CN109810225A - A kind of crystal type composite gel electrolyte and its preparation method and application - Google Patents
A kind of crystal type composite gel electrolyte and its preparation method and application Download PDFInfo
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- CN109810225A CN109810225A CN201910190477.3A CN201910190477A CN109810225A CN 109810225 A CN109810225 A CN 109810225A CN 201910190477 A CN201910190477 A CN 201910190477A CN 109810225 A CN109810225 A CN 109810225A
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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
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to a kind of preparation method and application of crystal type composite gel electrolyte, it is characterized in that, the following steps are included: plastic component and soluble-salt are added to the water by (1), stir to being completely dissolved as transparent uniform solution, obtain gel precursor liquid；(2) the gel precursor liquid for obtaining step (1) carries out plastic, and the hydrogel containing saturation soluble-salt is prepared；(3) crystal seed is placed above the hydrogel that step (2) is prepared to get the composite gel electrolyte of crystal type is arrived.Compared with prior art, preparation process of the present invention is simple and efficient, material is cheap and easy to get, the composite gel electrolyte being prepared has higher mechanical strength and ionic conductivity, it can be applied to the energy storage devices such as supercapacitor, it can be from main regulation material temperature, even in extreme environment for varying environment temperature, also can maintenance system keep temperature to stablize in a short time, be of great significance when coping with the disasters such as fire.
Description
Technical field
The present invention relates to a kind of gel rubber materials, more particularly, to a kind of crystal type composite gel electrolyte and its preparation and answer
With.
Background technique
More stringent requirements are proposed for the growing development to energy storage device of energy demand.Common electrochemical energy accumulator
Part includes lithium ion battery, supercapacitor, solar battery etc., the performance of these energy storage devices mainly by its electrode material and
Electrolyte determines.Wherein according to the existing forms of electrolyte, electrolyte can be divided into liquid electrolyte and solid electrolyte.
Liquid electrolyte is due to its mobility, the phenomenon that being easy to appear leakage in use, so as to cause burning even explosion etc.
Danger, and solid electrolyte then solves the problems, such as this, while the encapsulation process of device being made also to become relatively simpler.
Gel electrolyte is a kind of solid electrolyte being widely studied, and has the characteristics that containing large amount of liquid amount and fixed form,
Have both some advantages of liquid electrolyte and other solid electrolytes.Compared to liquid electrolyte, gel electrolyte is solid due to it
State attribute can effectively solve the problems, such as energy storage device leakage and encapsulation；Compared to ceramic-like solid electrolyte, and because it is high
Liquid content greatly improves the ionic conductivity of electrolyte, improves the chemical property of solid-state energy storage device.
In addition to above-mentioned advantage, gel electrolyte also has some unique advantages.Due to the semisolid of gel electrolyte,
Most of gel electrolyte all has fabulous flexibility, can bear to be bent, and winding even folds etc., in conjunction with electrode material flexible
Material, can prepare energy storage device flexible, have great application value in wearable device field.In addition, gel electrolyte
The flexibility of matter and certain caking property can be effectively improved its contact with electrode material, reduce device contacts resistance, improve whole
Performance.
But there is also some problems for gel electrolyte, wherein most important is exactly between mechanical performance and ionic conductivity
Contradiction.Although gel electrolyte is solid, but its mechanical strength is not high, especially water system gel electrolyte, compression
Usually only several kPas to more than ten kPas of modulus, mechanical damage can not be much resisted, when device is destroyed by external force, is still deposited
In the danger that device failure is even exploded, it is difficult to meet demand for security.And by improving solid content or addition inorganic filler
Etc. modes improve the mechanical strength of gel electrolyte, and will lead to being greatly lowered for its ionic conductivity, damage the electricity of device
Chemical property.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind is taken precautions against natural calamities, type is compound to coagulate
Glue electrolyte and its preparation method and application.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of crystal type composite gel electrolyte, comprising the following steps:
(1) plastic component and soluble-salt are added to the water, stir to being completely dissolved as transparent uniform solution, obtains
Gel precursor liquid；
(2) the gel precursor liquid for obtaining step (1) carries out plastic, and the water-setting containing saturation soluble-salt is prepared
Glue；
(3) crystal seed that corresponding soluble-salt is placed above the hydrogel that step (2) is prepared, causes in hydrogel
Supersaturated soluble-salt orientation is precipitated to get the composite gel electrolyte of crystal type is arrived.
Preferably, in step (1): the plastic group is divided into monomer polymerization system or physics plastic system.
Preferably, the monomer polymerization system contains monomer, crosslinking agent and ultraviolet initiator, and the monomer is acryloyl
Amine monomers or acrylic ester monomer, the crosslinking agent are N, and N'- methylene-bisacrylamide (MBAA), the ultraviolet light draws
Sending out agent is 2,2- diethoxy acetophenone (DEAP).
Preferably, the physics plastic system only contains polymer substance, for one in gelatin or hydroxymethyl cellulose
Kind is a variety of, and the additive amount of the polymer substance is the 5%~15% of water quality.
Preferably, the monomer is acrylamide (AAm), N hydroxymethyl acrylamide (N-MMAA), 3- (2- metering system
Acyloxyethyl dimethylamino) one of propane sulfonic acid salt (DMAPS) or a variety of.
Preferably, the additive amount of the monomer is the 10%~20% of water total weight, and the additive amount of the crosslinking agent is single
The 0.1%~1% of body total weight, the additive amount of the ultraviolet initiator are the 0.1%~1% of total monomer weight.
Preferably, the plastic mode when plastic component is monomer polymerization system, in step (2) are as follows: by gel precursor liquid
Being placed in light intensity is 25~30mW/cm2Ultraviolet lamp under radiate, the reaction time be 10~30min；
Plastic mode when plastic component is physics plastic system, in step (2) are as follows: placement cools down at room temperature
30min。
Preferably, in step (1): the soluble-salt is anhydrous sodium acetate (NaAc), Sodium Thio Sulphate(Anhydrous)
(Na2S2O3), anhydrous magnesium sulfate (MgSO4One of), the additive amount of soluble-salt is that 0.4 times of the quality of water arrives solubility
The maxima solubility of salt.
Preferably, in step (1): whipping temp is 80 DEG C, mixing time 5-30min.
A kind of application of crystal type composite gel electrolyte in energy storage device.
Process conditions in the present invention are most suitable preparation condition.Heating is the quick dissolution for soluble-salt, and
Temperature is excessively high, easily causes solution boiling, and temperature is too low, will cause salt dissolution slowly, or even insoluble；Intensity of illumination with react
Time is corresponding, and intensity of illumination is too low to extend the required reaction time；Reactant additive amount will affect finally obtained compound solidifying
The performance of glue electrolyte, especially its mechanical performance, such as monomer or content of crosslinking agent is too low can reduce composite gel electrolyte
Mechanical strength even results in not plastic；And the additive amount of dissolubility salt is influencing the same of the mechanical strength of composite gel electrolyte
When, it also will affect its ionic conductivity, additive amount is higher, and mechanical strength is higher, but ionic conductivity is lower.
The present invention by causing supersaturated salt crystallographic orientation in the Common hydrogels matrix containing supersaturated soluble-salt,
Obtain the composite gel electrolyte with superelevation mechanical strength.Wherein, composite gel electrolyte is containing crosslinking macromolecule water-setting
Glue basis material, the soluble salt solutions of saturation and regular soluble-salt crystal；Macromolecule hydrogel matrix can pass through monomer
Polymerization or Polymer Physics are cross-linked to form three-dimensional space net structure, the soluble-salt electrolyte aqueous solution of saturation and it is regular can
Dissolubility salt crystal is filled in network structure gap.
The present invention is a kind of method of high-intensitive solid gel electrolyte of novel preparation, first will be excessive by high temperature
Soluble-salt is dissolved in precursor liquid, and cooling forms hypersaturated state after precursor liquid plastic, finally causes soluble-salt crystallization
Obtain the solid gel electrolyte of superhigh intensity.
This method simple process, controllability is strong, easy to operate.Solid union gel electrolyte made from this method has super
High mechanical strength, maximum compression modulus arrive several hundred megapascal up to tens, are thousands of to tens of thousands of times of pure water gel.Further, since
Plural gel still dissolved with the salt ion being saturated, makes it have good ionic conductivity, or else needs to introduce after crystallisation
In the case where other electrolytic salts, it can be used as safe and reliable solid union gel electrolyte materials applied to energy storage device
In.During soluble-salt crystallization, a large amount of Free waters in aquogel system can be made to be changed into the crystallization water, reduce the electricity of water
Chemical activity makes the operating voltage and energy density of energy storage device to improve the electrochemical window of gel rubber material.
In addition, the presence of soluble-salt crystal allows plural gel by dissolving and heat absorbing or crystallization exotherm from main regulation material
Material temperature degree becomes a kind of potential constant-temp material, and in phase transition process, energy maintenance system temperature is stablized, so that using the electrolysis
The energy storage device of matter has longer service life under the fire condition of burst, has certain Disaster Defense Capability.
Compared with prior art, the invention has the following advantages:
(1) with traditional hydrogel electrolyte phase ratio, crystal type composite gel electrolyte prepared by the present invention is due to solvable
Property salt crystal humidification, there is higher mechanical strength, in solid-state energy storage device using upper more safety；
(2) with solid polymer electrolyte and solid-state ceramic class electrolyte phase ratio, crystal type prepared by the present invention is compound to coagulate
Glue electrolyte contains more free conductive ions, has higher ionic conductivity, and energy storage device can be made to obtain more preferably
Chemical property；
(3) the characteristics of water dissolves is met using soluble-salt crystal, when assembling energy storage device, can be smeared in electrolyte two sides
Micro water makes the composite gel electrolyte of outer layer be changed into hydrogel electrolyte, generates good bonding with electrode material and imitates
Fruit assembles convenient for device, and reduces the contact resistance between electrolyte and electrode material, improves device chemical property；
(4) since during soluble-salt crystallizes, a large amount of Free waters in aquogel system are changed into the crystallization water, drop
The low electro-chemical activity of water improves the operating voltage of energy storage device to improve the electrochemical window of gel rubber material；
(5) high salt concentration in crystal type composite gel electrolyte can effectively reduce the freezing point of aqueous solution, widen energy storage
The temperature window of device work normally it still can at low temperature；
(6) soluble-salt crystal at high temperature can dissolving and heat absorbing, crystallization at low temperatures heat release, pass through this phase transition performance, knot
Crystal form composite gel electrolyte can be according to environment temperature from main regulation material temperature, even if in the extreme temperatures ring such as baked wheaten cake or liquid nitrogen
Under border, also system temperature can be kept to stablize in the short time so that using the electrolyte energy storage device burst fire condition
There is down longer service life, have certain Disaster Defense Capability.
(7) preparation process of the invention is simple, and raw material is cheap and easy to get.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram of the crystal type composite gel electrolyte of embodiment 1；
Fig. 2 is the compression curve figure of the crystal type composite gel electrolyte of embodiment 1；
Fig. 3 is the ac impedance spectroscopy of the crystal type composite gel electrolyte of embodiment 1；
Fig. 4 is that the crystal type composite gel electrolyte of embodiment 1 is used as the linear volt-ampere curve figure of supercapacitor；
Fig. 5 is that the crystal type composite gel electrolyte of embodiment 1 is used as perseverance of the supercapacitor under different current densities
Flow charging and discharging curve figure；
Fig. 6 is that the crystal type composite gel electrolyte of embodiment 2 is filled as the constant current of supercapacitor at different temperatures
Discharge curve；
Fig. 7 is that the crystal type composite gel electrolyte of embodiment 2 shows as what supercapacitor worked normally in liquid nitrogen
It is intended to；
Fig. 8 is that the crystal type composite gel electrolyte of embodiment 2 shows as what supercapacitor worked normally in flame
It is intended to.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
By 0.15g acrylamide (AAm), 0.45mg N, N'- methylene-bisacrylamide (MBAA), 1 μ L 2,2- diethyl
Oxygroup acetophenone (DEAP), 1.02g anhydrous sodium acetate (NaAc) are added in 0.85mL distilled water, the heating stirring at 80 DEG C
5min forms the transparent uniform precursor liquid containing high-concentration acetic acid sodium.Under the conditions of 25 DEG C, precursor liquid is subject to ultraviolet light spoke
It penetrates, intensity of illumination about 25mW/cm2, the obtained hydrogel electrolyte containing supersaturated sodium acetate of reaction 15min.In hydrogel electricity
It solves and places an acetic acid sodium crystal above matter, cause the supersaturated sodium acetate crystallographic orientation inside hydrogel, obtain crystal type
High-strength composite gel electrolyte.The compression modulus of gained composite gel electrolyte is 16.27MPa, and ionic conductivity is
4.4mS/cm, with specific surface area 2100m2The active carbon of/g is assembled into double electric layers supercapacitor, work electricity as active material
Pressure is 2V, and gained specific capacity is 120.8F/g at current density 1A/g.
As shown in Figure 1, the crystal type high-strength composite gel electrolyte quality sample of the present embodiment is after freeze-drying process,
There is the acetic acid sodium crystal of regular arrangement in scanning electron microscope image, and crystalline size is at 2~3 μm.It is illustrated in figure 2 compound
The compression curve of gel electrolyte can learn that the compression modulus of the present embodiment sample is 16.27MPa, be much higher than by calculating
The mechanical strength of Common hydrogels electrolyte.Fig. 3 is the AC impedance spectroscopy of crystal type high-strength composite gel electrolyte quality sample,
Sample is diameter 1.4cm, and the cylinder of high 0.9cm passes through the ionic conductivity for the composite gel electrolyte that AC impedence method measures
For 4.4mS/cm, good conductive characteristic is shown.
It is 2100m by the high-strength composite gel electrolyte of resulting crystal type and specific surface area2The activated carbon electrodes of/g
It it is assembled into double electric layers supercapacitor, carries out linear voltammetric scan test, as a result as shown in figure 4, the composite gel electrolyte
Decomposition voltage, which is greater than 2V, can provide higher work much higher than common hydrogel electrolyte for energy storage devices such as supercapacitors
Make voltage and energy density.Fig. 5 is constant current charge and discharge of the above-mentioned supercapacitor at different current densities (0.2A/g~20A/g)
Electric curve, according to this curve, it can be seen that had using the supercapacitor of crystal type high-strength composite gel electrolyte excellent
Different high rate performance.
Embodiment 2
By 0.15g 3- (2- methylacryoyloxyethyl dimethylamino) propane sulfonic acid salt (DMAPS), 0.45mg N, N'- are sub-
Bisacrylamide (MBAA), 1 μ L 2,2- diethoxy acetophenone (DEAP), 1.02g anhydrous sodium acetate (NaAc) are added to
In 0.85mL distilled water, the heating stirring 5min at 80 DEG C forms the transparent uniform precursor liquid containing high-concentration acetic acid sodium.?
Under the conditions of 25 DEG C, precursor liquid is subject to ultraviolet radiation, intensity of illumination about 25mW/cm2, reaction 30min, which is made, contains supersaturation
The hydrogel electrolyte of sodium acetate.An acetic acid sodium crystal is placed above hydrogel electrolyte, causes the mistake inside hydrogel
It is saturated sodium acetate crystallographic orientation, obtains the high-strength composite gel electrolyte of crystal type.The compression of gained composite gel electrolyte
Modulus is 4.64MPa, ionic conductivity 8.9mS/cm, with specific surface area 2100m2The active carbon of/g is assembled as active material
At double electric layers supercapacitor, operating voltage 2V, gained specific capacity is 175.9F/g at current density 1A/g.
The supercapacitor of the present embodiment is placed in constant temperature under different temperatures (- 40 DEG C~80 DEG C) and handles 30min, with 1A/g
Current density to supercapacitor carry out constant current charge-discharge test, as shown in fig. 6, supercapacitor still can in different temperatures
It is enough to work normally, and show good cryogenic property.As shown in Figure 7 and Figure 8, the supercapacitor of the present embodiment is placed in
In liquid nitrogen (- 196 DEG C) or flame (> 200 DEG C), can still it be worked normally in the short time, compared to Common hydrogels electrolyte system
At device, can adhere to the time of 10s or more more, show the ability of certain anti-extreme temperature, it is prominent in reply fire etc.
Effect is combated a natural disaster with certain when sending out disaster.
Embodiment 3
By 0.15g acrylamide (AAm), 0.45mg N, N'- methylene-bisacrylamide (MBAA), 1 μ L 2,2- diethyl
Oxygroup acetophenone (DEAP), 0.34g anhydrous sodium acetate (NaAc) are added in 0.85mL distilled water, the heating stirring at 80 DEG C
5min forms the transparent uniform precursor liquid containing high-concentration acetic acid sodium.Under the conditions of 25 DEG C, precursor liquid is subject to ultraviolet light spoke
It penetrates, intensity of illumination about 25mW/cm2, the obtained hydrogel electrolyte containing supersaturated sodium acetate of reaction 15min.In hydrogel electricity
It solves and places an acetic acid sodium crystal above matter, cause the supersaturated sodium acetate crystallographic orientation inside hydrogel, obtain crystal type
High-strength composite gel electrolyte.The compression modulus of gained composite gel electrolyte is 0.018MPa, and ionic conductivity is
50.8mS/cm。
Embodiment 4
By 0.15g acrylamide (AAm), 0.45mg N, N'- methylene-bisacrylamide (MBAA), 1 μ L 2,2- diethyl
Oxygroup acetophenone (DEAP), 0.51g anhydrous sodium acetate (NaAc) are added in 0.85mL distilled water, the heating stirring at 80 DEG C
5min forms the transparent uniform precursor liquid containing high-concentration acetic acid sodium.Under the conditions of 25 DEG C, precursor liquid is subject to ultraviolet light spoke
It penetrates, intensity of illumination about 25mW/cm2, the obtained hydrogel electrolyte containing supersaturated sodium acetate of reaction 15min.In hydrogel electricity
It solves and places an acetic acid sodium crystal above matter, cause the supersaturated sodium acetate crystallographic orientation inside hydrogel, obtain crystal type
High-strength composite gel electrolyte.The compression modulus of gained composite gel electrolyte is 0.034MPa, and ionic conductivity is
38.3mS/cm。
Embodiment 5
By 0.15g acrylamide (AAm), 0.45mg N, N'- methylene-bisacrylamide (MBAA), 1 μ L 2,2- diethyl
Oxygroup acetophenone (DEAP), 0.68g anhydrous sodium acetate (NaAc) are added in 0.85mL distilled water, the heating stirring at 80 DEG C
5min forms the transparent uniform precursor liquid containing high-concentration acetic acid sodium.Under the conditions of 25 DEG C, precursor liquid is subject to ultraviolet light spoke
It penetrates, intensity of illumination about 25mW/cm2, the obtained hydrogel electrolyte containing supersaturated sodium acetate of reaction 15min.In hydrogel electricity
It solves and places an acetic acid sodium crystal above matter, cause the supersaturated sodium acetate crystallographic orientation inside hydrogel, obtain crystal type
High-strength composite gel electrolyte.The compression modulus of gained composite gel electrolyte is 0.48MPa, and ionic conductivity is
20.5mS/cm。
Embodiment 6
By 0.15g acrylamide (AAm), 0.45mg N, N'- methylene-bisacrylamide (MBAA), 1 μ L 2,2- diethyl
Oxygroup acetophenone (DEAP), 0.85g anhydrous sodium acetate (NaAc) are added in 0.85mL distilled water, the heating stirring at 80 DEG C
5min forms the transparent uniform precursor liquid containing high-concentration acetic acid sodium.Under the conditions of 25 DEG C, precursor liquid is subject to ultraviolet light spoke
It penetrates, intensity of illumination about 25mW/cm2, the obtained hydrogel electrolyte containing supersaturated sodium acetate of reaction 15min.In hydrogel electricity
It solves and places an acetic acid sodium crystal above matter, cause the supersaturated sodium acetate crystallographic orientation inside hydrogel, obtain crystal type
High-strength composite gel electrolyte.The compression modulus of gained composite gel electrolyte is 3.62MPa, and ionic conductivity is
10.8mS/cm。
Embodiment 7
By 0.15g acrylamide (AAm), 0.45mg N, N'- methylene-bisacrylamide (MBAA), 1 μ L 2,2- diethyl
Oxygroup acetophenone (DEAP), 1.19g anhydrous sodium acetate (NaAc) are added in 0.85mL distilled water, the heating stirring at 80 DEG C
5min forms the transparent uniform precursor liquid containing high-concentration acetic acid sodium.Under the conditions of 25 DEG C, precursor liquid is subject to ultraviolet light spoke
It penetrates, intensity of illumination about 25mW/cm2, the obtained hydrogel electrolyte containing supersaturated sodium acetate of reaction 15min.In hydrogel electricity
It solves and places an acetic acid sodium crystal above matter, cause the supersaturated sodium acetate crystallographic orientation inside hydrogel, obtain crystal type
High-strength composite gel electrolyte.The compression modulus of gained composite gel electrolyte is 37.65MPa, and ionic conductivity is
2.6mS/cm。
Embodiment 8
By 0.15g acrylamide (AAm), 0.45mg N, N'- methylene-bisacrylamide (MBAA), 1 μ L 2,2- diethyl
Oxygroup acetophenone (DEAP), 1.36g anhydrous sodium acetate (NaAc) are added in 0.85mL distilled water, the heating stirring at 80 DEG C
5min forms the transparent uniform precursor liquid containing high-concentration acetic acid sodium.Under the conditions of 25 DEG C, precursor liquid is subject to ultraviolet light spoke
It penetrates, intensity of illumination about 25mW/cm2, the obtained hydrogel electrolyte containing supersaturated sodium acetate of reaction 15min.In hydrogel electricity
It solves and places an acetic acid sodium crystal above matter, cause the supersaturated sodium acetate crystallographic orientation inside hydrogel, obtain crystal type
High-strength composite gel electrolyte.The compression modulus of gained composite gel electrolyte is 474.24MPa, and ionic conductivity is
0.9mS/cm。
Embodiment 9
By 0.075g acrylamide (AAm) and 0.075g 3- (2- methylacryoyloxyethyl dimethylamino) propane sulfonic acid salt
(DMAPS), 0.45mg N, N'- methylene-bisacrylamide (MBAA), 1 μ L 2,2- diethoxy acetophenone (DEAP), 1.02g
Anhydrous sodium acetate (NaAc) is added in 0.85mL distilled water, the heating stirring 5min at 80 DEG C, and formation contains high-concentration acetic acid
The transparent uniform precursor liquid of sodium.Under the conditions of 25 DEG C, precursor liquid is subject to ultraviolet radiation, intensity of illumination about 25mW/cm2,
It reacts 30min and the hydrogel electrolyte containing supersaturated sodium acetate is made.A sodium acetate is placed above hydrogel electrolyte
Crystal causes the supersaturated sodium acetate crystallographic orientation inside hydrogel, obtains the high-strength composite gel electrolyte of crystal type.Institute
The compression modulus for obtaining composite gel electrolyte is 10.21MPa, ionic conductivity 5.6mS/cm.
Embodiment 10
By 0.15g N hydroxymethyl acrylamide (N-MMAA), 0.45mg N, N'- methylene-bisacrylamide (MBAA), 1
μ L 2,2- diethoxy acetophenone (DEAP), 1.02g anhydrous sodium acetate (NaAc) is added in 0.85mL distilled water, at 80 DEG C
Lower heating stirring 5min forms the transparent uniform precursor liquid containing high-concentration acetic acid sodium.Under the conditions of 25 DEG C, by precursor liquid plus
With ultraviolet radiation, intensity of illumination about 25mW/cm2, the obtained hydrogel electrolyte containing supersaturated sodium acetate of reaction 30min.
An acetic acid sodium crystal is placed above hydrogel electrolyte, is caused the supersaturated sodium acetate crystallographic orientation inside hydrogel, is obtained
To the high-strength composite gel electrolyte of crystal type.The compression modulus of gained composite gel electrolyte is 5.55MPa, ionic conductance
Rate is 7.6mS/cm.
Embodiment 11
By 0.1g gelatin (AG), 1.08g anhydrous sodium acetate (NaAc) is added in 0.9mL distilled water, heats at 80 DEG C
30min is stirred, the transparent uniform precursor liquid containing high-concentration acetic acid sodium is formed.It is under the conditions of 25 DEG C, precursor liquid is cooling
The hydrogel electrolyte containing supersaturated sodium acetate is made in 30min.A sodium acetate crystalline substance is placed above hydrogel electrolyte
Body causes the supersaturated sodium acetate crystallographic orientation inside hydrogel, obtains the high-strength composite gel electrolyte of crystal type.Gained
The compression modulus of composite gel electrolyte is 42.70MPa, ionic conductivity 6.1mS/cm.
Embodiment 12
By 0.1g hydroxymethyl cellulose (CMC), 1.08g anhydrous sodium acetate (NaAc) is added in 0.9mL distilled water, 80
Heating stirring 30min at DEG C forms the transparent uniform precursor liquid containing high-concentration acetic acid sodium.Under the conditions of 25 DEG C, by forerunner
The hydrogel electrolyte containing supersaturated sodium acetate is made in liquid cooling but 30min.An acetic acid is placed above hydrogel electrolyte
Sodium crystal causes the supersaturated sodium acetate crystallographic orientation inside hydrogel, obtains the high-strength composite gel electrolyte of crystal type.
The compression modulus of gained composite gel electrolyte is 23.87MPa, ionic conductivity 7.9mS/cm.
Embodiment 13
By 0.1g hydroxymethyl cellulose (CMC), 1.8g Sodium Thio Sulphate(Anhydrous) (Na2S2O3) it is added to 0.9mL distilled water
In, the heating stirring 30min at 80 DEG C forms the transparent uniform precursor liquid containing high concentration sodium thiosulfate.In 25 DEG C of items
Under part, by the cooling 30min of precursor liquid, the hydrogel electrolyte containing supersaturated sodium thiosulfate is made.In hydrogel electrolyte
A thiosulfuric acid sodium crystal is placed in top, causes the supersaturated sodium thiosulfate crystallographic orientation inside hydrogel, is crystallized
The high-strength composite gel electrolyte of type.The compression modulus of gained composite gel electrolyte is 69.65MPa, and ionic conductivity is
4.2mS/cm。
Embodiment 14
By 0.15g acrylamide (AAm), 0.45mg N, N'- methylene-bisacrylamide (MBAA), 1 μ L 2,2- diethyl
Oxygroup acetophenone (DEAP), 0.425g anhydrous magnesium sulfate (MgSO4) be added in 0.85mL distilled water, the heating stirring at 80 DEG C
5min forms the transparent uniform precursor liquid containing high-concentration sulfuric acid magnesium.Under the conditions of 25 DEG C, precursor liquid is subject to ultraviolet light spoke
It penetrates, intensity of illumination about 25mW/cm2, the obtained hydrogel electrolyte containing supersaturated magnesium sulfate of reaction 15min.In hydrogel electricity
It solves and places a magnesium sulfate crystals above matter, cause the supersaturated magnesium sulfate crystallographic orientation inside hydrogel, obtain crystal type
High-strength composite gel electrolyte.The compression modulus of gained composite gel electrolyte is 0.13MPa, and ionic conductivity is
14.4mS/cm。
Embodiment 15
By 0.085g acrylamide (AAm), 0.85mg N, N'- methylene-bisacrylamide (MBAA), 0.85mg2,2- bis-
Acetophenone (DEAP), 1.36g anhydrous sodium acetate (NaAc) are added in 0.85mL distilled water, the heating stirring at 80 DEG C
20min forms the transparent uniform precursor liquid containing high-concentration acetic acid sodium.Under the conditions of 25 DEG C, precursor liquid is subject to ultraviolet light
Radiation, intensity of illumination about 30mW/cm2, the obtained hydrogel electrolyte containing supersaturated sodium acetate of reaction 10min.In hydrogel
An acetic acid sodium crystal is placed above electrolyte, is caused the supersaturated sodium acetate crystallographic orientation inside hydrogel, is obtained crystal type
High-strength composite gel electrolyte.
Embodiment 16
By 0.17g acrylamide (AAm), 0.085mg N, N'- methylene-bisacrylamide (MBAA), 0.085mg 2,2-
Diethoxy acetophenone (DEAP), 0.51g anhydrous sodium acetate (NaAc) are added in 0.85mL distilled water, heat and stir at 80 DEG C
5min is mixed, the transparent uniform precursor liquid containing high-concentration acetic acid sodium is formed.Under the conditions of 25 DEG C, precursor liquid is subject to ultraviolet light
Radiation, intensity of illumination about 27mW/cm2, the obtained hydrogel electrolyte containing supersaturated sodium acetate of reaction 10min.In hydrogel
An acetic acid sodium crystal is placed above electrolyte, is caused the supersaturated sodium acetate crystallographic orientation inside hydrogel, is obtained crystal type
High-strength composite gel electrolyte.
Embodiment 17
By 0.1275g acrylamide (AAm), 0.1275mg N, N'- methylene-bisacrylamide (MBAA), 0.1275mg
2,2- diethoxy acetophenones (DEAP), 0.51g anhydrous sodium acetate (NaAc) are added in 0.85mL distilled water, are added at 80 DEG C
Thermal agitation 20min forms the transparent uniform precursor liquid containing high-concentration acetic acid sodium.Under the conditions of 25 DEG C, precursor liquid is subject to
Ultraviolet radiation, intensity of illumination about 27mW/cm2, the obtained hydrogel electrolyte containing supersaturated sodium acetate of reaction 10min.?
An acetic acid sodium crystal is placed above hydrogel electrolyte, is caused the supersaturated sodium acetate crystallographic orientation inside hydrogel, is obtained
The high-strength composite gel electrolyte of crystal type.
Embodiment 18
By 0.0425g gelatin (AG), 1.08g anhydrous sodium acetate (NaAc) is added in 0.85mL distilled water, at 80 DEG C
Heating stirring 30min forms the transparent uniform precursor liquid containing high-concentration acetic acid sodium.Under the conditions of 25 DEG C, by forerunner's liquid cooling
But the hydrogel electrolyte containing supersaturated sodium acetate is made in 30min.A sodium acetate crystalline substance is placed above hydrogel electrolyte
Body causes the supersaturated sodium acetate crystallographic orientation inside hydrogel, obtains the high-strength composite gel electrolyte of crystal type.
Embodiment 19
By 0.135g hydroxymethyl cellulose (CMC), 1.08g anhydrous sodium acetate (NaAc) is added in 0.9mL distilled water,
Heating stirring 30min at 80 DEG C forms the transparent uniform precursor liquid containing high-concentration acetic acid sodium.Under the conditions of 25 DEG C, will before
Liquid cooling but 30min is driven, the hydrogel electrolyte containing supersaturated sodium acetate is made.A second is placed above hydrogel electrolyte
Sour sodium crystal causes the supersaturated sodium acetate crystallographic orientation inside hydrogel, obtains the high-strength composite gel electrolyte of crystal type
Matter.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of preparation method of crystal type composite gel electrolyte, which comprises the following steps:
(1) plastic component and soluble-salt are added to the water, stir to being completely dissolved as transparent uniform solution, obtains gel
Precursor liquid；
(2) the gel precursor liquid for obtaining step (1) carries out plastic, and the hydrogel containing saturation soluble-salt is prepared；
(3) crystal seed of corresponding soluble-salt is placed above the hydrogel that step (2) is prepared to get the compound of crystal type is arrived
Gel electrolyte.
2. a kind of preparation method of crystal type composite gel electrolyte according to claim 1, which is characterized in that step
(1) in: the plastic group is divided into monomer polymerization system or physics plastic system.
3. a kind of preparation method of crystal type composite gel electrolyte according to claim 2, which is characterized in that the list
Body polymerization system contains monomer, crosslinking agent and ultraviolet initiator, and the monomer is acrylamide monomers or esters of acrylic acid
Monomer, the crosslinking agent are N, and N'- methylene-bisacrylamide, the ultraviolet initiator is 2,2- diethoxy acetophenone；
The physics plastic system only contains polymer substance, is one of gelatin or hydroxymethyl cellulose or a variety of, institute
The additive amount for stating polymer substance is the 5%~15% of water quality.
4. a kind of preparation method of crystal type composite gel electrolyte according to claim 3, which is characterized in that the list
Body is one of acrylamide, N hydroxymethyl acrylamide, 3- (2- methylacryoyloxyethyl dimethylamino) propane sulfonic acid salt
Or it is a variety of.
5. a kind of preparation method of crystal type composite gel electrolyte according to claim 3, which is characterized in that the list
The additive amount of body is the 10%~20% of water total weight, and the additive amount of the crosslinking agent is the 0.1%~1% of total monomer weight,
The additive amount of the ultraviolet initiator is the 0.1%~1% of total monomer weight.
6. a kind of preparation method of crystal type composite gel electrolyte according to claim 2, which is characterized in that work as plastic
Plastic mode when group is divided into monomer polymerization system, in step (2) are as follows: it is 25~30mW/cm that gel precursor liquid, which is placed in light intensity,2
Ultraviolet lamp under radiate, the reaction time be 10~30min；
Plastic mode when plastic component is physics plastic system, in step (2) are as follows: place and cool down 30min at room temperature.
7. a kind of preparation method of crystal type composite gel electrolyte according to claim 1, which is characterized in that step
(1) in: the soluble-salt is one of anhydrous sodium acetate, Sodium Thio Sulphate(Anhydrous), anhydrous magnesium sulfate, and soluble-salt adds
Dosage is 0.4 times of the quality of water and reaches the maxima solubility of soluble-salt.
8. a kind of preparation method of crystal type composite gel electrolyte according to claim 1, which is characterized in that step
(1) in: whipping temp is 80 DEG C, mixing time 5-30min.
9. a kind of crystal type composite gel electrolyte is electrolysed using any one crystal type plural gel described in claim 1-8
The preparation method of matter is prepared.
10. a kind of application of crystal type composite gel electrolyte in energy storage device.
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| CN113549242A (en) * | 2021-07-28 | 2021-10-26 | 同济大学 | Sponge-like structure gel for water purification and preparation and application thereof |
| CN113549242B (en) * | 2021-07-28 | 2023-02-10 | 同济大学 | Sponge-like structure gel for water purification and preparation and application thereof |
| CN113921793A (en) * | 2021-10-10 | 2022-01-11 | 郑州大学 | Inorganic composite hydrogel electrolyte membrane, preparation thereof and application thereof in water-based zinc ion battery |
| CN113921793B (en) * | 2021-10-10 | 2022-10-28 | 郑州大学 | Inorganic composite hydrogel electrolyte membrane, preparation thereof and application thereof in water-based zinc ion battery |
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