WO2017084252A1 - Abuse capacitor having wide temperature range, and manufacturing method therefor - Google Patents

Abstract

Disclosed in the present invention an abuse capacitor having a wide temperature range, and a manufacturing method therefor. A pole piece of the abuse super capacitor is prepared from a current collector containing carbon or a high conducting polymer and a mesoporous carbon material. A membrane of the abuse super capacitor is a hydrophilic membrane. An electrolyte of the abuse super capacitor is an ionic liquid electrolyte or a mixed electrolyte of an ionic liquid and an organic solvent. The stable working voltage range of the super capacitor is 0 V to 10 V, and the stable working temperature range of the super capacitor is minus 90 degrees centigrade to 300 degrees centigrade; the ionic liquid electrolyte is nontoxic, free of pollution and free of combustion; sources of available membranes are wide in variety; and the abuse capacitor is a safe and environmentally-friendly abuse super capacitor having a high energy density in a real sense.

Description

Wide temperature interval abuseable capacitor and manufacturing method thereof Technical field:

The invention relates to an abuseable supercapacitor and a manufacturing method thereof, and belongs to the field of electrochemistry.

Background technique:

Supercapacitors are new types of green energy storage devices that have developed rapidly in recent years. They have fast charge and discharge characteristics, and the power density is several tens or even hundreds of times that of ordinary batteries. In addition, its cycle life is long, the number of charge and discharge cycles can reach 100,000 times, which is hundreds or even thousands of times of ordinary batteries. Based on this unique performance of supercapacitors, some countries including China have launched research and development projects using supercapacitors as power sources for electric vehicles and tuned energy storage for intermittent renewable energy such as wind and solar. However, supercapacitors also have weak operating voltages (lower energy density), poor safety at high temperatures, and large capacity attenuation. The commercial organic capacitor has a low boiling point, low decomposition voltage, and toxicity, and has a large safety and environmental protection hazard, and cannot operate stably at more than 55 degrees Celsius, resulting in inconvenience in use. For example, in the summer, the super-capacity bus that runs in Shanghai often has a “high temperature error alarm”, which increases operating costs. How to further upgrade the material system, improve the working voltage (specific energy) and safety and environmental performance of supercapacitors is a key issue to be solved in the development of supercapacitors and industrial development.

Summary of the invention:

SUMMARY OF THE INVENTION The object of the present invention is to overcome the above deficiencies and to provide a wide temperature range abusable capacitor which is safe, environmentally friendly, high energy density, and abuseable, and a method of manufacturing the same.

The object of the present invention is achieved by the following technical solutions: a wide temperature range abuseable capacitor, the pole piece of the abuseable supercapacitor being composed of a carbon-containing or high-conducting polymer current collector and a mesoporous carbon material; The separator of the supercapacitor is a hydrophilic separator; the electrolyte of the abuseable supercapacitor is an ionic liquid electrolyte or a mixed electrolyte of an ionic liquid and an organic solvent; the abuseable supercapacitor has a stable operating voltage ranging from 0 to 10V, The temperature range for stable operation is -90-300 °C.

A further improvement of the present invention is that, in the carbon-containing or high-conductivity polymer-containing current collector, the carbon-containing current collector is a current collector having high-conductivity carbon inside or on the surface, and the high-conductivity polymer-containing current collector is a highly conductive polymer on the surface. Current collector.

A further improvement of the present invention is that the mesoporous carbon material is a graded porous three-dimensional carbon material comprising micropores, mesopores and macropores, and the pores of the macropores and mesopores are from 1 to 50 nm.

A further improvement of the present invention is that the mesoporous structure is a three-dimensional structure in which an extremely thin graphene-like carbon layer is deposited.

A further improvement of the present invention is that the rich mesoporous carbon material has a BET specific surface area of 3000-4000 m ² /g, and the pore volume of the large micropores and mesopores accounts for more than 80% of the total pore volume, and the pore size distribution is narrow, concentrated in 1 -5 nm with an average pore diameter of 2-4 nm.

A further improvement of the present invention is that the mesoporous carbon material is fixed to carbon or high conductivity by self-assembly or adhesive. On the electropolymer collector, the binder is an emulsion type large colloidal aqueous binder.

A further improvement of the present invention is that the hydrophilic separator is a tailings slag and a fly ash-based porous membrane, porous alumina, porous silica, or a hydrophilic membrane modified by a surface, and the polymer is polypropylene or polyethylene. .

A further improvement of the present invention is that the ionic liquid electrolyte is a mixed ionic liquid electrolyte of one or more of imidazoles, pyridines, pyrrolidines, quaternary ammoniums, morpholines, and piperidines.

A further improvement of the present invention is that in the mixed electrolyte of the ionic liquid electrolyte and the organic solvent, the ionic liquid electrolyte is one of an imidazole, a pyridine, a pyrrolidine, a quaternary ammonium, a morpholine or a piperidine. One or more mixed ionic liquid electrolytes, the organic solvent being polycarbonate or butyrolactone.

A further improvement of the present invention is: preparing a slurry by mixing and adding a mesoporous carbon material, an aqueous binder and a conductive agent in a mass ratio of 75-90%: 3-15%: 3-15%; coating the slurry It is coated on a carbon-containing or highly conductive polymer current collector, dried and compacted to form a pole piece; an ionic liquid electrolyte and a hydrophilic separator are used to form a soft-pack capacitor.

A further improvement of the invention is that the aqueous binder is styrene butadiene rubber, PTFE, CMC or polyacrylic acid.

A further improvement of the present invention is that the conductive agent is conductive carbon black, Super-P, nano carbon fiber, carbon nanotube, graphene or conductive polymer.

Compared with the prior art, the invention has the following advantages: the invention proposes an abuseable supercapacitor and a manufacturing method thereof, the stable working voltage range of the supercapacitor is 0-10V, and the stable working temperature range is -90- 300 ° C, and ionic liquid electrolyte is non-toxic, non-polluting, non-combustion, the wide variety of available diaphragm types, is a true sense of safety, environmental protection, high energy density, abuseable supercapacitors.

BRIEF DESCRIPTION OF THE DRAWINGS:

Figure 1 shows the charge and discharge curves of the capacitor in Example 1 at 25 °C.

Figure 2 shows the performance of the capacitor in Example 1 at 1500 cycles at 25 °C.

Fig. 3 shows the charge and discharge curves of the capacitor in Example 2 at 150 °C.

Figure 4 shows the performance of the capacitor in Example 2 at 1500 cycles at 150 °C.

Figure 5 shows the charge and discharge curves of the capacitor in Example 3 at -40 °C.

Figure 6 shows the performance of the capacitor in Example 4 at 10,000 °C for 10,000 cycles.

detailed description:

The present invention will be clearly and completely described in the following embodiments of the present invention. It is obvious that the described embodiments are a part of the embodiments of the present invention, and not all of them. An embodiment. The elements and features described in one embodiment of the invention may be combined with the elements and features illustrated in one or more other embodiments. It should be noted that for the sake of clarity, the description omits Representations and descriptions of components and processes that are not relevant to those of ordinary skill in the art to which the present invention pertains. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without departing from the inventive scope are the scope of the present invention.

The capacitor can work stably at 0-10V, and the stable operating temperature range of the capacitor is -90-300 °C. Again, the capacitor will not burn under a series of extreme conditions such as needling, extrusion, high temperature and falling. Explosion, and the electrolyte is non-toxic and non-polluting. It is a safe, environmentally friendly, high energy density, misusable supercapacitor.

The pole piece of the abuseable supercapacitor is composed of a carbon-containing or highly conductive polymer current collector and a mesoporous carbon material. The membrane that can abuse the supercapacitor is a hydrophilic membrane. The electrolyte that can abuse the supercapacitor is an ionic liquid electrolyte or a mixed electrolyte of an ionic liquid and an organic solvent. The abuseable supercapacitor has a stable operating voltage range of 0-10V and a stable operating temperature range of -90-300 °C.

The carbon-containing current collector is a current collector having high conductive carbon inside or on the surface. The high-conductivity carbon protects the current collector by high-temperature carburizing or low-temperature carbon coating to prevent the ionic liquid electrolyte from corroding the surface of the current collector under electrochemical conditions during charging and discharging. The high-conductivity polymer-containing current collector is a current collector with a highly conductive polymer on the surface, which protects the current collector and prevents the ionic liquid electrolyte from corroding the surface of the current collector under electrochemical conditions during charging and discharging. Carbon-containing or highly conductive polymers act to reduce the internal resistance of the capacitor.

The carbon material is a graded porous three-dimensional carbon material containing a small amount of micropores, a large number of mesopores and a small number of macropores. The mesoporous structure is a three-dimensional structure formed by stacking extremely thin graphene-like carbon layers. The carbon material has a BET specific surface area of 3000-4000 m ² /g, and the pore volume of the large pores and mesopores (pore size of 1-50 nm) accounts for more than 80% of the total pore volume, and the pore size distribution is narrow, concentrated at 1-5 nm. Its average pore diameter is 2-4 nm. The larger mesopores can facilitate the passage of large ionic liquid electrolyte ions, ensuring that the carbon material still has a good kinetic effect at low temperatures.

The carbon material is fixed on the carbon-containing current collector by self-assembly or adhesive, and the adhesive is an emulsion-type large-size aqueous binder. The colloidal particles of the adhesive should be sufficiently large (greater than 50 nm) to avoid clogging the pores of the mesoporous carbon material and to withstand high pressures and high temperatures.

The hydrophilic separator is a tailings slag and a fly ash-based porous film, porous alumina, porous silica, or a surface hydrophilically modified polymer (polypropylene, polyethylene) separator.

The ionic liquid electrolyte is a mixed ionic liquid electrolyte of one or more of imidazoles, pyridines, pyrrolidines, quaternary ammoniums, morpholines, and piperidines. The decomposition voltage can reach 10V, the chemically stable temperature can reach 400 °C, and the solidification temperature can reach -90 °C. In order to increase the ionic conductivity of the ionic liquid and lower the viscosity of the electrolyte, polycarbonate or butyrolactone may be mixed with the ionic liquid.

The technical solution of the present invention is further described below in conjunction with specific embodiments:

Example 1

The rich mesoporous carbon material, styrene-butadiene rubber, CMC and conductive carbon black are mixed with water at a mass ratio of 80:10:3:7 to prepare a slurry, which is coated on a carbon coated aluminum foil, dried and compacted to form a pole. sheet. The EMIMBF _{4 was} used as the electrolyte, and the porous alumina film was used as the separator to form a soft-pack capacitor. The capacitor obtained at 25 ° C and 0-3.8V, the test charge and discharge curve shown in Figure 1, the capacitor has a specific capacity of 205F / g, cycle 10000 ring capacity attenuation of 5%, as shown in Figure 2.

Example 2

The rich mesoporous carbon material, PTFE and conductive carbon black were mixed with water at a mass ratio of 85:10:5 to prepare a slurry, which was coated on graphene paper, dried and compacted to form a pole piece. A BBMBF _{4 was} used as the electrolyte, and a porous alumina film was used as the separator to form a soft-pack capacitor. The charge-discharge curve obtained by testing the capacitor at 150 ° C is shown in Fig. 3. The specific capacity of the capacitor is 350 F/g, and the capacity of the cycle is 10000 cycles is 10%, as shown in Fig. 4.

Example 3

The rich mesoporous carbon material, the water-based PVDF, CMC, and the conductive carbon black were mixed with water at a mass ratio of 80:10:3:7 to prepare a slurry, which was coated on a nickel mesh, dried, and compacted to form a pole piece. A mixed electrolyte of EMIMBF ₄ and butyrolactone was used as an electrolyte, and a porous silicon oxide film was used as a separator to form a soft-pack capacitor. The charge-discharge curve obtained by testing the capacitor at -40 ° C is shown in Fig. 5. The specific capacity of the capacitor is 140 F/g, and the capacity of the cycle of 10000 cycles is not attenuated, as shown in Fig. 6.

Example 4

The rich mesoporous carbon material, styrene-butadiene rubber, CMC and conductive carbon black are mixed with water to prepare a slurry according to a mass ratio of 80:10:5:5, and the slurry is coated on carbon coated stainless steel, dried and compacted to form a pole. sheet. An electrolyte solution using EMIM TFSI is used as an electrolyte, and a PP modified film is used as a separator to form a soft-pack capacitor. The capacitor measured a specific capacity of 160 F/g at 60 ° C and a 4% attenuation of the cycle of 10,000 cycles.

It is to be understood that the present invention and its advantages are described in detail, and it is understood that various changes, substitutions and changes can be made without departing from the spirit and scope of the invention as defined by the appended claims. Transform. Further, the scope of the invention is not limited to the specific embodiments of the processes, devices, means, methods and steps described in the specification. It will be readily apparent to those skilled in the art from this disclosure that the present invention can be used in accordance with the present invention to perform substantially the same functions as the corresponding embodiments described herein or to obtain substantially the same results as the present and future Process, equipment, means, method or step to be developed. Therefore, the appended claims are intended to cover such a process, apparatus, means, methods or steps.

Claims (10)

1. A wide temperature range abuseable capacitor, characterized in that the pole piece of the abuseable capacitor is composed of a carbon-containing or highly conductive polymer current collector and a mesoporous carbon material; the membrane of the abuseable capacitor is a hydrophilic membrane The electrolyte that can abuse the capacitor is an ionic liquid electrolyte or a mixed electrolyte of an ionic liquid and an organic solvent; the abuseable capacitor has a stable operating voltage ranging from 0 to 10 V, and the stable working temperature range is -90 to 300 ° C. .
2. A wide temperature interval abuseable capacitor according to claim 1, wherein in said carbon-containing or high-conductivity polymer current collector, said carbon-containing current collector is a set of highly conductive carbon inside or on the surface. The fluid, the high-conducting polymer-containing current collector is a current collector having a highly conductive polymer on its surface.
3. A wide temperature interval abuseable capacitor according to claim 1, wherein said rich mesoporous carbon material is a graded porous three-dimensional carbon material comprising micropores, mesopores and macropores. The pores of the large pores and mesopores are 1-50 nm.
4. A wide temperature interval abuseable capacitor according to claim 3, wherein the mesoporous structure is a three-dimensional structure formed by stacking an extremely thin graphene-like carbon layer.
5. A wide temperature interval abuseable capacitor according to claim 3 or 4, wherein the rich mesoporous carbon material has a BET specific surface area of 3000-4000 m ² /g, and the pores of the large micropores and mesopores It accounts for more than 80% of the total pore volume, and has a narrow pore size distribution, concentrated at 1-5 nm, and its average pore diameter is 2-4 nm.
6. The wide temperature interval abuseable capacitor according to claim 1, wherein the rich mesoporous carbon material is fixed on the carbon-containing or high-conducting polymer current collector by self-assembly or adhesive. The binder is an emulsion type large colloidal aqueous binder.
7. A wide temperature interval abuseable capacitor according to claim 1, wherein said hydrophilic separator is a tailing slag and a fly ash based porous membrane, porous alumina, porous silica, or surface hydrophilic Modified polymer separator, the polymer is polypropylene, polyethylene.
8. The wide temperature interval abuseable capacitor according to claim 1, wherein the ionic liquid electrolyte is one of an imidazole, a pyridine, a pyrrolidine, a quaternary ammonium, a morpholine or a piperidine. One or more mixed ionic liquid electrolytes; in the mixed electrolyte of the ionic liquid electrolyte and the organic solvent, the ionic liquid electrolyte is imidazole, pyridine, pyrrolidine, quaternary ammonium, morpholine A mixed ionic liquid electrolyte of one or more of piperidines, the organic solvent being polycarbonate or butyrolactone.
9. A method for manufacturing a wide temperature interval abuseable capacitor, characterized in that a rich mesoporous carbon material, an aqueous binder and a conductive agent are mixed and added in a mass ratio of 75-90%: 3-15%: 3-15%. Preparing a slurry; coating the slurry Drying and compacting on a carbon-containing or high-conducting polymer current collector to form a pole piece; using an ionic liquid electrolyte and a hydrophilic separator to form a soft-pack capacitor.
10. A method for manufacturing a wide temperature interval abuseable capacitor according to claim 9, wherein the aqueous adhesive is styrene butadiene rubber, PTFE, CMC or polyacrylic acid, and the conductive agent is conductive carbon black, Super-P, nano carbon fiber, Carbon nanotubes, graphene or conductive polymers.

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