CN106549186B - The preparation method of attapulgite hydridization polymethyl methacrylate lithium battery gel electrolyte - Google Patents
The preparation method of attapulgite hydridization polymethyl methacrylate lithium battery gel electrolyte Download PDFInfo
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- CN106549186B CN106549186B CN201611109450.XA CN201611109450A CN106549186B CN 106549186 B CN106549186 B CN 106549186B CN 201611109450 A CN201611109450 A CN 201611109450A CN 106549186 B CN106549186 B CN 106549186B
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- attapulgite
- polymethyl methacrylate
- gel electrolyte
- hydridization
- lithium battery
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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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- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M2300/0085—Immobilising or gelification of electrolyte
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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
- H01M2300/0088—Composites
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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
Abstract
The invention discloses a kind of preparation methods of attapulgite hydridization polymethyl methacrylate lithium battery gel electrolyte, it is the following steps are included: disperse the attapulgite that mass fraction is 1 ~ 15 part in 100 parts of solvent, the cationic monomer that mass fraction is 5 ~ 40 parts is added, obtains cation-modified attapulgite；The methyl methacrylate that mass fraction is 4 ~ 40 parts is added in cation-modified attapulgite solution and the initiator that mass fraction is 0.002 ~ 0.2 part carries out polymerization reaction, obtains attapulgite hydridization polymethyl methacrylate；Attapulgite hydridization polymethyl methacrylate is formed a film, then impregnates 2 ~ 24 hours in the electrolytic solution to get attapulgite hydridization polymethyl methacrylate lithium battery gel electrolyte, conductivity > 1 × 10 of the gel electrolyte are arrived‑3S/cm.The interface stability of attapulgite hydridization polymethyl methacrylate lithium battery gel electrolyte and lithium electrode of the invention is good, and interface impedance is low, easily forms, and chemical property is stablized.
Description
Technical field
The present invention relates to a kind of preparation methods of attapulgite hydridization polymethyl methacrylate lithium battery gel electrolyte.
Background technique
Electrolyte decides specific energy, service life, the security performance, charge and discharge of battery as the critical material of lithium ion battery
A variety of macroscopical electrochemical properties such as performance and high temperature performance.Liquid electrolyte plastidome since conductivity is high, fast response time, and
It is widely used in field of batteries, but its large viscosity, inflammable, poor safety performance and is not easy to form a film, limits and further answer
With.The conductivity of full solid state polymer electrolyte is poor, apart from each other with application request.In order to overcome the problems, such as this,
It is added a certain amount of liquid plasticizer in solid electrolyte and electrolytic salt can form a kind of complex compound, similar gels, usually
Referred to as gel electrolyte.It compares with solid electrolyte, containing the liquid solvent of small-molecular-weight in gel electrolyte plastidome, has
Very high ionic conductivity.In gel-form solid polymer electrolyte, especially most with polymethyl methacrylate (PMMA) gel electrolyte
For protrusion because the maximum feature of PMMA system gel electrolyte be it is good with the interface stability of lithium electrode, interface impedance is low.By
There is a carbonyl side group in MMA unit, has very strong interaction with the oxygen atom in carbonates plasticizer, therefore can include
A large amount of liquid electrolyte embodies good compatibility.But the mechanical strength of PMMA gel electrolyte is poor, limits answering for it
With.For this reason, it may be necessary to be modified to PMMA to improve the mechanical performance of PMMA.
Summary of the invention
It is an object of the invention to: a kind of attapulgite hydridization polymethyl methacrylate lithium battery gel electrolyte is provided
Preparation method, the interface stability of obtained gel electrolyte and lithium electrode is good, and interface impedance is low, easily forms, and changes
Property is learned to stablize.
The technical solution of the invention is as follows it the following steps are included:
(1) it under gas shield, disperses the attapulgite that mass fraction is 1 ~ 15 part in 100 parts of solvent, is added
The functional monomer that mass fraction is 5 ~ 40 parts carries out ion exchange, obtains functional attapulgite；
(2) be added in above-mentioned functional attapulgite solution methyl methacrylate that mass fraction is 4 ~ 40 parts and
The initiator that mass fraction is 0.002 ~ 0.2 part carries out polymerization reaction, obtains attapulgite hydridization polymethyl methacrylate；
Wherein, reaction temperature is 30-90 DEG C, mixing speed >=200r/min, and the reaction time is 2 ~ 48h；
(3) by attapulgite hydridization polymethyl methacrylate form a film, then in the electrolyte containing lithium salts impregnate 2 ~
For 24 hours to get arrive attapulgite hydridization polymethyl methacrylate lithium battery gel electrolyte.
Wherein, the functional monomer is acrylamidopropyl-benzyl ammonium chloride, dimethyl diallyl ammonium chloride, ring
At least one of oxygen propyl group trimethyl ammonium chloride, vinyltrimethoxysilane.
Wherein, the initiator be potassium peroxydisulfate-sodium hydrogensulfite, benzoyl peroxide, in azodiisobutyronitrile extremely
Few one kind.
Wherein, the solvent is one or both of water, ethyl alcohol, methanol, toluene.
Wherein, the gas is at least one of nitrogen, helium.
Wherein, the electrolyte is propene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate
One of ester or a variety of mixtures.
Wherein, the lithium salts is lithium perchlorate, lithium hexafluoro phosphate, at least one in the amide lithium of bis trifluoromethyl sulfonic acid Asia
Kind, mass fraction is the 1 ~ 40% of electrolyte.
Wherein, the membrance casting condition be attapulgite hydridization polymethyl methacrylate is dissolved in organic solution after in
It forms a film on tetrafluoroethene plate；The organic solution is at least one of acetone, ethyl acetate.
Compared with prior art, the present invention has the advantage that as follows:
1) present invention carries out ion exchange using functional monomer and attapulgite, makes attapulgite surface with reactive group
Then functional attapulgite is used to synthesize attapulgite hydridization polymethyl methacrylate by group, realize attapulgite-height
Molecular material molecular level is other compound.
It 2) is to be linked together between attapulgite and polymer by way of chemical bond, the organic principle in polymer
Macromolecule matrix is provided, the corresponding performance of polymer is assigned, and inorganic constituents provides included nano modified filler, it can
It assigns polymer more excellent performance, while solving the problems, such as that dispersion is difficult again, change traditional organic-inorganic material physics
The mode of composite.
3) interface stability of obtained gel electrolyte and lithium electrode is good, and interface impedance is low, easily forms, chemistry
Property is stablized, conductivity > 1 × 10 of the gel electrolyte-3 S/cm。
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, but protection scope of the present invention is not limited in
This.
Embodiment 1: gel electrolyte is prepared according to following steps
(1) under nitrogen protection, it disperses the attapulgite that mass fraction is 1 part in 100 parts of aqueous solution, matter is added
It measures the dimethyl diallyl ammonium chloride that number is 5 parts and carries out ion exchange, obtain functional attapulgite；
(2) methyl methacrylate and the matter that mass fraction is 20 parts is added in above-mentioned functional attapulgite solution
It measures potassium peroxydisulfate-sodium hydrogensulfite that number is 0.002 part and carries out polymerization reaction, obtain attapulgite hydridization polymethylacrylic acid
Methyl esters；Wherein, 30 DEG C of reaction temperature, mixing speed >=200r/min, 2 h of reaction time；
(3) attapulgite hydridization polymethyl methacrylate is dissolved in acetone, then fall on tetrafluoroethene plate at
Film, then 2h is impregnated in the carbonic allyl ester solution that mass fraction is 1% lithium perchlorate to get the poly- methyl of attapulgite hydridization is arrived
Methyl acrylate lithium battery gel electrolyte；The conductivity of the gel electrolyte is 1.4 × 10-3 S/cm。
Embodiment 2: gel electrolyte is prepared according to following steps
(1) it under helium protection, disperses the attapulgite that mass fraction is 1 part in 100 parts of methanol solution, is added
The epoxypropyltrimethylchloride chloride that mass fraction is 40 parts carries out ion exchange, obtains functional attapulgite；
(2) methyl methacrylate and the quality that mass fraction is 40 parts is added in above-mentioned functional attapulgite solution
The benzoyl peroxide that number is 0.2 part carries out polymerization reaction, obtains attapulgite hydridization polymethyl methacrylate；Wherein,
Reaction temperature is 90 DEG C, mixing speed >=200r/min, and the reaction time is 48 h；
(3) attapulgite hydridization polymethyl methacrylate is dissolved in ethyl acetate, is then fallen in tetrafluoroethene plate
Upper film forming, then 24 h are impregnated in the ethylene carbonate ester solution that mass fraction is 15% lithium hexafluoro phosphate to get miscellaneous to attapulgite
Change polymethyl methacrylate lithium battery gel electrolyte；The conductivity of the gel electrolyte is 2.8 × 10-3 S/cm。
Embodiment 3: gel electrolyte is prepared according to following steps
(1) under nitrogen protection, it disperses the attapulgite that mass fraction is 1 part in 100 parts of ethanol solution, is added
The vinyl trimethylsilane that mass fraction is 10 parts carries out ion exchange, obtains functional attapulgite；
(2) methyl methacrylate and the quality that mass fraction is 4 parts is added in above-mentioned functional attapulgite solution
The azodiisobutyronitrile that number is 0.1 part carries out polymerization reaction, obtains attapulgite hydridization polymethyl methacrylate；Wherein,
Reaction temperature is 60 DEG C, mixing speed >=200r/min, and the reaction time is 12 h；
(3) attapulgite hydridization polymethyl methacrylate is dissolved in acetone, then fall on tetrafluoroethene plate at
Film, then immersion 20h is recessed to get arriving in the dimethyl carbonate solution that mass fraction is 40% bis trifluoromethyl sulfonic acid Asia amide lithium
Convex stick stone hydridization polymethyl methacrylate lithium battery gel electrolyte；The conductivity of the gel electrolyte is 3.6 × 10-3 S/
cm。
Embodiment 4: gel electrolyte is prepared according to following steps
(1) under nitrogen protection, it disperses the attapulgite that mass fraction is 8 parts in 100 parts of toluene solution, is added
The dimethyl diallyl ammonium chloride that mass fraction is 30 parts carries out ion exchange, obtains functional attapulgite；
(2) methyl methacrylate and the matter that mass fraction is 30 parts is added in above-mentioned functional attapulgite solution
It measures the benzoyl peroxide that number is 0.15 part and carries out polymerization reaction, obtain attapulgite hydridization polymethyl methacrylate；Its
In, reaction temperature is 80 DEG C, mixing speed >=200r/min, and the reaction time is 18 h；
(3) attapulgite hydridization polymethyl methacrylate is dissolved in acetone, then fall on tetrafluoroethene plate at
Film, then impregnate for 24 hours in the methyl ethyl carbonate ester solution that mass fraction is 10% lithium hexafluoro phosphate to get poly- to attapulgite hydridization
Methyl methacrylate lithium battery gel electrolyte；The conductivity of the gel electrolyte is 1.1 × 10-3 S/cm。
Embodiment 5: gel electrolyte is prepared according to following steps
(1) under nitrogen protection, the attapulgite that mass fraction is 2 parts is dispersed in 100 parts of methanol-water mixed solution
In, it adds the acrylamidopropyl-benzyl ammonium chloride that mass fraction is 25 parts and carries out ion exchange, obtain functional bumps
Stick stone；
(2) methyl methacrylate and the quality that mass fraction is 15 parts is added in above-mentioned functional attapulgite solution
The azodiisobutyronitrile that number is 0.008 part carries out polymerization reaction, obtains attapulgite hydridization polymethyl methacrylate；Its
In, reaction temperature is 70 DEG C, mixing speed >=200r/min, and the reaction time is for 24 hours；
(3) attapulgite hydridization polymethyl methacrylate is dissolved in acetone, then fall on tetrafluoroethene plate at
Film, then 20h is impregnated in the diethyl carbonate solution that mass fraction is 15% lithium hexafluoro phosphate to get poly- to attapulgite hydridization
Methyl methacrylate lithium battery gel electrolyte, the conductivity of the gel electrolyte are 1.9 × 10-3 S/cm。
Claims (7)
1. the preparation method of attapulgite hydridization polymethyl methacrylate lithium battery gel electrolyte, it is characterized in that it include with
Lower step:
(1) it under gas shield, disperses the attapulgite that mass fraction is 1 ~ 15 part in 100 parts of solvent, quality is added
The functional monomer that number is 5 ~ 40 parts carries out ion exchange, obtains functional attapulgite；The functional monomer is propylene
Amidopropyl benzyl ammonium chloride, dimethyl diallyl ammonium chloride, epoxypropyltrimethylchloride chloride, vinyl trimethoxy
At least one of silane；
(2) methyl methacrylate and the quality that mass fraction is 4 ~ 40 parts is added in above-mentioned functional attapulgite solution
The initiator that number is 0.002 ~ 0.2 part carries out polymerization reaction, obtains attapulgite hydridization polymethyl methacrylate；Wherein,
Reaction temperature is 30-90 DEG C, mixing speed >=200r/min, and the reaction time is 2 ~ 48h；
(3) by attapulgite hydridization polymethyl methacrylate form a film, then in the electrolyte containing lithium salts impregnate 2 ~ for 24 hours, i.e.,
Obtain attapulgite hydridization polymethyl methacrylate lithium battery gel electrolyte.
2. the preparation side of attapulgite hydridization polymethyl methacrylate lithium battery gel electrolyte according to claim 1
Method, it is characterized in that: the initiator be potassium peroxydisulfate-sodium hydrogensulfite, benzoyl peroxide, in azodiisobutyronitrile at least
It is a kind of.
3. the preparation side of attapulgite hydridization polymethyl methacrylate lithium battery gel electrolyte according to claim 1
Method, it is characterized in that: the solvent is one or both of water, ethyl alcohol, methanol, toluene.
4. the preparation side of attapulgite hydridization polymethyl methacrylate lithium battery gel electrolyte according to claim 1
Method, it is characterized in that: the gas is at least one of nitrogen, helium.
5. the preparation side of attapulgite hydridization polymethyl methacrylate lithium battery gel electrolyte according to claim 1
Method, it is characterized in that: the electrolyte is propene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate
One of ester or a variety of mixtures.
6. the preparation side of attapulgite hydridization polymethyl methacrylate lithium battery gel electrolyte according to claim 1
Method, it is characterized in that: the lithium salts be at least one of lithium perchlorate, lithium hexafluoro phosphate, bis trifluoromethyl sulfonic acid Asia amide lithium,
Its mass fraction is the 1 ~ 40% of electrolyte.
7. the preparation side of attapulgite hydridization polymethyl methacrylate lithium battery gel electrolyte according to claim 1
Method, it is characterized in that: the membrance casting condition be attapulgite hydridization polymethyl methacrylate is dissolved in organic solution after in
It forms a film on tetrafluoroethene plate；The organic solution is acetone, tetrahydrofuran, ethyl acetate, dimethylformamide.
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| CN108041604A (en) * | 2018-02-09 | 2018-05-18 | 重庆医科大学附属永川医院 | A kind of galactic processing method of puerpera |
| CN108878968A (en) * | 2018-06-25 | 2018-11-23 | 江苏大学 | A kind of organic/inorganic composite solid electrolyte based on concave convex rod or wollastonite |
| CN109585910B (en) * | 2018-11-13 | 2021-06-18 | 吉林师范大学 | Solid composite electrolyte and preparation method and application of electrolyte membrane thereof |
| CN109970900A (en) * | 2019-03-26 | 2019-07-05 | 中科院广州能源所盱眙凹土研发中心 | The preparation method of attapulgite modified cation styrene-acrylic emulsion |
| CN110048156B (en) * | 2019-05-06 | 2021-07-20 | 浙江大学 | Solid electrolyte and preparation method and application thereof |
| CN117050367B (en) * | 2023-10-12 | 2023-12-19 | 上海雷磁传感器科技有限公司 | High-stability solid polymer electrolyte and preparation method thereof |
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