CN102504301B - Process for combining amphipathy segmented copolymer electrolyte of POEM-PDMS - Google Patents
Process for combining amphipathy segmented copolymer electrolyte of POEM-PDMS Download PDFInfo
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- CN102504301B CN102504301B CN201110335946XA CN201110335946A CN102504301B CN 102504301 B CN102504301 B CN 102504301B CN 201110335946X A CN201110335946X A CN 201110335946XA CN 201110335946 A CN201110335946 A CN 201110335946A CN 102504301 B CN102504301 B CN 102504301B
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Abstract
The invention discloses a process for combining amphipathy segmented copolymer electrolyte of POEM (polyoxyethylene methyl methacrylate)- PDMS (polydimethylsiloxane). The prepared electrolyte film is used for manufacturing a novel full solid lithium ion battery. In the combining process of a copolymer, users can control the length of the hydrophilic POEM section and the component proportion of the POEM and the PDMS to simultaneously increase glass-transition temperature of the copolymer, reduce room temperature viscosity coefficient of the copolymer, increases dosage concentration of lithium ions in the POEM-g-PDMS amphipathy segmented copolymer electrolyte, and improves conductivity of the lithium ions of the copolymer electrolyte. The copolymer electrolyte is simple in combining process, less in equipment investment and suitable for industrial production.
Description
Technical field
The present invention relates to the electrolytical technique of amphipathic nature block polymer of a kind of synthetic POEM (polyoxyethylene methyl methacrylate)-PDMS (polydimethylsiloxane), belonged to new material technology field.
Background technology
Lithium ion battery is the charged and discharged battery of a new generation, have that energy/power density is high, operating voltage is high (～3.7V), the advantages such as little, the memory-less effect of self-discharge, green non-pollution, be the cell apparatus of overall performance optimum up to now.Recent two decades comes, and lithium ion battery obtains develop rapidly, with its high performance price ratio advantage at portable electric appts such as notebook computer, mobile phone, digital cameras, and field of power tools dominate.Lithium ion battery has been developed to the electrical source of power of hybrid-electric car (HEV) and electromobile (EV) at present, is also progressively expanded the static electric energy storage media for renewable energy sources such as sun power, wind energies.The market scale of lithium ion battery in 2010 has surpassed 10,000,000,000 dollars, sharply enlarges in sustainable growth and the vehicle mounted dynamic battery market of portable electric appts demand, and estimating will be above 30,000,000,000 dollar in the market scale of lithium ion battery in 2018.The liquid electrolyte lithium ion battery since research starting early, technology maturation, cost are lower, have occupied current 90% finished product lithium ion battery market.Because liquid electrolyte is the lower organism of flash point, in heavy-current discharge or situation about overcharging, the electrolytic solution that can ignite causes lithium ion battery blast on fire, and therefore, the security of liquid lithium ionic cell is relatively poor.In order to improve battery security, polymer Li-ion battery then is to adopt polymer dielectric film as the organic electrolyte carrier, does not have flowable organic electrolyte in the battery, has solved the existing leakage problem of liquid electrolyte battery.Simultaneously, polymer Li-ion battery is owing to adopt the aluminum plastic film outer packaging, and is responsive to inner pressure ratio, can avoid the battery unsafe acts such as burning of blasting, and improved the safety performance of battery.But, owing to still have organic electrolyte in the battery, fundamentally do not solve all safety problems of lithium ion battery.Wherein, distinct issues are that polymer Li-ion battery is under the condition of overcharging, the same with liquid lithium ionic cell, lithium cobaltate cathode material generation decomposition reaction, discharge a large amount of heats and active oxygen, cause the serial thermopositive reaction that negative material, binding agent and ionogen occur, can cause the battery thermal runaway equally, cause the battery catching fire.Therefore, the full solid state polymer electrolyte film that develop a kind of novel high ionic conductivity, need not organic electrolyte is the effective way that fundamentally solves the safety problem of lithium ion battery.
At present, the electrolytical research and comparison of all solid state segmented copolymer take polyoxyethylene as segment is extensive.Patrick E. Trapa et al. discloses in " Synthesis and Characterization of Single-Ion Graft Copolymer Electrolytes " literary composition and has a kind ofly prepared P (OEM-r-MAA)-electrolytical method of g-PDMS graftomer with radical polymerization.The present invention therewith key distinction of documents is characterised in that: three kinds of used monomers are methacrylic acid list polydimethylsiloxanemacromer macromer (PDMSMA) in (1) documents, methoxypolyethylene glycol methacrylic ester macromonomer (PEGMEM) and methacrylic acid (MMA), method by radical polymerization is prepared into P (OEM-r-MAA)-g-PDMS amphipathic nature polyalcohol presoma, then add lithium methoxide with the presoma lithiumation, obtain solid electrolyte P (OEM-r-LiMA)-g-PDMS amphipathic nature polyalcohol (referring to A2281 page or leaf summary).As seen chemical reaction has occured and has generated solid electrolyte P (OEM-r-LiMA)-g-PDMS in amphipathic nature polyalcohol presoma P (OEM-r-MAA)-g-PDMS and lithium methoxide, the adding of methacrylic acid is in order to carry out complexing with conductive lithium ion, and prepared polymer dielectric reaches as high as 7 * 10 in room-temperature conductivity
-6S/cm (under the left hurdle of A2283 page or leaf).And be prepared into the POEM-g-PDMS amphiphilic graft polymers with monomer methacrylic acid list polydimethylsiloxane (PDMSMA) and two kinds of monomers of methoxypolyethylene glycol methacrylic ester (PEGMEM) method by radical polymerization among the present invention, the trifluoromethanesulfonic acid lithium that will contain again conductive lithium ion mixes in the POEM-g-PDMS amphiphilic graft polymers, the mode that conductive lithium ion is mixed with physics enters into polymkeric substance but not the mode of chemical reaction, and the prepared room-temperature conductivity of the present invention reaches as high as 1 * 10
-3S/cm.Clearly, the used monomer of the present invention is few, and the mode of mixing with physics but not the method for chemical reaction introduce lithium ion in the polymkeric substance, and preparation technology is simple, and room-temperature conductivity is high, is fit to suitability for industrialized production.(2) productive rate of the prepared POEM-g-PDMS graftomer of the present invention is the highest, can reach 92.5%, is fit to suitability for industrialized production; (3) the oxygen ethene EO segment in the ethylene glycol monomethyl ether methacrylic ester macromonomer can " dissolve " lithium ion, and for the transmission of lithium ion provides channel, so the more lithium ions transmission of EO hop count are more, faster, and specific conductivity is higher; After but how the EO hop count became, methoxypolyethylene glycol methacrylic ester (PEOM) was easy to crystallization, thereby caused the polymer dielectric specific conductivity to descend.Therefore, by the parallel laboratory test of many groups relatively, the specific conductivity of the polymer dielectric that the EO hop count of selecting among the present invention is prepared is the highest.(4) the present invention defines the reaction soaking time, because show by the parallel test contrast, polyreaction is passed in time always and is showed a rising trend at the productive rate of front 24 hours interpolymers, and the productive rate of 24 hours post polymerization things is substantially constant, and time expand is also nonsensical again.(5) using the prepared P (OEM-r-MAA) of washed with de-ionized water-g-PDMS amphipathic nature polyalcohol in the documents, mainly is because hydrophilic residual monomer, oligopolymer etc. are many in this polymkeric substance, so need use washed with de-ionized water; And oil loving residual monomer in the prepared POEM-g-PDMS amphiphilic graft polymers among the present invention, oligopolymer are many, need to clean with petrolene.The selection of clean-out system is to select according to the chemical property of reaction system residue composition.(6) polymer dielectric film be prepared with three kinds of methods: 1) silk screen print method, this method working method is easy, film forming is even, but the thickness of film is difficult to accurate adjusting; 2) casting filming therapy, film forming is even, and width, the thickness of film are controlled, are applicable to suitability for industrialized production; 3) be cast into embrane method, make carrier with sheet glass, simple to operate, suitable laboratory prepares the fritter film.The present invention adopts casting filming therapy, is fit to suitability for industrialized production.
Summary of the invention
The object of the present invention is to provide the electrolytical technique of amphipathic nature block polymer of a kind of synthetic POEM (polyoxyethylene methyl methacrylate)-PDMS (polydimethylsiloxane), the dielectric film of preparation is for the manufacture of all solid state multipolymer lithium ion battery with characteristics such as high-temperature stability, high-energy-density, long lifetime, charge-discharge performance are stable.
Technical solution of the present invention is: the electrolytical technique of amphipathic nature block polymer of a kind of synthetic POEM (polyoxyethylene methyl methacrylate)-PDMS (polydimethylsiloxane) comprises the steps:
A) with 130～200 milliliters of methoxypolyethylene glycol methacrylate monomer (PEGMEM), oxygen ethene (EO) hop count wherein is 5～30,60 milliliters of polydimethylsiloxane monomers (PDMS), is dissolved into 1000 milliliters of vinyl acetic monomers;
B) with 60mg initiator 2,2 '-Diisopropyl azodicarboxylate is dissolved in 100 milliliters of vinyl acetic monomers;
C) above-mentioned two kinds of vinyl acetic monomer solution are mixed, transfer to the resistance to air loss flask;
D) with pure argon (air in the emptying vinyl acetic monomer mixing solutions of oxygen partial pressure＜50ppm), 30 minutes;
E) the vinyl acetic monomer mixing solutions is warmed to 60～80 ℃, is incubated 24 hours;
F) with petrolene cleaning step e resulting polymers product, vacuum-drying obtains the POEM-g-PDMS amphipathic nature block polymer;
G) take tetrahydrofuran (THF) as solvent, the trifluoromethanesulfonic acid lithium mixes in lithium ion and oxygen ethene (EO) fragment (Li: EO=1:5～30) ratio and enters multipolymer;
H) use doctor-blade casting process, through coating, the controlled dry AA-Na Copolymer Electrolyte film that obtains.
The present invention adopts the amphipathic nature block polymer dielectric film of free radical polymerisation process synthesizing new POEM (polyoxyethylene methyl methacrylate)-PDMS (polydimethylsiloxane).Because the properties of POEM-g-PDMS AA-Na Copolymer Electrolyte, comprising lithium ion conductivity and mechanical property, is to be determined by the length (being oxygen ethene (EO) hop count in the POEM chain) of hydrophilic POEM chain in the multipolymer, the ratio of doping content and the POEM of lithium ion on the POEM chain: PDMS.In order to realize high lithium ion conductivity, should improve as far as possible length and the POEM of POEM chain: the component proportions of PDMS, but can greatly reduce the mechanical property of AA-Na Copolymer Electrolyte film, so that gradually forfeiture of " barrier film " of AA-Na Copolymer Electrolyte film effect.Therefore; in the preparation process of POEM-g-PDMS amphipathic nature block polymer; mainly be by changing synthetic parameters; comprise the component proportions of POEM chain length, lithium ion doped concentration, wetting ability POEM etc.; be implemented under the prerequisite of not sacrificing the multipolymer mechanical property; improve as far as possible lithium ion conductivity, be laying the foundation of large-scale production multipolymer.Simultaneously, based on the tetrahydrofuran solution of POEM-g-PDMS and trifluoromethanesulfonic acid lithium, through coating, controlled drying process (coating speed, coating thickness, time of drying, drying temperature and temperature homogeneity), obtain high-performance AA-Na Copolymer Electrolyte film.
The present invention uses doctor-blade casting process (also claiming to scrape the skill in using a kitchen knife in cookery) large-scale production POEM-g-PDMS amphipathic nature block polymer dielectric film.Doctor-blade casting process is ripe production technology, flow casting molding equipment mainly comprises automatic rolling device, automatic releasing winding apparatus, solution apparatus for placing, loft drier and Mechatronic control system etc., and doctor-blade casting process is by accurately control coating speed, coating thickness, time of drying, drying temperature and temperature homogeneity obtain dielectric film.In sum, polymer dielectric film preparation technology of the present invention is simple, easy to operate, and required equipment drops into little, is suitable for suitability for industrialized production.
Embodiment
The below provide a kind of according to the present invention the embodiment of the indefiniteness of technique.
Embodiment 1:a) with 200 milliliters of methoxypolyethylene glycol methacrylate monomer (PEGMEM, oxygen ethene EO hop count wherein is 5), 60 milliliters of polydimethylsiloxane monomers (PDMS) by weight 80:20, be dissolved into 1000 milliliters of vinyl acetic monomers; B) with 60 milligrams of initiators 2,2 '-Diisopropyl azodicarboxylate is dissolved in 100 milliliters of vinyl acetic monomers; C) above-mentioned two kinds of vinyl acetic monomer solution are mixed, transfer to the resistance to air loss flask; D) with the air in the emptying vinyl acetic monomer mixing solutions of pure argon, 30 minutes; E) the vinyl acetic monomer mixing solutions is warmed to 60 ℃, is incubated 24 hours; F) with petrolene cleaning step e resulting polymers product, vacuum-drying obtains the POEM-g-PDMS amphipathic nature block polymer; G) take tetrahydrofuran (THF) as solvent, with the trifluoromethanesulfonic acid lithium in Li: EO=1:5 ratio doping POEM-g-PDMS multipolymer; H) use doctor-blade casting process, through coating, the controlled dry POEM-g-PDMS AA-Na Copolymer Electrolyte film that obtains.
Its lithium ion conductivity reaches 5 * 10
-4S/cm, its mechanical property satisfies the barrier film effect of positive and negative electrode substantially.
Embodiment 2:a) 130 milliliters of methoxypolyethylene glycol methacrylate monomer (PEGMEM, oxygen ethene EO hop count wherein is 15), 60 milliliters of polydimethylsiloxane monomers (PDMS) are dissolved into 1000 milliliters of vinyl acetic monomers by design proportion (weight ratio 70:30); B) with 60 milligrams of initiators 2,2 '-Diisopropyl azodicarboxylate is dissolved in 100 milliliters of vinyl acetic monomers; C) above-mentioned two kinds of vinyl acetic monomer solution are mixed, transfer to the resistance to air loss flask; D) with the air in the emptying vinyl acetic monomer mixing solutions of pure argon, 30 minutes; E) the vinyl acetic monomer mixing solutions is warmed to 68 ℃, is incubated 24 hours; F) with petrolene cleaning step e resulting polymers product, vacuum-drying obtains the POEM-g-PDMS amphipathic nature block polymer; G) take tetrahydrofuran (THF) as solvent, with the trifluoromethanesulfonic acid lithium in Li: EO=1:20 ratio doping POEM-g-PDMS multipolymer; H) use doctor-blade casting process, through coating, the controlled dry POEM-g-PDMS AA-Na Copolymer Electrolyte film that obtains.
Its lithium ion conductivity is about 5 * 10
-4S/cm, its satisfactory mechanical property reaches the barrier film effect as positive and negative electrode.
Embodiment 3:a) with 130 milliliters of methoxypolyethylene glycol methacrylate monomer PEGMEM, oxygen ethene EO hop count wherein is 30), 60 milliliters of polydimethylsiloxane monomers (PDMS) are dissolved into 1000 milliliters of vinyl acetic monomers by weight 70:30; B) with 60 milligrams of initiators 2,2 '-Diisopropyl azodicarboxylate is dissolved in 100 milliliters of vinyl acetic monomers; C) above-mentioned two kinds of vinyl acetic monomer solution are mixed, transfer to the resistance to air loss flask; D) with the air in the emptying vinyl acetic monomer mixing solutions of high-purity argon gas, 30 minutes; E) the vinyl acetic monomer mixing solutions is warmed to 80 ℃, is incubated 24 hours; F) with petrolene cleaning step e resulting polymers product, vacuum-drying obtains the POEM-g-PDMS amphipathic nature block polymer; G) take tetrahydrofuran (THF) as solvent, with the trifluoromethanesulfonic acid lithium in Li: EO=1:30 ratio doping POEM-g-PDMS multipolymer; H) use doctor-blade casting process, through coating, the controlled dry POEM-g-PDMS AA-Na Copolymer Electrolyte film that obtains.
Its lithium ion conductivity reaches 1 * 10
-3S/cm, its satisfactory mechanical property reaches the barrier film effect as positive and negative electrode.
The above; only for the better embodiment of the present invention, but protection scope of the present invention is not limited to this, anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (1)
1. the electrolytical technique of the amphipathic nature block polymer of a synthetic POEM-g-PDMS comprises the steps:
A) with 130～200 milliliters of methoxypolyethylene glycol methacrylate monomer, oxygen ethene hop count wherein is 5～30,60 milliliters of polydimethylsiloxane monomers, is dissolved into 1000 milliliters of vinyl acetic monomers;
B) with 60mg initiator 2,2 '-Diisopropyl azodicarboxylate is dissolved in 100 milliliters of vinyl acetic monomers;
C) above-mentioned two kinds of vinyl acetic monomer solution are mixed, transfer to the resistance to air loss flask;
D) with the air in the emptying vinyl acetic monomer mixing solutions of pure argon, 30 minutes;
E) the vinyl acetic monomer mixing solutions is warmed to 60～80 ℃, is incubated 24 hours;
F) with petrolene cleaning step e resulting polymers product, vacuum-drying obtains the POEM-g-PDMS amphipathic nature block polymer;
G) take tetrahydrofuran (THF) as solvent, the trifluoromethanesulfonic acid lithium is pressed lithium ion and oxygen ethene fragment according to Li
+: EO=1:5～30 ratios are mixed and are entered multipolymer;
H) use doctor-blade casting process, through coating, the controlled dry AA-Na Copolymer Electrolyte film that obtains.
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| CN105732862B (en) * | 2016-02-29 | 2018-02-13 | 南京林业大学 | Trisiloxanes amphipathic nature block polymer and preparation method with pH responses |
| CN109065931B (en) * | 2018-08-02 | 2020-07-14 | 大连融科储能技术发展有限公司 | Additive for vanadium battery electrolyte and preparation method and application thereof |
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Non-Patent Citations (2)
| Title |
|---|
| "Synthesis and Characterization of Single-Ion Graft Copolymer Electrolytes";Patrick E.Trapa et al.;《Journal of The Electrochemical Society》;20051231;第152卷(第12期);第2281～2284页 * |
| Patrick E.Trapa et al.."Synthesis and Characterization of Single-Ion Graft Copolymer Electrolytes".《Journal of The Electrochemical Society》.2005,第152卷(第12期),第2281～2284页. |
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Effective date of registration: 20180125 Address after: 327 State Road 274000 east of Shandong Province, Heze City Development Zone, south of the river in three communities Patentee after: Heze Tianyu lithium energy technology Co Ltd Address before: 410013 Hunan province Changsha City Lugu high tech Development Zone, Road No. 627 building two Changhai entrepreneurial base Patentee before: Changsha Baofeng Energy Technology Co., Ltd. |