CN101222055B - Co-polymer based polymer electrolyte material for lithium battery, compound electrolyte film and its preparation method - Google Patents
Co-polymer based polymer electrolyte material for lithium battery, compound electrolyte film and its preparation method Download PDFInfo
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- CN101222055B CN101222055B CN2008100558417A CN200810055841A CN101222055B CN 101222055 B CN101222055 B CN 101222055B CN 2008100558417 A CN2008100558417 A CN 2008100558417A CN 200810055841 A CN200810055841 A CN 200810055841A CN 101222055 B CN101222055 B CN 101222055B
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- metal salt
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 52
- 229920001577 copolymer Polymers 0.000 title claims abstract description 34
- 239000003792 electrolyte Substances 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 150000001875 compounds Chemical class 0.000 title description 4
- -1 alkali metal salts Chemical class 0.000 claims abstract description 22
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 20
- 239000012528 membrane Substances 0.000 claims abstract description 19
- 229920002521 macromolecule Polymers 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 20
- 238000005303 weighing Methods 0.000 claims description 18
- 230000004888 barrier function Effects 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 claims description 4
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000013335 mesoporous material Substances 0.000 claims description 3
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
- 229910015044 LiB Inorganic materials 0.000 claims description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 2
- 229910013398 LiN(SO2CF2CF3)2 Inorganic materials 0.000 claims description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 239000011244 liquid electrolyte Substances 0.000 abstract description 12
- 238000005266 casting Methods 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- 238000001802 infusion Methods 0.000 abstract 1
- 238000005215 recombination Methods 0.000 abstract 1
- 230000006798 recombination Effects 0.000 abstract 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 12
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 12
- 230000009477 glass transition Effects 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000011833 salt mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910013423 LiN(SO2F)2 (LiFSI) Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a copolymer based polymer electrolyte material used for a lithium cell, which comprises a copolymer matrix and alkali metal salts, wherein, the copolymer matrix consists of ethylene oxide cells and propylene oxide cells. The invention also provides a composite electrolyte membrane which comprises the polymer electrolyte material and a preparation method thereof. The copolymer based polymer electrolyte material used for the lithium cell of the invention adopts copolymers as matrix materials; the polymer electrolyte material is prepared through a simple solution casting method, and recombination of the active polymer electrolyte material and a macromolecule diaphragm material is realized by adoption of an infusion method. The polymer electrolyte material of the invention does not comprise organic liquid electrolyte and is incombustible. Moreover, compared with the prior PEO based polymer electrolyte, conductivity is obviously improved; thermorunaway can be prevented; mechanical property is good.
Description
Technical field
The present invention relates to base polymer electrolyte and preparation method thereof, specifically, relate to energy storage that a class can be applicable to novel high-performance lithium battery (comprising disposable lithium-battery, secondary lithium battery and secondary metals lithium battery), fuel cell fields such as power conversion, solar cell, chemical sensor and electrochemical capacitor utilize copolymer as the polymer dielectric of matrix, its composite electrolyte membrane and preparation method thereof.
Background technology
Polymer dielectric especially is suitable as the electrolyte for Lithium Battery material owing to have not flammable and the packaging efficiency advantages of higher.The polymer dielectric that traditional polyethylene glycol oxide (PEO) and alkali metal salt form can reach high ionic conductivity (greater than 10 more than 80 ℃
-4Scm
-1), and can be actually used in fields such as communication apparatus back-up source.But at room temperature, this electrolyte is owing to have higher crystalline phase, and limited solvability and relatively poor sub-chain motion ability cause conductivity significantly to descend, and can not satisfy requirement of actual application.Be commonly used to improve the method for room-temperature conductivity, a kind of is to add a large amount of organic liquid electrolyte, but this has brought the problem of fail safe aspects such as combustion explosion.
Another kind is to add solid-state inorganic particle to prepare compound polymer electrolyte, is raw material such as adopting the nano inorganic oxide powder, with simple solution casting method this composite powder and the compound compound polymer electrolyte that is prepared into of polymer lithium salts.This method can only limited raising room-temperature conductivity.Simultaneously, polymer dielectric still has potential safety hazard because the thermal runaway that lacks under the battery abuse condition is controlled.
Therefore, people need research and develop a kind of room-temperature conductivity height, the polymer electrolyte that fail safe is good.
Summary of the invention
The purpose of this invention is to provide a kind of conductivity height, fail safe is good and cheaply based on the new polymers electrolyte of copolymer.
Another object of the present invention provides a kind of preparation method of polymer electrolyte.
A further object of the present invention provides a kind of composite electrolyte membrane that is composited by polymer electrolyte and macromolecule barrier film based on copolymer.
It is simple that further purpose of the present invention provides a kind of technology, is suitable for the preparation method of the polymer dielectric film of suitability for industrialized production.
In order to realize the object of the invention, a kind of co-polymer based polymer electrolyte material for lithium battery of the present invention, it contains polymer matrices and alkali metal salt, and described polymer matrices is by ethylene oxide unit (CH
2CH
2O-) and propylene oxide unit [CH
2CH (CH
3) O-] form.
Ethylene oxide unit (CH in the described copolymer
2CH
2O-) and propylene oxide unit [CH
2CH (CH
3) O-] be any molecular weight, any ratio shared in copolymer, the arrangement and the compound mode of ethylene oxide and propylene oxide in copolymer arbitrarily.Block copolymer preferably, its molecular weight is 1000～20000, the ratio of ethylene oxide unit and propylene oxide unit is 0.1～9 block type copolymer.
Described alkali metal salt is LiClO
4, LiPF
6, LiBF
4, LiAsF
6, LiB (C
2O
4)
2(LiBOB), LiN (SO
2CF
3)
2(LiTFSI), LiSO
2CF
3(LiTf), LiN (SO
2F)
2(LiFSI) or LiN (SO
2CF
2CF
3)
2(LiBETI) any one in or the combination in any between them, preferably LiClO
4, LiTFSI.
Wherein, the O/Li mol ratio of copolymer and alkali metal salt is 6～100, preferably 6～40, and most preferred is 8～20.
Polymer electrolyte of the present invention also can further contain 0～30% the inorganic oxide powder that accounts for copolymer and alkali metal salt total amount percentage by weight.
Described inorganic oxide powder is Al
2O
3, SiO
2, ZrO
2With the mesoporous material of montmorillonite particle and formation thereof, wherein said mesoporous material is the new material with huge surface area and three-dimensional open-framework of a kind of aperture between micropore and macropore.The fineness of described inorganic oxide powder is 1 nanometer to 10 micron.
Inorganic oxide powder of the present invention can also be used the alkali metal salt soln immersion treatment, makes to have alkali metal salt soln in the inorganic matter duct, can overcome the ionic conduction inertia of inorganic material.
Polymer electrolyte of the present invention can adopt solution casting method to be prepared, detailed process is as follows: be 6～100 to take by weighing copolymer and lithium salts by the O/Li mol ratio earlier, take by weighing 0～30% inorganic oxide powder of copolymer and alkali metal salt total amount percentage by weight again, then the three is joined and dissolve in the acetonitrile solvent and disperseed 1～24 hour, the ultrasonic dispersion of middle use 0～30 minute, solvent flashing forms then.
Electrolyte of the present invention is a gel state, the glue-like of similar thickness.
Polymer electrolyte of the present invention further is combined into composite electrolyte membrane with the macromolecule barrier film.
Composite electrolyte membrane of the present invention, it is composited by described polymer electrolyte and macromolecule barrier film.
Described macromolecule barrier film is any one in polyolefin or the PETG (PET).
The preparation method of composite electrolyte membrane of the present invention, comprise the steps: the macromolecule barrier film is dipped in the described polymer electrolyte, at 20～90 ℃, under 0～100kPa, left standstill 10～300 minutes, and removed the unnecessary polymer electrolyte of macromolecule membrane surface then.
The preparation method of described composite electrolyte membrane, also can be prepared as follows: the macromolecule barrier film is dipped in the acetonitrile solution of the copolymer, alkali metal salt and the inorganic oxide powder that mix, solvent flashing, then at 20～90 ℃, under 0～100kPa, left standstill 10～300 minutes, and removed the unnecessary polymer electrolyte of macromolecule membrane surface then.
Co-polymer based polymer electrolyte material for lithium battery of the present invention, adopt copolymer as basis material, adopt simple solution casting method to be prepared into polymer electrolyte, and adopting soaking method is realized the compound of living polymer electrolyte and macromolecule diaphragm material.Polymer electrolyte of the present invention does not have the organic liquid electrolyte, and is not flammable, and compares with traditional PEO base polymer electrolyte, and conductivity obviously improves, and can prevent thermal runaway and good mechanical property.
Description of drawings
Fig. 1 is the differential thermal curve of the polymer electrolyte of the SBA-15 powder that soaks through liquid electrolyte of the adding 20% among the embodiment 1;
Fig. 2 is the glass transition temperature T of the polymer electrolyte of the SBA-15 powder that soaks through liquid electrolyte of the adding different content among the embodiment 1
g
Fig. 3 is the ionic conductivity of the polymer electrolyte of 30 ℃ of following different additive content among the embodiment 1;
Fig. 4 is the 51 μ Acms of battery under different temperatures among the embodiment 1
-1Discharge curve;
Fig. 5 is that battery capacity among the embodiment 1 is with the relation curve of temperature and current density;
Fig. 6 is the battery 51 μ Acm under 60 ℃ among the embodiment 1
-1Capability retention and coulombic efficiency;
Fig. 7 is that 30 ℃ of following ionic conductivities among the embodiment 2 are with the variation of LiTFSI concentration;
Fig. 8 is the differential thermal curve of 16 sample for the O/Li mol ratio among the embodiment 2;
Fig. 9 is the glass transition temperature T among the embodiment 2
gVariation with LiTFSI concentration;
Figure 10 is that 30 ℃ of following ionic conductivities among the embodiment 3 are with LiClO
4The variation of concentration;
Figure 11 is the differential thermal curve of 8 polymer electrolyte for O/Li mol ratio among the embodiment 3;
Figure 12 is the glass transition temperature T among the embodiment 3
gWith LiClO
4The variation of concentration;
Figure 13 is that 30 ℃ of following conductivity among the embodiment 4 are with the variation of LITFSI content;
Figure 14 is that 30 ℃ of following ionic conductivities among the embodiment 5 are with ZrO
2The variation of content;
Figure 15 is that 30 ℃ of following ionic conductivities among the embodiment 6 are with Al
2O
3The variation of content.
Embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
(a) use mesoporous SiO
2, at first the template of removing in the duct in 6 hours 500 ℃ of calcinings is called for short SBA-15, and its particle diameter is approximately 1 micron.Configuration 1M LiTFSI/ (ethylene carbonate+propene carbonate) liquid electrolyte, wherein the percentage by weight of ethylene carbonate and propene carbonate is 1: 1.In glove box, the SBA-15 powder is soaked in the liquid electrolyte.Soak time is 4 days.Then solution is filtered.
(b) take by weighing 0.5 gram EO
20-PO
70-EO
20Copolymer is called for short P123.Take by weighing 0.170 gram LiTFSI (the LiTFSI molecular weight is 287.08, and the P123 molecular weight is 5800, contains 110 O atoms, and mean molecule quantity is 580/11, and mol ratio is 16).0%, 5%, 10%, 15%, 20%, 25%, the 30% SBA-15 powder that takes by weighing through the liquid electrolyte immersion according to accounting for copolymer and lithium salts total amount percentage by weight joins this three in the 5ml acetonitrile, stirs the ultrasonic dispersion of middle use 10 minutes 12 hours.Solvent flashing 12 hours in glove box then, further 80 ℃ of oven dry 5 hours down in vacuum drying oven.
(c) Fig. 1 has provided the differential thermal curve of the polymer electrolyte that adds the 20% SBA-15 powder that soaks through liquid electrolyte, and Dupont TA 2910 differential thermal analyzers are adopted in test, and programming rate is 10 ℃ of min
-1The ladder at 1 place is represented sample generation glass transition.Fig. 2 is for adding the glass transition temperature T of different content through the polymer electrolyte of the SBA-15 powder of liquid electrolyte immersion
g, as seen, electrolyte of the present invention is non-crystallizable, has low T
g, illustrate that its segment mobility is strong.Fig. 3 has contrasted 30 ℃ of ionic conductivities of the polymer electrolyte of different additive content down, occasion China CHI760B type electrochemical workstation is adopted in test, sample is placed between two stainless steel electrodes its ac impedance spectroscopy of test, and then be conductivity by the area and the thickness conversion of sample.Adding 20% is 8.0 * 10 through the sample of the SBA-15 powder that liquid electrolyte soaks 30 ℃ of following ionic conductivities
-5Scm
-1
Celgard 2500 barrier films (material is polypropylene (PP)) are dipped into adding 20% in the polymer electrolyte of the SBA-15 powder that liquid electrolyte soaks, and 80 ℃ left standstill 5 hours under vacuum, further wiped the electrolyte of membrane surface off.Use LiFePO
4Base is anodal, wherein LiFePO
4, carbon black, the weight ratio of PVDF binding agent is 90: 5: 5, LiFePO
4Load capacity be 4.1mg cm
-2, use aluminium foil as plus plate current-collecting body.Use metal lithium sheet as negative pole.Assemble 2032 type button cells.Battery has good capacity and capability retention in different temperatures under the different charge-discharge velocities, as Fig. 4, and Fig. 5, shown in Figure 6.Battery can obtain greater than 140mAh g under 60 ℃ as seen from the figure
-1Capacity, even temperature drops to 30 ℃, the capacity of battery is still near 100mAh g
-1Through 40 circulations, capacity can remain on more than 90%, has high coulombic efficiency simultaneously under 60 ℃.As a comparison, reported recently that the capacity of composite polymer electrolyte under 60 ℃ of PEO base had only 60mAh g abroad
-1About (F.Croce, S.Sacchetti, B.Scrosati, Journal of Power Sources 162 (2006) 685).
Embodiment 2
Take by weighing 0.5 gram EO
20-PO
70-EO
20Copolymer.According to the O/Li mol ratio is 7,8,10,12,16,20, and 25,40 take by weighing LiTFSI.Both join in the 5ml acetonitrile with this, stir 12 hours.Solvent flashing 12 hours in glove box then, further 80 ℃ of oven dry 5 hours down in vacuum drying oven.
Fig. 7 has provided the situation of change of 30 ℃ of following ionic conductivities with LiTFSI concentration.Fig. 8 has provided the differential thermal curve that the O/Li mol ratio is 16 polymer electrolyte.Fig. 9 has provided the glass transition temperature T of sample
gVariation with LiTFSI concentration.As seen from the figure, conductivity reaches maximum about n=20, is 4.6 * 10
-5Scm
-1And this electrolyte is non-crystallizable, has low T
g, illustrate that its segment mobility is strong.
Embodiment 3
Take by weighing 0.5 gram EO
20-PO
70-EO
20Copolymer.According to the O/Li mol ratio is 6,7,8,10, and 12 take by weighing LiClO
4Both join in the 5ml acetonitrile with this, stir 12 hours.Solvent flashing 12 hours in glove box then, further 80 ℃ of oven dry 5 hours down in vacuum drying oven.
Figure 10 has provided 30 ℃ of following ionic conductivities with LiClO
2The situation of change of concentration.Figure 11 has provided the differential thermal curve that the O/Li mol ratio is 8 polymer electrolyte.Fig. 12 has provided the glass transition temperature T of polymer electrolyte
gWith LiClO
4The variation of concentration.As seen from the figure, conductivity reaches maximum about n=8, is 8.9 * 10
-6Scm
-1And this electrolyte is non-crystallizable, has low T
g, illustrate that its segment mobility is strong.
Embodiment 4
Take by weighing 0.5 gram EO
20-PO
70-EO
20Copolymer.Use LiTFSI and LiClO
4Salt-mixture, wherein LiTFSI accounts for 0%, 48%, 60%, 75%, 100% of the total amount of substance of two kinds of salt, total O/Li mol ratio is fixed as 12.This three is joined in the 5ml acetonitrile, stirred 12 hours.Solvent flashing 12 hours in glove box then, further 80 ℃ of oven dry 5 hours down in vacuum drying oven.
Figure 13 has provided the situation of change of 30 ℃ of following ionic conductivities with two kinds of salt ratios.As seen from the figure, the conductivity of using the salt-mixture sample is between the conductivity of using single salt sample, and this helps the low alkali metal salt of use cost and optimizes performance and cost.
Take by weighing 1 gram EO
2-PO
30-EO
2Copolymer is 50 to take by weighing LiPF according to the O/Li mol ratio
6According to accounting for 0,5%, 10%, 15% of copolymer and lithium salts total amount percentage by weight, 20% takes by weighing ZrO
2, its particle diameter is approximately 10 microns.This three is joined in the 8ml acetonitrile, stirred 24 hours, the ultrasonic dispersion of middle use 5 minutes.Solvent flashing 12 hours in glove box then, further 80 ℃ of oven dry 5 hours down in vacuum drying oven.
Nonwoven fabrics barrier film (material is polyester (PET)) is dipped in the adding polymer electrolyte,, under the 20kPa, leaves standstill 100 fens kinds, further wipe the electrolyte of membrane surface off at 60 ℃.
Figure 14 has provided 30 ℃ of following ionic conductivities with ZrO
2The situation of change of content.As seen from the figure, along with ZrO
2The increase of content, conductivity present increases the trend that afterwards reduces earlier, and optimum content is 10%.
Take by weighing 2 gram PE
10-EO
20-PO
10Copolymer is 100 to take by weighing LiN (SO according to the O/Li mol ratio
2F)
2According to accounting for 0%, 10% of copolymer and lithium salts total amount percentage by weight, 20%, 30% takes by weighing Al
2O
3, its particle diameter is approximately 5 nanometers.This three is joined in the 10ml acetonitrile, stirred 5 hours, the ultrasonic dispersion of middle use 30 minutes.Solvent flashing 12 hours in glove box then, further 80 ℃ of oven dry 5 hours down in vacuum drying oven.
Celgard 2730 barrier films (material is polyethylene (PE)) are dipped in the adding polymer electrolyte,, under the 100kPa, leave standstill 10 fens kinds, further wipe the electrolyte of membrane surface off at 90 ℃.
Figure 15 has provided 30 ℃ of following ionic conductivities with Al
2O
3The situation of change of content.As seen from the figure, along with Al
20
3The increase of content, conductivity present increases the trend that afterwards reduces earlier, and optimum content is 20%.
Though above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a co-polymer based polymer electrolyte material for lithium battery is characterized in that, described electrolyte is a gel state, contains polymer matrices and alkali metal salt, and the O/Li mol ratio of described copolymer and described alkali metal salt is 6～100; Described electrolyte also contains 0～30% the inorganic oxide powder that accounts for copolymer and alkali metal salt total amount percentage by weight; Described polymer matrices is made up of ethylene oxide unit and propylene oxide unit; Wherein said copolymer is a block copolymer, and its molecular weight is 1000～20000, and the ratio of ethylene oxide unit and propylene oxide unit is 0.1～9;
It is 6～100 to take by weighing copolymer and lithium salts that the preparation of described electrolyte comprises the steps: earlier by the O/Li mol ratio, take by weighing 0～30% inorganic oxide powder of copolymer and alkali metal salt total amount percentage by weight again, then the three is joined and dissolve in the acetonitrile solvent and disperseed 1～24 hour, the ultrasonic dispersion of middle use 0～30 minute, solvent flashing forms then.
2. polymer electrolyte according to claim 1 is characterized in that, described alkali metal salt is LiClO
4, LiPF
6, LiBF
4, LiAsF
6, LiB (C
2O
4)
2, LiN (SO
2CF
3)
2, LiSO
2CF
3, LiN (SO
2F)
2Or LiN (SO
2CF
2CF
3)
2In any one or the combination in any between them.
3. polymer electrolyte according to claim 2 is characterized in that, described alkali metal salt is LiClO
4, LiN (SO
2CF
3)
2
4. according to any described polymer electrolyte of claim 1-3, it is characterized in that the O/Li mol ratio of described copolymer and described alkali metal salt is 6～40.
5. according to the described polymer electrolyte of claim 4, it is characterized in that the O/Li mol ratio of described copolymer and described alkali metal salt is 8～20.
6. according to any described polymer electrolyte of claim 1-3, it is characterized in that described inorganic oxide powder is Al
2O
3, SiO
2, ZrO
2Mesoporous material with montmorillonite particle and formation thereof.
7. composite electrolyte membrane that is composited by any described polymer electrolyte of claim 1-6 and macromolecule barrier film.
8. composite electrolyte membrane according to claim 7 is characterized in that, described macromolecule barrier film is any one in polyolefin or the PETG.
9. method for preparing claim 7 or 8 described composite electrolyte membranes, it is characterized in that, comprise the steps: the macromolecule barrier film is dipped in the described polymer electrolyte, at 20～90 ℃, under 0～100kPa, left standstill 10～300 minutes, and removed the unnecessary polymer electrolyte of macromolecule membrane surface then.
10. method for preparing claim 7 or 8 described composite electrolyte membranes, it is characterized in that, comprise the steps: the macromolecule barrier film is dipped in the acetonitrile solution of the copolymer, alkali metal salt and the inorganic oxide powder that mix, solvent flashing, then at 20～90 ℃, under 0～100kPa, left standstill 10～300 minutes, remove the unnecessary polymer electrolyte of macromolecule membrane surface then.
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| WO2010093681A1 (en) * | 2009-02-11 | 2010-08-19 | Dow Global Technologies Inc. | Ductile polymer binders and battery components using the same |
| JP2014524146A (en) | 2011-07-08 | 2014-09-18 | ファーストキャップ・システムズ・コーポレイション | High temperature energy storage device |
| US9558894B2 (en) | 2011-07-08 | 2017-01-31 | Fastcap Systems Corporation | Advanced electrolyte systems and their use in energy storage devices |
| CN102299378A (en) * | 2011-07-21 | 2011-12-28 | 北京大学 | Composite polymer electrolyte for lithium ion secondary battery and preparation method thereof |
| CN103178226A (en) * | 2011-12-22 | 2013-06-26 | 北京好风光储能技术有限公司 | Membrane and preparation method and application thereof |
| CN102544527B (en) * | 2012-02-08 | 2014-08-27 | 张关池 | Preparation method of battery system using ionic selective film |
| US10872737B2 (en) | 2013-10-09 | 2020-12-22 | Fastcap Systems Corporation | Advanced electrolytes for high temperature energy storage device |
| EP3251133A4 (en) * | 2015-01-27 | 2018-12-05 | FastCAP Systems Corporation | Wide temperature range ultracapacitor |
| CN104650375B (en) * | 2015-03-17 | 2017-08-11 | 长沙理工大学 | Preparation method of composite polymer electrolyte membrane |
| CN106009210B (en) * | 2016-05-13 | 2019-03-05 | 上海师范大学 | A kind of YAB/SiO2Micro-nano composite luminescent material synergy EVA film of near-infrared and its preparation method and application |
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