CN110858522B - Reversible overheating self-protection water system electrolyte based on poloxamer-polyacrylic acid graft copolymer, preparation method and application - Google Patents
Reversible overheating self-protection water system electrolyte based on poloxamer-polyacrylic acid graft copolymer, preparation method and application Download PDFInfo
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/64—Liquid electrolytes characterised by additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- 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 invention relates to a preparation method and application of a reversible overheating self-protection water system electrolyte based on a poloxamer-polyacrylic acid graft copolymer. When the temperature rises to be higher than the critical phase transition temperature, the molecular acting force among the hydrophobic groups takes the leading action, the sol-gel transition occurs, and the gel formed after the temperature rise restrains the movement of the conductive ions due to the transition of the molecular conformation, so that the effect of cutting off the conductive path at high temperature is achieved, the effect of inhibiting the internal temperature of the electrochemical energy storage device from continuously rising is achieved, and the reversible overheat self-protection effect of normal-temperature working-high-temperature circuit breaking is achieved.
Description
Technical Field
The invention relates to the technical field of conductive materials, in particular to a reversible overheating self-protection water system electrolyte based on a poloxamer-polyacrylic acid graft copolymer, a preparation method and application thereof.
Background
The super capacitor has high energy density and stable cycle performance, so that the super capacitor is widely applied. However, if not handled properly, chemical energy can be suddenly released in the form of combustion or explosion. Accidents related to fire and explosion of the super capacitor occur frequently all over the world, and some of the accidents cause serious threats to human life and health. The safety problem is a problem that needs to be solved first before applying a high-energy battery system in the future. Methods of ensuring security include external or internal protection mechanisms. External protection relies on electronics, and internal protection mechanisms are where the battery assembly materials are intrinsically safe, and are also considered to be the fundamental solution to address battery safety. But existing safety protection measures for supercapacitors cannot meet the requirement of fast intelligent response to temperature changes.
The temperature-sensitive polymer is a material which can be subjected to thermal response and can generate sol-gel reversible phase transformation along with temperature change. Recently, it has been reported that a responsive polymer having sol-gel reversible transition or phase separation properties at high temperatures is used in an electrolyte to solve the thermal runaway problem of electrochemical energy storage devices including supercapacitors and lithium ion batteries. The temperature-sensitive polymer is a liquid capable of flowing at low temperature, conductive ions can freely move in the temperature-sensitive polymer, the polymer is changed into gel through phase transition after the temperature is raised, and the temperature-sensitive polymer restricts the free movement of the conductive ions due to the change of conformation, so that the effect of cutting off current is achieved, further temperature rise can be prevented, and the effect of overheat self-protection on the battery is achieved. In the system, the charge and discharge rate of the electrochemical battery is correspondingly changed according to the change of low temperature and high temperature, and the electrochemical performance of the energy storage battery is recovered once the temperature of the energy storage battery is reduced to the room temperature due to the thermal reversibility of the temperature-sensitive gel, so that the system is considered as an active and effective intelligent overheating protection measure.
Disclosure of Invention
The invention aims to solve the problem that the existing electrochemical energy storage battery in the prior art cannot meet the requirement of quick intelligent reversible response to temperature change, and provides a reversible overheating self-protection water system electrolyte based on a poloxamer-polyacrylic acid graft copolymer, a preparation method and application thereof, wherein the poloxamer-polyacrylic acid graft copolymer is used as an additive, hydrogen bonds formed between hydrophilic groups in the molecules of the graft copolymer and water molecules of the electrolyte at the critical gel temperature (LCST) are expressed as a solution, and the electrochemical performance is basically not influenced; and (3) dehydration is carried out at high temperature (> LCST) to form a gel network structure, and the transmission of ions in the electrolyte is inhibited to close a conductive path, so that the quick intelligent response of the aqueous electrolyte to the temperature change is realized, and the ideal reversible overheat protection of normal-temperature working-temperature rise closing is achieved.
The technical scheme adopted for realizing the purpose of the invention is as follows:
a reversible overheating self-protection water-based electrolyte based on a poloxamer-polyacrylic acid graft copolymer is completely converted into a gel state at a temperature higher than 80 ℃ and is recovered into a sol state at a temperature lower than 78 ℃, and the reversible overheating self-protection water-based electrolyte is prepared by the following steps:
and 4, dissolving the grafted copolymer serving as a temperature-sensitive copolymer in an aqueous solution of an electrolyte to be uniformly dispersed to obtain a transparent homogeneous solution, wherein the addition amount of the temperature-sensitive copolymer is 0.2-0.4 times of the mass of the aqueous solution of the electrolyte.
In the above technical solution, the protective gas in step 2 is nitrogen, argon or helium.
In the technical scheme, the electrolyte is sulfuric acid, potassium hydroxide, lithium hydroxide, anhydrous sodium sulfate, lithium nitrate, sodium nitrate or potassium nitrate, and the concentration of the electrolyte is 0.5-6M.
In the technical scheme, the molecular weight of the poloxamer-F127 is 4400-8500.
In another aspect of the invention, the invention also comprises a preparation method of the reversible overheating self-protection water-based electrolyte based on the poloxamer-polyacrylic acid graft copolymer, which comprises the following steps:
and 4, dissolving the grafted copolymer serving as a temperature-sensitive copolymer in an aqueous solution of an electrolyte to be uniformly dispersed to obtain a transparent homogeneous solution, wherein the addition amount of the temperature-sensitive copolymer is 0.2-0.4 times of the mass of the aqueous solution of the electrolyte.
In the above technical solution, the protective gas in step 2 is nitrogen, argon or helium.
In the technical scheme, the electrolyte is sulfuric acid, potassium hydroxide, lithium hydroxide, anhydrous sodium sulfate, lithium nitrate, sodium nitrate or potassium nitrate, and the concentration of the electrolyte is 0.5-6M.
On the other hand, the invention also comprises the application of the poloxamer-polyacrylic acid graft copolymer as a temperature-sensitive copolymer in preparing the water system electrolyte with reversible overheat protection to form intelligent reversible protection of a low-temperature conduction-high-temperature gel cutting off passage, wherein the addition of the poloxamer-polyacrylic acid graft copolymer does not influence the conductivity of the water system electrolyte at the normal temperature of 20-25 ℃, and the conductivity of the water system electrolyte is 0 at the temperature higher than 80 ℃;
the poloxamer-polyacrylic acid graft copolymer is prepared by the following steps:
and 3, cleaning the product obtained in the step 2 by using n-hexane, dissolving the product by using hot absolute ethyl alcohol, filtering, refrigerating the filtrate, standing the filtrate to separate out a polymer, pouring out an upper-layer solvent, and drying the solvent under reduced pressure to obtain the poloxamer-polyacrylic acid graft copolymer.
In the technical scheme, the reversible overheat protection water system electrolyte is completely converted into a gel state at the temperature higher than 80 ℃ and is recovered into a sol state at the temperature lower than 78 ℃.
In the technical scheme, after the reversible overheat protection water system electrolyte is converted for 50-100 times between sol-gel two-phase states, the conductivity is not lost, and an intelligent reversible protection mechanism for cutting off a path by low-temperature conduction-high-temperature gel can be realized.
In the technical scheme, the aqueous electrolyte is an aqueous solution of a solute, namely sulfuric acid, potassium hydroxide, lithium hydroxide, anhydrous sodium sulfate, lithium nitrate, sodium nitrate or potassium nitrate, and the concentration of the solute is 0.5-6M.
In the technical scheme, the addition amount of the temperature-sensitive copolymer is 0.2-0.4 times of the mass of the aqueous electrolyte.
Compared with the prior art, the invention has the beneficial effects that:
1. the poloxamer-polyacrylic acid graft copolymer is used as an additive, the low-temperature sol-high-temperature gel intelligent reversible response performance of the aqueous solution of the poloxamer-polyacrylic acid graft copolymer is utilized to prepare the overheating reversible self-protection aqueous safety electrolyte, the thermal response temperature of the electrolyte can be adjusted, and the self-protection effect can be achieved at a plurality of temperatures by adjusting the molecular weight of the polymer and the monomer ratio.
2. The electrolyte has obvious and rapid response effect, can spontaneously recover after the temperature of the electrochemical energy storage device is reduced to a safe range, can still be repeatedly used after the sol-gel two-phase state is converted for 50-100 times, and can be rapidly repeated for many times.
Drawings
FIG. 1 is a photograph of the reversible overheat self-protecting aqueous electrolyte prepared in example 1 based on a poloxamer-polyacrylic acid graft copolymer at room temperature;
FIG. 2 is a photograph of an overheated self-protecting aqueous electrolyte prepared in example 2 at a high temperature;
FIG. 3 is a cyclic voltammogram of the reversible superheat self-protecting aqueous electrolyte based on the poloxamer-polyacrylic acid graft copolymer prepared in example 1 at room temperature;
FIG. 4 is the cyclic voltammogram of the reversible overheat self-protecting aqueous electrolyte based on the poloxamer-polyacrylic acid graft copolymer prepared in example 2 at high temperature.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
5ml of Acrylic Acid (AA) are taken and placed in a 100ml three-necked flask and are neutralized by slowly adding a suitable amount of 0.4ml of 10M sodium hydroxide solution. Adding a certain amount of poloxamer-F127 into a three-necked bottle, and adding an initiator Azobisisobutyronitrile (AIBN) after complete dissolution. Another 50ml of dodecane and 0.5g of poly (vinylpyrrolidone-co-hexadecene) copolymer (Antaron V216) were added to a three-necked flask and mixed well, and oxygen was removed by passing nitrogen gas for 3 hours. The reaction was heated in a water bath at 80 ℃ for 5h with continuous stirring and introduction of nitrogen. And (3) cleaning the obtained product by using n-hexane, dissolving the product by using hot absolute ethyl alcohol, filtering, refrigerating the filtrate, standing the filtrate to separate out a polymer, pouring out an upper layer solvent, and drying the solvent under reduced pressure to obtain the poloxamer-polyacrylic acid graft copolymer. And dissolving the graft copolymer in 0.5M sulfuric acid solution to obtain the reversible overheat protection water-based electrolyte based on the temperature-sensitive graft copolymer. A homogeneous solution that is flowable at 25 c as shown.
Example 2
5ml of Acrylic Acid (AA) are taken and placed in a 100ml three-necked flask and are neutralized by slowly adding a suitable amount of 0.4ml of 10M sodium hydroxide solution. Adding a certain amount of poloxamer-F127 into a three-necked bottle, and adding an initiator Azobisisobutyronitrile (AIBN) after complete dissolution. Another 50ml of dodecane and 0.5g of poly (vinylpyrrolidone-co-hexadecene) copolymer (Antaron V216) were added to a three-necked flask and mixed well, and oxygen was removed by passing nitrogen gas for 3 hours. The reaction was heated in a water bath at 80 ℃ for 5h with continuous stirring and introduction of nitrogen. And (3) cleaning the obtained product by using n-hexane, dissolving the product by using hot absolute ethyl alcohol, filtering, refrigerating the filtrate, standing the filtrate to separate out a polymer, pouring out an upper layer solvent, and drying the solvent under reduced pressure to obtain the poloxamer-polyacrylic acid graft copolymer. And dissolving the graft copolymer in 0.5M sulfuric acid solution to obtain the reversible overheat protection water-based electrolyte based on the temperature-sensitive graft copolymer. The electrolyte was heated in a water bath at 80 ℃ to undergo a sol-gel phase transition to form a milky white gel.
The reversible overheat protection aqueous electrolyte obtained in example 1 and example 2 is used in a supercapacitor, N-methylpyrrolidone is used as a solvent, and the weight ratio of activated carbon: conductive carbon black: the mass ratio of 8:1:1 of polyvinylidene fluoride is used for manufacturing a supercapacitor electrode, the capacitance of the electrode at scanning speeds of 10 mV/S, 50 mV/S and 100mV/S is tested by adopting cyclic voltammetry, the activated carbon electrode normally works at the room temperature of 20-25 ℃, the specific capacitance is 60-65F/g at the temperature of 2A/g, typical carbon capacitance characteristics are shown, and the capacitance is rapidly reduced to be close to 0 at the temperature of more than 80 ℃.
3-4, after the sol-gel phase cycle is changed for 50-100 times, the intelligent self-protection electrolyte still has excellent capacitance characteristics, the conductivity is hardly lost, and the intelligent reversible protection mechanism of the low-temperature conduction-high-temperature gel cut-off path can still be quickly realized.
And when the current density is 2A/g, testing the capacitance of the activated carbon electrode at the room temperature of 20-25 ℃ and at high temperature by adopting a charge-discharge curve. The carbon has excellent carbon capacitance performance at room temperature of 20-25 ℃ and 2A/g; whereas above 80 c its capacitance decreases rapidly, approaching 0. The impedance spectrum shows that the ion and electron transmission capability is rapidly reduced under the high temperature condition, and the resistance is obviously increased.
Example 3
5ml of Acrylic Acid (AA) are taken and placed in a 100ml three-necked flask and are neutralized by slowly adding a suitable amount of 0.4ml of 10M sodium hydroxide solution. Adding a certain amount of poloxamer-F127 into a three-necked bottle, and adding an initiator Azobisisobutyronitrile (AIBN) after complete dissolution. Another 50ml of dodecane and 0.5g of poly (vinylpyrrolidone-co-hexadecene) copolymer (Antaron V216) were added to a three-necked flask and mixed well, and oxygen was removed by passing nitrogen gas for 3 hours. The reaction was heated in a water bath at 80 ℃ for 5h with continuous stirring and introduction of nitrogen. And (3) cleaning the obtained product by using n-hexane, dissolving the product by using hot absolute ethyl alcohol, filtering, refrigerating the filtrate, standing the filtrate to separate out a polymer, pouring out an upper layer solvent, and drying the solvent under reduced pressure to obtain the poloxamer-polyacrylic acid graft copolymer. And dissolving the graft copolymer in 0.5M lithium hydroxide solution to obtain the reversible overheat protection water-based electrolyte based on the temperature-sensitive graft copolymer. The electrolyte is in a flowable state at room temperature, and is changed into milky gel after being heated to 75 ℃.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A reversible overheating self-protection water-based electrolyte based on a poloxamer-polyacrylic acid graft copolymer is characterized in that the reversible overheating self-protection water-based electrolyte is completely converted into a gel state at the temperature higher than 80 ℃ and is recovered into a sol state at the temperature lower than 78 ℃, and the reversible overheating self-protection water-based electrolyte is prepared by the following method:
step 1, slowly adding acrylic acid into 9-10M sodium hydroxide solution for neutralization so that the neutralization degree of acrylic acid monomer is 5.7-8%;
step 2, adding poloxamer-F127 with the same mass parts as the acrylic acid into the reaction system obtained in the step 1, adding azodiisobutyronitrile which is an initiator and is 0.01-0.05 times of the total mass of the acrylic acid and the poloxamer-F127 after completely dissolving, then adding dodecane and poly (vinyl pyrrolidone-co-hexadecene) copolymer which is 0.4-0.6 times of the total mass of the acrylic acid and the poloxamer-F127 after uniformly dispersing, introducing protective gas to remove oxygen for 2-5h, and carrying out water bath heating reaction for 4-6h at 70-90 ℃ under the protection of continuous protective gas;
step 3, cleaning the product obtained in the step 2 by using n-hexane, dissolving the product by using hot absolute ethyl alcohol, filtering, refrigerating the filtrate, standing the filtrate to separate out a polymer, pouring out an upper-layer solvent, and drying the solvent under reduced pressure to obtain the poloxamer-polyacrylic acid graft copolymer;
and 4, dissolving the graft copolymer serving as a temperature-sensitive copolymer in an aqueous solution of an electrolyte to be uniformly dispersed to obtain a transparent homogeneous solution, wherein the addition amount of the temperature-sensitive copolymer is 0.2-0.4 times of the mass of the aqueous solution of the electrolyte, the electrolyte is sulfuric acid, potassium hydroxide, lithium hydroxide, anhydrous sodium sulfate, lithium nitrate, sodium nitrate or potassium nitrate, and the concentration of the electrolyte is 0.5-6M.
2. The reversible overheat self-protecting aqueous electrolyte based on poloxamer-polyacrylic acid graft copolymer as claimed in claim 1, wherein the protecting gas in step 2 is nitrogen, argon or helium.
3. The reversible overheat self-protecting aqueous electrolyte based on poloxamer-polyacrylic acid graft copolymer as in claim 1, wherein the molecular weight of poloxamer-F127 in step 2 is 4400-8500.
4. A preparation method of a reversible overheating self-protection water system electrolyte based on a poloxamer-polyacrylic acid graft copolymer comprises the following steps:
step 1, slowly adding acrylic acid into 9-10M sodium hydroxide solution for neutralization so that the neutralization degree of acrylic acid monomer is 5.7-8%;
step 2, adding poloxamer-F127 with the same mass parts as the acrylic acid into the reaction system obtained in the step 1, adding azodiisobutyronitrile which is an initiator and is 0.01-0.05 times of the total mass of the acrylic acid and the poloxamer-F127 after completely dissolving, then adding dodecane and poly (vinyl pyrrolidone-co-hexadecene) copolymer which is 0.4-0.6 times of the total mass of the acrylic acid and the poloxamer-F127 after uniformly dispersing, introducing protective gas to remove oxygen for 2-5h, and carrying out water bath heating reaction for 4-6h at 70-90 ℃ under the protection of continuous protective gas;
step 3, cleaning the product obtained in the step 2 by using n-hexane, dissolving the product by using hot absolute ethyl alcohol, filtering, refrigerating the filtrate, standing the filtrate to separate out a polymer, pouring out an upper-layer solvent, and drying the solvent under reduced pressure to obtain the poloxamer-polyacrylic acid graft copolymer;
and 4, dissolving the graft copolymer serving as a temperature-sensitive copolymer in an aqueous solution of an electrolyte to be uniformly dispersed to obtain a transparent homogeneous solution, wherein the addition amount of the temperature-sensitive copolymer is 0.2-0.4 times of the mass of the aqueous solution of the electrolyte, the electrolyte is sulfuric acid, potassium hydroxide, lithium hydroxide, anhydrous sodium sulfate, lithium nitrate, sodium nitrate or potassium nitrate, and the concentration of the electrolyte is 0.5-6M.
5. The application of the poloxamer-polyacrylic acid graft copolymer as a temperature-sensitive copolymer in preparing a reversible overheat protection water system electrolyte is characterized in that the water system electrolyte forms intelligent reversible protection of a low-temperature conduction-high-temperature gel cutting off passage, the conductivity of the water system electrolyte is not influenced by the addition of the poloxamer-polyacrylic acid graft copolymer under the condition of normal temperature of 20-25 ℃, and the conductivity of the water system electrolyte is 0 under the condition of temperature higher than 80 ℃;
the poloxamer-polyacrylic acid graft copolymer is prepared by the following steps:
step 1, slowly adding acrylic acid into 9-10M sodium hydroxide solution for neutralization so that the neutralization degree of acrylic acid monomer is 5.7-8%;
step 2, adding poloxamer-F127 with the same mass parts as the acrylic acid into the reaction system obtained in the step 1, adding azodiisobutyronitrile which is an initiator and is 0.01-0.05 times of the total mass of the acrylic acid and the poloxamer-F127 after completely dissolving, then adding dodecane and poly (vinyl pyrrolidone-co-hexadecene) copolymer which is 0.4-0.6 times of the total mass of the acrylic acid and the poloxamer-F127 after uniformly dispersing, introducing protective gas to remove oxygen for 2-5h, and carrying out water bath heating reaction for 4-6h at 70-90 ℃ under the protection of continuous protective gas;
step 3, cleaning the product obtained in the step 2 by using n-hexane, dissolving the product by using hot absolute ethyl alcohol, filtering, refrigerating the filtrate, standing the filtrate to separate out a polymer, pouring out an upper-layer solvent, and drying the solvent under reduced pressure to obtain the poloxamer-polyacrylic acid graft copolymer;
the water system electrolyte is an aqueous solution of solute sulfuric acid, potassium hydroxide, lithium hydroxide, anhydrous sodium sulfate, lithium nitrate, sodium nitrate or potassium nitrate, and the concentration of the solute is 0.5-6M.
6. The use according to claim 5, wherein the reversible aqueous electrolyte is fully converted to a gel state at a temperature above 80 ℃ and reverts to a sol state at a temperature below 78 ℃.
7. The use according to claim 5, wherein the reversible overheat protection water-based electrolyte has no loss of conductivity after 50-100 times of transition between sol-gel two-phase states, and can still realize intelligent reversible protection mechanism of low-temperature conduction-high-temperature gel cut-off passage.
8. The use according to claim 5, wherein the amount of the temperature-sensitive copolymer added is 0.2 to 0.4 times the mass of the aqueous electrolyte.
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| "Properties of aqueous solutions and gels of poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide)-g-poly(acrylic acid)";Bromberg, L;《JOURNAL OF PHYSICAL CHEMISTRY B》;19981224;第102卷(第52期);第10736-10742页 * |
| "Thermoplastic Elastomer-Enabled Smart Electrolyte for Thermoresponsive Self-Protection of Electrochemical Energy Storage Devices";Shi, Ye；Ha, Heonjoo；Al-Sudani, Atheer；et al.;《ADVANCED MATERIALS》;20160928;第28卷(第36期);第7921页-第7923页，第7927页，附图1-2 * |
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Application publication date: 20200303 Assignee: Tianjin Hezheng measurement and Testing Co.,Ltd. Assignor: Beijing Legend Yousheng Culture Media Co.,Ltd. Contract record no.: X2023980040386 Denomination of invention: Reversible overheating self-protection aqueous electrolyte based on poloxamer polyacrylic acid graft copolymer and its preparation method and application Granted publication date: 20210713 License type: Common License Record date: 20230825 |