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 PDF

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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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polymer electrolyte
copolymer
electrolyte
alkali metal
metal salt
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CN101222055A (en
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南策文
王晓亮
林元华
梅骜
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Tsinghua University
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    • Y02E60/10—Energy storage using batteries
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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

A kind of co-polymer based polymer electrolyte material for lithium battery, composite electrolyte membrane and preparation method thereof
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.
Embodiment 5
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%.
Embodiment 6
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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