CN107134587A - A kind of solid electrolyte inorganic nano particle filler and preparation method thereof - Google Patents
A kind of solid electrolyte inorganic nano particle filler and preparation method thereof Download PDFInfo
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- CN107134587A CN107134587A CN201710282317.2A CN201710282317A CN107134587A CN 107134587 A CN107134587 A CN 107134587A CN 201710282317 A CN201710282317 A CN 201710282317A CN 107134587 A CN107134587 A CN 107134587A
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
- C09C1/407—Aluminium oxides or hydroxides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a kind of solid electrolyte inorganic nano particle filler and preparation method thereof, the inorganic nano-particle that wherein solid electrolyte is mainly modified with inorganic nano particle filler by sulfonic acid group is linked with amino-terminated polyethers via sulfonic acid amino ionic bond to be formed；The inorganic nano-particle of sulfonic acid group modification is 10/1~1/10 with the mass ratio of both amino-terminated polyethers.The present invention to filler key core component, shell component and proportioning between them etc. by being adjusted, and the Parameter Conditions of the integral process flow design of preparation method and each reactions steps are improved, the solid electrolyte inorganic nano particle filler of acquisition, one side filler surface grafting has same sex electric charge, mutual repulsion effect between electric charge ensure that nano-particle is dispersed in system, on the other hand, equally distributed filler can effectively suppress the growth of polymer crystallization, and showing the ionic conductivity of electrolyte is improved.
Description
Technical field
The invention belongs to lithium ion battery electrolyte field, more particularly, to a kind of solid electrolyte inorganic nano
Particle filler and preparation method thereof.
Background technology
In recent years, especially autumn and winter almost spreads the serious of China Middle Eastern and In Wulumuqi
Haze has aroused concern of the people to current cruel Environmental Status again, and is arranged using traditional fossil energy by the automobile of power
The tail gas put is to cause one of chief-criminal misfortune person of this environmental problem, and this just makes exploitation to clean, efficient secondary cell is
The electric automobile in power source becomes particularly urgent.Because secondary cell will directly affect the performance of electric automobile, so, have benefited from
Higher energy density and longer cycle life, lithium ion battery have caused the extensive concern of people.However, due to mesh
Preceding lithium ion battery, as electrolyte, makes it there is huge peace during long-term use mostly using flammable organic liquid
Full hidden danger.Although the destruction brought when accident occurs can be reduced by reinforcing, thickening the encapsulating material of lithium ion battery,
It is that this can undoubtedly increase the deadweight of battery in itself, hinders its application in practice.
To improve the security effectiveness of lithium ion battery, liquid electrolyte has been substituted using relatively reliable all solid state electrolyte
Into important selection to solve this problem.Polyethylene glycol oxide is using solid electrolyte polymer matrix material the most ripe
Material, lithium ion reaches the purpose conducted in system by the complexing with ethoxy segment in polyethylene glycol oxide.But, line style it is poly-
Ethylene oxide is easily crystallized at room temperature, hinders the conduction of lithium ion, it is impossible to directly as solid electrolyte material.Except passing through
The methods such as crosslinking, copolymerization adjustment polyethylene oxide base electrolyte structure can suppress the crystallization of matrix, inorganic receive of adulterating wherein
It is also to destroy the feasible means of polymer segment regularity that rice filler, which builds composite solid electrolyte system,.In polyethylene oxide base
In body doped alumina nano-particle be on compound electrolyte material earliest report (Solid State Ionics,
1982,7,75-79), but inevitable reunion can occur for unmodified nano-particle, cause it not to be dispersed in
In electrolyte system.Then, through ionic liquid (Adv.Mater., 2012,24,4430-4435) or sulfonic acid group
The nano-particle of (Adv.Funct.Mater., 2013,23,1019-1027) modification also is used to build compound electric as filler
Solve material, although therefore the dispersiveness of nano-particle is improved, but raw material used in above method is price
Higher experiment level reagent, and preparation process is more harsh, it is impossible to the need for meeting large-scale industrial production.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, it is an object of the invention to provide a kind of solid electrolyte use
Inorganic nano particle filler and preparation method thereof, wherein by between key core component, shell component and core-shell structure copolymer component
The adjustment of the factors such as proportioning, and integral process flow design and the parameter bar of each reactions steps to corresponding preparation method
Part (species and proportioning of such as reactant, reaction temperature and time) etc. is improved, and obtains a series of modifying by sulfonic acid group
Inorganic nano-particle linked with amino-terminated polyethers via sulfonic acid-amino ionic bond, via ionic bond modify it is inorganic
Nanoparticulate fillers；Compared with the existing technology, on the one hand, such filler surface grafting has the mutual exclusion between same sex electric charge, electric charge to make
With ensure that nano-particle is dispersed in system；On the other hand, equally distributed filler can effectively suppress polymer
The growth of crystallization, making the ionic conductivity of electrolyte is improved；In addition, the ion component of inorganic nano-particle surface grafting exists
The effect of similar " plasticizer " is play in system, the flexibility of electrolyte is further improved.In the production process of such filler
Used raw material, including inorganic nano-particle, mercaptopropyl trimethoxysilane, hydrogen peroxide, amino-terminated polyethers and have
Machine solvent etc. is Industrial raw material, because these raw material production technologies are ripe, therefore can meet this solid electrolyte nothing
The need for machine nanoparticulate fillers are produced；Meanwhile, preparation method and post-processing step are simple and easy to apply, and these advantages make on a large scale
Industrialized production is possibly realized；Through solid electrolyte prepared by this method inorganic nano particle filler performance stabilization and nothing
Poison, can the long term storage in the case where drying light protected environment.
To achieve the above object, according to one aspect of the present invention, there is provided a kind of solid electrolyte inorganic nano-particle
Sub- filler, it is characterised in that the inorganic nano that the solid electrolyte is mainly modified with inorganic nano particle filler by sulfonic acid group
Particle is linked and formed via sulfonic acid-amino ionic bond with amino-terminated polyethers；The inorganic nano-particle of the sulfonic acid group modification
The sub mass ratio with both amino-terminated polyethers is 10/1~1/10.
As present invention further optimization, the inorganic nano-particle is that Nano particles of silicon dioxide, titanium dioxide are received
At least one of rice corpuscles and alundum (Al2O3) nano-particle；The particle diameter of the inorganic nano-particle is 10~200nm.
As present invention further optimization, the amino-terminated polyethers be selected from average weight-molecular mass be 600,
1000th, at least one of 2000.
It is another aspect of this invention to provide that the invention provides a kind of system of solid electrolyte inorganic nano particle filler
Preparation Method, it is characterised in that comprise the following steps：
(1) inorganic nano-particle is placed in activation process in alkaline aqueous solution, is washed out, dries, obtaining surface has
The inorganic nano-particle of hydroxyl；The ratio of the inorganic nano-particle and the alkaline aqueous solution is 1g/100mL~1g/2mL；
The pH value of the alkaline aqueous solution is 9~12；
(2) inorganic nano-particle that the surface for obtaining the step (1) has hydroxyl is distributed in deionized water,
Then the organic solution dissolved with mercaptopropyl trimethoxysilane is added thereto, and heating response is then carried out successively, cools down, wash
Wash and dry, obtain the inorganic nano-particle of surface grafting sulfydryl；The surface has inorganic nano-particle and the institute of hydroxyl
The ratio for stating deionized water is 1g/10mL~1g/2mL；The surface have the inorganic nano-particle of hydroxyl with it is described dissolved with mercapto
The mass ratio of both mercaptopropyl trimethoxysilanes is 10/1~1/10 in the organic solution of propyl trimethoxy silicane；
(3) inorganic nano-particle for the surface grafting sulfydryl for obtaining the step (2) is scattered in 30wt.% mistake
In hydrogen oxide deionized water solution, reaction, washing are then stirred successively and is dried, surface grafting sulfonic acid group is obtained
Inorganic nano-particle；The inorganic nano-particle of the surface grafting sulfydryl and the hydrogen peroxide deionized water of the 30wt.%
The ratio of solution is 1g/50mL~1g/2mL；
(4) inorganic nano-particle of the surface grafting sulfonic acid group obtained by step (3) is scattered in deionized water, Xiang Qi
The middle deionized water solution for adding amino-terminated polyethers, carries out heating response, then cools down, washs, dries, obtains sulfonic acid-ammonia
Base ionic bond modifies inorganic nano-particle, and the sulfonic acid-amino ionic bond modification inorganic nano-particle is solid electrolyte with inorganic
Nanoparticulate fillers；The inorganic nano-particle of the surface grafting sulfonic acid group and the ratio of deionized water are 1g/10mL~1g/
2mL；The inorganic nano-particle of the surface grafting sulfonic acid group and amino in the deionized water solution of the amino-terminated polyethers
The mass ratio of both end capped polyethers is 10/1~1/10.
As present invention further optimization, in the step (1), the alkaline aqueous solution is sodium hydrate aqueous solution,
The concentration of the sodium hydrate aqueous solution is 0.1~5mol/L；The activation process be at a temperature of 60~90 DEG C reaction 2~
24h；
It is preferred that, it is first cooling treatment after the activation process, the washing is then carried out again.
As present invention further optimization, in the step (2), the surface has the inorganic nano-particle point of hydroxyl
It is scattered in the deionized water, is to use 10~40min of ultrasonic disperse；It is described dissolved with the organic molten of mercaptopropyl trimethoxysilane
The organic solvent that liquid is used is one kind in acetone, methanol, ethanol, ethyl acetate or chloroform；It is described dissolved with mercapto propyl group front three
Its concentration of the organic solution of TMOS is 1~10g/mL；The heating response is to make the table at a temperature of 60~90 DEG C
There is the inorganic nano-particle of hydroxyl and the mercaptopropyl trimethoxysilane to react 12~36h in face.
As present invention further optimization, in the step (3), the inorganic nano-particle point of the surface grafting sulfydryl
Dissipate in the hydrogen peroxide deionized water solution of the 30wt.%, be to use 10~40min of ultrasonic disperse；The stirring reaction
It is 12~36h of stirring reaction at a temperature of 10 DEG C~30 DEG C.
As present invention further optimization, in the step (4), the inorganic nano-particle of the surface grafting sulfonic acid group
Son is distributed in the deionized water, is to use 10~40min of ultrasonic disperse；The deionized water solution of the amino-terminated polyethers
Concentration be 1~10g/mL；The heating response is to make the nothing of the surface grafting sulfonic acid group at a temperature of 60~90 DEG C
Machine nano-particle and the amino-terminated polyether reactant.
As present invention further optimization, in the step (4), the heating response is by monitoring reaction solution
PH value determines the terminal of the heating response, and the heating response is terminated when pH value keeps stable.
As present invention further optimization, in the step (4), the amino-terminated polyethers is that Industrial raw material weight is equal
Relative molecular mass is 600M-600, average weight-molecular mass is 1000M-1000, or average weight-molecular mass are 2000One kind in M-2000.
This solid electrolyte modifies inorganic nano particle filler with ionic bond in the present invention, is core texture and shell knot
By obtained from sulfonic acid-amino ionic bond link between structure.Specifically, first, activation inorganic nano-particle makes its surface rich
Hydroxyl；Then, by reacting the sulfydryl in inorganic nano-particle surface modification with silane coupler；Then, peroxidating is utilized
The sulfydryl of hydroxide nanoparticle surface is sulfonic acid group；Finally, the nano-particle and amino for making surface grafting sulfonic acid group are sealed
Sulfonic acid-amino acid-base neutralization reaction occurs between the polyethers at end, ionic bond modification inorganic nano particle filler is obtained.
By the contemplated above technical scheme of the present invention, compared with prior art, combined by sulfonic acid-amino ionic bond
Inorganic nano-particle preparation process it is simple and easy to apply, the raw material of use is technical grade reagent, greatly reduces production cost
And improve production efficiency.For example, the present invention using mercaptopropyl trimethoxysilane it is this can industrialized production sulfydryl block
Silane coupler, production cost can be substantially reduced；For another example, sulfhydryl oxidase uses hydrogenperoxide steam generator, can use
(the hydrogenperoxide steam generator industrialization product is cheap for the 30wt.% hydrogen peroxide deionized water solutions industrialization product directly bought
It is easy to get), you can efficiently accomplish the oxidizing process of sulfydryl.
The step of activation inorganic nano-particle of the present invention is to be able to ensure that inorganic nano-particle surface is rich in hydroxyl,
So that next to provide necessary group with the reaction of silane coupler；Step reaction is in the alkaline atmosphere that pH value is 9~12
Middle progress is enclosed, also, to ensure to cover sufficient hydroxyl on inorganic nano-particle surface, reaction is preferably in 60~90 DEG C of temperature
2~24h of the lower reaction of degree.In addition, it is of the present invention by sulfhydryl oxidase be sulfonic acid group the step of be use 30wt.% peroxidating
What hydrogen deionized water solution was completed, and this step is exothermic reaction, it is therefore desirable to the temperature of reaction system is monitored in real time, if warm
Spend the high method cooling that can be cooled down using water-bath.In addition, the inorganic nano-particle of grafting sulfonic groups group gathers with amino-terminated
It is acid-base neutralization reaction in the reacting quintessence of ether, but in view of change and the ammonia of inorganic nano-particle sulfonic acid surfactant group grafting density
The reactivity of base itself is weaker, and this step reaction is slower, it is therefore desirable to which stage monitors the pH of reaction system to judge reaction eventually
Node.The core group for the inorganic nano-particle modified through sulfonic acid group being noted above is divided into by vinyl trimethoxy silicon
The Nano particles of silicon dioxide of the obtained surface grafting double bond of hydrolytic condensation effect between alkane, and the present invention is directly using industry
Silica inorganic nano-particle, titanium oxide inorganic nano-particle or the alundum (Al2O3) inorganic nano-particle of change are used as core
Component, so as to greatly reduce the difficulty and cost of production.
Have benefited from the interionic mutual repulsion effect of the same sex, the inorganic nano-particle of heretofore described ionic bond modification can be with
It is dispersed in electrolyte system, the crystallization of polymeric matrix is effectively inhibited, and then ensured solid electrolyte ion-conductance
The raising of conductance.Further, since the link ability of ionic bond is relatively weak, carried in the ion component of nanoparticle surface grafting
Locomitivity of the polyether segment in solid state electrolysis plastidome it is stronger, this largely enables the flexibility of electrolyte change
It is kind.This kind of ionic bond modification inorganic nano particle filler that the present invention is provided and preparation method thereof rarely has report in the prior art
Road, the present invention provides new Research Thinking for the research of solid electrolyte filler.
The preparation method of solid electrolyte inorganic nano particle filler in the present invention, passes through preparation method each step
Overall co-ordination, carries out hydroxylating, mercaptolation and sulfonated reaction to inorganic nano-particle successively, each by control
The species and proportioning of the Parameter Conditions of individual reactions steps, such as reactant, surface grafting sulfonic group is made in reaction temperature and time etc.
The inorganic nano-particle of group, then makes itself and amino-terminated polyether reactant, so that final production goes out via sulfonic acid-amino ion
The nanoparticulate fillers of key link, and cause these fillers are doped in polymeric matrix can improve the ionic conductance of electrolyte
Interface stability between rate and electrolyte and electrode.Because the same sex electric charge that nanoparticle surface is coated causes it mutually to arrange
Reprimand, this Nano filling can be dispersed in electrolyte system, so as to effectively suppress polymer crystallization, reaches lifting solid-state electricity
Solve the purpose of matter ionic conductivity.In addition, the preparation method mainly uses Industrial raw material, production cost can be reduced；Meanwhile,
Preparation method and post-processing step are simple and easy to apply, and these advantages make large-scale industrial production be possibly realized.
The structure of the inorganic nano particle filler of ionic bond modification of the present invention can be modified by changing sulfonic acid group
Inorganic nano-particle, amino-terminated polyethers, and sulfonic acid group modification inorganic nano-particle and amino-terminated polyethers
Between ratio controlled, specifically can by change the ratio between core component, shell component and core-shell structure copolymer component come
Regulation and control.During core component can be Nano particles of silicon dioxide, titanium dioxide nano-particle or alundum (Al2O3) nano-particle
One kind, and particle diameter is between 10~200nm.Smaller nano-particle has the surface energy of bigger specific surface area and Geng Gao,
It is doped in the interface stability between the ionic conductivity and electrolyte and electrode that can improve electrolyte in polymeric matrix.
Shell component can be amino-terminated polyethers Industrial raw materialM-600(Mw=600),M-1000(Mw=1000) orM-2000(Mw=2000) in one kind.Have benefited from
The weaker link effect of ionic bond, motility of the polyether segment in system is stronger, plays a part of similar " plasticizer ", solid-state
Therefore the mechanical performance of electrolyte improves.Longer segment helps lend some impetus to the flexibility of solid electrolyte, and shorter segment
It is favorably improved the rigidity of solid electrolyte.Ratio between core-shell structure copolymer component decides that ionic bond modification inorganic nano-particle is filled out
The viscosity of material.When core component ratio is higher, the viscosity of the filler of production is higher；When shell component ratio is higher, production
Filler viscosity it is relatively low；The present invention is exactly based on the inorganic nano-particle and amino-terminated polyethers two for modifying sulfonic acid group
The mass ratio control of person is 10/1~1/10 so that the pasty state sulfonic acid ultimately generated-amino ionic bond modification inorganic nano-particle
Performance is stable, can the long term storage under the conditions of lucifuge is dried；And the polyether segment grafting of inorganic nano-particle surface grafting is close
Degree is moderate, it can be ensured that polyether segment free movement in solid state electrolysis plastidome, be particularly suitable for use in solid electrolyte.
To sum up, the solid electrolyte being related in the present invention modifies inorganic nano particle filler and its preparation side with ionic bond
Method, is connect by carrying out the obtained surface of hydroxylating, mercaptolation and sulfonated reaction successively to inorganic nano-particle
The inorganic nano-particle of branch sulfonic acid group, then makes itself and amino-terminated polyether reactant, produces via sulfonic acid-amino ion
The nanoparticulate fillers of key link.Because the same sex electric charge that nanoparticle surface is coated causes its mutually exclusive, this Nano filling
Can be dispersed in electrolyte system, so as to effectively suppress polymer crystallization, reach lifting solid electrolyte ionic conductance
The purpose of rate.In addition, the polyether segment of filler surface grafting has preferable motility, the mechanicalness of electrolyte can be improved
Energy.Meanwhile, preparation process of the present invention is realized using Industrial raw material, and production and last handling process are simple and easy to apply,
The need for meeting industrialized production.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of preparation method of the present invention；
Fig. 2 is that the ionic bond prepared in embodiment 1,2 and 3 modifies the pictorial diagram of inorganic nano particle filler；
Fig. 3 is the amino-terminated polyethers raw material of industrializationChemical structural formula.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
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 each embodiment of invention described below
Not constituting conflict each other can just be mutually combined.
Heretofore described composite solid electrolyte modifies inorganic nano particle filler and preparation method thereof with ionic bond,
It is that surface grafting sulphur is made by carrying out hydroxylating, mercaptolation and sulfonated reaction successively to inorganic nano-particle
The inorganic nano-particle of acid groups, then makes itself and amino-terminated polyether reactant, produces and is repaiied via sulfonic acid-amino ionic bond
This solid electrolyte of nanoparticulate fillers of decorations modifies inorganic nano particle filler with ionic bond.As shown in figure 1, the present invention
Preparation method is to obtain the inorganic nano-particle of inorganic nano-particle, surface rich in sulfydryl, the surface of surface grafting hydroxyl successively
Inorganic nano-particle and final sulfonic acid-amino ionic bond modification inorganic nano-particle rich in sulfonic acid group, finally give
Pasty state sulfonic acid-amino ionic bond modification inorganic nano-particle be solid electrolyte inorganic nano particle filler.
Preparation method specifically may include following steps：
(1) inorganic nano-particle is placed in alkaline aqueous solution (e.g., sodium hydrate aqueous solution) at 60~90 DEG C of activation
The ratio of 2~24h of reason, inorganic nano-particle and alkaline aqueous solution is 1g/100mL~1g/2mL, is subsequently cooled to room temperature, spends
Ionized water cyclic washing, obtains the inorganic nano-particle of surface grafting hydroxyl after drying；The pH value of the alkaline aqueous solution can be 9
~12；
(2) inorganic nano-particle of the surface obtained by step (1) rich in hydroxyl is scattered in deionized water, both ratios
Example is 1g/10mL~1g/2mL, after 10~40min of room temperature ultrasonic disperse, is added thereto dissolved with mercaptopropyl trimethoxysilane
The mass ratio of the organic solution of (that is, mercaptopropyl trimethoxysilane coupling agent), inorganic nano-particle and silane coupler is 10/
1~1/10, by 60~90 DEG C of 12~36h of stirring reaction of mixed solution, it is cooled to after room temperature and is filtered by vacuum, and washed repeatedly with ethanol
Wash 3~5 times, gained solid matter is dried in vacuo 12~48h at 50~80 DEG C, obtains the inorganic nano-particle of surface grafting sulfydryl
Son；
(3) hydrogen peroxide that inorganic nano-particle of the surface obtained by step (2) rich in sulfydryl is scattered in 30wt.% is gone
In deionized water solution, both ratios are 1g/50mL~1g/2mL, 10 DEG C~30 DEG C (e.g., room temperature) 10~40min of ultrasonic disperse
Afterwards, mixed solution is continued into 10 DEG C~30 DEG C (e.g., room temperature) 12~36h of stirring reaction, be then filtered by vacuum, and use deionized water
Cyclic washing 3~5 times, gained solid matter is dried in vacuo 12~48h at 50~80 DEG C, obtains the nothing of surface grafting sulfonic acid group
Machine nano-particle；
(4) inorganic nano-particle of the surface obtained by step (3) rich in sulfonic acid group is scattered in deionized water, both
Ratio be 1g/10mL~1g/2mL, after 10~40min of room temperature ultrasonic disperse, add thereto amino-terminated polyethers go from
The sub- aqueous solution, the mass ratio of inorganic nano-particle and amino-terminated polyethers is 10/1~1/10, and by mixed solution, 60~90 DEG C are stirred
Reaction is mixed, reaction end is determined by the pH value for monitoring reaction solution, is terminating reaction when pH value keeps stable, then, decompression
Distillation removes the deionized water in reaction solution, and products therefrom is dried in vacuo into 12~48h at 50~80 DEG C, the sulphur of pasty state is obtained
Acid-amino ionic bond modification inorganic nano-particle, sulfonic acid-amino ionic bond modification inorganic nano-particle of these pasty states is solid-state
Electrolyte inorganic nano particle filler.
Inorganic nano-particle described in the above method, i.e. ionic bond modification inorganic nano particle filler, its core,
It can be one kind in Nano particles of silicon dioxide, titanium dioxide nano-particle or alundum (Al2O3) nano-particle；Inorganic nano
Particle diameter is between 10~200nm.
The concentration of sodium hydrate aqueous solution used in activation inorganic nano-particle described in step (1) for 0.1~
5mol/L。
The organic solvent of dissolving mercaptopropyl trimethoxysilane described in step (2) can be acetone, methanol, ethanol,
One kind in ethyl acetate or chloroform.
Amino-terminated polyethers described in step (4) can be Industrial raw materialM-600(Mw=
600),M-1000(Mw=1000) orM-2000(Mw=2000) in one kind.
The inorganic nano particle filler of ionic bond modification of the present invention, searches to the bottom, is modified by sulfonic acid group
Inorganic nano-particle prepare with the sulfonic acid between amino-terminated polyethers-amino acid-base neutralization reaction, wherein, nano-particle
The sulfonic acid group on surface is that the sulfydryl for being grafted to nanoparticle surface in advance using hydrogen peroxide oxidation is obtained.Sealed using sulfydryl
The nano-particle that the silane coupler at end acts on production surface modification sulfydryl in aqueous phase system by hydrolysis-condensation is heterogeneous
Reaction, so churned mechanically dynamics can be increased in process of production to promote Nano particles of silicon dioxide raw material in reaction system
In it is scattered.In addition, adding the mistake of the silane coupler of sulfydryl end-blocking to the deionized water dispersion liquid of Nano particles of silicon dioxide
Journey will be carried out slowly, so just be can ensure that the reaction between silane coupler and Nano particles of silicon dioxide is gently orderly and entered
OK, the Nano particles of silicon dioxide of the uniform sulfydryl modification of grafting degree may finally be obtained.Turned using hydrogen peroxide oxidation sulfydryl
The process for turning to sulfonic acid group is an exothermic process, therefore this step reaction is carried out at room temperature, and needs monitoring reaction in real time
The change of system temperature, needs with frozen water to be cooled immediately if temperature is suddenly raised.The nano-particle and ammonia of grafting sulfonic groups group
It is an acid-base neutralization reaction in reacting quintessence between the polyethers of base end-blocking, it is necessary to every the pH value of set time test system
Change conditions judge reaction end, and when pH value keeps stable, explanation acid-base neutralization reaction is complete.
It is specific embodiment below：
Embodiment 1：
Ionic bond modifies inorganic nano particle filler, is specifically same point of the Nano particles of silicon dioxide modified by sulfonic acid group
Son amount 600 amino-terminated polyethers (M-600) obtained through sulfonic acid-amino ionic bond link, the two
Mass ratio is 10/1.
Specifically preparation method is：
1g average grain diameters 10nm silicon dioxide granule is dispersed in the sodium hydroxide that 100mL concentration is 0.1mol/L water-soluble
In liquid, ultrasonic vibration 30min, then 60 DEG C of heating reflux reaction 2h, deionization washing is multiple after suction filtration, is dried to obtain surface work
Change the Nano particles of silicon dioxide for having great amount of hydroxy group.The 50g Nano particles of silicon dioxide for being modified with hydroxyl is scattered in 100mL
In ionized water, acetone solns of the 5mL dissolved with 5g mercaptopropyl trimethoxysilanes, drop is then added dropwise in sonic oscillation 10min thereto
Add after finishing, acetone washing is multiple after mixed liquor is heated to reflux 12h, suction filtration at 60 DEG C, is dried to obtain the two of surface grafting sulfydryl
Silicon oxide nanoparticle.The Nano particles of silicon dioxide of 1g surface grafting sulfydryls is scattered in 50mL 30wt.% hydrogen peroxide
In deionized water solution, ultrasonic vibration 10min promotes the scattered of nano-particle, then stirring reaction 12h at room temperature, is gone after suction filtration
Ion water washing repeatedly, is dried to obtain the Nano particles of silicon dioxide of surface grafting sulfonic acid group.50g is modified with sulfonic acid group
Nano particles of silicon dioxide be scattered in 100mL deionized waters, sonic oscillation 10min, then thereto be added dropwise 5mL dissolved with 5gAfter M-600 deionized water solution, completion of dropping, mixed liquor passes through prison in 60 DEG C of heating reflux reactions
The pH value of control reaction solution determines reaction end, is terminating reaction when pH value keeps stable, and vacuum distillation is removed in reaction solution
Sulfonic acid-amino ionic bond modification inorganic nano particle filler is obtained after deionized water, vacuum drying.
Sulfonic acid made from the present embodiment-amino ionic bond modification inorganic nano particle filler is pasty mass, passes through heat mistake
The constituent content that weight analysis (TGA) measure Nano particles of silicon dioxide surface grafting accounts for the 13wt.% (inorganic nanos of packing quality
The component of particle surface grafting is in addition to amino-terminated polyethers, in addition to end group is oxidized to the silane coupler of sulfonic acid group), this
Solid electrolyte inorganic nano particle filler can the long term storage in the case where drying light protected environment.
Embodiment 2：
Ionic bond modifies inorganic nano particle filler, is specifically same point of the Nano particles of silicon dioxide modified by sulfonic acid group
Son amount 1000 amino-terminated polyethers (M-1000) obtained through sulfonic acid-amino ionic bond link, the two
Mass ratio be 5/1.
Specifically preparation method is：
20g average grain diameters 100nm silicon dioxide granule is dispersed in the sodium hydroxide that 100mL concentration is 2mol/L water-soluble
In liquid, ultrasonic vibration 30min, then 80 DEG C of heating reflux reaction 12h, deionization washing is multiple after suction filtration, is dried to obtain surface
Activation has the Nano particles of silicon dioxide of great amount of hydroxy group.The 20g Nano particles of silicon dioxide for being modified with hydroxyl is scattered in 100mL
In deionized water, methanol solutions of the 4mL dissolved with 4g mercaptopropyl trimethoxysilanes is then added dropwise in sonic oscillation 20min thereto,
After completion of dropping, methanol washing is multiple after mixed liquor is heated to reflux 24h, suction filtration at 80 DEG C, is dried to obtain surface grafting sulfydryl
Nano particles of silicon dioxide.The Nano particles of silicon dioxide of 10g surface grafting sulfydryls is scattered in 50mL 30wt.% peroxide
Change in hydrogen deionized water solution, ultrasonic vibration 20min promotes the scattered of nano-particle, then stirring reaction 24h, suction filtration at room temperature
Deionized water washing is multiple afterwards, is dried to obtain the Nano particles of silicon dioxide of surface grafting sulfonic acid group.20g is modified with sulfonic acid
The Nano particles of silicon dioxide of group is scattered in 100mL deionized waters, sonic oscillation 20min, 4mL is then added dropwise thereto molten
There is 4gAfter M-1000 deionized water solution, completion of dropping, mixed liquor in 80 DEG C of heating reflux reactions,
Reaction end is determined by the pH value for monitoring reaction solution, is terminating reaction when pH value keeps stable, vacuum distillation removes reaction
Sulfonic acid-amino ionic bond modification inorganic nano particle filler is obtained after deionized water in liquid, vacuum drying.
Sulfonic acid made from the present embodiment-amino ionic bond modification inorganic nano particle filler is pasty mass, silica
The constituent content of nanoparticle surface grafting accounts for the 21wt.% of packing quality, this solid electrolyte inorganic nano particle filler
Can the long term storage in the case where drying light protected environment.
Embodiment 3：
Ionic bond modifies inorganic nano particle filler, is specifically same point of the Nano particles of silicon dioxide modified by sulfonic acid group
Son amount 2000 amino-terminated polyethers (M-2000) obtained through sulfonic acid-amino ionic bond link, the two
Mass ratio be 1/10.
Specifically preparation method is：
50g average grain diameters 200nm silicon dioxide granule is dispersed in the sodium hydroxide that 100mL concentration is 5mol/L water-soluble
In liquid, ultrasonic vibration 30min, then 90 DEG C of heating reflux reaction 24h, deionization washing is multiple after suction filtration, is dried to obtain surface
Activation has the Nano particles of silicon dioxide of great amount of hydroxy group.The 10g Nano particles of silicon dioxide for being modified with hydroxyl is scattered in 100mL
In deionized water, ethanol of the 100mL dissolved with 100g mercaptopropyl trimethoxysilanes is then added dropwise in sonic oscillation 40min thereto
After solution, completion of dropping, ethanol washing is multiple after mixed liquor is heated to reflux 36h, suction filtration at 90 DEG C, is dried to obtain surface grafting mercapto
The Nano particles of silicon dioxide of base.The Nano particles of silicon dioxide of 25g surface grafting sulfydryls is scattered in 50mL 30wt.%'s
In hydrogen peroxide deionized water solution, ultrasonic vibration 40min promotes the scattered of nano-particle, then stirring reaction 36h at room temperature,
Deionized water washing is multiple after suction filtration, is dried to obtain the Nano particles of silicon dioxide of surface grafting sulfonic acid group.10g is modified with
The Nano particles of silicon dioxide of sulfonic acid group is scattered in 100mL deionized waters, sonic oscillation 40min, is then added dropwise thereto
100mL is dissolved with 100gAfter M-2000 deionized water solution, completion of dropping, mixed liquor is heated back at 90 DEG C
Stream reaction, reaction end is determined by the pH value for monitoring reaction solution, is terminating reaction when pH value keeps stable, vacuum distillation is gone
Except the deionized water in reaction solution, sulfonic acid-amino ionic bond modification inorganic nano particle filler is obtained after vacuum drying.
Sulfonic acid made from the present embodiment-amino ionic bond modification inorganic nano particle filler is pasty mass, silica
The constituent content of nanoparticle surface grafting accounts for the 91wt.% of packing quality, this solid electrolyte inorganic nano particle filler
Can the long term storage in the case where drying light protected environment.
Embodiment 4：
Ionic bond modifies inorganic nano particle filler, is specifically same point of the titanium dioxide nano-particle modified by sulfonic acid group
Son amount 600 amino-terminated polyethers (M-600) obtained through sulfonic acid-amino ionic bond link, the two
Mass ratio is 10/1.
Specifically preparation method is：
1g average grain diameters 10nm TiO 2 particles are dispersed in the sodium hydroxide that 100mL concentration is 0.1mol/L water-soluble
In liquid, ultrasonic vibration 30min, then 60 DEG C of heating reflux reaction 2h, deionization washing is multiple after suction filtration, is dried to obtain surface work
Change the titanium dioxide nano-particle for having great amount of hydroxy group.The 50g titanium dioxide nano-particles for being modified with hydroxyl are scattered in 100mL
In ionized water, it is molten dissolved with the ethyl acetate of 50g mercaptopropyl trimethoxysilanes that 5mL is then added dropwise in sonic oscillation 10min thereto
After liquid, completion of dropping, ethyl acetate washing is multiple after mixed liquor is heated to reflux 12h, suction filtration at 60 DEG C, is dried to obtain surface grafting
The titanium dioxide nano-particle of sulfydryl.The titanium dioxide nano-particle of 1g surface grafting sulfydryls is scattered in 50mL 30wt.%'s
In hydrogen peroxide deionized water solution, ultrasonic vibration 10min promotes the scattered of nano-particle, then stirring reaction 12h at room temperature,
Deionized water washing is multiple after suction filtration, is dried to obtain the titanium dioxide nano-particle of surface grafting sulfonic acid group.50g is modified with
The titanium dioxide nano-particle of sulfonic acid group is scattered in 100mL deionized waters, sonic oscillation 10min, is then added dropwise thereto
5mL is dissolved with 5gAfter M-600 deionized water solution, completion of dropping, mixed liquor is heated to reflux instead at 60 DEG C
Should, reaction end is determined by the pH value for monitoring reaction solution, is terminating reaction when pH value keeps stable, vacuum distillation removes anti-
Answer and sulfonic acid-amino ionic bond modification inorganic nano particle filler is obtained after the deionized water in liquid, vacuum drying.
Sulfonic acid made from the present embodiment-amino ionic bond modification inorganic nano particle filler is pasty mass, titanium dioxide
The constituent content of nanoparticle surface grafting accounts for the 12wt.% of packing quality, this solid electrolyte inorganic nano particle filler
Can the long term storage in the case where drying light protected environment.
Embodiment 5：
Ionic bond modifies inorganic nano particle filler, is specifically same point of the titanium dioxide nano-particle modified by sulfonic acid group
Son amount 1000 amino-terminated polyethers (M-1000) obtained through sulfonic acid-amino ionic bond link, the two
Mass ratio be 5/1.
Specifically preparation method is：
20g average grain diameters 100nm TiO 2 particles are dispersed in the sodium hydroxide that 100mL concentration is 2mol/L water-soluble
In liquid, ultrasonic vibration 30min, then 80 DEG C of heating reflux reaction 12h, deionization washing is multiple after suction filtration, is dried to obtain surface
Activation has the titanium dioxide nano-particle of great amount of hydroxy group.The 20g titanium dioxide nano-particles for being modified with hydroxyl are scattered in 100mL
In deionized water, chloroformic solutions of the 4mL dissolved with 8g mercaptopropyl trimethoxysilanes is then added dropwise in sonic oscillation 20min thereto,
After completion of dropping, chloroform repeatedly, is dried to obtain surface grafting sulfydryl after mixed liquor is heated to reflux 24h, suction filtration at 80 DEG C
Titanium dioxide nano-particle.The titanium dioxide nano-particle of 10g surface grafting sulfydryls is scattered in 50mL 30wt.% peroxide
Change in hydrogen deionized water solution, ultrasonic vibration 20min promotes the scattered of nano-particle, then stirring reaction 24h, suction filtration at room temperature
Deionized water washing is multiple afterwards, is dried to obtain the titanium dioxide nano-particle of surface grafting sulfonic acid group.20g is modified with sulfonic acid
The titanium dioxide nano-particle of group is scattered in 100mL deionized waters, sonic oscillation 20min, 4mL is then added dropwise thereto molten
There is 4gAfter M-1000 deionized water solution, completion of dropping, mixed liquor in 80 DEG C of heating reflux reactions,
Reaction end is determined by the pH value for monitoring reaction solution, is terminating reaction when pH value keeps stable, vacuum distillation removes reaction
Sulfonic acid-amino ionic bond modification inorganic nano particle filler is obtained after deionized water in liquid, vacuum drying.
Sulfonic acid made from the present embodiment-amino ionic bond modification inorganic nano particle filler is pasty mass, titanium dioxide
The constituent content of nanoparticle surface grafting accounts for the 19wt.% of packing quality, this solid electrolyte inorganic nano particle filler
Can the long term storage in the case where drying light protected environment.
Embodiment 6：
Ionic bond modifies inorganic nano particle filler, is specifically same point of the titanium dioxide nano-particle modified by sulfonic acid group
The amino-terminated polyethers of son amount 2000M-2000) obtained through sulfonic acid-amino ionic bond link, the two
Mass ratio be 1/10.
Specifically preparation method is：
50g average grain diameters 200nm TiO 2 particles are dispersed in the sodium hydroxide that 100mL concentration is 5mol/L water-soluble
In liquid, ultrasonic vibration 30min, then 90 DEG C of heating reflux reaction 24h, deionization washing is multiple after suction filtration, is dried to obtain surface
Activation has the titanium dioxide nano-particle of great amount of hydroxy group.The 10g titanium dioxide nano-particles for being modified with hydroxyl are scattered in 100mL
In deionized water, acetone of the 100mL dissolved with 100g mercaptopropyl trimethoxysilanes is then added dropwise in sonic oscillation 40min thereto
After solution, completion of dropping, acetone washing is multiple after mixed liquor is heated to reflux 36h, suction filtration at 90 DEG C, is dried to obtain surface grafting mercapto
The titanium dioxide nano-particle of base.The titanium dioxide nano-particle of 25g surface grafting sulfydryls is scattered in 50mL 30wt.%'s
In hydrogen peroxide deionized water solution, ultrasonic vibration 40min promotes the scattered of nano-particle, then stirring reaction 36h at room temperature,
Deionized water washing is multiple after suction filtration, is dried to obtain the titanium dioxide nano-particle of surface grafting sulfonic acid group.10g is modified with
The titanium dioxide nano-particle of sulfonic acid group is scattered in 100mL deionized waters, sonic oscillation 40min, is then added dropwise thereto
100mL is dissolved with 100gAfter M-2000 deionized water solution, completion of dropping, mixed liquor is heated back at 90 DEG C
Stream reaction, reaction end is determined by the pH value for monitoring reaction solution, is terminating reaction when pH value keeps stable, vacuum distillation is gone
Except the deionized water in reaction solution, sulfonic acid-amino ionic bond modification inorganic nano particle filler is obtained after vacuum drying.
Sulfonic acid made from the present embodiment-amino ionic bond modification inorganic nano particle filler is pasty mass, titanium dioxide
The constituent content of nanoparticle surface grafting accounts for the 90wt.% of packing quality, this solid electrolyte inorganic nano particle filler
Can the long term storage in the case where drying light protected environment.
Embodiment 7：
Ionic bond modifies inorganic nano particle filler, is specifically that the alundum (Al2O3) nano-particle modified by sulfonic acid group is same
Molecular weight 600 amino-terminated polyethers (M-600) obtained through sulfonic acid-amino ionic bond link, the two
Mass ratio be 5/1.
Specifically preparation method is：
1g average grain diameters 10nm alundum (Al2O3) particle is dispersed in the sodium hydroxide water that 100mL concentration is 0.1mol/L
In solution, ultrasonic vibration 30min, then 60 DEG C of heating reflux reaction 2h, deionization washing is multiple after suction filtration, is dried to obtain surface
Activation has the alundum (Al2O3) nano-particle of great amount of hydroxy group.The 50g alundum (Al2O3) nano-particles for being modified with hydroxyl are scattered in
In 100mL deionized waters, chloroforms of the 5mL dissolved with 5g mercaptopropyl trimethoxysilanes is then added dropwise in sonic oscillation 10min thereto
After solution, completion of dropping, chloroform repeatedly, is dried to obtain surface grafting mercapto after mixed liquor is heated to reflux 12h, suction filtration at 60 DEG C
The alundum (Al2O3) nano-particle of base.The alundum (Al2O3) nano-particle of 1g surface grafting sulfydryls is scattered in 50mL 30wt.%
Hydrogen peroxide deionized water solution in, ultrasonic vibration 10min promotes the scattered of nano-particle, then stirring reaction at room temperature
Deionized water washing is multiple after 12h, suction filtration, is dried to obtain the alundum (Al2O3) nano-particle of surface grafting sulfonic acid group.By 50g
The alundum (Al2O3) nano-particle for being modified with sulfonic acid group is scattered in 100mL deionized waters, sonic oscillation 10min, and backward
5mL is wherein added dropwise dissolved with 10gAfter M-600 deionized water solution, completion of dropping, mixed liquor is at 60 DEG C
Heating reflux reaction, reaction end is determined by the pH value for monitoring reaction solution, is terminating reaction when pH value keeps stable, decompression
Distillation removes the deionized water in reaction solution, and sulfonic acid-amino ionic bond modification inorganic nano particle filler is obtained after vacuum drying.
Sulfonic acid made from the present embodiment-amino ionic bond modification inorganic nano particle filler is pasty mass, three oxidations two
The constituent content of aluminum nanoparticles surface grafting accounts for the 20wt.% of packing quality, and this solid electrolyte is filled out with inorganic nano-particle
Material can the long term storage in the case where drying light protected environment.
Embodiment 8：
Ionic bond modifies inorganic nano particle filler, is specifically that the alundum (Al2O3) nano-particle modified by sulfonic acid group is same
The amino-terminated polyethers of molecular weight 1000M-1000) obtained through sulfonic acid-amino ionic bond link, the two
Mass ratio be 1/2.
Specifically preparation method is：
20g average grain diameters 100nm alundum (Al2O3) particle is dispersed in the sodium hydroxide water that 100mL concentration is 2mol/L
In solution, ultrasonic vibration 30min, then 80 DEG C of heating reflux reaction 12h, deionization washing is multiple after suction filtration, is dried to obtain table
Face activates the alundum (Al2O3) nano-particle for having great amount of hydroxy group.The 20g alundum (Al2O3) nano-particles for being modified with hydroxyl are disperseed
In 100mL deionized waters, second of the 4mL dissolved with 4g mercaptopropyl trimethoxysilanes is then added dropwise in sonic oscillation 20min thereto
After alcoholic solution, completion of dropping, ethanol washing is multiple after mixed liquor is heated to reflux 24h, suction filtration at 80 DEG C, is dried to obtain surface grafting
The alundum (Al2O3) nano-particle of sulfydryl.The alundum (Al2O3) nano-particle of 10g surface grafting sulfydryls is scattered in 50mL
In 30wt.% hydrogen peroxide deionized water solution, ultrasonic vibration 20min promotes the scattered of nano-particle, then stirs at room temperature
Mix deionized water washing after reaction 24h, suction filtration and repeatedly, be dried to obtain the alundum (Al2O3) nanoparticle of surface grafting sulfonic acid group
Son.The 20g alundum (Al2O3) nano-particles for being modified with sulfonic acid group are scattered in 100mL deionized waters, sonic oscillation
20min, is then added dropwise 4mL dissolved with 40g theretoAfter M-1000 deionized water solution, completion of dropping,
Mixed liquor determines reaction end in 80 DEG C of heating reflux reactions by the pH value for monitoring reaction solution, when pH value keeps stable
Terminating reaction, vacuum distillation removes the deionized water in reaction solution, sulfonic acid-amino ionic bond modification is obtained after vacuum drying inorganic
Nanoparticulate fillers.
Sulfonic acid made from the present embodiment-amino ionic bond modification inorganic nano particle filler is pasty mass, three oxidations two
The constituent content of aluminum nanoparticles surface grafting accounts for the 71wt.% of packing quality, and this solid electrolyte is filled out with inorganic nano-particle
Material can the long term storage in the case where drying light protected environment.
Embodiment 9：
Ionic bond modifies inorganic nano particle filler, is specifically that the alundum (Al2O3) nano-particle modified by sulfonic acid group is same
The amino-terminated polyethers of molecular weight 2000M-2000) obtained through sulfonic acid-amino ionic bond link, the two
Mass ratio be 1/10.
Specifically preparation method is：
50g average grain diameters 200nm alundum (Al2O3) particle is dispersed in the sodium hydroxide water that 100mL concentration is 5mol/L
In solution, ultrasonic vibration 30min, then 90 DEG C of heating reflux reaction 24h, deionization washing is multiple after suction filtration, is dried to obtain table
Face activates the alundum (Al2O3) nano-particle for having great amount of hydroxy group.The 10g alundum (Al2O3) nano-particles for being modified with hydroxyl are disperseed
In 100mL deionized waters, 100mL is then added dropwise dissolved with 100g mercaptopropyl trimethoxysilanes in sonic oscillation 40min thereto
Methanol solution, after completion of dropping, methanol washing is multiple after mixed liquor is heated to reflux 36h, suction filtration at 90 DEG C, is dried to obtain surface
It is grafted the alundum (Al2O3) nano-particle of sulfydryl.The alundum (Al2O3) nano-particle of 25g surface grafting sulfydryls is scattered in 50mL
In 30wt.% hydrogen peroxide deionized water solution, ultrasonic vibration 40min promotes the scattered of nano-particle, then stirs at room temperature
Mix deionized water washing after reaction 36h, suction filtration and repeatedly, be dried to obtain the alundum (Al2O3) nanoparticle of surface grafting sulfonic acid group
Son.The 10g alundum (Al2O3) nano-particles for being modified with sulfonic acid group are scattered in 100mL deionized waters, sonic oscillation
40min, is then added dropwise 100mL dissolved with 100g theretoM-2000 deionized water solution, completion of dropping
Afterwards, mixed liquor determines reaction end in 90 DEG C of heating reflux reactions by the pH value for monitoring reaction solution, when pH value keeps stable
That is terminating reaction, vacuum distillation removes the deionized water in reaction solution, and sulfonic acid-amino ionic bond modification nothing is obtained after vacuum drying
Machine nanoparticulate fillers.
Sulfonic acid made from the present embodiment-amino ionic bond modification inorganic nano particle filler is pasty mass, three oxidations two
The constituent content of aluminum nanoparticles surface grafting accounts for the 90wt.% of packing quality, and this solid electrolyte is filled out with inorganic nano-particle
Material can the long term storage in the case where drying light protected environment.
What the structure of the solid electrolyte inorganic nano particle filler in the present invention can be modified by changing sulfonic acid group
Between inorganic nano-particle, amino-terminated polyethers, and the inorganic nano-particle and amino-terminated polyethers of sulfonic acid group modification
Ratio controlled.In addition, the inorganic nano-particle modified except sulfonic acid group, in addition to amino-terminated polyethers, in the filler
It may also contain other impurities；Certainly as needed, other materials of known function are also may also include in the filler.
Ultrasonic disperse in the present invention can be carried out under room temperature (such as 10 DEG C~30 DEG C).
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, it is not used to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the invention etc., it all should include
Within protection scope of the present invention.
Claims (10)
1. a kind of solid electrolyte inorganic nano particle filler, it is characterised in that the solid electrolyte inorganic nano-particle
Filler mainly the inorganic nano-particle modified by sulfonic acid group and amino-terminated polyethers link via sulfonic acid-amino ionic bond and
Into；The mass ratio of both the inorganic nano-particle and the amino-terminated polyethers of the sulfonic acid group modification is 10/1~1/
10。
2. solid electrolyte inorganic nano particle filler as claimed in claim 1, it is characterised in that the inorganic nano-particle
It is at least one of Nano particles of silicon dioxide, titanium dioxide nano-particle and alundum (Al2O3) nano-particle；The nothing
The particle diameter of machine nano-particle is 10~200nm.
3. solid electrolyte inorganic nano particle filler as claimed in claim 1, it is characterised in that described amino-terminated gathers
It is 600,1000, at least one of 2000 that ether, which is selected from average weight-molecular mass,.
4. a kind of preparation method of solid electrolyte inorganic nano particle filler, it is characterised in that comprise the following steps：
(1) inorganic nano-particle is placed in activation process in alkaline aqueous solution, is washed out, dries, obtaining surface has hydroxyl
Inorganic nano-particle；The ratio of the inorganic nano-particle and the alkaline aqueous solution is 1g/100mL~1g/2mL；It is described
The pH value of alkaline aqueous solution is 9~12；
(2) inorganic nano-particle that the surface for obtaining the step (1) has hydroxyl is distributed in deionized water, then
Add the organic solution dissolved with mercaptopropyl trimethoxysilane thereto, then successively carry out heating response, cooling, washing, with
And dry, obtain the inorganic nano-particle of surface grafting sulfydryl；The inorganic nano-particle that the surface has hydroxyl is gone with described
The ratio of ionized water is 1g/10mL~1g/2mL；The surface have the inorganic nano-particle of hydroxyl with it is described dissolved with mercapto propyl group
The mass ratio of both mercaptopropyl trimethoxysilanes is 10/1~1/10 in the organic solution of trimethoxy silane；
(3) inorganic nano-particle for the surface grafting sulfydryl for obtaining the step (2) is scattered in 30wt.% peroxidating
In hydrogen deionized water solution, reaction, washing are then stirred successively and is dried, the nothing of surface grafting sulfonic acid group is obtained
Machine nano-particle；The inorganic nano-particle of the surface grafting sulfydryl and the hydrogen peroxide deionized water solution of the 30wt.%
Ratio be 1g/50mL~1g/2mL；
(4) inorganic nano-particle of the surface grafting sulfonic acid group obtained by step (3) is scattered in deionized water, added thereto
Enter the deionized water solution of amino-terminated polyethers, carry out heating response, then cool down, wash, dry, obtain sulfonic acid-amino from
Sub-key modifies inorganic nano-particle, and the sulfonic acid-amino ionic bond modification inorganic nano-particle is solid electrolyte inorganic nano
Particle filler；The inorganic nano-particle of the surface grafting sulfonic acid group and the ratio of deionized water are 1g/10mL~1g/2mL；
The inorganic nano-particle of the surface grafting sulfonic acid group with it is amino-terminated in the deionized water solution of the amino-terminated polyethers
The mass ratio of both polyethers is 10/1~1/10.
5. the preparation method of solid electrolyte inorganic nano particle filler as claimed in claim 4, it is characterised in that the step
Suddenly in (1), the alkaline aqueous solution is sodium hydrate aqueous solution, and the concentration of the sodium hydrate aqueous solution is 0.1~5mol/L；Institute
It is 2~24h of reaction at a temperature of 60~90 DEG C to state activation process；
It is preferred that, it is first cooling treatment after the activation process, the washing is then carried out again.
6. the preparation method of solid electrolyte inorganic nano particle filler as claimed in claim 4, it is characterised in that the step
Suddenly in (2), there is the inorganic nano-particle of hydroxyl to be distributed in the deionized water on the surface, be using ultrasonic disperse 10~
40min；The organic solvent that the organic solution dissolved with mercaptopropyl trimethoxysilane is used is acetone, methanol, ethanol, second
One kind in acetoacetic ester or chloroform；Its concentration of the organic solution dissolved with mercaptopropyl trimethoxysilane is 1~10g/mL；Institute
It is the inorganic nano-particle and the mercapto propyl group three for the surface is had hydroxyl at a temperature of 60~90 DEG C to state heating response
Methoxy silane reacts 12~36h.
7. the preparation method of solid electrolyte inorganic nano particle filler as claimed in claim 4, it is characterised in that the step
Suddenly in (3), the inorganic nano-particle of the surface grafting sulfydryl is scattered in the hydrogen peroxide deionized water solution of the 30wt.%
In, it is to use 10~40min of ultrasonic disperse；The stirring reaction is 12~36h of stirring reaction at a temperature of 10 DEG C~30 DEG C.
8. the preparation method of solid electrolyte inorganic nano particle filler as claimed in claim 4, it is characterised in that the step
Suddenly in (4), the inorganic nano-particle of the surface grafting sulfonic acid group is distributed in the deionized water, is to use ultrasonic disperse
10~40min；The concentration of the deionized water solution of the amino-terminated polyethers is 1~10g/mL；The heating response is 60
Make the inorganic nano-particle and the amino-terminated polyether reactant of the surface grafting sulfonic acid group at a temperature of~90 DEG C.
9. the preparation method of solid electrolyte inorganic nano particle filler as claimed in claim 4, it is characterised in that the step
Suddenly in (4), the heating response is the terminal that the heating response is determined by monitoring the pH value of reaction solution, when pH value keeps steady
Timing terminates the heating response.
10. the preparation method of solid electrolyte inorganic nano particle filler as claimed in claim 4, it is characterised in that described
In step (4), the amino-terminated polyethers is that Industrial raw material average weight-molecular mass is 600M-
600, average weight-molecular mass is 1000M-1000, or average weight-molecular mass are 2000One kind in M-2000.
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| CN108281631A (en) * | 2018-01-19 | 2018-07-13 | 王群华 | A kind of preparation method of nano-particle cladding lithium cobaltate cathode material |
| CN108346784A (en) * | 2018-01-19 | 2018-07-31 | 王群华 | A kind of preparation method of the compound nickel manganese lithium composite positive pole of inorganic filler |
| CN108878960A (en) * | 2018-07-03 | 2018-11-23 | 宁德卓高新材料科技有限公司 | Solid electrolyte anode and solid state battery |
| CN108878751A (en) * | 2018-07-03 | 2018-11-23 | 宁德卓高新材料科技有限公司 | Conductivity ceramics composite diaphragm and solid state battery |
| CN108899579A (en) * | 2018-06-14 | 2018-11-27 | 北京工业大学 | A kind of all-solid lithium-ion battery of self-crosslinking composite solid electrolyte prepared and its constitute |
| CN111653824A (en) * | 2020-06-22 | 2020-09-11 | 武汉瑞科美新能源有限责任公司 | Gel polymer electrolyte, rapid preparation method thereof and battery |
| CN111969252A (en) * | 2020-08-31 | 2020-11-20 | 蜂巢能源科技有限公司 | Solid-state battery and method for manufacturing same |
| CN113054247A (en) * | 2019-12-27 | 2021-06-29 | 张家港市国泰华荣化工新材料有限公司 | Composite solid electrolyte, preparation method thereof and solid lithium-sulfur battery |
| CN113659198A (en) * | 2021-07-29 | 2021-11-16 | 青岛中科赛锂达新能源技术合伙企业(有限合伙) | All-solid-state electrolyte and application thereof in lithium-sodium battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045830A (en) * | 2007-04-16 | 2007-10-03 | 杜洪彦 | Functional group linken on surface of polymer electrolyte nano SiO2 and preparation method thereof |
| CN101885905A (en) * | 2009-05-12 | 2010-11-17 | 无锡纳奥新材料科技有限公司 | Polymer/ inorganic nano particle composite nano-particle and preparation method thereof |
| CN102044702A (en) * | 2010-12-14 | 2011-05-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Composite polymer electrolyte for lithium ion battery and preparation method thereof |
| CN103342870A (en) * | 2013-07-26 | 2013-10-09 | 武汉理工大学 | Modified SiO2/PVA (polyvinyl alcohol) film and preparation method thereof |
| CN103647107A (en) * | 2013-11-28 | 2014-03-19 | 中国东方电气集团有限公司 | All-solid-state electrolyte membrane of lithium ion battery and preparation method thereof |
| CN103985900A (en) * | 2014-04-24 | 2014-08-13 | 中山大学 | Modified polymer electrolyte, preparing method of modified polymer electrolyte and application of modified polymer electrolyte to lithium battery |
-
2017
- 2017-04-26 CN CN201710282317.2A patent/CN107134587B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045830A (en) * | 2007-04-16 | 2007-10-03 | 杜洪彦 | Functional group linken on surface of polymer electrolyte nano SiO2 and preparation method thereof |
| CN101885905A (en) * | 2009-05-12 | 2010-11-17 | 无锡纳奥新材料科技有限公司 | Polymer/ inorganic nano particle composite nano-particle and preparation method thereof |
| CN102044702A (en) * | 2010-12-14 | 2011-05-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Composite polymer electrolyte for lithium ion battery and preparation method thereof |
| CN103342870A (en) * | 2013-07-26 | 2013-10-09 | 武汉理工大学 | Modified SiO2/PVA (polyvinyl alcohol) film and preparation method thereof |
| CN103647107A (en) * | 2013-11-28 | 2014-03-19 | 中国东方电气集团有限公司 | All-solid-state electrolyte membrane of lithium ion battery and preparation method thereof |
| CN103985900A (en) * | 2014-04-24 | 2014-08-13 | 中山大学 | Modified polymer electrolyte, preparing method of modified polymer electrolyte and application of modified polymer electrolyte to lithium battery |
Non-Patent Citations (1)
| Title |
|---|
| YOUNGJUNE PARK,ET AL.: "Investigation of CO2 capture mechanisms of liquid-like nanoparticle organic hybrid materials via structural characterization", 《PHYS.CHEM.CHEM.PHYS.》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108281631A (en) * | 2018-01-19 | 2018-07-13 | 王群华 | A kind of preparation method of nano-particle cladding lithium cobaltate cathode material |
| CN108346784A (en) * | 2018-01-19 | 2018-07-31 | 王群华 | A kind of preparation method of the compound nickel manganese lithium composite positive pole of inorganic filler |
| CN108172810A (en) * | 2018-01-19 | 2018-06-15 | 王群华 | A kind of method of nanoparticle cladding nickel lithium manganate cathode material |
| CN108899579A (en) * | 2018-06-14 | 2018-11-27 | 北京工业大学 | A kind of all-solid lithium-ion battery of self-crosslinking composite solid electrolyte prepared and its constitute |
| CN108899579B (en) * | 2018-06-14 | 2021-03-05 | 北京工业大学 | Preparation of self-crosslinking composite solid electrolyte and all-solid-state lithium ion battery formed by same |
| CN108878960A (en) * | 2018-07-03 | 2018-11-23 | 宁德卓高新材料科技有限公司 | Solid electrolyte anode and solid state battery |
| CN108878960B (en) * | 2018-07-03 | 2020-06-09 | 宁德卓高新材料科技有限公司 | Solid electrolyte positive electrode and solid battery |
| CN108878751A (en) * | 2018-07-03 | 2018-11-23 | 宁德卓高新材料科技有限公司 | Conductivity ceramics composite diaphragm and solid state battery |
| CN113054247A (en) * | 2019-12-27 | 2021-06-29 | 张家港市国泰华荣化工新材料有限公司 | Composite solid electrolyte, preparation method thereof and solid lithium-sulfur battery |
| CN113054247B (en) * | 2019-12-27 | 2022-11-04 | 张家港市国泰华荣化工新材料有限公司 | Composite solid electrolyte, preparation method thereof and solid lithium-sulfur battery |
| CN111653824A (en) * | 2020-06-22 | 2020-09-11 | 武汉瑞科美新能源有限责任公司 | Gel polymer electrolyte, rapid preparation method thereof and battery |
| CN111969252A (en) * | 2020-08-31 | 2020-11-20 | 蜂巢能源科技有限公司 | Solid-state battery and method for manufacturing same |
| CN113659198A (en) * | 2021-07-29 | 2021-11-16 | 青岛中科赛锂达新能源技术合伙企业(有限合伙) | All-solid-state electrolyte and application thereof in lithium-sodium battery |
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