Kneader and manufacturing method of electrode body including electrode active material using the same
10497926 ยท 2019-12-03
Assignee
Inventors
Cpc classification
B01F27/72
PERFORMING OPERATIONS; TRANSPORTING
B29C48/57
PERFORMING OPERATIONS; TRANSPORTING
H01M4/133
ELECTRICITY
H01M4/1393
ELECTRICITY
B29B7/488
PERFORMING OPERATIONS; TRANSPORTING
Y02E60/10
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
B29B7/483
PERFORMING OPERATIONS; TRANSPORTING
International classification
B29C48/57
PERFORMING OPERATIONS; TRANSPORTING
H01M4/133
ELECTRICITY
H01M4/62
ELECTRICITY
Abstract
A kneader has a rotational conveyance member configured to knead the kneading material and convey the kneading material from an inlet toward an outlet by a rotational motion around an axis. The rotational conveyance member has a kneading zone configured to knead the kneading material, a first conveyance zone placed on an upstream side relative to the kneading zone and configured to convey the kneading material, and a second conveyance zone placed on a downstream side relative to the kneading zone and configured to convey the kneading material, and a conveyance force of the second conveyance zone is smaller than a conveyance force of the first conveyance zone in a case where the same conveyance object is conveyed.
Claims
1. A kneader comprising: an extruder housing having an inlet into which a battery material is put and an outlet from which a kneaded mixture obtained by kneading the battery material is discharged; and a rotational conveyance member having a kneading zone configured to knead the battery material, a first conveyance zone placed on an upstream side relative to the kneading zone and configured to convey the battery material, and a second conveyance zone placed on a downstream side relative to the kneading zone and configured to convey the battery material, the second conveyance zone having a conveyance force smaller than a conveyance force of the first conveyance zone, wherein the rotational conveyance member includes a first screw blade in the first conveyance zone; the rotational conveyance member includes a second screw blade in the second conveyance zone; wherein the kneading zone includes a stirring member having the same shape as a rotor portion of the first screw blade and having no thread portion; and a ratio of an outside diameter of the first screw blade to an outside diameter of the second screw blade is 1.4 or more.
2. The kneader according to claim 1, wherein the first screw blade includes a rotor portion and a thread portion, wherein the rotor portion has a triangular prism shape.
3. The kneader according to claim 1, wherein the second screw blade includes a rotor portion and a thread portion, wherein the rotor portion has a triangular prism shape.
4. The kneader according to claim 1, wherein the rotational conveyance member consists of the kneading zone, the first conveyance zone and the second conveyance zone.
5. The kneader according to claim 1, wherein the ratio of an outside diameter of the first screw blade to an outside diameter of the second screw blade is 1.4 or more and 2.0 or less.
6. The kneader according to claim 1, wherein the rotational conveyance member includes two conveyance screws in parallel to each other in the extruder housing.
7. A manufacturing method of an electrode body including an electrode active material, the manufacturing method comprising: providing the kneader according to claim 1, kneading the kneading material including the electrode active material by the kneader, so as to obtain an electrode active material paste; and applying, to a collector, the obtained electrode active material paste, so as to obtain the electrode body in which an electrode active material layer is formed on the collector, wherein: the kneading material including the electrode active material is put into the inlet; and the electrode active material paste is obtained from the outlet.
8. The manufacturing method according to claim 7, wherein a solid content ratio in the kneading material to be put into the inlet of the kneader is 60% by weight or more.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) Features, advantages, and technical and industrial significance of exemplary embodiments of the invention will be described below with reference to the accompanying drawings, in which like numerals denote like elements, and wherein:
(2)
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DETAILED DESCRIPTION OF EMBODIMENTS
(12) The following describes an embodiment for embodying the present invention in detail with reference to the attached drawings. In the present embodiment, the present invention is applied to manufacture of an electrode body according to a process procedure (see
Active Material Paste (Active Material Layer Formation Step)
(13) The kneading step includes a first conveyance stage, a kneading stage, and a second conveyance stage as illustrated in
(14) Hereby, the kneader 1 is configured to knead and convey a kneading material put into the inlet 4 toward a right side in
(15) The kneader 1 is further described. Two conveyance screws 3 are actually placed in parallel to each other inside the housing 2 as illustrated in
(16) The first screw blade 11 and the second screw blade 12 are described with reference to a perspective view of
(17) The first screw blade 11 and the second screw blade 12 both have the above shape, but have different sizes. The size as used herein indicates an outside diameter A of the thread portion 14 or a diameter B of the rotor portion 13, as illustrated in a front view of
(18) The two conveyance screws 3 of
(19) The two conveyance screws 3 rotate in the same direction in
(20) Here, in the kneader 1 configured as described above, a conveyance force of the first conveyance zone 6 on an upstream side is stronger than that of the second conveyance zone 7 on a downstream side, in a case where the same conveyance object is conveyed. More specifically, the difference between their conveyance forces is attained by the size difference between the first screw blade 11 and the second screw blade 12.
(21) For example, the conveyance force is stronger as the outside diameter A of the thread portion 14 illustrated in
(22) A measure to make a difference in conveyance force between the first conveyance zone 6 and the second conveyance zone 7 is not limited to the outside diameter A and the diameter B. For example, the following measures are conceivable: the number of threads of the thread portion 14 (the conveyance force is stronger as the number of threads is larger); and a size of a notch in a case the notch is provided in the thread portion 14 (the conveyance force is stronger as the notch is smaller). Further, the difference in conveyance force can be achieved by making a difference in rotation speed of the conveyance screws 3 between the first conveyance zone 6 and the second conveyance zone 7 (the conveyance force is stronger as the rotation speed is faster). Two or more of them may be used in combination.
(23) With the use of the kneader 1 configured as described above, an electrode active material paste to be used for an electrode body of a battery can be manufactured. The following description is made by taking, as an example, a case of manufacturing a negative-electrode active material paste to be used for a negative electrode of a lithium-ion secondary battery. A kneading material to be used herein includes the followings. Active Material: Graphite Thickener: CMC (carboxymethyl cellulose) Binder: SBR (styrene-butadiene rubber) Kneading Solvent: Water (ion-exchange water)
(24) The kneading material is put into the inlet 4 of the kneader 1 as has been described above. The kneading material thus put therein is conveyed from the left side toward the right side in
(25) The operation of the kneader 1 has the following effects due to the difference in conveyance force between the first conveyance zone 6 and the second conveyance zone 7. That is, in the kneading zone 8, inflow from the first conveyance zone 6 is predominant over outflow to the second conveyance zone 7. Because of this, the kneading zone 8 does not become a negative-pressure state. Hereby, in the kneader 1, a degree of kneading in the negative-electrode active material paste to be discharged is uniform, so the discharge thereof is not interrupted. That is, the negative-electrode active material paste having a uniform viscosity can be obtained stably.
(26) If the first conveyance zone 6 and the second conveyance zone 7 have the same conveyance force, the above effect cannot be obtained. That is, in this case, in the kneading zone 8, the outflow to the second conveyance zone 7 is slightly predominant over the inflow from the first conveyance zone 6. This is because the negative-electrode active material paste that has been kneaded is slightly easily conveyed as compared with the kneading material that has not been kneaded. On this account, by execution of the kneading, the kneading material existing in the kneading zone 8 is gradually decreased. Accordingly, a negative pressure occasionally occurs during the execution of the kneading though temporarily, as indicated by D in a graph on an upper side in
(27) In contrast, the kneader 1 of the present embodiment is configured such that the conveyance forces of the first conveyance zone 6 and the second conveyance zone 7 made different from each other, thereby preventing such an inconvenience. That is, in the kneader 1 according to the present embodiment, a viscosity and a flow rate of the negative-electrode active material paste to be obtained are relatively stable. That is, a marked fluctuation in viscosity, like the peak E in the graph on the lower side of
(28)
(29) In a case of the condition with a small discharge flow rate, even if there is no difference in conveyance force, a viscosity variation is about 300 mPa.Math.s, which is not a very large value. However, when the discharge flow rate is increased without the difference in conveyance force, the viscosity variation is increased to about 1700 mPa.Math.s. In contrast, in a case where there is a difference in conveyance force, like the present embodiment, even if the discharge flow rate is large, it is possible to restrain the viscosity variation to an equivalent level to or less than the viscosity variation at the small discharge flow rate without the difference in conveyance force.
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(31) In a case of the condition with a small discharge flow rate, even if there is no difference in conveyance force, the variation in solid-matter residual ratio is about 0.2% by weight, which is not a very large value. However, when the discharge flow rate is increased without the difference in conveyance force, the variation in solid-matter residual ratio is increased to about 0.9% by weight. In contrast, in a case where there is a difference in conveyance force like the present embodiment, even if the discharge flow rate is large, it is possible to restrain the variation in solid-matter residual ratio to about 0.1% by weight, which is smaller than a case of the small discharge flow amount without the difference in conveyance force.
(32) As such, in
(33) The negative-electrode active material paste obtained as such is applied on a collector, so that a negative-electrode active material layer can be formed on the collector. Hereby, an electrode body for a secondary battery or the like is obtained. The electrode body includes the collector and the negative-electrode active material layer provided of a surface thereof. In general, after the application, a layer of the negative-electrode active material paste is dried to remove the kneading solvent, thereby forming the negative-electrode active material layer. Further, it is common to form the negative-electrode active material layer on both sides of the collector. Here, as described above, since the variations in viscosity and solid-matter residual ratio of the negative-electrode active material paste obtained by the kneader 1 are small, the quality of the negative-electrode active material layer of the electrode body is also stable. Further, it is possible to stably perform a step of application.
EXAMPLES
(34) The following describes Examples. In Examples, in terms of a kneading material, the afore-mentioned material used to manufacture the negative-electrode active material paste was used, and a target viscosity of a negative-electrode active material paste to be obtained was set to 4000 mPa.Math.s. Further, the following two process conditions were employed. Discharge flow rate: 0.7 L/m (axis rotation speed: 600 rpm) Discharge flow rate: 1.4 L/m (axis rotation speed: 1200 rpm)
(35) Details of Comparative Examples 1 and 2 and Examples 1 to 4 are shown in Table 1. In Table 1, three items, i.e., Solid Content, Discharge Flow Rate, and Screw Outside Diameter Ratio are shown as manufacturing conditions for respective examples, and four items, i.e., Paste Viscosity, Viscosity Variation, Residual Solid Content Variation, and Evaluation are shown as results. First described are these items.
(36) Solid Content indicates a weight ratio of a solid content in a kneading material to be put, that is, a weight ratio of all components except a kneading solvent in the kneading material. Discharge Flow Rate indicates a flow rate of a negative-electrode active material paste to be discharged, that is, a throughput speed of kneading. Screw Outside Diameter Ratio indicates a ratio obtained by dividing an outside diameter A of a first screw blade 11 by an outside diameter A of a second screw blade 12. In Comparative Examples 1, 2, there is no difference in outside diameter and their screw outside diameter ratios are 1.0, which does not satisfy the feature of the present embodiment. On this account, they are shown in italic type in Table 1. Note that, in terms of a diameter B of a rotor portion 13, the first screw blade 11 and the second screw blade 12 have the same diameter B in all of Comparative Examples and Examples. Screw Capacity Ratio indicates a ratio obtained by dividing a conveyance force of the second screw blade 12 by a conveyance force of the first screw blade 11 (a conveyance amount per unit time, an actual value herein). As a value of Screw Outside Diameter Ratio is larger, Screw Capacity Ratio has a smaller value. In Comparative Examples 1, 2, there is no difference in outside diameter and their screw outside diameter ratios are 1.0, so their screw capacity ratios are shown in italic type in Table 1, similarly to Screw Outside Diameter Ratio.
(37) Paste Viscosity is an average value of a viscosity of a negative-electrode active material paste obtained by kneading. Viscosity Variation indicates a variation (standard deviation) in viscosity of the negative-electrode active material paste obtained by kneading. Residual Solid Content Variation indicates a variation (standard deviation) in solid-matter residual ratio (described in indicates a paste in which Viscosity Variation is 300 mPa.Math.s or less and Residual Solid Content Variation is 0.2 wt % or less.
indicates a paste in which Viscosity Variation is 1050 mPa.Math.s or less and Residual Solid Content Variations is 0.5 wt % or less, but which does not satisfy the condition of
. # indicates a paste that does not satisfy the conditions of
and
. Values as grounds for # evaluation are shown in italic type in Table 1.
(38) TABLE-US-00001 TABLE 1 Condition Result Screw Residual Solid Discharge Outside Screw Paste Solid Content Flow Rate Diameter Capacity Viscosity Viscosity Content (wt %) (L/min) Ratio Ratio (mPa .Math. s) (mPa .Math. s) (wt %) Evaluation Comparative 54 0.7 1.0 1.0 3800 287 0.2 Example 1 Comparative 60 1.4 1.0 1.0 4200 1713 0.9
Example 2 Example 1 60 1.4 1.2 0.84 4100 1012 0.5
Example 2 60 1.4 1.4 0.72 3900 253 0.1
Example 3 60 1.4 1.6 0.58 3900 226 0.07
Example 4 60 1.4 2.0 0.45 3800 210 0.05
(39) The following things are found from Table 1. First, in a case of a condition in which the solid content ratio is low and the discharge flow rate is small, even if there is no difference in conveyance force, any particular problem does not occur (Comparative Example 1). However, if the solid content ratio and the discharge flow rate are increased, a markedly bad result is obtained without the difference in conveyance force (Comparative Example 2). However, in Examples 1 to 4 in which there is a difference in conveyance force, both Viscosity Variation and Residual Solid Content Variation are improved as compared with Comparative Example 2. Particularly, in Examples 2 to 4 in which Screw Outside Diameter Ratio is 1.4 or more (Screw Capacity Ratio is 0.72 or less), excellent results with evaluation are obtained.
(40) Examples 5 to 7 shown in Table 2 are examples in which an amount of a thickener in a kneading material is increased so that a target viscosity of a negative-electrode active material paste to be obtained is set to 7000 mPa.Math.s. Even in a case of forming such a high-viscosity negative-electrode active material paste, since Examples 5 to 7 have a difference in conveyance force, or
evaluations are obtained. Particularly, in Examples 6, 7 in which Screw Outside Diameter Ratio is 1.6 or more (Screw Capacity Ratio is 0.58 or less), excellent results with
evaluation are obtained.
(41) TABLE-US-00002 TABLE 2 Condition Result Screw Residual Solid Discharge Outside Screw Paste Solid Content Flow Rate Diameter Capacity Viscosity Viscosity Content (wt %) (L/min) Ratio Ratio (mPa .Math. s) (mPa .Math. s) (wt %) Evaluation Example 5 60 1.4 1.4 0.72 6800 319 0.3 Example 6 60 1.4 1.6 0.58 7000 235 0.12
Example 7 60 1.4 2.0 0.45 6900 232 0.07
(42) Example 8 shown in Table 3 is an example in which a discharge flow rate (throughput speed) is further increased (shaft rotation speed: 1800 rpm). A target viscosity of a negative-electrode active material paste is set to 4000 mPa.Math.s similarly to Examples in Table 1. Even in a case where the negative-electrode active material paste is obtained with a high throughput speed as such, since Example 8 has a difference in conveyance force is 1.6 (Screw Capacity Ratio is 0.58), an excellent result with evaluation is obtained.
(43) TABLE-US-00003 TABLE 3 Condition Result Screw Residual Solid Discharge Outside Screw Paste Solid Content Flow Rate Diameter Capacity Viscosity Viscosity Content (wt %) (L/min) Ratio Ratio (mPa .Math. s) (mPa .Math. s) (wt %) Evaluation Example 8 60 2.1 1.6 0.58 3700 265 0.1
(44) As described above specifically, according to the present embodiment and Examples, in the kneader 1 for manufacturing a negative-electrode active material paste by stirring (kneading) a kneading material while conveying the kneading material by the conveyance screws 3, respective conveyance zones (the first conveyance zone 6 and the second conveyance zone 7) are provided on the upstream side and the downstream side of the kneading zone 8. The first conveyance zone 6 and the second conveyance zone 7 are configured to have a difference in conveyance force in a case where the same conveyance object is conveyed. That is, the first conveyance zone 6 on the upstream side is configured to have a stronger conveyance force than the second conveyance zone 7 on the downstream side. This prevents a temporary occurrence of a negative pressure state in the kneading zone 8 and a temporary increase in viscosity of the negative-electrode active material paste along with the temporary occurrence of the negative pressure state. This accordingly attains the kneader 1 that can stably manufacture the negative-electrode active material paste while restraining the variations in viscosity and residual solid content of the negative-electrode active material paste to be obtained, and the manufacturing method of the electrode body with the use of the kneader 1.
(45) Note that the present embodiment is merely an example, and does not limit the present invention at all. Accordingly, the present invention can be naturally altered and modified without deviating from the gist thereof. For example, a paste to be manufactured is not limited to the negative-electrode active material paste. The present invention is applicable to a case where a positive-electrode active material paste is manufactured by kneading. Further, a target battery type is not limited in particular. Further, the present invention is applicable to manufacture of a paste for purposes other than the battery.
(46) Further, the configuration of the conveyance screw 3 of the kneader 1 is also modifiable. A first conceivable modification about the conveyance screw 3 is a modification in shapes of the first screw blade 11 and the second screw blade 12. The first screw blade 11 and the second screw blade 12 illustrated in
(47) Further, it is conceivable to modify a shape of a part of the conveyance screw 3 in the kneading zone 8. The above embodiment describes that the stirring member 16 in the kneading zone 8 has only a stirring function, but does not have a conveyance function. However, the stirring member 16 may be configured to also have the conveyance function to some extent. Further, an overall configuration of the kneader 1 is not limited to the configuration including two conveyance screws 3. The kneader 1 may be constituted by one conveyance screw 3, or may be constituted by three (or more) conveyance screws 3.
(48) Further, about the putting of the kneading material into the kneader 1, the above embodiment describes that the kneading material is just put into the inlet 4, which may be a little more complicated. For example, only part of the kneading solvent (water in the present embodiment) is put into the inlet 4, and the remaining part thereof may be additionally put at around a boundary between the kneading zone 8 and the second conveyance zone 7. Further, the binder (SBR in the above embodiment) may not be put into the inlet 4, but may be put additionally at around the second conveyance zone 7.