JP6080044B2 - Nonaqueous secondary battery plate manufacturing method - Google Patents

Description

The present invention relates to a method for producing a nonaqueous secondary battery electrode plate having excellent internal short circuit safety.

  A non-aqueous electrolyte secondary battery such as a non-aqueous secondary battery includes a layer that electrically insulates a positive electrode plate and a negative electrode plate. Examples of these insulating layers include microporous film separators made of polyethylene, polypropylene, etc. used in non-aqueous secondary batteries, or gel-like electrolytes impregnated with a polymer matrix used in polymer batteries. Examples thereof include an electrolyte sheet.

  In addition, since these insulating layers are easily deformed and melted when an internal short circuit occurs, an example in which a ceramic filler is formed on an electrode plate has been proposed (see, for example, Patent Document 1).

  FIG. 6 is a cross-sectional view schematically showing a battery configuration described in Patent Document 1 in which a ceramic filler layer is laminated on a negative electrode active material layer.

  In FIG. 6, a porous insulating layer 104 formed of a fibrous ceramic filler is laminated on a negative electrode active material layer 102a on a negative electrode 102. In addition, the positive electrode active material layer 101 a exists on the positive electrode 101 with the separator 103 interposed therebetween.

  The porous insulating layer 104 is applied and formed on the negative electrode active material layer 102a by using a continuous coating method such as gravure coating or die coating, a drawing method using an ink jet nozzle, a splate coating method, or the like.

Japanese Patent No. 4529511

  However, even when the porous insulating layer 104 is applied on the negative electrode active material 102a layer using the above-described conventional application method, a non-aqueous secondary battery electrode plate with sufficient quality cannot be produced.

  Further, in the above-described conventional configuration, a ceramic insulating layer (porous insulating layer 104) that does not accept lithium is formed so as to cover the active material layer (negative electrode active material layer 102a), so that output characteristics are deteriorated. In addition, there is a problem that the capacity density of the battery decreases due to the volume of the film that does not contribute to the taking in and out of Li ions.

In consideration of the above-described conventional problems, the present invention can ensure the safety of preventing an internal short circuit in a non-aqueous secondary battery, and can realize higher output and higher capacity density of the non-aqueous secondary battery. and to provide a method of manufacturing an aqueous secondary battery electrode plate.

In order to solve the above-described problem, the first aspect of the present invention provides:
A mixture material is made to enter a gap between a first roll having a surface coated with an insulating material containing silicone and a second roll rotating in a direction opposite to the first roll, and the peripheral surface of the second roll 1 mg / m ² or more of the insulating substance on the surface of the mixture material formed in the coating film shape by forming the mixture material in a coating film shape on the surface of the article to be coated. It is a manufacturing method of a non-aqueous secondary battery electrode plate, which is adhered so as to be present in the form of particles or layers at 500 mg / m ² or less.

The second aspect of the present invention
The first roll rotates in the opposite direction to the first roll, and the mixture material enters the gap between the second roll whose surface is coated with an insulating material containing silicone , The mixture material is formed in a coating on the insulating material on the surface, and the insulating material and the mixture material formed on the surface of the second roll are in the opposite direction to the second roll. The coating material is transferred to the coated object running on the peripheral surface of the third roll that rotates in a coating, and the insulating material is applied to the surface of the coating material material in the coated film that is transferred to the coated object. It is a method for producing a non-aqueous secondary battery electrode plate, characterized in that the active substance is adhered in the form of particles or layers at 1 mg / m ² or more and 500 mg / m ² or less.

The third aspect of the present invention
The peripheral speed of said 1st roll and said 2nd roll is mutually different, It is a manufacturing method of the non-aqueous secondary battery electrode plate of 1st this invention characterized by the above-mentioned.

The fourth aspect of the present invention is
Among the first roll, the second roll, and the third roll, at least in a pair of two rolls adjacent to each other, the peripheral speeds of the two rolls are different from each other. It is a manufacturing method of the non-aqueous secondary battery electrode plate of this invention.

The fifth aspect of the present invention provides
The insulating material has a rubber hardness of 10 or more and 100 or less, according to any one of the first to fourth methods of manufacturing a nonaqueous secondary battery electrode plate of the present invention.

The sixth aspect of the present invention provides
The method for producing a nonaqueous secondary battery electrode plate according to any one of the first to fourth aspects of the present invention, wherein the insulating substance is silicone.

The seventh aspect of the present invention
The volume solid content concentration of the mixture material that enters between the first roll and the second roll is 40% or more and 90% or less, wherein any one of the first to sixth It is a manufacturing method of the nonaqueous system rechargeable battery electrode board of the present invention.

In addition, the eighth aspect of the present invention
The load applied to the mixture material by the first roll and the second roll is 100 N / cm or more, wherein the non-aqueous secondary battery plate of the first or third aspect of the present invention is used. It is a manufacturing method.

The ninth aspect of the present invention provides
The load applied to the mixture material by the second roll and the third roll is 100 N / cm or more. The non-aqueous secondary battery electrode plate of the second or fourth aspect of the present invention is characterized in that It is a manufacturing method.

  According to the first and second aspects of the present invention, a non-aqueous secondary battery electrode plate with sufficient quality can be produced.

  In addition, according to the fifth and sixth aspects of the present invention, it is possible to produce a non-aqueous secondary battery electrode plate in which the output characteristics do not deteriorate and the capacity density of the battery does not decrease.

  That is, according to the present invention, a non-aqueous secondary battery electrode plate capable of realizing higher output and higher capacity density of a non-aqueous secondary battery while ensuring safety of preventing an internal short circuit in the non-aqueous secondary battery and its A manufacturing method, a non-aqueous secondary battery using the non-aqueous secondary battery electrode plate, and a moving body can be provided.

Roll configuration diagram according to the embodiment of the present invention Schematic cross-sectional view of an electrode plate in an embodiment of the present invention Roll configuration diagram of a system for transferring a coating film once formed on the surface of a roll to an object to be coated in an embodiment of the present invention Roll configuration diagram when the peripheral speeds of the first roll and the second roll are different in the embodiment of the present invention FIG. 2 is a schematic vertical sectional view of a lithium secondary battery in an embodiment of the present invention. Sectional schematic diagram showing the battery configuration of a conventional non-aqueous secondary battery

  Embodiments of the present invention will be described below with reference to the drawings. In the following description, the same components are denoted by the same reference numerals, and description thereof is omitted as appropriate.

(Embodiment)
FIG. 1 is a roll configuration diagram according to an embodiment of the present invention.

  In FIG. 1, the mixture paint 22 enters between the first roll 11 and the second roll 12 that rotates in the opposite direction to the first roll 11, and between the first roll 11 and the second roll 12, A state is shown in which the mixture paint 22 is transferred in the form of a coating film to the application object 21 that travels in the same direction as the rotation direction of the second roll 12 at a speed equal to the peripheral speed of the second roll 12. . The electrode plate 23 to which the mixture paint 22 has been transferred in the form of a coating film is conveyed to a subsequent process such as a pressing process.

  In this coating step, the material of the first roll 11 and the second roll 12 is preferably a material having a high surface hardness that is not affected by the hardness of the mixture paint 22 such as SUS. In some cases, surface treatment such as hard chrome plating treatment may be performed.

  As shown in FIG. 1, a roll coating layer 10 made of an insulating material is present on the surface of the first roll 11.

  Examples of the material constituting the insulating substance include polymer materials such as silicone, fluoro rubber, urethane rubber, chlorobrene rubber, nitrile rubber, and butyl rubber, or inorganic materials such as alumina, silica, titania, zirconia, zinc oxide, and magnesia. Materials or composite compound materials can be used. These materials may be used alone or in combination as necessary. The insulating material to be coated on the surface of the first roll 11 is not limited to these materials as long as it has insulating properties.

  In order to transfer the mixture paint into a coating film, the insulating substance is preferably an elastic body, and it is preferable to use a resin containing silicone and fluororubber and a composite material thereof. In insulating material materials with poor transferability, it is difficult to form a mixture paint from a roll to a roll or from a roll to an object to be coated in a coating film.

  FIG. 2 shows a schematic cross-sectional view of the electrode plate 23 produced by the coating process of FIG.

  1, the insulating material roll coating layer 10 is brought into contact, and the mixture coating 22 is formed as a coating material mixture 25 in the form of a coating on the object to be coated 21. It adheres as 24. FIG. 2 shows the electrode plate 23 to which the insulating material 24 is attached.

  Due to the adhesion of the insulating material 24, when the positive and negative electrodes are short-circuited, an excessive current does not flow through the short-circuit point, so that abnormal heat generation can be prevented.

  In addition, the mixture paint 22 supplied between the 1st roll 11 and the 2nd roll 12 as shown in FIG. 1 is not restricted to the structure which transcribe | transfers to the to-be-coated object 21, The mixture paint 22 supplied Thus, a coating film may be once formed on the surface of the roll, and the coating film formed on the surface of the roll may be transferred to the article 21 to be coated.

  In FIG. 3, the roll block diagram of the system which transfers the coating film once formed on the surface of the roll to a to-be-coated object is shown.

  In FIG. 3, the mixture paint 22 that has entered between the first roll 11 and the second roll 12 is once formed on the surface of the second roll 12 in the form of a coating film. Shows a state of being transferred from the second roll 12 to the workpiece 21 running on the third roll 13.

  In this case, the roll coating layer 10 of an insulating substance is present on the surface of the second roll 12, and the mixture paint 22 supplied between the first roll 11 and the second roll 12 is the second roll 12. The film-like mixture coating material 22 formed on the surface of the roll coating layer 10 on the surface and formed on the surface of the second roll 12 is transferred to the article 21 to be applied running on the third roll 13. In this case, the roll coating layer 10 covering the surface of the second roll 12 adheres on the coating mixture 25 as the insulating material 24.

  In this case, the third roll 13 rotates in the opposite direction to the second roll 12, and the coating object 21 moves between the second roll 12 and the third roll 13 and the peripheral speed of the third roll 13. The vehicle travels at the same speed in the same direction as the rotation direction of the third roll 13.

  In addition, another roll may exist between the 2nd roll 12 and the 3rd roll 13 as needed.

  In addition, the mixture paint 22 supplied between the 1st roll 11 and the 2nd roll 12 corresponds to an example of the mixture material of this invention.

  In the above description, the configuration in which the mixture paint 22 is applied to one side of the article to be coated 21 has been described. However, after the mixture paint 22 is formed in a coating on one side of the article to be coated 21, the article to be coated is applied. The mixture paint 22 can be formed on both surfaces of the article to be coated 21 by turning over 21 and applying the mixture paint 22 to the back surface again by the above-described application method.

  The volume solid content concentration of the mixture paint 22 supplied between the first roll 11 and the second roll 12 is desirably 40% or more and 90% or less.

  When the volume solid content concentration is lower than 40%, the mixture paint 22 is soft, so that the contact between the first roll 11 and the object to be coated 21 becomes weak and the adhesion of the insulating substance 24 (FIG. 2) is reduced. Alternatively, the mixture paint 22 adheres to both sides of the first roll 11 and the object to be coated 21, and it becomes difficult to form the mixture paint 22 in a film form.

  On the other hand, if the volume solid content concentration is higher than 90%, the mixture paint 22 becomes hard, so that the contact with the object 21 becomes strong, so that the adhesion amount of the insulating substance 24 increases, or the mixture paint. Since the particle | grains in 22 are hardly coat | covered with the solvent, the mixture coating material 22 cannot be formed in a coating-film shape, and cannot be transcribe | transferred to the to-be-coated article 21 side in a film form.

The gap between the first roll 11 and the second roll 12 can be freely set in order to set the mixture paint 22 to be supplied to a predetermined electrode plate mixture weight (g / m ² ), or The peripheral speed ratio between the first roll 11 and the second roll 12 can be freely set.

  The peripheral speed ratio of the second roll 12 to the first roll 11 at this time (the peripheral speed of the second roll 12 / the peripheral speed of the first roll 11) is preferably 1 or more.

  FIG. 4 shows a roll configuration diagram when the peripheral speeds of the first roll 11 and the second roll 12 are different.

  In FIG. 4, a second roll 14 that rotates at a different peripheral speed with respect to the first roll 11 is installed. When this peripheral speed ratio (peripheral speed of the second roll 14 / peripheral speed of the first roll 11) is smaller than 1, the mixture paint 22 is transferred from the first roll 11 onto the coated object 21 in the form of a coating film. Is difficult.

  Further, in the state where the film is transferred from the first roll 11 onto the coating object 21, the peripheral speed ratio may be considerably large. However, in order to produce a uniform film thickness, the peripheral speed ratio is 10 or less is desirable. That is, the peripheral speed ratio is desirably in the range of 1 or more and 10 or less.

  Also in the configuration shown in FIG. 3, the peripheral speeds of the adjacent first roll 11 and second roll 12 may be different. In the configuration shown in FIG. 3, the peripheral speeds of the adjacent second roll 12 and third roll 13 may be different.

  The rubber hardness of the insulating material forming the roll coating layer 10 on the surface of the first roll 11 in FIG. 1 and the surface of the second roll 12 in FIG. 3 is preferably 10 or more and 100 or less.

  If the insulating material has a rubber hardness of less than 10, when the mixture paint 22 is transferred, more than the necessary amount of the insulating material adheres to the electrode plate 23 or in the electrode plate 23. The shape of the substance changes and it is difficult to transfer it to a uniform coating. Further, although the upper limit value of the rubber hardness is defined as 100, even when the rubber hardness is 100, it is possible to transfer to a uniform coating.

The adhesion amount of the insulating substance 24 adhered by contact with the roll coating layer 10 of the insulating substance on the surface of the first roll 11 in FIG. 1 or the second roll 12 in FIG. 3 is 1 mg / m ² or more and 500 mg. / M ² or less is preferable because safety of preventing an internal short circuit of the electrode plate 23 can be secured.

When the adhesion amount of the insulating substance 24 is less than 1 mg / m ^2, it is difficult to ensure insulation at the time of short circuit, and problems such as thermal runaway of the battery occur. On the other hand, when the amount is more than 500 mg / m ² , the ion permeability is inhibited and the impedance is increased, which impedes the output characteristics.

  The insulating substance 24 at this time is present on the coating mixture 25 in the form of fine particles or layers.

  The mixture paint 22 may be either a negative electrode paint or a positive electrode paint.

  For the negative electrode paint (or positive electrode paint), put the negative electrode active material (or positive electrode active material), the conductive agent, and the binder in an appropriate dispersion medium, and mix and disperse with a dispersing machine such as a planetary mixer. A negative electrode (or positive electrode) paint is prepared by adjusting the volume solid content concentration and kneading.

  As the negative electrode active material, various natural graphites and artificial graphites, silicone composite materials such as silicide, lithium titanium composite oxides, and various alloy composition materials can be used.

  As the binder for the negative electrode, various binders such as polyvinylidene fluoride (PVdF) and modified products thereof can be used. From the viewpoint of improving lithium acceptability, styrene-butadiene copolymer rubber particles (SBR) and It can be said that it is more preferable to use a cellulose resin such as carboxymethyl cellulose (CMC) in combination or to add a small amount to the modified body.

  In the case of a positive electrode paint, examples of the positive electrode active material include lithium cobaltate and modified products thereof (such as lithium cobaltate in which aluminum or magnesium is dissolved), lithium nickelate and modified products thereof (partially nickel is cobalt). And the like, and complex oxides such as lithium manganate and modified products thereof.

  As the conductive agent species at this time, for example, carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black and thermal black, and various graphites may be used alone or in combination.

  As the positive electrode binder, for example, polyvinylidene fluoride (PVdF), a modified polyvinylidene fluoride, polytetrafluoroethylene (PTFE), a rubber particle binder having an acrylate unit, or the like can be used. In this case, an acrylate monomer or an acrylate oligomer into which a reactive functional group is introduced can be mixed in the binder.

For the electrolytic solution, it is possible to use various lithium compounds such as LiPF ₆ and LiBF ₄ as an electrolyte salt. As the solvent, ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and methyl ethyl carbonate (MEC) can be used alone or in combination. It is also preferable to use vinylene carbonate (VC), cyclohexylbenzene (CHB), and modified products thereof in order to form a good film on the positive and negative electrodes and to ensure stability during overcharge.

  The separator is not particularly limited as long as it has a composition that can withstand the range of use of the non-aqueous secondary battery, but it is common to use a single or composite microporous film of an olefin resin such as polyethylene or polypropylene. Yes, and preferred as an embodiment. The thickness of the separator is not particularly limited, but may be 10 to 25 μm.

  FIG. 5 shows a schematic vertical sectional view of a lithium secondary battery using the electrode plate produced in this embodiment.

  As shown in FIG. 5, the cylindrical lithium secondary battery is assembled by separating a positive electrode plate 1 using a composite lithium oxide as an active material and a negative electrode plate 2 using a material capable of holding lithium as an active material. After that, the spiral electrode plate group 5 is housed inside a bottomed cylindrical battery case 4, and then an electrolytic solution composed of a predetermined amount of a nonaqueous solvent is placed in the battery case 4. After the liquid injection, a sealing plate 6 having a gasket 7 attached to the periphery is inserted into the opening of the battery case 4, and the opening of the battery case 4 is bent inward to seal it.

  Note that the lithium secondary battery shown in FIG. 6 manufactured using the electrode plate of the present embodiment manufactured as described above as at least one of the positive electrode plate 1 and the negative electrode plate 2 is the non-aqueous secondary battery of the present invention. This is an example.

  As described above, in the non-aqueous secondary battery of the present invention, the presence of the insulating material on the surface of the active material layer improves the safety in an internal short circuit.

  In the method of manufacturing the nonaqueous secondary battery electrode plate according to the present embodiment, the insulating material forming the roll coating layer 10 coated on the surface of the first roll 11 in FIG. 1 or the second roll 12 in FIG. By bringing the film into contact with the coating film, it is possible to attach an insulating material onto the surface of the active material layer.

  When there is no insulating material layer on the surface of the active material layer, if a hole is opened in the separator 3 due to foreign matter or the like and the positive and negative electrodes are short-circuited, an excessive current may flow to the short-circuit point and Joule heat may be generated. In that case, the generated heat causes the separator 3 around the short-circuiting point to melt or contract, expanding the hole, further expanding the short-circuiting area and continuing to generate Joule heat. By repeating this, the temperature of the battery continues to rise and abnormal heat generation occurs. And may cause external deformation.

  In the non-aqueous secondary battery of the present invention, when a hole is formed in the separator 3 and the positive and negative electrodes are short-circuited, an insulating substance is present even if the separator 3 melts or contracts and the hole expands. The short-circuit area between the negative electrodes does not increase. Therefore, the generation of Joule heat does not expand and does not lead to abnormal heat generation.

  Hereinafter, each example in the experiment conducted by the inventors will be described.

(Example)
First, sample 1 will be described.

  First, a negative electrode plate was prepared.

  First, a coating material for a negative electrode mixture was prepared as follows.

  100 parts by volume of artificial graphite as an active material for the negative electrode, and 2.3 parts by volume in terms of solid content of the binder with respect to 100 parts by volume of the styrene-butadiene copolymer rubber particle dispersion as a binder, As a thickener, carboxymethyl cellulose is stirred with a double arm kneader together with 1.4 parts by volume of water and 100 parts by volume of the active material, and the negative electrode composite having a volume solid content of 55%. An agent paint was prepared.

  About the structure of the roll used for preparation of negative mix paint, it was as follows.

  As shown in FIG. 1, the first roll 11 and the second roll 12 were installed in parallel with a gap of 100 μm. The material of the first roll 11 and the second roll 12 was SUS, and the surface was hard chrome plated. Both the first roll 11 and the second roll 12 are further coated with silicone on their surfaces. The curing agent component was adjusted so that the rubber hardness of the silicone at this time was 50.

  A copper foil having a thickness of 15 μm was used as the object 21 to be passed between the first roll 11 and the second roll 12, and the copper foil was moved at the same speed as the peripheral speed of the second roll 12. The peripheral speed of the first roll 11 is set so that the peripheral speed of the second roll 12 is set to 30 m / min and the peripheral speed ratio (the peripheral speed of the second roll 12 / the peripheral speed of the first roll 11) is 1. Set. The pressing load between the first roll 11 and the second roll 12 was 2000 N / cm.

  And the produced negative mix paint was supplied between the 1st roll 11 and the 2nd roll 12, and after making it transfer on copper foil, it compression-molded at the press process, and produced the negative electrode plate.

  Next, a positive electrode plate was produced as follows.

  100 parts by weight of lithium cobaltate as an active material, 2 parts by weight of acetylene black as a conductive agent with respect to 100 parts by weight of the active material, and 2 parts by weight of polyvinylidene fluoride as a binder with respect to 100 parts by weight of the active material, A positive electrode mixture paint was prepared by stirring and kneading with an appropriate amount of N-methyl-2-pyrrolidone in a double-arm kneader, and then the positive electrode paint was applied onto the Al foil to prepare a positive electrode plate.

These positive electrode plate and negative electrode plate were wound using a polyethylene microporous film having a thickness of 20 μm as a separator, inserted into a cylindrical battery case, and 1 part of LiPF ₆ and 3 parts by weight of VC in an EC / DMC / MEC mixed solvent. 5.5 g of the dissolved electrolyte solution was added and sealed to produce a cylindrical 18650 non-aqueous secondary battery with a design capacity of 2000 mAh.

  The output characteristics were evaluated as follows.

  That is, discharge measurement was performed at a current of 0.2 C and 5 C with respect to the rated cell capacity (1 C), and the ratio of the capacity of 5 C to 0.2 C was evaluated as a capacity maintenance rate. As the capacity retention rate, there is a demand for characteristics in which the capacity does not decrease even when a high current is passed, and it is generally desirably 90% or more.

  The safety evaluation by the internal short circuit test was performed as follows.

  For each sample, five cylindrical non-aqueous secondary batteries were prepared. After charging, the electrode plate group 5 was taken out from the battery case 4. A metal piece of an arbitrary size was interposed between the positive electrode plate 1 and the separator 3 located on the outermost periphery of the electrode plate group 5. Then, the electrode plate group 5 interposing the metal piece was accommodated again in the battery case 4. Each cylindrical non-aqueous secondary battery was pressed with a predetermined pressure. And in each cylindrical non-aqueous secondary battery, the number of cells short-circuited among the five cells (the number of short-circuited cells / 5 cells) was confirmed.

  The content of silicone rubber in the electrode plate was measured as follows.

That is, before and after coating, the volume decreased from the amount of change in the thickness of the silicone rubber coated on the first roll 11 was calculated, and the silicone rubber content per 1 m ^{2 of} the electrode plate was calculated. Silicone rubber does not adhere to any electrode other than the electrode plate during the electrode plate manufacturing process.

  The judgment as to whether or not the film thickness can be controlled in the coating was performed as follows.

  In other words, the coating material mixture 25 that was controlled to a thickness within a predetermined range was evaluated as ◯, and the coating material mixture 25 that was not formed was rated as ×.

  For Samples 2 to 4, a non-aqueous secondary battery was produced by the same production method as Sample 1, except that the peripheral speed ratio was set to 2, 5, and 10 in the production of the negative electrode plate in the production method of Sample 1 above. Then, the same evaluation as that of Sample 1 was performed.

  That is, for samples 1 to 4, only the peripheral speed ratio at the time of production of the negative electrode plate was varied.

  For sample 5, a non-aqueous secondary battery was produced by the same production method as sample 1 except that the peripheral speed ratio was 2 and the rubber hardness was 5 in the production of the negative electrode plate of the production method of sample 1 above, Evaluation similar to Sample 1 was performed.

  Samples 6 to 8 were manufactured in the same manner as Sample 1 except that the peripheral speed ratio was set to 2 and the rubber hardness was set to 10, 60, and 100 in the production of the negative electrode plate in the manufacturing method of Sample 1 above. An aqueous secondary battery was prepared and evaluated in the same manner as Sample 1.

  That is, for samples 5 to 8, only the rubber hardness at the time of producing the negative electrode plate was made different from each other.

  Sample 9 was manufactured in the same manner as Sample 1 except that the peripheral speed ratio was 2, rubber hardness was 50, and volume solid content was 35% in the production of the negative electrode plate of Sample 1 above. An aqueous secondary battery was prepared and evaluated in the same manner as Sample 1.

  For Samples 10 to 13, in the production of the negative electrode plate of Sample 1 above, the peripheral speed ratio was 2, the rubber hardness was 50, and the volume solid content ratios were 40%, 70%, 90%, and 95%, respectively. Except that, a non-aqueous secondary battery was produced by the same production method as Sample 1, and the same evaluation as Sample 1 was performed.

  That is, about samples 9-13, only the volume solid content ratio at the time of preparation of a negative electrode plate was varied.

  Sample 14 was prepared except that the peripheral speed ratio was 2, rubber hardness was 50, volume solid content was 55%, and the pressing load between rolls was 50 N / cm in the production of the negative electrode plate of the production method of Sample 1 above. A non-aqueous secondary battery was produced by the same manufacturing method as Sample 1, and the same evaluation as Sample 1 was performed.

  For Samples 15 to 17, in the production of the negative electrode plate in the production method of Sample 1, the peripheral speed ratio was 2, the rubber hardness was 50, the volume solid content was 55%, and the pressing load between the rolls was 100 N / cm, respectively. A non-aqueous secondary battery was produced by the same manufacturing method as Sample 1 except that 1000 N / cm and 2000 N / cm, and the same evaluation as Sample 1 was performed.

  That is, about the samples 14-17, only the press load between rolls at the time of preparation of a negative electrode plate was varied.

  The results of Samples 1 to 13 produced as described above are shown in Table 1, and the results of Samples 14 to 17 are shown in Table 2.

As is apparent from Table 1, in Samples 1 to 4, even if the peripheral speed ratio of the second roll 12 to the first roll 11 is changed in the range of 1 or more and 10 or less, there is no defect in the internal short circuit test, In addition, all the output characteristics (capacity maintenance ratio) were 90% or more, and a non-aqueous secondary battery excellent in safety and battery performance could be realized.

In Samples 5 to 8, when the rubber hardness of the silicone was 5, the content in the electrode plate was 1000 mg / m ² , and the output characteristics (capacity retention rate) were deteriorated. This is considered to be because the insulating material has increased the electrode plate resistance, and it is difficult to realize a non-aqueous secondary battery with excellent safety and battery performance.

  Therefore, it was found that the rubber hardness is preferably in the range of 10 or more and 100 or less.

  In Samples 9 to 13, the volume solid content concentration of the negative electrode paint was changed.

  In the case of Sample 9 having a volume solid content concentration of 35%, defective products were confirmed by the internal short circuit test. This is thought to be because the amount of silicone deposited was small because the negative electrode mixture paint was soft. At the same time, it was also found that when the volume solid content concentration is low, it is difficult to ensure transferability from the first roll 11 to the copper foil (coating object 21).

On the other hand, in the case of Sample 13 having a volume solid content concentration of 95%, the silicone content of the electrode plate was 2000 mg / m ² , and the output characteristics (capacity maintenance ratio) deteriorated. This is also considered to be because the insulating material increased the electrode plate resistance as well as the reason why the output characteristics deteriorated in Sample 5, and it is difficult to realize a non-aqueous secondary battery with excellent safety and battery performance. . At the same time, it was also found that when the volume solid content concentration is higher than 90%, it is difficult to form a coating film because the negative electrode mixture paint becomes hard.

  Further, as apparent from Table 2, in Samples 14 to 17, even when the pressing load between the rolls was changed in the range of 100 N / cm or more and 2000 N / cm or less, the coating film mixture was formed into a desired film thickness. I was able to make it.

  On the other hand, when the pressing load of the roll was 50 N / cm (sample 14), it was not possible to produce a desired film thickness. This is considered because the force which spreads between the rolls generated when the negative electrode mixture paint is supplied between the rolls is larger than the press between the rolls. Note that it is theoretically possible to produce a desired film thickness for the above reason even with a pressing load exceeding 2000 N / cm.

  From the above evaluation, the peripheral speed ratio of the second roll 12 to the first roll 11 is set to 1 or more, preferably 1 or more and 10 or less, and the rubber hardness of the insulating substance is 10 or more and 100 or less. Within the range, the volume solid content concentration of the mixture paint is in the range of 40% or more and 90% or less, and the pressing load between the rolls is set to 100 N / cm or more, thereby improving safety and battery performance. It was found that an excellent non-aqueous secondary battery can be provided.

  Since the non-aqueous secondary battery of the present invention is excellent in safety and charging characteristics, electronic devices (personal computers, mobile phones, smartphones, digital still cameras, televisions, video cameras, etc.), electric tools (electric drills, electric motors, etc.) Drivers) and vehicles (wheelchairs, bicycles, scooters, motorcycles, cars, welfare vehicles, trains, trains, etc.) and the like. Furthermore, the present invention can be applied to a power storage system as an emergency power source.

  The non-aqueous secondary battery according to the present invention is excellent in safety and charging characteristics, and is useful as a power source for which high output is desired, such as a vehicle-mounted battery. Specifically, the non-aqueous secondary battery according to the present invention includes electronic devices (personal computers, mobile phones, smartphones, digital still cameras, televisions, video cameras, etc.), electric tools (electric drills, electric drivers, etc.). , And vehicles (wheelchairs, bicycles, scooters, motorcycles, cars, welfare vehicles, trains, trains, etc.) are useful for mobile objects. Furthermore, the present invention can be applied to a power storage system as an emergency power source. That is, it can be used for everything that requires a power source.

DESCRIPTION OF SYMBOLS 1 Positive electrode plate 2 Negative electrode plate 3 Separator 4 Battery case 5 Electrode plate group 6 Sealing plate 7 Gasket 10 Roll coating layer 11 1st roll 12 2nd roll 13 3rd roll 14 2nd roll rotated at a different peripheral speed from the 1st roll DESCRIPTION OF SYMBOLS 21 To-be-coated object 22 Mixture coating material 23 Electrode plate 24 Insulating substance 25 Coating-like mixture 101 Positive electrode 101a Positive electrode active material layer 102 Negative electrode 102a Negative electrode active material layer 103 Separator 104 Porous insulating layer

Claims (9)

A mixture material is made to enter a gap between a first roll having a surface coated with an insulating material containing silicone and a second roll rotating in a direction opposite to the first roll, and the peripheral surface of the second roll 1 mg / m ² or more of the insulating substance on the surface of the mixture material formed in the coating film shape by forming the mixture material in a coating film shape on the surface of the article to be coated. A method for producing a non-aqueous secondary battery electrode plate, wherein the non-aqueous secondary battery electrode plate is adhered so as to be present in the form of particles or layers at 500 mg / m ² or less. The first roll rotates in the opposite direction to the first roll, and the mixture material enters the gap between the second roll whose surface is coated with an insulating material containing silicone, The mixture material is formed in a coating on the insulating material on the surface, and the insulating material and the mixture material formed on the surface of the second roll are in the opposite direction to the second roll. The coating material is transferred to the coated object running on the peripheral surface of the third roll that rotates in a coating, and the insulating material is applied to the surface of the coating material material in the coated film that is transferred to the coated object. A method for producing a non-aqueous secondary battery electrode plate, characterized in that the active substance is adhered in a particulate or layered form at 1 mg / m ² or more and 500 mg / m ² or less.   The method for manufacturing a non-aqueous secondary battery electrode plate according to claim 1, wherein peripheral speeds of the first roll and the second roll are different from each other.   The peripheral speed of the two rolls is different from each other in at least one set of two rolls adjacent to each other among the first roll, the second roll, and the third roll. The manufacturing method of the non-aqueous secondary battery electrode plate of 2.   The method for producing a non-aqueous secondary battery electrode plate according to any one of claims 1 to 4, wherein the insulating substance has a rubber hardness of 10 or more and 100 or less.   The method for manufacturing a non-aqueous secondary battery electrode plate according to claim 1, wherein the insulating substance is silicone.   The volume solid content concentration of the mixture material that enters between the first roll and the second roll is 40% or more and 90% or less, according to any one of claims 1 to 6. The manufacturing method of the non-aqueous secondary battery electrode plate of description.   4. The nonaqueous secondary battery electrode plate according to claim 1, wherein a load pressed against the mixture material by the first roll and the second roll is 100 N / cm or more. 5. Method.   5. The nonaqueous secondary battery electrode plate according to claim 2, wherein a load pressed against the mixture material by the second roll and the third roll is 100 N / cm or more. 6. Method.