CN112133568A - Super capacitor capable of being used for airport ferry vehicle and manufacturing method of electrode of super capacitor - Google Patents
Super capacitor capable of being used for airport ferry vehicle and manufacturing method of electrode of super capacitor Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000243 solution Substances 0.000 claims abstract description 38
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 239000008367 deionised water Substances 0.000 claims abstract description 31
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004202 carbamide Substances 0.000 claims abstract description 20
- 239000011258 core-shell material Substances 0.000 claims abstract description 17
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000007772 electrode material Substances 0.000 claims abstract description 12
- DEPMYWCZAIMWCR-UHFFFAOYSA-N nickel ruthenium Chemical compound [Ni].[Ru] DEPMYWCZAIMWCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 238000007600 charging Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 25
- 239000003792 electrolyte Substances 0.000 claims description 12
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- 238000007599 discharging Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
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- 239000001913 cellulose Substances 0.000 claims description 3
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- 238000001914 filtration Methods 0.000 claims description 3
- 239000002070 nanowire Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 239000000047 product Substances 0.000 description 13
- 238000006479 redox reaction Methods 0.000 description 5
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 238000010521 absorption reaction Methods 0.000 description 1
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- 239000013543 active substance Substances 0.000 description 1
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L50/00—Electric propulsion with power supplied within the vehicle
- B60L50/40—Electric propulsion with power supplied within the vehicle using propulsion power supplied by capacitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/14—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors
- H01G11/18—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors against thermal overloads, e.g. heating, cooling or ventilating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/52—Separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
- H02J7/34—Parallel operation in networks using both storage and other dc sources, e.g. providing buffering
- H02J7/345—Parallel operation in networks using both storage and other dc sources, e.g. providing buffering using capacitors as storage or buffering devices
-
- 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
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Transportation (AREA)
- Mechanical Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a super capacitor for an airport ferry vehicle and a preparation method of an electrode thereof, wherein the preparation method of an electrode material comprises the following steps: (1) modifying the foamed nickel material by adopting a graphene solution to obtain a reduced graphene (rG) film(ii) a (2) Putting rG film into NiCl2、RuCl2Reacting in a mixed solution of urea in a reactor to obtain a Ni-Ru hydroxide film; (3) adding Ni-Ru hydroxide film into a container filled with deionized water and Na2Heating and reacting in the S container to obtain an rG/NRS film; (4) inserting rG/NRS film into NiCl-containing film2、RuCl2And heating the mixture and a deionized water ethanol solution of urea in a reactor for reaction to obtain the rG/NRS/NRO electrode material with the core-shell structure. The super capacitor disclosed by the invention keeps the basic advantages of the traditional super capacitor, is high in power density and high in charging speed, and can adapt to a low-temperature environment.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a super capacitor applicable to airport ferry vehicles and a preparation method of an electrode of the super capacitor.
Background
The airport ferry vehicle is used as an important device for airport transportation, and the performance of the airport ferry vehicle directly influences the ferry efficiency of an airport. Currently, airport ferry vehicles are typically electrically driven, taking into account the overall performance of the vehicle and the passenger riding experience. However, the traditional electrically-driven energy storage unit mainly uses a storage battery, and can support the normal running of the vehicle, but the problems of frequent charging, slow charging speed, poor low-temperature performance, high failure rate and the like also become factors for restricting the vehicle performance. With the continuous research on the super capacitor, vehicles using the super capacitor as an energy storage unit walk into the visual field of people.
The super capacitor is an electrochemical energy storage device depending on the ion adsorption/desorption on the surface of an electrode or the oxidation-reduction reaction in an electrode material, and is widely applied to the fields of automobiles, aviation, power grids and the like due to the characteristics of high power density, long cycle life and the like.
As an energy storage device, a supercapacitor is fabricated and assembled similarly to a battery, and includes two current collectors, an electrolyte solution, and a separator. The storage charge mechanism of the super capacitor is different, and the storage charge mechanism can be divided into a double electric layer super capacitor and a pseudo capacitor. The working principle of the double electric layer super capacitor is that charges are collected through a cross-section double electric layer formed by an electrode and electrolyte so as to realize energy storage, in the discharging process, due to the fact that no external voltage is applied, positive and negative charges accumulated on two poles in the electrolyte move into the solution to enable the solution to be neutral, and meanwhile, in order to keep the charges flat, the negative electrode releases electrons through an external circuit and returns to the positive electrode to form current. The pseudocapacitance is a capacitor formed by means of a chemical reaction, and is characterized in that an electrode active substance is firstly subjected to the deposition of an underpotential in a surface or a bulk phase and then is formed through a chemical adsorption desorption or an oxidation reduction reaction.
At present, there are also many designs and developments of new supercapacitors, for example: the patent CN206877845U of the chinese utility model proposes a super capacitor suitable for wind power generator; a super capacitor with a multilayer structure proposed in chinese utility model patent CN 204375578U; chinese patent CN106057492B discloses a super capacitor using gaseous carbon dioxide as an inner core. These supercapacitors have excellent electrochemical properties, but insufficient redox reactions occurring between the electrodes and the electrolyte become a bottleneck limiting the development of the supercapacitors.
Disclosure of Invention
In order to solve the problems, the invention provides a super capacitor for an airport ferry vehicle and a preparation method of an electrode of the super capacitor.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of an electrode material of a super capacitor for an airport ferry vehicle comprises the following steps:
(1) modifying the foamed nickel material by using a graphene solution to obtain a reduced graphene film;
(2) putting the reduced graphene film into NiCl2、RuCl2And urea, heating the mixed solution in a reactor to 100-130 ℃, and heating for 8-12 h to obtain a Ni-Ru hydroxylate film;
(3) adding Na dissolved in deionized water into Ni-Ru hydroxide film2Heating the solution S in a container to 150-180 ℃ for reaction for 4-8 h to obtain reduced graphene/NiRu2S4A film;
(4) reducing graphene/NiRu2S4Film insert containing NiCl2、RuCl2Heating the mixture and urea in deionized water ethanol solution to 150-170 ℃ in a reactor, reacting for 4-8 h, and drying to obtain the reduced graphene/NiRu with the core-shell structure2S4/NiRu2O4An electrode material.
Further, the step (1) specifically includes: inserting foamed nickel into graphene solution with the concentration of 10% -30%, heating to 100-130 ℃ in a reactor, and reacting for 5-10 h to obtain the reduced graphene film.
Further, NiCl2、RuCl2The mass ratio of the urea to the mixed solution of the urea and the urea is 1:1: 2-1: 1: 6; deionized water and Na2The ratio of S is 1: 4-1: 6; NiCl2、RuCl2The ratio of the urea to the deionized water ethanol solution is 1:1:2: 3-1: 1:6: 9.
Further, between the steps (1) and (2), the method also comprises the steps of cleaning and drying the reduced graphene film obtained in the step (1); between the steps (2) and (3), the method also comprises the steps of cleaning and drying the Ni-Ru hydroxylate film obtained in the step (2); in the step (4), the drying step specifically includes: the obtained product is heated to 280-320 ℃ at the speed of 5 ℃/min in the air environment, and is dried for 1-4 h.
The electrode material structure prepared by the preparation method comprises a flaky base material and a plurality of protrusions protruding out of the surface of the flaky base material, wherein the surface of the flaky base material is provided with a reduced graphene layer, the protrusions are of a core-shell structure, and the core part is NiRu2S4The shell part is NiRu2O4And a nanowire layer.
A super capacitor capable of being used for an airport ferry vehicle comprises an outer shell, a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode and the negative electrode are oppositely arranged, the diaphragm is arranged between the positive electrode and the negative electrode, and the positive electrode, the negative electrode, the diaphragm and the electrolyte are all packaged in the outer shell2S4/NiRu2O4An electrode material.
Further, the negative electrode comprises activated carbon, and the electrolyte comprises one or more of sodium sulfate, potassium chloride and potassium hydroxide.
Further, the diaphragm includes a substrate, a thermally conductive layer disposed outside the substrate, and an insulating layer disposed outside the thermally conductive layer.
Further, the substrate comprises one or more of a polyethylene diaphragm and a cellulose diaphragm, the heat conduction layer comprises one or more of graphene and carbon nanotubes, and the insulation layer comprises a porous ceramic material.
The electric energy charging and discharging control system comprises a super capacitor unit and a rectification inverter circuit, wherein the super capacitor unit comprises the super capacitor, the rectification inverter circuit comprises an inverter circuit formed by connecting three triode branches in parallel and a rectification circuit formed by connecting three diode branches in parallel, each triode branch comprises two triodes connected in series, each diode branch comprises two diodes connected in series, the three triode branches and the three diode branches are connected in parallel, the inverter circuit and the rectification circuit are arranged between a ferry vehicle motor and the super capacitor unit, three electrodes of the ferry vehicle motor are respectively connected to the diode branches of the rectification circuit and the three triode branches of the inverter circuit, two triodes VT1, VT1 and three triodes connected in series are connected between the super capacitor unit and the rectification inverter circuit, The device comprises a VT2, two serially connected diodes VD1 and VD2, an inductor L and a protection resistor R, wherein the two triodes VT1 and VT2 are connected in parallel with the two serially connected diodes VD1 and VD2, and the inductor L is serially connected with the protection resistor R; when the ferry vehicle normally runs, current emitted by a super capacitor is amplified by VT1, enters an inverter circuit through voltage stabilization and filtering of a resistor R and an inductor L, provides three alternating current power supplies for a motor through controlling triodes from T1 to T6, and when the ferry vehicle performs regenerative braking, the current generated by the regenerative braking passes through the rectifying circuit to convert the alternating current into direct current to supply power to the super capacitor.
Compared with the prior art, the invention has the remarkable advantages that:
(1) the invention reserves the basic advantages of the super capacitor, has high power density and fast charging speed, and can adapt to low temperature environment, etc.;
(2) the invention realizes charging and discharging by utilizing a series of reactions between the negative electrode and the electrolyte, and compared with a super capacitor with a double electric layer structure, the invention has more excellent performances;
(3) the heat conducting material on the diaphragm can timely discharge heat generated by the super capacitor during working; the insulating layer made of the ceramic material can effectively prevent the short circuit caused by the fact that the pole piece of the super capacitor falls off the membrane of the acne boat in the using process, and the porous structure of the insulating layer can enhance the liquid absorption capacity of the membrane and prolong the service life of the super capacitor;
(4) the conductive polymer of binary and ternary transition metal oxides and sulfides has the capability of generating redox reaction under the influence of multiple oxidation states and electrochemical activity, and the electrode made of the materials has better electrochemical property. In addition, the core-shell structure and the conductive substrate structure can solve the problems of low oxidation-reduction reaction speed on the surface of the traditional material, low ion diffusion process rate and the like.
Drawings
FIG. 1 is a positive electrode plate structure of rG/NRS/NRO core-shell structure material;
FIG. 2 is a constant current charge and discharge curve diagram of the super capacitor of the present invention;
FIG. 3 is an SEM scan of the positive electrode plate made of rG/NRS/NRO core-shell structure material;
FIG. 4 is a diagram of a power charging and discharging control system of the super capacitor;
FIG. 5 is a diagram of the structure of the super capacitor of the present invention;
FIG. 6 is a diagram of a supercapacitor separator according to the present invention.
Detailed Description
The technical solution of the present invention will be described clearly and completely with reference to the following embodiments, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in FIG. 5, the super capacitor provided by the invention comprises a shell 1, and a positive electrode plate 2, a diaphragm 3 and a positive electrode plate encapsulated in the shellAnd the negative electrode plate 4 is formed, and the electrolyte 5 is filled in the shell. The diaphragm is arranged between the positive electrode plate and the negative electrode plate, wherein the positive electrode plate is made of activated carbon, and the negative electrode plate is RuO2-CNTs-RuO2The electrolyte is made of sodium sulfate (Na)2SO4) One or more of potassium chloride (KCl), potassium hydroxide (KOH), etc. and the reaction equation during the operation of the super capacitor is as follows:
as shown in fig. 2, the constant current charging and discharging curve of the super capacitor of the present invention is, from left to right: 3A/g 5A/g 7A/g8A/g 9A/g 10A/g 15A/g 20A/g.
Further, as shown in fig. 6, the separator of the super capacitor proposed by the present invention is composed of three parts, i.e., a substrate 6, a heat conductive layer 7 outside the substrate, and an insulating layer 8 outside the heat conductive layer 7.
Further, the substrate of the diaphragm is formed by stacking one or more of a polyethylene diaphragm or a cellulose diaphragm. The heat conduction layer is formed by mutually overlapping one or more of Graphene (GO) or Carbon Nano Tubes (CNT). The insulating layer is composed of a porous ceramic material.
The manufacturing method of the electrode made of the rG/NRS/NRO core-shell structure material comprises the following steps:
(1) weighing a certain amount of foam nickel material, cleaning with deionized water, and drying to constant weight. The foam nickel is vertically inserted into the graphene solution, and is heated to 100-130 ℃ in a reactor with a polytetrafluoroethylene lining for reaction for 5-10 h.
(2) And cleaning the graphene modified foamed nickel with deionized water, drying for 2-5 h, and calling a product obtained after drying as a reduced graphene (rG) film.
(3) Respectively adding a certain amount of NiCl2、RuCl2And adding urea into deionized water, and magnetically stirring for 10-40 min to obtain a solution.
(4) And (3) vertically inserting the rG film obtained in the step (2) into the solution obtained in the step (3), heating the solution to 100-130 ℃ in a polytetrafluoroethylene-lined reactor, and heating the solution for 8-12 h to obtain the Ni-Ru hydroxide film, namely the reduced graphene/Ni-Ru hydroxide film (rG/NR-LDH).
(5) And (3) respectively washing the product obtained in the step (4) by deionized water and ethanol to remove impurities attached to the product, and drying the rG/NR-LDH membrane to constant weight at the temperature of 50-80 ℃.
(6) Adding rG/NR-LDH into deionized water containing 50-80 mL of deionized water and a certain amount of Na2Heating the mixture in a heating kettle of S to 150-180 ℃ for reaction for 4-8 h to obtain rG/NRS (reduced graphene/NiRu)2S4) A film.
(7) Inserting rG/NRS film into the film containing a certain amount of NiCl2、RuCl2And urea in deionized water ethanol solution, heating to 150-170 ℃ in a reactor, and reacting for 4-8 h to obtain the core-shell structure.
(8) The product obtained in the step (7) is heated to 280-320 ℃ at the speed of 5 ℃/min in the air environment, and is dried for 1-4 h to obtain rG/NRS/NRO (reduced graphene/NiRu) with a core-shell structure2S4/NiRu2O4) SEM scanning of the material, final product, is shown in figure 3.
Wherein:
in the step (1), the heating temperature of the heater is optimally 120 ℃, and the reaction time is optimally 8 h;
the drying time in the step (2) is most preferably 3 hours;
the optimal magnetic stirring time in the step (3) is 30 min;
in the step (4), the optimal heating temperature of the reactor is 120 ℃, and the optimal heating time is 10 hours;
the optimal drying temperature in the step (5) is 70 ℃;
in the step (6), the optimal volume of the deionized water is 60mL, the optimal heating temperature is 160 ℃, and the optimal reaction time is 6 h;
in the step (7), the optimal reaction heating temperature is 160 ℃, and the optimal reaction time is 6 hours;
in the step (8), the temperature is optimally 300 ℃, and the drying time is optimally 3 h.
The electrode material structure prepared by the preparation method comprises a flaky base material 1 and a plurality of protrusions protruding out of the surface of the flaky base material, wherein the surface of the flaky base material is provided with a reduction graphene layer 2, the protrusions are of a core-shell structure, and a core part 3 is NiRu2S4Material, shell part 4 is NiRu2O4Nanowires (NRO layer). Among them, the sheet-like base material is preferably a foamed nickel-based material.
An electric energy charging and discharging control system based on the super capacitor is shown in fig. 4, and an inverter circuit mainly composed of six triodes T1 and T2-T6 and a rectifier circuit composed of six diodes V1 and V2-V6 are arranged between a motor and the super capacitor. The electric energy charging and discharging control system comprises an inverter circuit formed by connecting three triode branches in parallel and a rectifier circuit formed by connecting three diode branches in parallel, wherein each triode branch comprises two triodes connected in series, each diode branch comprises two diodes connected in series, the three triode branches and the three diode branches are connected in parallel, and the inverter circuit and the rectifier circuit are arranged between the motor and the super capacitor; when the ferry vehicle normally operates, current emitted by a super capacitor is amplified by VT1, enters an inverter circuit through voltage stabilization and filtering of a resistor R and an inductor L, provides three alternating current power supplies for a motor through controlling triodes T1 to T6, and when the ferry vehicle performs regenerative braking, the current generated by the regenerative braking changes the alternating current into direct current to supply power to the super capacitor through a rectifying circuit consisting of six diodes V1 to V6. In the control circuit, three electrodes of the ferry vehicle motor are respectively connected to three branches of the rectification and inversion circuit, so that mutual charging and power supply between the motor and the super capacitor unit are realized. Two triodes VT1 and VT2 which are in charge of voltage stabilization are arranged between the super capacitor unit and the rectification inverter circuit, the two triodes are connected in parallel with two diodes which are in series, an inductor L is connected in series with a protection resistor R and is connected between the super capacitor and the rectification inverter circuit to play a role in protecting the whole circuit. The introduction of the bridge rectifier circuit can ensure that the electric energy generated in the regenerative braking process of the motor can be completely supplemented into the super capacitor unit. In addition, the voltage stabilizing part consisting of the VT1 and the VT2 and the protection part consisting of the resistor R can ensure that the current emitted in the super capacitor unit cannot damage the motor and the circuit, thereby ensuring the safety of the whole circuit.
Example 1
(1) Weighing a certain amount of foam nickel material, cleaning with deionized water, and drying to constant weight. The foamed nickel is vertically inserted into the graphene solution, and is heated to 100 ℃ in a reactor with a polytetrafluoroethylene lining for reaction for 5 hours.
(2) And (3) cleaning the graphene modified foamed nickel with deionized water, drying for 5h, and calling a product obtained after drying as an rG film.
(3) Respectively adding a certain amount of NiCl2、RuCl2And adding urea into deionized water, and magnetically stirring for 40min to obtain a solution.
(4) Vertically inserting the rG film obtained in the step (2) into the solution obtained in the step (3), heating the solution to 100 ℃ in a polytetrafluoroethylene-lined reactor, and heating the solution for 12 hours to obtain the Ni-Ru hydroxide film (rG/NR-LDH).
(5) Washing the product obtained in the step (4) with deionized water and ethanol respectively to remove impurities attached to the product, and drying the rG/NR-LDH membrane to a constant weight at 50 ℃.
(6) rG/NR-LDH was added to a solution containing 80mL of deionized water and a quantity of Na2And heating the mixture in a heating kettle of the S to 150-180 ℃ for reaction for 4 h. The rG/NRS film was obtained.
(7) Inserting rG/NRS film into the film containing a certain amount of NiCl2、RuCl2And urea in deionized water ethanol solution, heating to 150 ℃ in a reactor, and reacting for 4 h. Obtaining the core-shell structure.
(8) And (4) raising the product obtained in the step (7) to 320 ℃ at the speed of 5 ℃/min in the air environment, and drying for 1h to obtain the rG/NRS/NRO material with the core-shell structure.
Example 2
(1) Weighing a certain amount of foam nickel material, cleaning with deionized water, and drying to constant weight. The foamed nickel is vertically inserted into the graphene solution, and is heated to 110 ℃ in a polytetrafluoroethylene-lined reactor to react for 7 hours.
(2) And (3) cleaning the graphene modified foamed nickel with deionized water, drying for 4h, and calling a product obtained after drying as an rG film.
(3) Respectively adding a certain amount of NiCl2、RuCl2And adding urea into deionized water, and magnetically stirring for 20min to obtain a solution.
(4) And (3) vertically inserting the rG film obtained in the step (2) into the solution obtained in the step (3), heating the solution to 130 ℃ in a polytetrafluoroethylene-lined reactor, and heating the solution for 10 hours to obtain the Ni-Ru hydroxide film (rG/NR-LDH).
(5) Washing the product obtained in the step (4) with deionized water and ethanol respectively to remove impurities attached to the product, and drying the rG/NR-LDH membrane to a constant weight at 60 ℃.
(6) Adding rG/NR-LDH into deionized water containing 50-80 mL of deionized water and a certain amount of Na2And heating the mixture in a heating kettle of the S to 150-180 ℃ for reaction for 7 h. The rG/NRS film was obtained.
(7) Inserting rG/NRS film into the film containing a certain amount of NiCl2、RuCl2And urea in deionized water ethanol solution, heating to 150 ℃ in a reactor, and reacting for 7 h. Obtaining the core-shell structure.
(8) And (4) raising the product obtained in the step (7) to 320 ℃ at the speed of 5 ℃/min in the air environment, and drying for 3h to obtain the rG/NRS/NRO material with the core-shell structure.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of an electrode material of a super capacitor for an airport ferry vehicle is characterized by comprising the following steps:
(1) modifying the foamed nickel material by using a graphene solution to obtain a reduced graphene film;
(2) putting the reduced graphene film into NiCl2、RuCl2And urea, heating the mixed solution in a reactor to 100-130 ℃, and heating for 8-12 h to obtain a Ni-Ru hydroxylate film;
(3) adding Na dissolved in deionized water into Ni-Ru hydroxide film2Heating the solution S in a container to 150-180 ℃ for reaction for 4-8 h to obtain reduced graphene/NiRu2S4A film;
(4) reducing graphene/NiRu2S4Film insert containing NiCl2、RuCl2Heating the mixture and urea in deionized water ethanol solution to 150-170 ℃ in a reactor, reacting for 4-8 h, and drying to obtain the reduced graphene/NiRu with the core-shell structure2S4/NiRu2O4An electrode material.
2. The preparation method according to claim 1, wherein the step (1) specifically comprises: inserting foamed nickel into graphene solution with the concentration of 10% -30%, heating to 100-130 ℃ in a reactor, and reacting for 5-10 h to obtain the reduced graphene film.
3. The process according to claim 1, whereinCharacterized in that NiCl2、RuCl2The mass ratio of the urea to the mixed solution of the urea and the urea is 1:1: 2-1: 1: 6; deionized water and Na2The ratio of S is 1: 4-1: 6; NiCl2、RuCl2The ratio of the urea to the deionized water ethanol solution is 1:1:2: 3-1: 1:6: 9.
4. The preparation method according to claim 1, wherein between the steps (1) and (2), the method further comprises the steps of cleaning and drying the reduced graphene film obtained in the step (1); between the steps (2) and (3), the method also comprises the steps of cleaning and drying the Ni-Ru hydroxylate film obtained in the step (2); in the step (4), the drying step specifically includes: the obtained product is heated to 280-320 ℃ at the speed of 5 ℃/min in the air environment, and is dried for 1-4 h.
5. The electrode material structure prepared by the preparation method of any one of claims 1 to 4, which is characterized by comprising a flaky base material and a plurality of protrusions protruding out of the surface of the flaky base material, wherein the surface of the flaky base material is provided with a reduced graphene layer, the protrusions are of a core-shell structure, and the core part is NiRu2S4The shell part is NiRu2O4And a nanowire layer.
6. A super capacitor capable of being used for an airport ferry vehicle comprises an outer shell, a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode and the negative electrode are oppositely arranged, the diaphragm is arranged between the positive electrode and the negative electrode, and the positive electrode, the negative electrode, the diaphragm and the electrolyte are all packaged in the outer shell, and the super capacitor is characterized in that the positive electrode adopts reduced graphene/NiRu with a core-shell structure prepared by the preparation method of any one of claims 1 to 42S4/NiRu2O4An electrode material.
7. The supercapacitor of claim 6, wherein the negative electrode comprises activated carbon, and the electrolyte comprises one or more of sodium sulfate, potassium chloride, and potassium hydroxide.
8. The supercapacitor of claim 6, wherein the separator comprises a substrate, a thermally conductive layer disposed outside the substrate, and an insulating layer disposed outside the thermally conductive layer.
9. The supercapacitor of claim 8, wherein the substrate comprises one or more of a polyethylene membrane and a cellulose membrane, the thermally conductive layer comprises one or more of graphene and carbon nanotubes, and the insulating layer comprises a porous ceramic material.
10. An electric energy charging and discharging control system of a super capacitor applicable to an airport ferry vehicle is characterized by comprising a super capacitor unit and a rectification inverter circuit, wherein the super capacitor unit comprises the super capacitor as claimed in any one of claims 6 to 9, the rectification inverter circuit comprises an inverter circuit formed by three triode branches connected in parallel and a rectification circuit formed by three diode branches connected in parallel, each triode branch comprises two triodes connected in series, each diode branch comprises two diodes connected in series, the three triode branches and the three diode branches are connected in parallel, the inverter circuit and the rectification circuit are arranged between a ferry vehicle motor and the super capacitor unit, three electrodes of the ferry vehicle motor are respectively connected to the diode branches of the rectification circuit and the three triode branches of the inverter circuit, and two triodes VT1 connected in series are connected between the super capacitor unit and the rectification inverter circuit, The device comprises a VT2, two serially connected diodes VD1 and VD2, an inductor L and a protection resistor R, wherein the two triodes VT1 and VT2 are connected in parallel with the two serially connected diodes VD1 and VD2, and the inductor L is serially connected with the protection resistor R; when the ferry vehicle normally runs, current emitted by a super capacitor is amplified by VT1, enters an inverter circuit through voltage stabilization and filtering of a resistor R and an inductor L, provides three alternating current power supplies for a motor through controlling triodes from T1 to T6, and when the ferry vehicle performs regenerative braking, the current generated by the regenerative braking passes through the rectifying circuit to convert the alternating current into direct current to supply power to the super capacitor.
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