CN108475819A - Solid electrolyte, solid electrolyte membrane and its manufacturing method and secondary cell - Google Patents

Solid electrolyte, solid electrolyte membrane and its manufacturing method and secondary cell Download PDF

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Publication number
CN108475819A
CN108475819A CN201680073615.4A CN201680073615A CN108475819A CN 108475819 A CN108475819 A CN 108475819A CN 201680073615 A CN201680073615 A CN 201680073615A CN 108475819 A CN108475819 A CN 108475819A
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solid electrolyte
ionic liquid
liquid polymer
battery
lithium
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杨立
章正熙
李晓伟
李斯剑
田阳
小川信之
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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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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Abstract

A kind of solid electrolyte, solid electrolyte membrane and its manufacturing method and secondary cell.The solid electrolyte includes ion liquid polymer, nitrile compounds and lithium salts.Including the battery of the solid electrolyte has extraordinary specific discharge capacity and excellent cycle performance under high charge-discharge magnification (such as 0.5C and 1.0C), it is suitable as battery use, is used particularly suitable for lithium secondary battery.

Description

Solid electrolyte, solid electrolyte membrane and method for producing same, and secondary battery
Cross Reference to Related Applications
The present application claims priority to chinese patent application No.201510955695.3, filed in china on 12/17/2015, which is incorporated herein by reference in its entirety.
Technical Field
The present invention relates to a solid electrolyte, a solid electrolyte membrane and a method for manufacturing the same, and a secondary battery.
Background
Electrolytes are an important component in electrochemical devices. At present, an electrolyte of a lithium secondary battery mainly comprises an organic solvent and lithium salt, and the organic solvent has a low boiling point and a low flash point, is flammable and volatile, and greatly influences the safety of the lithium secondary battery; meanwhile, with the expansion of the application field of lithium secondary batteries, the power density and energy density of the batteries are also continuously improved, and the potential safety hazard caused by organic electrolytes is more and more prominent.
The development of high specific energy lithium ion batteries is severely restricted by potential safety hazards such as ignition, explosion, liquid leakage and the like caused by organic electrolyte. Therefore, a solid electrolyte having advantages of high safety, good flexibility, and being capable of suppressing the growth of lithium dendrites has received much attention. However, the current solid electrolyte generally has the problems of low room temperature ionic conductivity, excessive electrode/solid electrolyte interface impedance and the like, and the practical application of the solid electrolyte in the lithium ion battery is limited.
Solid electrolytes for lithium secondary batteries have attracted much attention because they have good mechanical properties and high safety, can prevent leakage of an electrolyte solution, and do not require a separator. However, most solid-state electrolytes have low room temperature ionic conductivity (10)-5～10-6S cm-1) Limiting its practical application. To date, strategies have been taken to enhance the ionic conductivity, such as doping fillers, polymer blending, copolymerization, and crosslinking, however, the ionic conductivity is still less than ideal.
The ionic liquid has a series of excellent characteristics of basically non-volatility, high heat resistance, nonflammability, good electrochemical stability and the like, and can be compounded with lithium salt to be used as an electrolyte for a lithium secondary battery, so that the safety of the battery can be improved. So far, ionic liquids in the prior art exist single-center cationic ionic liquids and double-center cationic ionic liquids. However, such electrolytes still exist in a liquid phase in a lithium secondary battery, so that the problem of leakage of the battery cannot be solved, and the safety and stability of the battery are difficult to ensure.
Nitrile compounds have high polarity, which has good ability to dissolve various lithium salts.
For example, it was found that the electrolyte of succinonitrile/lithium bis (trifluoromethylsulfonyl) imide system has an ionic conductivity of 10 at room temperature-3S cm-1(Nature materials，2004，3，476-481)。
There are also electrolytes in which succinonitrile is introduced into the polymer matrix, for example, electrolytes including polyacrylonitrile (Electrochemistry Communications, 2008, 10, 1912-; electrolytes including chitin (Journal of Membrane Science, 2014, 468, 149-.
Recently, researchers have also developed the use of in situ synthesis techniques to produce a nitrile solid electrolyte (Advanced Energy Materials, 2015, 5, 1500353). The solid electrolyte is prepared by dissolving a nitrile ethylation polyvinyl alcohol (PVA-CN) monomer in a succinonitrile solid electrolyte to form a precursor, and then immersing the precursor into a polyacrylonitrile electrospun fiber membrane network for in-situ polymerization. However, when it is applied to a lithium secondary battery, the specific discharge capacity of the battery at room temperature and a low charge/discharge rate (0.1C) is also acceptable, but the specific discharge capacity is greatly reduced as the charge/discharge rate (for example, 0.5C or 1.0C) is increased.
Therefore, the electrolyte which does not reduce the discharge specific capacity of the prepared lithium secondary battery under high charge and discharge multiplying power, and has high discharge specific capacity and good cycle performance under high charge and discharge multiplying power is urgently required to be developed.
It is important for the electrolyte of a lithium secondary battery to ensure a high specific discharge capacity and excellent cycle performance of the battery at a high charge-discharge rate.
Disclosure of Invention
The present inventors have intensively studied the combination of an ionic liquid polymer and a nitrile compound in view of the above-described drawbacks of the prior art, and developed a solid electrolyte, a solid electrolyte membrane and a method for producing the same, and a secondary battery, each of which comprises the ionic liquid polymer, the nitrile compound, and a lithium salt according to the present invention.
The present invention provides a solid electrolyte comprising an ionic liquid polymer, a nitrile compound and a lithium salt.
In the solid electrolyte of the present invention, the ionic liquid polymer is one selected from a polymer of the following formula (1), and a polymer of the following formula (2):
wherein in the formula (1), n is more than or equal to 300 and less than or equal to 4000;
wherein m is more than or equal to 50 and less than or equal to 2000 in the formula (2); r1Is a hydrogen atom, or a linear aliphatic alkyl group of C1 to C10; r2Is a C1-C10 linear chain aliphatic alkyl group or an ether group.
B in the formulae (1) and (2)-Is BF4 -、PF6 -、(CF3SO2)2N-、(FSO2)2N-、[C(SO2F)3]-、CF3BF3 -、C2F5BF3 -、C3F7BF3 -、C4F9BF3 -、[C(SO2CF3)3]-、CF3SO3 -、CF3COO-、CH3COO-Any one of the above.
In the above formula (2), R2The ether group(s) may be: -CH2OCH3、-CH2CH2OCH3、-CH2CH2OCH2CH3、-CH2CH2OCH2CH2CH3or-CH2CH2CH2OCH3。
In the solid electrolyte of the present invention, the nitrile compound is one selected from malononitrile, succinonitrile, ethoxymethylenemalononitrile, terephthalonitrile, isophthalonitrile, phthalonitrile, and 4-fluorophthalonitrile.
The nitrile compound is preferably ethoxymethylenemalononitrile or succinonitrile.
In the solid electrolyte of the present invention, the lithium salt is LiY; wherein Y is BF4 -、PF6 -、(FSO2)2N-、[C(SO2F)3]-Or (CF)3SO2)2N-。
In the solid electrolyte, the mass ratio of the ionic liquid polymer to the nitrile compound is 1: 0.1-1: 2.0.
In addition, the mass ratio of the ionic liquid polymer to the lithium salt is 1: 0.1-1: 1.0.
The present invention also provides a solid electrolyte membrane containing the aforementioned solid electrolyte.
The present invention also provides a secondary battery containing the above solid electrolyte membrane.
The present invention also provides a secondary battery containing the above solid electrolyte.
Further, the present invention provides a solid electrolyte membrane using a solid electrolyte that is in an amorphous state and has a glass transition temperature of-80 ℃ or lower, and a secondary battery using the solid electrolyte membrane.
The secondary battery of the present invention may be a lithium ion battery.
The present invention also provides a method for producing the aforementioned solid electrolyte membrane, comprising the steps of:
(1) dissolving an ionic liquid polymer, a nitrile compound and a lithium salt in a solvent according to the mass ratio of the ionic liquid polymer to the nitrile compound of 1: 0.1-1: 2.0 and the mass ratio of the ionic liquid polymer to the lithium salt of 1: 0.1-1: 1.0, and mixing to prepare a mixed solution;
(2) and (2) coating the mixed solution obtained in the step (1) on a template to prepare the solid electrolyte membrane.
Technical effects
In the present invention, not only a combination of new components of the solid electrolyte but also a specific compounding ratio of these new components is provided, and the battery using the solid electrolyte of the present invention has very good specific discharge capacity and excellent cycle performance at high charge and discharge rates of 0.5C and 1.0C, compared to the prior art and its conventional polymer matrix.
Moreover, the solid electrolyte is in an amorphous state, has low glass transition temperature (minus 80 ℃), is beneficial to the movement of lithium ions of the battery, and also ensures that the battery has very good specific discharge capacity and excellent cycle performance under high charge-discharge rates of 0.5C and 1.0C.
Drawings
FIG. 1 shows the ionic liquid polymer obtained in example 11H NMR spectrum (deuterated solvent: deuterated acetone).
FIG. 2 shows Li/LiFePO formed by the solid electrolyte prepared in example 14The specific discharge capacity and the cycle performance of the battery under different charge-discharge rates (0.1C, 0.5C and 1.0C) are shown in the figure.
FIG. 3 shows the ionic liquid polymer obtained in example 21H NMR spectrum (deuterated solvent: deuterated dimethyl sulfoxide).
FIG. 4 shows Li/LiFePO formed by the solid electrolyte prepared in example 24The specific discharge capacity and the cycle performance of the battery under different charge-discharge rates (0.1C, 0.5C and 1.0C) are shown in the figure.
FIG. 5 shows the ionic liquid polymer obtained in example 31H NMR spectrum (deuterated solvent: deuterated dimethyl sulfoxide).
FIG. 6 shows Li/LiFePO formed by the solid electrolyte prepared in example 34The specific discharge capacity and the cycle performance of the battery under different charge-discharge rates (0.1C, 0.5C and 1.0C) are shown in the figure.
FIG. 7 shows Li/LiFePO formed by the solid electrolyte prepared in example 44The specific discharge capacity and the cycle performance of the battery under different charge-discharge rates (0.1C, 0.5C and 1.0C) are shown in the figure.
Fig. 8 is a schematic cross-sectional view showing an example of a lithium secondary battery.
Detailed Description
Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps) are not essential unless otherwise explicitly stated. The same applies to values and ranges, without limiting the invention.
In the present specification, the numerical range indicated by "to" includes numerical values before and after "to" as a minimum value and a maximum value, respectively.
In the numerical ranges recited in the present specification, the upper limit or the lower limit recited in a certain numerical range may be replaced with the upper limit or the lower limit recited in another numerical range recited in a stepwise manner. In the numerical ranges described in the present specification, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the examples.
In the present specification, the term "layer" or "film" includes a case where the layer or the film is formed over the entire region when the region is observed, and also includes a case where the layer or the film is formed only in a part of the region.
In the present specification, the term "laminate" means that layers are stacked, and two or more layers may be combined or two or more layers may be detachable.
The invention provides a solid electrolyte, which comprises an ionic liquid polymer, a nitrile compound and a lithium salt.
< Ionic liquid Polymer >
The ionic liquid polymer is one selected from the group consisting of a polymer of the following formula (1) and a polymer of the following formula (2). In the present invention, the ionic liquid polymer is a polymer obtained by introducing a polymerizable unsaturated group into a cationic species or an anionic species constituting an ionic liquid and polymerizing the resultant.
Wherein in the formula (1), n is more than or equal to 300 and less than or equal to 4000.
Wherein m is more than or equal to 50 and less than or equal to 2000 in the formula (2); r1Is a hydrogen atom, or a linear aliphatic alkyl group of C1 to C10; r2Is a C1-C10 linear chain aliphatic alkyl group or an ether group.
Specifically, in the formula (1), n represents an integer of 300 to 4000, preferably 500 to 3900, more preferably 1000 to 3700, still more preferably 1500 to 3500, and particularly preferably 2000 to 3000. In the formula (2), m represents an integer of 50 to 2000, preferably 200 to 1800, and more preferably 500 to 1500.
B in the formulae (1) and (2)-Examples thereof include: BF (BF) generator4 -、PF6 -、(CF3SO2)2N-、(FSO2)2N-、[C(SO2F)3]-、CF3BF3 -、C2F5BF3 -、C3F7BF3 -、C4F9BF3 -、[C(SO2CF3)3]-、CF3SO3 -、CF3COO-、CH3COO-Any one of the above.
The aforementioned C1-C10 linear aliphatic alkyl groups are, for example: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl.
The straight chain aliphatic alkyl group is preferably a straight chain aliphatic alkyl group of C1 to C5, and is exemplified by: methyl, ethyl, propyl, butyl, pentyl.
R mentioned above2The ether group of (a) is, for example: -CH2OCH3、-CH2CH2OCH3、-CH2CH2OCH2CH3、-CH2CH2OCH2CH2CH3or-CH2CH2CH2OCH3preferably-CH2CH2OCH3or-CH2CH2OCH2CH3。
R1Preferably a hydrogen atom or a methyl group.
R2Preferably methyl, ethyl, or-CH2CH2OCH3An ether group of (a).
< method for producing Ionic liquid Polymer >
The method for producing the ionic liquid polymer is not particularly limited, and the following production method may be used.
The method for producing the ionic liquid polymer of the general formula (1) can be, for example, the method described in the publications A. -L.Pont, R.Marcilla, I.De Meatza, H.Grande, D.Mecerreyes, Journal of Power Sources (2009, 188, 558. 563).
The ionic liquid polymer of the general formula (1) can be produced by the following production method:
an aqueous solution of polydimethyldiallylammonium chloride (20.00 mass% concentration) was dissolved in deionized water, and the solution was stirred to form a solution containing polydimethyldiallylammonium chloride.
The lithium salt is dissolved in deionized water and stirred to form a solution containing the lithium salt.
And mixing the two solutions according to the molar ratio of poly (dimethyl diallyl ammonium chloride) to lithium salt of 1: 1.2-1: 2.0, reacting for 2-8 hours under stirring to generate a solid, and filtering to collect the solid. And washing with deionized water until the eluate is detected to contain no halogen anion by silver nitrate, and finally drying in vacuum for 12-48 hours to prepare the ionic liquid polymer of the general formula (1).
The lithium salt may be used: lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium hexafluorophosphate, lithium tetrafluoroborate, and the like.
Viscosity average molecular weight M of the Ionic liquid Polymer of the general formula (1) of the present inventionvPreferably 1.0X 105～5.0×106g mol-1More preferably 3.0X 105～5.0×106g mol-1(polymethyl methacrylate as standard). If the viscosity average molecular weight M of the ionic liquid polymer of the formula (1)vGreater than or equal to 1.0 x 105g mol-1The sheet strength of the ionic liquid polymer obtained by dissolving the ionic liquid polymer in a solvent and drying the solution by coating can be sufficiently secured, and if the sheet strength is not more than 5.0X 106g mol-1The ionic liquid polymer can be easily dissolved in the solvent, and the workability of coating formation can be improved.
The ionic liquid polymer (1) is confirmed by1H NMR spectrum.
As the method for producing the ionic liquid polymer of the general formula (2), for example, the production methods described in the publications K.Yin, Z.X.Zhang, L.Yang, S. -i.Hirano, Journal of Power Sources (2014, 258, 150-154) can be used.
The ionic liquid polymer of the general formula (2) can be produced by the following production method:
the first step is as follows: dissolving an imidazole monomer containing olefin unsaturated groups in a solvent, and adding an initiator in a proportion that the initiator accounts for 0.2-1.0% of the mass of the imidazole monomer containing olefin unsaturated groups to carry out free radical polymerization. Stirring and reacting for 6-12 hours at 60-90 ℃ under the protection of protective gas such as argon and the like under a reflux state, filtering and washing the polymer by using a solvent after solid is generated, and drying in vacuum for 12-48 hours at 60-90 ℃ to prepare the polymer containing the imidazole structure.
The imidazole monomer containing olefin unsaturated groups can be: 1-vinylimidazole, 1-propenylimidazole, and the like.
The polymerization initiator may be: azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate.
The solvent may be: toluene, benzene, tetrahydrofuran, acetone, gamma-butyrolactone, N-methylpyrrolidone, and the like. Among them, acetone is preferred.
These solvents may be used alone or in combination of two or more.
Molecular weight of the polymer produced: its viscosity average molecular weight MvIs 1.0X 104～5.0×105g mol-1(polymethyl methacrylate as standard).
The second step is that: dissolving the imidazole structure-containing polymer prepared in the first step and halogenated hydrocarbon or halogenated ether in a molar ratio of 1: 1.5-1: 2.0 in a solvent, stirring and reacting at 40-80 ℃ for 24-72 hours, and removing the solvent by reduced pressure distillation. Collecting the solid, namely the separated polymer, washing the solid with anhydrous ether for 3 times, removing the ether by rotary evaporation, and drying in vacuum for 12-48 hours to obtain the halogen-containing anionic liquid polymer.
Among them, the solvents include: n, N-dimethylformamide, methanol, and the like.
The halogenated hydrocarbon may be: ethyl bromide, propyl bromide, butyl bromide, and the like.
The halogenated ether may be: 2-bromoethyl methyl ether, bromomethyl methyl ether, 2-bromoethyl ether, and the like.
The molecular weight of the prepared halogen-containing anionic liquid polymer is as follows: its viscosity average molecular weight MvPreferably 1.0X 105～5.0×106g mol-1(polymethyl methacrylate as standard).
The third step: and (3) dissolving the halogen-containing anionic liquid polymer and lithium salt obtained in the second step in deionized water according to the molar ratio of 1: 1.2-1: 2.0, stirring and reacting for 2-8 hours, generating solids, filtering and collecting the solids (precipitated polymer), and washing with deionized water until the eluate is detected to contain no halogen anions by using silver nitrate. And finally, drying for 12-48 hours in vacuum to obtain the ionic liquid polymer of the general formula (2).
The lithium salt may be: lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium hexafluorophosphate, lithium tetrafluoroborate, and the like.
Viscosity average molecular weight M of the Ionic liquid Polymer of the general formula (2) of the present inventionvPreferably 1.0X 105～5.0×106g mol-1(polymethyl methacrylate as a standard), more preferably 1.0X 105～1.0×106g mol-1. If the viscosity average molecular weight M of the ionic liquid polymer of the formula (2)vGreater than or equal to 1.0 x 105g mol-1The sheet strength of the ionic liquid polymer obtained by dissolving the ionic liquid polymer in a solvent and drying the solution by coating can be sufficiently secured, and if the sheet strength is not more than 5.0X 106g mol-1The ionic liquid polymer can be easily dissolved in the solvent, and the workability of coating formation can be improved.
The ionic liquid polymer is confirmed by1H NMR spectrum.
The nitrile compound used in the present invention is one selected from malononitrile, succinonitrile, ethoxymethylenemalononitrile, terephthalonitrile, isophthalonitrile, phthalonitrile and 4-fluorophthalonitrile, and preferably ethoxymethylenemalononitrile or succinonitrile.
The nitrile compound can be produced by a conventional production method or can be directly obtained from the market.
For example, succinonitrile produced by Fujian Xin scientific development Co., Ltd can be used as succinonitrile among nitrile compounds used in the present invention. The malononitrile, ethoxymethylenemalononitrile, terephthalonitrile, isophthalonitrile, phthalonitrile, and 4-fluorophthalonitrile of the present invention may also be nitrile compounds produced by the alatin company, and may be purchased as commercial products. Further, succinonitrile, malononitrile, ethoxymethylenemalononitrile, terephthalonitrile, isophthalonitrile, phthalonitrile, tetrafluorophthalonitrile, and 4-fluorophthalonitrile, which are available from Tokyo chemical industry Co., Ltd., can also be used.
The lithium salt used in the solid electrolyte of the present invention is not particularly limited as long as it can be used as an electrolyte of an electrolyte solution for a lithium ion battery, and examples thereof include inorganic lithium salts, fluorine-containing organic lithium salts, and oxalatoborate salts shown below.
The inorganic lithium salt may include LiPF6、LiBF4、LiAsF6、LiSbF6Etc. inorganic fluoride salt, LiClO4、LiBrO4、LiIO4Of a salt of a halogen acid of equal height, LiAlCl4And inorganic chloride salt, etc.
As the fluorine-containing organic lithium salt, LiCF is exemplified3SO3And perfluoroalkyl sulfonate, LiN (CF)3SO2)2、LiN(FSO2)2、LiN(CF3CF2SO2)2、LiN(CF3SO2)(C4F9SO9) And salts of perfluoroalkanesulfonyl amines, LiC (CF)3SO2)3、LiC(SO2F)3Salts of isoperfluoroalkylsulfonylmethylate, Li [ PF ]5(CF2CF2CF3)]、Li[PF4(CF2CF2CF3)2]、Li[PF3(CF2CF2CF3)3]、Li[PF5(CF2CF2CF2CF3)]、Li[PF4(CF2CF2CF2CF3)2]、Li[PF3(CF2CF2CF2CF3)3]And fluoroalkyl fluorophosphates, etc.
Examples of the oxalato borate salt include lithium dioxaoxalato borate and lithium difluorooxalato borate.
The lithium salt used in the solid electrolyte of the present invention is preferably lithium tetrafluoroborate, lithium hexafluorophosphate or lithium bis (trifluoromethylsulfonyl) imide, and any of the lithium salts produced by seonta chemical (zhang) ltd can be used and purchased as commercial products. Further, a lithium salt sold by Tokyo chemical industry Co., Ltd can be used.
In the invention, the mass ratio of the ionic liquid polymer to the nitrile compound is preferably 1: 0.1-1: 2.0, more preferably 1: 0.2-1: 1.8, and further preferably 1: 0.3-1: 1.5. If the mass ratio of the nitrile compound is more than 0.1, the electrochemical characteristics of the solid electrolyte membrane are improved, and if it is more than or equal to 0.3, the electrochemical characteristics are further improved. If the mass ratio of the nitrile compound is less than 2.0, the solid electrolyte membrane is inhibited from being sticky and easily peeled off from the mold, and preferably 1.5 or less.
In the invention, the mass ratio of the ionic liquid polymer to the lithium salt is 1: 0.1-1: 1.0, more preferably 1: 0.2-1: 0.9, and further preferably 1: 0.3-1: 0.8. If the mass ratio of the lithium salt is less than 0.1, the lithium ion carrier concentration in the solid electrolyte becomes low, the ionic conductivity tends to decrease, and if the mass ratio of the lithium salt exceeds 1.0, the solid electrolyte membrane tends to become brittle.
The invention also provides a solid electrolyte membrane which contains the solid electrolyte.
The present invention also provides a method for producing the aforementioned solid electrolyte membrane, comprising the steps of:
(1) the mass ratio of the ionic liquid polymer to the nitrile compound is preferably 1: 0.1-1: 2.0, more preferably 1: 0.2-1: 1.8, and further preferably 1: 0.3-1: 1.5. The mass ratio of the ionic liquid polymer to the lithium salt is preferably 1: 0.1-1: 1.0, more preferably 1: 0.2-1: 0.9, and even more preferably 1: 0.3-1: 0.8. Dissolving the ionic liquid polymer, the nitrile compound and the lithium salt in a solvent according to the proportion, and uniformly mixing to prepare a mixed solution;
(2) and (2) coating the mixed solution obtained in the step (1) on a template to prepare the solid electrolyte membrane.
The thickness of the solid electrolyte membrane is not particularly limited, and is greatly different depending on the cell configuration.
The solid electrolyte is applied to a secondary battery, namely the invention also provides a secondary battery which contains the ionic liquid polymer solid electrolyte membrane.
The solid electrolyte of the invention is preferably used in Li/LiFePO4In the battery.
In addition, the solid electrolyte of the present invention can contribute to improvement of safety of the lithium secondary battery due to flame retardancy. Further, since the electrolyte of the present invention is a solid state, a bipolar electrode can be used. By using the bipolar electrode, a battery having a high energy density, which cannot be achieved by a conventional lithium secondary battery, can be manufactured.
< methods for producing and assembling lithium Secondary Battery >
The description will be given with reference to fig. 8 of an example of the structure of the lithium secondary battery of the present embodiment, but the lithium secondary battery is not limited to the structure of fig. 8.
In the lithium secondary battery shown in fig. 8, the solid electrolyte membrane 3 is disposed between the negative electrode active material layer 2 and the positive electrode active material layer 4. The negative electrode active material layer 2 is formed on the negative electrode current collector 1, and the positive electrode active material layer 4 is formed on the positive electrode current collector 5. (hereinafter, the negative electrode active material layer 2 formed on the negative electrode current collector 1 is also referred to as a negative electrode sheet, and the positive electrode active material layer 4 formed on the positive electrode current collector 5 is also referred to as a positive electrode sheet.)
Hereinafter, each configuration of the lithium secondary battery of the present invention will be described.
1. Solid electrolyte layer
The solid electrolyte layer in the lithium secondary battery of the present invention is a layer formed between the positive electrode active material layer and the negative electrode active material layer. The solid electrolyte layer may include a solid electrolyte membrane, and may be formed by applying a solid electrolyte to an electrode, for example. In the present invention, the thickness of the solid electrolyte layer is not particularly limited, and is greatly different depending on the battery configuration.
2. Positive plate
The positive electrode sheet in the lithium secondary battery of the present invention is a layer containing at least a positive electrode active material (i.e., a positive electrode active material layer). The positive electrode active material layer may further contain at least one of a conductive material and a binder in addition to the positive electrode active material.
The kind of the positive electrode active material is not particularly limited, and examples thereof include an oxide active material, and examples thereof include LiCoO2、LiMnO2、LiNiO2、LiVO2、LiNi1/3Co1/3Mn1/3O2Iso-halite lamellar type active substances; LiMn2O4、Li(Ni0.5Mn1.5)O4Isospinel type active materials; LiFePO4、LiMnPO4、LiNiPO4、LiCuPO4And olivine-type active substances. From the viewpoint of thermal stability, lithium iron phosphate (LiFePO) is preferably used4)。
The conductive material is not particularly limited as long as it has a desired electron conductivity, and examples thereof include carbon materials. Examples of the carbon material include carbon black such as acetylene black, ketjen black, furnace black, and thermal black.
On the other hand, the binder is not particularly limited as long as it is chemically and electrically stable, and examples thereof include fluorine-based binders such as polyvinylidene fluoride (PVDF) and Polytetrafluoroethylene (PTFE). From the viewpoint of capacity, the content of the positive electrode active material in the positive electrode active material layer is preferably increased. The thickness of the positive electrode active material layer is not particularly limited, and is greatly different depending on the battery configuration.
Examples of the material of the positive electrode current collector include SUS, aluminum, nickel, iron, titanium, and carbon.
3. Negative plate
The negative electrode sheet in the lithium secondary battery of the present invention is a layer containing at least a negative electrode active material (i.e., a negative electrode active material layer). The negative electrode active material layer may further contain at least one of a conductive material and a binder in addition to the negative electrode active material.
The kind of the negative electrode active material is not particularly limited, and examples thereof include a metal active material and a carbon active material. Examples of the metal active material include a metal simple substance, an alloy, and a metal oxide. Examples of the metal element contained In the metal active material include Li, Al, Mg, In, Si, and Sn. As the negative electrode active material, Li metal, carbon, Li are preferably used4Ti5O12。
As the conductive material and the binder, the same materials as those described in the positive electrode active material layer can be used. From the viewpoint of capacity, the more the content of the anode active material in the anode active material layer is, the more preferable it is. The thickness of the negative electrode active material layer is not particularly limited, and varies greatly depending on the battery configuration.
Examples of the material of the negative electrode current collector include SUS, copper, nickel, and carbon.
4. Other constitution
The material of the battery case may be any general material, and examples thereof include SUS, Al laminated films, and the like. Examples of the shape of the lithium secondary battery of the present invention include a coin shape, a laminate shape, a cylindrical shape, and a square shape.
The method of assembling the lithium secondary battery of the present invention may be:
and stacking the positive plate shell cover, the positive plate, the prepared solid electrolyte membrane, the negative plate and the negative plate shell cover of the battery in a glove box under the protection of argon according to the sequence from bottom to top to form a lamination, and then placing the lamination on a punching machine for punching to ensure that the positive plate shell cover and the negative plate shell cover of the battery are tightly locked with each other, thus finishing the preparation and assembly of the lithium secondary battery. Specifically, the negative electrode sheet was cut into a circular shape having a diameter of 1.6cm, the positive electrode sheet was cut into a circular shape having a diameter of 1.4cm, and the solid electrolyte membrane was cut into a circular shape having a diameter of 1.9cm, respectively. Next, a positive electrode sheet, a solid electrolyte membrane, a negative electrode sheet, (and a circular copper foil cut to a diameter of 1.4cm as a separator) were stacked in this order in a coin outer case (positive electrode case cover) made of stainless steel having a diameter of 2.0cm and a thickness of 0.3cm (CR2032 type). Next, a lid (negative electrode case lid) made of stainless steel was placed on the container through a gasket made of polypropylene, and the container was sealed by pressing. Thus, a lithium secondary battery (button battery) was produced.
The battery components other than the solid electrolyte membrane of the present invention, such as the positive electrode case, the positive electrode tab, the negative electrode tab, and the negative electrode case, can be obtained by using the battery components manufactured by the known methods, or by various vendors.
In addition, a bipolar type in which a plurality of single cells in which a negative electrode mixture layer, a solid electrolyte, and a positive electrode mixture layer are stacked may be produced.
< measurement of molecular weight >
The viscosity average molecular weight test method comprises the following steps:
the viscosity of the polymer at 25 ℃ was measured using a Ubbelohde viscometer using polymethyl methacrylate as a standard [ η%]Then by the formula [ η ]]＝KMv(where K represents a dilatation factor whose value depends on temperature, polymer, solvent properties, MvRepresents a viscosity average molecular weight, [ η ]]Representing the viscosity of the polymer) to obtain a viscosity average molecular weight Mv。
<Glass transition temperature T of the solid electrolyte of the inventiongMeasurement of (2)>
The measurement was carried out by Differential Scanning Calorimetry (DSC) using a TA Instruments model Q2000 differential thermal analyzer. Two cycles are typically performed, and using the DSC curve data for cycle 2, the glass transition temperature is obtained: firstly, cooling a solid electrolyte sample from room temperature to minus 80 ℃, keeping the temperature for 10 minutes, then heating to 200 ℃ at the speed of 10 ℃/minute, keeping the temperature for 5 minutes, and then cooling to minus 80 ℃ at the speed of 10 ℃/minute as the 1 st cycle. The above operation was repeated 1 time as the 2 nd cycle.
< measurement of the ion conductivity of the solid electrolyte according to the present invention >
The ionic conductivity of the solid electrolyte was measured by the ac impedance method using the apparatus of CHI600D electrochemical workstation. The sample to be tested is prepared by the following steps: the stainless steel electrode/solid electrolyte/stainless steel electrode composition sequence constitutes a simulated cell, which was then tested for ac impedance at 25 ℃. Before testing, the simulated battery is kept stand at each temperature point for 1h at constant temperature, the frequency range is 1 Hz-100 KHz, and the alternating current amplitude is 5 mV. The conductivity calculation formula is as follows:
wherein R is a bulk impedance (Ω) of the solid electrolyte, L represents a thickness (cm) of the solid electrolyte membrane, and S represents an effective area (cm) of the solid electrolyte membrane2)。
< measurement of specific discharge Capacity >
The specific discharge capacity of the battery is measured by the following method:
the obtained solid electrolyte was used to prepare a battery, and the battery was charged and discharged at a voltage range of 2.5 to 4.0V and a constant current of 0.1C, 0.5C or 1.0C while being left at a temperature of 25C, and the first discharge capacity and the discharge capacity up to 10 cycles of the battery were measured using a charging and discharging device of CT2001A (testing device, lan battery testing system-CT 2001A, blue bo, mart).
The calculation formula of the specific discharge capacity is as follows:
specific discharge capacity (mAh g)-1) Actual discharge capacity (mAh)/mass (g) of the active material in the positive electrode sheet.
Further, the data of the cycle performance graph in the drawings are obtained as follows:
the obtained data of specific discharge capacity was plotted on the ordinate and the number of cycles was plotted on the abscissa to prepare a cycle performance chart.
< example >
The following examples are further illustrative of the present invention and do not limit the scope of the invention.
< example 1>
[1] Preparation of poly (dimethyldiallylammonium bis (trifluoromethylsulfonyl) imide) -based solid electrolyte
Preparation of [1-1] poly (dimethyldiallylammonium bis (trifluoromethylsulfonyl) imide) ionic liquid polymer:
into a 250.00mL beaker were added 20.00g of an aqueous solution (20 mass%) of poly (dimethyldiallylammonium chloride) (manufactured by Aldrich Co.) and 100.00mL of deionized water, and the mixture was magnetically stirred for 1 hour to form a solution containing poly (dimethyldiallylammonium chloride).
In another 50.00mL beaker, 8.52g (29.68mmol) of lithium bis (trifluoromethylsulfonyl) imide (a product of Sentian chemical Co., Ltd.) and 10.00mL of deionized water were added in this order, and the mixture was completely dissolved by magnetic stirring to form a solution containing lithium bis (trifluoromethylsulfonyl) imide.
The two solutions were mixed and ion-exchanged for 2 hours to form a solid (precipitated polymer), which was collected by filtration, washed with water until the eluate was free of chloride ions by silver nitrate detection, and finally dried under vacuum at 105 ℃ for 72 hours. The structural formula of the obtained ionic liquid polymer poly (dimethyl diallyl ammonium bis (trifluoromethyl sulfonyl) imide) is as follows:
the viscosity average molecular weight of the ionic liquid polymer is 2.11 multiplied by 106g mol-1。
The chemical structure of the ionic liquid polymer adopts1The H NMR spectrum was characterized as shown in FIG. 1.
For the solid electrolyte prepared in example 11The H NMR spectrum was measured by the following method using AVANCE III HD 400 manufactured by Bruker BioSpin.
Deuterated solvents: deuterated acetone
Resonance frequency: 6 to 440MHz
Resolution ratio: < 0.005Hz
Pulse width: 1H is less than or equal to 9 mu sec
Chemical shift value benchmark: tetramethylsilane (TMS)0ppm
It can be seen that the results of the spectra are consistent with the expected structure.
[1-2] preparation of solid electrolyte:
1.00g of the prepared poly (dimethyldiallylammonium bis (trifluoromethylsulfonyl) imide) was added to a single-neck round-bottom flask, 20.00g of acetone was added as a solvent, the mixture was dissolved by magnetic stirring, 1.00g of succinonitrile (a product of Fujia Xin scientific and technological development Co., Ltd.) as a nitrile compound and 0.50g of lithium bis (trifluoromethylsulfonyl) imide (a product of Sentian chemical Co., Ltd.) as a lithium salt were added, and the mixture was magnetically stirred at 25 ℃ for 12 hours to obtain a transparent poly (dimethyldiallylammonium bis (trifluoromethylsulfonyl) imide) solid electrolyte as a mixed solution.
[1-3] preparation of solid electrolyte Membrane:
the poly (dimethyldiallylammonium bis (trifluoromethylsulfonyl) imide) solid electrolyte of the obtained mixed solution was coated on a polytetrafluoroethylene template, and then vacuum-dried at 30 ℃ for 48 hours to obtain a solid electrolyte membrane. The glass transition temperature T of the solid electrolyte membranegLess than-80 deg.C, and has an ionic conductivity of 5.74 × 10 at 25 deg.C-4S cm-1。
[1-4] preparation of lithium secondary batteries:
will contain lithium iron phosphate (LiFePO)4) A positive electrode sheet as a positive electrode active material, the solid electrolyte membrane obtained, and a negative electrode sheet with lithium (Li) as a negative electrode active material are stacked in this order from bottom to top to form a stacked electrode, and then the stacked electrode is pressed by a press machine to obtain Li/LiFePO4A battery.
The prepared Li/LiFePO4The cell was tested for constant current charge and discharge at 25 deg.C and a voltage range of 2.5-4.0V for 10 cycles each at charge and discharge rates of 0.1C, 0.5C and 1.0C.
The measurement data results of example 1 are summarized in tables 2 to 3 and fig. 1 to 2.
< example 2>
[2] Preparation of poly (1- (2-methoxyethyl) -3-vinylimidazolium bis (trifluoromethylsulfonyl) imide) based solid electrolyte
Preparation of [2-1] poly (1- (2-methoxyethyl) -3-vinylimidazolium bis (trifluoromethylsulfonyl) imide) ionic liquid polymer:
(1) 1-vinyl imidazole is used as a reaction monomer, azobisisobutyronitrile is used as an initiator, and toluene is used as a reaction solvent to carry out free radical polymerization, wherein the initiator accounts for 0.5 percent of the mass of the monomer. The reaction was stirred and refluxed for 8 hours at 65 ℃ under the protection of Ar atmosphere. After solid generation, filtering, washing with acetone, and vacuum drying at 75 ℃ for 24 hours to obtain the polyvinyl imidazole.
Viscosity average molecular weight M of polyvinyl imidazolevIs 3.39X 105g mol-1。
(2) 4.00g of the thus-prepared polyvinylimidazole and 8.90g of 2-bromoethyl methyl ether (63.83mmol) were dissolved in 60.00mL of N, N-dimethylformamide, and the reaction was stirred at 60 ℃ for 48 hours, the solvent was distilled off under reduced pressure, the solid was collected, washed 3 times with anhydrous diethyl ether, the diethyl ether was removed by rotary evaporation, and dried under vacuum for 24 hours to obtain poly (1- (2-methoxyethyl) -3-vinylimidazolium bromide).
Viscosity average molecular weight M of poly (1- (2-methoxyethyl) -3-vinylimidazole bromide)vIs 5.62X 105g mol-1。
(3) 3.50g of the prepared poly (1- (2-methoxyethyl) -3-vinylimidazole bromide) and 5.17g (18.02mmol) of lithium bis (trifluoromethylsulfonyl) imide (a product of Sentian chemical Co., Ltd.) were dissolved in 20.00mL of deionized water, and magnetically stirred at room temperature for 6 hours to form a solid, which was collected by filtration. Washing with deionized water until the eluate is detected to be free of halogen anions by silver nitrate, and finally drying under vacuum at 75 ℃ for 24 hours to obtain an ionic liquid polymer poly (1- (2-methoxyethyl) -3-vinylimidazolium bis (trifluoromethylsulfonyl) imide) with a structural formula:
the chemical structure of the ionic liquid polymer adopts1The H NMR spectrum was characterized as shown in FIG. 3. For the solid electrolyte prepared in example 21The H NMR spectrum was measured by the following method using AVANCE III HD 400 manufactured by Bruker BioSpin.
Deuterated solvents: deuterated dimethyl sulfoxide
Resonance frequency: 6 to 440MHz
Resolution ratio: < 0.005Hz
Pulse width: 1H is less than or equal to 9 mu sec
Chemical shift value benchmark: tetramethylsilane (TMS)0ppm
It can be seen that the spectral results are consistent with the expected structure.
Viscosity average molecular weight M of the ionic liquid polymervIs 7.32X 105g mol-1。
[2-2] preparation of solid electrolyte:
1.00g of the prepared poly (1- (2-methoxyethyl) -3-vinylimidazo bis (trifluoromethylsulfonyl) imide) was charged into a single-neck round-bottom flask, 20.00g of acetone as a solvent was added and dissolved by magnetic stirring, and 0.60g of ethoxymethylenemalononitrile (a product of Aladdin Co.) and 0.50g of lithium bis (trifluoromethylsulfonyl) imide (a product of Sengstand Co., Ltd.) as a nitrile compound were further added and mixed by magnetic stirring at 25 ℃ for 12 hours to obtain a transparent mixed solution of poly (1- (2-methoxyethyl) -3-vinylimidazo bis (trifluoromethylsulfonyl) imide) solid electrolyte.
[2-3] preparation of solid electrolyte Membrane:
the poly (1- (2-methoxyethyl) -3-vinylimidazolium bis (trifluoromethylsulfonyl) imide) solid electrolyte of the obtained mixed solution was coated on a polytetrafluoroethylene template, and then vacuum-dried at 25 ℃ for 48 hours to obtain a solid electrolyte membrane. The glass transition temperature T of the solid electrolyte membranegLess than-80 deg.C, and has an ionic conductivity of 2.98 × 10 at 25 deg.C-4S cm-1。
[2-4] preparation of lithium secondary battery:
will contain lithium iron phosphate (LiFePO)4) A positive electrode sheet as a positive electrode active material, the solid electrolyte membrane obtained, and a negative electrode sheet with lithium (Li) as a negative electrode active material are stacked in this order from bottom to top to form a stacked electrode, and then the stacked electrode is pressed by a press machine to obtain Li/LiFePO4A battery.
The prepared Li/LiFePO4The cell was tested for constant current charge and discharge at 25 deg.C and a voltage range of 2.5-4.0V for 10 cycles each at charge and discharge rates of 0.1C, 0.5C and 1.0C.
The measurement data results of example 2 are summarized in tables 2 to 3 and fig. 3 to 4.
< example 3>
[3] Preparation of poly (1- (2-methoxyethyl) -3-vinylimidazole hexafluorophosphate) based solid electrolyte
Preparation of [3-1] poly (1- (2-methoxyethyl) -3-vinylimidazole hexafluorophosphate) ionic liquid polymer:
(1) 1-vinyl imidazole is used as a reaction monomer, azobisisobutyronitrile is used as an initiator, and toluene is used as a reaction solvent to carry out free radical polymerization, wherein the initiator accounts for 0.5 percent of the mass of the monomer. The reaction was stirred and refluxed for 8 hours at 65 ℃ under the protection of Ar atmosphere. After solid generation, filtering, washing with acetone, and vacuum drying at 75 ℃ for 24 hours to obtain the polyvinyl imidazole.
Viscosity average molecular weight M of polyvinyl imidazolevIs 3.39X 105g mol-1。
(2) 4.00g of the thus-prepared polyvinylimidazole and 8.90g of 2-bromoethyl methyl ether (63.83mmol) were dissolved in 60.00mL of N, N-dimethylformamide, and the reaction was stirred at 60 ℃ for 48 hours, the solvent was distilled off under reduced pressure, the solid was collected, washed 3 times with anhydrous diethyl ether, the diethyl ether was removed by rotary evaporation, and dried under vacuum for 24 hours to obtain poly (1- (2-methoxyethyl) -3-vinylimidazolium bromide).
Viscosity average molecular weight M of poly (1- (2-methoxyethyl) -3-vinylimidazole bromide)vIs 5.62X 105g mol-1。
(3) 3.50g of the prepared poly (1- (2-methoxyethyl) -3-vinylimidazolium bromide) and 2.74g (18.02mmol) of lithium hexafluorophosphate (product of Sengsta chemical Co., Ltd.) were dissolved in 20.00mL of deionized water, and magnetic stirring was carried out at room temperature for 6 hours to form a solid, which was collected by filtration. Then washing with deionized water until the eluate is detected to be free of halogen anions by silver nitrate, and finally drying in vacuum at 75 ℃ for 24 hours to obtain an ionic liquid polymer poly (1- (2-methoxyethyl) -3-vinylimidazole hexafluorophosphate), which has the structural formula:
the chemical structure of the ionic liquid polymer adopts1The H NMR spectrum was characterized as shown in FIG. 5. For the solid electrolyte prepared in example 31The H NMR spectrum was measured by the following method using AVANCE III HD 400 manufactured by Bruker BioSpin.
Deuterated solvents: deuterated dimethyl sulfoxide
Resonance frequency: 6 to 440MHz
Resolution ratio: < 0.005Hz
Pulse width: 1H is less than or equal to 9 mu sec
Chemical shift value benchmark: tetramethylsilane (TMS)0ppm
It can be seen that the spectral results are consistent with the expected structure.
Viscosity average molecular weight M of the ionic liquid polymervIs 6.35X 105g mol-1。
[3-2] preparation of solid electrolyte:
1.00g of the prepared poly (1- (2-methoxyethyl) -3-vinylimidazolium hexafluorophosphate) was charged into a single-neck round-bottom flask, 20.00g of acetone was added as a solvent, and dissolved by magnetic stirring, and 0.60g of ethoxymethylenemalononitrile (a product of Alatin Co.) as a nitrile compound and 0.40g of lithium hexafluorophosphate (a product of Sengstaken chemical Co., Ltd.) as a lithium salt were further added and mixed by magnetic stirring at 25 ℃ for 12 hours to obtain a poly (1- (2-methoxyethyl) -3-vinylimidazolium hexafluorophosphate) solid electrolyte as a transparent mixed solution.
[3-3] preparation of solid electrolyte Membrane:
the poly (1- (2-methoxyethyl) -3-vinylimidazolium hexafluorophosphate) solid electrolyte of the obtained mixed solution was coated on a polytetrafluoroethylene template, and then vacuum-dried at 30 ℃ for 48 hours to obtain a solid electrolyte membrane. The glass transition temperature T of the solid electrolyte membranegLess than-80 deg.C, and has an ionic conductivity of 1.08X 10 at 25 deg.C-4S cm-1。
[3-4] preparation of lithium secondary batteries:
will contain lithium iron phosphate (LiFePO)4) A positive electrode sheet as a positive electrode active material, the solid electrolyte membrane obtained, and a negative electrode sheet with lithium (Li) as a negative electrode active material are stacked in this order from bottom to top to form a stacked electrode, and then the stacked electrode is pressed by a press machine to obtain Li/LiFePO4A battery.
The measurement data results of example 3 are summarized in tables 2 to 3 and fig. 5 to 6.
< example 4>
A solid electrolyte and a solid electrolyte membrane, and a lithium secondary battery were formed as in example 1, except that the weight ratio of the ionic liquid polymer and succinonitrile in example 1 was changed to 1: 1.5.
The glass transition temperature T of the solid electrolyte membranegLess than-80 deg.C, and has an ionic conductivity of 3.56 × 10 at 25 deg.C-4S cm-1。
The measurement data results of example 4 are summarized in tables 2 to 3 and fig. 7.
< example 5>
A solid electrolyte and a solid electrolyte membrane were formed in the same manner as in example 2, except that the weight ratio of the ionic liquid polymer and ethoxymethylenemalononitrile in example 2 was changed to 1: 0.3.
The glass transition temperature T of the solid electrolyte membranegLess than-80 deg.C, and has an ionic conductivity of 1.01 × 10 at 25 deg.C-4S cm-1。
The results of the data measured in example 5 are summarized in table 2.
< comparative example >
The composition and the related preparation of the solid electrolyte of the comparative examples can be referred to in the cited document Advanced Energy Materials (2015, 5, 1500353).
The solid electrolyte comprises the following components: polyacrylonitrile (product of J & KScientific ltd.), nitrile ethylated polyvinyl alcohol (product of Shin-Etsu Chemical), succinonitrile (product of alatin corporation), and LiTFSI lithium salt (product of TCI corporation). Nitrile ethylated polyvinyl alcohol: succinonitrile: LiTFSI ═ 5: 83: 10 (mass ratio). The ionic liquid polymer of the present invention was not used and contained in comparative example 1.
Polyacrylonitrile is used as a matrix, nitrile ethylated polyvinyl alcohol is used as a crosslinking component to be compounded with succinonitrile and lithium salt to prepare the solid electrolyte, and the obtained solid electrolyte is applied to Li/LiFePO4In the battery.
At 25 deg.C and 2.4-4.2V voltage, constant current of 0.1CThe first discharge specific capacity of the charge-discharge determination battery is 155mAh g-1And the specific discharge capacity after 10 cycles is 150mAh g-1And discharge specific capacities at 0.5C and 1.0C were 125mAh g, respectively-1And 98mAh g-1And the specific discharge capacity after 10 cycles is 120mAh g respectively-1And 85mAh g-1。
Compounding them to prepare solid electrolyte with ion conductivity of 4.49X 10 at 25 deg.C-4S cm-1。
The results are shown in tables 2 to 3.
TABLE 1
FIG. 2 shows Li/LiFePO formed by the solid electrolyte prepared in example 14The specific discharge capacity and the cycle performance of the battery under different charge-discharge rates (0.1C, 0.5C and 1.0C) are shown in the figure.
The battery is charged and discharged at constant current at 25 ℃ with the multiplying power of 0.1C, 0.5C and 1.0C respectively, and the first discharge specific capacity is 150mAh g-1、132mAh g-1And 121mAh g-1And the discharge specific capacities after 10 cycles are 152mAh g respectively-1、130mAh g-1And 116mAh g-1。
FIG. 4 shows Li/LiFePO formed by the solid electrolyte prepared in example 24The specific discharge capacity and the cycle performance of the battery under different charge-discharge rates (0.1C, 0.5C and 1.0C) are shown in the figure.
The battery is charged and discharged at constant current at 25 deg.C with multiplying power of 0.1C, 0.5C and 1.0C, and the discharge specific capacity is 135mAh g-1(0.1C)、129mAh g-1(0.5C) and 119mAh g-1(1.0C), the specific discharge capacity after 10 cycles is 143mAh g respectively-1(0.1C)、128mAh g-1(0.5C) and 113mAh g-1(1.0C)。
FIG. 6 shows Li/LiFePO formed by the solid electrolyte prepared in example 34The specific discharge capacity and the cycle performance of the battery under different charge-discharge rates (0.1C, 0.5C and 1.0C) are shown in the figure.
The battery is charged and discharged at constant current at 25 deg.C with 0.1C, 0.5C and 1.0C multiplying power, and the specific discharge capacityIs 132mAh g-1(0.1C)、128mAh g-1(0.5C) and 112mAh g-1(1.0C), the specific discharge capacity after 10 cycles is 138mAh g respectively-1(0.1C)、126mAh g-1(0.5C) and 110mAh g-1(1.0C)。
FIG. 7 shows Li/LiFePO formed by the solid electrolyte prepared in example 44The specific discharge capacity and the cycle performance of the battery under different charge-discharge rates (0.1C, 0.5C and 1.0C) are shown in the figure.
The battery is charged and discharged at constant current at 25 deg.C with multiplying power of 0.1C, 0.5C and 1.0C, and the discharge specific capacity is 145mAh g-1(0.1C)、127mAh g-1(0.5C) and 116mAh g-1(1.0C), the specific discharge capacity after 10 cycles is 146mAh g respectively-1(0.1C)、126mAh g-1(0.5C) and 111mAh g-1(1.0C)。
The foregoing data are summarized in tables 2 and 3 below.
TABLE 2
The solid electrolyte membranes of examples 1-5 were amorphous, had only a glass transition temperature, and had no melting point.
The solid electrolyte membrane of the comparative example is a crystalline polymer and has a melting point.
TABLE 3 Li/LiFePO4Comparison of specific discharge capacity of batteries
As is apparent from table 3, in the batteries formed of the solid electrolytes of examples 1, 2, 3 and 4 of the present invention, the first discharge specific capacities at the charge and discharge rate of 0.5C were all 125mAh g or more-1It is a high specific discharge capacity. The batteries of examples 1 to 4 all had a specific first discharge capacity of 112mAh g or more even at a high charge-discharge rate of 1.0C-1。
In the comparative example, the specific first discharge capacity was 125mAh g at a charge/discharge rate of 0.5C-1However, its first discharge specific capacity is reduced to 100mAh g or less at a high charge-discharge rate of 1.0C-198mAh g-1It cannot work normally.
The cycle performance was evaluated as the decay of the specific discharge capacity after 10 cycles.
At a charge-discharge rate of 0.5C, the attenuation ratio of example 1 of the present invention was 1.51%, that of example 2 was 0.78%, that of example 3 was 1.56%, and that of example 4 was 0.79%. From this, it is understood that the average attenuation ratio of examples 1 to 4 is 1.16%, which shows that the attenuation is very small even after 10 cycles.
In the comparative example, the decay rate of the specific discharge capacity after 10 cycles at the charge-discharge rate of 0.5C is 4.00%, the decay is obvious, and the cycle performance is poor.
In addition, the decay rate of the specific discharge capacity after 10 cycles at the charge and discharge rate of 1.0C was 4.13% in example 1, 5.04% in example 2, 1.79% in example 3, and 4.31% in example 4. From this, it was found that the average value of the attenuation ratio was 3.82% and only about 4% even after 10 cycles.
In contrast, in the comparative example, the decay rate of the specific discharge capacity after 10 cycles at a charge/discharge rate of 1.0C was 13.27%, and the decay was very significant, and the cycle performance was poor.
From the above analysis of the attenuation data, the following can be found:
(1) at a charge-discharge rate of 0.5C, the average value of the specific discharge capacity decay rate after 10 cycles of the batteries of examples 1 to 4 of the present invention was only 1.16%, which was much less than 4.00% of that of the comparative example.
(2) At a charge-discharge rate of 1.0C, the average value of the decay rate of the specific discharge capacity after 10 cycles at a charge-discharge rate of 1.0C in the batteries formed from the solid electrolytes of examples 1 to 4 of the present invention was 3.82%, which corresponds to the decay rate (4.00%) of the specific discharge capacity after 10 cycles at a charge-discharge rate of comparative example 0.5C.
The decay rate of the specific discharge capacity after 10 cycles at the charge and discharge rate of 1.0C in the comparative example is 13.27%, which is 3.5 times of the decay rate of the specific discharge capacity after 10 cycles at the charge and discharge rate of 1.0C in the batteries formed by the solid electrolytes in examples 1 to 4 of the present invention, and the decay rate is very high, the cycle performance of the battery is very poor, and the battery has poor cycle usability.
That is, the batteries formed of the solid electrolytes of examples 1 to 4 according to the present invention are very important as a battery, which has a small decrease in specific discharge capacity after 10 cycles at a high charge/discharge rate of 1.0C, and can maintain a very stable specific discharge capacity after 10 cycles.
From the analysis of the initial discharge specific capacity data and the attenuation ratio of the initial discharge specific capacity to the discharge specific capacity after 10 cycles, the solid electrolyte and the battery thereof have very good discharge specific capacity and excellent cycle performance under high charge-discharge multiplying power (0.5C and 1.0C), are very suitable for being used as a battery, and are particularly suitable for being used in a lithium secondary battery.
That is, in the present invention, not only a combination of new components of the solid electrolyte but also a specific compounding ratio of these new components is provided, so that the battery thereof has very good specific discharge capacity and excellent cycle performance at high charge and discharge rates of 0.5C and 1.0C, compared to the prior art and its conventional polymer matrix.
Moreover, the solid electrolyte is amorphous, has very low glass transition temperature (minus 80 ℃), is beneficial to the movement of lithium ions of the battery, and also ensures that the battery has very good specific discharge capacity and excellent cycle performance under high charge-discharge multiplying power (0.5C and 1.0C).
Possibility of industrial utilization
By applying the solid electrolyte of the present invention to a lithium secondary battery, particularly in Li/LiFePO4In the lithium secondary battery, excellent specific discharge capacity and cycle performance can be obtained at a high charge-discharge rate.

Claims (16)

  1. A solid electrolyte characterized by comprising an ionic liquid polymer, a nitrile compound and a lithium salt.
  2. The solid-state electrolyte of claim 1, wherein the ionic liquid polymer is one selected from the group consisting of a polymer of the following formula (1), and a polymer of the following formula (2):
    wherein in the formula (1), n is more than or equal to 300 and less than or equal to 4000;
    wherein m is more than or equal to 50 and less than or equal to 2000 in the formula (2); r1Is a hydrogen atom, or a linear aliphatic alkyl group of C1 to C10; r2Is a C1-C10 linear chain aliphatic alkyl group or an ether group.
  3. The solid electrolyte of claim 2, wherein B in formulas (1) and (2)-Is BF4 -、PF6 -、(CF3SO2)2N-、(FSO2)2N-、[C(SO2F)3]-、CF3BF3 -、C2F5BF3 -、C3F7BF3 -、C4F9BF3 -、[C(SO2CF3)3]-、CF3SO3 -、CF3COO-、CH3COO-Any one of the above.
  4. The solid electrolyte of claim 2, wherein R is2The ether group of (A) is: -CH2OCH3、-CH2CH2OCH3、-CH2CH2OCH2CH3、-CH2CH2OCH2CH2CH3or-CH2CH2CH2OCH3。
  5. The solid electrolyte of claim 1, wherein the nitrile compound is selected from one of malononitrile, succinonitrile, ethoxymethylenemalononitrile, terephthalonitrile, isophthalonitrile, phthalonitrile, and 4-fluorophthalonitrile.
  6. The solid electrolyte of claim 5, wherein the nitrile compound is ethoxymethylenemalononitrile or succinonitrile.
  7. The solid-state electrolyte of claim 1, wherein the lithium salt is LiY; wherein Y is BF4 -、PF6 -、(FSO2)2N-、[C(SO2F)3]-Or (CF)3SO2)2N-。
  8. The solid electrolyte according to claim 1, wherein the mass ratio of the ionic liquid polymer to the nitrile compound is 1: 0.1 to 1: 2.0.
  9. The solid-state electrolyte of claim 1, wherein the mass ratio of the ionic liquid polymer to the lithium salt is 1: 0.1 to 1: 1.0.
  10. A solid electrolyte membrane comprising the solid electrolyte according to any one of claims 1 to 8.
  11. A secondary battery comprising the solid electrolyte membrane according to claim 10.
  12. A secondary battery comprising the solid electrolyte according to any one of claims 1 to 9.
  13. A solid electrolyte membrane uses a solid electrolyte that is in an amorphous state and has a glass transition temperature of-80 ℃ or lower.
  14. A secondary battery using the solid electrolyte membrane according to claim 13.
  15. The secondary battery according to claim 11, 12 or 14, which is a lithium ion battery.
  16. A method for manufacturing a solid electrolyte membrane, characterized by comprising the steps of:
    (1) dissolving an ionic liquid polymer, a nitrile compound and a lithium salt in a solvent according to the mass ratio of the ionic liquid polymer to the nitrile compound of 1: 0.1-1: 2.0 and the mass ratio of the ionic liquid polymer to the lithium salt of 1: 0.1-1: 1.0, and mixing to prepare a mixed solution;
    (2) and (2) coating the mixed solution obtained in the step (1) on a template to prepare the solid electrolyte membrane.
CN201680073615.4A 2015-12-17 2016-12-16 Solid electrolyte, solid electrolyte membrane and its manufacturing method and secondary cell Pending CN108475819A (en)

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