CN101557017A - Full solid state polymer electrolyte used for lithium sulphur battery and preparation thereof - Google Patents
Full solid state polymer electrolyte used for lithium sulphur battery and preparation thereof Download PDFInfo
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- CN101557017A CN101557017A CNA2009100433257A CN200910043325A CN101557017A CN 101557017 A CN101557017 A CN 101557017A CN A2009100433257 A CNA2009100433257 A CN A2009100433257A CN 200910043325 A CN200910043325 A CN 200910043325A CN 101557017 A CN101557017 A CN 101557017A
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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
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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
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention designs and synthesizes a novel principal chain containing sulphur polymer electrolyte. PEG is stem grafted on the principal chain of an organic dihalo-compound, and sulphur containing polymer (PSPEG) is prepared by polymerization of sulphur-sulphur bonds; finally THF is used as solvent, sulphur containing polymer is mixed with lithium salts, the solvent THF is evaporated and removed to obtain the sulphur containing polymer electrolyte. The polymer electrolyte combines the advantages of polysulfide and low molecular weight PEG; the sulphur containing polymer principal chain has certain rigidity to reinforce the mechanical performance of the electrolyte. At the same time, the sulphur containing principal chain leads the polymer to have better bonding performance, so that the compatibility of electrolyte and electrode materiel can be improved. The low molecular weight PEG stem grafted at the lateral chain has a lower glass transition temperature, the ether-oxygen group on the PEG chain can be complexed with lithium ions and can swing back and forth around the polymer principal chain to achieve the aim of transmitting the lithium ions, thus having higher ion electrical conductivity.
Description
Technical field
The invention belongs to polymer secondary lithium-sulfur cell field, be specifically related to a kind of full solid state polymer electrolyte that is used for lithium-sulfur cell and preparation method thereof.
Background technology
The used electrolyte system of lithium-sulfur cell of research report is mainly liquid electrolyte at present, but uses remain the same with other lithium metal secondary battery of Li/S battery of organic electrolyte needing some technical problems of solution badly.The safety issue of first battery, the difficult processing of this liquid electrolyte (needing metal shell), poor heat stability explosive.It two is lithium anode and electrolyte reactions in charge and discharge process, causes the battery capacity decay.Its three, elemental sulfur and discharging product Li
2S etc. are non-conductive, constantly assemble forming non-conductive zone in the charge and discharge cycles process, finally lose electro-chemical activity; In addition, the sulphur positive pole is created on soluble polysulfide in the organic electrolyte in discharge process, electrolyte was lost efficacy, thereby reduce its cycle performance.
Summary of the invention
The object of the invention provides that a kind of fail safe is good, raw material are easy to get productive rate height, easily processing, conductivity height, Heat stability is good (more than 250 ℃), and good with the compatibility of sulfur electrode, there is not novel sulphur containing principal chain polymer dielectric of the molten damage of electrode and preparation method thereof.
The objective of the invention is to realize in the following manner.
A kind of full solid state polymer electrolyte that is used for lithium-sulfur cell is that the ether oxygen groups complexing on the PEG side chain of structural polymer shown in formula A or the B has lithium ion,
Formula A formula B
The value of m is 8 or 12, and the value of n is 60～120.
The molecular weight of described formula A or formula B polymer is between 30000～45000.
The described preparation method who is used for the full solid state polymer electrolyte of lithium-sulfur cell is with PEG and organic dihalide compound hybrid reaction, after the petroleum ether layering, get the upper solution decompression distillation and go out benzinum, obtain the polyglycol ether of organic dihalide compound, again with Na
2S
2Aggregating into sulfur-containing polymer, is solvent at last with THF, and sulfur-containing polymer is mixed with lithium salts, and solvent THF volatilization is removed, and promptly obtains the sulfur-containing polymer electrolyte.
Described organic dihalide compound is 1,3-two chloro-2-propyl alcohol or 1,2-dihalo--2 Methylpropionic acid.
Described PEG is the polyethylene glycol of PEG400 or 600.
The preparation method of the described full solid state polymer electrolyte that is used for lithium-sulfur cell is specific as follows: successively PEG and organic dihalide compound were pressed amount of substance 1.3: 1, catalyst adds in the three-necked bottle, 110～140 ℃ of oil baths heating, condensing reflux, nitrogen protection; The mixed solution petroleum ether of reaction after finishing behind the standing demix, got the upper solution decompression distillation and gone out benzinum, obtains the polyglycol ether of organic dihalide compound, again with the polyglycol ether and the Na of organic dihalide compound
2S
2By 1: 1 amount of substance hybrid reaction, leave standstill reaction 3 hours under 70 ℃ of water-bath heating, leave standstill cooling 1 hour then, the bottle end, form yellow thick colloid; It is dry to take out the colloid washing; Be dissolved in oxolane after the drying, staticly settle, filter the collection mother liquid evaporation and fall THF, residue is a sulfur-containing polymer, is solvent with THF more at last, and sulfur-containing polymer is mixed with lithium salts, and solvent THF volatilization is removed, and promptly obtains the sulfur-containing polymer electrolyte.
Organic dihalide compound molecular backbone is for containing hydroxyl, organic dihalide compound that carboxyl etc. can react with the terminal hydroxy group of PEG, and as 1,3-two chloro-2-propyl alcohol, 1,2-dihalo--2 Methylpropionic acid etc.; Said PEG can be the polyethylene glycol of molecular weight 400,600; Wherein said lithium salts is for the various corresponding organic-inorganic salt of lithium ion can be provided, as lithium perchlorate, and periodic acid lithium, lithium hexafluoro phosphate etc.
Polymer dielectric of the present invention is in conjunction with the advantage of polysulfides and low-molecular-weight PEG, and the main polymer chain of sulfur-bearing has certain rigid, to strengthen electrolytical mechanical performance.Simultaneously, sulphur containing principal chain makes polymer that adhesive property preferably be arranged, and can improve the compatibility of electrolyte and electrode material.The small component PEG of side chain scion grafting has lower glass transition temperature, the ether oxygen group on the PEG chain can with the lithium ion complexing, reach the purpose of transmission lithium ion by near main polymer chain, swinging back and forth, have higher ionic conductivity.
The present invention compares with the liquid electrolyte that existing lithium-sulfur cell is used, and has following advantage: one, polymer dielectric have suppressed the growth of lithium dendrite arm; Its two, do not have leak of liquid, thereby improved the fail safe of battery; Its three, suppress the problems that sulphur, lithium and electrolyte interaction are caused; Its four, the adaptability of cell shapes strengthens, discharging and recharging number of times increases, and makes its range of application more extensive.
The solid polymer electrolyte of the present invention preparation, the raw material productive rate height that is easy to get, processing simple (the plastics Soft Roll gets final product), the conductivity height, there is not the problem of the molten damage of electrode in Heat stability is good (more than 250 ℃), and good with the compatibility of sulfur electrode.
Embodiment
The invention will be further described below by embodiment and Comparative Examples, rather than restriction the present invention.
Embodiment 1
Measure 8ml (about 0.1mol) concentrated hydrochloric acid (15.6mol/L) and put into the 100ml round-bottomed flask, 55 ℃ of following water-baths add thermal agitation, with Drop-adding device 4.630g (0.05mol) epoxychloropropane are slowly splashed in the bottle.React after 4 hours, bottle internal reaction liquid is poured in the separatory funnel, isolate lower floor's liquid,, remove impurity and promptly get 1,3-two chloro-2-propyl alcohol 55 ℃ of left and right sides decompression distillation.Successively with PEG400,1,3-two chloro-2-propyl alcohol are pressed amount of substance, and 1.3: 1, the catalyst concentrated sulfuric acid add in the three-necked bottle 140 ℃ of oil baths heating, condensing reflux, nitrogen protection.When the back-flow velocity of vapour-liquid in the reflux condensing tube is very slow, can think that then etherification reaction finishes substantially.Stop reaction and take out mixed solution, use petroleum ether, standing demix, lower floor is unreacted 1,3-two chloro-2-propyl alcohol, at 50 ℃ of following decompression distillation benzinum mixed liquors, the collection remaining liq is product.With previous step obtain 1,3-two chloro-2-propyl alcohol polyglycol ether and Na
2S
2Carry out hybrid reaction by 1: 1 amount of substance.Leave standstill reaction 3 hours under 70 ℃ of water-bath heating, leave standstill cooling 1 hour then, the bottle end, form yellow thick colloid.Add the distilled water boiling washing then for several times with washing in the distilled water after taking out this colloid, when distilled water becomes muddy, change water and repeat obviously muddy until no longer taking place for several times.Take out colloid 70 ℃ of following aeration-dryings in drying box.Dry fully after with its stirring and dissolving in oxolane, leave standstill 0.5h under 0 ℃, make the insoluble matter precipitation, filter and collect mother liquor and in vacuum drying chamber, evaporate THF under 50 ℃, residue is a final objective product sulfur-containing polymer.With sulfur-containing polymer and LiClO
4Before the use respectively at 50 ℃ and 120 ℃ of following vacuumize 24h.With sulfur-containing polymer, LiClO
4[EO] in molar ratio: the ratio of [Li]=8: 1 is dissolved among the THF, stirs and obtains uniform solution.Pour electrolyte solution into the polytetrafluoroethylene mould, make it natural film forming in dry environment, remove residual solvent at 40 ℃ of following vacuumize 48h then, promptly make composite polymer electrolyte membrane.
Embodiment 2
Identical with embodiment 1 step, change PEG400 into PEG600
Embodiment 3
Take by weighing 0.432g (about 0.05mol) methacrylic acid and put into the 100ml round-bottomed flask, 0 ℃ of following water-bath adds thermal agitation, with Drop-adding device 12ml (about 0.1mol) liquid bromine is slowly splashed in the bottle.React after 1 hour, bottle internal reaction liquid is poured in the separatory funnel, isolate lower floor's liquid,, remove impurity and promptly get 1,2-two bromo-2 Methylpropionic acids 55 ℃ of left and right sides decompression distillation.Successively with PEG400,1,2-two bromo-2 Methylpropionic acids are pressed amount of substance, and 1.3: 1, catalyst add in the three-necked bottle 110 ℃ of oil baths heating, condensing reflux, nitrogen protection.When the back-flow velocity of vapour-liquid in the reflux condensing tube is very slow, can think that then esterification finishes substantially.Stop reaction and take out mixed solution, use petroleum ether, standing demix, lower floor is unreacted 1,2-two bromo-2 Methylpropionic acids, at 50 ℃ of following decompression distillation benzinum mixed liquors, the collection remaining liq is product.With previous step obtain 1,2-two bromo-2 Methylpropionic acid polyglycol ether and Na
2S
2Carry out hybrid reaction by 1: 1 amount of substance.Leave standstill reaction 3 hours under 70 ℃ of water-bath heating, leave standstill cooling 1 hour then, the bottle end, form yellow thick colloid.Add the distilled water boiling washing then for several times with washing in the distilled water after taking out this colloid, when distilled water becomes muddy, change water and repeat obviously muddy until no longer taking place for several times.Take out colloid 70 ℃ of following aeration-dryings in drying box.Dry fully after with its stirring and dissolving in oxolane, leave standstill 0.5h under 0 ℃, make the insoluble matter precipitation, filter and collect mother liquor and in vacuum drying chamber, evaporate THF under 50 ℃, residue is a final objective product sulfur-containing polymer.With sulfur-containing polymer and LiClO
4Before the use respectively at 50 ℃ and 120 ℃ of following vacuumize 24h.With sulfur-containing polymer, LiClO
4[EO] in molar ratio: the ratio of [Li]=8: 1 is dissolved among the THF, stirs and obtains uniform solution.Pour electrolyte solution into the polytetrafluoroethylene mould, make it natural film forming in dry environment, remove residual solvent at 40 ℃ of following vacuumize 48h then, promptly make composite polymer electrolyte membrane.
Embodiment 4
Identical with embodiment 3 steps, change PEG400 into PEG600
Comparative example 1
With PEO (600,000) and LiClO
4Before the use respectively at 50 ℃ and 120 ℃ of following vacuumize 24h.To contain PEO, LiClO
4[EO] in molar ratio: the ratio of [Li]=8: 1 is dissolved among the THF, stirs and obtains uniform solution.Pour electrolyte solution into the polytetrafluoroethylene mould, make it natural film forming in dry environment, remove residual solvent at 40 ℃ of following vacuumize 48h then, promptly make composite polymer electrolyte membrane.
Respectively embodiment 1～4 and comparative example 1 prepared polymer dielectric film are tested by CHI660 electrochemical workstation (occasion China, Shanghai), exchanging the disturbance voltage magnitude is 30mV, and frequency range is 1～10000Hz.Obtain the conductivity (σ) under the different temperatures, its result is as shown in the table.
The conductivity of each polymer dielectric of table 1
As can be known from the results, the polymer dielectric of embodiment 1～4 on conductivity, all is better than the PEO based polyalcohol of comparative example 1.
Respectively embodiment 1～4 and comparative example 1 prepared polymer dielectric film are carried out the DSC Q-10 tester that differential scanning calorimetry (DSC) is tested employing U.S. TA company, temperature range is-70 ℃～100 ℃, and sweep speed is 10 ℃/min, N
2Protection.Obtain various electrolytical glass transition temperatures (Tg), its result is as shown in the table
The Tg of each polymer dielectric of table 2
As can be known from the results, the glass transition temperature of embodiment 1～4 all is comparable to the glass transition temperature of comparative example 1 PEO, and this shows the Tg that does not improve polymer when improving the polymer machinery performance, has guaranteed the transmission of lithium ion.
Claims (6)
1, a kind of full solid state polymer electrolyte that is used for lithium-sulfur cell is characterized in that, described electrolyte is that the ether oxygen groups complexing on the PEG side chain of structural polymer shown in formula A or the B has lithium ion,
Formula A formula B
The value of m is 8 or 12, and the value of n is 60～120.
2, the full solid state polymer electrolyte that is used for lithium-sulfur cell according to claim 1 is characterized in that, the molecular weight of described formula A or formula B polymer is between 30000～45000.
3, the described preparation method who is used for the full solid state polymer electrolyte of lithium-sulfur cell of claim 1, it is characterized in that, with PEG and organic dihalide compound hybrid reaction, after the petroleum ether layering, get the upper solution decompression distillation and go out benzinum, obtain the polyglycol ether of organic dihalide compound, again with Na
2S
2Aggregating into sulfur-containing polymer, is solvent at last with THF, and sulfur-containing polymer is mixed with lithium salts, and solvent THF volatilization is removed, and promptly obtains the sulfur-containing polymer electrolyte.
4, the preparation method who is used for the full solid state polymer electrolyte of lithium-sulfur cell according to claim 3 is characterized in that, described organic dihalide compound is 1,3-two chloro-2-propyl alcohol or 1,2-dihalo--2 Methylpropionic acid.
5, the preparation method who is used for the full solid state polymer electrolyte of lithium-sulfur cell according to claim 3 is characterized in that, described PEG is the polyethylene glycol of PEG400 or 600.
6, the preparation method who is used for the full solid state polymer electrolyte of lithium-sulfur cell according to claim 3 is characterized in that, successively PEG and organic dihalide compound is pressed amount of substance 1.3: 1, catalyst adds in the three-necked bottle, 110～140 ℃ of oil bath heating, condensing reflux, nitrogen protection; The mixed solution petroleum ether of reaction after finishing behind the standing demix, got the upper solution decompression distillation and gone out benzinum, obtains the polyglycol ether of organic dihalide compound, again with the polyglycol ether and the Na of organic dihalide compound
2S
2By 1: 1 amount of substance hybrid reaction, leave standstill reaction 3 hours under 70 ℃ of water-bath heating, leave standstill cooling 1 hour then, the bottle end, form yellow thick colloid; It is dry to take out the colloid washing; Be dissolved in oxolane after the drying, staticly settle, filter the collection mother liquid evaporation and fall THF, residue is a sulfur-containing polymer, is solvent with THF more at last, and sulfur-containing polymer is mixed with lithium salts, and solvent THF volatilization is removed, and promptly obtains the sulfur-containing polymer electrolyte.
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| CN2009100433257A CN101557017B (en) | 2009-05-08 | 2009-05-08 | Full solid state polymer electrolyte used for lithium sulphur battery and preparation thereof |
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| CN101557017B CN101557017B (en) | 2011-05-18 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104319404A (en) * | 2014-10-16 | 2015-01-28 | 常州大学 | Gel polymer binder for lithium sulfur battery electrode material and preparation method thereof |
| WO2020119750A1 (en) * | 2018-12-13 | 2020-06-18 | 深圳新宙邦科技股份有限公司 | Polymer, polymer electrolyte, polymer electrolyte membrane, non-aqueous electrolyte solution, and lithium ion battery |
| CN111320753A (en) * | 2018-12-13 | 2020-06-23 | 深圳新宙邦科技股份有限公司 | Polymer, polymer electrolyte membrane, nonaqueous electrolyte solution, and lithium ion battery |
| CN111326797A (en) * | 2018-12-13 | 2020-06-23 | 深圳新宙邦科技股份有限公司 | Liquid polymer electrolyte, polymer electrolyte membrane and lithium ion battery |
| CN113381060A (en) * | 2021-06-21 | 2021-09-10 | 浙江大学 | All-solid-state composite electrolyte and preparation method and application thereof |
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2009
- 2009-05-08 CN CN2009100433257A patent/CN101557017B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104319404A (en) * | 2014-10-16 | 2015-01-28 | 常州大学 | Gel polymer binder for lithium sulfur battery electrode material and preparation method thereof |
| CN104319404B (en) * | 2014-10-16 | 2017-04-05 | 常州大学 | A kind of lithium sulphur battery electrode material gelatin polymer binding agent and preparation method thereof |
| WO2020119750A1 (en) * | 2018-12-13 | 2020-06-18 | 深圳新宙邦科技股份有限公司 | Polymer, polymer electrolyte, polymer electrolyte membrane, non-aqueous electrolyte solution, and lithium ion battery |
| CN111320753A (en) * | 2018-12-13 | 2020-06-23 | 深圳新宙邦科技股份有限公司 | Polymer, polymer electrolyte membrane, nonaqueous electrolyte solution, and lithium ion battery |
| CN111326797A (en) * | 2018-12-13 | 2020-06-23 | 深圳新宙邦科技股份有限公司 | Liquid polymer electrolyte, polymer electrolyte membrane and lithium ion battery |
| CN111320753B (en) * | 2018-12-13 | 2021-08-13 | 深圳新宙邦科技股份有限公司 | Polymer, polymer electrolyte membrane, nonaqueous electrolyte solution, and lithium ion battery |
| CN111326797B (en) * | 2018-12-13 | 2021-08-13 | 深圳新宙邦科技股份有限公司 | Liquid polymer electrolyte, polymer electrolyte membrane and lithium ion battery |
| CN113381060A (en) * | 2021-06-21 | 2021-09-10 | 浙江大学 | All-solid-state composite electrolyte and preparation method and application thereof |
| CN113381060B (en) * | 2021-06-21 | 2022-06-21 | 浙江大学 | All-solid-state composite electrolyte and preparation method and application thereof |
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