CN103259041A - Speek solid electrolyte and method for manufacturing the same - Google Patents
Speek solid electrolyte and method for manufacturing the same Download PDFInfo
- Publication number
- CN103259041A CN103259041A CN2012102848092A CN201210284809A CN103259041A CN 103259041 A CN103259041 A CN 103259041A CN 2012102848092 A CN2012102848092 A CN 2012102848092A CN 201210284809 A CN201210284809 A CN 201210284809A CN 103259041 A CN103259041 A CN 103259041A
- Authority
- CN
- China
- Prior art keywords
- speek
- solid electrolyte
- carbonate
- ether
- ketone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Abstract
Provided is an SPEEK solid electrolyte and a method for manufacturing the same. The SPEEK solid electrolyte contains sulfonated polyetheretherketone, lithium salt and a polar aprotic solvent.
Description
Technical field
The invention relates to a kind of electrolyte and its preparation method, and particularly relevant for a kind of solid electrolyte and its preparation method.
Background technology
Lithium rechargeable battery (hereinafter to be referred as lithium battery) has advantages such as operating voltage height, energy density is big, weight is light and handy, the life-span is long, applies in a large number at present in consumption electronic products and the part high power products.In general, can use liquid state or solid electrolyte in the lithium battery.
The employed electrolyte kind of lithium battery can be divided into liquid electrolyte and solid electrolyte.Though liquid electrolyte has higher ionic conductance, liquid electrolyte spills easily, therefore needs comparatively complicated encapsulating structure.Also therefore, use the size of the lithium battery of liquid electrolyte to be difficult to reduce.
In comparison, the lithium battery (claiming solid-state thin-film battery again) of use solid electrolyte does not then have the anxiety of leakage, and fail safe is higher in the use.In addition, the thickness of solid-state thin-film battery is about 1-20 μ m only, therefore can make virtually any size and profile on demand.Moreover the power density height of solid-state thin-film battery, cycle charge-discharge number of times can reach thousands of times, can discharge and recharge under hot environment again.Just because of solid-state thin-film battery has above characteristic, it having been applied to IC-card, soft electronic product and living doctor's product etc. at present needs in the field of thin type flexible power supply.
In the research and development field of solid-state thin-film battery, main target comprises energy density, increase charge-discharge cycle, the elevating mechanism intensity that improves solid electrolyte and improves thermal stability.
Summary of the invention
Therefore, an aspect of the present invention is that a kind of SPEEK solid electrolyte is being provided, and the 25-80 of its electrical conductivity ℃ of thermal change rate is less than 80%, and the 25-80 of its capacitance ℃ of thermal change rate is less than 110%.
Above-mentioned SPEEK solid electrolyte comprises sulfonated polyether-ether-ketone, lithium salts and polar non-solute.
According to an embodiment, above-mentioned sulfonated polyether-ether-ketone molecular weight is 10,000-50,000Da.
According to another embodiment, above-mentioned lithium salts is LiClO
4, LiBF
4, LiPF
6, LiAsF
6, LiCF
3SO
3, LiN (CF
3SO
3)
2, LiBr or above-mentioned combination in any.
According to another embodiment, above-mentioned lithium salts and the weight ratio of sulfonated polyether-ether-ketone mostly are 2 most.
Foundation is an embodiment again, and above-mentioned polar non-solute is dimethyl sulfoxide (DMSO) (Dimethyl sulfoxide; DMSO), N-N-methyl 2-pyrrolidone N-(N-methyl pyrrolidinone; NMP), dimethyl formamide (Dimethyl formamide; DMF), dimethylacetylamide (dimethylacetamide; DMAc) or the combination in any of above-mentioned solvent.
Foundation is an embodiment again, and the content of above-mentioned polar non-solute mostly is 40wt% most.
Foundation is an embodiment again, and above-mentioned SPEEK solid electrolyte also comprises a lithium salt solution.Above-mentioned lithium salt solution system is attached on this SPEEK solid electrolyte via immersion or enters among this SPEEK solid electrolyte.
Foundation is an embodiment again, and the solvent of above-mentioned lithium salt solution is water, ethylene carbonate (ethylene carbonate; EC), methyl ethyl carbonate (ethyl methyl carbonate; EMC), dimethyl carbonate (dimethyl carbonate; DMC) or propene carbonate (propylene carbonate; PC).
Foundation is an embodiment again, and the lithium salts of above-mentioned lithium salt solution is LiOH, LiNO
3, Li
2SO
4, LiClO
4, LiCF
3SO
3, LiN (CF
3SO
3)
2Or above-mentioned combination in any.
Another aspect of the present invention provides the preparation method of above-mentioned various SPEEK solid electrolytes.The preparation method of above-mentioned SPEEK solid electrolyte comprises following step.
At first, preparation monosulfonic acid polyether-ether-ketone solution allows above-mentioned sulfonated polyether-ether-ketone be dissolved in the above-mentioned polar non-solute.Then, allow above-mentioned lithium salts be dissolved in the above-mentioned sulfonated polyether-ether-ketone solution, to form the SPEEK electrolyte solution.Then, coating SPEEK electrolyte solution is on a base material, and is dry again, to form above-mentioned SPEEK solid-state electrolyte layer.
According to an embodiment, the temperature of above-mentioned drying steps is 60-120 ℃, and be maximum 72 hours drying time.
According to another embodiment, the preparation method of above-mentioned SPEEK solid electrolyte also comprises dried SPEEK solid-state electrolyte layer is immersed in the above-mentioned lithium salt solution, continues 1-60 second.
Electrical conductivity and capacitance according to the SPEEK solid electrolyte of said method gained can have good thermal stability, make in its application applicable to the various associated electrical products that need high-temperature operation.
The foregoing invention content aims to provide the simplification summary of this disclosure, so that the reader possesses basic understanding to this disclosure.This summary of the invention is not the complete overview of this disclosure, and its purpose is not at the key/critical element of pointing out the embodiment of the invention or defines scope of the present invention.After consulting hereinafter execution mode, the persond having ordinary knowledge in the technical field of the present invention be when can understanding essence spirit of the present invention and other goals of the invention easily, and the technology used in the present invention means with implement aspect.
Embodiment
According to above-mentioned, provide a kind of SPEEK solid electrolyte.This SPEEK solid electrolyte has preferable thermal stability.In the narration below, will introduce the illustration structure manufacture method illustrative with it of above-mentioned SPEEK solid electrolyte.In order to understand the event of described embodiment easily, will provide many ins and outs below.Certainly, not all embodiment all needs these ins and outs.Simultaneously, the structure that some are widely known by the people or element only can be drawn in graphic in the mode of signal, with simplicity of illustration content suitably.
The SPEEK solid electrolyte
Provide a kind of SPEEK solid electrolyte at this, its composition comprises lithium salts, sulfonated polyether-ether-ketone (sulfonated polyetheretherketone; SPEEK) with the aprotic solvent of polarity.In the temperature range of 80 ℃ of 25 –, the electrical conductivity of SPEEK solid electrolyte (conductivity) is all very little with the thermal change rate (thermal change rate) of capacitance (capacity).The thermal change rate of SPEEK solid electrolyte electrical conductivity can be less than 80%, and the thermal change rate of capacitance can be less than 60%.
According to an execution mode, above-mentioned lithium salts can be the lithium salts with low lattice energy, for example can be lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), lithium hexafluoro phosphate (LiPF
6), hexafluoroarsenate lithium (LiAsF
6), trifluoromethayl sulfonic acid lithium (LiCF
3SO
3), trifluoromethayl sulfonic acid nitrogen lithium (LiN (CF
3SO
3)
2) or lithium bromide lithium salts such as (LiBr).Lithium salts with low lattice energy can increase the ionic conductance of SPEEK solid electrolyte.In addition, the lithium salt in the SPEEK solid electrolyte mostly is 9.4mmol/g most, for example can be 1.6-4.7mmol/g.In general, the content of lithium salts is more high, and the ionic conductance of resulting solid electrolyte also can be preferable.Yet, in process of the test, find, when improving the lithium salts ratio, in film forming procedure, the white casse thing can occur in the film material, and deflection, irregular phenomenon appear in film material surface because film forming is inhomogeneous.This may be that lithium salt is too high, thereby has destroyed the crystallinity of sulfonated polyetheretherketonepolymer polymer.
According to another execution mode, the molecular weight of above-mentioned sulfonated polyether-ether-ketone is 10,000-50, and 000Da for example can be 20,000-30,000Da.Because sulfonated polyether-ether-ketone is a kind of polymer, therefore above-mentioned molecular weight ranges may influence its membrance casting condition (for example Gan Zao temperature and time) and its mechanical strength (for example hot strength).
According to another execution mode, the content of above-mentioned polar non-solute is for being less than 40wt%.Polar non-solute for example can be dimethyl sulfoxide (DMSO) (Dimethyl sulfoxide; DMSO), N-N-methyl 2-pyrrolidone N-(N-methyl pyrrolidinone; NMP), dimethyl formamide (Dimethyl formamide; DMF), dimethylacetylamide (dimethylacetamide; DMAc) or the combination in any of above-mentioned solvent.
The preparation method of SPEEK solid electrolyte
Above-mentioned SPEEK solid electrolyte preparation method is as described below.At first, sulfonated polyether-ether-ketone can be carried out sulfonated reaction and got by polyether-ether-ketone (polyetheretherketone PEEK).The sulfonated reagent that is used for carrying out sulfonated reaction for example can be sulfuric acid.Sulfonated reaction for example can be reacted about 12 hours down at about 50 ℃.The illustration chemical constitution of the sulfonated polyether-ether-ketone of gained is as follows.
Then, allow sulfonated polyether-ether-ketone be dissolved in the polar non-solute, form sulfonated polyether-ether-ketone solution.According to an embodiment, above-mentioned sulfonated polyether-ether-ketone solution contains the sulfonated polyether-ether-ketone of 1 – 12wt%.Above-mentioned polar non-solute for example can be dimethyl sulfoxide (DMSO) (Dimethyl sulfoxide; DMSO), N-N-methyl 2-pyrrolidone N-(N-methyl pyrrolidinone; NMP), dimethyl formamide (Dimethyl formamide; DMF), dimethylacetylamide (dimethylacetamide; DMAc) or the combination in any of above-mentioned solvent.
According to another execution mode, when the sulfonated polyether-ether-ketone solution of preparation, can also optionally heat sulfonated polyether-ether-ketone solution, to increase the rate of dissolution of sulfonated polyether-ether-ketone in polar non-solute.For example, when the weight of sulfonated polyether-ether-ketone solution was 105 grams (DMSO of the 5 sulfonated polyether-ether-ketones of gram and 100 grams), the heating-up temperature of sulfonated polyether-ether-ketone solution can be about 60 ℃, heats about 2-4 hour, dissolves polyether-ether-ketone in DMSO with essence.
Next, allow lithium salts be dissolved in the sulfonated polyether-ether-ketone solution, to form the SPEEK electrolyte solution.The addition of lithium salts can be 2 times of sulfonated polyether-ether-ketone weight at most.
According to another embodiment, can directly add lithium salts to sulfonated polyether-ether-ketone solution, form the SPEEK electrolyte solution with direct dissolving lithium salts.In this step, the SPEEK electrolyte solution can be stirred again, be heated or agitating heating together, to mix every kind of composition in the SPEEK electrolyte solution equably.Heating-up temperature can be 60 ℃ to 70% of above-mentioned polar non-solute boiling point.If heating-up temperature is too low, the solubility of sulfonated polyether-ether-ketone in polar non-solute can be relatively poor, and the viscosity of SPEEK electrolyte solution can be too big, unfavorablely carries out follow-up application step.
If in the process of preparation SPEEK electrolyte solution, the SPEEK of stirring electrolyte solution is arranged, then may in the SPEEK electrolyte solution, produce bubble.These bubbles may influence the quality of SPEEK solid electrolyte, therefore preferably allow the SPEEK electrolyte solution leave standstill a period of time (for example 5 – 10 minutes), to remove the bubble in the SPEEK electrolyte solution.
Then, the SPEEK electrolyte solution is coated on the base material, drying again is to form one deck SPEEK solid electrolyte at base material.Above-mentioned base material can be hard base material (for example stainless steel substrate) or flexible substrate (for example fabric).
Above-mentioned baking temperature and drying time are normally decided by the required solvent of final SPEEK solid electrolyte.And, also can influence baking temperature and drying time mechanical strength and the electrical conductivity of SPEEK solid electrolyte.Therefore, above-mentioned baking temperature for example can be 120 ℃ of 60 –, as 60,65,70,75,80,85,90,95,100,105,110,115 or 120 ℃.Can be 72 hours drying time at most.
At last, dried SPEEK solid electrolyte also optionally is immersed in the lithium salt solution, time is about 1 – 60 seconds, with the charge-conduction impedance (charge transfer resistance) between minimizing SPEEK solid electrolyte and contact electrode, and the ion mobility in the increase SPEEK solid electrolyte.
The used solvent of above-mentioned lithium salt solution can be water, ethylene carbonate (ethylene carbonate; EC), methyl ethyl carbonate (ethyl methyl carbonate; EMC), dimethyl carbonate (dimethyl carbonate; DMC) or propene carbonate (propylene carbonate; PC).The used lithium salts of above-mentioned lithium salt solution for example can be LiOH, LiNO
3, Li
2SO
4, LiClO
4, LiCF
3SO
3, LiN (CF
3SO
3)
2Or above-mentioned combination in any.The concentration of lithium salts in above-mentioned lithium salt solution is preferably maximum 10M.
The solid film lithium battery of SPEEK solid electrolyte is used in preparation
Provide the preparation method of the solid film lithium battery that uses the SPEEK solid electrolyte at this.This preparation method utilizes the preparation method of above-mentioned SPEEK solid electrolyte to increase the relevant usefulness of solid film lithium battery.
After the preparation process of above-mentioned SPEEK electrolyte solution, the SPEEK electrolyte solution is coated on relative two surfaces of flexible substrate respectively.The method of above-mentioned coating for example can be spraying (spray coating), scraper coating (knife coating), cylinder coating (roller coating), rotation coating (spinning coating), dip coated (dip coating) or curtain formula coating (curtain coating).Then, allow the flexible substrate that is coated with the SPEEK electrolyte solution descend dry maximum 72 hours 120 ℃ of 60 –, to obtain the equally distributed composite solid electrolyte structure of SPEEK.
Above-mentioned flexible substrate for example can be fabric, and for example the useable glass fabric is strengthened the overall mechanical strength of the equally distributed composite solid electrolyte structure of SPEEK, also increases the mechanical strength of the solid film lithium battery of last gained.
Then, on relative two surfaces of the equally distributed composite solid electrolyte structure of above-mentioned SPEEK, form a positive electrode layer and a positive electrode layer respectively, get final product the solid film lithium battery.
Then, above-mentioned solid film lithium battery also can utilize following method to assemble it, but the present invention is not limit by this.In the method, the positive and negative electrode layer can utilize suitable material independently to form it earlier.Then, allow the equally distributed composite solid electrolyte composite construction of SPEEK be clipped between the positive and negative electrode layer, the step of carrying out hot pressing again attaches the positive and negative electrode layer to the SPEEK solid-state electrolyte layer.In above-mentioned hot pressing step, the solvent of SPEEK solid-state electrolyte layer might be lowered.
In addition, the SPEEK solid electrolyte also can be used to prepare soft capacitor.For example, available fabric is manufactured the equally distributed composite solid electrolyte structure of composite S PEEK as flexible substrate, and this composite construction of recycling prepares the fabric capacitor device.
In order to understand preparation method and the correlation properties of SPEEK solid electrolyte more, provide some experimental results below.
Experiment one: the influence of different lithium salt pair impedance
In this experiment, the SPEEK electrolyte solution is to be prepared from following method.In the DMSO of 100 grams, add the sulfonated polyether-ether-ketone of 5 grams, stir down in 60 ℃ again, to dissolve sulfonated polyether-ether-ketone.Then, add different types of lithium salts to the SPEEK electrolyte solution, contain the SPEEK electrolyte solution of different lithium salts with formation.Then each above-mentioned SPEEK electrolyte solution is coated on the base material, dry under 60 ℃ again, to obtain the SPEEK solid electrolyte.At last, soak the composite construction of SPEEK solid electrolyte and base material in water 10 seconds.Correlated condition with the results are shown in the following table one.
Table one: the influence of different lithium salt pair SPEEK solid electrolyte impedance
| Experimental example | Lithium salts | Impedance (Ω) |
| 1-1 | -- | 1.739 |
| 1-2 | LiClO 4 | 1.537 |
| 1-3 | LiCF 3SO 3 | 1.087 |
| 1-4 | LiN(CF 3SO 3) 2 | 0.874 |
By the result of table one as can be known, LiN (CF
3SO
3)
2The impedance minimum, show LiN (CF
3SO
3)
2Transmission in the SPEEK solid electrolyte is the easiest.
Experiment two: lithium salt content is to the influence of ionic conductance
In this experiment, the SPEEK electrolyte solution is to be prepared from following method.In the DMSO of 100 grams, add the sulfonated polyether-ether-ketone of 5 grams, stir down in 60 ℃ again, to dissolve sulfonated polyether-ether-ketone.Then, the LiClO that adds different amounts
4To the SPEEK electrolyte solution, contain the SPEEK electrolyte solution of variable concentrations lithium salts with formation.Then each above-mentioned SPEEK electrolyte solution is coated on the base material, dry under 60 ℃ again, to obtain the SPEEK solid electrolyte.At last, soak the composite construction of SPEEK solid electrolyte and base material in water 10 seconds.Correlated condition with the results are shown in the following table two.
Table two: lithium salt is to the influence of SPEEK solid electrolyte ionic conductance
| Experimental example | LiClO 4Concentration (mmol/g) | Ionic conductance * (S/cm) |
| 2-1 | 0 | 6.21×10 -3 |
| 2-2 | 1.6 | 9.40×10 -3 |
| 2-3 | 2.7 | 12.63×10 -3 |
| 2-4 | 3.5 | 16.04×10 -3 |
* ionic conductance=thickness/(resistance * area), wherein resistance is to measure with the ac resistance analysis instrument.The ac resistance analysis instrument comprises the potentiostat/galvanostat (Potentiostat/Galvanostat that is bought by Princeton Applied Research; Model 263A) and amplitude-frequency response analyzer (Frequency Response Detector; Model FRD 100).
From the result of table two as can be known, when lithium salt increased, the ionic conductance of SPEEK solid electrolyte was also along with increase.
Experiment three: LiClO
4-SPEEK solid electrolyte
The heat stability of electrical conductivity and capacitance
In experimental example 3-1,3-2 and 3-3, the SPEEK electrolyte solution is to be prepared from following method.In the DMSO of 100 grams, add the sulfonated polyether-ether-ketone of 5 grams, stir down in 60 ℃ again, to dissolve sulfonated polyether-ether-ketone.Then, add LiClO
4To the SPEEK electrolyte solution, contain the SPEEK electrolyte solution of lithium salts with formation.Then above-mentioned SPEEK electrolyte solution is coated on the base material, dry under 60 ℃ again, to obtain to contain the LiClO of concentration 4.7mmol/g
4The SPEEK solid electrolyte.At last, SPEEK solid electrolyte and the composite construction of base material are immersed in the different infiltration liquid 10 seconds.Allow each experimental example carry out 25 ℃ of measurements with 80 ℃ electrical conductivity and capacitance respectively then.
As for comparative example 3-1 and 3-2, then use polyethylene (poly vinyl alcohol; PVA) with polyoxyethylene (polyethylene oxide; PEO) come the substituted sulfonic acid polyether-ether-ketone, with preparation PVA solid electrolyte and PEO solid electrolyte.The solid polyelectrolyte of comparative example 3-1 contains the LiClO of concentration 3.2mmol/g
4, the document of comparative example 3-2 is not mentioned the LiClO in its solid electrolyte
4Concentration.Allow each comparative example carry out 25 ℃ of measurements with 80 ℃ electrical conductivity and capacitance respectively then.
Above-mentioned employed preparation condition and gained result all are listed in the table three.
Table three: LiClO
4The heat stability of-SPEEK solid electrolyte electrical conductivity and capacitance
1By formula (σ
80 ℃-σ
25 ℃)/σ
25 ℃* 100 calculate and get
2By formula (C
80 ℃-C
25 ℃)/C
25 ℃* 100 calculate and get
3From Choi paper (Materials Science and Engineering, B107 (2004), the 2nd figure pp244-250)
From the result of table three as can be known, the thermal change rate of the electrical conductivity of SPEEK solid electrolyte and capacitance is minimum in three kinds of solid electrolytes (PSEEK, PVA and PEO).In addition, different infiltration liquid also can influence the electrical conductivity of SPEEK solid electrolyte and the thermal change rate of capacitance.Wherein soak into LiNO
3The thermal change rate minimum of experimental example 3-3, heat stability is the highest.The thermal change rate of its electrical conductivity has only 15.0%, and the thermal change rate of capacitance has only 16.4%.
Experiment four: LiCF
3SO
3-SPEEK solid electrolyte
The heat stability of electrical conductivity and capacitance
In experimental example 4-1,4-2 and 4-3, the SPEEK electrolyte solution is to be prepared from following method.In the DMSO of 100 grams, add the sulfonated polyether-ether-ketone of 5 grams, stir down in 60 ℃ again, to dissolve sulfonated polyether-ether-ketone.Then, add LiCF
3SO
3To the SPEEK electrolyte solution, contain the SPEEK electrolyte solution of lithium salts with formation.Then above-mentioned SPEEK electrolyte solution is coated on the base material, dry under 60 ℃ again, to obtain to contain the LiCF of concentration 3.2mmol/g
3SO
3The SPEEK solid electrolyte.At last, SPEEK solid electrolyte and the composite construction of base material are immersed in the different infiltration liquid 10 seconds.Allow each experimental example carry out 25 ℃ of measurements with 80 ℃ electrical conductivity and capacitance respectively then.Above-mentioned employed preparation condition and gained result all are listed in the table four.
Table four: LiCF
3SO
3The heat stability of-SPEEK solid electrolyte electrical conductivity and capacitance
1By formula (σ
80 ℃-σ
25 ℃)/σ
25 ℃* 100 calculate and get
2By formula (C
80 ℃-C
25 ℃)/C
25 ℃* 100 calculate and get
By the result of table four as can be known, with the LiClO of the lithium salts in the SPEEK solid electrolyte by experiment three
4Change LiCF into
3SO
3Afterwards, the thermal change rate of electrical conductivity and capacitance is still to soak LiNO
3The solution person is minimum.
The inventor finds to soak the LiCF of pure water
3SO
3-SPEEK solid electrolyte can carry out oxidation reaction under greater than the operating voltage of 0.5V, make whole charge and discharge cycles capacitance thereby significantly increase.This may be for soaking the LiCF of pure water
3SO
3The electrical conductivity of-SPEEK solid electrolyte and capacitance thermal change rate so big because of.But, if allow LiCF
3SO
3-SPEEK solid electrolyte soaks the aqueous solution of lithium salts, then can suppress oxidation reaction effectively, therefore can reduce the thermal change rate of electrical conductivity and capacitance, promotes its thermal stability.
Experiment five: LiN (CF
3SO
3)
2-SPEEK solid electrolyte
The heat stability of electrical conductivity and capacitance
In experimental example 5-1,5-2 and 5-3, the SPEEK electrolyte solution is to be prepared from following method.In the DMSO of 100 grams, add the sulfonated polyether-ether-ketone of 5 grams, stir down in 60 ℃ again, to dissolve sulfonated polyether-ether-ketone.Then, add LiN (CF
3SO
3)
2To the SPEEK electrolyte solution, contain the SPEEK electrolyte solution of lithium salts with formation.Then above-mentioned SPEEK electrolyte solution is coated on the base material, dry under 60 ℃ again, to obtain to contain the LiN (CF of concentration 1.6mmol/g
3SO
3)
2The SPEEK solid electrolyte.At last, SPEEK solid electrolyte and the composite construction of base material are immersed in the different infiltration liquid 10 seconds.Allow each experimental example carry out 25 ℃ of measurements with 80 ℃ electrical conductivity and capacitance respectively then.Above-mentioned employed preparation condition and gained result all are listed in the table five.
Table five: LiN (CF
3SO
3)
2The heat stability of-SPEEK solid electrolyte electrical conductivity and capacitance
1By formula (σ
80 ℃-σ
25 ℃)/σ
25 ℃* 100 calculate and get
2By formula (C
80 ℃-C
25 ℃)/C
25 ℃* 100 calculate and get
By the result of table five as can be known, with the LiClO of the lithium salts in the SPEEK solid electrolyte by experiment three
4Change LiN (CF into
3SO
3)
2Afterwards, soak LiNO
3Be more or less the same with LiOH person's electrical conductivity and the thermal change rate of capacitance, slightly better to soak LiOH person again.
The inventor finds to soak the LiN (CF of pure water
3SO
3)
2-SPEEK solid electrolyte can carry out oxidation reaction under greater than the operating voltage of 0.5V, make whole charge and discharge cycles capacitance thereby significantly increase.This may be for soaking the LiN (CF of pure water
3SO
3)
2The electrical conductivity of-SPEEK solid electrolyte and capacitance thermal change rate so big because of.But, if allow LiN (CF
3SO
3)
2-SPEEK solid electrolyte soaks the aqueous solution of lithium salts, then can suppress oxidation reaction effectively, therefore can reduce the thermal change rate of electrical conductivity and capacitance, promotes its thermal stability.
Experiment six: the thermal change rate of the electrical conductivity of SPEEK solid electrolyte
The preparation condition of SPEEK solid electrolyte that contains various lithium salts is the same, therefore repeats no more it.And not containing the SPEEK solid electrolyte of lithium salts, its preparation method is when preparation SPEEK electrolyte solution, omits the step of adding lithium salts.Gained the results are shown in the following table six.
Table six: the thermal change rate * of the 25-80 of the electrical conductivity of SPEEK solid electrolyte ℃ electrical conductivity
* by formula (σ
80 ℃-σ
25 ℃)/σ
25 ℃* 100 calculate and get
As shown in Table 6, the influencing factor of the electrical conductivity thermal change rate of SPEEK solid electrolyte has two, and one for soaking into the lithium salts kind in the liquid, another lithium salts kind for adding in the SPEEK solid electrolyte.In table six, do not add the thermal change rate of electrical conductivity of SPEEK solid electrolyte of lithium salts for maximum, represent that its heat stability is bad.Other best persons of heat stability that each sample that adds lithium salts is arranged are for soaking LiNO
3The LiCF of solution
3SO
3-SPEEK solid electrolyte, it has only surprising 2%, and other have the electrical conductivity rates of change that add the lithium salts sample also all below 56%.
By the invention described above execution mode as can be known, the electrical conductivity of the SPEEK solid electrolyte of above-mentioned interpolation lithium salts and capacitance have good thermal stability.This result shows, the SPEEK solid electrolyte is fit in the application of various associated electrical products of needs high-temperature operation very much.For example in conjunction with above-mentioned solid film lithium battery and soft capacitor, can be applicable on automobile-used (carrying) electronic product.
Though the present invention discloses as above with execution mode; right its is not in order to limiting the present invention, anyly has the knack of this skill person, without departing from the spirit and scope of the present invention; when can being used for a variety of modifications and variations, so protection scope of the present invention is as the criterion when looking appended the claim person of defining.
Claims (11)
1. SPEEK solid electrolyte, 80 ℃ of thermal change rates of 25 – of its electrical conductivity are less than 80%, and 80 ℃ of thermal change rates of 25 – of its capacitance are less than 110%, and this SPEEK solid electrolyte comprises:
Sulfonated polyether-ether-ketone, its molecular weight are 10,000 – 50,000Da;
One first lithium salts is distributed among this sulfonated polyether-ether-ketone, and the weight ratio of this first lithium salts and this sulfonated polyether-ether-ketone mostly is 2 most, and this first lithium salts is LiClO
4, LiBF
4, LiPF
6, LiAsF
6, LiCF
3SO
3, LiN (CF
3SO
3)
2, LiBr or above-mentioned combination in any; And
One polar non-solute, its content mostly is 40wt% most.
2. SPEEK solid electrolyte as claimed in claim 1 is characterized in that, this polar non-solute is dimethyl sulfoxide (DMSO) (Dimethyl sulfoxide; DMSO), N-N-methyl 2-pyrrolidone N-(N-methyl pyrrolidinone; NMP), dimethyl formamide (Dimethyl formamide; DMF), dimethylacetylamide (dimethylacetamide; DMAc) or the combination in any of above-mentioned solvent.
3. SPEEK solid electrolyte as claimed in claim 1 or 2 is characterized in that, more comprises a lithium salt solution, and this lithium salt solution system is attached on this SPEEK solid electrolyte via immersion or enters among this SPEEK solid electrolyte.
4. SPEEK solid electrolyte as claimed in claim 3 is characterized in that, the solvent of this lithium salt solution is water, ethylene carbonate (ethylene carbonate; EC), methyl ethyl carbonate (ethyl methyl carbonate; EMC), dimethyl carbonate (dimethyl carbonate; DMC) or propene carbonate (propylene carbonate; PC).
5. SPEEK solid electrolyte as claimed in claim 3 is characterized in that, second lithium salts of this lithium salt solution is LiOH, LiNO
3, Li
2SO
4, LiClO
4, LiCF
3SO
3, LiN (CF
3SO
3)
2Or above-mentioned combination in any.
6. the preparation method of a SPEEK solid electrolyte, this preparation method comprises:
Preparation monosulfonic acid polyether-ether-ketone solution allows sulfonated polyether-ether-ketone be dissolved in the polar non-solute, and the molecular weight of this sulfonated polyether-ether-ketone is 10,000 – 50,000Da;
Dissolve one first lithium salts in this sulfonated polyether-ether-ketone solution, to form a SPEEK electrolyte solution, this first lithium salts is LiClO
4, LiBF
4, LiPF
6, LiAsF
6, LiCF
3SO
3, LiN (CF
3SO
3)
2, LiBr or above-mentioned combination in any;
Be coated with this SPEEK electrolyte solution on a base material; And
Dry this SPEEK electrolyte solution is to form a SPEEK solid-state electrolyte layer on this base material.
7. the preparation method of SPEEK solid electrolyte as claimed in claim 6 is characterized in that, this polar non-solute is dimethyl sulfoxide (DMSO) (Dimethyl sulfoxide; DMSO), N-N-methyl 2-pyrrolidone N-(N-methyl pyrrolidinone; NMP), dimethyl formamide (Dimethyl formamide; DMF), dimethylacetylamide (dimethylacetamide; DMAc) or the combination in any of above-mentioned solvent.
8. the preparation method of SPEEK solid electrolyte as claimed in claim 6 is characterized in that, the temperature of this drying steps is 120 ℃ of 60 –, and the time of this drying steps is maximum 72 hours.
9. the preparation method of SPEEK solid electrolyte as claimed in claim 6 is characterized in that, more comprises dried SPEEK solid-state electrolyte layer is immersed in the lithium salt solution, continues 1-60 second.
10. the preparation method of SPEEK solid electrolyte as claimed in claim 9 is characterized in that, the solvent of this lithium salt solution is water, ethylene carbonate (ethylene carbonate; EC), methyl ethyl carbonate (ethyl methyl carbonate; EMC), dimethyl carbonate (dimethyl carbonate; DMC) or propene carbonate (propylene carbonate; PC).
11. the preparation method of SPEEK solid electrolyte as claimed in claim 9 is characterized in that, second lithium salts of this lithium salt solution is LiOH, LiNO
3, Li
2SO
4, LiClO
4, LiCF
3SO
3, LiN (CF
3SO
3)
2Or above-mentioned combination in any.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/397,883 | 2012-02-16 | ||
| US13/397,883 US20120208091A1 (en) | 2011-02-16 | 2012-02-16 | Polymer-Based Solid Electrolytes and Preparation Methods Thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103259041A true CN103259041A (en) | 2013-08-21 |
Family
ID=48964005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012102848092A Pending CN103259041A (en) | 2012-02-16 | 2012-08-10 | Speek solid electrolyte and method for manufacturing the same |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN103259041A (en) |
| TW (1) | TWI493768B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107464950A (en) * | 2017-07-27 | 2017-12-12 | 中国科学院化学研究所 | A kind of high salt concentration solid electrolyte and application |
| CN109285983A (en) * | 2018-09-28 | 2019-01-29 | 东北大学 | Using lithium ion solid electrolyte piece as button lithium battery of diaphragm and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101159332A (en) * | 2006-10-04 | 2008-04-09 | 三星Sdi株式会社 | Polymer electrolyte membrane comprising inorganic nanoparticle bonded with proton-conducting group and solid acid, fuel cell including the same, and method of preparing the polymer electrolyte membran |
| US20120052397A1 (en) * | 2010-08-24 | 2012-03-01 | Basf Se | Electrolyte materials for use in electrochemical cells |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003535940A (en) * | 2000-06-02 | 2003-12-02 | エスアールアイ インターナショナル | Polymer composition |
| WO2008105547A1 (en) * | 2007-02-27 | 2008-09-04 | Teijin Limited | Solid polymer electrolyte |
-
2012
- 2012-08-10 TW TW101129026A patent/TWI493768B/en active
- 2012-08-10 CN CN2012102848092A patent/CN103259041A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101159332A (en) * | 2006-10-04 | 2008-04-09 | 三星Sdi株式会社 | Polymer electrolyte membrane comprising inorganic nanoparticle bonded with proton-conducting group and solid acid, fuel cell including the same, and method of preparing the polymer electrolyte membran |
| US20120052397A1 (en) * | 2010-08-24 | 2012-03-01 | Basf Se | Electrolyte materials for use in electrochemical cells |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107464950A (en) * | 2017-07-27 | 2017-12-12 | 中国科学院化学研究所 | A kind of high salt concentration solid electrolyte and application |
| CN109285983A (en) * | 2018-09-28 | 2019-01-29 | 东北大学 | Using lithium ion solid electrolyte piece as button lithium battery of diaphragm and preparation method thereof |
| CN109285983B (en) * | 2018-09-28 | 2020-07-14 | 东北大学 | Button lithium battery with lithium ion solid electrolyte sheet as diaphragm and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI493768B (en) | 2015-07-21 |
| TW201336148A (en) | 2013-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20120208091A1 (en) | Polymer-Based Solid Electrolytes and Preparation Methods Thereof | |
| Yang et al. | A sodium ion conducting gel polymer electrolyte | |
| Sekhon | Conductivity behaviour of polymer gel electrolytes: Role of polymer | |
| CN101164122B (en) | Conductive material and conductive film and process for producing them | |
| Li et al. | Polymerized ionic liquids with guanidinium cations as host for gel polymer electrolytes in lithium metal batteries | |
| Xiao et al. | Effect of urea as pore-forming agent on properties of poly (vinylidene fluoride-co-hexafluoropropylene)-based gel polymer electrolyte | |
| Mohamed et al. | Electrochemical studies on epoxidised natural rubber-based gel polymer electrolytes for lithium–air cells | |
| Ueno et al. | Electrochemical properties of cross-linked polymer electrolyte by electron beam irradiation and application to lithium ion batteries | |
| US20120308899A1 (en) | Polymer-Based Solid Electrolytes and Preparation Methods Thereof | |
| Li et al. | Li/LiFePO4 batteries with gel polymer electrolytes incorporating a guanidinium-based ionic liquid cycled at room temperature and 50° C | |
| Gu et al. | A porous cross-linked gel polymer electrolyte separator for lithium-ion batteries prepared by using zinc oxide nanoparticle as a foaming agent and filler | |
| CN107771351A (en) | Solid polymer electrolyte and the electrochemical appliance for including it | |
| Li et al. | Composite electrolytes of pyrrolidone-derivatives-PEO enable to enhance performance of all solid state lithium-ion batteries | |
| Appetecchi et al. | A poly (vinylidene fluoride)-based gel electrolyte membrane for lithium batteries | |
| WO2021098685A1 (en) | Solid-state polymer electrolyte, preparation method therefor, and lithium battery | |
| Hou et al. | Studies on comb-like polymer electrolyte with a nitrile group | |
| CN109193027A (en) | A kind of lithium ion polymer electrolyte film and the preparation method and application thereof | |
| Tian et al. | Preparation of poly (acrylonitrile–butyl acrylate) gel electrolyte for lithium-ion batteries | |
| CN108417890A (en) | A kind of solid polyelectrolyte material, solid electrolyte membrane and preparation method thereof | |
| CN102403533A (en) | Gel-state polymer electrolyte of lithium-ion battery and preparation method | |
| Wang et al. | High conductivity polymer electrolyte with comb-like structure via a solvent-free UV-cured method for large-area ambient all-solid-sate lithium batteries | |
| CN109888369A (en) | A kind of all solid state electrolyte and preparation method thereof and a kind of lithium battery | |
| CN104098785A (en) | Pvdf gel polymer electrolyte and preparation method thereof | |
| CN103254432A (en) | Self-doped electric active polyamic acid, preparation method and application thereof in electrochromic aspect | |
| Wang et al. | PEGDA/PVdF/F127 gel type polymer electrolyte membranes for lithium secondary batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130821 |
|
| WD01 | Invention patent application deemed withdrawn after publication |