WO2011105348A1

WO2011105348A1 - Method for drying electrode coating film for lithium ion battery

Info

Publication number: WO2011105348A1
Application number: PCT/JP2011/053776
Authority: WO
Inventors: 道郎青木; 良夫近藤
Original assignee: 日本碍子株式会社
Priority date: 2010-02-26
Filing date: 2011-02-22
Publication date: 2011-09-01
Also published as: TW201205932A; JPWO2011105348A1; JP4801233B1

Abstract

Provided is a method for drying an electrode coating film for lithium ion batteries, the method comprising applying an electrode material paste comprising an electrode material (3), a binder, a conductive material (4), and a solvent (5) to a metal sheet (1) and drying the paste. In the initial stage of the drying, hot air is blown against the surface of the coating film, and heating with infrared rays is simultaneously conducted to rapidly elevate the temperature of the coating film. In the middle stage of the drying when particles of the electrode material (4) have begun to be exposed on the surface, the whole coating film is heated by irradiation with infrared rays while controlling the sheet temperature with hot air having a temperature lower than the sheet temperature. Thus, the binder present on the surface-layer side is diffused inward toward the intermediate-layer side on the basis of a difference in binder concentration within the coating film, and solvent vaporization also from inside the coating film mainly through interstices among particles of the electrode material present on the surface side is simultaneously caused to proceed.

Description

Method for drying electrode coating film for lithium ion battery

The present invention relates to a method for drying an electrode coating film for a lithium ion battery in the production process of the lithium ion battery.

For the electrode of a lithium ion battery, an active material powder (referred to as an electrode material), which is a positive electrode material or a negative electrode material, is applied to a metal sheet such as aluminium or copper by kneading together with a binder, a conductive material and a solvent. In addition, a coating film having a thickness of about 100 μm is formed and then dried. The electrode material is generally lithium cobaltate as a positive electrode material, PVDF as a binder, carbon as a conductive material, and NMP as a solvent.

Of these, the binder has a role of bonding the electrode material and the conductive material in the dried electrode. For this reason, in order to improve the performance of the lithium ion battery, it is desirable that the distribution in the thickness direction of the binder in the electrode after drying is as uniform as possible.

Conventionally, as a method of drying an electrode coating film for a lithium ion battery, a method of drying from the sheet surface by blowing hot air has been adopted. Since such drying by blowing is performed exclusively from the surface of the coating film, when the solvent moves to the surface layer side and evaporates, the binder dissolved in the solvent also moves to the surface layer side together with the solvent, and on the surface layer side of the coating film An increase in binder concentration is inevitable. In particular, PVDF widely used as a binder reaches saturation when the concentration in the solvent reaches 12%, and begins to precipitate, and the PVDF particles combine to form a film on the surface. When this state is reached, there is a risk that the evaporation of the solvent in the middle layer and the lower layer is hindered, and the binder that has moved to the surface layer is fixed at that position. Usually, in order to accelerate the drying of the solvent in hot air drying, there are only two methods of increasing the hot air temperature or increasing the wind speed. Of these, the temperature cannot be raised above the allowable temperature of the product, so the wind speed will increase, but in this case as well, the heat flux into the interior will drop significantly as the difference between the hot air temperature and the seat temperature decreases. Even if a very high evaporation rate is obtained, it is extremely difficult to maintain a constant evaporation rate for a long period of time. In some cases, the solvent concentration decreased only in the surface layer portion at a relatively early stage of drying, and the binder was fixed there. Separately, in simulations, etc., in hot-air drying, the drying speed and the uniform distribution of the binder after drying are also in conflict, and there is an inherent dilemma between productivity and quality improvement. It was.

Since PVDF has good compatibility with the aluminum sheet, the binder concentration is relatively high in the lower layer in direct contact with the aluminum sheet. As described above, the binder concentration of the surface layer increases as the solvent evaporates. On the other hand, since the binder concentration is low in the middle layer, the bonding strength of the intermediate layer is reduced. As a result, the surface of the electrode after drying is easily peeled off from the aluminum sheet, and there is a risk of peeling or cracking during the winding operation of the aluminum sheet performed during battery assembly. In order to avoid this problem, if the binder concentration is increased, the amount of the electrode material is relatively reduced, which causes a decrease in battery output.

In order to solve the above-mentioned problem, Patent Document 1 proposes a method in which the drying process is divided into a plurality of processes having different coating film temperatures. In the method of Patent Document 1, it is described that the heating means for drying may be an infrared heater, hot air, or dielectric heating. However, according to the study of the present inventor, drying by an infrared heater is performed relatively uniformly in the entire coating film because infrared rays reach the inside of the coating film, but drying by hot air is performed only from the surface layer, and the inside is mainly heated. Since it is heated by conduction, the behavior of the solvent and binder during the drying process is greatly different. For this reason, the method of Patent Document 1 focusing only on the drying temperature of the coating film still cannot sufficiently equalize the distribution in the thickness direction of the binder in the electrode.

Japanese Patent No. 39539911 (Claims, paragraph 0041)

Therefore, the object of the present invention is to solve the above-mentioned conventional problems, and by appropriately using the drying means, the binder distribution in the thickness direction in the electrode after drying is made more uniform than in the past, and the peeling of the electrode and the occurrence of cracks are caused. It is providing the drying method of the electrode coating film for lithium ion batteries which can be prevented.

The method for drying an electrode coating film for a lithium ion battery according to the present invention made to solve the above-described problems is obtained by applying an electrode material paste containing an electrode agent, a binder, a conductive material, and a solvent on a metal sheet. A method for drying an electrode coating film for a battery, comprising an initial stage in which the coating film temperature is quickly raised, and an intermediate stage in which the entire coating film is heated by hot air and infrared irradiation at a temperature lower than the sheet temperature. The boundary between the stage and the middle stage is a period when the electrode agent is exposed on the surface.

As in claim 2, it is preferable to reduce infrared heating at the end of drying to further lower the hot air temperature.

Further, as in claim 3, it is preferable that the electrode material is lithium cobalt oxide as a positive electrode material, the binder is PVDF, the conductive material is carbon powder, and the solvent is NMP.

The aim of the method for drying an electrode coating film for a lithium ion battery in the present invention is to maintain a liquid phase inside the coating film at a high concentration and a high temperature as much as possible while ensuring the necessary solvent evaporation rate, particularly from the initial stage to the middle stage of drying. It is to secure a long time and to reversely diffuse the binder from the surface layer to the middle layer or lower during that period. The binder is initially dissolved in a solvent, and electrode agent particles exist in the mixed solution. Since the evaporation of the solvent that occupies the main part of the mixture proceeds in order from the surface layer, the mixture liquid mass fraction based on the electrode agent mass in the surface layer decreases early, and between the mixture liquid mass fraction in the lower layer Differences occur. This difference is a kind of concentration difference, which becomes a driving force, and the liquid mixture sequentially moves from the lower layer to the upper layer by diffusion. Therefore, the binder dissolved in this also inevitably gathers on the surface layer. However, since the binder cannot evaporate, the result is that the binder concentration has a distribution with the surface layer as the apex within the coating thickness. The concentration difference becomes a driving force, and this time, the binder is diffused from the surface layer to the lower layer, that is, in the direction opposite to the diffusion of the whole liquid mixture. This phenomenon is called despreading in the present invention. The above two types of diffusion are considered to occur almost simultaneously. In particular, controlling the latter despreading is the key to realizing uniform binder concentration.

In the present invention, at the initial stage of drying, the coating film temperature is quickly raised by hot air spraying and infrared heating. As a result, the above-mentioned period is extended ahead. In the middle of drying, when the evaporation of the solvent begins to expose the electrode material on the surface, the entire coating film is heated by infrared irradiation while controlling the sheet temperature to be below the allowable temperature with hot air lower than the sheet temperature. To do. This makes it possible to ensure a long period during which the evaporation rate is constant and the coating film temperature is maintained at a relatively high temperature without excessively rising. During that period, binder despreading is promoted. Further, the absorption of the infrared rays inside the coating film does not form a continuous film due to the binder deposited on the surface, and the evaporation of the solvent can proceed from the inside of the coating film through the surface electrode materials. As a result, it is possible to efficiently manufacture an electrode in which the binder distribution in the thickness direction is more uniform than in the past.

It is typical sectional drawing which shows the coating film of the drying initial stage. It is typical sectional drawing which shows the coating film of the drying middle stage. It is typical sectional drawing which shows the coating film of the drying final stage. It is a graph which shows the temperature change of the coating film at the time of drying only with a hot air. It is a graph which shows the amount of solvent movement to the surface layer at the time of drying only by a hot air. It is a graph which shows the temperature change of the coating film at the time of drying by hot air and infrared rays combined use. It is a graph which shows the amount of solvent migration to the surface layer at the time of drying by combined use of a hot air and infrared rays. It is a schematic perspective view of the drying apparatus used for the Example.

Embodiments of the present invention will be described below. The present invention is a method for drying an electrode coating film for a lithium ion battery in which an electrode material paste containing an electrode material, a binder, a conductive material, and a solvent is applied onto a metal sheet such as an aluminum sheet. In this embodiment, lithium cobaltate is used as the electrode material for the positive electrode, but lithium nickelate or lithium manganate may be used. The electrode material for the negative electrode is, for example, graphite. These are all fine powders.

The binder is a component for adhering the electrode material and the carbon powder as the conductive material as described above. In this embodiment, the binder is PVDF (polyvinylidene fluoride). The solvent in this embodiment is NMP (N-methyl-pyrrolidone). However, the kind of the binder and the solvent is not limited to this, and various known substances can be used as the constituent material of the electrode coating film for the lithium ion battery.

These electrode material, binder, conductive material, and solvent are kneaded to form an electrode material paste, which is applied onto an aluminum sheet by a general application method, and a coating film having a thickness of about 50 to 200 μm is formed. FIG. 1 is a schematic diagram showing the state, in which 1 is a metal sheet, 2 is a coating film, 3 is an electrode material, 4 is a conductive material, and 5 is a solvent. In this state, the binder is dissolved in the solvent.

First, in the initial stage of drying, hot air is blown onto the surface of the coating film 2 and infrared heating is performed. A general infrared heater can be used as the heating means. Since the thickness of the coating film 2 is about 200 μm at the maximum, the infrared rays reach the inside thereof, and the coating film 2 is also heated from the inside. The temperature of the infrared heating is about 250 to 330 ° C., and the internal temperature of the coating film 2 is raised at an early stage. On the other hand, the temperature of the hot air is preferably a medium temperature of about 110 to 120 ° C., and it is a weak wind. As a result, the solvent starts to evaporate from the surface of the coating film 2, and the solvent and the binder flow from the inside of the coating film 2 toward the surface layer, so that the binder concentration in the surface layer inevitably increases. In the present invention, the solvent starts to evaporate from the surface of the coating film 2, and the electrode material 3 appears on the surface and shifts from the initial stage of drying to the middle stage of drying.

In the middle of drying, the entire coating film is heated by infrared heating while preventing overheating of the surface layer with hot air lower than the sheet temperature. This period overlaps with the main period of solvent evaporation, and is also the main period during which binder reverse diffusion is possible because the difference in the binder concentration between the surface layer and the middle layer increases. The factor governing the binder reverse diffusion rate other than the concentration difference is the diffusion coefficient, which depends on the temperature. The higher the coating temperature, the larger the diffusion coefficient, and the higher the diffusion rate. In the drying method according to the present invention, the effective reverse diffusion period can be kept longer and further as high as possible by a combination of infrared heating and convection cooling. Can be realized. As described above, it is difficult to obtain a constant evaporation rate only by heating with hot air. Therefore, if the hot air velocity is increased in order to promote drying, the evaporation rate temporarily increases excessively and the surface layer is overdried. For this reason, it is difficult to prevent binder segregation. In the present invention, the temperature of the hot air may be a low temperature of about 90 to 100 ° C., and the wind speed may be stronger than the initial stage of drying. As shown in FIG. 7, the wind speed contributes to the constant evaporation rate, and can be appropriately changed depending on the coating film physical properties of the sheet. The infrared heating temperature is preferably a high temperature of the initial set temperature ± 20 ° C. As a result, a state in which the temperature inside the coating film 2 is relatively high and the inside of the coating film is kept wet is realized, and the surface layer side binder is changed to the middle layer side by utilizing the binder concentration difference inside the coating film 2. Can be despread. The surface layer of the coating film 2 is controlled in evaporation speed by low temperature and strong air blowing, but even if the solvent concentration is lowered, the solvent is evaporated through the

surface electrode materials

3 and 3 by the internal absorption of infrared rays. It progresses from the inside of the coating film. The evaporated solvent is quickly removed by the wind.

After reducing the binder concentration difference in the inside of the coating film 2 in this way, if the concentration of the solvent is below the allowable value, it may be cooled as it is, but in order to improve the quality, the infrared heating is relaxed. It is preferable to add an end of drying in which the hot air temperature is further lowered. A preferable infrared heating temperature at the end of drying is a low temperature of 200 to 250 ° C., a hot air temperature is a low temperature of 80 to 90 ° C., and a wind speed is a strong wind. This completes evaporation of the solvent from the interior of the coating film 2 and prevents overheating of the surface. In the electrode manufactured by using the drying method of the present invention, the binder distribution in the thickness direction is made more uniform than before, and it is possible to prevent electrode peeling and cracking even in the step of winding an aluminum sheet. In some cases, the infrared heater is not used in the third zone. In such a case, it is effective to increase the hot air temperature to about 120 to 130 ° C.

4 and 5 show graphs of the temperature of the coating film when the drying is performed only with hot air and the amount of solvent transfer to the surface layer, and FIGS. 6 and 7 show the coating film when the drying is performed according to the present invention. The graph of the temperature of this and the amount of solvent movement to the surface layer is shown. Each horizontal axis is time (s). As shown in FIG. 4 and FIG. 5, the heating with only hot air causes a gradual rise in temperature, and the period during which the solvent movement to the surface layer is accelerated, which is correlated with the surface layer evaporation promotion period and the binder reverse diffusion period, is short-pointed. On the other hand, as shown in FIG. 6 and FIG. 7, in the heating using both hot air and an infrared heater, the temperature of the coating film rises rapidly, the solvent movement promotion period to the surface layer is relatively long, and the amount of solvent movement there is Maintained constant. During this time, a large amount of the binder can be back-diffused to the middle layer side.

Examples of the present invention are shown below. First, an electrode coating film for a lithium ion battery was prepared by applying an electrode material paste containing an electrode material, a binder, a conductive material, and a solvent on an aluminum sheet having a thickness of 20 μm and a width of 200 mm to a thickness of 80 μm. As for the coating method, an extrusion type nozzle was used as in Patent Document 1.

As the drying apparatus, an apparatus including an infrared heater 10 and a hot air chamber 11 for sending hot air to a roll-to-roll roll apparatus having a furnace length of 12 m as shown in FIG. 8 was used. Moreover, from the hot air chamber 11, the apparatus which can control the hot air of the upper direction and the downward hot air which are shown in figure was used.

The temperature of the infrared heater 10 was set to the same temperature in the coating width direction, and the following conditions were used in the coating film transport direction. As for the hot air, the upper hot air was defined as the upper hot air, and the lower hot air was defined as the lower hot air. Table 1 shows the method of the present invention, and Table 2 shows a comparative example using only hot air. Note Table 1, the air volume 19.5 m ³ / min in Table 2, 12m ³ / min, respectively correspond to the air speed of about 6.5m / s and about 4m / s.

In this example, 1 zone was the initial state, 2 zones were in the mid-term state, 3 zones, and 4 zones were in the final state. The medium-term state is a stage where the electrode material appears on the surface. As the detection method, the reflectivity of the surface changes as the coating film becomes thinner, and the reflectivity hardly changes after the electrode material appears on the surface. Transition to state control. In addition, the transition to the final state is intended to promote evaporation in consideration of mass productivity and the like, and can be appropriately set as long as the reverse diffusion state in the intermediate state can be secured for a certain period.

Comparative example

Table 3 shows the results of measuring the residual amount of the solvent and the mass fraction of the binder for the surface layer, middle layer and lower layer of the electrode obtained by drying the coating film by the method of the present invention and the method of the comparative example as described above. Summarized. The defect rate was indicated by the number of peeling or cracking that occurred during the 200 m electrode winding operation.

As described above, according to the method for drying an electrode coating film for a lithium ion battery of the present invention, the binder distribution in the thickness direction in the electrode after drying is made more uniform than before by properly using a drying means, There is an advantage that electrode peeling and cracking can be prevented.

DESCRIPTION OF SYMBOLS 1 Metal sheet 2 Coating film 3 Electrode material 4 Conductive material 5 Solvent 10 Infrared heater 11 Hot air chamber

Claims

A method for drying an electrode coating film for a lithium ion battery in which an electrode material paste containing an electrode agent, a binder, a conductive material, and a solvent is applied onto a metal sheet, the initial stage for quickly increasing the coating film temperature, and the sheet temperature A lithium ion battery comprising a lower temperature hot air and an intermediate stage in which the entire coating film is heated by infrared irradiation, and the boundary between the initial stage and the intermediate stage is a period when the electrode material is exposed on the surface Method for drying electrode coating film.
2. The method for drying an electrode coating film for a lithium ion battery according to claim 1, wherein at the end of drying, infrared heating is relaxed and the temperature of hot air is further lowered.
3. The electrode coating for a lithium ion battery according to claim 1, wherein the electrode agent is lithium cobalt oxide as a positive electrode material, the binder is PVDF, the conductive material is carbon powder, and the solvent is NMP. How to dry the membrane.