Double-hybrid electrochemical capacitor and preparation method thereof

Abstract

The invention belongs to but is not limited to the technical field of electrochemical containers, and particularly relates to a double-hybrid electrochemical capacitor and a preparation method thereof, the double-hybrid electrochemical capacitor comprises a hybrid positive electrode and a hybrid negative electrode, and the hybrid positive electrode and the hybrid negative electrode simultaneously comprise two energy storage mechanism active materials of double-electric-layer electrostatic energy storage and Faraday quasi-capacitance energy storage. An active material of the double-electrode-layer electrostatic energy storage mechanism is open-pore activated carbon, the port aperture of the open-pore activated carbon is smaller than or equal to 0.2 nm, and the pore web size is 1-1.5 nm. In the manufacturing process of the capacitor, the electrochemical principle is utilized, the positive electrode and the negative electrode are subjected to electrochemical hybridization design at the same time, on one hand, the upper limit of the working voltage of the electrochemical capacitor is increased to 4.4 V from 2.7 V through introduction of a Faraday quasi-capacitor energy storage mechanism active material at the positive electrode end, and therefore effective energy storage of the capacitor is greatly enhanced; the volume energy density is greatly improved; and on the other hand, high-power output characteristic matching of the system is simultaneously introduced and maintained at the positive electrode end and the negative electrode end through a double-electric-layer electrostatic energy storage mechanism active material.

Description

Technical Field

[0001] The present invention belongs to but is not limited to the technical field of electrochemical containers, and in particular relates to a dual hybrid electrochemical capacitor and a preparation method thereof. Background Art

[0002] Electrochemical capacitor (EC), also known as supercapacitor or ultracapacitor, is a new type of energy storage device that has attracted people's attention in recent years. It uses the pseudo-capacitance principle formed by spontaneous separation of charges at the interface (usually solid / liquid interface) or rapid Faraday reaction to quickly store energy. It has the high specific energy and high power characteristics of secondary chemical batteries and traditional capacitors. It is also a highly safe "three highs" electrochemical energy storage device, which is widely used in consumer electronics, transportation, engineering machinery, new energy, national defense and military industries.

[0003] Carbon-carbon electrochemical capacitors are the earliest electrochemical capacitors to achieve commercial success. They use a symmetrical electrode structure design, that is, both the positive and negative electrodes use activated carbon (AC) with a large specific surface area as the main active material, and rely on the solid-liquid interface formed with the electrolyte during operation to quickly separate the charge, thereby achieving rapid energy storage, forming the so-called "symmetrical electrochemical double layer capacitor (EDLC)", with a volume power density of more than 10,000 W / L and a cycle life of 500,000 to 1 million times, but a volume energy density of only about 10 Wh / L. It is precisely because of the limitation of the system's volume energy density that it cannot be used on a large scale in some fields, such as mobile phones, laptops, drones, and weapons and equipment.

[0004] Hybrid electrochemical capacitors (also called "asymmetric electrochemical capacitors") provide a new idea for improving the volume density of electrochemical capacitors. By electrochemically hybridizing one of the positive and negative electrodes (i.e., introducing non-double-layer electrostatic energy storage materials, usually fast Faraday pseudocapacitor energy storage materials such as RuO2, polyaniline and polythiophene), the overall energy storage density can be improved. In 2001, Amatucci et al. first constructed a hybrid electrochemical capacitor with activated carbon as the positive electrode and nano-Li4Ti5O12 as the negative electrode, with a volume energy density of 18Wh / kg (about 20Wh / L) [Amatucci GG, Badway F, DU Pasquier A, et al. An asymmetric hybrid nonaqueous energy storage cell. Journal of the Electrochemical Society, 2001, 148 (8): A930-A939], the performance was improved by more than 1 times, setting a precedent for negative electrode electrochemical hybridization. In 2004, Pasquier et al. further improved the volume energy density of the capacitor by introducing LiCo2 into the positive electrode, opening the precedent for electrochemical hybridization of the positive electrode [Pasquier AD, Plitz I, Gural J, et al. Power-ion battery: bridging the gap between Li-ion and supercapacitor chemistries. Journal of Power Sources, 2004, 136(1): 160-170].

[0005] In view of the above analysis, the technical problems that urgently need to be solved in the existing technology are: the current hybrid technology only focuses on one pole (positive or negative), resulting in the overall volume energy density of the capacitor being limited to 50-100Wh / L, which is still far behind the volume energy density of lithium-ion batteries (300-600Wh / L). Summary of the invention

[0006] In response to the problems existing in the prior art, the present invention provides a dual hybrid electrochemical capacitor, which can greatly increase the volume energy density of the system to more than 420Wh / L, which is significantly higher than lithium iron phosphate batteries (300Wh / L) and reaches 70% of the level of ternary lithium-ion batteries (600Wh / L), and has obvious market competitiveness.

[0007] The present invention is achieved in this way: a dual hybrid electrochemical capacitor includes a hybrid positive electrode and a hybrid negative electrode, and the hybrid positive electrode and the hybrid negative electrode simultaneously contain two energy storage mechanism active materials of double electric layer electrostatic energy storage and Faraday pseudocapacitive energy storage.

[0008] Furthermore, the active material of the double-layer electrostatic energy storage mechanism is open-pore activated carbon. Preferably, the port pore diameter of the open-pore activated carbon is ≤0.2 nm, and the pore size is 1-1.5 nm.

[0009] Furthermore, the active material of the Faraday pseudo-capacitive energy storage mechanism is one of manganese-based binary lithium oxide and pre-lithiated carbon.

[0010] Further, the manganese-based binary lithium oxide is distributed in the positive electrode, preferably an iron-manganese-based lithium oxide, and the mass ratio of iron to manganese is 1:0.5-1:2, and more preferably the mass ratio of iron to manganese is 1:1;

[0011] Furthermore, the pre-lithiated carbon is preferably pre-lithiated lignin lithium-intercalated carbon, which is distributed in the negative electrode.

[0012] Another object of the present invention is to provide a method for preparing the dual hybrid electrochemical capacitor, comprising the following steps:

[0013] S1, mechanically mixing the open-pore activated carbon, manganese-based binary lithium oxide, conductive agent and binder in a dry mixer for 10-30 minutes, adding the mixture into a solvent containing dimethylpyrrolidone (NMP) at one time, and stirring at high speed for 90-120 minutes to form a viscous slurry;

[0014] S2, uniformly coating the slurry on both sides of the aluminum foil current collector, and vacuum drying at 120° C. to form a hybrid electrochemical capacitor positive electrode;

[0015] S3, mechanically mixing the open-pore activated carbon, pre-lithiated carbon, conductive agent and binder in a dry mixer for 10-30 minutes, adding the mixture into a solvent containing dimethylpyrrolidone (NMP) at one time, and stirring at high speed for 90-120 minutes to form a viscous slurry;

[0016] S4, uniformly coating the slurry on both sides of the copper current collector, and vacuum drying at 105° C. to form a hybrid electrochemical capacitor negative electrode;

[0017] S5, rolling the loaded positive electrode and the loaded negative electrode obtained in S2 and S4 into a designed thickness on a Cr plating roller press, and cutting them into the positive electrode and the negative electrode of the dual hybrid electrochemical capacitor of the present invention;

[0018] S6, winding or stacking the electrodes obtained in S5 in the order of positive electrode, separator, and negative electrode into a bare cell, and encapsulating them in shells of different materials to form a dual hybrid electrochemical capacitor.

[0019] Furthermore, the shell is one of an aluminum-plastic film, an aluminum shell or a steel shell.

[0020] In combination with the above technical solutions and the technical problems solved, the advantages and positive effects of the technical solutions to be protected by the present invention are as follows:

[0021] First, in the process of manufacturing capacitors, the present invention utilizes electrochemical principles to simultaneously perform electrochemical hybrid design on the positive and negative electrodes. On the one hand, by introducing Faraday pseudo-capacitive energy storage mechanism active materials at the positive terminal, the upper limit of the working voltage of the electrochemical capacitor is increased from 2.7V to 4.4V, thereby greatly enhancing its effective energy storage, thereby significantly improving its volume energy density; on the other hand, by simultaneously introducing double-layer electrostatic energy storage mechanism active materials at the positive and negative electrode terminals, the high power output characteristics of the system are matched.

[0022] In the capacitor manufacturing process, the present invention introduces a double-layer electrostatic energy storage mechanism active material at the negative terminal, and the reversible electrochemical adsorption characteristics of the special pore configuration of the open-pore activated carbon can effectively prevent lithium deposition at the negative electrode of the electrochemical capacitor when working at a high rate, thereby enhancing the safety of the system.

[0023] Second, the present invention solves the problem in the prior art that it is difficult to strike a balance between energy density and power density in electrochemical capacitors. Traditional capacitors usually rely on a single energy storage mechanism, either through double-layer electrostatic energy storage to achieve high power density, but with low energy density; or through Faraday pseudo-capacitor energy storage to increase energy density, but with a slow response speed and difficulty meeting high power requirements. The present invention successfully overcomes this technical bottleneck by combining the two mechanisms of double-layer electrostatic energy storage and Faraday pseudo-capacitor energy storage.

[0024] In terms of technological progress, the present invention significantly improves the overall performance of electrochemical capacitors. By introducing open-pore activated carbon and manganese-based binary lithium oxide as active materials for the positive and negative electrodes, the present invention achieves efficient charge storage and rapid release. In particular, the optimized pore structure and material ratio enable the capacitor to maintain a high energy density while delivering high power, a performance improvement that is difficult to achieve with traditional technologies.

[0025] In addition, the present invention solves the problem of low initial charging efficiency of capacitors by using pre-lithiated lignin lithium-intercalated carbon as the negative electrode material. The pre-lithiation treatment not only enhances the conductivity of the negative electrode material, but also reduces the internal resistance, further improving the charge and discharge efficiency and cycle life of the capacitor. This innovation significantly improves the stability and service life of the capacitor, especially in high-frequency charge and discharge applications.

[0026] In summary, the present invention has made significant technological progress in the field of electrochemical capacitors and successfully solved the key problems existing in the prior art. By organically combining the two energy storage mechanisms and optimizing the material and structural design, the present invention not only improves the energy density and power density of the capacitor, but also enhances its long-term stability and reliability, providing new ideas and directions for the development of electrochemical energy storage technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is a schematic diagram of the preparation process of the dual hybrid electrochemical capacitor provided by an embodiment of the present invention.

[0028] Figure 2 This is a charge and discharge curve diagram of the dual hybrid electrochemical capacitor provided in Example 1 of the present invention. DETAILED DESCRIPTION

[0029] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0030] In an embodiment of the present invention, a dual hybrid electrochemical capacitor includes a hybrid positive electrode and a hybrid negative electrode, wherein the hybrid positive electrode and the hybrid negative electrode simultaneously contain active materials of two energy storage mechanisms: double-layer electrostatic energy storage and Faraday pseudocapacitive energy storage.

[0031] Furthermore, the double-layer electrostatic energy storage material is open-pore activated carbon, and preferably the port pore diameter of the activated carbon opening is ≤0.2nm, and the pore size is 1-1.5nm.

[0032] Furthermore, the Faraday pseudo-capacitor energy storage active material is one of a manganese-based binary lithium oxide and pre-lithiated carbon.

[0033] Furthermore, the manganese-based binary lithium oxide is one or both of iron-manganese-based and vanadium-manganese-based oxides, distributed in the positive electrode, preferably iron-manganese-based lithium oxide, with an iron-manganese mass ratio of 1:0.5-1:2, more preferably an iron-manganese mass ratio of 1:1.

[0034] This dual hybrid electrochemical capacitor is designed to combine the two energy storage mechanisms of double-layer electrostatic energy storage and Faraday pseudocapacitive energy storage to improve the energy density and power density of the capacitor. Its core working principle is as follows:

[0035] First, the positive and negative electrodes of the dual hybrid electrochemical capacitor contain active materials of both the double-layer electrostatic energy storage mechanism and the Faraday pseudocapacitive energy storage mechanism. In the double-layer electrostatic energy storage mechanism, the open-pore activated carbon material forms a large number of electric double layers through its extremely high specific surface area, which allows the charge to be stored in the form of electrostatic adsorption. The preferred open-pore activated carbon port pore size is ≤0.2nm, and the pore size is 1-1.5nm. This fine pore structure helps to increase the charge storage capacity, thereby improving the overall capacitance of the capacitor.

[0036] Secondly, in the Faraday pseudocapacitive energy storage mechanism, the positive electrode material uses manganese-based binary lithium oxide, especially iron-manganese-based lithium oxide. This material can store charge through the Faraday reaction, that is, charge transfer within the material through a reversible redox reaction. The mass ratio of iron to manganese is between 1:0.5-1:2, and the optimal ratio is 1:1. This ratio optimizes the electrochemical properties of the material, giving the electrode a higher capacity and more stable cycle performance.

[0037] Third, the negative electrode material uses pre-lithiated carbon, especially pre-lithiated lignin embedded lithium carbon. This material is pre-lithiated during the manufacturing process and can provide lithium ions before the first charge, which plays an important role in improving the initial charging efficiency of the capacitor and reducing the internal resistance. Pre-lithiated lignin embedded lithium carbon has good conductivity and stability, and plays a dual role of double-layer energy storage and quasi-capacitor energy storage in the negative electrode.

[0038] Finally, the combination of these two energy storage mechanisms enables the dual hybrid electrochemical capacitor to exhibit excellent performance under different working conditions: under high power demand, the double electric layer mechanism provides fast electrostatic energy storage, while under high energy demand, the Faraday pseudocapacitive mechanism provides additional energy storage through electrochemical reactions. The synergistic effect of this dual mechanism enables the capacitor to maintain high power density while increasing energy density and having a long cycle life.

[0039] Furthermore, the pre-lithiation carbon is preferably lignin lithium-intercalated carbon, which is distributed in the negative electrode.

[0040] The method for preparing a dual hybrid electrochemical capacitor provided by the present invention comprises the following steps:

[0041] Step 1: dry-mix the open-pore activated carbon, manganese-based binary lithium oxide, conductive agent and binder in a dry mixer for 10-30 minutes, add them into a solvent containing dimethylpyrrolidone (NMP) at one time, and stir at high speed for 90-120 minutes to form a viscous slurry;

[0042] Step 2, the slurry is evenly coated on both sides of the aluminum foil current collector, and vacuum dried at 120° C. to form a hybrid electrochemical capacitor positive electrode;

[0043] Step 3, dry-mixing the open-pore activated carbon, pre-lithiation carbon, conductive agent and binder in a dry mixer for 10-30 minutes, adding the mixture into a solvent containing dimethylpyrrolidone (NMP) at one time, and stirring at high speed for 90-120 minutes to form a viscous slurry;

[0044] Step 4, evenly coating the slurry on both sides of the copper current collector, and vacuum drying at 105° C. to form a hybrid electrochemical capacitor negative electrode;

[0045] Step 5, rolling the loaded electrodes obtained in step 2 and step 4 into a designed thickness on a Cr plating roller press, and cutting them into the positive electrode and the negative electrode of the dual hybrid electrochemical capacitor of the present invention;

[0046] Step six, winding or stacking the electrodes obtained in step five in the order of positive electrode, separator, and negative electrode into a bare cell, and encapsulating them in a shell to form the dual hybrid electrochemical capacitor of the present invention.

[0047] The following is explained with more specific examples.

[0048] Example 1

[0049] The dual hybrid electrochemical capacitor comprises the following preparation steps:

[0050] Step 1: 2 parts (mass fraction, the same below) of commercially available open-pore activated carbon (manufactured by Shenzhen Beiterry, BAC-1), 93 parts of commercially available iron-manganese-based lithium oxide (SLMFP-64, Tianjin Stran), 3 parts of conductive carbon black (manufactured by Swiss Termeco, Sp), and 2 parts of binder PVDF (manufactured by Solvay, USA, 5130) were mechanically mixed in a dry mixer for 25 minutes, and then added to a solvent of dimethylpyrrolidone (manufactured by Changxin Chemical, battery-grade NMP) at one time, and stirred at high speed for 110 minutes to form a viscous slurry;

[0051] Step 2: evenly apply the slurry onto both sides of a 15um aluminum foil (manufactured by Huizhou Xinfei Le, 1060H15) current collector, with the surface density controlled at 252g / m2, and dry in a vacuum oven at 115°C to form a positive electrode for a dual hybrid electrochemical capacitor;

[0052] Step 3: 4 parts of open-pore activated carbon (manufactured by Shenzhen BAC-P), 92 parts of pre-lithiated hard carbon (manufactured by Shenzhen BAC-400), 1 part of electric carbon black (manufactured by Switzerland Temigo, Sp) and 3 parts of binder PVDF (manufactured by Solvay, USA, 5130) were mechanically mixed in a dry mixer for 25 minutes, and then added into a solvent containing dimethylpyrrolidone (manufactured by Changxin Chemical, battery grade NMP) at one time, and stirred at high speed for 110 minutes to form a viscous slurry;

[0053] Step 4: evenly apply the slurry to both sides of a 10um copper foil (Guangdong Jiayuan copper foil, Tuv oxygen-free copper), control the surface density at 137g / m2, and vacuum dry at 105°C to form a loaded negative electrode;

[0054] Step 5: Roll the positive and negative electrodes obtained in Step 2 and Step 4 on a Cr-plating roller press to a designed thickness (positive electrode 152um, negative electrode 135um), and cut them into positive and negative electrodes with a width of 105mm and 108mm on a slitting machine;

[0055] Step six, winding the electrodes obtained in step five into a bare cell in the order of positive electrode, separator and negative electrode, and assembling them in an aluminum-plastic film shell after welding to form the dual hybrid electrochemical capacitor of the present invention.

[0056] Reference Figure 1 and Figure 2 The aluminum-plastic film soft-pack electrochemical capacitor prepared under the above conditions was electrochemically activated and tested for performance. The test results show that the capacity of the electrochemical capacitor provided in Example 1 under 1.0C conditions reaches 25Ah, the corresponding volume energy density reaches 420Wh / L, and the capacity retention rate after 1000 cycles at 3C is 95%.

[0057] Example 2

[0058] The dual hybrid electrochemical capacitor comprises the following preparation steps:

[0059] Step 1: 3 parts (mass fraction, the same below) of commercially available open-pore activated carbon (manufactured by Zhejiang Chuheng Technology, CH-YP), 92 parts of commercially available iron-manganese-based lithium oxide (manufactured by Zhongke Zhiliang, ZLPP333), 2 parts of conductive carbon black (manufactured by Swiss Termeco, Sp) and 3 parts of binder PVDF (manufactured by Arkema, France, hsv900) were mechanically mixed in a dry mixer for 20 minutes, and then added to a solvent of dimethylpyrrolidone (manufactured by Changxin Chemical, battery-grade NMP) at one time, and stirred at high speed for 100 minutes to form a viscous slurry;

[0060] Step 2: evenly apply the slurry to both sides of a 15um aluminum foil (manufactured by Henan Mingtai Aluminum, 1060H15) current collector, with the surface density controlled at 235g / m2, and dry in a vacuum oven at 120°C to form a hybrid electrochemical capacitor positive electrode;

[0061] Step 3: 3 parts of activated carbon (manufactured by Zhejiang Chuheng Technology, CH-YN), 90 parts of pre-lithiated lignin lithium-embedded carbon (manufactured by Shenzhen Xismi Technology, Type 2), 2 parts of electric carbon black (manufactured by Swiss Termeco, Sp), and 5 parts of binder PVDF (manufactured by Akema, France, lsv900) were mechanically mixed in a dry mixer for 20 minutes, and then added into a solvent containing dimethylpyrrolidone (manufactured by Changxin Chemical, battery-grade NMP) at one time, and stirred at high speed for 100 minutes to form a viscous slurry;

[0062] Step 4: evenly apply the slurry to both sides of a 10um copper foil (Guangdong Jiayuan copper foil, Tuv oxygen-free copper), control the surface density at 132g / m2, and vacuum dry at 105°C to form a loaded negative electrode;

[0063] Step 5: Roll the positive and negative electrodes obtained in Step 2 and Step 4 on a Cr-plating roller press to a designed thickness (positive electrode 141um, negative electrode 130um), and cut them into positive and negative electrodes with a width of 95mm and 97mm on a slitting machine;

[0064] Step six, winding the electrodes obtained in step five into a bare cell in the order of positive electrode, separator and negative electrode, and assembling them in an aluminum-plastic film shell after welding to form the soft-package dual hybrid electrochemical capacitor of the present invention.

[0065] The aluminum-plastic film soft-pack electrochemical capacitor prepared under the above conditions was subjected to electrochemical activation and performance testing. The test results show that the capacity of the electrochemical capacitor provided in Example 1 under 1.0C conditions reaches 30Ah, the corresponding volume energy density energy reaches 435Wh / L, and the capacity retention rate after 1000 cycles at 3C is 93%, and the performance is significantly better than the existing technology.

[0066] Example 3

[0067] The same procedures as in Example 1 were followed except that the negative electrode used pre-lithiated soft carbon (PSCAM280, manufactured by PCT Corporation of Korea) instead of lignin pre-lithiated carbon.

[0068] Example 4

[0069] Except that the bare core is manufactured by the lamination process, the rest is the same as in Example 1.

[0070] Example 5

[0071] Except for being made into a cylindrical battery cell, other aspects are the same as those of Example 1.

[0072] Example 6

[0073] Except for being made into a square battery cell, other aspects are the same as those of Example 1.

[0074] Example 7

[0075] Except that the bare core is manufactured by the lamination process, the rest is the same as in Example 2.

[0076] Example 8

[0077] Except for being made into a cylindrical battery cell, other aspects are the same as those of Example 2.

[0078] Example 9

[0079] Except for being made into a square battery cell, other aspects are the same as those of Example 2.

[0080] The basic electrochemical performance test results of the above examples are shown in Table 1.

[0081] Table 1 Basic performance parameters of dual hybrid electrochemical capacitors

[0082]

[0083] Example 1 relates to a dual hybrid soft-pack electrochemical capacitor (25AH).

[0084] Reference Figure 1 and Figure 2 The capacity of the electrochemical capacitor provided in Example 1 under 1.0C conditions reaches 25Ah, the corresponding volume energy density energy reaches 420Wh / L, and the capacity retention rate after 1000 cycles at 3C is 95%, which is much higher than the existing technical level.

[0085] In the description of the present invention, unless otherwise specified, “plurality” means two or more than two; the terms “first”, “second”, “third”, etc. are used for descriptive purposes only and cannot be understood as indicating or implying relative importance.

[0086] The above description is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Any modifications, equivalent substitutions and improvements made by any technician familiar with the technical field within the technical scope disclosed by the present invention and within the spirit and principle of the present invention should be covered by the protection scope of the present invention.

Claims

1. A dual hybrid electrochemical capacitor, characterized in that: It comprises a hybrid positive electrode and a hybrid negative electrode, and the hybrid positive electrode and the hybrid negative electrode simultaneously comprise active materials of two energy storage mechanisms, namely, double-layer electrostatic energy storage and Faraday pseudo-capacitive energy storage.

2. The dual hybrid electrochemical capacitor according to claim 1, characterized in that: The active material of the double-layer electrostatic energy storage mechanism is open-pore activated carbon, the port pore diameter of the open-pore activated carbon is ≤0.2nm, and the pore size is 1-1.5nm.

3. The dual hybrid electrochemical capacitor according to claim 1, characterized in that: The active material of the Faraday pseudocapacitive energy storage mechanism is one of manganese-based binary lithium oxide and pre-lithiated carbon.

4. The dual hybrid electrochemical capacitor according to claim 1, characterized in that: Manganese-based binary lithium oxide is distributed in the positive electrode, with a mass ratio of iron to manganese of 1:

1.

5. The dual hybrid electrochemical capacitor according to claim 1, characterized in that: The pre-lithiated carbon is preferably pre-lithiated lignin lithium-intercalated carbon, which is distributed in the negative electrode.

6. A method for preparing a dual hybrid electrochemical capacitor according to any one of claims 1 to 5, characterized in that: The steps include: S1, mechanically mixing the open-pore activated carbon, manganese-based binary lithium oxide, conductive agent and binder in a dry mixer for 10-30 minutes, adding the mixture into a solvent containing dimethylpyrrolidone (NMP) at one time, and stirring at high speed for 90-120 minutes to form a viscous slurry; S2, uniformly coating the slurry on both sides of the aluminum foil current collector, and vacuum drying at 120° C. to form a hybrid electrochemical capacitor positive electrode; S3, mechanically mixing the open-pore activated carbon, pre-lithiated carbon, conductive agent and binder in a dry mixer for 10-30 minutes, adding the mixture into a solvent containing dimethylpyrrolidone (NMP) at one time, and stirring at high speed for 90-120 minutes to form a viscous slurry; S4, uniformly coating the slurry on both sides of the copper current collector, and vacuum drying at 105° C. to form a hybrid electrochemical capacitor negative electrode; S5, rolling the loaded positive electrode and the loaded negative electrode obtained in S2 and S4 into a designed thickness on a Cr plating roller press, and cutting them into the positive electrode and the negative electrode of the dual hybrid electrochemical capacitor of the present invention; S6, winding or stacking the electrodes obtained in S5 in the order of positive electrode, separator, and negative electrode into a bare cell, and encapsulating them in shells of different materials to form a dual hybrid electrochemical capacitor.

7. The dual hybrid electrochemical capacitor according to claim 1, characterized in that: The shell is one of aluminum-plastic film, aluminum shell or steel shell.

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