CN105017171B - The electrolyte preparation method of copolyamide containing benzoxazole and application - Google Patents
The electrolyte preparation method of copolyamide containing benzoxazole and application Download PDFInfo
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- CN105017171B CN105017171B CN201510409009.2A CN201510409009A CN105017171B CN 105017171 B CN105017171 B CN 105017171B CN 201510409009 A CN201510409009 A CN 201510409009A CN 105017171 B CN105017171 B CN 105017171B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
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- 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
Abstract
Benzoxazole and its copolyamide electrolyte preparation method and application, the present invention relates to a kind of new type benzoxazole compound and the synthetic method of its copolyamide, it is relatively low in order to solve the problems, such as the mechanical property and electrical conductivity of existing PEO polymer dielectrics.2,2' of present invention butylidenes two [5 An bases benzoxazole] are that, with 2,4 diaminophenol hydrochlorides and adipic acid are raw material, are prepared what is obtained by solvent of polyphosphoric acids.By 2,2' butyl two [5 An bases benzoxazole] and polyethylene glycol dicarboxylic acids, two kinds of copolyamide I and copolyamide II are obtained respectively containing Sulfonic Lithium (sodium) dicarboxylic acids or containing Sulfonic Lithium (sodium) diamine reactant.And application copolyamide is used as the electrolyte of solid lithium ion battery.The present invention is incorporated into polyamide structure by 2,2' butylidenes two [5 An bases benzoxazole], so as to improve the electrical conductivity and mechanical property of thin polymer film.
Description
Technical field
The present invention relates to a kind of new type benzoxazole compound and the synthetic method of its copolyamide, and in particular to
2,2'- butylidenes two [5- An bases benzoxazole] and synthesize two kinds of methods of copolyamide as reactant by it, and be related to
Application in full solid state polymer lithium ion battery.
Background technology
Full solid state polymer lithium ion battery is the high specific energy of new generation grown up on the basis of liquid lithium ionic cell
Battery system, is a kind of lithium ion battery of use polymer dielectric as electrolyte.Such battery not only has liquid
The features such as high voltage of state lithium ion battery, long-life and cleanliness without any pollution, and overcome liquid electrolyte battery presence
The safety problem such as easy-to-leak liquid, and energy density is high and machining shape is unrestricted, can be widely applied to mobile device, electronic
The fields such as car, aviation.The key technology of full solid state polymer lithium ion battery is to prepare polymer dielectric, it is desirable to electrostrictive polymer
Solution matter has electrical conductivity high, suitable mechanical strength, electrochemical stability etc., wherein polyether-based polymers (such as PEO) polymerization
Thing electrolyte is the focus of research.Single-ion polymer conductor is that anion is fixed on polymer lateral chain, only cation
It is transmitted, transference number of ions is 1, is also a kind of polymer dielectric.
The content of the invention
Mechanical property and electrical conductivity the invention aims to solve existing PEO polymer dielectrics are relatively low to ask
Topic, and benzoxazole and its copolyamide electrolyte preparation method and application are provided.
The preparation method of 2,2'- butylidenes two [5- An bases benzoxazole] of the present invention follow these steps to realize：
First, under inert gas shielding atmosphere, by phosphoric acid and P2O5It is well mixed, form poly phosphoric acid solution；
2nd, it is in molar ratio (2.05~2.2): 1 weighs 2,4- diaminophenol hydrochlorides and adipic acid as reaction original
Material, to adding SnCl in the poly phosphoric acid solution that step one is obtained2Reducing agent, control temperature adds under conditions of 140~160 DEG C
Enter reaction raw materials 2,4- diaminophenol hydrochlorides and adipic acid, then heat to 160~210 DEG C, reaction is obtained after 5~8 hours
To product；
3rd, product is neutralized through sodium carbonate or NaOH, then obtains head product after washing, drying；
4th, head product is extracted with absolute ethyl alcohol, is finally vacuum dried, obtained [the 5- aminobenzenes of 2,2'- butylidenes two
Bing oxazoles] powder.
The preparation method of 2,2'- of present invention butylidenes two [5- An bases benzoxazole] is carried out in polyphosphoric acids, relatively
In organic solvent, reacted using in polyphosphoric acids, improve the purity of product, yield is high, and low cost, yield can reach
80%~90%.
The preparation method of copolyamide I of the present invention follow these steps to realize：
Under inert gas shielding atmosphere, to solvent NMP and TPP is added in reaction vessel, stirred after being heated to 100 DEG C
Mix, 120 DEG C are warming up to again after adding lithium chloride, 2,2'- butylidenes two [5- An bases benzoxazole] are subsequently adding, after dissolving completely
Polyethylene glycol dicarboxylic acids and 2,5- diamino sulfonic acid sodium or 2,5- diamino sulfonic acid lithium are added, at a temperature of 130~140 DEG C
Reaction 70~75 hours, purging adds deionized water by polymer fibrids after removing solvent, then is cleaned through washing and methyl alcohol, filtering
Vacuum drying afterwards obtains copolyamide I.
The present invention is by 2,2'- butylidenes two [5- An bases benzoxazole] and 2,5- diamino sulfonic acids lithium or 2,5- diaminourea sulphurs
Sour sodium, polyethylene glycol dicarboxylic acids synthesize copolyamide I.
The preparation method of copolyamide II of the present invention follow these steps to realize：
Under inert gas shielding atmosphere, to solvent NMP and TPP is added in reaction vessel, stirred after being heated to 100 DEG C
Mix, 120 DEG C are warming up to again after adding lithium chloride, 2,2'- butylidenes two [5- An bases benzoxazole] are subsequently adding, after dissolving completely
Polyethylene glycol dicarboxylic acids and 5-sodium sulfo isophthalate or M-phthalic acid -5- Sulfonic Lithiums are added, at 130~140 DEG C
At a temperature of react 70~75 hours, purging remove solvent after add deionized water by polymer fibrids, then through washing and methyl alcohol it is clear
Wash, vacuum drying obtains copolyamide II after filtering.
The present invention is by 2,2'- butylidenes two [5- An bases benzoxazole] and 5-sodium sulfo isophthalate or isophthalic diformazan
Acid -5- Sulfonic Lithiums, polyethylene glycol dicarboxylic acids carry out synthetically prepared copolyamide II.
The present invention applies copolyamide I or copolyamide II as the electrolyte of all-solid lithium-ion battery.
The method that present invention application copolyamide prepares thin polymer film follow these steps to realize：
Copolyamide I or copolyamide II are dissolved in DMF solvent, polymer solution is obtained, at a temperature of 70~100 DEG C
Heating for dissolving 1~3 hour, pours into mould, in atmosphere solvent flashing after filtering, then heating 48~75 is small at 60~80 DEG C
When, thin polymer film is obtained after vacuum drying treatment.
Copolyamide of the present invention is by introducing new benzoxazole and 2,5- diamino benzene sulfonic acid lithiums
The rigid structure of (sodium) or M-phthalic acid -5- Sulfonic Lithiums (sodium), improves intermolecular force, improves its mechanical property.Simultaneously
There is highly polar amido link, while polymer keeps high thermal stability, good mechanical property, second is aoxidized in PEO bases
Alkene segment can dissolve lithium salts, and can coordinate with lithium ion, lithium salts is dissociated, and form the amorphous region in polymer, reduce glass
Glass transition temperature, improves the electrical conductivity of its electrolyte, the lithium ion conductivity of the film prepared using the copolyamide
1 × 10 can be reached-5S/cm~6 × 10-6More than S/cm.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the 2,2'- butylidenes two [5- An bases benzoxazole] that embodiment one is obtained；
Fig. 2 is the 2,2'- butylidenes two [5- An bases benzoxazole] (with dimethyl sulfoxide (DMSO) as solvent) that embodiment one is obtained
Hydrogen nuclear magnetic resonance spectrogram；
Fig. 3 is the 2,2'- butylidenes two [5- An bases benzoxazole] (with dimethyl sulfoxide (DMSO) as solvent) that embodiment one is obtained
Carbon-13 nmr spectra figure；
Copolyamide I (lithium ion molar concentration is 25%) proton nmr spectra that Fig. 4 is obtained for embodiment two is (with diformazan
Base sulfoxide be solvent) hydrogen nuclear magnetic resonance spectrogram；
Copolyamide II (lithium ion molar concentration is 15%) proton nmr spectra that Fig. 5 is obtained for embodiment three is (with two
Methyl sulfoxide is solvent) hydrogen nuclear magnetic resonance spectrogram；
Fig. 6 is the appearing diagram of copolyamide I thin polymer films；
Fig. 7 is the appearing diagram of copolyamide II thin polymer films.
Specific embodiment
Specific embodiment one：The preparation method of present embodiment 2,2'- butylidenes two [5- An bases benzoxazole] is pressed
Row step is realized：
First, under inert gas shielding atmosphere, by phosphoric acid and P2O5It is well mixed, form poly phosphoric acid solution；
2nd, it is in molar ratio (2.05~2.2): 1 weighs 2,4- diaminophenol hydrochlorides and adipic acid as reaction original
Material, to adding SnCl in the poly phosphoric acid solution that step one is obtained2Reducing agent, control temperature adds under conditions of 140~160 DEG C
Enter reaction raw materials 2,4- diaminophenol hydrochlorides and adipic acid, then heat to 160~210 DEG C, reaction is obtained after 5~8 hours
To product；
3rd, product is neutralized through sodium carbonate or NaOH, then obtains head product after washing, drying；
4th, head product is extracted with absolute ethyl alcohol, is finally vacuum dried, obtained [the 5- aminobenzenes of 2,2'- butylidenes two
Bing oxazoles] powder.
The reaction equation of present embodiment sand 2,2'- butylidenes two [5- An bases benzoxazole] powder is as follows：
Specific embodiment two：Present embodiment from step one poly phosphoric acid solution unlike specific embodiment one
P2O5Mass concentration be 80%~86%.Other steps and parameter are identical with specific embodiment one.
Specific embodiment three：Present embodiment is accounted for from step 2 reaction raw materials unlike specific embodiment one or two
The 13%~16% of poly phosphoric acid solution quality.Other steps and parameter are identical with specific embodiment one or two.
Specific embodiment four：Step 2 SnCl unlike one of present embodiment and specific embodiment one to three2
The addition molal weight of reducing agent is 5~10g/mol of reaction raw materials.Other steps and parameter and specific embodiment one to three
One of it is identical.
Specific embodiment five：The preparation method of present embodiment copolyamide I follow these steps to realize：
Under inert gas shielding atmosphere, to solvent NMP and TPP is added in reaction vessel, stirred after being heated to 100 DEG C
Mix, 120 DEG C are warming up to again after adding lithium chloride, 2,2'- butylidenes two [5- An bases benzoxazole] are subsequently adding, after dissolving completely
Polyethylene glycol dicarboxylic acids (Mn=600) and 2,5- diamino sulfonic acid sodium or 2,5- diamino sulfonic acid lithium are added, 130~140
Reacted 70~75 hours at a temperature of DEG C, purging adds deionized water by polymer fibrids after removing solvent, then through washing and first
Alcohol is cleaned, and vacuum drying obtains copolyamide I after filtering.
The reaction equation of present embodiment copolyamide I is as follows：
Specific embodiment six：Present embodiment and [the 5- amino of 2,2'- butylidenes two unlike specific embodiment five
Benzoxazole], the mol ratio of polyethylene glycol dicarboxylic acids and 2,5- diamino sulfonic acids sodium or 2,5- diamino sulfonic acid lithiums be 0.27：
0.5：0.23.Other steps and parameter are identical with specific embodiment five.
Specific embodiment seven：Present embodiment from unlike specific embodiment five or six at a temperature of 136 DEG C
Reaction 70~75 hours.Other steps and parameter are identical with specific embodiment five or six.
Specific embodiment eight：The preparation method of present embodiment copolyamide II follow these steps to realize：
Under inert gas shielding atmosphere, to solvent NMP and TPP is added in reaction vessel, stirred after being heated to 100 DEG C
Mix, 120 DEG C are warming up to again after adding lithium chloride, 2,2'- butylidenes two [5- An bases benzoxazole] are subsequently adding, after dissolving completely
Polyethylene glycol dicarboxylic acids (Mn=600) and 5-sodium sulfo isophthalate or M-phthalic acid -5- Sulfonic Lithiums are added, 130
Reacted 70~75 hours at a temperature of~140 DEG C, purging adds deionized water by polymer fibrids after removing solvent, then through washing
With methyl alcohol cleaning, vacuum drying obtains copolyamide II after filtering.
In present embodiment, the reaction equation of copolyamide II is as follows：
Specific embodiment five provide benzoxazole and polyethylene glycol dicarboxylic acids and 2,5- diamino sulfonic acids sodium or
2,5- diamino sulfonic acid lithium copolyamide I, specific embodiment eight provide benzoxazole and polyethylene glycol dicarboxylic acids and
5-sodium sulfo isophthalate or M-phthalic acid -5- Sulfonic Lithiums react to form copolyamide II, and benzoxazole is conducive to
Improve the mechanical property of polyether-based polymers, the easy film forming of polymer of formation.Lone pair electrons in amido link on nitrogen-atoms are favourable
In the transmission of lithium ion.
Specific embodiment nine：Present embodiment and [the 5- amino of 2,2'- butylidenes two unlike specific embodiment eight
Benzoxazole], the mol ratio of polyethylene glycol dicarboxylic acids and 5-sodium sulfo isophthalate or M-phthalic acid -5- Sulfonic Lithiums be
0.5：0.2：0.3.Other steps and parameter are identical with specific embodiment eight.
Specific embodiment ten：The method that present embodiment application copolyamide prepares thin polymer film follow these steps to reality
It is existing：
Copolyamide I or copolyamide II are dissolved in DMF solvent, polymer solution is obtained, at a temperature of 70~100 DEG C
Heating for dissolving 1~3 hour, pours into mould, in atmosphere solvent flashing after filtering, then heating 48~75 is small at 60~80 DEG C
When, thin polymer film is obtained after vacuum drying treatment.
The mass concentration of copolyamide I or copolyamide II is 4~10% in polymer solution described in present embodiment.
Specific embodiment 11：Present embodiment is from the thickness of thin polymer film unlike specific embodiment ten
50~200 μm.Other steps and parameter are identical with specific embodiment ten.
Specific embodiment 12：Present embodiment from will obtain gathering containing sodium sulfonate unlike specific embodiment ten
Compound film is immersed in LiClO4In the aqueous solution, thin polymer film of the synthesis containing Sulfonic Lithium.
Specific embodiment 13：Application copolyamide I or copolyamide II are used as all solid state lithium ion for present embodiment
The electrolyte of battery.
Specific embodiment 14：Using copolyamide I or copolyamide II as all-solid lithium-ion battery barrier film,
The just extremely lithium cobaltate cathode of all-solid lithium-ion battery, metal lithium sheet is negative pole, is specific embodiment eight between both positive and negative polarity
The thin polymer film of preparation.
Present embodiment lithium cobaltate cathode is that, using cobalt acid lithium as active material, acetylene black is conductive agent, Kynoar
It is bonding agent, the polymer dielectric film between both positive and negative polarity is all solid state electrolyte film, plays a part of to separate both positive and negative polarity, together
Shi Zuowei electrolyte is used.The charging and discharging capacity of the lithium ion battery assembled by copolyamide I films is 11mAh/g, by altogether
The charging and discharging capacity of the lithium ion battery of polyamide II films assembling is 2.9mAh/g.
Specific embodiment 15：Present embodiment is electric using copolyamide I or copolyamide II as all solid state lithium ion
The anodic composition in pond.
Embodiment one：The preparation method of the present embodiment 2,2'- butylidenes two [5- An bases benzoxazole] follow these steps to reality
It is existing：
First, to nitrogen is passed through in reaction vessel, by 9.78g phosphoric acid (phosphoric acid concentration is 85%) and 19.47gP2O5Mixing is equal
It is even, form poly phosphoric acid solution；
2nd, 4.3g (0.0105mol) 2,4- diaminophenol hydrochlorides and 1.46g (0.01mol) adipic acid conduct are weighed
Reaction raw materials, are cooled to 130 DEG C after poly phosphoric acid solution is heated into 150 DEG C of mechanic whirl-nett reactions 6 hours, molten to polyphosphoric acids
0.5gSnCl is added in liquid2Reducing agent, control temperature adds reaction raw materials 2,4- diaminobenzene phenates under conditions of 140 DEG C
Hydrochlorate and adipic acid, reaction are warming up to 210 DEG C after 3 hours, reaction obtains product after 5 hours；
3rd, in product plus distilled water is washed, and neutralized through sodium carbonate, then washing until product in it is neutral,
Head product is obtained after drying；
4th, head product is extracted with absolute ethyl alcohol, is finally vacuum dried 12h at 80 DEG C, obtain 2.9g sands 2,2'- is sub-
Butyl two [5- An bases benzoxazole] powder.
Embodiment two：The preparation method of the present embodiment copolyamide I follow these steps to realize：
In the case where nitrogen protective atmosphere encloses, in there-necked flask add solvent 60ml NMP and 3ml TPP, be heated to 100 DEG C it is laggard
Row stirring, 120 DEG C are warming up to after adding 4.2g lithium chlorides again, are subsequently adding 1.61g 2, [the 5- An base Ben Bing Evil of 2'- butylidenes two
Azoles], 6g polyethylene glycol dicarboxylic acids and 0.97g 2,5- diamino benzene sulfonic acid lithium are added after dissolving completely, in 140 DEG C of temperature
Lower reaction 72 hours, reaction solution is poured into beaker, is purged with air pump, deionized water is added by polymer fibrids, through washing, first
Filtered after alcohol cleaning, copolyamide I is obtained with 60 DEG C of vacuum drying 24h, the logarithmic specific concentration viscosity of copolyamide I is 3.7dL/g
(with DMF as solvent).
Embodiment three：The preparation method of the present embodiment copolyamide II follow these steps to realize：
In the case where nitrogen protective atmosphere encloses, in there-necked flask add solvent 60ml NMP and 3ml TPP, be heated to 100 DEG C it is laggard
Row stirring, 120 DEG C are warming up to after adding 4.2g lithium chlorides again, are subsequently adding [the 5- ammonia of 3.22g (0.01mol) 2,2'- butylidenes two
Base benzoxazole], 4.2g polyethylene glycol dicarboxylic acids and 0.756g M-phthalic acid -5- Sulfonic Lithiums are added after dissolving completely,
Reacted 72 hours at a temperature of 140 DEG C, reaction solution is poured into beaker, purged with air pump, add deionized water that polymer sinks
Analysis, through washing, is filtered after methyl alcohol cleaning, and copolyamide II is obtained with 60 DEG C of vacuum drying 24h, and the logarithm ratio of copolyamide II is dense
Viscosity is 3.9dL/g (with DMF as solvent).
Application Example one：The method that the present embodiment application copolyamide prepares thin polymer film follow these steps to realize：
0.2 gram of copolyamide I is dissolved in 6mL DMF solvents, polymer solution is obtained, the heating for dissolving at a temperature of 80 DEG C
2 hours, poured into mould after filtering, in atmosphere solvent flashing, then heated 72 hours in 70 DEG C of baking ovens, vacuum is done at 80 DEG C
After dry treatment 24 hours, thickness is obtained for 100 μm of thin polymer films.
The lithium ion conductivity of the thin polymer film that the present embodiment is obtained is 1.00 × 10-5S/cm, fracture strength is
13.24MPa。
Application Example two：The method that the present embodiment application copolyamide prepares thin polymer film follow these steps to realize：
0.2 gram of copolyamide II is dissolved in 6mL DMF solvents, polymer solution is obtained, heated at a temperature of 80 DEG C molten
Solution 2 hours, pours into mould, in atmosphere solvent flashing after filtering, then is heated 72 hours in 70 DEG C of baking ovens, vacuum at 80 DEG C
After dried process 6 hours, thickness is obtained for 100 μm of thin polymer films.
The lithium ion conductivity of the thin polymer film that the present embodiment is obtained is 6.70 × 10-6S/cm, fracture strength is
14.74MPa。
Claims (5)
1. the preparation method of copolyamide I, it is characterised in that be to follow these steps to realize：
Under inert gas shielding atmosphere, to solvent NMP and TPP is added in reaction vessel, it is stirred after being heated to 100 DEG C,
120 DEG C are warming up to again after adding lithium chloride, are subsequently adding 2,2'- butylidenes two [5- An bases benzoxazole], after dissolving completely again
Polyethylene glycol dicarboxylic acids and 2,5- diamino sulfonic acid sodium or 2,5- diamino sulfonic acid lithium are added, it is anti-at a temperature of 130~140 DEG C
Answer 70~75 hours, purging adds deionized water by polymer fibrids after removing solvent, then is cleaned through washing and methyl alcohol, after filtering
Vacuum drying obtains copolyamide I.
2. the preparation method of copolyamide I according to claim 1, it is characterised in that [the 5- aminobenzenes of 2,2'- butylidene two
Bing oxazoles], the mol ratio of polyethylene glycol dicarboxylic acids and 2,5- diamino sulfonic acids sodium or 2,5- diamino sulfonic acid lithiums be 0.27：0.5：
0.23。
3. the method that thin polymer film is prepared using copolyamide I, it is characterised in that be to follow these steps to realize：
Copolyamide I as claimed in claim 1 is dissolved in DMF solvent, polymer solution is obtained, in 70~100 DEG C of temperature
Lower heating for dissolving 1~3 hour, is poured into mould, in atmosphere solvent flashing after filtering, then 48~75 are heated at 60~80 DEG C
Hour, thin polymer film is obtained after vacuum drying treatment.
4. the method that application copolyamide I according to claim 3 prepares thin polymer film, it is characterised in that polymer thin
The thickness of film is 50~200 μm.
5. the electrolyte of all-solid lithium-ion battery, it is characterised in that copolyamide I as claimed in claim 1 is used as complete for application
The electrolyte of solid lithium ion battery.
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| CN201611261714.3A CN106749079B (en) | 2015-07-13 | 2015-07-13 | The amide electrolyte preparation method of diamines containing benzoxazoles and application |
| CN201510409009.2A CN105017171B (en) | 2015-07-13 | 2015-07-13 | The electrolyte preparation method of copolyamide containing benzoxazole and application |
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| CN105801830B (en) * | 2016-05-03 | 2018-01-19 | 中国航空工业集团公司北京航空材料研究院 | A kind of high temperature resistant makrolon and preparation method thereof |
| CN112442172A (en) * | 2019-08-30 | 2021-03-05 | 比亚迪股份有限公司 | Polymer matrix, electrolyte, preparation method of polymer matrix, preparation method of electrolyte, battery pole piece and lithium ion battery |
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| CN1271118C (en) * | 2004-05-27 | 2006-08-23 | 上海交通大学 | Polybenzoaazole with sulfonate as side group and its preparation |
| CN1250609C (en) * | 2004-05-27 | 2006-04-12 | 上海交通大学 | Benzimidazole with sulfonate as side group and benzoxaazole copolymer and its preparation |
| CN104183869B (en) * | 2014-08-25 | 2017-01-25 | 江苏明魁高分子材料技术有限公司 | Lithium single ionic conductive microporous electrolyte membrane and preparation method thereof |
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| CN105017171A (en) | 2015-11-04 |
| CN106749079A (en) | 2017-05-31 |
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