CN110117370A - It is a kind of heat-resisting/low temperature resistant to glue tough based aquagel electrolyte preparation method - Google Patents
It is a kind of heat-resisting/low temperature resistant to glue tough based aquagel electrolyte preparation method Download PDFInfo
- Publication number
- CN110117370A CN110117370A CN201910412379.XA CN201910412379A CN110117370A CN 110117370 A CN110117370 A CN 110117370A CN 201910412379 A CN201910412379 A CN 201910412379A CN 110117370 A CN110117370 A CN 110117370A
- Authority
- CN
- China
- Prior art keywords
- heat
- water
- electrolyte
- low temperature
- resisting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Heat-resisting/low temperature resistant tough based aquagel electrolyte preparation method is glued the invention discloses a kind of.The hydrogel electrolyte is using phosphoric acid and water as mixed solvent, utilize the supercooling characteristic of phosphoric acid and the powerful hydrogen bond action between water, it allows the water to be firmly secured in gel rubber system, it is not easy to crystallize at low temperature, also the volatilization of moisture can be effectively prevented at high temperature, and then impart hydrogel long-time stability, frost resistance and heat resistance.In addition, phosphoric acid is a kind of electrolyte haveing excellent performance, on the one hand its introducing assigns hydrogel excellent electric conductivity, certain electric conductivity is even also able to maintain under high temperature/cryogenic conditions, on the other hand acid condition also is provided for the dissolution of chitosan, and then effectively improves the mechanical property and adhering performance of hydrogel.Hydrogel electrolyte of the invention will greatly extend the application range of flexible energy storage device, such as supercapacitor and rechargeable battery, and provide new theory for the design of other flexible electronic devices.
Description
The present invention provides it is a kind of it is heat-resisting/low temperature resistant glue tough based aquagel electrolyte preparation method, belong to macromolecule
Technical field of hydrogel.
Background technique
With various flexible, wearable electronic product fast developments, electrochemical energy storage is become more and more important；Various
Under mechanical strain, especially under bending and shear strain, keeping chemical property is one of the basic performance of flexible energy storage device；
Not only to electrode material, more stringent requirements are proposed for this, to other components such as electrolyte, separator, collectors in device and
Higher requirements are also raised for interfacial adhesion between different materials；However, to be the flexibility for realizing device, it is considered as tripe systems
The special performance of part material inevitably strains mismatch and lamination to mitigate in deformation process；In addition, flexible in manufacture
When energy storage device, electrolyte sometimes even it is more even more important than electrode material because they directly with the electrochemically stable electricity of system
Ion transport efficiency when position window occurs with electrochemical reaction is related；But often there are a series of defects in traditional electrolyte material,
The ionic conductivity if caused by electrolyte wetability is insufficient is limited, bad mechanical strength and interfacial adhesion is poor leads to active material
Be detached from electrode and lead to inter-electrode short-circuit etc., this may bring serious problem to energy storage device；
For hydrogel material due to its interesting structure and by more and more research interests, these structures include polymer chain
Cross-linked network and gap full of aqueous solvent；The characteristics of this characteristic makes material have both moist and flexibility, become flexibility
The ideal chose of energy storage device electrolyte, the supercapacitor such as currently furtherd investigate and rechargeable battery；It is more important
, the height of these hydrogels is abundant and adjustable chemical/physical properties so that existing hydrogel is introduced new function (viscous
The multiple functions such as property, tensility, heat-resisting, low temperature resistant), it is possible to producing the unprecedented storage with additional function
It can equipment；Therefore, it develops and a kind of heat-resisting/low temperature resistant glues tough based aquagel as the electrolyte of flexible energy storage device with far-reaching
Meaning will greatly widen the application field of energy storage device.
Summary of the invention
In order to solve the problems, such as that prior art exists, heat-resisting/low temperature resistant tough based aquagel is glued the present invention provides a kind of
Electrolyte preparation method；
One kind of the invention it is heat-resisting/low temperature resistant glue tough based aquagel, which is characterized in that mixed using phosphoric acid with water conduct molten
Agent allows the water to be firmly secured at gelinite using the supercooling characteristic of phosphoric acid and the powerful hydrogen bond action between water
It in system, i.e., is not easy to crystallize at low temperature, also can effectively prevent the volatilization of moisture at high temperature, and then it is long-term to impart hydrogel
Stability, frost resistance and heat resistance；In addition, phosphoric acid is a kind of electrolyte haveing excellent performance, on the one hand its introducing assigns water-setting
The excellent electric conductivity of glue, or even remain to be able to maintain certain electric conductivity under high temperature/cryogenic conditions, it is on the other hand also chitosan
Dissolution acid condition is provided, and then effectively improve the mechanical property of hydrogel and various matrix shown excellent
Adhering performance；
One kind of the invention it is heat-resisting/low temperature resistant the step of gluing tough based aquagel electrolyte preparation method and condition is as follows:
A, 20~30 minutes formation phosphoric acid/water mixed solutions are stirred at room temperature in the phosphoric acid and water for weighing different volumes ratio；So
A certain amount of chitosan (0.1~0.5g) is added in backward above-mentioned solution, is placed in water-bath and stirs and be warming up to 40~50 DEG C；
After chitosan is completely dissolved, acrylamide is added thereto, continues to heat；After acrylamide is completely dissolved, stop heating,
And crosslinking agent and initiator is added, it stirs 20~30 minutes, obtains uniform mixed solution；
B, the obtained homogeneous mixture solotion of above-mentioned steps a is put into the mold of sealing, is heated to 60~70 DEG C, constant temperature 6~8 is small
When, reaction terminates, and obtained gel is placed 2~3 hours at room temperature, obtains a kind of heat-resisting/low temperature resistant gluing tough base water-setting
Glue electrolyte；
Beneficial effects of the present invention:
Heat-resisting/low temperature resistant tough based aquagel that glues of one kind of the invention is to utilize phosphoric acid using phosphoric acid and water as mixed solvent
Characteristic and the powerful hydrogen bond action between water is subcooled, allows the water to be firmly secured in gel rubber system, i.e., in low temperature
Under be not easy to crystallize, also can effectively prevent the volatilization of moisture at high temperature, enable temperature model of the hydrogel at -20 DEG C~70 DEG C
Viscosity, toughness and restorability are still maintained in enclosing；After being even used continuously 5 months in the environment of room temperature, gel electricity
Solution matter is still able to maintain certain viscosity, toughness and restorability；In addition, phosphoric acid is a kind of electrolyte haveing excellent performance, it draws
On the one hand entering can assign hydrogel excellent electric conductivity, or even electric conductivity is still able to maintain under high temperature/cryogenic conditions, another
Aspect phosphoric acid also provides acid condition for the dissolution of chitosan, and then effectively improves the mechanical property of hydrogel and to various
Matrix shows excellent adhering performance；Therefore, what this was heat-resisting/freeze proof, which glue tough based aquagel, is expected to as flexible energy storage device
Electrolyte, greatly widen the application field of energy storage device.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described in further detail, but the present invention is not limited only to this；
The one kind of the invention of embodiment 1 is heat-resisting/low temperature resistant the step of gluing tough based aquagel electrolyte preparation method and condition
It is as follows:
A, 10ml phosphoric acid and 10ml water are weighed, 20 minutes formation phosphoric acid/water mixed solutions are stirred at room temperature；It states then up
The chitosan of 0.2g is added in solution, is placed in water-bath and stirs and be warming up to 40 DEG C；After chitosan is completely dissolved, thereto
4.0g acrylamide is added, continues to heat；After acrylamide is completely dissolved, stop heating, and crosslinking agent and initiator is added,
Stirring 20 minutes, obtains uniform mixed solution；
B, the obtained homogeneous mixture solotion of above-mentioned steps a is put into the mold of sealing, is heated to 70 DEG C, constant temperature 6 hours, reacts
Terminate, obtained gel is placed 2 hours at room temperature, obtains a kind of heat-resisting/low temperature resistant gluing tough based aquagel electrolyte；
Heat-resisting/low temperature resistant adhering performance test method for gluing tough based aquagel electrolyte of one kind prepared by the present invention: mould is used
Long tool preparation is about 80mm, and width 10mm, thickness is the rectangle hydrogel batten of 5mm, takes 3 battens under the conditions of the present embodiment
Sticky peeling force experiment, gauge length 80mm, peeling rate 5mm/min are carried out on CT3-1000 Texture instrument, peel angle is
90°Measure its adhering performance；
Heat-resisting/low temperature resistant mechanic property test method for gluing tough based aquagel electrolyte of one kind prepared by the present invention: it will be made
Hydrogel be cut into the dumbbell structure that width is 4cm, is 6cm with a thickness of 3cm, length, take 3 samples under the conditions of the present embodiment
Item carries out mechanical stretch experiment on Instron6022 universal testing machine, gauge length 15mm, tensile speed 100mm/min,
Measure its mechanical property；
Heat-resisting/low temperature resistant mechanic property test method for gluing tough based aquagel electrolyte of one kind prepared by the present invention: electricity is used
Chemical apparatuses Autolab(AUT86925) record electrochemical properties；By four probe AC impedance methods 1-106Hz frequency model
Enclose the resistance of interior measurement hydrogel；The ionic conductivity of hydrogel can be prepared by the following as a result:
σ= L/RS
Wherein σ is the ionic conductivity as unit of mS/cm, and L is the distance between every two electrode (cm), and R is hydrogel electricity
It hinders (Ω), S is the cross-sectional area of hydrogel；
Heat-resisting/low temperature resistant sticky peeling force average value for gluing tough based aquagel electrolyte of one kind prepared by embodiment 1 is
235.12N/m；Its tensile strength and elongation at break, average value are respectively 75kPa and 2300%；；The conductivity of hydrogel is
0.89S/cm or so；And flexible state is still maintained after 24 hours at subzero 20 DEG C and 70 DEG C；
Embodiment 2
A, 15ml phosphoric acid and 5ml water are weighed, 30 minutes formation phosphoric acid/water mixed solutions are stirred at room temperature；It states then up
The chitosan of 0.3g is added in solution, is placed in water-bath and stirs and be warming up to 40 DEG C；After chitosan is completely dissolved, thereto
4.0g acrylamide is added, continues to heat；After acrylamide is completely dissolved, stop heating, and crosslinking agent and initiator is added,
Stirring 20 minutes, obtains uniform mixed solution；
B, the obtained homogeneous mixture solotion of above-mentioned steps a is put into the mold of sealing, is heated to 70 DEG C, constant temperature 7 hours, reacts
Terminate, obtained gel is placed 3 hours at room temperature, obtains a kind of heat-resisting/low temperature resistant gluing tough based aquagel electrolyte；
With the test method of example 1, heat-resisting/low temperature resistant viscosity for gluing tough based aquagel electrolyte of one kind prepared by embodiment 2
Peeling force average value is 375.50N/m；Its tensile strength and elongation at break, average value are respectively 120kPa and 3000%；；Water
The conductivity of gel is 0.951S/cm or so；And flexible state is still maintained after 24 hours at subzero 20 DEG C and 70 DEG C；
Embodiment 3
A, 15ml phosphoric acid and 5ml water are weighed, 20 minutes formation phosphoric acid/water mixed solutions are stirred at room temperature；It states then up
The chitosan of 0.5g is added in solution, is placed in water-bath and stirs and be warming up to 50 DEG C；After chitosan is completely dissolved, thereto
4.0g acrylamide is added, continues to heat；After acrylamide is completely dissolved, stop heating, and crosslinking agent and initiator is added,
Stirring 30 minutes, obtains uniform mixed solution；
B, the obtained homogeneous mixture solotion of above-mentioned steps a is put into the mold of sealing, is heated to 70 DEG C, constant temperature 8 hours, reacts
Terminate, obtained gel is placed 2 hours at room temperature, obtains a kind of heat-resisting/low temperature resistant gluing tough based aquagel electrolyte；
With the test method of example 1, heat-resisting/low temperature resistant viscosity for gluing tough based aquagel electrolyte of one kind prepared by embodiment 3
Peeling force average value is 255.30N/m；Its tensile strength and elongation at break, average value are respectively 74kPa and 2438%；；Water-setting
The conductivity of glue is 0.941S/cm or so；And flexible state is still maintained after 24 hours at subzero 20 DEG C and 70 DEG C.
Claims (3)
1. heat-resisting/low temperature resistant tough based aquagel electrolyte is glued a kind of, it is characterised in that mixed solvent is used as using phosphoric acid and water, it is sharp
Electrolyte properties, supercooling characteristic and the powerful hydrogen bond action between water impart the excellent electric conductivity of hydrogel, long-term
Stability, frost resistance and heat resistance；In addition, being based on system acid condition, chitosan is also introduced into and effectively improves hydrogel
Mechanical property and adhering performance.
2. what one kind was heat-resisting/low temperature resistant as described in claim 1 glues tough based aquagel electrolyte, which is characterized in that it is prepared
The step of method and condition are as follows:
A, 20~30 minutes formation phosphoric acid/water mixed solutions are stirred at room temperature in the phosphoric acid and water for weighing different volumes ratio；So
A certain amount of chitosan (0.1~0.5g) is added in backward above-mentioned solution, is placed in water-bath and stirs and be warming up to 40~50 DEG C；
After chitosan is completely dissolved, acrylamide is added thereto, continues to heat；After acrylamide is completely dissolved, stop heating,
And crosslinking agent and initiator is added, it stirs 20~30 minutes, obtains uniform mixed solution；
B, the obtained homogeneous mixture solotion of above-mentioned steps a is put into the mold of sealing, is heated to 60~70 DEG C, constant temperature 6~8 is small
When, reaction terminates, and obtained gel is placed 2~3 hours at room temperature, obtains a kind of heat-resisting/low temperature resistant gluing tough base water-setting
Glue electrolyte.
3. what one kind was heat-resisting/low temperature resistant as claimed in claim 2 glues tough based aquagel electrolyte, which is characterized in that it is prepared
The step of method and condition are as follows:
A, 10ml phosphoric acid and 10ml water are weighed, 20 minutes formation phosphoric acid/water mixed solutions are stirred at room temperature；Then up
The chitosan that 0.2g is added in solution is stated, is placed in water-bath and stirs and be warming up to 40 DEG C；After chitosan is completely dissolved, Xiang Qi
Middle addition 4.0g acrylamide, continues to heat；After acrylamide is completely dissolved, stop heating, and crosslinking agent and initiation is added
Agent stirs 20 minutes, obtains uniform mixed solution；
B, the obtained homogeneous mixture solotion of above-mentioned steps a is put into the mold of sealing, is heated to 70 DEG C, constant temperature 6 hours, reacts
Terminate, obtained gel is placed 2 hours at room temperature, obtains a kind of heat-resisting/low temperature resistant gluing tough based aquagel electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910412379.XA CN110117370A (en) | 2019-05-17 | 2019-05-17 | It is a kind of heat-resisting/low temperature resistant to glue tough based aquagel electrolyte preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910412379.XA CN110117370A (en) | 2019-05-17 | 2019-05-17 | It is a kind of heat-resisting/low temperature resistant to glue tough based aquagel electrolyte preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110117370A true CN110117370A (en) | 2019-08-13 |
Family
ID=67522635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910412379.XA Pending CN110117370A (en) | 2019-05-17 | 2019-05-17 | It is a kind of heat-resisting/low temperature resistant to glue tough based aquagel electrolyte preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110117370A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012129805A1 (en) * | 2011-03-31 | 2012-10-04 | 南京大学 | Conductive polymer, synthesis method thereof, and electroactive electrode covered with said conductive polymer |
| CN107481869A (en) * | 2017-08-11 | 2017-12-15 | 北京大学 | A kind of double-network hydrogel electrolyte and its preparation and application |
| CN108102150A (en) * | 2017-12-18 | 2018-06-01 | 北京理工大学 | A kind of method for building the polyelectrolyte composite material based on chitosan |
| CN108178838A (en) * | 2017-12-29 | 2018-06-19 | 长春工业大学 | A kind of chitosan/acrylamide glues tough double-network hydrogel and preparation method thereof |
| CN109134762A (en) * | 2018-09-13 | 2019-01-04 | 长春工业大学 | A kind of high intensity, freeze proof, conductive chitosan/acrylamide double-network hydrogel and preparation method thereof |
-
2019
- 2019-05-17 CN CN201910412379.XA patent/CN110117370A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012129805A1 (en) * | 2011-03-31 | 2012-10-04 | 南京大学 | Conductive polymer, synthesis method thereof, and electroactive electrode covered with said conductive polymer |
| CN107481869A (en) * | 2017-08-11 | 2017-12-15 | 北京大学 | A kind of double-network hydrogel electrolyte and its preparation and application |
| CN108102150A (en) * | 2017-12-18 | 2018-06-01 | 北京理工大学 | A kind of method for building the polyelectrolyte composite material based on chitosan |
| CN108178838A (en) * | 2017-12-29 | 2018-06-19 | 长春工业大学 | A kind of chitosan/acrylamide glues tough double-network hydrogel and preparation method thereof |
| CN109134762A (en) * | 2018-09-13 | 2019-01-04 | 长春工业大学 | A kind of high intensity, freeze proof, conductive chitosan/acrylamide double-network hydrogel and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| LI HENYI ET AL.: "Three-Dimensional Polyacrylamide-Poly(Ethylene Glycol)/Phosphoric Acid for High-Temperature Proton Exchange Membranes", 《POLYMERS & POLYMER COMPOSITES》 * |
| YUAN SHUANGSHUANG ET AL.: "Three-dimensional hydrogel frameworks for high-temperature proton exchange membrane fuel cells", 《JOURNAL OF MATERIALS SCIENCE》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111668539B (en) | PVA/Li + Preparation method of/PEO interpenetrating network structure composite gel electrolyte | |
| CN109503765B (en) | Preparation method of cellulose ion conductive hydrogel and hydrogel prepared by same | |
| CN107482221B (en) | Polymer crosslinked binder and preparation method and application thereof | |
| CN108475788A (en) | Nonaqueous battery electrode binding agent copolymer, nonaqueous battery electrode slurry, nonaqueous battery electrode and nonaqueous battery | |
| CN109796716B (en) | Self-repairable polymer electrolyte and preparation method and application thereof | |
| Han et al. | Phase-separated polymer electrolyte based on poly (vinyl chloride)/poly (ethyl methacrylate) blend | |
| CN102382588A (en) | Adhesive tape for non-aqueous battery | |
| CN107771351A (en) | Solid polymer electrolyte and the electrochemical appliance for including it | |
| CN108484836B (en) | In-situ self-forming preparation method of composite polymer solid electrolyte membrane | |
| US11499018B2 (en) | Hydrogel, use thereof, and production method therefor | |
| KR20160045142A (en) | Binder composition for nonaqueous battery electrodes, slurry for nonaqueous battery electrodes, nonaqueous battery electrode, and nonaqueous battery | |
| CN105153338B (en) | A kind of preparation method of polymethyl methacrylate Signa Gel | |
| CN112735849A (en) | Anti-freezing zwitterion hydrogel electrolyte and preparation method thereof | |
| CN113402651A (en) | Preparation method of high-strength self-healing hydrogel electrolyte, flexible supercapacitor assembled by high-strength self-healing hydrogel electrolyte and preparation method of flexible supercapacitor | |
| CN112159533A (en) | Sodium caseinate/carboxymethyl chitosan conductive adhesive-tough hydrogel and preparation method thereof | |
| CN109705274B (en) | All-solid-state polymer electrolyte membrane and preparation method thereof | |
| CN113185715B (en) | Self-healing conductive polyvinyl alcohol-based hydrogel and preparation method and application thereof | |
| CN110117370A (en) | It is a kind of heat-resisting/low temperature resistant to glue tough based aquagel electrolyte preparation method | |
| CN110698611A (en) | Conductive hydrogel and preparation method and application thereof | |
| Yarovoy et al. | Dynamic mechanical spectroscopy and conductivity studies of gel electrolytes based on stereocomplexed poly (methyl methacrylate) | |
| CN111704728B (en) | Transparent ion-conductive cellulose hydrogel and preparation method and application thereof | |
| CN111613832A (en) | Five-membered monomer copolymerized polymer lithium secondary battery and preparation method thereof | |
| CN111848982A (en) | Self-healing conductive ionic gel and preparation method and application thereof | |
| Sukri et al. | Dielectric and conduction mechanism studies of PEMA/ENR-50 blend with LiCF3SO3 salt | |
| Mo et al. | A self-healable silk fibroin-based hydrogel electrolyte for silver-zinc batteries with high stability |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190813 |
|
| WD01 | Invention patent application deemed withdrawn after publication |