to the size of required polymer film, and under preferable case, the total time of electrostatic spinning is 1 ~ 20h.
After electrostatic spinning completes, first annealing in process is carried out to rete, then dry, described polymer film can be obtained.Under preferable case, annealing temperature is 30 ~ 60 DEG C, and annealing time is 30 ~ 120min.Dry run can be directly: vacuumize 24h at 50 DEG C.The thickness of described polymer film is 0.01 ~ 110 μm, preferably 0.1 ~ 80 μm, and more excellent selects 0.1 ~ 30 μm.
Polymer film provided by the invention, its heat endurance is very good, and heat decomposition temperature is up to 300 DEG C; Mechanical strength is further enhanced compared to PVDF and P (AN-co-MMA), and porosity is up to 72%, and pick up is up to 480%, and the polymeric matrix that can be used as gel polymer electrolyte is used widely.Therefore, the invention provides a kind of gel polymer electrolyte, described gel polymer electrolyte is formed by swelling after polymer film Electolyte-absorptive, and described polymer film is polymer film provided by the invention.
Particularly, after polymer film provided by the invention can being cut into suitable size, at 60 DEG C after vacuumize 12h, transfer to rapidly in glove box (content of water and oxygen is less than 3ppm); Then this polymer film is soaked in the electrolytic solution after 24h, described gel polymer electrolyte can be obtained.
Wherein, described electrolyte is conventionally known to one of skill in the art, is made up of electrolyte lithium salt and organic solvent.Wherein electrolyte lithium salt adopts dissociable lithium salts, such as, can be selected from lithium hexafluoro phosphate (LiPF
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4) in any one, organic solvent is selected from least one in ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) and diethyl carbonate (DEC), vinylene carbonate (VC).Under preferable case, in described electrolyte, the concentration of electrolyte lithium salt is 0.8 ~ 1.5mol/L.
Adopt the gel polymer electrolyte of polymer film provided by the invention, its ionic conductivity be high, high voltage withstanding, security improves greatly, stable electrochemical property.Therefore, the invention provides a kind of polymer Li-ion battery, this lithium ion battery comprises positive pole, negative pole, barrier film and gel polymer electrolyte, described gel polymer electrolyte is between positive pole and negative pole, and described gel polymer electrolyte is gel polymer electrolyte provided by the invention.Polymer Li-ion battery provided by the invention, its security improves greatly, charge-discharge performance good, can suppress generation, the no leakage of Li dendrite.
Present invention also offers a kind of preparation method of described polymer Li-ion battery, comprise and first polymer film, barrier film and polymer film are separated positive pole and negative pole in three stacked modes of putting, then overall stacked or be wound into pole piece, in pole piece, inject electrolyte, after sealing, obtain described polymer Li-ion battery.
Described barrier film can adopt PP barrier film, PE barrier film or PE/PP/PE tri-layers of barrier film.Described positive pole, negative pole are conventionally known to one of skill in the art, do not repeat herein.
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.In embodiment and comparative example adopt raw material to be all commercially available, the present invention is not particularly limited.
Embodiment 1
(1) copolymer A a1 is prepared: be that the AN monomer of 90:10 and the mixture of BuMA monomer and deionized water add in two mouthfuls of flasks by molar ratio, the total mol concentration of monomer is 8.905mol/L, adds initator NaHSO under magnetic stirring
3(consumption accounts for 0.64% of monomer molar total amount).After flask being placed in ice-water bath inflated with nitrogen magnetic agitation 20in, add K
2s
2o
8the aqueous solution (K
2s
2o
8consumption accounts for 7.3 × 10 of monomer molar total amount
-4), temperature is increased to 60 DEG C, under the magnetic agitation of 1100 revs/min, continues inflated with nitrogen and carry out polymerisation.Stop polymerisation after 6h, products therefrom is poured out, rinse 4 times with the hot deionized waters of 80 DEG C, filter, then purify 2 times (DMSO is solvent, and deionized water is precipitating agent) with dissolving precipitated method.Dry to constant weight in 80 DEG C of vacuum drying chambers.Obtain copolymer A a1, the mol ratio that nuclear-magnetism result shows wherein AN construction unit and BuMA construction unit is 74:26.
Change the molar ratio of AN monomer and BuMA monomer into 75:25, repeat said process, obtain copolymer A b1, the molar ratio that nuclear-magnetism result shows wherein AN construction unit and BuMA construction unit is 47:53.
(2) preparation of mixed liquid B a1, Bb1
By the nano-TiO of the 8wt% relative to copolymer A a1 quality
2be scattered under magnetic stirring in DMF, form dispersion liquid.The copolymer A a1 of the 6wt% relative to DMF quality is fully dissolved in dispersion liquid under 80 DEG C of magnetic agitation, forms mixed liquid B a1.
Change copolymer A a1 into Ab1, repeat said process, obtain mixed liquid B b1.
(3) preparation of polymer film Ca1
Using mixed liquid B a1 and Bb1 as two spray sources, adopt two shower nozzles to carry out electrostatic spinning, voltage is 8KV, and receiving range is 10cm, and shower nozzle translational speed is 5.5mm/s simultaneously;
Flow control situation is: mixed liquid B a1 starts first to increase gradually with initial flow rate 0.7mL/min, and increase 0.02mL/min every 5min, reduce gradually after flow velocity is 1.42mL/min, reducing 0.02mL/min every 5min, is 0.7mL/min to final flow rate; Mixed liquid B b1 then first reduces with initial flow rate 1.42mL/min simultaneously gradually, 0.02mL/min is reduced every 5min, increase gradually after flow velocity is 0.7mL/min, 0.02mL/min is increased every 5min, be 1.42mL/min to final flow rate, namely electrostatic spinning total time is 6h, and in electrostatic spinning process, the overall flow rate of mixed liquid B a2 and Bb2 is constant is 2.12mL/min.
After spinning terminates, anneal 30min at 50 DEG C, then at 50 DEG C of vacuumize 24h, obtain the polymer film Ca1 of the present embodiment, thickness is 23 μm, it consists of: the content of polymer film Ca1 both sides AN construction unit is 56%, and the content of middle AN construction unit is 65%, successively decreases from centre to the content of both sides AN construction unit; The content of polymer film Ca1 both sides BuMA construction unit is 44%, and the content of middle BuMA construction unit is 35%, increases progressively from centre to the content of both sides BuMA construction unit.
(4) preparation of polymer Li-ion battery E1
Polymer film Ca1 is cut into the disk that diameter is 17mm, at 60 DEG C after vacuum bakeout 12h, transfers to rapidly and be full of in the glove box of argon gas.By LiCoO
2(100wt%), binding agent (0.8wt%) and carbon black (0.5wt%) furnishing slurry are coated on aluminium foil and are made LiCoO
2positive pole.
Lithium sheet negative pole and LiCoO is separated in three stacked modes of putting with Ca1|PE|Ca1
2positive pole, adds enough electrolyte, seals into 2016 type Li/LiCoO
2polymer Li-ion battery, is designated as E1.
Embodiment 2
(1) method identical with embodiment 1 step (1) is adopted to prepare copolymer A a2 and copolymer A b2, difference is, the molar ratio of monomer is different: during preparation copolymer A a2, the molar ratio of AN monomer and BuMA monomer is 95:5, and in the copolymer A a2 obtained, the mol ratio of AN construction unit and BuMA construction unit is 82:18;
During preparation copolymer A b2, the molar ratio of AN monomer and BuMA monomer is 80:20, and in the copolymer A b2 obtained, the mol ratio of AN construction unit and BuMA construction unit is 51:49.
(2) preparation of mixed liquid B a2, Bb2
By the nanometer Al of the 10wt% relative to copolymer A a2 quality
2o
3be scattered under magnetic stirring in DMF, form dispersion liquid.The copolymer A a2 of the 7wt% relative to DMF quality is fully dissolved in dispersion liquid under 80 DEG C of magnetic agitation, forms mixed liquid B a2.
Change copolymer A a2 into Ab2, repeat said process, obtain mixed liquid B b2.
(3) preparation of polymer film Ca2
Using mixed liquid B a2 and Bb2 as two spray sources, adopt two shower nozzles to carry out electrostatic spinning, voltage is 10KV, and receiving range is 11cm, and shower nozzle translational speed is 5.5mm/s simultaneously;
Flow control situation is: mixed liquid B a2 starts first to increase gradually with initial flow rate 0.7mL/min, and increase 0.02mL/min every 3min, reduce gradually after flow velocity is 1.6mL/min, reducing 0.02mL/min every 3min, is 0.7mL/min to final flow rate; Mixed liquid B b2 then first reduces with initial flow rate 1.6mL/min simultaneously gradually, 0.02mL/min is reduced every 3min, increase gradually after flow velocity is 0.7mL/min, 0.02mL/min is increased every 3min, be 1.6mL/min to final flow rate, namely electrostatic spinning total time is 4.5h, and in electrostatic spinning process, the overall flow rate of mixed liquid B a2 and Bb2 is constant is 2.3mL/min.
After spinning terminates, anneal 30min at 50 DEG C, then at 50 DEG C of vacuumize 24h, obtain the polymer film Ca2 of the present embodiment, thickness is 16 μm, it consists of: the content of polymer film Ca2 both sides AN construction unit is 60%, and the content of middle AN construction unit is 73%, successively decreases from centre to the content of both sides AN construction unit; The content of polymer film Ca2 both sides BuMA construction unit is 40%, and the content of middle BuMA construction unit is 27%, increases progressively from centre to the content of both sides BuMA construction unit.
(4) adopt the Ca1 in polymer film Ca2 alternate embodiment 1, then adopt the step 2016 type Li/LiCoO identical with embodiment 1 step (4)
2polymer Li-ion battery, is designated as E2.
Embodiment 3
(1) method identical with embodiment 1 step (1) is adopted to prepare copolymer A a3 and copolymer A b3, difference is, the molar ratio of monomer is different: during preparation copolymer A a3, the molar ratio of AN monomer and BuMA monomer is 98:2, and in the copolymer A a2 obtained, the mol ratio of AN construction unit and BuMA construction unit is 91:9;
During preparation copolymer A b3, the molar ratio of AN monomer and BuMA monomer is 85:15, and in the copolymer A b2 obtained, the mol ratio of AN construction unit and BuMA construction unit is 66:34.
(2) preparation of mixed liquid B a3, Bb3
By the Nano-meter SiO_2 of the 12wt% relative to copolymer A a3 quality
2be scattered under magnetic stirring in DMF, form dispersion liquid.The copolymer A a3 of the 8wt% relative to DMF quality is fully dissolved in dispersion liquid under 80 DEG C of magnetic agitation, forms mixed liquid B a3.
Change copolymer A a3 into Ab3, repeat said process, obtain mixed liquid B b3.
(3) preparation of polymer film Ca3
Using mixed liquid B a3 and Bb3 as two spray sources, adopt two shower nozzles to carry out electrostatic spinning, voltage is 11KV, and receiving range is 13cm, and shower nozzle translational speed is 5.5mm/s simultaneously;
Flow control situation is: mixed liquid B a3 starts first to increase gradually with initial flow rate 0.7mL/min, and increase 0.02mL/min every 2min, reduce gradually after flow velocity is 2.5mL/min, reducing 0.02mL/min every 2min, is 0.7mL/min to final flow rate; Mixed liquid B b3 then first reduces with initial flow rate 2.5mL/min simultaneously gradually, 0.02mL/min is reduced every 2min, increase gradually after flow velocity is 0.7mL/min, 0.02mL/min is increased every 2min, be 2.5mL/min to final flow rate, namely electrostatic spinning total time is 6h, and in electrostatic spinning process, the overall flow rate of mixed liquid B a3 and Bb3 is constant is 3.2mL/min.
After spinning terminates, anneal 30min at 50 DEG C, then at 50 DEG C of vacuumize 24h, obtain the polymer film Ca3 of the present embodiment, thickness is 29 μm, it consists of: the content of polymer film Ca3 both sides AN construction unit is 71%, and the content of middle AN construction unit is 86%, successively decreases from centre to the content of both sides AN construction unit; The content of polymer film Ca3 both sides BuMA construction unit is 29%, and the content of middle BuMA construction unit is 14%, increases progressively from centre to the content of both sides BuMA construction unit.
(4) adopt the Ca1 in polymer film Ca3 alternate embodiment 1, then adopt the step 2016 type Li/LiCoO identical with embodiment 1 step (4)
2polymer Li-ion battery, is designated as E3.
Comparative example 1
With PBuMA(polybutyl methacrylate) be polymer matrices, by the nano-TiO of the 8wt% relative to PBuMA quality
2be scattered under magnetic stirring in acetone, form dispersion liquid.The PBuMA of the 6wt% relative to acetone quality is fully dissolved in dispersion liquid under magnetic stirring, forms mixed liquor L1.
Adopt method of electrostatic spinning to carrying out spinning using mixed liquor L1 as spray source, voltage is 8KV, and receiving range is 10cm, and shower nozzle translational speed is 5.5mm/s, and the constant flow rate of mixed liquor L1 is 0.85mL/min, the total duration 4h of spinning.After spinning terminates, anneal at 50 DEG C 30min, and then namely 50 DEG C of vacuumize 24h obtain the polymer film M1 of this comparative example, and thickness is 22 μm.
Adopt the Ca1 in polymer film M1 alternate embodiment 1, then adopt the step 2016 type Li/LiCoO identical with embodiment 1 step (4)
2polymer Li-ion battery, is designated as P1.
Comparative example 2
With PAN(polyacrylonitrile) be polymer matrices, by the Nano-meter SiO_2 of the 10wt% relative to PAN quality
2be scattered under 80 DEG C of magnetic agitation in DMF, form dispersion liquid.The PAN of the 11wt% relative to DMF quality is fully dissolved in dispersion liquid under magnetic stirring, forms mixed liquor L2.
Adopt method of electrostatic spinning to carry out spinning using mixed liquor L2 as spray source, voltage is 8KV, and receiving range is 10cm, and shower nozzle translational speed is 5.5mm/s, and the constant flow rate of mixed liquor L2 is 0.85mL/min, the total duration 4h of spinning.After spinning terminates, anneal at 50 DEG C 30min, and then namely 50 DEG C of vacuumize 24h obtain the polymer film M2 of this comparative example, and thickness is 17 μm.
Adopt the Ca1 in polymer film M2 alternate embodiment 1, then adopt the step 2016 type Li/LiCoO identical with embodiment 1 step (4)
2polymer Li-ion battery, is designated as P2.
Performance test
1, copolymer composition quantitative analysis:
1h-NMR adopts AV400 nuclear magnetic resonance chemical analyser (German Bruker company), DMSO-d
6for solvent, tetramethylsilane (TMS) is standard substance, measures under temperature is 298K to the copolymer A a1 obtained in embodiment 1, and test result as shown in Figure 1.
By the integration ratio at the characteristic resonances peak of the two kinds of structures of AN and BuMA in Fig. 1, obtaining the mol ratio of two kinds of construction units in copolymer A a1 is 74:26.
2, copolymer vitrification point test:
The differential scanning calorimeter (DSC, METTLER, DSC823e) that employing is furnished with cryogenic system (FT100) carries out thermal analyses to the copolymer A b3 obtained in embodiment 3, measures its vitrification point.Adopt indium reference material to correct, example weight is 8 ~ 10mg, and temperature range is from 0 ~ 150 DEG C, and the rate of heat addition is 5 DEG C/min, and cooldown rate is 5 DEG C/min.Test result as shown in Figure 2.
A glass transition temperature (50.36 DEG C) has only been there is in Fig. 2, and between PBuMA(24 DEG C) and PAN(90 DEG C) between, illustrate and define random copolymer.And the glass transition temperature of the copolymer p obtained (AN-co-BuMA) (i.e. Ab3) is also lower than P (AN-co-BuA) (77.7 DEG C) and P (AN-co-MMA) (98 DEG C).
3, heat stability testing:
Adopted by polymer film Ca1-3 and M1-2 the STA449PC type synchronous solving of German NETZSCH company to carry out thermogravimetric analysis (TGA) test, example weight is 10 ~ 15mg.Temperature range is from 30 DEG C ~ 800 DEG C, and heating rate is 10 DEG C/min, argon gas atmosphere.Test result is as shown in table 1.Wherein the thermogravimetric curve of polymer film Ca2 as shown in Figure 3.
As shown in Table 1, the heat decomposition temperature of polymer film provided by the invention is all very high, and illustrate that the polymer film heat endurance that the present invention obtains is very good, being applied to polymer Li-ion battery can improve security performance greatly.
4, surface topography is observed:
Adopt scanning electronic microscope (SEM, JEOL, JSM-7600FE) to observe the microscopic appearance on polymer film Ca2 surface, result as shown in Figure 4.
As shown in Figure 4, the polymer film obtained with method of electrostatic spinning is very even, and fiber diameter is 400nm.
5, Mechanics Performance Testing:
Mechanics Performance Testing is carried out to polymer film Ca1-3 and M1-2.Adopt conventional pull test instrument (Shenzhen monarch is auspicious), sample is dumbbell shaped, and it is of a size of 4mm × 10mm, and the strain rate of instrument is 20mm/min.Fracture strength and the result of elongation at break of test are as shown in table 1.
As shown in Table 1, the mechanical strength of polymer film provided by the invention is all very high, and has suitable flexibility.
6, porosity test:
Polymer film Ca1-3 and M1-2 is carried out to the test of porosity.Porosity test is carried out according to following formula: P (%)=(M-M
0)/(ρ
buOH× π r
2d) × 100%;
Wherein, P is porosity, M
0for the quality of dry film, M is the quality soak 2h in n-butanol after, and r is the radius of film, and d is the thickness of film.Test result such as table 1 represents.
As shown in Table 1, polymer film porosity provided by the invention is high, is conducive to the raising of pick up.
7, pick up test:
By dried for polymer film Ca1-3 and M1-2, be immersed in 24h in electrolyte after weighing up quality, then taking-up filter paper blots the liquid on film surface, obtains corresponding gel polymer electrolyte D1-4 and DD1-2, weigh quality now, operation is all carried out in the glove box being full of argon gas.
According to formulae discovery pick up %=(Wi-W)/W × 100%;
Wherein, W is the quality of dry film; Wi is the quality after dry film has soaked 24h in the electrolytic solution.Test result such as table 1 represents.
As shown in Table 1, the pick up of polymer film provided by the invention is very high, illustrate that the compatibility of polymer film provided by the invention and electrolyte is very good, sufficiently high ionic conductivity can be provided, thus ensure can play excellent chemical property when using it for polymer Li-ion battery.
8, electrical conductivity test:
Polymer film Ca1-3 and M1-2 is placed between two stainless steel (SS) electrodes, absorb the electrolyte of q.s, obtain corresponding gel polymer electrolyte D1-3 and DD1-2, after being sealed in 2016 type button cells, carry out AC impedance experiment, intersection point that is linear and real axis is the bulk resistance of gel polymer electrolyte, the ionic conductivity of gel polymer electrolyte can be obtained thus: σ=L/ (AR), wherein L represents the thickness of gel polymer electrolyte, A is the contact area of corrosion resistant plate and film, R is the bulk resistance of polymer dielectric).The electrical conductivity obtaining gel polymer electrolyte D1-3 and DD1-2 is as shown in table 2.
As shown in Table 2, the electrical conductivity of gel polymer electrolyte provided by the invention is all very high, can play excellent chemical property when can ensure to use it for polymer Li-ion battery.
9, electrochemical stability window test:
Electrochemical stability window test adopts electrochemical workstation (Shanghai occasion China, CHI660C) to carry out.Separate metal lithium sheet and stainless steel substrates (SS) with polymer film Ca1-3 and M1-2, after injecting enough electrolyte, seal into 2016 type Li/SS polymer Li-ion batteries.Stainless steel is working electrode, and metal lithium sheet is to electrode and reference electrode.Wherein, namely film becomes gel polymer electrolyte after absorbing enough electrolyte, and adopt linear sweep voltammetry to determine the electrochemical window of gel polymer electrolyte, sweep speed is 0.0005V/s.Gained decomposition voltage is as shown in table 2.
As shown in Table 2, gel polymer electrolyte electrochemical stability window provided by the invention is all very wide, can be used for high voltage withstanding polymer Li-ion battery.
10, button cell charge-discharge property test:
Adopt (Guangzhou is blue strange, BK6016) performance of lithium ion battery test cabinet, first charge-discharge test is carried out to polymer Li-ion battery E1-E3 and P1-P2 that embodiment 1-3 and comparative example 1-2 obtains.With 0.075mA/cm
2electric current first by constant-current charging of battery to 4.2V, then constant-voltage charge at 4.2v, cut-off current is 0.038mA/cm
2, record charging capacity, then with 0.075mA/cm
2by battery constant-current discharge to 3.0V, record discharge capacity.
Specific capacity=discharge capacity/LiCoO
2quality;
First charge-discharge efficiency=discharge capacity first/initial charge capacity × 100%.
Gained specific capacity and first charge-discharge efficiency as shown in table 2.
As shown in Table 2, the gel polymer electrolyte formed after adopting polymer film Electolyte-absorptive provided by the invention shows excellent charge-discharge property for polymer Li-ion battery.
Table 1
Table 2
。
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (15)
1. a polymer film, is characterized in that, described polymer film is prepared by following steps:
S1, acrylonitrile monemer and butylmethacrylate monomer are carried out copolymerization, obtain component different copolymer A a and copolymer A b respectively, acrylonitrile unit unit wherein in copolymer A a is 91:9 ~ 70:30 with the molar percentage of butyl methacrylate construction unit, and the acrylonitrile unit unit in copolymer A b is 66:34 ~ 43:57 with the molar percentage of butyl methacrylate construction unit;
S2, copolymer A a, nanoparticle dispersion are formed mixed liquid B a in organic solvent, copolymer A b, nanoparticle dispersion are formed mixed liquid B b in organic solvent;
S3, using mixed liquid B a, mixed liquid B b as spray source, adopt two shower nozzles to carry out electrostatic spinning simultaneously; In electrostatic spinning process, the flow velocity of mixed liquid B a, Bb is 0.4 ~ 5mL/min, and the flow velocity of mixed liquid B a increases with constant amplitude and/or reduces, the flow velocity of mixed liquid B b then reduces with identical constant amplitude and/or increases simultaneously, makes the overall flow rate of mixed liquid B a and mixed liquid B b be definite value; After spinning terminates, annealing in process, obtains described polymer film after drying.
2. polymer film according to claim 1, is characterized in that, in step S1, the step that acrylonitrile monemer and butylmethacrylate monomer carry out copolymerization is comprised: mixed in proportion with butylmethacrylate monomer by acrylonitrile monemer, add NaHSO
3after be filled with inert atmosphere, then add K
2s
2o
8carry out polymerisation, wash purification after reaction terminating and obtain copolymer; Wherein during preparation copolymer A a, the mol ratio of acrylonitrile monemer and butylmethacrylate monomer is 99:1 ~ 87:13, and during preparation copolymer A b, the mol ratio of acrylonitrile monemer and butylmethacrylate monomer is 85:15 ~ 70:30.
3. polymer film according to claim 2, is characterized in that, in step S1, the total mol concentration of described acrylonitrile monemer and butylmethacrylate monomer is 3 ~ 10mol/L; With the integral molar quantity of acrylonitrile monemer and butylmethacrylate monomer for benchmark, NaHSO
3consumption accounts for 1 × 10 of this integral molar quantity
-5~ 1 × 10
-2, K
2s
2o
8account for 1 × 10 of monomer integral molar quantity
-5~ 1 × 10
-2, and NaHSO
3with K
2s
2o
8mol ratio be (5 ~ 15): 1.
4. polymer film according to claim 2, is characterized in that, in step S1, adds NaHSO
3after be filled with inert atmosphere before, first whole system is cooled to ﹣ 18 ~ 0 DEG C; The condition of polymerisation comprises: reaction temperature is 40 ~ 100 DEG C, and the described reaction time is 2 ~ 10h.
5. the polymer film according to any one of claim 1-4, is characterized in that, in step S1, the molecular weight of copolymer A a, Ab is 500000 ~ 2000000g/mol.
6. polymer film according to claim 1, is characterized in that, in step S2, in mixed liquid B a, with the quality of copolymer A a for benchmark, the consumption of nano particle is 1 ~ 25wt%; With the quality of organic solvent for benchmark, the consumption of copolymer A a is 3 ~ 15wt%;
In mixed liquid B b, with the quality of copolymer A b for benchmark, the consumption of nano particle is 1 ~ 25wt%; With the quality of organic solvent for benchmark, the consumption of copolymer A b is 3 ~ 15wt%.
7. the polymer film according to claim 1 or 6, is characterized in that, in step S2, described nano particle is selected from titanium dioxide, Al
2o
3, SiO
2, CuO, MgO, LiAlO
2, ZrO
2, CNT, BN, SiC, Si
3n
4, WC, BC, AlN, Fe
2o
3, BaTiO
3, MoS
2, α – V
2o
5, PbTiO
3, TiB
2, CaSiO
3, molecular sieve ZSM – 5, any one in clay, the particle diameter of described nano particle is 1 ~ 200nm; Described organic solvent be selected from N ' dinethylformamide, N ' N-dimethylacetylamide, dimethyl sulfoxide (DMSO) one or more.
8. polymer film according to claim 1, is characterized in that, in step S3, the internal diameter of two shower nozzles is 0.2 ~ 1mm, and the condition of electrostatic spinning comprises: voltage is 5 ~ 20KV, and receiving range is 6 ~ 15cm, and shower nozzle translational speed is 5 ~ 6mm/s.
9. polymer film according to claim 1, is characterized in that, in step S3, described constant amplitude refers at interval of the increase of certain hour flow velocity and/or reduces by 0.01 ~ 0.5mL/min, and wherein interval time is 0.5 ~ 60min.
10. the polymer film according to claim 1 or 9, is characterized in that, in step S3, the flow velocity of mixed liquid B a increases successively, and the flow velocity of mixed liquid B b then reduces successively simultaneously; Or the flow velocity of mixed liquid B a reduces successively, the flow velocity of mixed liquid B b then increases successively simultaneously; Or the flow velocity of mixed liquid B a first increases rear reduction, the flow velocity of mixed liquid B b then first reduces to increase afterwards simultaneously.
11. polymer films according to claim 1 or 9, it is characterized in that, in step S3, the total time of electrostatic spinning is 1 ~ 20h; Annealing temperature is 30 ~ 60 DEG C, and annealing time is 30 ~ 120min; The thickness of polymer film is 0.01 ~ 110 μm.
12. 1 kinds of gel polymer electrolytes, described gel polymer electrolyte is formed by swelling after polymer film Electolyte-absorptive, it is characterized in that, described polymer film is the polymer film described in any one of claim 1-11.
13. gel polymer electrolytes according to claim 12, is characterized in that, described electrolyte is made up of electrolyte lithium salt and organic solvent; Wherein electrolyte lithium salt is selected from any one in lithium hexafluoro phosphate, lithium perchlorate, LiBF4, and organic solvent is selected from least one in ethylene carbonate, propene carbonate, dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate, vinylene carbonate; In described electrolyte, the concentration of electrolyte lithium salt is 0.8 ~ 1.5mol/L.
14. 1 kinds of polymer Li-ion batteries, this lithium ion battery comprises positive pole, negative pole, barrier film and gel polymer electrolyte, described gel polymer electrolyte is between positive pole and negative pole, it is characterized in that, described gel polymer electrolyte is the gel polymer electrolyte in claim 12 or 13 described in any one.
The preparation method of 15. polymer Li-ion batteries according to claim 14, it is characterized in that, comprise and first polymer film, barrier film and polymer film are separated positive pole and negative pole in three stacked modes of putting, then overall stacked or be wound into pole piece, in pole piece, inject electrolyte, after sealing, obtain described polymer Li-ion battery.
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