CN103268955A - Composite gel polymer electrolyte and preparation method and application thereof - Google Patents
Composite gel polymer electrolyte and preparation method and application thereof Download PDFInfo
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- CN103268955A CN103268955A CN2013100257124A CN201310025712A CN103268955A CN 103268955 A CN103268955 A CN 103268955A CN 2013100257124 A CN2013100257124 A CN 2013100257124A CN 201310025712 A CN201310025712 A CN 201310025712A CN 103268955 A CN103268955 A CN 103268955A
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Abstract
The invention belongs to the technical field of polymer materials and batteries, and specifically relates to a gel polymer electrolyte and a preparation method and application thereof. The gel polymer electrolyte is composed of a composite obtained by compositing glass fibers and a polymer material and a liquid electrolyte. The polymer material comprises polyether, polyacrylonitrile, polyacrylate, polyvinylidene fluoride (PVDF), polyamide, polyimide, aramid, and a homopolymer, a copolymer or a blend of the polyester. The composite is added with the liquid electrolyte to get the gel polymer electrolyte. The gel electrolyte has the characteristics of high security and low production cost as glass fibers, is high in conductivity, wide in electrochemical window, good in compatibility with electrode materials, and good in circulatory and rate performance, and can be used in lithium secondary batteries.
Description
Technical field
The invention belongs to macromolecular material and battery technology field, be specifically related to a class plural gel polymer dielectric, such plural gel polymer dielectric has the conductivity height, good cycle, low price, characteristics such as security performance height; The invention still further relates to the application of this plural gel method for preparing polymer electrolytes and such plural gel polymer dielectric, namely be used for the lithium secondary battery of high safety performance.
Background technology
In lithium secondary battery, what performance was more satisfactory at present is lithium ion battery.Lithium ion battery is as a kind of mechanism of new electrochemical power sources, have advantages such as energy density height, environmental friendliness, memory-less effect, since its commercialization, be widely used in the various portable electric appts such as notebook computer, digital camera, mobile phone, it also is mixed power electric car (HEV), plug-in hybrid electric automobile (PHEV) simultaneously, one of desirable energy storage device of pure electric automobile (EV) and small intelligent electrical network.Yet, because LiPF
6The extensive use that is organic electrolyte (to moisture sensitivity, inflammable, easily cause battery explosion) makes the fail safe of high capacity lithium ion battery and reliability be under suspicion.In order to solve the safety issue of conventional lithium ion battery, polymer Li-ion battery (Polymer lithium ion batteries) becomes the research focus gradually.The positive and negative electrode material of such battery is identical with conventional lithium ion battery, has just adopted solid polymer to replace organic bath and barrier film.Study maximum polymer and mainly contain following a few class: polyethers (mainly being PEO), polyacrylonitrile (PAN) class, polymethacrylates (PMMA) class and Kynoar (PVDF) class etc.Polymer Li-ion battery has solved traditional lithium ion battery leakage and the big problem of leakage current has easily taken place, and fail safe significantly improves; In addition, polymeric material plasticity is strong, so but such battery has advantages such as thin typeization, arbitrary areaization and arbitrary shapeization, thus can obviously improve the specific capacity of battery.Being used for electrolytical polymer can be pure solid-state (solid polymer electrolyte, solid polymer electrolytes, SPEs) also can be the gelinite that adds plasticizer (gel polymer electrolyte, gel polymer electrolytes, GPEs).Because the conductivity on the low side (＜10 of solid polymer electrolyte
-4S cm
-1), reach the level of practical application far away; Gel polymer electrolyte has the double properties of solid and liquid electrolyte, and conductivity and liquid organic electrolyte are suitable, and electrochemical window is wideer, and Heat stability is good is subjected to extensive concern.But, gel polymerisation electrolyte bad mechanical strength, the production cost height has limited its application in the high security lithium ion battery greatly.
Glass fibre is with glass marble or the discarded glass Inorganic Non-metallic Materials that to be raw material manufacture through high temperature melting, wire drawing, doff, technology such as weave cotton cloth, the diameter of its monofilament is between tens nanometer to twenties microns, this material has the raw material cheapness, good insulating, thermal endurance is strong, and corrosion resistance is good, the mechanical strength height, the characteristics of good flame resistance are widely used as reinforcing material, electrical insulating material and heat-insulating material etc. in the composite material.Glass fibre through processing can make fiberglass batts (glass fiber mat, GFM) and glass cloth.Fiberglass batts is the thigh yarn that is cut into by the glass fiber precursor weak point, evenly is scattered in the continuous glass fibre scraps of paper at random by paper process, forms with the emulsion bonding.This material has resistance to chemical attack, fire prevention, fire-retardant, waterproof, ageing-resistant, characteristics such as weatherability strong, insulation.Be widely used as fiberglass base cloth, anticorrosion, insulation, fire protection flame retarding, waterproof material, epoxy copperclad plate and electrical apparatus insulation goods etc.The pore size of glass mat is between 1 to 100 μ m, and homogeneity is very poor, and lithium ion battery separator requires pore size between 0.03-0.1 μ m, the porosity of 30-60% and high porous nickel.This shows that although the glass fibre low price has good flame and chemical resistance, it can not directly serve as the lithium secondary battery barrier film.
Because glass mat has good supporting role, extensively be used as the lead-acid battery barrier film, but it is less that its modification is used as the research of lithium ion battery polymer electrolyte, do not see relevant report.
Summary of the invention
The objective of the invention is to overcome existing gel polymer electrolyte poor heat stability, mechanical strength is low, the production cost height, extremely difficult shortcoming of in the macrocell of high security, being used widely, glass mat and other macromolecular materials is compound, one class high conductivity is provided, the macroion transport number, good mechanical property, security performance height, production cost is low, the plural gel polymer dielectric that electrochemical properties is stable.
Another object of the present invention is to provide a kind of preparation method of above-mentioned plural gel polymer dielectric and the application in lithium secondary battery thereof.
The invention provides a kind of plural gel polymer dielectric.The compound and the liquid electrolyte that obtain after described electrolyte is compound by glass mat and macromolecular material are formed.
Above-mentioned glass fibre is that main component is silicon dioxide, also can comprise in other oxides such as aluminium oxide, calcium oxide, boron oxide, magnesium oxide, the sodium oxide molybdena one or several.
Above-mentioned glass mat is one or more in short-cut original silk silk felt, continuous strand felt, surperficial felt, Nomex and the stitching felt.
Above-mentioned macromolecular material comprises one or more in polyethers, polyacrylonitrile, polyacrylate, Kynoar (PVDF), polyamide, polyimides, poly-aramid fiber, the polyester, the homopolymers, copolymer or the blend that also comprise them also can add suitable inorganic filler simultaneously.
Above-mentioned suitable inorganic filler comprises aluminium oxide, silica, titanium oxide, zirconia, aLi
2O-bAl
2O
3-cTiO
2-dP
2O
5The mixture of the compound that (a, b, c, d are between 1-100) forms, imvite, molecular sieve or they both or multiple compound.
Above-mentioned liquid electrolyte includes the solution of organic compounds or ionic liquid and lithium salts.
The present invention provides a kind of plural gel method for preparing polymer electrolytes in addition, and this method may further comprise the steps:
(1) adopt solwution method, heating mixing method, infusion method, casting method or electrospinning method, macromolecular material and glass mat is compound, form structure of composite membrane;
(2) compound is placed drying under the vacuum drying chamber 40-120 ℃ condition, remove trace solvent.
(3) compound that obtains after in the anhydrous and oxygen-free environment that the glass mat of drying and macromolecular material is compound is immersed in the electrolyte 1 minute to 24 hours, obtains gel polymer electrolyte.
The described anhydrous and oxygen-free environment of above-mentioned steps (3) is for being the glove box of argon gas in moisture less than 1 ppm, atmosphere.
The described electrolyte of above-mentioned steps (3) includes the solution of organic compounds or ionic liquid and lithium salts.
The present invention also provides a kind of application of plural gel polymer dielectric, this is applied as a kind of electrolyte of secondary cell and barrier film, the negative pole of this secondary cell is the alloy of alloy, silicon or silicon of alloy, material with carbon element, tin, the tin of lithium metal, lithium metal, just very LiMO
2(a kind of among M=Co, Ni, Mn, the Co, 2 kinds of elements or element more than 2 kinds) or LiM ＇ PO
4(a kind of among M ＇=Fe, Mn, the Co, more than two kinds or 2 kinds element).
After adopting glass mat and macromolecular material compound, the present invention makes compound and the liquid organic electrolyte gelation prepares the plural gel polymer dielectric.Gained plural gel polymer film has not only kept the glass mat high flame retardant, strong resistance to chemical attack, the characteristics of low production cost, and possessed the electrolyte stable ionic conduction, high conductivity, the broadening window reaches the characteristics with the fine compatibility of electrode material, and this product can be used for the lithium secondary battery of high safety performance.
Description of drawings
Fig. 1 is the embodiment of the invention 1 used glass mat (GFM), macromolecular material (PVDF) and gained compound (PVDF-GFM) infared spectrum.
Fig. 2 is that the embodiment of the invention 1 used glass mat (GFM) is positive, profile scanning Electronic Speculum figure (a, b) and the front of gained compound (PVDF-GFM), profile scanning Electronic Speculum figure (c, d).
Fig. 3 is the DSC figure of the embodiment of the invention 1 used glass mat (GFM), macromolecular material (PVDF), gained compound (PVDF-GFM) and Comparative Examples 1 used Celgard 2730 barrier films.
Fig. 4 is the pulling force-stress curve of the embodiment of the invention 1 gained glass mat (GFM), macromolecular material (PVDF), gained compound (PVDF-GFM) and Comparative Examples 1 used Celgard 2730 barrier films.
Fig. 5 be the embodiment of the invention 1 gained glass mat compound (PVDF-GFM) (b, d) and Comparative Examples 1 used Celgard 2730 barrier films (a, combustion testing figure c).
Fig. 6 is the embodiment of the invention 1 gained gel polymer electrolyte (PVDF-GFM) and Comparative Examples 1 gained 1 M LiPF
6The DSC curve of Celgard 2730 barrier films that electrolyte is saturated.
Fig. 7 is charging and discharging curve and the cycle performance figure of the embodiment of the invention 5 gained lithium secondary batteries.
Fig. 8 is charging and discharging curve and the cycle performance figure of Comparative Examples 2 gained lithium secondary batteries of the present invention.
Embodiment
(1) is that 10% ratio is dissolved in the N-N-methyl-2-2-pyrrolidone N-by mass percentage with PVDF (Kynoar), in 60 ℃ water-bath, dissolves that the uniform solution that obtains clarifying is chilled to room temperature.
(2) (component is the glass mat that will be made up of the continuous strand felt: 95SiO
2-2Al
2O
3-B
2O
3-2Na
2O) be fixed on the smooth clean glass plate, the PVDF solution casting that makes on glass mat, is used doctor blade, place solvent flashing on 80 ℃ of heating plates, take off after 4 hours and be chilled to room temperature.The glass mat face of pouring into a mould PVDF is close to glass plate fixes glass mat, coating solution is cast on the glass mat, use doctor blade, place solvent flashing on 80 ℃ of heating plates, take off after 6 hours and be chilled to room temperature and namely get PVDF composite glass fiber felt.
(3) PVDF composite glass fiber felt is cut into appropriate size after, place the dry trace solvent of removing of following 24 hours of 80 ℃ of conditions of vacuum drying chamber, vacuum is chilled to room temperature and shifts into glove box.The glass mat composite membrane is immersed in 1M LiPF
6Namely got PVDF composite glass fiber felt gel polymer electrolyte in the electrolyte (model LIB 315, available from Guotai Huarong Chemical New Material Co., Ltd., Zhangjiagang City) in 12 hours.
The PVDF composite glass fiber felt that said method is obtained has carried out infrared test, sem test, differential thermal analysis test, extension test, combustion testing, and the gained result is shown in Fig. 1, Fig. 2, Fig. 3, Fig. 4, Fig. 5 respectively.Gel polymer electrolyte is carried out the differential thermal analysis test, the results are shown in Fig. 6.
The test of composite glass fiber felt pick up is that compound was immersed in electrolyte after 6 hours, calculates according to formula (1):
η = (
W t –
W 0) /
W 0 × 100% (1)
Wherein,
W 0 With
W t Quality after representing dry film respectively and inhaling full electrolyte.The results are shown in the table 1 of gained.
Conductivity is calculated by formula (2):
σ = l / (R b A) (S cm
-1)
(2)
Wherein,
σBe conductivity,
R b Be the impedance of film,
lThe thickness of film,
AIt is the pole piece area.The results are shown in the table 1 of gained.
Lithium ion transference number is calculated by formula (3):
t
Li + = I
ss/ I
0 (3)
Wherein, I
SsBe the resulting steady-state current value of timing coulometry, I
0It is the resulting initial state current value of timing coulometry.The results are shown in the table 1 of gained.
Embodiment 2
(1) is 8% by mass percentage with P (VDF-HFP) (poly-(biasfluoroethylene-hexafluoropropylene)), joins in the dimethyl sulfoxide solvent, be heated to 100 ℃ of dissolvings, obtain clarifying uniform solution, be chilled to room temperature then.
(2) (component is: 95SiO will to form the glass mat of (mass ratio 1:1) by short-cut original silk silk felt and continuous strand felt
2-2Al
2O
3-B
2O
3-MgO-Na
2O) be fixed on the smooth clean glass plate, the P (VDF-HFP) that makes adopted on the method for electrostatic spinning and the glass mat form P (VDF-HFP) composite glass fiber felt, 100 ℃ of vacuumizes, remove residual solvent then.
(3) P (VDF-HFP) composite glass fiber felt is cut into appropriate size after, place the dry trace solvent of removing of following 24 hours of 80 ℃ of conditions of vacuum drying chamber, vacuum is chilled to room temperature and shifts into glove box.The glass mat composite membrane is immersed in 1 M LiPF
6Namely got PVDF composite glass fiber felt gel polymer electrolyte in the electrolyte (model LIB 315, available from Guotai Huarong Chemical New Material Co., Ltd., Zhangjiagang City) in 12 hours.
Measure pick up, ionic conductivity, the lithium ion transport coefficient of composite membrane then according to embodiment 1 described method, and the gained gel polymer electrolyte is carried out differential thermal analysis, relevant data is summarized in table 1.
Embodiment 3
(1) PMMA (polymethyl methacrylate) 9g is joined in N-N-methyl-2-2-pyrrolidone N-(100 ml) solvent, be heated to 60 ℃ of dissolvings, add 0.2g silica (average grain diameter 100 nanometers) then, mix.
(2) (component is the glass mat that will be made up of surperficial felt: 97SiO
2-3Al
2O
3) be fixed on the smooth clean aluminium foil surface, the PMMA that makes and the mixed liquor of silica are cast on the glass mat, use doctor blade, place solvent flashing on 80 ℃ of heating plates, take off after 12 hours and be chilled to room temperature, obtain PMMA composite glass fiber felt.
(3) PMMA composite glass fiber felt is cut into appropriate size after, place the dry trace solvent of removing of following 24 hours of 80 ℃ of conditions of vacuum drying chamber, vacuum is chilled to room temperature and shifts into glove box.The glass mat composite membrane is immersed in the 0.8 M LiBOB electrolyte (solvent is the mixture of vinyl carbonate, formic acid dimethyl ester, formic acid diethylester volume ratio 1:1:1) 40 hours and namely gets PMMA composite glass fiber felt gel polymer electrolyte.
Embodiment 4
(1) is that 10% ratio is dissolved in N by mass percentage with PET (poly-(ethylene glycol-terephthaldehyde's ester)), in N '-dimethyl formamide, in 70 ℃ water-bath, adds thermal agitation and must clarify uniform solution in 2 hours.
(2) (component is: 95SiO short-cut original silk silk felt and continuous strand felt to be formed the glass mat of (mass ratio 1:1)
2-2Al
2O
3-B
2O
3-MgO-Na
2O) be fixed on the smooth clean glass plate, the PET solution casting that makes on glass mat, is used doctor blade, place solvent flashing on 80 ℃ of heating plates, take off after 4 hours and be chilled to room temperature, namely get PET composite glass fiber felt gel polymer electrolyte.
(3) inferior PET composite glass fiber felt gel polymer electrolyte is cut into appropriate size after, place the dry trace solvent of removing of following 24 hours of 80 ℃ of conditions of vacuum drying chamber, vacuum is chilled to room temperature and shifts that into glove box is standby.Be immersed in the ionic liquid of 0.8 M LiBOB in (ionic liquid consists of 1-alkyl-2,3-methylimidazole trifluoromethyl sulfonic acid) 30 hours and namely get the plural gel polymer dielectric.
Measure pick up, ionic conductivity, the lithium ion transport coefficient of composite membrane then according to embodiment 1 described method, and the gained gel polymer electrolyte is carried out differential thermal analysis, relevant data is summarized in table 1.
Comparative Examples 1
With the commercial li-ion battery diaphragm (Celgard 2730, PE) be cut into appropriate size after, placed under 80 ℃ of conditions of vacuum drying chamber drying under reduced pressure 24 hours, vacuum is chilled to room temperature and shifts into glove box.Carry out needing Celgard 2730 barrier films are immersed in 1 M LiPF before the electro-chemical test
6In the electrolyte (available from Guotai Huarong Chemical New Material Co., Ltd., Zhangjiagang City) 6 hours.
Measure pick up, ionic conductivity, the lithium ion transport coefficient of Celgard 2730 films then according to the described method of embodiment 1, the infrared test of Celgard 2730 films, differential thermal performance test, burning test and with 1 M LiPF
6The test of differential thermal after electrolyte (model LIB315) is saturated, gained the results are shown among Fig. 3, Fig. 4, Fig. 5 and Fig. 6, and Fig. 3 shows that the temperature that embodiment 1 gained composite membrane begins to melt is 170 ℃, than 130 ℃ high 40 ℃ of Comparative Examples 1Celgard barrier film; Fig. 4 shows that the mechanical strength of Comparative Examples 1 gained composite membrane is than the obvious height of glass felt; Fig. 5 shows that Comparative Examples Celgard barrier film is met thermal contraction, and catches fire, and embodiment 1 gained composite membrane is missing of ignition at once; Fig. 6 shows that the solvent evaporates temperature is 65 ℃ behind the Comparative Examples 1Celgard barrier film Electolyte-absorptive, and is gel polymer electrolyte behind the embodiment 1 gained composite membrane absorption electrolyte, and the solvent evaporates temperature is up to 85 ℃.And the gained gel polymer electrolyte carried out differential thermal analysis, relevant data is summarized in table 1.
The electrochemical property test result of table 1 embodiment 1-4 and Comparative Examples 1
With the plural gel polymer dielectric of embodiment 1 gained as electrolyte and barrier film, with LiFePO
4, conductive black, adhesive PVDF (mass ratio 9:0.4:0.6) mixture as positive pole, as negative pole, form lithium secondary battery with lithium metal.Discharge and recharge experiment between the 2.5-4.2V then under 0.2C, the charging of gained, discharge curve, efficiency for charge-discharge and cycle performance are illustrated in Fig. 7.
Comparative Examples 2
(Celgard 2730, and PE) as barrier film, as electrolyte, other form lithium secondary battery with embodiment 5 with LIB315 with the commercial li-ion battery diaphragm.Discharge and recharge experiment between the 2.5-4.2V then under 0.2C, the charging of gained, discharge curve and cycle performance are illustrated in Fig. 8.
From Comparative Examples 1 and embodiment 1-4 to recently, after adopting glass mat and macromolecular material compound, the present invention makes compound and the liquid organic electrolyte gelation prepares composite glass fiber felt gel polymer electrolyte, gained gelatin polymer film has not only kept the glass mat high flame retardant, strong resistance to chemical attack, the characteristics of low production cost, and possessed the electrolyte stable ionic conduction, high conductivity, broadening window and and the good characteristics of electrode material compatibility.
From the contrast of Comparative Examples 2 and embodiment 5 as can be seen, adopt the lithium secondary battery of plural gel polymer dielectric, in charge and discharge process, has less polarization, and the capacity maintenance is stable, and lithium secondary battery that this explanation plural gel polymer dielectric is assembled into has higher energy efficiency.
The situation of comprehensive above-mentioned Comparative Examples and embodiment shows that the plural gel polymer dielectric has good attraction for the lithium secondary battery of high safety performance.
Claims (10)
1. plural gel polymer dielectric is characterized in that the compound and the liquid electrolyte that obtain after compound by glass mat and macromolecular material form.
2. plural gel polymer dielectric as claimed in claim 1, it is characterized in that described glass mat main component is silicon dioxide, also can comprise in other oxides such as aluminium oxide, calcium oxide, boron oxide, magnesium oxide, the sodium oxide molybdena one or several.
3. as any described plural gel polymer dielectric in claim 1 or 2, it is characterized in that described glass mat is one or more in short-cut original silk silk felt, continuous strand felt, surperficial felt, Nomex and the stitching felt.
4. as any described plural gel polymer dielectric among the claim 1-3, it is characterized in that described macromolecular material comprises one or more in polyethers, polyacrylonitrile, polyacrylate, Kynoar (PVDF), polyamide, polyimides, poly-aramid fiber, the polyester, the homopolymers, copolymer or the blend that also comprise them also can add suitable inorganic filler simultaneously.
5. plural gel polymer dielectric as claimed in claim 4 is characterized in that described inorganic filler comprises aluminium oxide, silica, titanium oxide, zirconia, aLi
2O-bAl
2O
3-cTiO
2-dP
2O
5The mixture of compound, imvite, molecular sieve or their two or more compounds that (a, b, c, d are between 1-100) forms.
6. as any described plural gel polymer dielectric among the claim 1-5, it is characterized in that described liquid electrolyte includes the solution of organic compounds or ionic liquid and lithium salts.
7. plural gel method for preparing polymer electrolytes as claimed in claim 1 is characterized in that may further comprise the steps:
(1) adopt solwution method, heating mixing method, infusion method, casting method or electrospinning method, macromolecular material and glass mat is compound, form structure of composite membrane;
(2) compound that obtains after glass mat and macromolecular material is compound places under the vacuum drying chamber 40-120 ℃ condition dry, removes trace solvent;
(3) compound that obtains after in the anhydrous and oxygen-free environment that the glass mat of drying and macromolecular material is compound is immersed in the electrolyte 1 minute to 24 hours, obtains gel polymer electrolyte.
8. method as claimed in claim 7 is characterized in that the described anhydrous and oxygen-free environment of step (3) is for being the glove box of argon gas in moisture less than 1 ppm, atmosphere.
9. as any described method in claim 7 or 8, it is characterized in that the described electrolyte of step (3) includes the solution of organic compounds or ionic liquid and lithium salts.
10. application as plural gel polymer dielectric as described among the claim 1-6 any, this is applied as a kind of electrolyte of secondary cell and barrier film, the negative pole of this secondary cell is the alloy of alloy, silicon or silicon of alloy, material with carbon element, tin, the tin of lithium metal, lithium metal, just very LiMO
2(a kind of among M=Co, Ni, Mn, the Co, 2 kinds of elements or element more than 2 kinds) or LiM ＇ PO
4(a kind of among M ＇=Fe, Mn, the Co, more than two kinds or 2 kinds element).
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Cited By (7)
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| CN107305937A (en) * | 2016-04-19 | 2017-10-31 | 微宏动力系统（湖州）有限公司 | A kind of aromatic polyamide composite diaphragm, its preparation method and secondary cell |
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| CN110577891A (en) * | 2019-08-21 | 2019-12-17 | 南开大学 | preparation method, use method and application of microbial electrochemical sensor |
| CN113897007A (en) * | 2021-11-02 | 2022-01-07 | 湖南大学 | High-strength composite material solid electrolyte, preparation method thereof and application of electrochromic device |
| CN113897007B (en) * | 2021-11-02 | 2022-11-11 | 湖南大学 | High-strength composite material solid electrolyte, preparation method thereof and application of electrochromic device |
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| CN103268955B (en) | 2016-12-28 |
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