CN101937774A - A kind of winding supercapacitor preparation method - Google Patents

Abstract

The invention provides a method for preparing a winding supercapacitor, comprising: 1) selecting a carbon nanotube film prepared by a direct growth method as an electrode material; 2) cutting the carbon nanotube film into a plurality of carbon nanotube films small piece; 3) tile the elongated diaphragm in a volatile organic solvent; 4) tile a plurality of carbon nanotube thin film slices on the diaphragm successively end to end; to be covered with the carbon nanotube thin film The organic solvent on the diaphragm is completely volatilized; 5) winding and packaging the diaphragm to obtain the wound supercapacitor. The present invention successfully prepares a wound supercapacitor with a carbon nanotube film electrode for the first time, which greatly improves the conductivity of the wound supercapacitor electrode, reduces the equivalent series resistance of the supercapacitor, and thus improves the carbon nanotube film electrode. Energy and power densities of wound supercapacitors, exhibiting good power characteristics and current responses.

Description

A kind of winding supercapacitor preparation method

technical field

This embodiment relates to the technical field of electrochemistry, and specifically, the present invention relates to a winding supercapacitor and a preparation method thereof.

Background technique

Supercapacitors, also known as electrochemical capacitors, are a new type of energy storage device whose performance is between traditional capacitors and batteries, and has the characteristics of high specific energy of batteries and high specific power of traditional capacitors. Its capacity can reach farad level or even thousands of farads, its mass specific capacitance or volume specific capacitance is 20 to 200 times that of traditional capacitors, and its energy density is 10 to 100 times that of traditional capacitors. At the same time, the power density of supercapacitors is about 10 times higher than that of batteries, and the cycle life is also better than that of batteries, with the number of cycles up to 106. In addition, supercapacitors also have the characteristics of high charging and discharging efficiency and safety, and can be used as high-power pulse power supplies. They have broad application prospects in many fields such as data memory storage systems, portable instruments and equipment, communication equipment, and hybrid power supplies for electric vehicles.

In the prior art, supercapacitors mainly have two structural forms: one is a button capacitor with a sandwich laminate structure, and the other is a wound capacitor formed by winding electrode sheets and diaphragms. Button-type supercapacitors are difficult to accommodate large-area electrodes, which limits the increase in the capacitance of button-type supercapacitors, and the sealed shell of button-type supercapacitors needs to withstand high pressure. Wound capacitors can accommodate large-area electrodes, are easy to realize industrialization, and are suitable for the preparation of high-capacity supercapacitors, but their electrode materials must be soft and foldable, so their applicable electrode materials are greatly limited. The limitation of electrode materials often becomes one of the main bottlenecks in improving the performance of wound supercapacitors in all aspects.

Currently, the main electrode material for wound supercapacitors is activated carbon fiber cloth (ACFC). Its defects include: 1. The preparation of activated carbon fiber cloth is relatively complicated, and its electrical conductivity is low. Before it is used as an electrode, a layer of aluminum film must be deposited on its surface to improve its electrical conductivity, and the existence of aluminum film will lead to inorganic Electrolytes such as sulfuric acid solutions will not work. 2. The equivalent series resistance (ESR) of activated carbon fiber cloth supercapacitor is relatively large, which leads to the low power density of activated carbon fiber cloth.

On the other hand, there have been some reports on the use of carbon nanotube-based film materials as electrode materials for button-type supercapacitors. Studies have shown that the specific surface area utilization, power characteristics and frequency characteristics of carbon nanotube-based thin film materials are far superior to commonly used electrode materials such as activated carbon and carbon aerogel. At present, there are two main types of electrode materials for supercapacitors based on carbon nanotube films: ① by mixing carbon nanotubes with conductive polymers, and then coating the mixture on a conductive substrate as a thin film electrode material (hereinafter referred to as carbon nanotube polymer film ). ②The pure carbon nanotube film prepared on the substrate (that is, the pure carbon nanotube film with the substrate).

①For carbon nanotube polymer film electrodes, the addition of polymer will reduce the conductivity and porosity of carbon nanotube electrodes, which will have an adverse effect on the transfer of charges in the electrode and the diffusion of ions in the electrolyte in the electrode gap. , leading to a decrease in the power density of the supercapacitor, and the carbon nanotube polymer film must use a metal substrate as a current collector to collect and transfer charges. The use of a metal substrate will increase the weight of the capacitor and affect its actual use; in addition, carbon nanotubes The preparation of polymer film electrodes is complicated, the thickness controllability is poor, and the specific capacitance of carbon nanotube polymer supercapacitor is relatively small. Although the specific capacitance can be improved by activating the polymer of carbon nanotubes, the activation needs to be carried out at high temperature. Therefore, many conductive substrates that are not resistant to high temperatures cannot be used. In addition, metal substrates and carbon nanotube polymers are poor in flexibility and foldability, so supercapacitors based on carbon nanotube polymer electrodes generally have a button structure, which is difficult to apply to wound supercapacitors.

②The pure carbon nanotube film with substrate has high conductivity and porous structure, which can be directly used as electrode material for supercapacitors. However, the binding force between the carbon nanotube film and the substrate is relatively small, and if the substrate and the carbon nanotube film are crimped together, the carbon nanotube film will be easily detached from the substrate. In addition, the poor flexibility and foldability of the substrate makes it difficult for the carbon nanotube film on the substrate to be directly used to prepare a wound supercapacitor.

To sum up, the winding supercapacitor can accommodate large-area electrodes to increase its capacitance, and can be used as a high-capacity, high-power pulse power supply. However, the electrode material needs to be soft, foldable and not easy to fall off. The application of thin film electrode materials with higher conductivity and porosity is limited. Therefore, a solution that enables the use of thin film materials with higher conductivity and porosity as electrodes for wound capacitors is urgently needed.

Contents of the invention

The object of the present invention is to provide a method for preparing a wound capacitor having a thin film electrode material with high conductivity and porosity.

In order to achieve the purpose of the above invention, the preparation method of the wound supercapacitor provided by the present invention includes the following steps:

1) Select the carbon nanotube film prepared by the direct growth method as the electrode material;

2) cutting the carbon nanotube film into a plurality of regular-shaped carbon nanotube film fragments;

3) Spread the strip-shaped diaphragm in a volatile organic solvent;

4) Tiling a plurality of small pieces of carbon nanotube film onto the diaphragm end to end in sequence; the organic solvent on the diaphragm to be covered with the carbon nanotube film is completely volatilized;

5) Winding and packaging the separator to obtain the wound supercapacitor.

Wherein, in the step 2), the length of the small piece of carbon nanotube film is 5-10 cm, and the width is 1-5 cm.

Wherein, in the step 3), the liquid level of the organic solvent is 0.5 mm to 1 mm higher than the surface of the diaphragm.

Wherein, said step 4) includes the following sub-steps:

41) Dip a small piece of carbon nanotube film into the volatile organic solvent, stretch it evenly and spread it on the separator;

42) Lifting the separator covered with the carbon nanotube film from the volatile organic solvent until the organic solvent is completely volatilized;

43) Steps 41) to 42) are repeated, and a plurality of small pieces of carbon nanotube thin films are tiled on the separator end-to-end in the length direction in sequence.

Wherein, the step 41) further includes: when the small piece of carbon nanotube film is stretched, maintaining the tensile stress of the carbon nanotube film at 50 GPa-150 GPa.

Wherein, the step 42) further includes: lifting one end of the membrane, and then lifting the membrane covered with the carbon nanotube film from the organic solvent at a constant speed of 3-5 cm/min.

Wherein, in the step 43), two adjacent carbon nanotube films are aligned in the width direction, and have an overlapping portion of 1 to 2 mm in the length direction; the width of the diaphragm is 2-3 mm wider than the laid carbon nanotube film, The length is 1-3cm long.

Wherein, the step 43) further includes: stacking a plurality of small carbon nanotube thin films in multiple layers, so that the carbon nanotube thin film reaches a required thickness.

Compared with the prior art, the present invention has the following technical effects:

1. For the first time, a wound supercapacitor with a carbon nanotube film electrode was successfully prepared, which greatly improved the conductivity of the wound supercapacitor electrode and reduced the equivalent series resistance of the supercapacitor, thereby improving the carbon nanotube film. Energy and power densities of wound supercapacitors, exhibiting good power characteristics and current responses.

2. It can ensure that the electrode of the wound supercapacitor has a high flatness.

3. It can ensure that the electrode of the wound supercapacitor has a high thickness consistency, thereby enhancing the stability of the wound supercapacitor.

4. The thickness and area of the electrode are highly controllable, and are not limited by the original area and thickness of the carbon nanotube film.

5. There is no need to use a metal substrate as a current collector, which reduces the weight of the capacitor and improves the adaptability of the capacitor to the electrolyte.

6. The process is relatively simple and the yield is high.

Description of drawings

Hereinafter, embodiments of the present invention will be described in detail in conjunction with the accompanying drawings, wherein:

Fig. 1 is the schematic diagram of the tiling mode of the carbon nanotube film on the diaphragm of the present invention and the preparation method of the carbon nanotube film winding type supercapacitor;

Fig. 2 is the cyclic voltammetry graph of the carbon nanotube film wound supercapacitor of an embodiment of the present invention at different scan rates;

Fig. 3 is the impedance spectrum of the carbon nanotube film wound supercapacitor of an embodiment of the present invention;

Fig. 4 is a charge and discharge curve of a carbon nanotube film wound supercapacitor according to an embodiment of the present invention.

Detailed ways

Below in conjunction with specific embodiment, from the selection of electrode material, the preparation of carbon nanotube film electrode, the assembly of carbon nanotube film wound supercapacitor and the comprehensive performance measured data of carbon nanotube film wound supercapacitor, do the present invention Further explanations and clarifications.

1. Selection of electrode materials

The carbon nanotube thin film used in this embodiment is directly grown by floating catalytic chemical vapor deposition (hereinafter referred to as direct growth method). Unlike the carbon nanotube polymer film, the carbon nanotube film prepared by the direct growth method can be directly tiled on the separator as a positive and negative electrode material without using a metal substrate as a current collector. At the same time, it has strong adsorption. Compared with the carbon nanotube film prepared by the post-deposition method, the carbon nanotube film prepared by the direct growth method has the advantages of strong flexibility and strong adsorption, so it is suitable as an electrode material for wound supercapacitors. . As an electrode material, the area and thickness of the carbon nanotube film can be adjusted as required. Carbon nanotube films can also be functionalized (such as pretreatment, activation, modification, etc.).

2. Preparation of carbon nanotube thin film electrodes

1. Cut the carbon nanotube film to the desired size.

A wound supercapacitor requires a long strip-shaped electrode material. However, the carbon nanotube film prepared by the direct growth method has strong self-adsorption, and it is difficult to spread the carbon nanotube film with a long length on the separator evenly. The inconsistency caused by this unevenness will reduce the stability of the supercapacitor. . In addition, the area of the carbon nanotube thin film prepared by the direct growth method is limited. Therefore, the present invention creatively proposes a method of block first and then splicing to ensure the uniformity of the carbon nanotube thin film electrode. At the same time, this method also expands the area of the carbon nanotube film electrode, breaking through the limitation of the area of the carbon nanotube film prepared by the direct growth method on the area of the supercapacitor electrode. In this embodiment, the width of a single carbon nanotube film is 1-5 cm, and the length is 5-10 cm. For the convenience of description, it is referred to as a carbon nanotube film block, or a film block for short. The selection of the width and length of the above-mentioned film small pieces comprehensively considered various factors such as tiling operation and capacitor design. The larger the area of each carbon nanotube film, the more difficult it is to evenly spread it on the separator during the tiling process; while the smaller the area, it will lead to too many splicing times of electrodes of the same length, increased contact resistance, and uniform thickness Sexual deterioration. The poor consistency of the thickness will lead to a decrease in the capacitance of the supercapacitor, and also lead to a decrease in the stability of the supercapacitor.

In addition, due to the strong self-adsorption of the carbon nanotube film prepared by the direct growth method used in this example, it is difficult to directly cut the carbon nanotube film into the size required for the preparation of the wound supercapacitor. Therefore, in this embodiment, the carbon nanotube film is sandwiched between two pieces of weighing paper, and then cut into the desired shape and size by using a cutting tool. Due to the special surface of the weighing paper, the carbon nanotube film can be completely peeled off from its surface. At the same time, in this embodiment, the diaphragm needs to be cut into the desired shape and size.

2. Lay the small pieces of film on the diaphragm in turn, and splice the small pieces of film in turn to form a complete electrode.

(1) In order to evenly spread the small pieces of film, this embodiment uses a volatile organic solvent (such as ethanol or acetone) to reduce the self-adsorption of the small pieces of film. In this step, the cut membrane is immersed in the organic solvent, and the height of the organic solvent is 0.5 mm to 1 mm higher than the thickness of the membrane and the carbon nanotube film. Because the organic solvent is volatile, this embodiment also needs to use the conduit to continuously add the organic solvent, and control the liquid level of the organic solvent by controlling the flow rate of the organic solvent in the conduit so that it is far less than the diaphragm (the thickness of the carbon nanotube film is much smaller than Diaphragm thickness) is always 0.5-1mm higher.

(2) a piece of carbon nanotube film is also immersed in the organic solvent, first simultaneously stretches the carbon nanotube along the directions of the four corners of the carbon nanotube film in the organic solvent, and then each of the carbon nanotube film Micro-stretch adjustment is performed to remove small wrinkles, so that the carbon nanotube film is evenly spread on the diaphragm. During the stretching process of the carbon nanotube film, the tensile stress of the carbon nanotube film is 50GPa to 150GPa. Excessive tensile stress will cause cracking of the carbon nanotube film, while too small tensile stress will make it difficult to remove wrinkles, resulting in uneven electrodes.

(3) After the carbon nanotube film is spread on the diaphragm, lift one end of the diaphragm, and then lift the diaphragm covered with the carbon nanotube film from the organic solvent at a constant speed of 3 to 5 cm/min, and let the diaphragm in the air And the organic solvent on the carbon nanotube film is completely volatilized. Since the carbon nanotube film will absorb a large amount of organic solvents, the self-adsorption force of the carbon nanotube film has not recovered during the lifting process, and it cannot be firmly adsorbed on the diaphragm. Therefore, if the speed of lifting the diaphragm is too fast (such as greater than 5cm/min) , the carbon nanotube film is easy to slip off the diaphragm, affecting its flatness on the diaphragm. On the other hand, if the lifting speed is too slow, the production efficiency will be too low. After a large number of experiments, it has been found that when the speed is lower than 3cm/min, further reducing the speed can not significantly improve the flatness of the carbon nanotube film. Therefore, the lifting of the diaphragm The speed is generally not lower than 3cm/min.

(4) According to the above-mentioned steps (2) and (3), spread a plurality of thin film pieces on the diaphragm in sequence, and splice each small thin film piece end-to-end in order to form a complete electrode.

Wherein the end-to-end splicing means that multiple small film pieces are aligned in the width direction, and tiled end-to-end in the length direction, and the overlap between two adjacent film pieces in the length direction is 1-2mm. Too much overlap will reduce the specific capacitance of the supercapacitor, and too little overlap will increase the contact resistance between the carbon nanotube films and affect the power density of the supercapacitor. Therefore, in a preferred embodiment, the overlapping portion in the length direction of two adjacent thin film pieces is limited to 1-2 mm.

In this embodiment, the width of the total carbon nanotube film after tiling should be less than the width of the diaphragm, the edge of the carbon nanotube film is generally 2-3mm smaller than the edge of the diaphragm, and the length of the total carbon nanotube film should also be less than the diaphragm. The width of the carbon nanotube film is generally 1-3 cm from the two ends of the membrane. The total size (such as: thickness and area) of the carbon nanotube film tiled on the diaphragm, that is, the size of the capacitor film electrode, will directly affect the capacitance and volume of the prepared supercapacitor.

Generally, when the thickness of the carbon nanotube film electrode is thinner, the specific capacitance of the carbon nanotube film supercapacitor is larger. However, when assembling a supercapacitor with the same capacitance, the thinner The area of the tube film electrode is large, and the required diaphragm area is large, and the thickness of the diaphragm is greater than the thickness of the carbon nanotube film, so the volume of the supercapacitor prepared by this is large; therefore, in order to reduce the carbon nanotube film supercapacitor The thickness of the carbon nanotube film electrode can be appropriately increased by stacking layers. However, when the thickness of the carbon nanotube film electrode is thicker, within a certain range, the specific capacitance of the carbon nanotube film supercapacitor will increase with the film electrode. decrease with increasing thickness. Therefore, when assembling a supercapacitor with the same capacitance, the thickness of the film electrode increases, and the total amount of carbon nanotube film required increases. In summary, the size of the carbon nanotube film electrode depends on the specific capacitance of the supercapacitor. and volume specific requirements to determine.

In this embodiment, the total area of the carbon nanotube film can be expanded according to the capacitance of the wound supercapacitor, which can be much larger than the original area of the directly prepared carbon nanotube film, that is, the electrode area of the wound supercapacitor can be reduced. Limited by the original area of the carbon nanotube film.

In addition, in the present invention, the film small pieces can also be stacked in multiple layers to control the thickness of the electrode. Multi-layer overlapping means that multiple film small pieces are overlapped and tiled on the separator. The thickness of the carbon nanotube film electrode is proportional to the number of layers it overlaps. The total thickness of the carbon nanotube film is generally controlled at 300nm-100μm. The way to realize multi-layer overlapping is to repeat the above-mentioned steps (2) and (3), and tile the small pieces of film one by one. Specifically, the first layer of thin film pieces are tiled on the diaphragm, and then the next layer of thin film pieces are tiled on the previous layer of thin film pieces according to the method of steps (2) and (3) until the carbon dioxide The total thickness of the nanotube film meets the required requirements.

In another embodiment, the splicing and overlapping methods can also be mixed to simultaneously control the length and thickness of the carbon nanotube thin film electrode. Only when the first, third, fifth and other odd-numbered layers are tiled, the small pieces of film can be spliced in the length direction, and when the second, fourth, and other even-numbered layers are tiled, the Small pieces may not be spliced in the length direction. The third layer, the fifth layer and other odd-numbered layers are spliced according to the same standard as the first layer. The area and number of layers of the carbon nanotube film laid on the diaphragm can be determined according to the size and capacitance of the carbon nanotube film wound supercapacitor required. Part (a) of FIG. 1 shows the electrode 1 with only the overlapping structure, the electrode 2 with both overlapping and spliced structures, and the electrode 3 with only the spliced structure.

3. Assembly of carbon nanotube film wound supercapacitor

Two identical separators covered with carbon nanotube thin film electrodes are overlapped, as shown in part (b) of Figure 1, wherein 4 is the separator and 5 is the electrode. The carbon nanotube thin film electrodes on the two diaphragms must be separated from each other by the diaphragm when overlapping. Use a reel to wind the above two overlapping diaphragms. The length of the reel is 0.3 to 0.5 cm longer than the width of the diaphragm. The carbon nanotube films on the two diaphragms are respectively used as the positive and negative electrodes of the supercapacitor, and the lead wires of the electrodes are drawn out during the winding process. , the contact length between the electrode lead and the carbon nanotube film is generally 0.5 to 1 cm. The wound diaphragm is assembled into the shell of the supercapacitor, the electrolyte is added, and finally the supercapacitor is sealed and assembled, as shown in part (c) of Figure 1.

4. Measured data of comprehensive performance of carbon nanotube film wound supercapacitor

In this test, the directly grown independent unsupported carbon nanotube film with a thickness of 400nm is used as the electrode material of the wound supercapacitor. The length and width of the small piece of carbon nanotube film are 10cm and 1.2cm; the separator is Celgard 2325, and the length and width are 25cm and 1.6cm, respectively. The electrolyte solution is 1M anhydrous lithium perchlorate solution (the solvent is diethyl carbonate, ethylene carbonate, dimethyl carbonate in a molar ratio of 1:1:1).

The following is the electrochemical performance characterization of the above-mentioned carbon nanotube film wound supercapacitor:

1. The cyclic voltammetry curve of the carbon nanotube film wound supercapacitor prepared in this example

Figure 2 is the cyclic voltammetry curves of the carbon nanotube film wound supercapacitor prepared in this example at different scan rates (scan rates are 2mV/s, 10mV/s, 50mV/s, respectively). Fig. 2 shows: the cyclic voltammetry curve of the carbon nanotube thin film wound supercapacitor prepared in this embodiment is approximately rectangular in the detected potential range, which shows that the carbon nanotube thin film wound supercapacitor prepared in this embodiment is Pure electric double layer capacitors with good current response to potential reversal. The capacitance increases with the scanning speed, but the specific capacitance relative to the mass of the carbon nanotube film remains basically unchanged, indicating that it has good power characteristics.

2. The impedance spectrum of the carbon nanotube film wound supercapacitor prepared in this embodiment

Fig. 3 is the impedance spectrum of the carbon nanotube film wound supercapacitor prepared in this embodiment. It can be seen from Fig. 3 that the imaginary part of the impedance of the capacitor increases rapidly at low frequencies, proving the capacitive behavior of the carbon nanotube electrode.

3. The charge-discharge curve of the carbon nanotube film wound supercapacitor prepared in this example

Fig. 4 is the charge-discharge curve of the carbon nanotube thin film wound supercapacitor prepared by the present embodiment, and the charging current is 5mA, as can be seen from Fig. 4 the charge and discharge of the carbon nanotube thin film wound supercapacitor prepared by the present embodiment The efficiency is very close to 100%, and the difference between the cut-off voltage of capacitor work and the discharge initial voltage is very small, which shows that the equivalent series resistance (ESR) of the carbon nanotube film supercapacitor prepared in this embodiment is very small, calculated from the charge-discharge curve The mass specific capacitance of the carbon nanotube film wound supercapacitor prepared in this example is 25 F/g, the volume specific capacitance is 65 F/cm ³ , the energy density is 13.6 Wh/kg, and the power density is 83.3 kW/kg. The equivalent series resistance (ESR) of the carbon nanotube thin film supercapacitor prepared in this embodiment is about 200mΩ/cm ² , which is far less than the value of the activated carbon fiber cloth supercapacitor reported in the literature (the ESR value of the latter is greater than 1Ω/cm ² ) (Journal of Applied Electrochemistry (2005) 35: 1067-1072), and the volume specific capacitance is greater than the value of the activated carbon fiber cloth supercapacitor reported in the literature (Journal of Applied Electrochemistry (2005) 35: 1067-1072); in addition, this The energy density and the power density value of the carbon nanotube film supercapacitor that embodiment prepares and the energy density and the power density value of the supercapacitor of electrode material such as general activated carbon fiber cloth (the energy density of the latter is generally less than 10Wh/kg, and power density is general Compared with less than 30kW/kg), there is a significant improvement.

The above-mentioned embodiment is only used to illustrate the description, and it should not be understood as any limitation on the protection scope of the description. Moreover, those skilled in the art can understand that without departing from the spirit and principle of this embodiment, various equivalent changes, modifications and various improvements not described in this embodiment are within the scope of protection of this patent. within.

Claims (8)

1. a winding type super capacitor preparation method comprises the following steps:

1) select the carbon nano-tube film of direct growth method preparation as electrode material;

2) described carbon nano-tube film is cut into a plurality of carbon nano-tube film fritters;

3) barrier film with strip is tiled in the volatile organic solvent;

4) the end to end successively Horizon of polylith carbon nano-tube film small pieces is taped against on the described barrier film; The organic solvent of waiting to be covered with on the described barrier film of carbon nano-tube film volatilizees fully;

5) with described membrane coil around and encapsulate, obtain described winding type super capacitor.

2. winding type super capacitor preparation method according to claim 1 is characterized in that, described step 2) in, the little block length of described carbon nano-tube film is 5-10cm, width is 1-5cm.

3. winding type super capacitor preparation method according to claim 1, in the described step 3), described organic solvent liquid level is higher than described membrane surface 0.5mm～1mm.

4. winding type super capacitor preparation method according to claim 1 is characterized in that, described step 4) comprises following substep:

41) a carbon nano-tube film fritter is immersed in the described volatile organic solvent, on the described barrier film that it is evenly stretched and tiles;

42) the described barrier film that will be covered with carbon nano-tube film is mentioned from described volatile organic solvent, treats that organic solvent volatilizees fully;

43) repeating step 41) to 42), the end to end in the longitudinal direction successively Horizon of polylith carbon nano-tube film small pieces is taped against on the described barrier film.

5. winding type super capacitor preparation method according to claim 4 is characterized in that, described step 41) also comprise: described carbon nano-tube film fritter is when being stretched, and keeping the carbon nano-tube film tensile stress is 50GPa～150GPa.

6. winding type super capacitor preparation method according to claim 4, it is characterized in that, described step 42) also comprise: mention an end of barrier film, the barrier film that at the uniform velocity will be covered with carbon nano-tube film with the speed of 3～5cm/min is mentioned from described organic solvent then.

7. winding type super capacitor preparation method according to claim 4, described step 43) in, align on adjacent two carbon nano-tube film fritter Widths, have the lap of 1～2mm on the length direction; The width of barrier film than the wide 2-3mm of the carbon nano-tube film of spreading, the long 1-3cm of length.

8. winding type super capacitor preparation method according to claim 4, described step 43) also comprise: polylith carbon nano-tube film fritter multilayer is overlapping, make described carbon nano-tube film arrive desired thickness.

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