CN110380118A - A kind of polymer dielectric and its preparation and application with flame retarding function - Google Patents
A kind of polymer dielectric and its preparation and application with flame retarding function Download PDFInfo
- Publication number
- CN110380118A CN110380118A CN201910648377.0A CN201910648377A CN110380118A CN 110380118 A CN110380118 A CN 110380118A CN 201910648377 A CN201910648377 A CN 201910648377A CN 110380118 A CN110380118 A CN 110380118A
- Authority
- CN
- China
- Prior art keywords
- reaction
- polymer dielectric
- polymer
- lithium
- flame retarding
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/335—Polymers modified by chemical after-treatment with organic compounds containing phosphorus
- C08G65/3356—Polymers modified by chemical after-treatment with organic compounds containing phosphorus having nitrogen in addition to phosphorus
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- 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
Abstract
The invention belongs to polymer dielectric fields, disclose a kind of polymer dielectric with flame retarding function and its preparation and application, the polymer dielectric includes metal salt and is the cross-linked polymer for being crosslinked arm and being constituted by kernel, polyethyleneglycol diglycidylether of six phenolamino ring phosphonitriles, wherein, the cross-linked polymer has chemical structural formula as follows, the integer that n is 4~113 in formula.The present invention by the polymer dielectric key structure and composition, the overall flow technological design of corresponding preparation method etc. improve, obtain can be applied to the polymer dielectric with flame retarding function of the metal ions battery such as lithium ion battery, it can effectively solve the problem that polymer dielectric ionic conductivity is low compared with prior art, mechanical performance is poor, the safety problems such as easy firing explosion.
Description
Technical field
The invention belongs to polymer dielectric fields, more particularly, to a kind of polymer electrolytic with flame retarding function
Matter and its preparation and application.
Background technique
Using lithium ion battery as the metal ion battery of representative, electrolyte is an important factor for influencing performance of lithium ion battery
One of.Currently, commercialized lithium battery is still based on liquid electrolyte, but a large amount of organic solvents in liquid electrolyte exist
The hidden danger such as inflammable and explosive propose severe challenge to the safety of lithium ion battery.Solid electrolyte is relative to liquid electrolyte
Have many advantages, such as that energy density is high, light, high mechanical strength, especially solid polymer electrolyte can be wanted according to different performance
It asks and is rationally designed, to obtain the electrolyte of functionalization.Based on the above advantage, polymer dielectric becomes the following electrolyte
One of important development direction of material.
Polyethylene glycol oxide base electrolyte is the earliest a kind of polymer dielectric of research, but its conductivity at room temperature it is low,
Mechanical performance is not good enough and it is inflammable the problems such as still have it is to be solved.If a kind of polymer electrolytic with flame retarding function can be designed
Matter is then expected to solve this problem: when lithium battery thermal runaway or when having open firing, the flame-retarding characteristic that material assigns can inhibit
Polymer dielectric burning is effectively prevented from cells burst explosion.
On the other hand, in order to improve the mechanical performance of polyethylene glycol oxide base electrolyte, doping inorganic filler is a kind of common
Strategy.However inorganic filler is difficult to compatible with polymer substrate, causes inorganic filler to be unevenly distributed, can not effectively inhibit lithium branch
Crystals growth.Li et al. people (Adv.Mater.2015,27,5995-6001) uses organic-inorganic hybrid material polysilsesquioxane
POSS is prepared for crosslinking net polymer dielectric, and polysilsesquioxane POSS kernel, which remains inorganic filler silica, to be had
Preferably inhibit the characteristic of lithium dendrite growth, while outer arm has good solubility, is a kind of to prepare hybrid polymer electrolyte
New strategy.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the purpose of the present invention is to provide one kind to have flame retarding function
Polymer dielectric and its preparation and application, wherein by key structure in the polymer dielectric and composition, corresponding
Overall flow technological design of preparation method etc. improves, and obtains the tool that can be applied to the metal ions battery such as lithium ion battery
There is the polymer dielectric of flame retarding function, can effectively solve the problem that polymer dielectric ionic conductivity is low compared with prior art,
Mechanical performance is poor, the safety problems such as easy firing explosion；The present invention is the six phenolamino ring phosphonitrile HCP that will have flame retarding function
It reacts to be formed with flame retarding function HCP-PEGDE crosslinking net polymer, with doping with polyethyleneglycol diglycidylether PEGDE
Metal salt (such as lithium salts) formed polymer dielectric (such as polymer electrolyte film), be applied to metal ion battery (such as lithium
Ion battery) when, there is good mechanical performance and conductivity, when polymer meets with open fire, polymer electrolytic mass-energy self-extinguishment,
To solve the safety problems such as the issuable combustion explosion of polymer dielectric, the safety that lithium battery etc. uses is promoted.
To achieve the above object, according to one aspect of the present invention, a kind of electrostrictive polymer with flame retarding function is provided
Xie Zhi, which is characterized in that the polymer dielectric includes metal salt and using six phenolamino ring phosphonitriles as kernel, polyethylene glycol
Diglycidyl ether is the cross-linked polymer for being crosslinked arm and constituting, wherein the cross-linked polymer has chemical structure as follows
Formula:
In the chemical structural formula, n be 4~113 integer.
As present invention further optimization, the cross-linked polymer mainly by six phenolamino ring phosphonitriles (HCP) and
Polyethyleneglycol diglycidylether (PEGDE) reaction obtains；Wherein,
The chemical structural formula of the six phenolaminos ring phosphonitrile (HCP) is as follows:
The chemical structural formula of the polyethyleneglycol diglycidylether (PEGDE) is as follows:
Wherein, the integer that n is 4~113；Also, the polyethylene glycol of the polyethyleneglycol diglycidylether (PEGDE)
Relative molecular mass is 200~5000.
As present invention further optimization, the lithium salts is bis trifluoromethyl sulfimide lithium, lithium perchlorate and hexafluoro
The one or more of lithium phosphate；Preferably, rememberIt is for a polyethylene oxide base unit, then, described
The amount of the amount of the substance of metallic element and the total material of polyethylene oxide base unit described in the cross-linked polymer in metal salt
Ratio between two meets 1:5~1:30.
It is another aspect of this invention to provide that the present invention provides prepare the above-mentioned polymer dielectric with flame retarding function
Preparation method, which comprises the following steps:
(1) hexachlorocyclotriph,sphazene and acetaminophenol are dissolved in organic solvent, alkali is added, and be stirred at reflux anti-
It answers, obtains reaction solution；
(2) reaction solution for obtaining step (1) and precipitant mix, which are formed, precipitates, and filtration drying obtains six acetamides
Base phenol ring phosphonitrile；
(3) the six acetaminophenols ring phosphonitrile for obtaining step (2) is dissolved in organic solvent, and alkali is added, and
It is stirred at reflux reaction, six phenolamino ring phosphonitriles (HCP) are obtained by filtration after reaction；
(4) alkali, epoxychloropropane and water, heating after polyethylene glycol heating melting, will be added into the polyethylene glycol of melting
Reaction obtains polyethyleneglycol diglycidylether (PEGDE)；
(5) polyethylene glycol for obtaining the six phenolaminos ring phosphonitrile (HCP) that step (3) obtains, step (4)
Diglycidyl ether (PEGDE) dissolves in organic solvent together with metal salt, then carries out the reaction that is heating and curing, is after dry
It can obtain the polymer dielectric with flame retarding function.
As present invention further optimization, the polymer dielectric with flame retarding function obtained is specially film
The polymer dielectric with flame retarding function of shape, the thickness of film are preferably 50~300 microns；The step (5) is specifically:
It is first that the six phenolaminos ring phosphonitrile (HCP) that step (3) obtains and the polyethylene glycol diglycidyl that step (4) obtains is sweet
Oily ether (PEGDE) is dissolved in organic solvent, obtains mixed solution, and metal salt is then added into the mixed solution, and stirring is equal
Casting film after even, heat drying obtain the polymer dielectric with flame retarding function.
As present invention further optimization, in the step (1), the chemical structural formula of the hexachlorocyclotriph,sphazene are as follows:
The chemical structural formula of the acetaminophenol are as follows:
In the step (2), the chemical structural formula of the six acetaminophenols ring phosphonitrile are as follows:
In the step (3), the chemical structural formula of the six phenolaminos ring phosphonitrile (HCP) are as follows:
In the step (4), the chemical structural formula of the polyethylene glycol are as follows:Also, this is poly-
The relative molecular mass of ethylene glycol is 200~5000；
The chemical structural formula of the polyethyleneglycol diglycidylether (PEGDE) are as follows:
Wherein, the integer that n is 4~113.
As present invention further optimization, in the step (1), the reaction temperature for being stirred at reflux reaction be 50~
70 DEG C, the reaction time is 1~5 day；
In the step (3), the reaction temperature for being stirred at reflux reaction is 60~100 DEG C, and the reaction time is 1~5 day；
In the step (4), the reaction temperature of the heating reaction is 60~120 DEG C, and the reaction time is 3~24 hours；
In the step (5), the reaction temperature of the reaction that is heating and curing is 100~120 DEG C, and the reaction time is 3
~24 hours.
As present invention further optimization, in the step (1), the organic solvent is tetrahydrofuran, acetone, methanol
In any one；The alkali is potassium carbonate, cesium carbonate, any one in sodium hydroxide；
In the step (2), the precipitating reagent is water, ether, any one in n-hexane；
In the step (3), the organic solvent is methanol, ethyl alcohol, any one in tetrahydrofuran；The alkali is carbon
Sour potassium, potassium hydroxide, any one in sodium hydroxide；
In the step (4), the alkali is potassium carbonate, potassium hydroxide, any one in sodium hydroxide；
In the step (5), the organic solvent is tetrahydrofuran, acetonitrile, any one in n,N-Dimethylformamide
Kind.
As present invention further optimization, in the step (5), the metal salt is specially lithium salts, the lithium
Salt is bis trifluoromethyl sulfimide lithium, the one or more of lithium perchlorate and lithium hexafluoro phosphate；Preferably, rememberFor a polyethylene oxide base unit, then, in the metal salt amount of the substance of metallic element with
The amount ratio between two of the total material of the polyethylene oxide base unit contained in the mixed solution meets 1:5~1:30.
Another aspect according to the invention, the present invention provides the above-mentioned polymer dielectrics with flame retarding function in metal
It is applied in ion battery；Preferably, the metal ion battery is lithium ion battery.
By taking metal salt is lithium salts as an example, designed above technical scheme passes through compared with prior art through the invention
Six phenolamino the ring phosphonitrile HCP and polyethyleneglycol diglycidylether PEGDE with flame retarding function are coupled to form netted friendship
Linked polymer, HCP structure can assign polymer dielectric flame retarding function in the polymer dielectric, and PEGDE structure then assigns electricity
Matter conducting lithium ions function is solved, both functions play a role simultaneously i.e. so that the polymer dielectric is with respect to traditional polymer electricity
The shortcomings that solution matter can effectively overcome conventional polymer electrolyte contact open fire to be easy burning, so as to avoid electrolyte from burning
Cause the safety issues such as combustion explosion, also, cross-linked structure is formd by amino-epoxy reaction, can further mention
The mechanical property of high crosslinking net polymer.Polymer dielectric provided by the invention can be realized polymer when contacting open fire
The self-extinguishment of electrolyte, while polymer dielectric ionic conductivity with higher.
Polymer dielectric in the present invention with flame retarding function is based on novel halogen-free fire retardant phosphonitrile kernel, this is new
Type halogen-free flame-retardant phosphonitrile kernel is due to excellent thermal stability, anti-flammability, flexibility, simultaneously because P-Cl is easy to official
Modifier keys can be changed to be suitable for preparing hybrid polymer electrolyte, compared to the prior art in polysilsesquioxane crosslinking net it is poly-
Polymer electrolyte, the present invention in the polyethylene oxide base crosslinking net polymer dielectric with ring phosphonitrile have preferably machinery
Performance and flexibility, can be simple and efficient by amino-epoxy epoxy reaction, prepare the polyethylene oxide base with ring phosphonitrile
Electrolyte is applied to metal ion battery including lithium ion battery including, and effectively solution mechanical performance is not good enough and inflammable etc. asks
Topic.
Since polyethyleneglycol diglycidylether forms continuous conducting path in flame-retardant polymer electrolyte, be conducive to
The conduction of metal ion (such as lithium ion), thus the polymer dielectric all has high ionic conductivity in room temperature and high temperature,
The cross-linked structure in crosslinking net polymer architecture and six phenolamino ring phosphonitrile HCP are assigned with good flexibility simultaneously
The polymer dielectric excellent mechanical performance.Containing with flame retarding function in HCP-PEGDE crosslinking net polymer architecture
Six phenolamino ring phosphonitrile HCP absorb heat during high temperature degradation, generate phosphate, metaphosphate and polyphosphoric acids
Salt forms protective film in polymer surfaces to completely cut off air, and the incombustibility gas such as release carbon dioxide, ammonia and nitrogen
Dilution oxygen, to reach flame retardant effect.
In general, by taking metal salt is lithium salts as an example, through the invention involved in above technical scheme and the prior art
Compared to can achieve the following beneficial effects:
(1) present invention is contracted fire-retardant six phenolamino ring phosphonitrile HCP of kernel with polyethylene glycol two using amino-epoxy reaction
Water glycerin ether PEGDE is coupled to form cross-linked polymer.At present with six phenolamino ring phosphonitrile HCP and polyethylene glycol diglycidyl
The cross-linked polymer that ether PEGDE is formed is used as, and there is flame retarding function polymer dielectric to be applied to all-solid lithium-ion battery also still
It does not have been reported that.Six phenolamino ring phosphonitriles can by absorbing heat during high temperature degradation, generate phosphate, metaphosphate and
Polyphosphate forms protective film in polymer surfaces to completely cut off air, it is non-combustible to release carbon dioxide, ammonia, nitrogen etc.
Property gas dilution oxygen, to reach flame retardant effect.When polymer dielectric burning, by means of six phenolamino ring phosphonitriles
Fire retardation can make polymer dielectric self-extinguishment.
(2) polymer dielectric provided by the invention with flame retarding function is in lithium battery polymer dielectric use process
Self-extinguishment can be generated after middle generation burning or contact open fire, can effectively avoid the safety problems such as combustion explosion；It effectively solves existing
There is polymer dielectric easy firing existing for technology, solve the problems such as cell safety.
(3) its fire-retardant principle of flame retarding function polymer dielectric that has of the invention is to contain flame retarding construction in polymer architecture
HCP absorbs heat during high temperature degradation, generates phosphate, metaphosphate and polyphosphate, is formed in polymer surfaces
Protective film releases carbon dioxide, ammonia, nitrogen to completely cut off air, to reach flame retardant effect.
(4) present invention carries out nucleophilic displacement of fluorine by hexachlorocyclotriph,sphazene and acetophenol, is prepared six after deacetylated
Phenolamino ring phosphonitrile adulterates lithium salts in a heated condition with polyethyleneglycol diglycidylether and polymer electrolytic is prepared
Matter.The present invention is reacted by hexachlorocyclotriph,sphazene with acetophenol, and the thermal stability and mechanical performance of ring phosphonitrile are improved.This
Invention obtains aniline structure relatively stable in air by deacetylation.The present invention prepares six phenylol amino ring phosphorus
The chemical equation of nitrile structure HCP are as follows:
The present invention prepares the chemical synthesis formula of HCP-PEGDE cross-linked polymer are as follows:
The present invention passes through the overall flow technique for controlling the polymer dielectric preparation method, each anti-particularly by controlling
Reactant species and the ratio etc. in step are answered, the polymer dielectric is made to meet specified chemical structure, is applied to lithium-ion electric
Chi Shi can generate self-extinguishment when polymer encounters open fire or is ignited, to solve polymer dielectric because combustion explosion produces
Raw safety problem improves the safety of lithium battery.
(5) present invention prepares polymer dielectric by amino-epoxy heat cure reaction, is not necessarily to starvation and moisture,
Preparation method is simple to operation.Method for preparing polymer electrolytes of the present invention, reaction condition is mild, operating method letter
It just, and can be by selecting the PEGDE of different molecular weight to regulate and control the conductivity and mechanical performance of cross-linked polymer.
(6) in addition, the present invention also passes through the screening of polyethyleneglycol diglycidylether chain length, and to lithium salts and ethylene oxide
Base molar ratio carries out further preferred control, can optimize to obtain the crosslinking net polymer electrolytic with compared with high ionic conductivity
Matter film.
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic resonance with six phenolamino ring phosphonitrile HCP of flame retarding construction prepared in the embodiment of the present invention 1
Spectrogram, abscissa are chemical shift.
Fig. 2 is the nuclear magnetic resonance phosphorus with six phenolamino ring phosphonitrile HCP of flame retarding construction prepared in the embodiment of the present invention 1
Spectrogram, abscissa are chemical shift.
Fig. 3 is that the conductivity of the polymer dielectric prepared in the embodiment of the present invention 1 varies with temperature figure.
Fig. 4 is that (this is poly- for the polymer for preparing in the obtained polymer of method known in the state of the art and the embodiment of the present invention 1
Closing ethyoxyl/lithium ion molar ratio in object is 12:1), both is prepared as to flame-retardant polymer electrolyte batten respectively and is lighted
Self-extinguishment process comparison diagram afterwards；(a), (b), (c) in Fig. 4 correspond to the prior art (Macromolecules 2017,50,
1970-1980) the polyethylene glycol oxide base polymer electrolyte that known method obtains, (d), (e), (f) in Fig. 4 correspond to this hair
Bright embodiment 1 has the polyethylene oxide base crosslinking net polymer dielectric of six phenolamino ring phosphonitriles.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
On the whole, the flame-retardant polymer in the present invention is by six phenolamino ring phosphonitriles, polyethyleneglycol diglycidylether
PEGDE reacts to form HCP-PEGDE cross-linked polymer, molecular structure by amino-epoxy are as follows:
Wherein, n=4~113, and be integer.
Correspondingly, by taking lithium ion battery is intended application object as an example, this has the system of flame retarding function polymer dielectric
Preparation Method may comprise steps of:
I, the synthesis of six phenolamino ring phosphonitrile HCP of flame retarding construction, specifically includes:
(1) hexachlorocyclotriph,sphazene and acetaminophenol are dissolved in organic solvent, alkali is added, and be stirred at reflux anti-
It answers, obtains reaction solution；
(2) reaction solution described in step (1) is poured into precipitating reagent and is precipitated, filtration drying obtains six acetaminophenol rings
Phosphonitrile；
(3) six acetaminophenol ring phosphonitriles described in step (2) are dissolved in organic solvent, alkali are added, and stir
Six phenolamino ring phosphonitrile HCP are obtained by filtration in back flow reaction after reaction；
The synthesis of II, crosslinking agent polyethyleneglycol diglycidylether PEGDE:
(4) alkali, epoxychloropropane and water, heating after polyethylene glycol heating melting, will be added into the polyethylene glycol of melting
Reaction obtains polyethyleneglycol diglycidylether PEGDE；
The synthesis of III, crosslinking net polymer HCP-PEGDE:
(5) six phenolamino ring phosphonitrile HCP and step (4) obtain described in step (3) polyethylene glycol diglycidyl is sweet
Oily ether PEGDE is dissolved in organic solvent, obtains HCP-PEGDE mixed solution；
The preparation of IV, flame-retardant polymer electrolyte:
(6) lithium salts is added into step (5) the HCP-PEGDE mixed solution, after mixing evenly casting film, heating is dry
The dry polymer dielectric for obtaining that there is flame retarding function；The polymer dielectric includes cross-linked polymer and lithium salts.
Wherein, for raw material used by step (1), the molecular structure of the hexachlorocyclotriph,sphazene are as follows:
The molecular structure of the acetaminophenol are as follows:
The molecular structure for the six acetaminophenols ring phosphonitrile that step (2) obtains are as follows:
The molecular structure of the resulting six phenolaminos ring phosphonitrile HCP of step (3) are as follows:
That is, step (1), (2), (3), that is, correspond to step I entirety, the chemistry of flame retarding construction HCP closes reaction equation are as follows:
Step (4) is raw materials used, the molecular structure of the polyethylene glycol are as follows:Polyethylene glycol
Relative molecular mass be 200~5000；
Step (4) products therefrom, the molecular structure of the polyethyleneglycol diglycidylether PEGDE are as follows:
With the polymer dielectric of flame retarding function in the present invention, other than addition lithium salts is to be applied to lithium ion battery,
The present invention can also replace lithium salts using other metal salts, to be suitable for the ion battery of other metallic elements.
The following are specific embodiments:
Embodiment 1
Six phenolamino ring phosphonitrile HCP- polyethyleneglycol diglycidylether PEGDE200Flame-retardant polymer electrolyte.
The flame-retardant polymer electrolyte preparation method is as follows: by 5.0g hexachlorocyclotriph,sphazene and 17.4g 4- acetylamino
Phenol is dissolved in 200mL acetone soln, and 29.9g potassium carbonate powder is added.Under argon gas protection, mechanical stirring, next time at 60 DEG C
Stream reaction 5 days.After reaction, remaining reaction solution is poured into water precipitating, stirring, washing.Filtering, water washing 3 times, is drained,
It is 48 hours dry in 50 DEG C of vacuum drying ovens, obtain white crystal.Six acetophenol basic ring phosphonitrile of 25.0g is dissolved in 300mL
In methanol, the aqueous solution for being dissolved with 58.0g NaOH is added dropwise and is warming up to 90 DEG C under argon gas protection, is stirred at reflux reaction 5 days.Instead
Cooling after answering, filtering is dried in vacuo 48h at washing 3 times, 50 DEG C, obtains solid powder.Polyethylene glycol 200 heating is molten
After melting, potassium carbonate, epoxychloropropane and water are added into the polyethylene glycol of melting, reaction obtains polyethylene glycol two at 120 DEG C
Glycidol ether PEGDE200。
Six phenolamino ring phosphonitriles and polyethyleneglycol diglycidylether PEGDE are put into according to equivalent proportion200, respectively according to
Ethyoxyl/lithium ion molar ratio is that lithium perchlorate is added in 8:1,12:1,16:1 in polymer, the dissolution of 3mL dimethyl sulfoxide is added, often
Solution is poured with mold after the lower stirring 15min of temperature, solvent volatilizees 3 hours at room temperature, and it is solid to place into heating in 100 DEG C of baking ovens
Change 12 hours, is finally putting into vacuum oven 24 hours dry.After completely removing the solvent in electrolyte, obtain having fire-retardant
The polymer electrolyte film of function, the lithium ion conductivity for measuring dielectric film is 1.3 × 10 at room temperature-6S cm-1, press
Lithium ion battery is assembled into according to the sequence of lithium piece, electrolytic thin-membrane, iron phosphate lithium positive pole piece.
Embodiment 2
Six phenolamino ring phosphonitrile HCP- polyethyleneglycol diglycidylether PEGDE4000Flame-retardant polymer electrolyte.
The flame-retardant polymer electrolyte preparation method is as follows: by 5.0g hexachlorocyclotriph,sphazene and 17.4g 4- acetylamino
Phenol is dissolved in 200mL tetrahydrofuran solution, and 29.9g potassium carbonate powder is added.Under argon gas protection, mechanical stirring, at 60 DEG C
Lower back flow reaction 1 day.After reaction, remaining reaction solution is poured into water precipitating, stirring, washing.Filtering water washing 3 times, is taken out
It is dry, it is 48 hours dry in 50 DEG C of vacuum drying ovens, obtain white crystal.Six acetophenol basic ring phosphonitrile of 25.0g is dissolved in
In 300mL methanol, the aqueous solution for being dissolved with 58.0g NaOH is added dropwise and is warming up to 100 DEG C under argon gas protection, is stirred at reflux reaction 5
It.After reaction, cooling, filtering is dried in vacuo 48h at washing 3 times, 50 DEG C, obtains solid powder.By Macrogol 4000
After heating melting, potassium carbonate, epoxychloropropane and water are added into the polyethylene glycol of melting, reaction obtains poly- second at 120 DEG C
Hexanediol diglycidyl ether PEGDE4000。
Six phenolamino ring phosphonitriles and polyethyleneglycol diglycidylether PEGDE are put into according to equivalent proportion4000, according to polymerization
Ethyoxyl/lithium ion molar ratio is that lithium perchlorate is added in 5:1 in object, and the dissolution of 3mL dimethyl sulfoxide is added, stirs 15min under room temperature
Solution is poured with mold afterwards, solvent volatilizees 3 hours at room temperature, places into 100 DEG C of baking ovens and is heating and curing 12 hours, finally
It is put into vacuum oven 24 hours dry.After completely removing the solvent in electrolyte, the polymer with flame retarding function is obtained
Electrolyte, the lithium ion conductivity for measuring dielectric film is 2.7 × 10 at room temperature-7S cm-1, according to lithium piece, electrolyte thin
The sequence of film, iron phosphate lithium positive pole piece is assembled into lithium ion battery.
Embodiment 3
Six phenolamino ring phosphonitrile HCP- polyethyleneglycol diglycidylether PEGDE2000Flame-retardant polymer electrolyte.
The flame-retardant polymer electrolyte preparation method is as follows: by 5.0g hexachlorocyclotriph,sphazene and 17.4g 4- acetylamino
Phenol is dissolved in 200mL tetrahydrofuran solution, and 29.9g potassium carbonate powder is added.Under argon gas protection, mechanical stirring, at 60 DEG C
Lower back flow reaction 2 days.After reaction, remaining reaction solution is poured into water precipitating, stirring, washing.Filtering water washing 3 times, is taken out
It is dry, it is 48 hours dry in 50 DEG C of vacuum drying ovens, obtain white crystal.Six acetophenol basic ring phosphonitrile of 25.0g is dissolved in
In 300mL methanol, the aqueous solution for being dissolved with 58.0g NaOH is added dropwise and is warming up to 60 DEG C under argon gas protection, is stirred at reflux reaction 1
It.After reaction, cooling, filtering is dried in vacuo 48h at washing 3 times, 50 DEG C, obtains solid powder.By polyethylene glycol 2000
After heating melting, potassium carbonate, epoxychloropropane and water are added into the polyethylene glycol of melting, reaction obtains poly- second at 120 DEG C
Hexanediol diglycidyl ether PEGDE2000。
Six phenolamino ring phosphonitriles and polyethyleneglycol diglycidylether PEGDE are put into according to equivalent proportion2000, according to polymerization
Ethyoxyl/lithium ion molar ratio is that bis trifluoromethyl sulfimide lithium is added in 16:1 in object, the dissolution of 3mL dimethyl sulfoxide is added, often
Solution is poured with mold after the lower stirring 15min of temperature, solvent volatilizees 3 hours at room temperature, and it is solid to place into heating in 120 DEG C of baking ovens
Change 12 hours, is finally putting into vacuum oven 24 hours dry.After completely removing the solvent in electrolyte, obtain having fire-retardant
The polymer dielectric of function, the lithium ion conductivity for measuring dielectric film is 2.5 × 10 at room temperature-5S cm-1, according to lithium
The sequence of piece, electrolytic thin-membrane, iron phosphate lithium positive pole piece is assembled into lithium ion battery.
Embodiment 4
Six phenolamino ring phosphonitrile HCP- polyethyleneglycol diglycidylether PEGDE1000Flame-retardant polymer electrolyte.
The flame-retardant polymer electrolyte preparation method is as follows: by 5.0g hexachlorocyclotriph,sphazene and 17.4g 4- acetylamino
Phenol is dissolved in 200mL tetrahydrofuran solution, and 29.9g potassium carbonate powder is added.Under argon gas protection, mechanical stirring, at 60 DEG C
Lower back flow reaction 2 days.After reaction, remaining reaction solution is poured into water precipitating, stirring, washing.Filtering water washing 3 times, is taken out
It is dry, it is 48 hours dry in 50 DEG C of vacuum drying ovens, obtain white crystal.Six acetophenol basic ring phosphonitrile of 25.0g is dissolved in
In 300mL methanol, the aqueous solution for being dissolved with 58.0g NaOH is added dropwise and is warming up to 100 DEG C under argon gas protection, is stirred at reflux reaction 5
It.After reaction, cooling, filtering is dried in vacuo 48h at washing 3 times, 50 DEG C, obtains solid powder.By cetomacrogol 1000
After heating melting, potassium carbonate, epoxychloropropane and water are added into the polyethylene glycol of melting, reaction obtains poly- second at 120 DEG C
Hexanediol diglycidyl ether PEGDE1000。
Six phenolamino ring phosphonitriles and polyethyleneglycol diglycidylether PEGDE are put into according to equivalent proportion1000, according to polymerization
Ethyoxyl/lithium ion molar ratio is that bis trifluoromethyl sulfimide lithium is added in 12:1 in object, the dissolution of 3mL dimethyl sulfoxide is added, often
Solution is poured with mold after the lower stirring 15min of temperature, solvent volatilizees 3 hours at room temperature, and it is solid to place into heating in 120 DEG C of baking ovens
Change 12 hours, is finally putting into vacuum oven 3 hours dry.After completely removing the solvent in electrolyte, obtain having fire-retardant
The polymer dielectric of function, the lithium ion conductivity for measuring dielectric film is 2.4 × 10 at room temperature-7S cm-1, according to lithium
The sequence of piece, electrolytic thin-membrane, iron phosphate lithium positive pole piece is assembled into lithium ion battery.
Embodiment 5
Six phenolamino ring phosphonitrile HCP- polyethyleneglycol diglycidylether PEGDE500Flame-retardant polymer electrolyte.
The flame-retardant polymer electrolyte preparation method is as follows: by 5.0g hexachlorocyclotriph,sphazene and 17.4g 4- acetylamino
Phenol is dissolved in 200mL tetrahydrofuran solution, and 29.9g potassium carbonate powder is added.Under argon gas protection, mechanical stirring, at 60 DEG C
Lower back flow reaction 4 days.After reaction, remaining reaction solution is poured into water precipitating, stirring, washing.Filtering water washing 3 times, is taken out
It is dry, it is 48 hours dry in 50 DEG C of vacuum drying ovens, obtain white crystal.Six acetophenol basic ring phosphonitrile of 25.0g is dissolved in
In 300mL methanol, the aqueous solution for being dissolved with 58.0g NaOH is added dropwise and is warming up to 90 DEG C under argon gas protection, is stirred at reflux reaction 5
It.After reaction, cooling, filtering is dried in vacuo 48h at washing 3 times, 50 DEG C, obtains solid powder.By polyethylene glycol 500
After heating melting, potassium carbonate, epoxychloropropane and water are added into the polyethylene glycol of melting, reaction obtains poly- second at 120 DEG C
Hexanediol diglycidyl ether PEGDE500。
Six phenolamino ring phosphonitriles and polyethyleneglycol diglycidylether PEGDE are put into according to equivalent proportion500, according to polymerization
Ethyoxyl/lithium ion molar ratio is that bis trifluoromethyl sulfimide lithium is added in 16:1 in object, the dissolution of 3mL dimethyl sulfoxide is added, often
Solution is poured with mold after the lower stirring 15min of temperature, solvent volatilizees 3 hours at room temperature, and it is solid to place into heating in 120 DEG C of baking ovens
Change 12 hours, is finally putting into vacuum oven 24 hours dry.After completely removing the solvent in electrolyte, obtain having fire-retardant
The polymer dielectric of function, the lithium ion conductivity for measuring dielectric film is 2.1 × 10 at room temperature-7S cm-1, according to lithium
The sequence of piece, electrolytic thin-membrane, iron phosphate lithium positive pole piece is assembled into lithium ion battery.
Embodiment 6
Six phenolamino ring phosphonitrile HCP- polyethyleneglycol diglycidylether PEGDE5000Flame-retardant polymer electrolyte.
The flame-retardant polymer electrolyte preparation method is as follows: by 5.0g hexachlorocyclotriph,sphazene and 17.4g 4- acetylamino
Phenol is dissolved in 200mL tetrahydrofuran solution, and 29.9g potassium carbonate powder is added.Under argon gas protection, mechanical stirring, at 60 DEG C
Lower back flow reaction 3 days.After reaction, remaining reaction solution is poured into water precipitating, stirring, washing.Filtering water washing 3 times, is taken out
It is dry, it is 48 hours dry in 50 DEG C of vacuum drying ovens, obtain white crystal.Six acetophenol basic ring phosphonitrile of 25.0g is dissolved in
It in 300mL methanol, is added dropwise and is dissolved with 58.0g NaOH aqueous solution, under argon gas protection, be warming up to 90 DEG C, be stirred at reflux reaction 120
Hour.After reaction, cooling, filtering is dried in vacuo 48h at washing 3 times, 50 DEG C, obtains solid powder.By polyethylene glycol
After 5000 heating meltings, potassium carbonate, epoxychloropropane and water are added into the polyethylene glycol of melting, reacts and obtains at 120 DEG C
Polyethyleneglycol diglycidylether PEGDE5000。
Six phenolamino ring phosphonitriles and polyethyleneglycol diglycidylether PEGDE are put into according to equivalent proportion5000, according to polymerization
Ethyoxyl/lithium ion molar ratio is that bis trifluoromethyl sulfimide lithium is added in 16:1 in object, the dissolution of 3mL dimethyl sulfoxide is added, often
Solution is poured with mold after the lower stirring 15min of temperature, solvent volatilizees 3 hours at room temperature, and it is solid to place into heating in 100 DEG C of baking ovens
Change 12 hours, is finally putting into vacuum oven 24 hours dry.After completely removing the solvent in electrolyte, obtain having fire-retardant
The polymer dielectric of function, the lithium ion conductivity for measuring dielectric film is 2.1 × 10 at room temperature-7S cm-1, according to lithium
The sequence of piece, electrolytic thin-membrane, iron phosphate lithium positive pole piece is assembled into lithium ion battery.
Embodiment 7
Six phenolamino ring phosphonitrile HCP- polyethyleneglycol diglycidylether PEGDE2000Flame-retardant polymer electrolyte.
The flame-retardant polymer electrolyte preparation method is as follows: by 5.0g hexachlorocyclotriph,sphazene and 17.4g 4- acetylamino
Phenol is dissolved in 200mL tetrahydrofuran solution, and 29.9g potassium carbonate powder is added.Under argon gas protection, mechanical stirring, at 50 DEG C
Lower back flow reaction 1 day.After reaction, remaining reaction solution is poured into ether and is precipitated, stirred, wash.Filtering, water washing 3 times,
It drains, it is 48 hours dry in 50 DEG C of vacuum drying ovens, obtain white crystal.Six acetophenol basic ring phosphonitrile of 25.0g is dissolved in
In 300mL methanol, the aqueous solution for being dissolved with 58.0g potassium carbonate is added dropwise and is warming up to 60 DEG C under argon gas protection, is stirred at reflux reaction 1
It.After reaction, cooling, filtering is dried in vacuo 48h at washing 3 times, 50 DEG C, obtains solid powder.By polyethylene glycol 2000
After heating melting, sodium hydroxide, epoxychloropropane and water are added into the polyethylene glycol of melting, reaction obtains poly- second at 60 DEG C
Hexanediol diglycidyl ether PEGDE2000。
Six phenolamino ring phosphonitriles and polyethyleneglycol diglycidylether PEGDE are put into according to equivalent proportion2000, according to polymerization
Ethyoxyl/lithium ion molar ratio is that bis trifluoromethyl sulfimide lithium is added in 30:1 in object, the dissolution of 3mL dimethyl sulfoxide is added, often
Solution is poured with mold after the lower stirring 15min of temperature, solvent volatilizees 3 hours at room temperature, and it is solid to place into heating in 100 DEG C of baking ovens
Change 3 hours, is finally putting into vacuum oven 24 hours dry.After completely removing the solvent in electrolyte, obtain having fire-retardant
The polymer dielectric of function, the lithium ion conductivity for measuring dielectric film is 2.0 × 10 at room temperature-7S cm-1, according to lithium
The sequence of piece, electrolytic thin-membrane, iron phosphate lithium positive pole piece is assembled into lithium ion battery.
Embodiment 8
Six phenolamino ring phosphonitrile HCP- polyethyleneglycol diglycidylether PEGDE2000Flame-retardant polymer electrolyte.
The flame-retardant polymer electrolyte preparation method is as follows: by 5.0g hexachlorocyclotriph,sphazene and 17.4g 4- acetylamino
Phenol is dissolved in 200mL tetrahydrofuran solution, and 29.9g potassium carbonate powder is added.Under argon gas protection, mechanical stirring, at 70 DEG C
Lower back flow reaction 5 days.After reaction, remaining reaction solution is poured into n-hexane and is precipitated, stirred, wash.Filtering, water washing 3
It is secondary, it drains, it is 48 hours dry in 50 DEG C of vacuum drying ovens, obtain white crystal.Six acetophenol basic ring phosphonitrile of 25.0g is dissolved
In 300mL methanol, the aqueous solution for being dissolved with 58.0g NaOH is added dropwise and is warming up to 100 DEG C under argon gas protection, is stirred at reflux anti-
It answers 5 days.After reaction, cooling, filtering is dried in vacuo 48h at washing 3 times, 50 DEG C, obtains solid powder.By polyethylene glycol
After 2000 heating meltings, potassium hydroxide, epoxychloropropane and water are added into the polyethylene glycol of melting, is reacted at 120 DEG C
To polyethyleneglycol diglycidylether PEGDE2000.Six phenolamino ring phosphonitriles and polyethylene glycol diglycidyl are put into according to equivalent proportion
Glycerin ether PEGDE2000, it is that bis trifluoromethyl sulfimide lithium is added in 5:1 according to ethyoxyl in polymer/lithium ion molar ratio,
The dissolution of 3mL dimethyl sulfoxide is added, pours solution with mold after 15min is stirred under room temperature, solvent volatilizees 3 hours at room temperature,
It places into 120 DEG C of baking ovens and is heating and curing 24 hours, be finally putting into vacuum oven 24 hours dry.Completely remove electrolyte
In solvent after, obtain the polymer dielectric with flame retarding function, measure the lithium ion conductivity of dielectric film at room temperature
It is 2.1 × 10-7S cm-1, lithium ion battery is assembled into according to the sequence of lithium piece, electrolytic thin-membrane, iron phosphate lithium positive pole piece.
Polymer dielectric in the present invention assigns polymer due to the six phenylamino basic ring phosphonitriles with flame retarding construction
Fire-retardant function；When polymer dielectric is ignited, since HCP absorbs heat during high temperature degradation, generate phosphate,
Metaphosphate and polyphosphate form protective film in polymer surfaces to completely cut off air, release carbon dioxide, ammonia, nitrogen
The incombustibility gas dilution oxygen such as gas, to reach flame retardant effect, as in Fig. 4 (d), (e), shown in (f), flame-retardant polymer
Electrolyte is ignited rear rapid self-extinguishment, and polyethylene glycol oxide base polymer electrolyte that method known in the state of the art obtains (that is,
With reference to existing technical literature Flexible Organic-Inorganic Hybrid Solid Electrolytes Formed
What via Thiol-Acrylate Photopolymerization, Macromolecules 2017,50,1970-1980 was recorded
Photosensitizer is dissolved in polyethyleneglycol diacrylate PEGDA and is made through ultraviolet light by preparation method), then burning rapidly,
As in Fig. 4 (a), (b), shown in (c).
Since the polymer dielectric in the present invention can be applied to lithium ion battery, employed in process of the present invention
Lithium salts can be (such as lithium perchlorate, LiBF4, lithium hexafluoro phosphate, double of lithium salts used in lithium battery in the prior art
The one or more of lithium trifluoromethanesulp,onylimide).In addition, the polymer dielectric produced by the present invention with flame retarding function is thin
Its thickness of film can be adjusted flexibly according to actual needs, naturally it is also possible to according to practical application request, prepare the tool of non-thin film shape
There is the polymer dielectric of flame retarding function.Finally, except what above-described embodiment obtained has fire-retardant function suitable for lithium ion battery
Outside the polymer dielectric of energy, the present invention can also replace lithium salts using other metal salts, to obtain being suitable for other metals
Ion battery, the same polymer dielectric with flame retarding function.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of polymer dielectric with flame retarding function, which is characterized in that the polymer dielectric include metal salt and
It is the cross-linked polymer for being crosslinked arm and being constituted by kernel, polyethyleneglycol diglycidylether of six phenolamino ring phosphonitriles, wherein institute
Cross-linked polymer is stated with chemical structural formula as follows:
In the chemical structural formula, n be 4~113 integer.
2. as described in claim 1 with the polymer dielectric of flame retarding function, which is characterized in that the cross-linked polymer is main
It is to be obtained by six phenolamino ring phosphonitriles (HCP) and polyethyleneglycol diglycidylether (PEGDE) reaction；Wherein,
The chemical structural formula of the six phenolaminos ring phosphonitrile (HCP) is as follows:
The chemical structural formula of the polyethyleneglycol diglycidylether (PEGDE) is as follows:
Wherein, the integer that n is 4~113；Also, the polyethylene glycol of the polyethyleneglycol diglycidylether (PEGDE) is opposite
Molecular mass is 200~5000.
3. as described in claim 1 with the polymer dielectric of flame retarding function, which is characterized in that the metal salt is lithium salts,
The lithium salts is bis trifluoromethyl sulfimide lithium, the one or more of lithium perchlorate and lithium hexafluoro phosphate；Preferably, rememberFor a polyethylene oxide base unit, then, in the metal salt amount of the substance of metallic element with
The amount ratio between two of the total material of polyethylene oxide base unit described in the cross-linked polymer meets 1:5~1:30.
4. the method for preparing polymer electrolytes as described in claim 1-3 any one with flame retarding function is prepared, it is special
Sign is, comprising the following steps:
(1) hexachlorocyclotriph,sphazene and acetaminophenol are dissolved in organic solvent, alkali are added, and be stirred at reflux reaction, obtain
To reaction solution；
(2) reaction solution for obtaining step (1) and precipitant mix, which are formed, precipitates, and filtration drying obtains six acetamido benzene
Phenol ring phosphonitrile；
(3) the six acetaminophenols ring phosphonitrile for obtaining step (2) is dissolved in organic solvent, alkali is added, and stir
Six phenolamino ring phosphonitriles (HCP) are obtained by filtration in back flow reaction after reaction；
(4) alkali, epoxychloropropane and water, heating reaction after polyethylene glycol heating melting, will be added into the polyethylene glycol of melting
Obtain polyethyleneglycol diglycidylether (PEGDE)；
(5) polyethylene glycol two for obtaining the six phenolaminos ring phosphonitrile (HCP) that step (3) obtains, step (4) contracts
Water glycerin ether (PEGDE) dissolves in organic solvent together with metal salt, then carries out the reaction that is heating and curing, can obtain after dry
To the polymer dielectric with flame retarding function.
5. preparation method as claimed in claim 4, which is characterized in that the polymer dielectric with flame retarding function obtained
The specially polymer dielectric with flame retarding function of film shape, the thickness of film are preferably 50~300 microns；The step
(5) it is specifically: first by the six phenolaminos ring phosphonitrile (HCP) that step (3) obtains and the poly- second two that step (4) obtains
Alcohol diglycidyl ether (PEGDE) is dissolved in organic solvent, obtains mixed solution, and metal then is added into the mixed solution
Salt, casting film, heat drying obtain the polymer dielectric with flame retarding function after mixing evenly.
6. preparation method as claimed in claim 4, which is characterized in that in the step (1), the chemistry of the hexachlorocyclotriph,sphazene
Structural formula are as follows:
The chemical structural formula of the acetaminophenol are as follows:
In the step (2), the chemical structural formula of the six acetaminophenols ring phosphonitrile are as follows:
In the step (3), the chemical structural formula of the six phenolaminos ring phosphonitrile (HCP) are as follows:
In the step (4), the chemical structural formula of the polyethylene glycol are as follows:Also, the poly- second two
The relative molecular mass of alcohol is 200~5000；
The chemical structural formula of the polyethyleneglycol diglycidylether (PEGDE) are as follows:
Wherein, the integer that n is 4~113.
7. preparation method as claimed in claim 4, which is characterized in that in the step (1), the reaction for being stirred at reflux reaction
Temperature is 50~70 DEG C, and the reaction time is 1~5 day；
In the step (3), the reaction temperature for being stirred at reflux reaction is 60~100 DEG C, and the reaction time is 1~5 day；
In the step (4), the reaction temperature of the heating reaction is 60~120 DEG C, and the reaction time is 3~24 hours；
In the step (5), the reaction temperature of the reaction that is heating and curing is 100~120 DEG C, and the reaction time is 3~24
Hour.
8. preparation method as claimed in claim 4, which is characterized in that in the step (1), the organic solvent is tetrahydro furan
It mutters, any one in acetone, methanol；The alkali is potassium carbonate, cesium carbonate, any one in sodium hydroxide；
In the step (2), the precipitating reagent is water, ether, any one in n-hexane；
In the step (3), the organic solvent is methanol, ethyl alcohol, any one in tetrahydrofuran；The alkali is carbonic acid
Potassium, potassium hydroxide, any one in sodium hydroxide；
In the step (4), the alkali is potassium carbonate, potassium hydroxide, any one in sodium hydroxide；
In the step (5), the organic solvent is tetrahydrofuran, acetonitrile, any one in n,N-Dimethylformamide.
9. preparation method as claimed in claim 4, which is characterized in that in the step (5), the metal salt is specially lithium salts,
The lithium salts is bis trifluoromethyl sulfimide lithium, the one or more of lithium perchlorate and lithium hexafluoro phosphate；Preferably, rememberFor a polyethylene oxide base unit, then, in the metal salt amount of the substance of metallic element with
The amount ratio between two of the total material of the polyethylene oxide base unit contained in the mixed solution meets 1:5~1:30.
10. the polymer dielectric as described in claim 1-3 any one with flame retarding function is answered in metal ion battery
With；Preferably, the metal ion battery is lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910648377.0A CN110380118A (en) | 2019-07-18 | 2019-07-18 | A kind of polymer dielectric and its preparation and application with flame retarding function |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910648377.0A CN110380118A (en) | 2019-07-18 | 2019-07-18 | A kind of polymer dielectric and its preparation and application with flame retarding function |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110380118A true CN110380118A (en) | 2019-10-25 |
Family
ID=68253797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910648377.0A Pending CN110380118A (en) | 2019-07-18 | 2019-07-18 | A kind of polymer dielectric and its preparation and application with flame retarding function |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110380118A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111224147A (en) * | 2020-02-21 | 2020-06-02 | 四川大学 | Flame-retardant polymer solid electrolyte membrane, preparation method thereof and all-solid-state battery |
| CN112189278A (en) * | 2020-01-11 | 2021-01-05 | 山东理工大学 | Preparation method of flame-retardant lithium ion battery electrolyte easy to dissolve in organic solvent |
| CN112204795A (en) * | 2020-01-11 | 2021-01-08 | 山东理工大学 | Method for improving solubility in organic solvent by lithium salt of novel flame-retardant electrolyte |
| CN115084646A (en) * | 2022-06-24 | 2022-09-20 | 江西师范大学 | Cyclotriphosphazene-based flame-retardant polymer electrolyte and preparation method and application thereof |
| CN117720721A (en) * | 2024-02-18 | 2024-03-19 | 国家电投集团氢能科技发展有限公司 | Anion exchange polymer, ion exchange membrane, and preparation methods and application thereof |
| EP4270579A3 (en) * | 2022-04-27 | 2024-04-03 | Industrial Technology Research Institute | Electrolyte composition, quasi-solid electrolyte and lithium-ion battery employing the same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104466242A (en) * | 2014-12-09 | 2015-03-25 | 西南石油大学 | Sponge substrate carrier gel polymer electrolyte and preparation method thereof |
| CN104885289A (en) * | 2013-10-29 | 2015-09-02 | 株式会社Lg化学 | Gel polymer electrolyte and lithium secondary battery including same |
| CN107154512A (en) * | 2017-05-05 | 2017-09-12 | 华中科技大学 | A kind of polymer dielectric and its preparation and application with self-healing function |
| CN108598567A (en) * | 2018-04-26 | 2018-09-28 | 吉林大学 | A kind of fire-retardant gel electrolyte, preparation method and its application in lithium ion battery and ultracapacitor |
| CN108878970A (en) * | 2018-06-29 | 2018-11-23 | 华中科技大学 | A kind of composition polymer solid electrolyte, solid state lithium battery and preparation method thereof |
| CN109755630A (en) * | 2017-11-03 | 2019-05-14 | 深圳格林德能源集团有限公司 | A kind of Recombination gel polymer dielectric preparation method and its lithium ion battery |
-
2019
- 2019-07-18 CN CN201910648377.0A patent/CN110380118A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104885289A (en) * | 2013-10-29 | 2015-09-02 | 株式会社Lg化学 | Gel polymer electrolyte and lithium secondary battery including same |
| CN104466242A (en) * | 2014-12-09 | 2015-03-25 | 西南石油大学 | Sponge substrate carrier gel polymer electrolyte and preparation method thereof |
| CN107154512A (en) * | 2017-05-05 | 2017-09-12 | 华中科技大学 | A kind of polymer dielectric and its preparation and application with self-healing function |
| CN109755630A (en) * | 2017-11-03 | 2019-05-14 | 深圳格林德能源集团有限公司 | A kind of Recombination gel polymer dielectric preparation method and its lithium ion battery |
| CN108598567A (en) * | 2018-04-26 | 2018-09-28 | 吉林大学 | A kind of fire-retardant gel electrolyte, preparation method and its application in lithium ion battery and ultracapacitor |
| CN108878970A (en) * | 2018-06-29 | 2018-11-23 | 华中科技大学 | A kind of composition polymer solid electrolyte, solid state lithium battery and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| CAI ZUO ET AL.: ""Cyclophosphazene-based hybrid polymer electrolytes obtained via epoxy-amine reaction for high-performance all-solid-state lithium-ion batteries"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112189278A (en) * | 2020-01-11 | 2021-01-05 | 山东理工大学 | Preparation method of flame-retardant lithium ion battery electrolyte easy to dissolve in organic solvent |
| CN112204795A (en) * | 2020-01-11 | 2021-01-08 | 山东理工大学 | Method for improving solubility in organic solvent by lithium salt of novel flame-retardant electrolyte |
| WO2021138921A1 (en) * | 2020-01-11 | 2021-07-15 | 山东理工大学 | Method for improving solubility of lithium salt of novel flame-retardant electrolyte in organic solvent |
| WO2021138922A1 (en) * | 2020-01-11 | 2021-07-15 | 山东理工大学 | Preparation method for flame-retardant lithium ion battery electrolyte easy to dissolve in organic solvent |
| CN112204795B (en) * | 2020-01-11 | 2022-05-17 | 山东理工大学 | Preparation method of flame-retardant electrolyte |
| CN112189278B (en) * | 2020-01-11 | 2022-07-29 | 山东理工大学 | Preparation method of flame-retardant lithium ion battery electrolyte easily soluble in organic solvent |
| CN111224147A (en) * | 2020-02-21 | 2020-06-02 | 四川大学 | Flame-retardant polymer solid electrolyte membrane, preparation method thereof and all-solid-state battery |
| CN111224147B (en) * | 2020-02-21 | 2021-01-05 | 四川大学 | Flame-retardant polymer solid electrolyte membrane, preparation method thereof and all-solid-state battery |
| EP4270579A3 (en) * | 2022-04-27 | 2024-04-03 | Industrial Technology Research Institute | Electrolyte composition, quasi-solid electrolyte and lithium-ion battery employing the same |
| CN115084646A (en) * | 2022-06-24 | 2022-09-20 | 江西师范大学 | Cyclotriphosphazene-based flame-retardant polymer electrolyte and preparation method and application thereof |
| CN117720721A (en) * | 2024-02-18 | 2024-03-19 | 国家电投集团氢能科技发展有限公司 | Anion exchange polymer, ion exchange membrane, and preparation methods and application thereof |
| CN117720721B (en) * | 2024-02-18 | 2024-04-30 | 国家电投集团氢能科技发展有限公司 | Anion exchange polymer, ion exchange membrane, and preparation methods and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110380118A (en) | A kind of polymer dielectric and its preparation and application with flame retarding function | |
| Liu et al. | In situ polymerization for integration and interfacial protection towards solid state lithium batteries | |
| WO2020107857A1 (en) | Method for preparing solid polymer electrolyte and solid secondary battery using same | |
| CN110994013B (en) | Hybrid polymer electrolyte, preparation method and application thereof | |
| CN109608592B (en) | Cross-linking polymerization preparation method of polyion liquid solid electrolyte | |
| CN111748095B (en) | Cross-linked modified polyimide single ion polymer and gel polymer electrolyte thereof | |
| CN107154512A (en) | A kind of polymer dielectric and its preparation and application with self-healing function | |
| CN101076908A (en) | Safety battery solvent | |
| WO2001096446A1 (en) | Conductive polymeric compositions for lithium batteries | |
| CN107863555B (en) | Non-combustible solid polymer electrolyte and application thereof in solid secondary battery | |
| CN110172115A (en) | A kind of method for preparing polymer electrolytes and its application | |
| CN105655641B (en) | A kind of electrolyte and its lithium ion battery | |
| CN113285118A (en) | Compound solid electrolyte based on MOF three-dimensional framework support and preparation method thereof | |
| Huang et al. | A facile in situ approach to ion gel based polymer electrolytes for flexible lithium batteries | |
| CN108598567A (en) | A kind of fire-retardant gel electrolyte, preparation method and its application in lithium ion battery and ultracapacitor | |
| CN116964808A (en) | Flame-resistant quasi-solid and solid electrolyte for lithium ion and lithium metal batteries and method for producing same | |
| CN111354975A (en) | Triblock hybrid polymer electrolyte, and preparation method and application thereof | |
| Liu et al. | Recent progress in flame retardant technology of battery: A review | |
| CN115084646B (en) | Cyclotriphosphazene-based flame-retardant polymer electrolyte, and preparation method and application thereof | |
| CN108070084A (en) | oligomer polymer and lithium battery | |
| CN111548490B (en) | Polyimide single-ion polymer, preparation method thereof and solid polymer electrolyte membrane | |
| CN109980274A (en) | Electrolyte, electrolyte composition and the lithium battery comprising it | |
| CN101210078B (en) | Anti-flaming polyelectrolyte composition containing maleimide | |
| CN114530629B (en) | Preparation and application of solid electrolyte and additive thereof | |
| CN111224147B (en) | Flame-retardant polymer solid electrolyte membrane, preparation method thereof and all-solid-state battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20191025 |