CN101924245B - Preparation method of polyphosphazene urethane single ion solid electrolyte - Google Patents

Preparation method of polyphosphazene urethane single ion solid electrolyte Download PDF

Info

Publication number
CN101924245B
CN101924245B CN2010102722409A CN201010272240A CN101924245B CN 101924245 B CN101924245 B CN 101924245B CN 2010102722409 A CN2010102722409 A CN 2010102722409A CN 201010272240 A CN201010272240 A CN 201010272240A CN 101924245 B CN101924245 B CN 101924245B
Authority
CN
China
Prior art keywords
polyphosphazene
solid electrolyte
single ion
ion solid
hours
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN2010102722409A
Other languages
Chinese (zh)
Other versions
CN101924245A (en
Inventor
黄小彬
张家维
唐小真
陈奎永
顾晓俊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Jiaotong University
Original Assignee
Shanghai Jiaotong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Jiaotong University filed Critical Shanghai Jiaotong University
Priority to CN2010102722409A priority Critical patent/CN101924245B/en
Publication of CN101924245A publication Critical patent/CN101924245A/en
Application granted granted Critical
Publication of CN101924245B publication Critical patent/CN101924245B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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

Landscapes

  • Conductive Materials (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Secondary Cells (AREA)

Abstract

The invention relates to a preparation method of a polyphosphazene urethane single ion solid electrolyte in the technical field of lithium battery. The polyphosphazene rethane single ion solid electrolyte is prepared by heating 1,4-butanediol and poly[(diethylene glycol monomethyl ether) 1.6 (lithium taurate) 0.4] phosphazene for reaction and carrying out aging treatment. The polyphosphazene urethane single ion solid electrolyte prepared by the method of the invention has convenient preparation, high room-temperature conductivity, good mechanical property, no liquid composition, high lithium-ion transport number and stable electrochemistry window. The steps of the method are simple, and the polyphosphazene urethane single ion solid electrolyte is high in conductivity, favorable in mechanical property and good in electrochemistry stability.

Description

The polyphosphazene urethane single ion solid electrolyte preparation method
Technical field
What the present invention relates to is dielectric of a kind of technical field of lithium batteries and preparation method thereof, specifically is a kind of polyphosphazene urethane single ion solid electrolyte preparation method.
Background technology
The portable type electronic products such as making notebook computer, mobile phone, digital camera that develops rapidly of microelectric technique has obtained popularizing widely.Supporting power supply as portable type electronic product; Lithium rechargeable battery because have that specific energy is big, operating voltage is high, temperature limit is wide, self-discharge rate is low, have extended cycle life, pollution-free, special advantages such as security performance is good, become one of optimal environmental protection power supply of 21st century.
According to the electrolytical difference that is adopted, lithium rechargeable battery can be divided into liquid lithium ionic cell and polymer Li-ion battery.Polymer Li-ion battery is except that the advantage with liquid lithium ionic cell; Owing to adopted immobilising polymer dielectric; Also has the better advantage of security performance; And can process the ultra-thin battery of arbitrary shape and size, thereby be more suitable for power supply as miniature electrical equipment, range of application is also wider.Since polymer Li-ion battery in 1999 was realized industrialization, part substituted liquid lithium ionic cell, and was expected to replace fully in future liquid lithium ionic cell.
Polymer dielectric is divided into double ion conductivity type electrolyte and single ionic conduction type electrolyte.Usually the polymer dielectric that adopts all is a double ion conductivity type electrolyte.Through knowing to the research of polyethers in the polymer dielectric-electrolytic salt complex compound electrical conduction mechanism; Anion and cation will be distinguished anode and cathode motion under effect of electric field; Form the carrier concentration gradient in inside; Produce and external electric field antipole electrochemical potential, its result will cause the ionic conductivity of material to be moved in time and decay rapidly, significantly reduce the energy efficiency of battery.The effective measures that solve polymer dielectric internal polarization problem are to adopt single ionic conduction type polymer dielectric.The electrolytical design principle of this base polymer is for to be fixed on anion on the polymer segment through covalent bond; Suppress anionic motion by relatively large volume of polymer and the mutual winding between strand, thereby obtain the single ion conductor that single cation is a charge carrier.So because have only a kind of ion can serve as the electrolytical conductivity of the single Ionomer of charge carrier generally than low 1～2 one magnitude of conventional polymer double ion conductor electrolyte; But single Ionomer electrolyte dc conductivity is moved in time hardly and changes, and this is very favourable to improving battery performance.
Thermoplastic polyurethane (TPU) has typical two phase structure, and its polyether segment can be used as soft section and alkali metal salt generation solvation, promotes the disassociation and the transmission of charged ion, guarantees that solid electrolyte has certain conductivity; Hard section of the molecule that is formed by carbamate isopolarity group can be used as the physical crosslinking point, makes polyurethane have good mechanical performance and film forming.Therefore, select for use polyurethane, can take into account the electric property and the mechanical property of copolymer solid electrolyte, can obtain having the new polyurethane polymer dielectric of excellent mechanical property and ionic conducting property through certain MOLECULE DESIGN as matrix.
Poly phosphazene (PDCP) is alternately to arrange with the phosphorus nitrogen-atoms on one type of main chain, and side chain is the novel organic inorganic hybridization macromolecule of different substituents.The main chain of poly phosphazene material has the replacement diversity of superior compliance and side group; The backbone that the main chain of poly phosphazene is made up of with the Dan Shuanjian that replaces the P that replaces, N atom; Owing to exist the pi-conjugated stabilization of d π-p between the P-N key on the main chain, so the chemical stability of main chain is higher.And because the Dan Shuanjian that replaces on the main chain fails to form the long-range conjugated system; Two keys do not cause obstacle to the rotation of P-N key; So compare with the main chain of organic polymer, the poly phosphazene high polymer main chain has higher torsional compliance, great majority are the low temperature elasticity body.Behind the side chain (being mostly the ether chain) that these architectural characteristics have determined the poly phosphazene macromolecule to connect to contain the solvation group, will be the macromolecule main body of one type of good solid electrolyte.But the poly phosphazene solid electrolyte exists poor dimensional stability, and molecular weight is not high, many problems such as poor mechanical property.How to utilize the excellent molecule designability of poly phosphazene polymer, let two kinds of mutual modifications of important polymer of poly phosphazene and polyurethane,, prepare a kind of new type of polymer electrolyte, cause polymer science man's attention already in conjunction with both advantages.
Literature search through to prior art is found; Chen Jianjun; Wang Lei, Tang Xiaozhen etc. rolled up 71～75 pages of the 1st phases in 2002 the 36th at " Shanghai Communications University's journal " and have delivered " polyurethane/hyperbranched poly ether sulfate list ion-type solid electrolyte ", mentioned in the literary composition; Polyethylene glycol oxide polyurethane (PEU) and hyperbranched poly ether sulfate (SHPG-Na) blend have been made single Ionomer solid electrolyte; Means such as utilization complex impedance spectra etc. characterize it, and the result shows, cation in this compound system and ether oxygen atom generation complexing also strengthen with the increase of salinity; Temperature is bigger to the influence of the complexing between the ehter bond in the high salt concentration system and carbonyl and cation, and less to the influence of low salt concn system; High ionic conductivity is 3.1 * 10 under the room temperature (25 ℃) -6S cm -1, moderate temperature (60 ℃) is issued to 10 -5The order of magnitude.But its preparation method is complicated, and step is various, changes proportioning and salinity difficulty, and therefore, a kind of synthetic convenient with modification, the exploitation of single ionic electrolytes that conductivity is high becomes problem demanding prompt solution.
Summary of the invention
The present invention is directed to the above-mentioned deficiency that prior art exists; A kind of polyphosphazene urethane single ion solid electrolyte preparation method is provided, and method step is simple, and the polyphosphazene urethane single ion solid electrolytic conductivity is high; Satisfactory mechanical property has good electrochemical stability.
The present invention realizes through following technical scheme, and the present invention is through with 1, the 4-butanediol with gather [(diglycol monomethyl ether) 1.6(taurine lithium) 0.4] phosphine nitrile reacting by heating and maturation process prepare the polyphosphazene urethane single ion solid electrolyte.
Described gathering [(diglycol monomethyl ether) 1.6(taurine lithium) 0.4] the phosphine nitrile prepares in the following manner:
1) tetrahydrofuran solution with the diglycol monomethyl ether is added drop-wise in the oxolane that contains sodium hydride, and under the nitrogen protection environment stirring reaction;
2) polydichlorophosphazene is dissolved in behind the oxolane drips successively again: contain oxolane, triethylamine and the TBAB of taurine lithium, after back flow reaction, further dropwise drip the sodium salt solution (NaO (CH that contains the diglycol monomethyl ether 2) 2O (CH 2) 2OCH 3) oxolane and standing and reacting 12～24 hours;
3) the reaction system filtrate filtered is rotated evaporation and removes THF, product is gathered [(diglycol monomethyl ether) after the washing with alcohol drying 1.6(taurine lithium) 0.4] phosphine nitrile (PDCP-Li).
Described stirring is 40 ℃ and under magnetic agitation, stirred 60～120 minutes.
Described back flow reaction was meant: magnetic agitation refluxed reaction 8～12 hours
Described drying is in vacuum drying oven under the room temperature dry 8～12 hours.
Described reacting by heating is meant: drips PTMG (PTMG1000) and keeps heated and stirred after in three-necked bottle, adding toluene di-isocyanate(TDI), and then with 1,4-butanediol (BDO) and gather [(diglycol monomethyl ether) 1.6(taurine lithium) 0.4] the phosphine nitrile is heated to 70 ℃ and add to pour into after the vigorous stirring in the polytetrafluoroethylene mould in the three-necked bottle and solidify.
Described heated and stirred is meant: under nitrogen protection, reaction temperature was controlled under the 70-80 ℃ of environment 2 hours;
The molar ratio of described toluene di-isocyanate(TDI) and PTMG is 2: 1;
Described being cured as at 80 ℃ solidified 6～8 hours down.
Described maturation process is meant: adopt baking oven 110 ℃ of matured 3～5 hours.
Poly phosphazene ammonia ester list ionic electrolytes prepared in accordance with the present invention, preparation is convenient, and not only room-temperature conductivity is high, and satisfactory mechanical property, does not contain any liquid component, and high lithium ion transference number and electrochemical stability window are arranged.
Description of drawings
Fig. 1 is the infrared spectrogram of gained PDCP-Li among the embodiment one.
Fig. 2 is gained PDCP-Li among the embodiment two 31The P nuclear magnetic spectrogram.
Fig. 3 is gained PDCP-Li among the embodiment three 1H nuclear-magnetism figure.
Fig. 4 is that the polyphosphazene urethane single ion solid electrolyte PU-PDCP ionic conductivity of different PDCP-Li content is with temperature changing curve diagram.The active reactive group of the PDCP-Li that 5% expression adds account for unreacted active group in the polyurethane prepolymer content 5%, by that analogy.
Embodiment
Elaborate in the face of embodiments of the invention down, present embodiment provided detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Embodiment 1
Step 1; In the there-necked flask of 250ml; The 50ml tetrahydrofuran THF solution that will contain 9.354g diglycol monomethyl ether (77.85mmol) is added drop-wise to constant pressure funnel among 1.779g (74.13mmol) the sodium hydride NaH that is dispersed among the 50mlTHF, and 40 ℃ are stirred at the nitrogen protection lower magnetic force and to react completely up to all NaH in 60 minutes;
Step 2; 5.00g (0.043mol) polydichlorophosphazene is dissolved among the 100ml THF; Pour in the 250ml single port flask, drip the THF dispersion liquid of 2.26 gram (0.0173mol) taurine lithiums again, add 5.5gTEA and make acid binding agent; Add the 0.01g TBAB and make catalyst, then stirring and refluxing reaction at room temperature is 12 hours.In above-mentioned solution, dropwise drip the sodium salt NaO (CH that is dispersed in the gram of 9.838 among 50mlTHF diglycol monomethyl ether then 2) 2O (CH 2) 2OCH 3, continue reaction 24 hours;
Step 3 after reaction finishes, is filtered, and filtrating is rotated evaporation and removes THF.Product is washed 3 times with ethanol, is placed on then in the vacuum drying oven, at room temperature dry 12 hours, obtains faint yellow solid and gathers [(diglycol monomethyl ether) 1.6(taurine lithium) 0.4] phosphine nitrile (PDCP-Li), product 5.648g, productive rate about 45.6%;
Step 4; In the 250ml three-necked bottle that thermometer, blender, constant pressure funnel and nitrogen air inlet are housed, add 3.48gTDI, drip 10gPTMG1000 with constant pressure funnel then, keep simultaneously stirring; Under the nitrogen protection system temperature is controlled at 70-80 ℃, stops reaction after 2 hours.
Step 5 is heated to 70 ℃ with 0.855gBDO and 0.7185gPDCP-Li, adds in the prepolymer, and vigorous stirring 10 minutes is then poured into and kept 80 ℃ in the good polytetrafluoroethylene mould of preheating and solidified 6 hours;
Step 6 was put into 110 ℃ of baking oven matured 3 hours with PU-PDCP at last.Poly phosphazene ammonia ester list ionic electrolytes is placed at normal temperatures after 7 days and is carried out performance test.
The implementation result of present embodiment: Fig. 1 is the infrared spectrogram of gained PDCP-Li among the embodiment one.At 730cm -1And 940cm -1The peak at place belongs to the characteristic peak of P-N and P-O-C, 1200cm respectively -1The place is the vibration peak of P=N, 1050cm -1Be SO 3The vibration peak of-Li, 2930cm -1Neighbouring is the absorption of C-H on the aliphatic chain.Fig. 4 is that polyphosphazene urethane single ion solid electrolyte PU-PDCP ionic conductivity is with temperature changing curve diagram.Can know that through calculating polyphosphazene urethane single ion solid electrolyte room temperature ionic conductivity is 1.1 * 10 -6S cm -1, lithium ion transference number is 1, electrochemical stability window is 5.0V.Above characterization result shows that this polyphosphazene urethane single ion solid electrolyte has high room-temperature conductivity and high electrochemical stability window, and high lithium ion transference number.
Embodiment 2
Step 1; In the there-necked flask of 250ml; The 50mlTHF solution that will contain 4..677g diglycol monomethyl ether (38.93mmol) is added drop-wise to constant pressure funnel among 0.889g (37.07mmol) NaH that is dispersed among the 50mlTHF, and 40 ℃ are stirred at the nitrogen protection lower magnetic force and to react completely up to all NaH in 80 minutes;
Step 2; 2.500g (0.022mol) polydichlorophosphazene is dissolved among the 100ml THF; Pour in the 250ml single port flask, drip the THF dispersion liquid of 1.13 gram (0.008mol) taurine lithiums again, add 2.75gTEA and make acid binding agent; Add the 0.01g TBAB and make catalyst, then stirring and refluxing reaction at room temperature is 12 hours.In above-mentioned solution, dropwise drip the sodium salt NaO (CH that is dispersed in the gram of 4.919 among 50mlTHF diglycol monomethyl ether then 2) 2O (CH 2) 2OCH 3, continue reaction 24 hours;
Step 3 after reaction finishes, is filtered, and filtrating is rotated evaporation and removes THF.Product is washed 3 times with ethanol, is placed on then in the vacuum drying oven, at room temperature dry 12 hours, obtains faint yellow solid and gathers [(diglycol monomethyl ether) 1.6(taurine lithium) 0.4] phosphine nitrile (PDCP-Li), product 2.824g, productive rate about 45.5%;
Step 4; In the 250ml three-necked bottle that thermometer, blender, constant pressure funnel and nitrogen air inlet are housed, add 1.74gTDI, use constant pressure funnel Dropwise 5 gPTMG1000 then, keep simultaneously stirring; Under the nitrogen protection system temperature is controlled at 70-80 ℃, stops reaction after 2 hours.
Step 5 is heated to 70 ℃ with 0.855gBDO and 0.719gPDCP-Li, adds in the prepolymer, and vigorous stirring 10 minutes is then poured into and kept 80 ℃ in the good polytetrafluoroethylene mould of preheating and solidified 6 hours;
Step 6 was put into 110 ℃ of baking oven matured 3 hours with PU-PDCP at last.Poly phosphazene ammonia ester list ionic electrolytes is placed at normal temperatures after 7 days and is carried out performance test.
The implementation result of present embodiment: Fig. 2 is gained PDCP-Li among the embodiment two 31The P nuclear magnetic spectrogram.PDCP-Li's 31The PNMR spectrogram has the spectrum peak of 2 broads; δ=-7.5 peaks corresponding be that chlorine atom on the poly phosphazene is replaced by the diglycol monomethyl ether entirely, in addition δ=-the 6.1ppm peak corresponding be that chlorine atom on the poly phosphazene is mixed replacement by diglycol monomethyl ether and taurine lithium.Fig. 4 is that polyphosphazene urethane single ion solid electrolyte PU-PDCP ionic conductivity is with temperature changing curve diagram.Can know that through calculating polyphosphazene urethane single ion solid electrolyte room temperature ionic conductivity is 1.3 * 10 -6S cm -1, lithium ion transference number is 1, electrochemical stability window is 5.0V.Above characterization result shows that this polyphosphazene urethane single ion solid electrolyte has high room-temperature conductivity and high electrochemical stability window, and high lithium ion transference number.
Embodiment 3
Step 1; In the there-necked flask of 250ml; The 50mlTHF solution that will contain 10.289g diglycol monomethyl ether (93.42mmol) is added drop-wise to constant pressure funnel among 2.135g (88.96mmol) NaH that is dispersed among the 50mlTHF, and 40 ℃ are stirred at the nitrogen protection lower magnetic force and to react completely up to all NaH in 60 minutes;
Step 2; 6.00g (0.052mol) polydichlorophosphazene is dissolved among the 100ml THF; Pour in the 250ml single port flask, drip the THF dispersion liquid of 2.712 gram (0.0173mol) taurine lithiums again, add 6.6gTEA and make acid binding agent; Add the 0.01g TBAB and make catalyst, then stirring and refluxing reaction at room temperature is 12 hours.In above-mentioned solution, dropwise drip the sodium salt NaO (CH that is dispersed in the gram of 11.806 among 50mlTHF diglycol monomethyl ether then 2) 2O (CH 2) 2OCH 3, continue reaction 24 hours;
Step 3 after reaction finishes, is filtered, and filtrating is rotated evaporation and removes THF.Product is washed 3 times with ethanol, is placed on then in the vacuum drying oven, at room temperature dry 12 hours, obtains faint yellow solid and gathers [(diglycol monomethyl ether) 1.6(taurine lithium) 0.4] phosphine nitrile (PDCP-Li), product 6.778g, productive rate about 45.4%;
Step 4; In the 250ml three-necked bottle that thermometer, blender, constant pressure funnel and nitrogen air inlet are housed, add 4.176gTDI; Drip 12gPTMG1000 with constant pressure funnel then; Keep simultaneously stirring, under the nitrogen protection system temperature is controlled at 70-80 ℃, stop reaction after 2 hours.
Step 5 is heated to 70 ℃ with 1.026gBDO and 0.862gPDCP-Li, adds in the prepolymer, and vigorous stirring 10 minutes is then poured into and kept 80 ℃ in the good polytetrafluoroethylene mould of preheating and solidified 6 hours;
Step 6 was put into 110 ℃ of baking oven matured 3 hours with PU-PDCP at last.Poly phosphazene ammonia ester list ionic electrolytes is placed at normal temperatures after 7 days and is carried out performance test.
The implementation result of present embodiment: Fig. 3 is gained PDCP-Li among the embodiment three 1H nuclear-magnetism figure.The peak at δ=3.34-3.48 place is CH 3The signal of hydrogen atom, the peak at 3.55-4.06ppm place are CH 2The signal of hydrogen atom, δ=7.35ppm peak is corresponding to the proton of NH base.Fig. 4 is that polyphosphazene urethane single ion solid electrolyte PU-PDCP ionic conductivity is with temperature changing curve diagram.Can know that through calculating polyphosphazene urethane single ion solid electrolyte room temperature ionic conductivity is 1.4 * 10 -6S cm -1, lithium ion transference number is 1, electrochemical stability window is 5.0V.Above characterization result shows that this polyphosphazene urethane single ion solid electrolyte has high room-temperature conductivity and high electrochemical stability window, and high lithium ion transference number.

Claims (9)

1. a polyphosphazene urethane single ion solid electrolyte preparation method is characterized in that, drip PTMG and keep heated and stirred after in three-necked bottle, adding toluene di-isocyanate(TDI), then with 1, the 4-butanediol with gather [(diglycol monomethyl ether) 1.6(taurine lithium) 0.4] the phosphine nitrile is heated to 70 ℃ and add to pour into after the vigorous stirring in the polytetrafluoroethylene mould in the three-necked bottle and solidify, and obtains the polyphosphazene urethane single ion solid electrolyte after the maturation process.
2. polyphosphazene urethane single ion solid electrolyte preparation method according to claim 1 is characterized in that, described gathering [(diglycol monomethyl ether) 1.6(taurine lithium) 0.4] the phosphine nitrile prepares in the following manner:
1) tetrahydrofuran solution with the diglycol monomethyl ether is added drop-wise in the oxolane that contains sodium hydride, and under the nitrogen protection environment stirring reaction;
2) polydichlorophosphazene is dissolved in behind the oxolane drips successively again: contain oxolane, triethylamine and the TBAB of taurine lithium, after back flow reaction, further dropwise drip oxolane and the standing and reacting 12～24 hours of the sodium salt solution that contains the diglycol monomethyl ether;
3) the reaction system filtrate filtered is rotated evaporation and removes THF, product is gathered [(diglycol monomethyl ether) after the washing with alcohol drying 1.6(taurine lithium) 0.4] the phosphine nitrile.
3. polyphosphazene urethane single ion solid electrolyte preparation method according to claim 2 is characterized in that, the said stirring reaction of step 1) is 40 ℃ and under magnetic agitation, stirred 60～120 minutes.
4. polyphosphazene urethane single ion solid electrolyte preparation method according to claim 2 is characterized in that, described back flow reaction is meant: magnetic agitation refluxed reaction 8～12 hours.
5. polyphosphazene urethane single ion solid electrolyte preparation method according to claim 2 is characterized in that, described drying is in vacuum drying oven under the room temperature dry 8～12 hours.
6. polyphosphazene urethane single ion solid electrolyte preparation method according to claim 1 is characterized in that, described heated and stirred is meant: under nitrogen protection, reaction temperature was controlled under 70～80 ℃ of environment 2 hours.
7. polyphosphazene urethane single ion solid electrolyte preparation method according to claim 1 is characterized in that, the molar ratio of described toluene di-isocyanate(TDI) and PTMG is 2: 1.
8. polyphosphazene urethane single ion solid electrolyte preparation method according to claim 1 is characterized in that, described being cured as at 80 ℃ solidified 6～8 hours down.
9. polyphosphazene urethane single ion solid electrolyte preparation method according to claim 1 is characterized in that, described maturation process is meant: adopt baking oven 110 ℃ of matured 3～5 hours.
CN2010102722409A 2010-09-07 2010-09-07 Preparation method of polyphosphazene urethane single ion solid electrolyte Expired - Fee Related CN101924245B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2010102722409A CN101924245B (en) 2010-09-07 2010-09-07 Preparation method of polyphosphazene urethane single ion solid electrolyte

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2010102722409A CN101924245B (en) 2010-09-07 2010-09-07 Preparation method of polyphosphazene urethane single ion solid electrolyte

Publications (2)

Publication Number Publication Date
CN101924245A CN101924245A (en) 2010-12-22
CN101924245B true CN101924245B (en) 2012-09-05

Family

ID=43338996

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2010102722409A Expired - Fee Related CN101924245B (en) 2010-09-07 2010-09-07 Preparation method of polyphosphazene urethane single ion solid electrolyte

Country Status (1)

Country Link
CN (1) CN101924245B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103804628A (en) * 2014-02-25 2014-05-21 偲众新材料科技（上海）有限公司 Polyphosphazene-modified cellular polyurethane elastomer and preparation method thereof
CN106898811B (en) * 2017-05-08 2019-07-23 北京化工大学 A kind of solid electrolyte and preparation method thereof with dual diversion sub-network
CN107342436B (en) * 2017-06-21 2020-09-29 中国科学院大学 Topological structure liquid crystal polymer electrolyte and synthetic method and application thereof
CN117524562B (en) * 2023-12-25 2024-05-28 安徽华海特种电缆集团有限公司 Molten steel sputtering prevention tensile moving round cable

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2740960B2 (en) * 1989-02-22 1998-04-15 大塚化学株式会社 Lithium secondary battery
FR2658199B1 (en) * 1990-02-13 1992-05-15 Atochem PROCESS FOR THE PREPARATION OF POLYPHOSPHAZENES BY SUBSTITUTION OF POLYDICHLOROPHOSPHAZENE.
CN1313516C (en) * 2005-03-31 2007-05-02 上海交通大学 Nano tube of cross linked polyphosphonitrile and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HARRYR.ALLCOCK, et al..Design and Synthesis of Ion-Conductive Polyphosphazenes for Fuel Cell Applications: Review.《Journal of Polymer Science: Part B: Polymer Physics》.2006,第44卷(第16期),2358-2368. *
周玉波.新型聚膦腈/聚氨酯无机/有机共聚材料的制备及性能研究.《中国优秀博士学位论文全文数据库 Engineering Science and TechnologyⅠ》.2010, *
江金贵.基于磷睛聚合物的合成及性能研究.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2007, *

Also Published As

Publication number Publication date
CN101924245A (en) 2010-12-22

Similar Documents

Publication Publication Date Title
EP1548750B1 (en) Nonaqueous electrolyte, electrical double layer capacitors, and nonaqueous electrolyte secondary cells
Yang et al. Poorly soluble 2, 6-dimethoxy-9, 10-anthraquinone cathode for lithium-ion batteries: the role of electrolyte concentration
CN101740754B (en) Preparation method of composite anode material for lithium element sulphur secondary battery
CN109786820B (en) Boron-containing plastic crystal polymer and preparation method and application thereof
CN106898812A (en) A kind of solid polymer electrolyte and preparation method thereof and anode composite and solid lithium ion battery
CN106058222A (en) Polymer carbonized in-situ coated ferric fluoride composite positive electrode material and preparation method thereof
CN101924245B (en) Preparation method of polyphosphazene urethane single ion solid electrolyte
CN109888369B (en) All-solid-state electrolyte, preparation method thereof and lithium battery
CN104364948A (en) Agent for forming electrode protection film
Zhang et al. Investigation of capacity increase in schiff-base networks as the organic anode for lithium-ion batteries
CN112768766B (en) Lithium-sulfur battery electrolyte and application thereof
CN105703003A (en) Comb-shaped polymer, electrolyte and composite electrode for lithium battery, and applications of electrolyte and composite electrode
CN107043457A (en) A kind of polymer comprising Azacrown ether containing structure and preparation method and application
CN107887573A (en) Positive active material and its application with topological structure
CN113594453A (en) Sodium-ion battery negative electrode material and preparation method thereof
CN106916308A (en) Polymer and preparation method thereof and solid polymer electrolyte and all-solid lithium-ion battery
Zhang et al. Electropolymerization stabilized bipolar metal coordination complex for high-performance dual-ion batteries
CN112409364A (en) Hexaazanaphthalene derivative and preparation method and application thereof
CN110590789B (en) Nitrogen-rich triphenylamine derivative conjugated polymer material and preparation and application of monomer thereof
CN112242554A (en) Composite solid electrolyte membrane, preparation method thereof and solid battery
CN110387036B (en) Random polyarylether electrode active material containing viologen side chain and preparation method thereof
Li et al. Conjugated microporous polymers with multiple redox-active sites as anode and cathode materials for symmetric all-organic lithium-ion batteries
CN114069044B (en) Positive electrode material and lithium ion battery containing same
CN102034959A (en) Composite electrode material and secondary battery made of same
CN111211327B (en) Compound for lithium ion battery anode material and preparation method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20120905

Termination date: 20150907

EXPY Termination of patent right or utility model