CN102361096A - Lithium ion gel electrolyte based on polymethyl methacrylate-polystyrene diblock copolymer, and preparation method thereof - Google Patents
Lithium ion gel electrolyte based on polymethyl methacrylate-polystyrene diblock copolymer, and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a lithium ion gel electrolyte based on a polymethyl methacrylate-polystyrene diblock copolymer, and a preparation method thereof. The technical scheme is characterized in that: the diblock copolymer comprises: 0.35-0.45 g of a polymer matrix, 0.55-0.65 g of a mixture, wherein the mixture comprises a plasticizer and a lithium salt, the concentration of the lithium salt in the plasticizer is 1 mol/L. The polymer matrix is the polymethyl methacrylate-polystyrene diblock copolymer synthesized by an atom transfer radical polymerization method. According to the present invention, the electrolyte system has good ionic conductivity; the required conditions by the preparation process are simple, and can be achieved by the ordinary laboratory, such that the method of the present invention is the method for preparing the gel electrolyte, wherein the method has characteristics of directness, simpleness, broad-applicability, and simple operation process.
Description
Technical field
The present invention relates to a kind of lithium ion gel electrolyte based on two block polymethyl methacrylate-polystyrene copolymers and preparation method thereof.
Background technology
Lithium ion battery is a kind of novel high-energy environment-friendly battery; For traditional ni-mh, ickel-cadmium cell; But lithium ion battery have voltage height, specific energy big, have extended cycle life, significant advantage such as the good fast charging and discharging of security performance; It is had broad application prospects in many-sides such as portable electric appts, electric automobile, space technology, national defense industry, become the research focus of widely paying close attention in recent years.It is gel polymer electrolyte (GPE) that lithium ion battery electrolyte can be divided into liquid electrolyte, full solid state polymer electrolyte (SPE) and solid-liquid composite electrolyte by its existence.Liquid electrolyte has higher ionic conductivity, but there is following problem in it in application process: safety problem, and high voltage or decompose when overcharging and produce gas, thus making the cell expansion distortion, might set off an explosion; Lithium ion battery difficult forming by the liquid electrolyte preparation; The liquid that is prone to produce electrolysis is revealed; And receive the restriction of extreme conditions such as high low temperature.Full solid state polymer electrolyte (SPE) is the transmission that " separating complexing-complexing again " process is accomplished lithium ion between the strong atom of the lithium ion that causes through polymer dielectric amorphous area sub-chain motion and electronegativity; So its ionic conductivity is limited by polymer architecture and sub-chain motion thereof, and be difficult to from the lower problem of basic solution conductivity.Gel-type polymer electrolyte (GPE) is the polymer network with suitable microstructure that is formed through the method for dissolving each other by polymer, plasticizer and solvent.Polymeric matrix mainly plays a supportive role, and electrolyte lithium salt mainly is dispersed in the swell gel, and ion transfer mechanism is similar with liquid electrolyte; Therefore ionic conductivity is high; In addition, simple liquid phase exists because liquid plasticizer is fixed in the gel, and its volatilization vaporization character is suppressed; When high temperature, can not produce expansion and the blast of moment, the heatproof fail safe is greatly enhanced.Because gel electrolyte has possessed the advantage of high-transmission performance two aspects of security performance and the liquid electrolyte of full solid state polymer electrolyte simultaneously, makes gel electrolyte have very vast potential for future development.
In the gel polymer electrolyte field, people are making great efforts to have simultaneously through the whole bag of tricks such as blend, copolymerization exploitations the gel polymer electrolyte of high ionic conductivity and heat, mechanical performance.One carbonyl side group is arranged in the MMA unit of polymethyl methacrylate (PMMA), very strong effect is arranged, therefore can contain a large amount of liquid electrolytes, have good compatibility with oxygen in the carbonates plasticizer; And PMMA series gel electrolyte has interface stability preferably to lithium electrode, and is low with the interface impedance of metal lithium electrode.Add the PMMA abundant raw material, preparation is simple, low price, thus cause the extensive interest of researcher to PMMA base gel electrolyte.But PMMA base GPE exists like defectives such as mechanical strength, structural stability, thermal stability and filming performance are relatively poor.
Summary of the invention
The technical problem that solves
For fear of the weak point of prior art, the present invention proposes a kind of lithium ion gel electrolyte based on two block polymethyl methacrylate-polystyrene copolymers and preparation method thereof.
Technical scheme
A kind of lithium ion gel electrolyte based on two block polymethyl methacrylate-polystyrene copolymers; It is characterized in that component is: polymeric matrix 0.35g～0.45g; Plasticizer and lithium salts gross mass are 0.55g～0.65g, and the concentration of lithium salts in plasticizer is 1mol/L; Said polymeric matrix is by the synthetic polymethyl methacrylate-polystyrene di-block copolymer of Transfer Radical Polymerization.
Said lithium salts is lithium perchlorate, lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium or two (trifluoromethyl sulphonyl) imines lithium.
Said plasticizer is one or more in propene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, carbonic acid Methylethyl ester, the dibutyl phthalate.
A kind ofly prepare above-mentioned any method, it is characterized in that step is following based on the lithium ion gel electrolyte of two block polymethyl methacrylate-polystyrene copolymers:
Step 1 adopts the synthetic polymethyl methacrylate macromole evocating agent of Transfer Radical Polymerization: monomer is methyl methacrylate MMA; Initator is 2-isobutyl ethyl bromide EBiB; Catalyst is stannous chloride CuCl and PMDETA PMDETA, and four kinds of material mol ratios are 50: 1: 2: 1～150: 1: 2: 1, mix being placed in the there-necked flask; Adopting oxolane is that solvent carries out polymerisation in solution; Nitrogen protection, reaction temperature are 50～65 ℃, and the reaction time is 4～6h; After reaction finished, solution was crossed the neutral alumina post and is removed copper ion, uses methanol extraction then, obtains white solid polymetylmethacrylate initator, puts into vacuum drying chamber and dries to constant weight in 40 ℃;
Step 2 adopts the polymethyl methacrylate-polystyrene copolymer PMMA-b-PS of the synthetic block ratio of Transfer Radical Polymerization: with reaction monomers is that styrene St, synthetic initator polymetylmethacrylate, the catalyst of step 1 are that CuCl and PMDETA mix styrene St: the mol ratio of MMA unit number: CuCl: PMDETA is 50～150 among the PMMA: 50: 1: 2; And then adopt N, and dinethylformamide is that solvent carries out polymerisation in solution, nitrogen protection, and reaction temperature is 80～100 ℃, the reaction time is 10～12h; After reaction finished, solution was crossed the neutral alumina post and is removed copper ion, uses methanol extraction then, obtains the white solid polymer, put into vacuum drying chamber and dried to constant weight in 40 ℃, obtained the polymethyl methacrylate-polystyrene copolymer of block ratio;
Step 3: lithium salts is dissolved in the plasticizer, is made into the solution that concentration is 1mol/L;
Step 4: the polymethyl methacrylate-polystyrene copolymer of the block ratio that step 2 is obtained is got 0.35～0.45g; Add 3～8mL oxolane; Treat to add the lithium salts plasticizer solution that 0.55～0.65g step 3 obtains after the polymer dissolution, ultrasonic 30min mixes solution under room temperature, uses the solution casting method film forming at last; Leave standstill 4～6h; Treat that oxolane partly volatilizees, put into baking oven, make lithium ion gel electrolyte based on two block polymethyl methacrylate-polystyrene copolymers in 40 ℃ of baking 12h.
Beneficial effect
The present invention proposes a kind of lithium ion gel electrolyte based on two block polymethyl methacrylate-polystyrene copolymers and preparation method thereof; Because containing the polymer of soft segment, rigid chain segment respectively is a kind of gel polymer electrolyte basis material with potential using value; Its rigid chain segment can provide stronger mechanical property and film forming preferably for gel rubber system; And soft segment can have with liquid electrolyte and combine preferably, thereby higher ionic conductivity is provided for gel electrolyte.Therefore we have selected for use methyl methacrylate and styrene to carry out ATRP, through regulating the molecular weight of polystyrene in the bi-block copolymer, have obtained the copolymer of three kinds of different block ratios, and have studied the influence of block comparison conductivity.
The present invention improves the combination property of PMMA base GPE through two aspects, mainly makes it form cross-linked network or changes its mechanical property and hot property with the rigid chain segment copolymerization through adding crosslinking agent on the one hand; On the other hand through improving the performance of gel polymer electrolyte with PMMA copolymerization or blend.This electrolyte system has good ionic conductivity.The required condition of prepared is simple, and common lab can reach, therefore be a kind of the most directly, the simplest, applicability is wide, operating procedure simply prepares gel electrolyte method.
Description of drawings
Fig. 1: be the present invention's two blocks polymethyl methacrylate-polystyrene copolymer synthesis and production process flow chart;
Fig. 2: be gel-type polymethyl methacrylate of the present invention-polystyrene-based electrolytical preparation technology's flow chart.
Embodiment
Combine embodiment, accompanying drawing that the present invention is further described at present:
Embodiment 1:
Step 1: the preparation of polymethyl methacrylate macromole evocating agent.Methyl methacrylate (MMA), initator 2-isobutyl ethyl bromide (EBiB), catalyst stannous chloride (CuCl)/PMDETA (PMDETA); Four kinds of material mol ratios are 50: 1: 2: 1～150: 1: 2: 1; Mix being placed in the there-necked flask, adopting oxolane is that solvent carries out polymerisation in solution, nitrogen protection; Reaction temperature is 50～65 ℃, and the reaction time is 4～6h.After reaction finishes; Solution is crossed the neutral alumina post and is removed copper ion; Use methanol extraction then, obtain white solid, put into vacuum drying chamber and dry to constant weight in 40 ℃; Be polymethyl methacrylate (PMMA) macromole evocating agent, it is 1.578 * 10 that gel permeation chromatography (GPC) records its number-average molecular weight
4, molecular weight distribution is 1.12.
Step 2: the preparation of di-block copolymer polymethyl methacrylate-polystyrene.With styrene, initator PMMA, Catalysts Cu Cl and PMDETA, four kinds of material mol ratios are 50: 1: 2: 1; Mix being placed in the there-necked flask, adopt N, dinethylformamide is that solvent carries out polymerisation in solution; Nitrogen protection, reaction temperature are 80～100 ℃, and the reaction time is 10～12h.After reaction finished, solution was crossed the neutral alumina post and is removed copper ion, uses methanol extraction then, obtains white solid, put into vacuum drying chamber and dried to constant weight in 40 ℃, obtained di-block copolymer PMMA-b-PS.It is 3.286 * 10 that gel permeation chromatography records its number-average molecular weight
3, molecular weight distribution is 1.38.Through calculating, MMA is 1: 1 with St block ratio in the block copolymer, and the copolymer note of present embodiment is made PMMA-b-1PS.
The preparation of step 3:PMMA-b-1PS base gel electrolyte: lithium salts is dissolved in the plasticizer, is made into the solution that concentration is 1mol/L; Take by weighing the di-block copolymer PMMA-b-1PS of 0.35g, add 3～8mL oxolane then, treat to add 0.65g after the polymer dissolution; The polymer quality mark is the lithium salts plasticizer solution of 35wt%, and ultrasonic 30min mixes solution under room temperature, uses the solution casting method film forming at last; Leave standstill 4～6h; Treat that oxolane partly volatilizees, put into baking oven, promptly make PMMA-b-1PS base lithium ion gel electrolyte in 40 ℃ of baking 12h.Said lithium salts is lithium perchlorate, lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium or two (trifluoromethyl sulphonyl) imines lithium; Said plasticizer is one or more in propene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, carbonic acid Methylethyl ester, the dibutyl phthalate.
The 2nd embodiment of embodiment 2:PMMA-b-1PS base gel electrolyte:
Step 1 is the same with embodiment 1 with step 2, and different is that the di-block copolymer PMMA-b-1PS that in step 3, adds is 0.40g; The lithium salts plasticizer solution that adds is 0.6g, and the polymer quality mark is 40wt%.
The 3rd embodiment of embodiment 3:PMMA-b-1PS base gel electrolyte:
Step 1 is the same with embodiment 1 with step 2, and different is that the di-block copolymer PMMA-b-1PS that in step 3, adds is 0.45g; The lithium salts plasticizer solution that adds is 0.55g, and the polymer quality mark is 45wt%.
Embodiment 4: step 1 is identical with embodiment 1, styrene in step 2, and initator PMMA, Catalysts Cu Cl and PMDETA, four kinds of material mol ratios are 100: 1: 2: 1, obtain di-block copolymer PMMA-b-1.5PS.It is 3.957 * 10 that gel permeation chromatography records its number-average molecular weight
3, molecular weight distribution is 1.21, and through calculating, MMA is 1: 1.5 with St block ratio in the block copolymer, and the copolymer note of present embodiment is made PMMA-b-1.5PS.
Carry out the preparation of the PMMA-b-1.5PS base gel electrolyte of step 3 with copolymer p MMA-b-1.5PS, lithium salts is dissolved in the plasticizer, be made into the solution that concentration is 1mol/L; Take by weighing the di-block copolymer PMMA-b-1.5PS of 0.35g, add 3～8mL oxolane then, treat the plasticizer solution of corresponding adding 0.65g lithium salts after the polymer dissolution; (the polymer quality mark is 35wt%), ultrasonic 30min mixes solution under room temperature, uses the solution casting method film forming at last; Leave standstill 4～6h; Treat that oxolane partly volatilizees, put into baking oven, make PMMA-b-1.5PS base lithium ion gel electrolyte in 40 ℃ of baking 12h.Said lithium salts is lithium perchlorate, lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium or two (trifluoromethyl sulphonyl) imines lithium; Said plasticizer is one or more in propene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, carbonic acid Methylethyl ester, the dibutyl phthalate.
The 2nd embodiment of embodiment 5:PMMA-b-1.5PS base gel electrolyte:
Step 1 is the same with embodiment 4 with step 2, and different is that the di-block copolymer PMMA-b-1.5PS that in step 3, adds is 0.40g, and the plasticizer solution of the lithium salts of adding is 060g, (the polymer quality mark is 40wt%).
The 3rd embodiment of embodiment 6:PMMA-b-1.5PS base gel electrolyte:
Step 1 is the same with embodiment 4 with step 2, and different is that the di-block copolymer PMMA-b-1.5PS that in step 3, adds is 0.45g, and the plasticizer solution of the lithium salts of adding is 055g, (the polymer quality mark is 45wt%).
Embodiment 7: step 1 is identical with embodiment 1, styrene in step 2, and initator PMMA, Catalysts Cu Cl and PMDETA, four kinds of material mol ratios are 150: 1: 2: 1, obtain di-block copolymer PMMA-b-1.8PS.It is 4.439 * 10 that gel permeation chromatography records its number-average molecular weight
3, molecular weight distribution is 1.15, and through calculating, MMA is 1: 1.8 with St block ratio in the block copolymer, and the copolymer note of present embodiment is made PMMA-b-1.8PS;
Carry out the preparation of the PMMA-b-1.8PS base gel electrolyte of step 3 with copolymer p MMA-b-1.8PS, lithium salts is dissolved in the plasticizer, be made into the solution that concentration is 1mol/L; Take by weighing the di-block copolymer PMMA-b-1.8PS of 0.35g, add 3～8mL oxolane then, treat the plasticizer solution (the polymer quality mark is 35wt%) of the lithium salts of corresponding adding 0.65g after the polymer dissolution; Ultrasonic 30min mixes solution under room temperature; Use the solution casting method film forming at last, leave standstill 4～6h, treat that oxolane partly volatilizees; Put into baking oven in 40 ℃ of baking 12h, promptly make PMMA-b-1.8PS base lithium ion gel electrolyte.Said lithium salts is lithium perchlorate, lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium or two (trifluoromethyl sulphonyl) imines lithium; Said plasticizer is one or more in propene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, carbonic acid Methylethyl ester, the dibutyl phthalate.
The 2nd embodiment of embodiment 8:PMMA-b-1.8PS base gel electrolyte:
Step 1 is the same with embodiment 7 with step 2, and different is that the di-block copolymer PMMA-b-1.8PS that in step 3, adds is 0.40g, and the plasticizer solution of the lithium salts of adding is 0.60g, (the polymer quality mark is 40wt%).
The 3rd embodiment of embodiment 9:PMMA-b-1.8PS base gel electrolyte:
Step 1 is the same with embodiment 7 with step 2, and different is that the di-block copolymer PMMA-b-1.8PS that in step 3, adds is 0.45g, and the plasticizer solution of the lithium salts of adding is 0.55g, (the polymer quality mark is 45wt%).
The performance based on the gel electrolyte film of two block polymethyl methacrylate-polystyrene copolymers of each item implementation condition and gained is as shown in table 1.
| Matrix | 35wt％ | 40wt％ | 45wt％ |
| PMMA | 3.18×10 -5 | 1.51×10 -5 | 1.27×10 -5 |
| PMMA-b-1PS | 2.71×10 -4 | 7.50×10 -5 | 5.73×10 -5 |
| PMMA-b-1.5PS | 9.80×10 -5 | 3.56×10 -5 | 2.55×10 -5 |
| PMMA-b-1.8PS | 7.65×10 -5 | 3.17×10 -5 | 2.06×10 -5 |
Claims (4)
1. lithium ion gel electrolyte based on two block polymethyl methacrylate-polystyrene copolymers; It is characterized in that component is: polymeric matrix 0.35g～0.45g; Plasticizer and lithium salts gross mass are 0.55g～0.65g, and the concentration of lithium salts in plasticizer is 1mol/L; Said polymeric matrix is by the synthetic polymethyl methacrylate-polystyrene di-block copolymer of Transfer Radical Polymerization.
2. according to the said lithium ion gel electrolyte based on two block polymethyl methacrylate-polystyrene copolymers of claim 1, it is characterized in that: said lithium salts is lithium perchlorate, lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium or two (trifluoromethyl sulphonyl) imines lithium.
3. according to the said lithium ion gel electrolyte based on two block polymethyl methacrylate-polystyrene copolymers of claim 1, it is characterized in that: said plasticizer is one or more in propene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, carbonic acid Methylethyl ester, the dibutyl phthalate.
4. one kind prepares said any method based on the lithium ion gel electrolyte of two block polymethyl methacrylate-polystyrene copolymers of claim 1～3, it is characterized in that step is following:
Step 1 adopts the synthetic polymethyl methacrylate macromole evocating agent of Transfer Radical Polymerization: monomer is methyl methacrylate MMA; Initator is 2-isobutyl ethyl bromide EBiB; Catalyst is stannous chloride CuCl and PMDETA PMDETA, and four kinds of material mol ratios are 50: 1: 2: 1～150: 1: 2: 1, mix being placed in the there-necked flask; Adopting oxolane is that solvent carries out polymerisation in solution; Nitrogen protection, reaction temperature are 50～65 ℃, and the reaction time is 4～6h; After reaction finished, solution was crossed the neutral alumina post and is removed copper ion, uses methanol extraction then, obtains white solid polymetylmethacrylate initator, puts into vacuum drying chamber and dries to constant weight in 40 ℃;
Step 2 adopts the polymethyl methacrylate-polystyrene copolymer PMMA-b-PS of the synthetic block ratio of Transfer Radical Polymerization: with reaction monomers is that styrene St, synthetic initator polymetylmethacrylate, the catalyst of step 1 are that CuCl and PMDETA mix styrene St: the mol ratio of MMA unit number: CuCl: PMDETA is 50～150 among the PMMA: 50: 1: 2; And then adopt N, and dinethylformamide is that solvent carries out polymerisation in solution, nitrogen protection, and reaction temperature is 80～100 ℃, the reaction time is 10～12h; After reaction finished, solution was crossed the neutral alumina post and is removed copper ion, uses methanol extraction then, obtains the white solid polymer, put into vacuum drying chamber and dried to constant weight in 40 ℃, obtained the polymethyl methacrylate-polystyrene copolymer of block ratio;
Step 3: lithium salts is dissolved in the plasticizer, is made into the solution that concentration is 1mol/L;
Step 4: the polymethyl methacrylate-polystyrene copolymer of the block ratio that step 2 is obtained is got 0.35～0.45g; Add 3～8mL oxolane; Treat to add the lithium salts plasticizer solution that 0.55～0.65g step 3 obtains after the polymer dissolution, ultrasonic 30min mixes solution under room temperature, uses the solution casting method film forming at last; Leave standstill 4～6h; Treat that oxolane partly volatilizees, put into baking oven, make lithium ion gel electrolyte based on two block polymethyl methacrylate-polystyrene copolymers in 40 ℃ of baking 12h.
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| CN105355972A (en) * | 2015-09-15 | 2016-02-24 | 江西省科学院能源研究所 | Interpenetrating polymer network structured nanometer SiO2 composite electrolyte and preparation method therefor |
| CN107946640A (en) * | 2017-11-07 | 2018-04-20 | 江汉大学 | A kind of preparation method of composite polymer electrolyte |
| CN108546308A (en) * | 2018-04-17 | 2018-09-18 | 华南理工大学 | Multiple response ionic gel and preparation method thereof based on super amphiphile, amphiphilic molecule |
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| CN109616697A (en) * | 2018-11-01 | 2019-04-12 | 深圳清华大学研究院 | Magnesium ion battery polymer dielectric film and preparation method thereof |
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| CN107946640B (en) * | 2017-11-07 | 2019-12-06 | 江汉大学 | Preparation method of composite polymer electrolyte |
| CN107946640A (en) * | 2017-11-07 | 2018-04-20 | 江汉大学 | A kind of preparation method of composite polymer electrolyte |
| CN108546308A (en) * | 2018-04-17 | 2018-09-18 | 华南理工大学 | Multiple response ionic gel and preparation method thereof based on super amphiphile, amphiphilic molecule |
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| CN109616697A (en) * | 2018-11-01 | 2019-04-12 | 深圳清华大学研究院 | Magnesium ion battery polymer dielectric film and preparation method thereof |
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| CN112457805B (en) * | 2020-10-27 | 2021-08-13 | 西安交通大学 | Adhesive, preparation method thereof, silicon-carbon negative electrode material and lithium battery |
| WO2023278996A1 (en) * | 2021-06-28 | 2023-01-05 | North Carolina State University | Gel polymer electrolyte composition and applications thereof |
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