CN108878963A - A kind of solid electrolyte, solid electrolyte film and its manufacturing method and lithium secondary battery - Google Patents

A kind of solid electrolyte, solid electrolyte film and its manufacturing method and lithium secondary battery Download PDF

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Publication number
CN108878963A
CN108878963A CN201710343166.7A CN201710343166A CN108878963A CN 108878963 A CN108878963 A CN 108878963A CN 201710343166 A CN201710343166 A CN 201710343166A CN 108878963 A CN108878963 A CN 108878963A
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solid electrolyte
ion liquid
formula
liquid polymer
secondary battery
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杨立
章正熙
李斯剑
李晓伟
小川秀之
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Shanghai Jiaotong University
Showa Denko Materials Co ltd
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Shanghai Jiaotong University
Hitachi Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention provides a kind of solid electrolyte, solid electrolyte film and its manufacturing method and lithium secondary battery.The solid electrolyte includes ion liquid polymer, polyethylene glycol and lithium salts.Solid electrolyte of the invention is formed by battery with excellent specific discharge capacity and cycle performance, so can apply to lithium secondary battery.

Description

A kind of solid electrolyte, solid electrolyte film and its manufacturing method and lithium are secondary Battery
Technical field
The present invention relates to a kind of solid electrolyte, solid electrolyte film and its manufacturing method and lithium secondary batteries.
Background technique
Electrolyte is most important in the use of electrochemical device.Currently, the electrolyte of lithium secondary battery is mainly by organic Both solvent and lithium salts composition.But the boiling point and flash-point because of organic solvent are low, so inflammable volatile.
For example, if the temperature of battery rapidly rises, electrolyte is gasified in abnormal situation, internal pressure is increased, and lithium is secondary Battery can rupture and electrolyte may be on fire.Prevent lithium secondary battery rupture and it is on fire in the design of lithium secondary battery It is more important.That is, in the lithium secondary battery, from now on, in addition to realizing higher energy density and enlargement, also requiring safety It can be further improved.
Therefore, the polymer dielectric with high security is by extensive concern.Polymer dielectric has good softness Property and the security performance with the leakage that can effectively prevent electrolyte etc., but led currently, usually there is ion at room temperature The problems such as electric rate is low, the impedance at interface between electrode and polymer dielectric is excessive, thus in practical applications, can not be Being used widely in lithium ion battery.
Although pair of the polymer etc. by using doping filler into copolymer solid electrolyte or using co-blended Plan, but ionic conductivity is still low, it cannot be practical extensively.
Ionic liquid has the good characteristic of non-volatile, high-fire resistance, noninflammability, good electrochemical stability etc., So being used as electrolyte by mixing it with lithium salts, the safety of battery can be improved.So far, it is in the prior art from There are single centre cationic ion liquid and double center cation ionic liquids for sub- liquid, but apply as electrolyte in lithium two Liquid phase is still had when primary cell, so there are the danger of leakage, it is difficult to ensure the safety of battery.
Polyethylene glycol can be used as plasticizer use since it has flexible chain structure.Research finds polyethylene glycol/bis- (three Fluorine mesyl) imine lithium system electrolyte, when temperature be greater than 60 DEG C when, ionic conductivity is up to 10-3S cm-1(it please join See《Investigation of materials year is comprehensive by (Annual Review of Materials Research)》,2013,43,503).
Polyethylene glycol has various molecular weights.In addition, the low molecular poly- second two such as molecular weight is 200,400,600 Alcohol is liquid at room temperature.Thus if ingredient as electrolyte, containing polyethylene glycol, there are liquid component in electrolyte, Total solids electrolyte cannot be made thus.
Although in addition, have by polyethylene glycol be used for polyvinyl butyral be made secondary lithium batteries electrolyte (referring to Chinese patent CN101381501), but without relevant battery performance is recorded, so being unaware of its ion-conductance at room temperature How is the correlated performance of conductance etc..
So an urgent demand can be developed even if under high temperature (60 DEG C of >, such as 80 DEG C), specific discharge capacity does not also drop It is low, while the total solids electrolyte of specific discharge capacity also with higher and good cycle performance.
Summary of the invention
The present inventor will use the ionic conductivity of the battery of solid electrolyte and as lithium secondary battery The cycle performance and specific discharge capacity of important performance indexes are furtherd investigate and are improved as emphasis, and result has developed tool There is high ionic conductivity, while also with the solid electrolyte of excellent specific discharge capacity and cycle performance.
The present invention provides a kind of solid electrolyte comprising ion liquid polymer, polyethylene glycol and lithium salts.
The ion liquid polymer is the polymer of following formula (1) or the polymer of following formula (2)：
In formula (1), n is positive integer；
In formula (2), m is positive integer；R1And R2For hydrogen atom or monovalent organic group；
B in formula (1) and (2)-For anion.
In formula (1), n is the integer of 300≤n≤4000.
In formula (2), m is the integer of 50≤m≤2000.
In formula (2), R1For hydrogen atom or or C1-C10 straight-chain aliphatic alkyl；R2For the straight-chain aliphatic of C1-C10 Alkyl or ether.
In formula (1) and (2), B-For BF4 -、PF6 -、(CF3SO2)2N-、(FSO2)2N-、[C(SO2F)3]-、CF3BF3 -、 C2F5BF3 -、C3F7BF3 -、C4F9BF3 -Or (CF3SO2)2N-。
The R2Ether be：-CH2OCH3、-CH2CH2OCH3、-CH2CH2OCH2CH3、-CH2CH2OCH2CH2CH3Or- CH2CH2CH2OCH3。
The number-average molecular weight of the polyethylene glycol is 700~10000.
The lithium salts is LiY, wherein Y-For BF4 -、PF6 -、(FSO2)2N-、[C(SO2F)3]-Or (CF3SO2)2N-。
The mass ratio of the ion liquid polymer and the polyethylene glycol is 1:0.05~1:2.0.
The mass ratio of the ion liquid polymer and the lithium salts is 1:0.1~1:1.0.
The present invention also provides a kind of solid electrolyte films, contain aforementioned described in any item solid electrolytes.
The present invention also provides a kind of lithium secondary batteries containing aforesaid solid dielectric film.
The present invention provides a kind of manufacturing method of solid electrolyte film, includes the following steps：
It (1), is 1 according to the mass ratio of ion liquid polymer and polyethylene glycol:0.05~1:2.0 and ionic liquid The mass ratio of polymer and lithium salts is 1:0.1~1:1.0 ratio by the ion liquid polymer, the polyethylene glycol and In a solvent, mixed liquor is made in mixing for the lithium salts dissolution；
(2), the resulting mixed liquor of step (1) is coated in template, solid electrolyte film is made.
Technical effect
By the present invention in that with the solid with the new group of subassembly comprising ion liquid polymer, polyethylene glycol and lithium salts Electrolyte can obtain excellent specific discharge capacity and cycle performance.
Detailed description of the invention
Fig. 1 is ion liquid polymer obtained by embodiment 11H NMR spectra (deuterated solvent：Deuterated acetone).
Fig. 2 is to be formed by Li/LiFePO with the solid electrolyte of embodiment 14Battery filling at 80 DEG C and with 0.2C The specific discharge capacity and cycle performance figure of discharge-rate progress charge and discharge.
Fig. 3 is to be formed by Li/LiFePO with the solid electrolyte of embodiment 24Battery filling at 80 DEG C and with 0.2C The specific discharge capacity and cycle performance figure of discharge-rate progress charge and discharge.
Fig. 4 is to be formed by Li/LiFePO with the solid electrolyte of embodiment 34Battery is at 80 DEG C and the charge and discharge of 0.2C Electric multiplying power carries out the specific discharge capacity and cycle performance figure of charge and discharge.
Fig. 5 is ion liquid polymer obtained by embodiment 41H NMR spectra (deuterated solvent：Deuterated diformazan is sub- Sulfone).
Fig. 6 is to be formed by Li/LiFePO with the solid electrolyte of embodiment 44Battery is at 80 DEG C and with 0.2C charge and discharge Electric multiplying power carries out the specific discharge capacity and cycle performance figure of charge and discharge.
Fig. 7 is to be formed by Li/LiFePO with the solid electrolyte of embodiment 54Battery filling at 80 DEG C and with 0.2C The specific discharge capacity and cycle performance figure of discharge-rate progress charge and discharge.
Fig. 8 is to be formed by Li/LiFePO with the solid electrolyte of embodiment 64Battery filling at 80 DEG C and with 0.2C The specific discharge capacity and cycle performance figure of discharge-rate progress charge and discharge.
Fig. 9 is to be formed by Li/LiFePO with the solid electrolyte of comparative example 14Battery filling at 80 DEG C and with 0.2C The specific discharge capacity and cycle performance figure of discharge-rate progress charge and discharge.
Figure 10 is the schematic diagram of an embodiment of lithium secondary battery of the invention.
Symbol：
1 negative electrode collector
2 negative electrode material layers
3 solid electrolyte films
4 positive electrode material layers
5 positive electrode collectors
10 lithium secondary batteries
Specific embodiment
Just implement mode of the invention below to be described in detail, but the present invention is not limited to the following embodiments and the accompanying drawings.? In the following embodiments and the accompanying drawings, constituent element (also including the case where element process etc.) is in addition to especially expressing, it is not necessary to.It is right In numerical value and its range, it is also not limited to the present invention.
The present invention provides a kind of solid electrolyte comprising ion liquid polymer, polyethylene glycol and lithium salts.
<Ion liquid polymer>
Foregoing ion liquid polymers are the polymer of following formula (1) or the polymer of following formula (2)：
In formula (1), n is positive integer；In formula (2), m is positive integer, R1And R2For hydrogen atom or monovalent organic group；Formula (1) and the B in (2)-For anion.
In formula (1), n is the integer of 300≤n≤4000.
The integer of n preferably 400~4000, more preferably 500~3900 integer, further preferably 1000~3700 Integer, particularly preferably 1500~3500 integer, further preferably 2000~3000 integer.
In formula (2), integer of the m for 50≤m≤2000, preferably 200~1800 integer, preferably 500~1500 Integer.
In formula (2), R1For hydrogen atom or the straight-chain aliphatic alkyl of C1-C10；R2For the straight-chain aliphatic alkyl of C1-C10 Or ether.
In formula (1) and (2), B-Anion be BF4 -、PF6 -、(CF3SO2)2N-、(FSO2)2N-、[C(SO2F)3]-、 CF3BF3 -、C2F5BF3 -、C3F7BF3 -、C4F9BF3 -Or (CF3SO2)2N-, preferably (CF3SO2)2N-Or (FSO2)2N-；It is special good For (CF3SO2)2N-。
The straight-chain aliphatic alkyl of aforementioned C1-C10 is, for example,：Methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, Octyl, nonyl, decyl.
The straight-chain aliphatic alkyl of aforementioned linear aliphatic alkyl preferably C1-C5, is exemplified by：Methyl, ethyl, propyl, Butyl, amyl.
The R2Ether be-CH2OCH3、-CH2CH2OCH3、-CH2CH2OCH2CH3、-CH2CH2OCH2CH2CH3Or- CH2CH2CH2OCH3, preferably-CH2CH2OCH3Or-CH2CH2OCH2CH3。
The R1More preferably hydrogen atom or methyl.
The R2More preferably methyl, ethyl or-CH2CH2OCH3Ether.
The preparation method of foregoing ion liquid polymers can be following manufacturing method.
Such as " power technology journal " (Journal of can be used in the manufacturing method of the ion liquid polymer of general formula (1) Power Sources) (A.-L.Pont, R.Marcilla, I.De Meatza, H.Grande, D.Mecerreyes) (2009, 188,558-563) manufacturing method documented by.
For example, the ion liquid polymer of general formula (1) can be made by following manufacturing method：
Polydimethyl diallyl ammonium chloride aqueous solution (concentration is 20.00 mass %) is dissolved in deionized water, is stirred It mixes to form the solution containing polydimethyl diallyl ammonium chloride.
Separately in deionized water by lithium salts dissolution, stirring forms the solution containing lithium salts.
According to polydimethyl diallyl ammonium chloride and the molar ratio of lithium salts 1:1.2~1:2.0 ratio is made aforementioned Two solution carry out mixed preparing, be stirred to react 2~8 hours, formed polymerization after solid content, the solid content is collected by filtration. It is washed with deionized again, until the detection of washings silver nitrate is halogen-free anion, is finally dried in vacuo 12~48 Hour, the ion liquid polymer of general formula (1) is made.
Two (trifyl) imine lithiums, two (fluorosulfonyl) imine lithiums, lithium hexafluoro phosphate, four can be used in the lithium salts Lithium fluoroborate etc..
The viscosity average molecular weigh M of the ion liquid polymer of general formula (1) of the present inventionvIt is 1.0 × 105~5.0 × 106gmol-1, Preferably 3.0 × 105~5.0 × 106g mol-1(polymethyl methacrylate is as standard specimen).
The confirmation method of the ion liquid polymer of the general formula (1) is1H NMR spectra.
If aforementioned viscosity average molecular weigh Mv1.0 × 105g mol-1More than, then it can substantially ensure and be dissolved in by polymer In solvent, the dry piece intensity for being formed by solid electrolyte of coating.If aforementioned viscosity average molecular weigh Mv5.0 × 106g mol-1Hereinafter, being then easy polymer dissolution in a solvent, to improve the operability that coating is formed.
Such as " power technology journal " (Journal of can be used in the manufacturing method of the ion liquid polymer of general formula (2) Power Sources) documented by (2014,258,150-154) (K.Yin, Z.X.Zhang, L.Yang, S.-i.Hirano) Manufacturing method.
For example, the ion liquid polymer of the polymer of general formula (2) can be made by following manufacturing method：
The first step：In a solvent by the dissolution of olefin-containing unsaturated group imidazoles monomer, aforementioned imidazoles are accounted for initiator Initiator is added in 0.2~1.0% ratio of monomer mass, carries out Raolical polymerizable.In the ring of the protective gas such as argon gas It in border, is stirred to react at reflux at 60~90 DEG C 6~12 hours, after the solid content after polymerization generates, with molten after filtering The polymer is washed in agent, is dried in vacuo 12~48 hours at 60~90 DEG C, and the polymer containing glyoxaline structure is made.
Olefin-containing unsaturated group imidazoles monomer：It can be 1- vinyl imidazole, 1- allyl imidazole etc..
Polymerization initiator：Azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl.
Solvent：Toluene, benzene, tetrahydrofuran, acetone, gamma-butyrolacton, N-Methyl pyrrolidone etc..Wherein, preferably third Ketone.
The viscosity average molecular weigh M of obtained polymervIt is 1.0 × 104~5.0 × 105g mol-1(poly-methyl methacrylate Ester is as standard specimen).
Second step：By the polymer and halogenated hydrocarbons or halogen ether in molar ratio 1 obtained by the first step containing glyoxaline structure: 1.5~1:2.0 dissolutions in a solvent, are stirred to react 24~72 hours at 40~80 DEG C, and vacuum distillation removes solvent, are collected poly- Solid content after conjunction is washed 3 times with anhydrous ether, and rotary evaporation removes the anhydrous ether, is dried in vacuo 12~48 hours, is obtained The liquid polymers of anionic ion containing halogen.
Solvent therein is：N,N-dimethylformamide, methanol etc..
The halogenated hydrocarbons：Bromoethane, N-Propyl Bromide, bromobutane etc..
The halogen ether：2- bromo-ethyl-methyl ether, bromomethyl methyl ether, 2- bromoethyl ethylether etc..
The viscosity average molecular weigh M of the obtained liquid polymers of anionic ion containing halogenvIt is 1.0 × 105~5.0 × 106g mol-1(polymethyl methacrylate is as standard specimen).
Third step：The liquid polymers of anionic ion containing halogen and lithium salts that second step is obtained in molar ratio 1:1.2~ 1:2.0 dissolutions in deionized water, are stirred to react 2~8 hours, and the solid is collected by filtration in the solid content after forming polymerization Object, then be washed with deionized, until the detection of washings silver nitrate is halogen-free anion, finally vacuum drying 12~48 is small When obtain the ion liquid polymer of general formula (2).
The lithium salts is：Two (trifyl) imine lithiums, two (fluorosulfonyl) imine lithiums, lithium hexafluoro phosphate, tetrafluoro Lithium borate etc..
The viscosity average molecular weigh M of the ion liquid polymer of general formula (2) of the present inventionvIt is 1.0 × 105~5.0 × 106gmol-1 (polymethyl methacrylate is as standard specimen), preferably 1.0 × 105~1.0 × 106g mol-1。
The confirmation method of the ion liquid polymer is1H NMR spectra.
The viscosity average molecular weigh M of ion liquid polymer of the inventionvIt is 1.0 × 105~5.0 × 106g mol-1(poly- methyl Methyl acrylate is as standard specimen).
The confirmation method of the ion liquid polymer：1H NMR spectra.
For aforementioned polyethylene glycols of the present invention, number-average molecular weight is 700~10000, preferably 750~6000, more preferably It is 800~4000, particularly preferably 800~2000.
The concrete example of the polyethylene glycol is：Polyethylene glycol-800 (PEG-800), gathers cetomacrogol 1000 (PEG-1000) Ethylene glycol 1500 (PEG-1500), polyethylene glycol 2000 (PEG-2000), Macrogol 4000 ((PEG-4000)), polyethylene glycol 6000 (PEG-6000), PEG 8000 (PEG-8000) and polyethylene glycol 10000 ((PEG-10000)) etc., it is preferably poly- Ethylene glycol 800 (PEG-800), cetomacrogol 1000 (PEG-1000), polyethylene glycol 2000 (PEG-2000), Macrogol 4000 (PEG-4000), Macrogol 6000 (PEG-6000).
Aforementioned polyethylene glycols can be made for conventional manufacturing method.
Such as can also be used by ethylene oxide and water or ethylene glycol, using sodium hydroxide or potassium hydroxide as catalyst, Progress addition polymerization, which is made, in polymeric kettle (refers to Xie Fuchun, Zhu Changchun, Yuqin etc. is written《Chemical propellant and high score Sub- material》" Synthesis Technology of Polyethylene Glycol [J] ", 2005,3 (4):6-9).
Can also directly be bought from market, for example, can be used as commodity directly buy by Aladdin company or Aldrich The polyethylene glycol of company's production.
Lithium salts of the present invention is LiY；Wherein Y-For BF4 -、PF6 -、(FSO2)2N-、[C(SO2F)3]-Or (CF3SO2)2N-；Preferably (CF3SO2)2N-(FSO2)2N-；Preferably (CF3SO2)2N-。
For example, can be two (trifyl) imine lithiums, two (fluorosulfonyl) imine lithiums, lithium hexafluoro phosphate, tetrafluoro Lithium borate etc..Any one all can be used as commodity and directly buy the lithium salts produced by gloomy field chemical industry (Zhangjiagang) Co., Ltd.
The ion liquid polymer of solid electrolyte of the invention and the mass ratio of the polyethylene glycol are 1:0.05 ~1:2.0, preferably 1：0.1~1：1.5.
If dielectric film can be improved 0.05 or more in the mass ratio of the ion liquid polymer and the polyethylene glycol Electrochemical properties；If further increasing electrochemical properties 0.1 or more.
If the mass ratio of the ion liquid polymer and the polyethylene glycol is 2.0 hereinafter, can inhibit dielectric film Adherency, easily removed from mold, if 1.5 hereinafter, more preferable.
The mass ratio of the ion liquid polymer and the lithium salts is 1:0.1~1:1.0, preferably 1：0.3~1： 0.8。
If lithium ion of the mass ratio of the ion liquid polymer and the lithium salts less than 0.1, in solid electrolyte Carrier concn is lower, and there are the low trend of ionic conductance.If the quality of the ion liquid polymer and the lithium salts Than more than 1.0, there is the trend to become fragile in solid electrolyte film.
The present invention also provides a kind of solid electrolyte films, contain aforementioned any solid electrolyte.
The present invention also provides a kind of manufacturing method of aforesaid solid dielectric film, which includes the following steps：
It (1) is 1 according to the mass ratio of ion liquid polymer and polyethylene glycol:0.05~1:2.0 (preferably 1：0.1~ 1：1.5) and the mass ratio of ion liquid polymer and lithium salts is 1:0.1~1:1.0 (preferably 1：0.3~1：0.8) ratio In a solvent by the dissolution of the ion liquid polymer, the polyethylene glycol and the lithium salts, mixed liquor is made in mixing to example；
(2) step (1) resulting mixed liquor is coated in template, dielectric film is made.
There are larger differences according to the composition of battery for the thickness of dielectric film, so being not particularly limited to this.
Solid electrolyte of the invention can be applicable in battery, especially lithium secondary battery.I.e. the present invention also provides one kind Lithium secondary battery containing aforesaid solid dielectric film.
Solid electrolyte of the invention is preferably applied in Li/LiFePO4In battery.
<The preparation and its manufacturing method of lithium secondary battery>：
The configuration example of the lithium secondary battery of 0 pair of present embodiment is illustrated referring to Fig.1, but lithium secondary battery is not limited to figure 10 composition.
In lithium secondary battery 10 shown in Fig. 10, configured with solid electricity between negative electrode material layer 2 and positive electrode material layer 4 Solve plasma membrane 3.Negative electrode material layer 2 is formed on negative electrode collector 1.Positive electrode material layer 4 is formed on positive electrode collector 5.Hereinafter, packet It includes the negative electrode material layer 2 being formed on negative electrode collector 1 and is also referred to as " negative electrode tab ", including being formed on positive electrode collector 5 just Pole material layer 4 is also referred to as " positive plate ".
Just each composition of lithium secondary battery of the invention is illustrated below.
1. solid electrolyte film
Solid electrolyte film of the invention is formed between positive electrode material layer and negative electrode material layer.In the present invention, solid Dielectric film is made up of aforesaid solid electrolyte.The difference that the thickness of solid electrolyte film is constituted according to battery exists very big Difference, so being not particularly limited to this.
2. positive plate
Positive plate is layer at least containing positive electrode.Positive electrode material layer can also contain conductive material in addition to positive electrode With at least one party of adhesives.
The type of positive electrode is not particularly limited, but such as oxide active material can be used.It is living as oxide Property substance, can be used such as LiCoO2、LiMnO2、LiNiO2、LiVO2、LiNi1/3Co1/3Mn1/3O2Deng rock salt layered-type activity Substance；LiMn2O4、Li(Ni0.5Mn1.5)O4Deng spinel active substance；LiFePO4、LiMnPO4、LiNiPO4、 LiCuPO4Deng olivine-type active material etc..From the viewpoint of thermal stability, LiFePO4 (LiFePO is preferably used4)。
As conductive material, as long as the substance with required electronic conductivity, is not particularly limited this.Such as it can make Use carbon material.As carbon material, the carbon black such as acetylene black, Ketjen black, furnace black, thermal black can be used.
In addition, as adhesives, as long as being in chemistry and electrically stable substance, to this without specific restriction.Such as It can be the fluorine class adhesives of Kynoar (PVDF), polytetrafluoroethylene (PTFE) (PTFE) etc..In addition, from the viewpoint of the capacity, just The content of positive electrode in the material layer of pole is more ideal.
In addition, the material as positive electrode collector, such as SUS, aluminium, nickel, iron, titanium and carbon can be used etc..
3. negative electrode tab
Negative electrode tab of the invention is layer at least containing negative electrode material.Negative electrode material layer can also contain in addition to negative electrode material At least one party of conductive material and adhesives.
The type of negative electrode material is not particularly limited, but such as metal active material and carbon active material can be used. As metal active material, can be used such as metallic monomer, alloy, metal oxide.As being contained in metal active material Metallic element can be used such as Li, Al, Mg, In, Si, Sn.As negative electrode material, preferably using Li metal, carbon, Li4Ti5O12。
It, can use material identical with material documented by aforementioned positive electrode material layer for conductive material and adhesives. In addition, the content of the negative electrode material in negative electrode material layer is more ideal from the viewpoint of the capacity.In addition, negative electrode material layer Thickness there are great differences due to the difference of the composition of battery, so to this without specific restriction.
4. others are constituted
As long as the material of battery case usually material, may be, for example, SUS Al stack membrane etc..As of the invention The shape of lithium secondary battery may be, for example, Coin shape, lamination-type, cylinder type, square etc..
By the positive cover of battery, positive plate, obtained solid electrolyte film, cathode in the glove box of argon gas protection Piece, negative cover are stacked by sequence from the bottom up and are placed, and form lamination, lamination is then placed on punching press on press machine, so that The mutually closed lock jail of the positive and negative polar cap of battery, completes the assembling of lithium secondary battery of the invention.
Battery unit other than the dielectric film of the invention of above-mentioned positive cover, positive plate, negative electrode tab, negative cover used etc. Associated batteries component obtained by known method can be used in part, and acquisition can also be bought by supplier.
Alternatively, it is also possible to which monocell is made in negative electrode tab, solid electrolyte film, positive plate lamination, it is more to form the monocell A lamination it is ambipolar.
<The measurement of molecular weight>：
Viscosity average molecular weigh test method：
Use polymethyl methacrylate as standard specimen, using the viscosity [η] of 25 DEG C of polymer of determination of ubbelohde viscometer, Pass through formula [η]=KM againv(wherein K represents broadening factor, and value is related with temperature, polymer, solvent property, MvIt represents viscous equal Molecular weight, the viscosity of [η] representation polymer) obtain viscosity average molecular weigh Mv。
<Number-average molecular weight measuring method>：
Measuring method well known in the art can be used, for example, following method can be used：
End-group analysis is carried out to the hydroxyl in polyethylene glycol, acetylation is carried out to it first, that is, excessive acetic anhydride is added The hydroxyl of molecule chain end is set to be transformed into acetyl group.Then unreacted acetic anhydride is hydrolyzed and uses standard
NaOH solution titrates the amount for acquiring superfluous acetic anhydride, to calculate the amount of the acetic anhydride reacted.From acetic anhydride Consumption can calculate the number of institute's hydroxyl in sample.Pass through formula Mn=m*1000/ (Nt-CNaOH(V0-Vf)) (wherein Nt For the amount of the substance of added acetic anhydride, CNaOHFor the molar concentration of sodium hydroxide used in the superfluous acetic anhydride of titration, V0Position drop The initial reading of timing, VfReading when for titration end-point, Mn is number-average molecular weight) obtain number-average molecular weight MN。
<The glass transition temperature T of electrolyte of the inventiongMeasurement>：
Using differential scanning calorimetry (DSC) method and using TA Instruments Q2000 type derivatograph into Row measurement.Secondary cycle is usually carried out, the DSC curve data recycled using the 2nd time obtain glass transition temperature：First will Electrolyte sample is cooled to -80 DEG C from room temperature, constant temperature 10 minutes, is then warming up to 200 DEG C with 10 DEG C/min of speed, constant temperature 5 Minute, then -80 DEG C are cooled to 10 DEG C/min of speed, it is recycled as the 1st time.Aforesaid operations 1 time is repeated to follow as the 2nd time Ring.
<The measurement of the ionic conductivity of electrolyte of the invention>：
The ionic conductivity of electrolyte is tested using AC impedence method, and instrument is that (Shanghai Chen Hua instrument has CHI600D The CHI600D electrochemical operation room of limit company).By sample to be tested with：Stainless steel electrode/electrolyte/stainless steel electrode composition Sequence constitutes simulated battery, then ac impedance measurement is carried out at 25 DEG C to the simulated battery.Before test, by simulated battery every A temperature spot constant temperature stands 1h, frequency range 1Hz~100KHz, AC amplitude 5mV.Conductivity Calculation formula is as follows：
σ=L/ (RS)
R is electrolyte ontology impedance (Ω) in formula, and L indicates that the thickness (cm) of dielectric film, S represent having for dielectric film Imitate area (cm2)。
<The measurement of specific discharge capacity>
The specific discharge capacity of battery measures in the following manner：
Battery is made using resulting electrolyte, which is placed in 80 DEG C of temperature, with the voltage of 2.5~4.0V The constant current of range and 0.2C are by its charge and discharge, and using CT2001A, (Lan Bo test equipment Co., Ltd of Wuhan City, LAND battery are surveyed Test system-CT2001A) charging/discharging apparatus measurement battery discharge capacity and the discharge capacity until being recycled to 30 times for the first time.
The calculation formula of specific discharge capacity：
Specific discharge capacity (mAh g-1The quality (g) of active material in)=actual discharge capacity (mAh)/positive plate.
Make cycle performance figure：
Using the data of specific discharge capacity obtained above as ordinate, circulation has been made using cycle-index as abscissa Performance map.
Embodiment
The following examples but are not limited the scope of the invention to further explanation of the invention.
<Embodiment 1>
[1] preparation of poly- (dimethyldiallylammonium two (trifyl) imines) based solid electrolyte：
The preparation of [1-1] poly- (dimethyldiallylammonium two (trifyl) imines) ion liquid polymer：
The polydimethyl diallyl ammonium chloride of 20.00g is added in 250mL beaker Aqueous solution (20.00 mass %) (Aldrich product) and 100.00mL deionized water magnetic agitation 1 hour, are contained with being formed There is the solution of polydimethyl diallyl ammonium chloride.
Two (trifyl) imine lithiums that 8.52g (29.68mmol) is sequentially added in another 50mL beaker are (gloomy Field chemical industry (Zhangjiagang) Co., Ltd manufacture) and 10.00mL deionized water, magnetic agitation be allowed to be completely dissolved, formed contain two The solution of (trifyl) imine lithium.
Aforementioned two kinds of solution is mixed, is stirred ion exchange 2 hours, the solid content having polymerize generates, and is collected by filtration aforementioned Solid content, then be washed with deionized to until silver nitrate detection washings not chloride ion-containing, finally vacuum is dry at 105 DEG C Poly- (dimethyldiallylammonium two (trifyl) imines) as ion liquid polymer is obtained within dry 48 hours, is tied Structure formula is：
The viscosity average molecular weigh of the ion liquid polymer is 2.11 × 106g mol-1。
The chemical structure of the ion liquid polymer uses1H NMR spectra characterization, as shown in Figure 1.
Solid electrolyte obtained by embodiment 11H NMR spectra is using the manufacture of Bruker Biospin company AVANCE III HD 400 is measured in following method：
Deuterated solvent：Deuterated acetone；
Resonant frequency：6~440MHz；
Resolution ratio：< 0.005Hz；
Impulse amplitude：1H≤9μsec；
Chemical displacement value benchmark：Tetramethylsilane (TMS) is set to 0ppm.
As can be seen that spectrogram result is consistent with desired structure.
The preparation of [1-2] solid electrolyte：
Poly- (dimethyldiallylammonium two (trifyl) obtained by 1.00g is added into single necked round bottom flask Imines), acetone of the 20.00g as solvent is added, magnetic agitation dissolution adds the polyethylene glycol-800 (PEG-800) of 0.20g (Aladdin Products) and 0.40g bis- (trifyl) imine lithium (gloomy field chemical industry (Zhangjiagang) Co., Ltd product), Poly- (two (the trifluoro of dimethyldiallylammonium of transparent uniform mixed liquor is made in magnetic agitation at 25 DEG C after mixing 12 hours Mesyl) imines) electrolyte.
The preparation of [1-3] solid electrolyte film：
Aforementioned [1-2] resulting solid electrolyte is coated in polytetrafluoroethylene (PTFE) template, then vacuum is dry at 30 DEG C Dry 48 hours, obtain solid electrolyte film.Solid electrolyte film glass transition temperature TgIt is -44 DEG C, the ion at 80 DEG C Conductivity is 1.13 × 10-4S cm-1, its result is summarized in table 2
The preparation of lithium secondary battery：
LiFePO4 (LiFePO will be contained4) as the positive plate of positive electrode, obtained solid electrolyte film, with lithium (Li) it stacks and places by sequence from top to bottom as the negative electrode tab of negative electrode material, the electrode of lamination-type is formed, then by the lamination The electrode of type is placed on punching press on press machine, obtains Li/LiFePO4Lithium secondary battery.
By obtained Li/LiFePO4Lithium secondary battery carries out constant current under 80 DEG C and 2.5~4.0V of voltage range and fills Discharge test, the specific discharge capacity recycled with 0.2C charge and discharge electrometric determination 30.
Fig. 2 be 1 battery of embodiment at 80 DEG C and with the charge-discharge magnification of 0.2C carry out charge and discharge specific discharge capacity and Cycle performance figure.
It will be put after the first discharge specific capacity of the lithium secondary battery of embodiment 1, maximum specific discharge capacity and 30 circulations The Data Summary of electric specific capacity is in table 3.
<Embodiment 2>
Other than the polyethylene glycol-800 of embodiment 1 (PEG-800) is changed to polyethylene glycol 2000 (PEG-2000), He forms solid electrolyte, solid electrolyte film and lithium secondary battery in the same manner as in Example 1.
The glass transition temperature T of the solid electrolyte filmgBe -41 DEG C, the ionic conductivity at 80 DEG C be 8.20 × 10-5S cm-1, referring to table 2
The determination data of the lithium secondary battery of embodiment 2 is summarised in table 3 and Fig. 3.
<Embodiment 3>
Other than the polyethylene glycol-800 of embodiment 1 (PEG-800) is changed to Macrogol 6000 (PEG-6000), He forms solid electrolyte, solid electrolyte film and battery in the same manner as in Example 1.
Solid electrolyte film glass transition temperature TgIt is -40 DEG C, ionic conductivity is 5.12 × 10 at 80 DEG C-5S cm-1, referring to table 2
The determination data result of the lithium secondary battery of embodiment 3 is summarised in table 3 and Fig. 4.
<Embodiment 4>
[2] poly- (1- (2- methoxy ethyl) -3- vinyl imidazole two (trifyl) imines) based solid electrolyte Preparation：
[2-1] poly- (1- (2- methoxy ethyl) -3- vinyl imidazole two (trifyl) imines) ionic liquid is poly- Close the preparation of object：
(1) using 1- vinyl imidazole as reaction monomers, using azodiisobutyronitrile as initiator, using toluene as reaction Solvent is carried out Raolical polymerizable, and wherein initiator accounts for the 0.5% of monomer mass.At Ar atmosphere protection and 65 DEG C, It is stirred at reflux reaction 8 hours.Solid generation to be had uses acetone washing, is dried in vacuo 24 hours, is gathered at 75 DEG C after filtering Vinyl imidazole.
Polyvinyl imidazol viscosity average molecular weigh MvIt is 3.39 × 105g mol-1。
(2) the 2- bromo-ethyl-methyl ether (63.83mmol) of polyvinyl imidazol obtained by 4.00g and 8.90g are dissolved It in the n,N-Dimethylformamide of 60.00mL, is stirred to react at 60 DEG C 48 hours, vacuum distillation removes solvent, collects solid Body is washed 3 times with anhydrous ether, and rotary evaporation removes anhydrous ether, is dried in vacuo 24 hours, is obtained poly- (1- (2- methoxyl group second Base) -3- vinyl imidazole bromine).
Poly- (1- (2- methoxy ethyl) -3- vinyl imidazole bromine) viscosity average molecular weigh MvIt is 5.62 × 105g mol-1。
(3) by (1- (2- methoxy ethyl) -3- vinyl imidazole bromine) poly- obtained by 3.50g and 5.17g (18.02mmol) two (trifyl) imine lithium (gloomy field chemical industry (Zhangjiagang) Co., Ltd product) is dissolved in 20.00mL In deionized water, there is polymer generation in magnetic agitation 6 hours at room temperature, aforementioned polymer are collected by filtration, then use deionized water Washing is finally dried in vacuo 24 hours at 75 DEG C until being halogen-free anion with silver nitrate detection washings and obtains conduct Poly- (1- (2- methoxy ethyl) -3- vinyl imidazole two (trifyl) imines) of ion liquid polymer, structure Formula is：
The chemical structure of the ion liquid polymer uses1H NMR spectra characterization, as shown in Figure 5.
Solid electrolyte obtained by embodiment 41H NMR spectra is using the manufacture of Bruker Biospin company AVANCE III HD 400 is measured in following method：
Deuterated solvent：Deuterated dimethyl sulfoxide；
Resonant frequency：6~440MHz；
Resolution ratio：< 0.005Hz；
Impulse amplitude：≤9μsec；
Chemical displacement value benchmark：Tetramethylsilane (TMS) is set to 0ppm.
As can be seen that spectrogram result is consistent with desired structure.
The viscosity average molecular weigh M of the ion liquid polymervIt is 7.32 × 105g mol-1。
The preparation of [2-2] solid electrolyte：
Poly- (1- (2- methoxy ethyl) -3- vinyl imidazole two obtained by 1.00g is added into single necked round bottom flask (trifyl) imines), 20.00g acetone is added, magnetic agitation dissolution adds the cetomacrogol 1000 of 0.20g (PEG-1000) (gloomy field chemical industry (Zhangjiagang) is limited for (Aladdin Products) and 0.40g bis- (trifyl) imine lithium Products), magnetic agitation obtains poly- (1- (the 2- methoxyl group second of transparent uniform mixed liquor after mixing 12 hours at 25 DEG C Base) -3- vinyl imidazole two (trifyl) imines) solid electrolyte.
The preparation of [2-3] solid electrolyte film：
Aforementioned [2-2] resulting solid electrolyte is coated in polytetrafluoroethylene (PTFE) template, then vacuum is dry at 25 DEG C Dry 48 hours, obtain dielectric film.Dielectric film glass transition temperature TgIt is -50 DEG C, ionic conductivity is at 80 DEG C 8.92×10-5S cm-1, referring to table 2
The preparation of [2-4] lithium secondary battery：
LiFePO4 (LiFePO will be contained4) as the positive plate of positive electrode, obtained solid electrolyte film, with lithium (Li) it stacks and places by sequence from top to bottom as the negative electrode tab of negative electrode material, the electrode of lamination-type is formed, then by lamination-type Electrode be placed on punching press on press machine, obtain Li/LiFePO4Lithium secondary battery.
By obtained Li/LiFePO4Battery carries out constant current charge-discharge survey under 80 DEG C, the voltage range of 2.5~4.0V The specific discharge capacity of 30 circulations is tested in examination under 0.2C charge-discharge magnification.
The determination data of the battery of embodiment 4 is summarised in table 3 and Fig. 6.
<Embodiment 5>
Other than the cetomacrogol 1000 of embodiment 4 (PEG-1000) is changed to Macrogol 4000 (PEG-4000), Other all form solid electrolyte, solid electrolyte film and lithium secondary battery in the same manner as in Example 4.
Solid electrolyte film glass transition temperature TgIt is -46 DEG C, ionic conductivity is 7.56 × 10 at 80 DEG C-5S cm-1, referring to table 2.
The determination data of the lithium secondary battery of embodiment 5 is summarised in table 3 and Fig. 7.
<Embodiment 6>
In addition to the polyethylene glycol-800 (PEG-800) of 1.0g is added to substitute the polyethylene glycol-800 (PEG- that 0.2g is added 800) other than, other all form solid electrolyte, solid electrolyte film and lithium secondary battery in the same manner as in Example 1.
Solid electrolyte film glass transition temperature TgIt is -48 DEG C, ionic conductivity is 2.55 × 10 at 80 DEG C-4S cm-1, referring to table 2.
The determination data of the lithium secondary battery of embodiment 6 is summarised in table 3 and Fig. 8.
<Comparative example 1>
The composition and relative production of the electrolyte of comparative example 1, can refer to citation《Journal of Power Sources》(2016,307,678-683)。
Its electrolyte composition：Poly- (dimethyldiallylammonium two (trifyl) imines), succinonitrile and two (three Fluorine mesyl) imine lithium.Poly- (dimethyldiallylammonium two (trifyl) imines):Succinonitrile:Two (trifluoro methylsulphurs Acyl group) imine lithium mass ratio be 1:1:0.5.According to aforementioned mass ratio by poly- ((the trifluoro methylsulfonyl of dimethyldiallylammonium two Base) imines) it is used as matrix, and succinonitrile, lithium salts is compound prepares polymer dielectric, and resulting electrolyte is applied to Li/LiFePO4In battery.
Dielectric film, obtained dielectric film glass transition temperature T is made in the electrolytegFor less than -80 DEG C, Ionic conductivity is 2.51 × 10 at 80 DEG C-2S cm-1, referring to table 2.
The determination data of the battery of comparative example 1 is summarized in table 3 and Fig. 9.
Comparative example 2：
The composition of the electrolyte of comparative example 2 and preparation, can refer to citation《Solid State Ionics》(2004, 175,261-265)。
Its electrolyte composition：Li4B7O12Cl and cetomacrogol 1000 (PEG-1000).Li4B7O12Cl:Cetomacrogol 1000 =0.8:0.2 (mass ratio).Not using ion liquid polymer of the invention in comparative example 2.
By Li4B7O12Cl is as matrix, and cetomacrogol 1000 (PEG-1000) is compound prepares polymer dielectric.
Dielectric film is made in the electrolyte, which is -37 DEG C, the ion at 80 DEG C Conductivity is 2.60 × 10-6S cm-1, referring to table 2.
Table 1
Table 2
Examples 1 to 6 and comparative example are in amorphous state, only glass transition temperature, without fusing point.
Fig. 2 is to be formed by Li/LiFePO with the solid electrolyte of embodiment 14Lithium secondary battery at 80 DEG C and with The charge-discharge magnification of 0.2C carries out the specific discharge capacity and cycle performance figure of charge and discharge.
The lithium secondary battery of embodiment 1 is first at 80 DEG C and in the case where carrying out charge and discharge with the charge-discharge magnification of 0.2C Secondary specific discharge capacity is 137mAh g-1, maximum specific discharge capacity is 150mAh g-1, 30 times circulation after specific discharge capacity be 147mAh g-1。
Fig. 3 is to be formed by Li/LiFePO with the solid electrolyte of embodiment 24Lithium secondary battery at 80 DEG C and with The charge-discharge magnification of 0.2C carries out the specific discharge capacity and cycle performance figure of charge and discharge.
The lithium secondary battery of embodiment 2 is first at 80 DEG C and in the case where carrying out charge and discharge with the charge-discharge magnification of 0.2C Secondary specific discharge capacity is 110mAh g-1, maximum specific discharge capacity is 136mAh g-1, 30 times circulation after specific discharge capacity be 132mAh g-1。
Fig. 4 is to be formed by Li/LiFePO with the solid electrolyte of embodiment 34Lithium secondary battery at 80 DEG C and with The charge-discharge magnification of 0.2C carries out the specific discharge capacity and cycle performance figure of charge and discharge.
The lithium secondary battery of embodiment 3 is first at 80 DEG C and in the case where carrying out charge and discharge with the charge-discharge magnification of 0.2C Secondary specific discharge capacity is 86mAh g-1, maximum specific discharge capacity is 120mAh g-1, 30 times circulation after specific discharge capacity be 118mAh g-1。
Fig. 6 is to be formed by Li/LiFePO with the solid electrolyte of embodiment 44Lithium secondary battery at 80 DEG C and with The charge-discharge magnification of 0.2C carries out the specific discharge capacity and cycle performance figure of charge and discharge.
The lithium secondary battery of embodiment 4 is first at 80 DEG C and in the case where carrying out charge and discharge with the charge-discharge magnification of 0.2C Secondary specific discharge capacity is 108mAh g-1, maximum specific discharge capacity is 140mAh g-1, 30 times circulation after specific discharge capacity be 137mAh g-1。
Fig. 7 is to be formed by Li/LiFePO with the solid electrolyte of embodiment 54Lithium secondary battery at 80 DEG C and with The charge-discharge magnification of 0.2C carries out the specific discharge capacity and cycle performance figure of charge and discharge.
The lithium secondary battery of embodiment 5 is first at 80 DEG C and in the case where carrying out charge and discharge with the charge-discharge magnification of 0.2C Secondary specific discharge capacity is 95mAh g-1, maximum specific discharge capacity is 128mAh g-1, 30 times circulation after specific discharge capacity be 124mAh g-1。
Fig. 8 is to be formed by Li/LiFePO with the solid electrolyte of embodiment 64Lithium secondary battery at 80 DEG C and with The charge-discharge magnification of 0.2C carries out the specific discharge capacity and cycle performance figure of charge and discharge.
The lithium secondary battery of embodiment 6 is first at 80 DEG C and in the case where carrying out charge and discharge with the charge-discharge magnification of 0.2C Secondary specific discharge capacity is 148mAh g-1, maximum specific discharge capacity is 148mAh g-1, 30 times circulation after specific discharge capacity be 117mAh g-1
Fig. 9 is to be formed by Li/LiFePO with the electrolyte of comparative example 14Lithium secondary battery is at 80 DEG C and with 0.2C's The specific discharge capacity and cycle performance figure of charge-discharge magnification progress charge and discharge.
The battery of comparative example 1 discharges for the first time at 80 DEG C and in the case where carrying out charge and discharge with the charge-discharge magnification of 0.2C Specific capacity is 131mAh g-1, maximum specific discharge capacity is 158mAh g-1, 30 times circulation after specific discharge capacity be 30mAh g-1。
Table 3Li/LiFePO4Battery discharge specific capacity
As known from Table 3：
(1), the first discharge specific capacity of 1~embodiment of the embodiment of the present invention 2, embodiment 4 and embodiment 6 all exists 100mAh g-1More than.Wherein the first discharge specific capacity of embodiment 1 and embodiment 6 respectively reaches 137mAhg-1With 148mAh g-1。
(2), the maximum specific discharge capacity of whole embodiments of the invention is all in 120mAh g-1More than, wherein embodiment 1, The maximum specific discharge capacity of embodiment 4 and embodiment 6 is up to 140mAh g-1More than, specific discharge capacity with higher.
(3), cycle performance：
Cycle performance is evaluated with the attenuation ratio of specific discharge capacity after 30 circulations.
Attenuation ratio=(specific discharge capacity after maximum specific discharge capacity -30 times circulations)/maximum specific discharge capacity * 100%.
The attenuation ratio of the embodiment of the present invention 1 is 2.00%, and embodiment 2 is 2.94%, and embodiment 3 is 1.67%, is implemented Example 4 is 2.14%, and embodiment 5 is 3.12%, it follows that the average value of the attenuation ratio of Examples 1 to 5 is 2.37%, that is, say Even if bright after 30 circulations, decay also considerably less.The attenuation ratio of embodiment 6 is 20.95%.
And specific discharge capacity rapid decay of the comparative example 1 in cyclic process, the specific capacity after 30 circulations are only 30mAh g-1, can not work normally, attenuation ratio reaches 81.01%, is far longer than Examples 1 to 6, shows comparative example 1 at 80 DEG C Lower poor circulation.
(4), comparative example 2
Because not being specific group grouping of the invention not using ion liquid polymer of the invention in comparative example 2 It closes, without corresponding specific discharge capacity and charge and discharge cycles data.
In conclusion the present invention has following result：
1. the embodiment of the present invention 1~6 has high specific discharge capacity.
2. the embodiment of the present invention 1~6 has excellent charge-discharge performance：
Even if after Examples 1 to 5 is with the charge-discharge magnification charge and discharge 30 times circulations of 0.2C, being put at a high temperature of 80 DEG C The decaying very little of electric specific capacity, while higher specific discharge capacity can also be remain after 30 circulations；Although embodiment 6 have compared with Big decaying, but since it is with biggish first discharge specific capacity and maximum specific discharge capacity, after 30 circulations Specific discharge capacity (117mAh g still with higher-1), or specific discharge capacity after 30 circulations of significantly larger than comparative example.
3. electrolyte of the invention is in amorphous state by using specific solid electrolyte of the invention, have low Glass transition temperature (is lower than -40 DEG C), is conducive to the movement using the lithium ion in battery prepared by the solid electrolyte, It also ensures at 80 DEG C and when its battery being carried out charge and discharge under the charge-discharge magnification of 0.2C, excellent electric discharge can be obtained Specific capacity and cycle performance.
A possibility that being utilized in industry
The present invention is a kind of with the new group of subassembly comprising ion liquid polymer, polyethylene glycol and lithium salts by providing Solid electrolyte can make that lithium secondary battery prepared by the solid electrolyte is utilized at a high temperature of 80 DEG C with very good Specific discharge capacity and excellent cycle performance.
By by solid electrolyte application above-mentioned in lithium secondary battery, especially in Li/LiFePO4Lithium secondary battery In, excellent specific discharge capacity and cycle performance can be obtained under high temperature (80 DEG C).

Claims (14)

1. a kind of solid electrolyte, which is characterized in that include ion liquid polymer, polyethylene glycol and lithium salts.
2. solid electrolyte as described in claim 1, which is characterized in that the ion liquid polymer is the poly- of following formula (1) Close the polymer of object or following formula (2)：
In formula (1), n is positive integer；
In formula (2), m is positive integer；R1And R2For hydrogen atom or monovalent organic group；
B in formula (1) and (2)-For anion.
3. solid electrolyte as claimed in claim 2, which is characterized in that in formula (1), n is the integer of 300≤n≤4000.
4. solid electrolyte as claimed in claim 2, which is characterized in that in formula (2), m is the integer of 50≤m≤2000.
5. solid electrolyte as claimed in claim 2, which is characterized in that in formula (2), R1For hydrogen atom or or C1-C10 Straight-chain aliphatic alkyl；R2For the straight-chain aliphatic alkyl or ether of C1-C10.
6. solid electrolyte as claimed in claim 2, which is characterized in that in formula (1) and (2), B-For BF4 -、PF6 -、 (CF3SO2)2N-、(FSO2)2N-、[C(SO2F)3]-、CF3BF3 -、C2F5BF3 -、C3F7BF3 -、C4F9BF3 -Or (CF3SO2)2N-。
7. solid electrolyte as claimed in claim 2, which is characterized in that the R2Ether be：-CH2OCH3、- CH2CH2OCH3、-CH2CH2OCH2CH3、-CH2CH2OCH2CH2CH3Or-CH2CH2CH2OCH3。
8. solid electrolyte as described in claim 1, which is characterized in that the number-average molecular weight of the polyethylene glycol be 700~ 10000。
9. solid electrolyte as described in claim 1, which is characterized in that the lithium salts is LiY, wherein Y-For BF4 -、PF6 -、 (FSO2)2N-、[C(SO2F)3]-Or (CF3SO2)2N-。
10. solid electrolyte as described in claim 1, which is characterized in that the ion liquid polymer and the poly- second two The mass ratio of alcohol is 1:0.05~1:2.0.
11. solid electrolyte as described in claim 1, which is characterized in that the ion liquid polymer and the lithium salts Mass ratio is 1:0.1~1:1.0.
12. a kind of solid electrolyte film, which is characterized in that contain solid electrolyte described in any one of claim 1~11.
13. a kind of lithium secondary battery, which is characterized in that contain the solid electrolyte film described in claim 12.
14. a kind of manufacturing method of solid electrolyte film, includes the following steps：
It (1), is 1 according to the mass ratio of ion liquid polymer and polyethylene glycol:0.05~1:2.0 and ion liquid polymerization The mass ratio of object and lithium salts is 1:0.1~1:1.0 ratio is by the ion liquid polymer, the polyethylene glycol and described Lithium salts dissolves in a solvent, and mixed liquor is made in mixing；
(2), the resulting mixed liquor of step (1) is coated in template, solid electrolyte film is made.
CN201710343166.7A 2017-05-16 2017-05-16 A kind of solid electrolyte, solid electrolyte film and its manufacturing method and lithium secondary battery Pending CN108878963A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109904519A (en) * 2019-01-18 2019-06-18 北京理工大学 A kind of all solid state electrolyte material and its preparation method and application
CN111446497A (en) * 2020-04-03 2020-07-24 上海电气集团股份有限公司 Solid electrolyte and application thereof
CN114300789A (en) * 2021-12-29 2022-04-08 吉林大学 Preparation method of COF-based solid air positive electrode for solid lithium-air battery

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109904519A (en) * 2019-01-18 2019-06-18 北京理工大学 A kind of all solid state electrolyte material and its preparation method and application
CN109904519B (en) * 2019-01-18 2021-04-13 北京理工大学 All-solid-state electrolyte material and preparation method and application thereof
CN111446497A (en) * 2020-04-03 2020-07-24 上海电气集团股份有限公司 Solid electrolyte and application thereof
CN114300789A (en) * 2021-12-29 2022-04-08 吉林大学 Preparation method of COF-based solid air positive electrode for solid lithium-air battery
CN114300789B (en) * 2021-12-29 2024-04-30 吉林大学 Preparation method of COF-based solid air positive electrode for solid lithium air battery

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Application publication date: 20181123