CN109096433A - Single ion conductor polymer lithium salts and preparation method thereof - Google Patents

Single ion conductor polymer lithium salts and preparation method thereof Download PDF

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CN109096433A
CN109096433A CN201710472018.5A CN201710472018A CN109096433A CN 109096433 A CN109096433 A CN 109096433A CN 201710472018 A CN201710472018 A CN 201710472018A CN 109096433 A CN109096433 A CN 109096433A
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lithium salts
styryl
maleic anhydride
ion conductor
single ion
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CN109096433B (en
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封伟
曹晨
李瑀
冯奕钰
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Tianjin University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • 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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    • 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

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Abstract

The present invention discloses single ion conductor polymer lithium salts and preparation method thereof, which is made by the double sulfimide lithium salt monomers of styryl and maleic anhydride by simple free radical polymerization.Styryl double sulfimide will be generated under the action of triethylamine and 4-dimethylaminopyridine to styrenesulphonyl chloride and benzsulfamide first and in lithium hydroxide and obtaining the double sulfimide lithium salt monomers of styryl.Using azodiisobutyronitrile as initiator, the double sulfimide lithiums of styryl are bonded to together by way of simple radical copolymerization with maleic anhydride and form vinyl benzene sulfimide lithium salts and maleic anhydride alternate polymer.The present invention will have this high dielectric constant unit of maleic anhydride to be introduced into existing polymer lithium salts skeleton or segment, and promote the dissociation of lithium ion to will be the concentration for effectively increasing " freedom " lithium ion by its interaction between lithium ion, improve the approach of room temperature lithium ion conductivity and transport number.

Description

Single ion conductor polymer lithium salts and preparation method thereof
Technical field
The present invention relates to a kind of preparation of novel lithium single-ion polymer lithium salts, specifically a kind of alternating structure The preparation of dibenzenesulfonimide lithium base single-ion polymer lithium salts and its application in polymer dielectric.
Background technique
Compared with traditional liquid electrolyte lithium secondary battery, the solid lithium battery based on organic polyelectrolyte exists Battery energy density, operating temperature section, cycle life etc. have biggish room for promotion, are the important of lithium secondary battery Developing direction.Organic full solid state polymer electrolyte system not only have light, viscoelasticity is good, easy film forming, electrochemical window mouth width, Many advantages, such as chemical stability is good, moreover it is possible to inhibit the dendrite problems of lithium metal battery well.Use organic all solid state polymerization The lithium battery of object electrolyte can overcome easy-to-leak liquid, short circuit existing for liquid electrolyte battery, inadequate security problems, simultaneously also Compensate for the deficiency that inorganic solid electrolyte brittleness is big, film forming is poor, mechanical deformation is poor.In addition, this kind of battery can also use Soft encapsulating material, such as aluminum plastic film makes it allow to be bent and fold, promotes battery appearance design can more flexible, side Just, and overall quality is light, and specific energy increases substantially.
Usual organic solid-state polymer dielectric is all that zwitterion is conductive simultaneously, and lithium ion transference number is relatively low, only exists Between 0.2~0.5, some is even less than 0.1, and which greatly limits the applications of polymer dielectric.Because of most of electrification It learns device and is directed to direct current polarization problem, in charge and discharge process, anion can concentrate at electrode/electrolyte interface, occur Concentration polarization phenomenon generates and cuts down battery as a result, hindering the migration of lithium ion with the reversed polarizing voltage of extra electric field and fill The stability of discharge stream reduces the energy efficiency and service life of battery.Solve organic solid-state polymer dielectric internal poles The effective way of change problem is to prepare lithium ion transference number close to 1 polymer dielectric, and most important one is exactly to make The standby high single-ion polymer lithium salts of lithium ion transference number.Lithium is used for currently based on single-ion polymer lithium salts polymer dielectric Maximum restraining factors are that its ionic conductivity and lithium ion transference number under room temperature is lower in battery.Therefore, how to have The raising organic solid-state polymer dielectric of effect ionic conductivity at room temperature and lithium ion transference number are always people The hot spot of research.
Summary of the invention
The present invention devises a kind of new for ionic conductivity and the lower problem of lithium ion transference number under room temperature The alternating structure single-ion polymer lithium salts of type simultaneously proposes preparation method.
Technical purpose of the invention is achieved using following technical scheme:
Single ion conductor polymer lithium salts, by the double sulfimide lithium salts (STSSILi) of styryl and maleic anhydride (MA) Copolymerization is formed, shown in structure such as formula (I)
Wherein n indicates the degree of polymerization, selects maleic anhydride excessive when being copolymerized, so that styryl derivative and Malaysia Alternating polymerization, mole of styryl double sulfimide lithium salts (STSSILi) and maleic anhydride (MA) are tended in the copolymerization of acid anhydrides Than for 1:(1-1.5), preferably 1:(1.05-1.2).
Polymerization degree n is at least 100, preferably 200-1000 or 500-800.
The preparation method of single ion conductor polymer lithium salts, by the double sulfimide lithium salts of styryl and maleic anhydride molten It is evenly dispersed in agent dimethyl sulfoxide (DMSO), after thermal initiator and deoxygenation is added, it is warming up on initiation temperature and is polymerize Reaction, is terminated, and the dimethyl sulphoxide solution of polymer is deposited in tetrahydrofuran to after reaction, be passed through air In, it precipitates three times to remove unreacted monomer.
Moreover, selecting maleic anhydride excessive when being copolymerized, so that the copolymerization of styryl derivative and maleic anhydride Tend to alternating polymerization, the double sulfimide lithium salts (STSSILi) of styryl and the molar ratio of maleic anhydride (MA) are 1:(1- 1.5), preferably 1:(1.05-1.2).
Moreover, thermal initiator is azodiisobutyronitrile (AIBN) or benzoyl peroxide (BPO), initiation temperature are 60-80 degrees Celsius.
Moreover, the ratio of the sum of the amount of the substance of thermal initiator and amount of substance of two kinds of monomers is 0.1~0.5% (i.e. Molar ratio), preferably 0.1~0.3%.
Moreover, causing the radical polymerization of monomer styrene base double sulfimide lithium salts and maleic anhydride using thermal initiator It closes, selects maleic anhydride excessive, so that alternating polymerization is tended in the copolymerization of styryl derivative and maleic anhydride, such as attached drawing 5 Shown, the peak at 136.6 in carbon spectrum demonstrates its alternating structure, and polymerization time at least 20 hours, so that addition monomer is abundant Polymerization, preferably 24-48 hours.
Moreover, the structure and preparation approach of the double sulfimide lithium salts (STSSILi) of styryl, shown in following chemical formula:
It is dispersed in acetonitrile using benzsulfamide, and triethylamine and the evenly dispersed juxtaposition of 4-dimethylaminopyridine is added In 0 DEG C of ice bath, the molar ratio of triethylamine and benzsulfamide is (1-3): Isosorbide-5-Nitrae-dimethylamino naphthyridine and benzsulfamide rub You are than being (1-2): 1；Styrenesulphonyl chloride will be dispersed in acetonitrile with benzsulfamide equimolar ratio, and is added drop-wise to It in the acetonitrile solution of benzsulfamide, is stood after being added dropwise, and is warming up to 20-25 degrees Celsius of room temperature and is reacted, can be obtained The double sulfimides of styryl, then the double sulfimides of the styryl of equimolar ratio and lithium hydroxide are placed in distilled water and are stirred To clear solution, distilled water is spin-dried for using Rotary Evaporators to obtain the double sulfimide lithium salt monomers (STSSILi) of styryl.
Specifically, benzsulfamide is dissolved in acetonitrile solution, is configured to the solution that concentration is 0.5~1mol/L.By three Ethamine (Et3N) and 4-dimethylaminopyridine (DMAP) puts into benzene sulfonyl according to 3 times of benzsulfamide mole and 1 times respectively The acetonitrile solution of amine is placed in 0 DEG C of ice bath 30 minutes.The bodies such as the concentration preparation according to above-mentioned benzsulfamide acetonitrile solution The long-pending acetonitrile solution to styrenesulphonyl chloride, and be slowly added drop-wise to in benzsulfamide solution.After being added dropwise, 30 are stood Minute, temperature is warmed to room temperature and is reacted 48 hours.After reaction, the acetonitrile in system is removed with Rotary Evaporators, it will Obtained solid re-dissolve in methylene chloride.Successively use excessive 4% saturated sodium bicarbonate (NaHCO3) aqueous solution and The hydrochloric acid of 1mol/L washs above-mentioned solution.After washed, methylene chloride is spin-dried for Rotary Evaporators obtaining benzene again The double sulfimides of vinyl.The double sulfimides of the styryl of equivalent mole and lithium hydroxide (LiOH) are placed in 50ml distillation Distilled water is spin-dried for obtaining the double sulfimide lithium salt monomers of styryl later with Rotary Evaporators by stirring to clear solution in water (STSSILi)。
Through nuclear magnetic resonance and examination of infrared spectrum, it is known that judge the double sulfimide lithium salt monomers (STSSILi) of styryl It is succeeded preparation, and single ion conductor polymer lithium salts shows the double sulfimide lithium salts of monomer styrene base and maleic anhydride Alternating copolymerization structure.
The present invention will have this high dielectric constant unit of maleic anhydride to be introduced into existing polymer lithium salts skeleton or segment In, and promote the dissociation of lithium ion to will be one by its interaction between lithium ion and effectively increase " freedom " lithium ion Concentration, improve the approach of room temperature lithium ion conductivity and transport number, i.e., single ion conductor polymer lithium salts of the invention mentioning Application in high room temperature (20-25 degrees Celsius) lithium ion conductivity and transport number.
Detailed description of the invention
Fig. 1 is the infrared suction of Fourier of the double sulfimide lithium salt monomers (STSSILi) of styryl synthesized in the present invention Receive spectrum spectrogram.
Fig. 2 is the nucleus magnetic hydrogen spectrum spectrogram of the double sulfimide lithium salt monomers (STSSILi) of styryl synthesized in the present invention.
Fig. 3 is that the Fourier of the single ion conductor polymer lithium salts P (STSSILi-alt-MA) synthesized in the present invention is infrared Absorption spectrum spectrogram.
The nucleus magnetic hydrogen spectrum spectrum that Fig. 4 is the single ion conductor polymer lithium salts P (STSSILi-alt-MA) synthesized in the present invention Figure.
The nuclear-magnetism carbon spectrum spectrum that Fig. 5 is the single ion conductor polymer lithium salts P (STSSILi-alt-MA) synthesized in the present invention Figure.
Fig. 6 is polymer made of the single ion conductor polymer lithium salts P (STSSILi-alt-MA) that synthesizes in the present invention The room temperature AC impedance figure of electrolyte.
Fig. 7 is polymer made of the single ion conductor polymer lithium salts P (STSSILi-alt-MA) that synthesizes in the present invention The current polarizing curve graph of electrolyte.
Fig. 8 is polymer made of the single ion conductor polymer lithium salts P (STSSILi-alt-MA) that synthesizes in the present invention AC impedance figure before and after the polarization of electrolyte.
Specific embodiment
Technical solution of the present invention is further illustrated combined with specific embodiments below.
The preparation of the double sulfimide lithium salt monomers (STSSILi) of styryl is carried out first
Benzsulfamide is dissolved in acetonitrile solution, the solution that concentration is 0.5mol/L is configured to.By triethylamine (Et3N) and 4-dimethylaminopyridine (DMAP) puts into the acetonitrile solution of benzsulfamide according to 3 times of benzsulfamide mole and 1 times respectively, It is placed in 0 DEG C of ice bath 30 minutes.It is prepared according to the concentration of above-mentioned benzsulfamide acetonitrile solution isometric to styrene The acetonitrile solution of sulfonic acid chloride, and be slowly added drop-wise to in benzsulfamide solution.After being added dropwise, 30 minutes are stood, by temperature It is warmed to room temperature and reacts 48 hours.After reaction, the acetonitrile in system is removed with Rotary Evaporators, the solid weight that will be obtained In new dissolution and methylene chloride.Successively with the saturated sodium bicarbonate (NaHCO of excess 4wt%3) aqueous solution and 1mol/L hydrochloric acid (aqueous solution of hydrogen chloride) washs above-mentioned solution.After washed, again methylene chloride is spin-dried for obtaining with Rotary Evaporators Obtain the double sulfimides of styryl.The double sulfimides of the styryl of equivalent mole and lithium hydroxide (LiOH) are placed in 50ml Distilled water is spin-dried for obtaining the double sulfimide lithium salts of styryl later with Rotary Evaporators by stirring to clear solution in distilled water Monomer (STSSILi).
The double sulfimide lithium salts of 1-styryl of embodiment and maleic anhydride alternate polymer P (STSSILi-alt-MA) Preparation
Lithium salts monomer STSSILi and maleic anhydride (MA) are poured into polymerization pipe according to molar ratio 1:1.2, dimethyl is added Sulfoxide (DMSO) is dissolved, and the azodiisobutyronitrile (AIBN) of 0.1% (molar ratio) is added.Polymerization pipe is put into cold in liquid nitrogen It lacks, carries out logical nitrogen-and vacuumize to be reacted 48 hours with alcohol blast burner tube sealing and being put into 60 DEG C of oil bath pan afterwards three times.Reaction knot Shu Hou opens polymerization pipe, in exposure air.The DMSO solution of polymer is deposited in tetrahydrofuran, precipitating is three times to remove Unreacted monomer.
The double sulfimide lithium salts of 2-styryl of embodiment and maleic anhydride alternate polymer P (STSSILi-alt-MA) Preparation
Lithium salts monomer STSSILi and maleic anhydride (MA) are poured into polymerization pipe according to molar ratio 1:1.05, diformazan is added Base sulfoxide (DMSO) is dissolved, and the azodiisobutyronitrile (AIBN) of 0.2% (molar ratio) is added.Polymerization pipe is put into liquid nitrogen It is cold to lack, it carries out logical nitrogen-and vacuumizes to be reacted 36 hours with alcohol blast burner tube sealing and being put into 80 DEG C of oil bath pan afterwards three times.Reaction After, polymerization pipe is opened, in exposure air.The DMSO solution of polymer is deposited in tetrahydrofuran, is precipitated three times to remove Remove unreacted monomer.
The double sulfimide lithium salts of 3-styryl of embodiment and maleic anhydride alternate polymer P (STSSILi-alt-MA) Preparation lithium salts monomer STSSILi and maleic anhydride (MA) are poured into polymerization pipe according to molar ratio 1:1.2, it is sub- that dimethyl is added Sulfone (DMSO) is dissolved, and the azodiisobutyronitrile (AIBN) of 0.3% (molar ratio) is added.Polymerization pipe is put into cold in liquid nitrogen It lacks, carries out logical nitrogen-and vacuumize to be reacted 40 hours with alcohol blast burner tube sealing and being put into 70 DEG C of oil bath pan afterwards three times.Reaction knot Shu Hou opens polymerization pipe, in exposure air.The DMSO solution of polymer is deposited in tetrahydrofuran, precipitating is three times to remove Unreacted monomer.
The double sulfimide lithium salts of 4-styryl of embodiment and maleic anhydride alternate polymer P (STSSILi-alt-MA) Preparation
Lithium salts monomer STSSILi and maleic anhydride (MA) are poured into polymerization pipe according to molar ratio 1:1.3, dimethyl is added Sulfoxide (DMSO) is dissolved, and the azodiisobutyronitrile (AIBN) of 0.5% (molar ratio) is added.Polymerization pipe is put into cold in liquid nitrogen It lacks, carries out logical nitrogen-and vacuumize to be reacted 48 hours with alcohol blast burner tube sealing and being put into 60 DEG C of oil bath pan afterwards three times.Reaction knot Shu Hou opens polymerization pipe, in exposure air.The DMSO solution of polymer is deposited in tetrahydrofuran, precipitating is three times to remove Unreacted monomer.
It regard the alternating polymer P (STSSILi-alt-MA) of the above embodiment of the present invention as polymer dielectric, uses Stainless steel substrates are yin-yang the two poles of the earth, carry out room temperature ac impedance measurement using Shanghai Chen Hua company electrochemical workstation, are fitted to it And it is average up to 2.5-2.8mS cm to calculate room-temperature conductivity-1；Stainless steel substrates are changed to lithium piece, carry out current polarizing survey The AC impedance figure of examination, typical room temperature AC impedance figure, current polarizing curve and polarization front and back is as shown in the picture, calculates and moves It moves number and averagely reaches 0.98 or more.
The adjustment of preparation technology parameter is carried out according to the content of present invention, and alternating polymer P (STSSILi-alt- can be achieved MA preparation), and the performance as polymer dielectric and above-described embodiment are almost the same.The present invention is done above exemplary Description, it should explanation, in the case where not departing from core of the invention, it is any it is simple deformation, modification or other Those skilled in the art can not spend the equivalent replacement of creative work to each fall within protection scope of the present invention.

Claims (9)

1. single ion conductor polymer lithium salts, which is characterized in that by the double sulfimide lithium salts of styryl and maleic anhydride It is formed, shown in structure such as formula (I)
Wherein n indicates the degree of polymerization, selects maleic anhydride excessive when being copolymerized, so that styryl derivative and maleic anhydride Copolymerization tend to alternating polymerization, the molar ratio of the double sulfimide lithium salts of styryl and maleic anhydride is 1:(1-1.5), it is excellent Select 1:(1.05-1.2).
2. single ion conductor polymer lithium salts according to claim 1, which is characterized in that polymerization degree n is at least 100, excellent It is selected as 200-1000 or 500-800.
3. the preparation method of single ion conductor polymer lithium salts, which is characterized in that by the double sulfimide lithium salts of styryl and horse It is evenly dispersed in solvent dimethyl sulfoxide to carry out acid anhydrides, after thermal initiator and deoxygenation is added, is warming up on initiation temperature and carries out Polymerization reaction selects maleic anhydride excessive, so that the copolymerization of styryl derivative and maleic anhydride is inclined to when being copolymerized In alternating polymerization, the molar ratio of the double sulfimide lithium salts of styryl and maleic anhydride is 1:(1-1.5), preferably 1:(1.05- 1.2)。
4. the preparation method of single ion conductor polymer lithium salts according to claim 3, which is characterized in that the end of reacting Afterwards, it is passed through air to be terminated, and the dimethyl sulphoxide solution of polymer is deposited in tetrahydrofuran, precipitating is three times to remove Unreacted monomer.
5. the preparation method of single ion conductor polymer lithium salts according to claim 3, which is characterized in that thermal initiator is Azodiisobutyronitrile or benzoyl peroxide, initiation temperature are 60-80 degrees Celsius.
6. the preparation method of single ion conductor polymer lithium salts according to claim 3, which is characterized in that thermal initiator The ratio of the sum of the amount of substance and the amount of substance of two kinds of monomers is 0.1~0.5% (i.e. molar ratio), preferably 0.1~0.3%.
7. the preparation method of single ion conductor polymer lithium salts according to claim 3, which is characterized in that polymerization time is extremely It is 20 hours few, so that addition monomer sufficiently polymerize, preferably 24-48 hours.
8. the preparation method of single ion conductor polymer lithium salts according to claim 3, which is characterized in that styryl is double Sulfimide lithium salts is prepared as steps described below: be dispersed in acetonitrile using benzsulfamide, and be added triethylamine and In the evenly dispersed ice bath for being placed in 0 DEG C of 4-dimethylaminopyridine, the molar ratio of triethylamine and benzsulfamide is (1-3): Isosorbide-5-Nitrae- The molar ratio of dimethylamino naphthyridine and benzsulfamide is (1-2): 1；By with benzsulfamide equimolar ratio to styrenesulphonyl chloride It is dispersed in acetonitrile, and is added drop-wise in the acetonitrile solution of benzsulfamide, stood after being added dropwise, and be warming up to room temperature 20- 25 degrees Celsius are reacted, and can be obtained the double sulfimides of styryl, then by the double sulfimides of the styryl of equimolar ratio Stirring in distilled water is placed in lithium hydroxide to be spin-dried for distilled water using Rotary Evaporators to obtain styryl pair to clear solution Sulfimide lithium salt monomer.
9. single ion conductor polymer lithium salts as described in claim 1 or 2 improve room temperature (20-25 degrees Celsius) lithium from Application in electron conductivity and transport number.
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CN112133962A (en) * 2020-09-25 2020-12-25 天津大学 Preparation method of bis (trifluoromethyl) sulfimide lithium-glucose carbon quantum dot solid electrolyte
CN112552450A (en) * 2019-09-10 2021-03-26 天津大学 Single-ion alternating copolymer lithium salt and preparation method thereof
CN112898457A (en) * 2019-12-03 2021-06-04 巴莱诺斯清洁能源控股公司 Single ion conducting polymers for electrochemical devices
CN113097566A (en) * 2021-04-01 2021-07-09 山东海科新源材料科技股份有限公司 Imide additive containing sulfonated side chain, electrolyte and lithium ion battery thereof
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CN112552450A (en) * 2019-09-10 2021-03-26 天津大学 Single-ion alternating copolymer lithium salt and preparation method thereof
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CN112018439A (en) * 2020-08-31 2020-12-01 天津大学 Preparation and application of solid electrolyte based on polyvinyl benzene sulfonic acid lithium-citric acid carbon dots
CN112133962A (en) * 2020-09-25 2020-12-25 天津大学 Preparation method of bis (trifluoromethyl) sulfimide lithium-glucose carbon quantum dot solid electrolyte
WO2022069384A1 (en) * 2020-09-30 2022-04-07 Fujifilm Manufacturing Europe Bv Compositions and polymer films
CN113097566A (en) * 2021-04-01 2021-07-09 山东海科新源材料科技股份有限公司 Imide additive containing sulfonated side chain, electrolyte and lithium ion battery thereof
CN116554804A (en) * 2023-07-12 2023-08-08 深圳海辰储能控制技术有限公司 Modified styrene-butadiene latex binder, preparation method thereof, battery pole piece and secondary battery
CN116554384A (en) * 2023-07-12 2023-08-08 深圳海辰储能控制技术有限公司 Modified polyvinylidene fluoride, preparation method thereof, active material composition, positive electrode plate and energy storage device
CN116554384B (en) * 2023-07-12 2023-09-22 深圳海辰储能控制技术有限公司 Modified polyvinylidene fluoride, preparation method thereof, active material composition, positive electrode plate and energy storage device
CN116554804B (en) * 2023-07-12 2023-09-26 深圳海辰储能控制技术有限公司 Modified styrene-butadiene latex binder, preparation method thereof, battery pole piece and secondary battery

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