CN115763689A - Positive plate coating method and equipment and positive plate - Google Patents
Positive plate coating method and equipment and positive plate Download PDFInfo
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- CN115763689A CN115763689A CN202211528190.5A CN202211528190A CN115763689A CN 115763689 A CN115763689 A CN 115763689A CN 202211528190 A CN202211528190 A CN 202211528190A CN 115763689 A CN115763689 A CN 115763689A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention provides a positive plate coating method, positive plate coating equipment and a positive plate, wherein the coating equipment comprises the following steps: the first coating device is used for coating a conductive slurry layer on the current collector; wherein the first coating device is a gravure coating device; and the active material layer coating device is used for extrusion coating of at least one active material layer on the conductive paste layer. In the technical scheme, the conductive slurry layer and the active material layer are coated in a gravure coating and extrusion coating mode respectively, and at least one active material layer is coated in the coating process to improve the content of the active material layer on the pole piece and improve the energy density of the lithium battery. In addition, the pressure of the die cavity is reduced during coating as compared to single layer coating.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a coating method and equipment for a positive plate and the positive plate.
Background
When the active material layer is coated on the current collector, the existing coating mode adopts a one-time coating mode, namely, the active material with the required surface density is coated on the current collector through one-time coating, and then the coating of the electrode can be completed. However, when the coating mode is adopted, the energy density of the lithium battery is improved to a limited extent, and the pressure of a die cavity is overlarge during coating.
Disclosure of Invention
Based on the problems of low volume energy density and high pressure of a die head cavity in pole piece coating, the invention provides a method and equipment for coating a positive plate and the positive plate so as to improve the pole piece coating effect.
In a first aspect, there is provided a coating apparatus comprising:
the first coating device is used for coating a conductive slurry layer on the current collector; wherein the first coating device is a gravure coating device;
and the active material layer coating device is used for extrusion coating at least one active material layer on the conductive slurry layer.
In the technical scheme, the conductive slurry layer and the active material layer are coated in a gravure coating and extrusion coating mode respectively, and at least one active material layer is coated in the coating process to improve the content of the active material layer on the pole piece and improve the energy density of the lithium battery. In addition, the die cavity pressure is reduced during coating as compared to single layer coating.
In a specific embodiment, the active material layer coating apparatus includes: at least two coating devices, each for extrusion coating of an active substance layer.
In a specific possible embodiment, the active material layer coating means includes a second coating means and a third coating means; wherein, the first and the second end of the pipe are connected with each other,
a second coating device for coating a first active material layer on the conductive paste layer;
a third coating device for coating a second active material layer on the first active material layer; wherein the content of the first and second substances,
the content of the active material in the first active material layer is larger than the content of the active material in the second active material layer.
In a specific embodiment, the method further comprises a first thickness gauge for detecting the first active material layer,
the coating device further comprises a control device; the control device is used for adjusting the power of a first feeding pump which is used for supplying the first active material in the second coating device when the thickness of the first active material layer detected by the first thickness gauge is smaller than a first set value.
In a specific embodiment, the method further comprises a second thickness gauge for detecting the second active material layer;
the control device is further configured to adjust the power of a second supply pump for supplying a second active material in the third coating device when the thickness of the second active material layer is smaller than a second set value.
In a specific embodiment, when the thickness of the first active material layer measured by the first thickness gauge is less than a first set value, the thickness of the second active material layer applied by the second application device is adjusted according to the set total thickness of the active material layer and the measured thickness of the first active material layer.
In a second aspect, there is provided a coating method for a positive electrode sheet, the coating method comprising the steps of:
coating a conductive slurry layer on the current collector;
coating a first active material layer and a second active material layer on the conductive slurry layer by layer; wherein the content of the first and second substances,
the content of the active material in the first active material layer is larger than the content of the active material in the second active material layer.
In a specific embodiment, the step of coating a layer of conductive paste on the current collector includes:
and coating a conductive slurry layer on the current collector by means of gravure coating.
In a specific possible embodiment, the thickness of the conductive paste layer is between 1 and 3 μm.
In a specific embodiment, the conductive paste layer is applied with the following components: 7-12% of conductive agent, 23-38% of binder and 55-65% of solvent.
In a specific possible embodiment, a first active material layer is coated on the conductive paste layer; the method specifically comprises the following steps:
detecting the thickness of the first active material layer;
when the thickness of the first active material layer is smaller than a first set value, the power of a first feed pump that feeds the first active material is adjusted.
In a specific embodiment, the coating of the first active material layer with the second active material layer; the method specifically comprises the following steps:
detecting the thickness of the second active material layer;
when the thickness of the second active material layer is smaller than a second set value, the power of a second feed pump for feeding the second active material is adjusted.
In a specific embodiment, the coating of the first active material layer with the second active material layer; the method specifically comprises the following steps:
determining the coating thickness of the second active material layer according to the detected thickness of the first active material layer and the set total thickness of the active material layers.
In a specific embodiment, the first active material layer applied is composed of:
95-97% of active substance, 1.5-3% of binder and 1.5-2% of conductive agent.
In a specific embodiment, the second active material layer applied is composed of:
92-97% of active substance, 1.5-4.5% of binder and 1.5-3.5% of conductive agent.
In a specific embodiment, the method further comprises: the thickness of the first active material layer applied is equal to or greater than the thickness of the second active material layer.
In a specific embodiment, the thickness of the first active material layer is between: 1/2 to 2/3 of the total thickness of the active material layer;
the thickness of the second active material layer is 1/3 to 1/2 of the total thickness of the active material layer; wherein the content of the first and second substances,
the total thickness of the set active material layers is the sum of the thicknesses of the first active material layer and the second active material layer.
In a specific embodiment, the thickness of the first active material layer is 150 μm to 350 μm.
In a specific possible embodiment, the proportion of the active material in the first active material layer is equal to the proportion of the active material in the second active material layer; and the thickness of the first active material layer applied is greater than the thickness of the second active material layer.
In a third aspect, a positive electrode sheet is provided, which includes a current collector, a conductive paste layer covering the current collector, a first active material layer covering the conductive paste layer, and a second active material layer covering the first active material layer; wherein a content of the active material in the first active material layer is larger than a content of the active material in the second active material layer.
In a specific embodiment, the first active material layer comprises the following components:
95-97% of active substance, 1.5-3% of binder and 1.5-2% of conductive agent.
In a specific embodiment, the second active material layer comprises the following components:
92-97% of active substance, 1.5-4.5% of binder and 1.5-3.5% of conductive agent.
In a specific possible embodiment, the thickness of the first active material layer is equal to or greater than the thickness of the second active material layer.
In a specific embodiment, the thickness of the first active material layer is between: 1/2 to 2/3 of the total thickness of the active material layer;
the thickness of the second active material layer is 1/3 to 1/2 of the total thickness of the active material layer; wherein, the first and the second end of the pipe are connected with each other,
the total thickness of the set active material layers is the sum of the thicknesses of the first active material layer and the second active material layer.
In a specific embodiment, the thickness of the first active material layer is 150 μm to 350 μm.
Drawings
Fig. 1 shows a schematic structural diagram of a pole piece coating apparatus provided in an embodiment of the present application;
fig. 2 shows a schematic structural diagram of a pole piece provided in an embodiment of the present application;
fig. 3 shows a flowchart of a pole piece coating method provided in an embodiment of the present application.
Detailed Description
The present application will be described in further detail below with reference to the accompanying drawings and examples. The features and advantages of the present application will become more apparent from the description.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. While the various aspects of the embodiments are presented in drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
In addition, the technical features described below in the different embodiments of the present application may be combined with each other as long as they do not conflict with each other.
First, the coating apparatus provided in the embodiments of the present application is used for coating a current collector to form a pole piece. In the current coating mode, one-time coating is often adopted, but one-time coating causes a cavity pressure of a coating device to be larger, and in addition, the porosity of an active material layer to be coated is lower, so that the embodiment of the application provides a coating device which is used for improving the coating effect on a current collector. The following detailed description is given with reference to the accompanying drawings and examples.
Referring to fig. 1, fig. 1 shows a schematic structural diagram of a coating apparatus provided in an embodiment of the present application. The coating apparatus provided by the embodiment of the present application includes at least a plurality of coating devices to coat the current collector 1 by the plurality of coating devices. The function of the plurality of coating devices is described in detail below with reference to fig. 1.
The coating apparatus includes a plurality of coating devices including at least a first coating device 10 and an active material layer coating device. The first coating device 10 is used for coating a conductive slurry layer on the current collector 1, and the active material layer coating device is used for extrusion coating at least one active material layer on the conductive slurry layer. These will be described below.
With continued reference to fig. 1, after being transferred to the coating apparatus, the current collector 1 first passes through the first coating device 10, and a layer of conductive paste is first coated on the current collector 1 by the first coating device 10. The first coating device 10 is a gravure coating device. Specifically, the first coating device 10 includes two rollers disposed opposite to each other, and the current collector 1 passes through a gap between the two rollers when being transferred. One of the two rollers is a pressing roller 11, the other one is a coating roller 12, and when the current collector 1 passes through the two rollers, a layer of conductive slurry is coated on one surface of the current collector 1 through the coating roller 12.
When the first conductive paste layer is coated, a layer of thinner conductive paste is coated on the current collector 1 through gravure coating, so that the conductive performance and the adhesion effect of the pole piece are enhanced. In the embodiment of the present application, the first coating device 10 employs gravure coating, and applies a coating method having a low viscosity and a small thickness to the slurry.
In particular, when the conductive paste layer is coated, the components of the coated conductive paste layer include a conductive agent, a binder, and a solvent. The conductive slurry layer mainly uses a conductive agent, so that the conductive performance of the battery is ensured, and the adhesion effect between the slurry and the current collector 1 is enhanced. Illustratively, the composition of the conductive paste layer is: 7-12% of conductive agent, 23-38% of binder and 55-65% of solvent. For example, the conductive paste layer may have a composition of 7% of a conductive agent, 30% of a binder, and 63% of a solvent; for example, the conductive paste layer may have a composition of 10% of a conductive agent, 25% of a binder, and 65% of a solvent; for example, the conductive paste layer may have a composition of 12% conductive agent, 38% binder, and 60% solvent.
The thickness of the conductive paste layer is between 1-3 μm, such as 1 μm, 2 μm, 3 μm, etc.
As an optional solution, the coating apparatus provided in the embodiment of the present application may further include a drying box, which is defined as a first drying box 40 for convenience of description, and the first drying box 40 is a thermal drying box, and is specifically configured to dry the conductive paste layer. Illustratively, when the first drying box 40 is provided, the first drying box 40 and the first coating device 10 are provided along the conveying direction of the current collector 1. Wherein the first coating device 10 is located upstream and the first drying box 40 is located downstream. That is, after the current collector 1 passes through the first coating device 10, the first coating device 10 coats the conductive slurry layer, the first drying box 40 is used, and the conductive slurry layer is dried by the first drying box 40. Also can not adopt first stoving case 40 to dry the conductive paste layer in this application embodiment, also can dry or dry again after the whole coating of mass flow body 1 is accomplished naturally, all can use in the embodiment of this application.
After the conductive slurry layer is coated on the current collector 1, the active material layer is further coated on the current collector 1. In the present embodiment, the active material layer is continuously coated on the current collector 1 by means of layer-by-layer coating.
The coating apparatus further includes an active material layer coating device for coating at least one active material layer. In an embodiment of the present application, the active material layer coating apparatus may include at least two coating apparatuses, wherein each coating apparatus is used for extrusion coating of one active material layer.
The number of the coating devices can be two, three, four or other different numbers, and at least two coating devices sequentially coat the active material layer on the conductive slurry layer. For convenience of description, two coating apparatuses are exemplified in the embodiments of the present application. Two coating devices for coating the active material layer are respectively named as a second coating device 20 and a third coating device 30. The description is continued with reference to fig. 1.
With continued reference to fig. 1, the active material layer coating apparatus provided in the embodiment of the present application includes a second coating apparatus 20 and a third coating apparatus 30. In fig. 1, the second coating device 20 and the third coating device 30 are illustrated, and the second coating device 20 and the third coating device 30 are disposed along the transfer direction of the current collector 1.
In conjunction with the first coating apparatus 10 described above, the three coating apparatuses are arranged such that the first coating apparatus 10 is located at the most upstream, the second coating apparatus 20 is located at the middle, and the third coating apparatus 30 is located at the most downstream, and the first coating apparatus 10, the second coating apparatus 20, and the third coating apparatus 30 are sequentially coated on the current collector 1 while the current collector 1 is being transported.
In the coating, the first coating device 10 coats a conductive paste layer on the current collector 1, the second coating device 20 coats an active material layer on the conductive paste layer, and the third coating device 30 coats an active material layer on the active material layer coated by the second coating device 20 again. The second coating device 20 and the third coating device 30 will be described below.
The second coating device 20 coats an active material layer on the conductive paste layer at the time of coating, and for convenience of description, the active material layer coated by the second coating device 20 is named as a first active material layer. It is to be understood that when the coating apparatus includes the first drying box 40, the first active material layer is coated on the dried first drying box 40, that is, the second coating device 20 is disposed downstream of the first drying box 40. At this time, the first active material layer is coated on the baked conductive paste layer.
The second coating device 20 employs an extrusion coating device. Illustratively, the second coating device 20 includes a first material tank 21 for carrying the material, and a first extrusion coating die 22 in communication with the first material tank 21. In addition, the second coating apparatus 20 may further include a first supply pump for pumping the material in the first material tank 21 to the first extrusion coating die 22, and the amount of the material coated on the current collector 1 by the extrusion coating die may be controlled by the power of the first supply pump.
In coating, the material is extrusion coated on the conductive paste layer through an extrusion coating die. In the embodiment of the present application, the material applied by the second application device 20 forms a first active material layer whose composition includes an active material, a binder, and a conductive agent.
The active material, the binder and the conductive agent may be made of different materials. For example, the active material may be different active materials such as lithium iron phosphate, lithium cobaltate, lithium nickel cobalt manganese oxide, lithium manganese oxide, and in the embodiment of the present application, one or more of lithium iron phosphate, lithium manganese oxide, lithium nickel cobalt manganese oxide, and the like may be selected as the active material. The binder may be one or more of sodium carboxymethylcellulose, styrene-butadiene latex, polytetrafluoroethylene, polyvinylidene fluoride (PVDF), and polyethylene oxide. The conductive agent may be one or more of conductive carbon black, acetylene black, carbon nanotubes, carbon nanofibers, and graphene. The conductive agent in the present embodiment may be selected from carbon nanotubes or conductive carbon black.
The respective components in the first active material layer may be used in different proportions, but when the first active material layer is formed, the content of the active material is the highest, and the contents of the conductive agent and the binder are small. Illustratively, the active material, binder, and conductive agent are: 95-97% of active substance, 1.5-3% of binder and 1.5-2% of conductive agent. Such as 95% active material, 3% binder and 2% conductive agent; or 96% of active material, 2.5% of binder and 1.5% of conductive agent; or 97% active material, 1.5% binder and 1.5% conductive agent.
When the first active material layer is coated, the coating thickness of the first active material layer is thick, and illustratively, the thickness of the first active material layer is between: 1/2 to 2/3 of the total thickness of the active material layer. Here, the total thickness of the active material layers means the total thickness of the active material layers formed after coating the active material layers a plurality of times, that is, the total thickness of the active material layers formed after completing the coating on the current collector 1. Illustratively, the thickness of the first active material layer is 1/2, 7/12, 8/13, 3/4, 2/3, etc. different thicknesses.
For example, in the specific coating, the coating thickness of the first active material layer may be 150 to 350 μm. For example, the thickness of the first active material layer is different from 150 μm, 180 μm, 220 μm, 280 μm, 300 μm, 350 μm, or the like. As an alternative embodiment, the thickness of the first active material layer can be specifically selected from 150 to 250 μm, and the coating thickness in the range is suitable for forming a lithium ion channel of a pole piece, suitable for surface density, suitable for roll compaction density and relatively good in electrolyte wettability.
The second coating device 20 has the following advantages over spray coating using extrusion coating: the spraying mode can only adjust the spraying flow, and the direction of the slurry sprayed out from the nozzle is not easy to control, so that the surface density of the coating is not easy to control, and the coating is easy to be uneven. In addition, the spraying mode is more suitable for spraying with low viscosity or dry powder, and the spraying mode is not suitable for spraying with high viscosity. The extrusion coating adopted by the application can enable the coated active material layer to be more uniform, and the coating surface density is easy to control.
The third coating device 30 is an extrusion coating device, which includes a second material tank 31 for carrying the material, a second extrusion coating die head 32 and a second material supply pump, and it can be referred to the second coating device 20, and detailed description thereof is omitted.
When the third coating device 30 is provided, the third coating device 30 is different from the second coating device 20 in the arrangement position and the active material layer applied at the time of coating is different. In the present example, the third coating apparatus 30 is used to coat one active material layer on the first active material layer, and for convenience of description, the active material layer coated by the third coating apparatus 30 is named as a second active material layer.
The composition of the second active material layer also includes an active material, a binder, and a conductive agent. However, the second active material layer includes a different ratio of the components of each substance from the ratio of the components of each substance in the first active material layer. When the second active material layer is prepared, the content of the active material in the second active material layer is less than that of the active material in the first active material layer, but the content of the conductive agent and the binder in the second active material layer is higher than those of the conductive agent and the binder in the first active material layer, so that the viscosity effect of the outermost active material layer is enhanced, and the porosity of the slurry can also be enhanced.
The active material, the binder and the conductive agent in the second active material layer can refer to the description of the active material, the binder and the conductive agent in the first active material layer, and are not described in detail herein. The component ratio of each substance of the second active material layer is described in detail below.
The respective components in the second active material layer may be used in different proportions, but when the second active material layer is formed, the active material content is the highest, and the contents of the conductive agent and the binder are small. Illustratively, the active material, binder, and conductive agent are: 92-97% of active substance, 1.5-4.5% of binder and 1.5-3.5% of conductive agent. Such as 92% active material, 4.5% binder, and 3.5% conductive agent; or 93% of active material, 3% of binder and 4% of conductive agent; or 94% active material, 1.5% binder and 4.5% conductive agent.
When the second active material layer is applied, the application thickness of the second active material layer is thin, and exemplarily, the thickness of the second active material layer is between: 1/3 to 1/2 of the total thickness of the active material layer. Here, the total thickness of the active material layers means the total thickness of the active material layers formed after coating the active material layers a plurality of times, that is, the total thickness of the active material layers formed after completing the coating on the current collector 1. Illustratively, the thickness of the second active material layer is 1/3, 2/5, 1/2, etc. different thicknesses.
When the first active material layer and the second active material layer are coated by the second coating device 20 and the third coating device 30, respectively, the porosity of the second active material layer is greater than the porosity of the first active material layer. Through setting up two-layer active material layer to make the active material's on first active material layer content be greater than the active material's on second active material layer content, both can guarantee the energy density of pole piece like this, can make the porosity on outer active material layer (second active material layer) be greater than inlayer active material layer (first active material layer) porosity again (the layer that the active material content is less, the porosity is higher), thereby do benefit to the infiltration nature of electrolyte to the pole piece.
For example, the proportion of the active material component in the first active material layer is greater than the proportion of the active material component in the second active material layer. If the active material in the first active material layer is 95% in composition and the active material in the second active material layer is 92% in composition ratio; alternatively, the active material in the first active material layer has a component ratio of 97%, and the active material in the second active material layer has a component ratio of 95%; alternatively, the active material in the first active material layer has a content of 95% and the active material in the second active material layer has a content of 92%. When the above ratio is employed, the thickness of the first active material layer may be greater than or equal to the thickness of the first active material layer. Alternatively, it is also possible to use an active material ratio component in the first active material layer equal to that in the second active material layer, but the thickness of the first active material layer is greater than that of the second active material layer, in order to ensure that the active material content in the first active material layer is greater than that in the second active material layer.
When the pole piece is prepared by the method, the active material layer is formed by layering the active material layer, so that the cavity pressure corresponding to each coating device is lower, and the requirement on the coating device is reduced. In addition, by means of multilayer coating, it is also possible to apply a relatively thick active substance layer such that the active substance layer has an increased areal density (surface density/planar density/area density), the engineering material being the mass per unit area of the substance of a given thickness). In addition, the porosity of the pole piece is improved through different active material contents of different coated active material layers. In addition, compare the monolayer coating, can promote lithium cell energy density, reduce the pressure of die cavity when coating.
With continued reference to fig. 1, the coating apparatus provided in the embodiment of the present application further includes a drying box corresponding to the second coating device 20 and the third coating device 30. The drying box corresponding to the second coating device 20 is a second drying box 50, and the drying box corresponding to the third coating device 30 is a third drying box 60. In a specific arrangement, a second drying box 50 is located downstream of the second coating device 20, and the coated first active material layer is dried by the second drying box 50. A third drying box 60 is located downstream of the third coating device 30, and the coated second active material layer is dried by the third drying box 60. The principles of the second drying box 50 and the third drying box 60 are the same as those of the first drying box 40, and thus, the description thereof is omitted.
The coating equipment that this application embodiment provided can also include a plurality of conveying rollers 400 except that including above-mentioned structure, and a plurality of conveying rollers 400 are used for transmitting current collector 1 between each equipment (coating device, stoving case), and it should be understood that the setting number or the position of conveying roller 400 can be adjusted as required, only needs a plurality of conveying rollers 400 when carrying current collector 1, can guarantee that current collector 1 can steady transport and when carrying, current collector 1 tensioning can.
As an alternative, the coating apparatus provided in the embodiments of the present application may also use a closed-loop control to adjust the coating effect. Specifically, in the coating process, one or all of the conductive paste layer, the first active material layer and the second active material layer are subjected to closed-loop control, so that the coating effect is improved.
In performing closed-loop control of the first active material layer, the coating apparatus further includes a first thickness gauge 200 for detecting the first active material layer. As shown in fig. 1, the first thickness gauge 200 is disposed downstream of the second coating device 20, and when the coating apparatus includes the second drying box 50, the first thickness gauge 200 may be disposed downstream of the second drying box 50. The first active material layer applied by the second application device 20 may be measured for thickness by the first thickness gauge 200 to obtain the thickness of the applied first active material layer.
The coating apparatus further includes a control device as a control center for adjusting the coating thickness of the second coating device 20 according to the data detected by the first thickness gauge 200. The first set value is a set thickness value of the first active material layer.
In the specific detection, when the thickness of the first active material layer detected by the first thickness gauge 200 is smaller than the first set value, the control device controls the output power of the first feed pump in the second coating device 20 to be increased until the thickness detected by the first thickness gauge 200 reaches the first set value. That is, when the thickness of the applied first active material layer is less than the first set value, the output amount of the active material from the second application device 20 is increased, thereby increasing the thickness value of the first active material layer to a desired thickness. When the thickness of the first active material layer detected by the first thickness gauge 200 is equal to a first set value, the control device controls the first supply pump in the second coating device 20 to maintain the current power; when the thickness of the first active material layer detected by the first thickness gauge 200 is larger than a first set value, the control device controls the first supply pump in the second coating device 20 to reduce the power.
Similarly, in performing closed-loop control of the thickness of the second active material layer, the coating apparatus further includes a second thickness gauge 300 for detecting the second active material layer; the second thickness gauge 300 functions similarly to the first thickness gauge 200, with the only difference that the second thickness gauge 300 is used to measure the thickness of the second active material layer. The second thickness gauge 300 is disposed downstream of the second coating device 20, and when the coating apparatus includes the third drying oven 60, the second thickness gauge 300 may be disposed downstream of the third drying oven 60. The second active material layer applied by the second application device 20 may be measured in thickness by a second thickness gauge 300 to obtain the thickness of the applied second active material layer.
In the specific control, the control device is also configured to adjust the power of the second supply pump for supplying the second active material in the second coating device 20 when the thickness of the second active material layer is smaller than the second set value. That is, when the thickness of the second active material layer is less than the second set value, the power of the second supply pump is increased, and when the thickness of the second active material layer is greater than the second set value, the power of the second supply pump is decreased until the thickness of the applied second active material layer is equal to the second set value. For a specific control method, the coating control of the first active material layer can be referred to, and details are not repeated herein.
The above control method can also be adopted when the conductive paste layer is subjected to closed-loop control. At this time, the coating apparatus further includes a third thickness gauge 100, and the third thickness gauge 100 is disposed downstream of the first coating device 10. The control device can adjust the coating amount of the first coating device 10 according to the data detected by the third thickness gauge 100, and the specific control method can refer to the coating control method of the first active material layer and the second active material layer, which is not described herein again.
Of course, other coating methods than the above-described coating method control may be adopted. If the coating amount for the first active material layer is lower than the first set value, the thickness of the entire active material layer can be secured by increasing the thickness of the coating for the second active material layer. For example, when the thickness of the first active material layer detected by the first thickness gauge 200 is lower than a first set value, and the region that has been coated cannot be coated with the active material again by the second coating device 20, the thickness of the second active material layer coated by the second coating device 20 is adjusted by the control device according to the set total thickness of the active material layer and the detected thickness of the first active material layer. If the thickness of the first active material layer is less than the first set value, the third coating device 30 increases the coating amount to ensure the total thickness of the entire active material layer during coating.
It should be understood that, in addition to the thickness gauge for detecting each layer of the above examples, a weight gauge for measuring the areal density by scanning the coating region with beta rays may be used. That is, the thickness of each layer can be adjusted according to the detected areal density as a parameter.
As an alternative, the coating apparatus provided by the present application may further include a display screen, and the coating areal density may be monitored by arranging the display screens before and after the coating machine. In the coating process, if the surface density is found to be low or high, the surface density is monitored by a thickness gauge and displayed on a display screen at the head and the tail of the coating machine, the monitoring is carried out through three colors, the green color shows normal, the yellow color shows early warning, and the red color shows abnormal. If the integral surface density is abnormal, the speed of the feed pump can be adjusted, and the flow of the slurry can be controlled to treat the abnormal integral surface density.
To facilitate understanding of the coating apparatus provided in the embodiments of the present application, a coating process is described below with reference to fig. 1. Firstly, gravure coating is carried out through a first coating device 10, a layer of thin conductive slurry is coated on a current collector 1, so that the conductive performance and the adhesion effect of a pole piece are enhanced through the conductive slurry, after the conductive slurry is dried through a first drying box 40, the thickness of the conductive layer coated through gravure is measured through a thickness gauge, then the conductive layer is conveyed to a second coating device 20 through a conveying roller 400, a layer of active substances with the thickness of 1/2 or 2/3 is coated, after the conductive layer is dried through a second drying box 50, the thickness of extrusion coating is measured through the thickness gauge, the extrusion coating is conveyed to a third coating device 30 through the conveying roller 400, a layer of active substances with the thickness of 1/2 or 1/3 is coated, and the coating thickness is measured through the thickness gauge, so that the aim of multi-layer coating is achieved.
The first conductive slurry layer is mainly coated with a conductive agent preferentially, so that the conductive performance of the battery is guaranteed, the adhesion effect between the slurry and the foil is enhanced, the active material content of the first active material layer is the highest, the conductive agent and the binder content are low, the active material content of the second active material layer is lower than that of the previous layer, and the conductive agent and the binder content are high, so that the purpose of enhancing the viscosity effect of the outermost layer is achieved, and the porosity of the slurry can be enhanced.
As can be seen from the above description, in the embodiments of the present application, the conductive paste layer and the active material layer are coated by gravure coating and extrusion coating, respectively, and at least one active material layer is coated in the coating process to improve the content of the active material layer on the electrode sheet, thereby increasing the energy density of the lithium battery. In addition, the die cavity pressure is reduced during coating as compared to single layer coating.
Referring to fig. 2, fig. 2 shows a schematic structural diagram of a positive electrode sheet provided in an embodiment of the present application. The positive electrode sheet provided by the present application includes a multi-layer structure, and illustratively, includes a current collector 1, a conductive paste layer 2, and an active material layer. In the specific lamination, the conductive paste layer 2 is located between the current collector 1 and the active material layer. And the conductive paste layer 2 is covered on the current collector 1, and the active substance layer is covered on the conductive paste layer 2.
In the present embodiment, the active material layer is divided into a two-layer structure, i.e., the first active material layer 3 and the second active material layer 4. When two active material layers are specifically arranged, the first active material layer 3 covers the current collector 1, and the first active material layer 3 is located on one side of the conductive slurry layer 2, which is far away from the current collector 1; the second active material layer 4 covers the first active material layer 3, and the second active material layer 4 is located on a side of the first active material layer 3 facing away from the conductive paste layer 2.
In forming the conductive paste layer 2, referring to the coating apparatus shown in fig. 1, the conductive paste layer 2 may be directly coated on the current collector 1 by a first coating device. The components of the applied conductive paste layer 2 include a conductive agent, a binder, and a solvent. The conductive slurry layer 2 is mainly made of a conductive agent, so that the conductive performance of the battery is ensured, and the adhesion effect between the slurry and the current collector 1 is enhanced. The composition ratio and thickness of the conductive paste layer 2 can be referred to the above description, and are not described again.
When the first active material layer 3 and the second active material layer 4 are applied, the porosity of the second active material layer 4 is larger than the porosity of the first active material layer 3. Through setting up two-layer active material layer to make the active material's of first active material layer 3 content be greater than the active material's of second active material layer 4 content, both can guarantee the energy density of pole piece like this, can make the porosity on outer active material layer (second active material layer 4) be greater than inlayer active material layer (first active material layer 3) porosity (the layer that active material content is less, the porosity is higher), thereby do benefit to the infiltration nature of electrolyte to the pole piece.
Each of the first active material layer 3 and the second active material layer 4 includes an active material, a binder, and a conductive agent. Specific examples of the active material, the binder, and the conductive agent may refer to the specific description above, and are not specifically limited herein.
The method can be realized in two ways during specific realization, and one way is as follows: the respective component ratios of the first active material layer 3 and the second active material layer 4 are the same, but the thickness of the first active material layer 3 is larger than that of the second active material layer 4; in another mode, the active material component in the first active material layer 3 is larger than the active material component in the second active material layer 4, and the thickness of the first active material layer 3 is larger than or equal to the thickness of the second active material layer 4. Two different arrangements are described below.
In the first mode, the first active material layer 3 contains the following components: 95-97% of active substance, 1.5-3% of binder and 1.5-2% of conductive agent. When the component ratio of the second active material layer 4 to the first active material layer 3 is the same as the component ratio of the first active material layer 3, the above component ratio can be adopted.
In the first mode, the thickness of the first active material layer 3 is larger than the thickness of the second active material layer 4. Wherein, the thickness of the first active material layer 3 is between: 1/2 to 2/3 of the total thickness of the active material layer; the thickness of the second active material layer 4 is set to a total active material layer thickness of 1/3 to 1/2. When the active material layer coated on the current collector 1 contains only the first active material and the second active material layer 4, the total thickness of the active material layers is set to be the sum of the thicknesses of the first active material layer 3 and the second active material layer 4. Illustratively, the first active material layer 3 has a thickness of 2/3 of the total active material layer thickness set, and the second active material layer 4 has a thickness of 1/3 of the total active material layer thickness set. Alternatively, the first active material layer 3 has a thickness of 3/5 of the total active material layer thickness set, and the second active material layer 4 has a thickness of 2/5 of the total active material layer thickness set.
In the second embodiment, the first active material layer 3 contains the following components: 95-97% of active substance, 1.5-3% of binder and 1.5-2% of conductive agent. The second active material layer 4 contains the following components: 92-97% of active substance, 1.5-4.5% of binder and 1.5-3.5% of conductive agent. Illustratively, the active material content of the first active material layer 3 is 97%, and the active material content of the second active material layer 4 is 95%; alternatively, the active material content in the first active material layer 3 is 96%, and the active material content in the second active material layer 4 is 95%; alternatively, the active material content in the first active material layer 3 is 95%, and the active material content in the second active material layer 4 is 92%.
When specifically providing the first active material layer 3 and the second active material layer 4, the thickness of the first active material layer 3 is between: 1/2 to 2/3 of the total thickness of the active material layer; the thickness of the second active material layer 4 is set to be 1/3 to 1/2 of the total thickness of the active material layers. Illustratively, the first active material layer 3 has a thickness of 2/3 of the total active material layer thickness set, and the second active material layer 4 has a thickness of 1/3 of the total active material layer thickness set. Alternatively, the first active material layer 3 has a thickness of 3/5 of the total active material layer thickness set, and the second active material layer 4 has a thickness of 2/5 of the total active material layer thickness set; alternatively, the first active material layer 3 and the second active material layer 4 each have a thickness of 1/2 of the total thickness of the active material layers.
As one example, when the first active material layer 3 is specifically provided, the thickness of the first active material layer 3 is 150 μm to 350 μm. For example, the first active material layer 3 may have a thickness of 150 μm, 180 μm, 220 μm, 280 μm, 300 μm, 350 μm, or the like. As an alternative embodiment, the thickness of the first active material layer 3 can be selected from 150 to 250 μm, and the coating thickness in this range forms a positive plate with moderate lithium ion channel, appropriate surface density, moderate rolling compaction density and relatively good electrolyte wettability.
It is to be understood that, when the different arrangements described above are used, it is ensured that the content of the active material in the first active material layer 3 is greater than the content of the active material in the second active material layer 4.
In the above-described aspect, by applying the active material layer in two layers, a thicker active material layer, that is, an active material layer with a higher areal density can be formed on the current collector 1 while reducing the cavity pressure of the coating apparatus. In addition, the porosity of the positive electrode sheet can be increased by varying the content of the active material in the active material layers to be applied. Compared with single-layer coating, the energy density of the lithium battery can be improved, and the pressure of a die head cavity during coating is reduced.
Referring to fig. 3, fig. 3 shows a flow chart of a coating method of a positive electrode sheet provided in an embodiment of the present application. In order to facilitate understanding of the coating equipment and the positive plate provided by the application, the application also provides a positive plate coating method, and the coating method comprises the following steps:
step 001: coating a conductive slurry layer on the current collector;
specifically, a conductive paste layer is coated on the current collector by means of gravure coating. With reference to the coating apparatus shown in fig. 1, when the conductive paste layer is coated, coating is performed by the first coating device, which may specifically refer to the related description in fig. 1 and will not be described again.
In particular, the thickness of the conductive paste layer is 1 to 3 μm. Such as 1 μm, 2 μm, 3 μm, etc.
In addition, the components of the conductive paste layer coated were: 7-12% of conductive agent, 23-38% of binder and 55-65% of solvent. Reference may be made to the related description in fig. 1, and details are not repeated herein.
Step 002: at least coating a first active material layer and a second active material layer on the conductive slurry layer by layer;
specifically, the active material layer is coated on the conductive paste layer by at least two-layer coating, and in the case of coating two layers, the coated active material layer includes a first active material layer and a second active material layer. And the porosity of the second active material layer is larger than the porosity of the first active material layer at the time of coating. Through setting up two-layer active material layer to make the active material's on first active material layer content be greater than the active material's on second active material layer content, both can guarantee the energy density of pole piece like this, can make the porosity on outer active material layer (second active material layer) be greater than inlayer active material layer (first active material layer) porosity again (the layer that active material content is less, the porosity is higher), thereby do benefit to the infiltration nature of electrolyte to the pole piece.
Taking the application of two active material layers as an example, the method specifically comprises the following steps:
step a: coating a first active material layer on the conductive paste layer;
specifically, referring to fig. 1, the first active material layer is coated by the second coating device, and the specific coating manner can refer to the related description in fig. 1, which is not repeated herein.
Wherein the first active material layer applied comprises the following components: 95-97% of active substance, 1.5-3% of binder and 1.5-2% of conductive agent. The active material, the binder and the conductive agent can be referred to the description in fig. 1, and are not repeated herein.
In applying the first active material layer, a closed-loop control method may be employed, specifically, the following steps may be performed: detecting the thickness of the first active material layer; when the thickness of the first active material layer is smaller than a first set value, the power of a first supply pump that supplies the first active material is adjusted. In the specific control, the thickness of the first active material layer applied is detected by a first thickness gauge, and then the second application device is controlled and adjusted by the control device according to the result of the detection by the first thickness gauge. The specific adjustment manner can refer to the related description in fig. 1, and is not described herein again.
Step b: a second active material layer is coated on the first active material layer.
Specifically, referring to fig. 1, the second active material layer is coated by the third coating device, and the specific coating manner can refer to the related description in fig. 1, and is not repeated herein.
Wherein the second active material layer applied comprises the following components: 92-97% of active substance, 1.5-4.5% of binder and 1.5-3.5% of conductive agent. The active material, the adhesive and the conductive agent can be referred to the description in fig. 1, and are not described herein again.
In the application of the second active material layer, a closed-loop control method may be employed, specifically, the following steps may be employed: detecting the thickness of the second active material layer; when the thickness of the second active material layer is smaller than a second set value, the power of a second feed pump that feeds the second active material is adjusted. In the specific control, the thickness of the second active material layer applied is detected by the second thickness gauge, and then the third application device is controlled and adjusted by the control device based on the result of the detection by the second thickness gauge. The specific adjustment manner can refer to the related description in fig. 1, and is not described herein again.
Alternatively, in another control manner, the method may further include determining a coating thickness of the second active material layer based on the detected thickness of the first active material layer and the set total thickness of the active material layers. That is, the thickness of the second active material layer is determined by the thickness of the first active material layer and the total active material layer, and control of the coating thickness of the second active material layer can also be achieved.
In the specific preparation of the above-described first active material layer and second active material layer, in order to ensure that the total amount of active material in the first active material layer is larger than that in the second active material layer, various modes may be adopted in specific arrangement.
In one mode, the proportion of the active material in the first active material layer is higher than the proportion of the active material in the second active material layer. As an example, the composition in the first active material layer is: 95-97% of active material, 1.5-3% of binder and 1.5-2% of conductive agent, and the second active material layer comprises the following components: 92-97% of active material, 1.5-4.5% of binder and 1.5-3.5% of conductive agent, the following modes can be adopted: the active material content in the first active material layer was 97%, and the active material content in the second active material layer was 95%; alternatively, the active material content in the first active material layer is 96%, and the active material content in the second active material layer is 95%; alternatively, the active material content in the first active material layer is 95%, and the active material content in the second active material layer is 92%.
In this manner, the thickness of the first active material layer applied is equal to or greater than the thickness of the second active material layer. In this case, the thickness of the first active material layer is 2/3 of the total thickness of the active material layer, and the thickness of the second active material layer is 1/3 of the total thickness of the active material layer. Or the first active material layer has a thickness of 3/5 of the total thickness of the active material layer, and the second active material layer has a thickness of 2/5 of the total thickness of the active material layer; alternatively, the first active material layer and the second active material layer each have a thickness of 1/2 of the total thickness of the active material layers.
As one example, when the first active material layer is specifically provided, the thickness of the first active material layer is 150 μm to 350 μm. For example, the thickness of the first active material layer is different from 150 μm, 180 μm, 220 μm, 280 μm, 300 μm, 350 μm, or the like. As an alternative embodiment, the thickness of the first active material layer can be selected from 150-250 μm, and the positive plate formed by the coating thickness in the range has moderate lithium ion channels, appropriate surface density, moderate rolling compaction density and relatively good electrolyte wettability.
In another mode, it may be adopted that the proportion of the active material in the first active material layer is equal to the proportion of the active material in the second active material layer; and the thickness of the first active material layer is greater than the thickness of the second active material layer. Illustratively, the first active material layer has the following composition: 95-97% of active substance, 1.5-3% of binder and 1.5-2% of conductive agent. When the component ratio of the second active material layer to the first active material layer is the same as the component ratio of the first active material layer, the above component ratio can be adopted.
In this embodiment, the thickness of the first active material layer is larger than the thickness of the second active material layer. Wherein, the thickness of the first active material layer is between: 1/2 to 2/3 of the total thickness of the active material layer; the thickness of the second active material layer is 1/3 to 1/2 of the total thickness of the active material layer. When the active material layer applied on the current collector includes only the first active material layer and the second active material layer, the total thickness of the active material layers is set to be the sum of the thicknesses of the first active material layer and the second active material layer. Illustratively, the first active material layer has a thickness of 2/3 of the total thickness of the active material layer set, and the second active material layer has a thickness of 1/3 of the total thickness of the active material layer set. Alternatively, the first active material layer has a thickness of 3/5 of the total thickness of the active material layer set, and the second active material layer has a thickness of 2/5 of the total thickness of the active material layer set.
According to the preparation method, the active material layer is formed by adopting a mode of at least twice coating, and the at least two coating devices are adopted for carrying out layered coating, so that the die cavity pressure of each coating device can be reduced, in addition, the whole coating active material quantity can be increased by adopting a multi-layer coating mode, and the surface density is improved. Meanwhile, the porosity of the positive electrode sheet formed after coating can also be improved by the difference between the active materials of the coated active material layers.
In the description of the present application, it is to be noted that the terms "mounted," "connected," and "connected" are to be construed broadly unless otherwise explicitly stated or limited. The specific meaning of the above terms in the present application can be understood in a specific case by those of ordinary skill in the art.
The present application has been described above with reference to preferred embodiments, but these embodiments are merely exemplary and merely illustrative. On the basis of the above, the present application can be subjected to various substitutions and modifications, which are all within the scope of protection of the present application.
Claims (25)
1. A coating apparatus, comprising:
the first coating device is used for coating a conductive slurry layer on the current collector; wherein the first coating device is a gravure coating device;
and the active material layer coating device is used for extrusion coating of at least one active material layer on the conductive paste layer.
2. The coating apparatus according to claim 1, wherein the active material layer coating device comprises: at least two coating devices, each for extrusion coating of an active substance layer.
3. The coating apparatus according to claim 2, wherein the active material layer coating device includes a second coating device and a third coating device; wherein the content of the first and second substances,
a second coating device for coating a first active material layer on the conductive paste layer;
a third coating device for coating a second active material layer on the first active material layer; wherein the content of the first and second substances,
the content of the active material in the first active material layer is larger than the content of the active material in the second active material layer.
4. The coating apparatus according to claim 3, further comprising a first thickness gauge for detecting the first active material layer,
the coating device further comprises a control device; the control device is used for adjusting the power of a first feeding pump which is used for supplying the first active material in the second coating device when the thickness of the first active material layer detected by the first thickness gauge is smaller than a first set value.
5. The coating apparatus according to claim 4, further comprising a second thickness gauge for detecting the second active material layer;
the control device is further configured to adjust the power of a second supply pump for supplying a second active material in the third coating device when the thickness of the second active material layer is smaller than a second set value.
6. The coating apparatus according to claim 5, wherein the control device is further configured to adjust the thickness of the second active material layer applied by the second application device in accordance with a set total thickness of the active material layer and the detected thickness of the first active material layer when the thickness of the first active material layer detected by the first thickness gauge is less than a first set value.
7. A coating method of a positive plate is characterized by comprising the following steps:
coating a conductive slurry layer on the current collector;
at least coating a first active material layer and a second active material layer on the conductive slurry layer by layer; wherein the content of the first and second substances,
the content of the active material in the first active material layer is larger than the content of the active material in the second active material layer.
8. The coating method of the positive plate according to claim 7, wherein the coating of the current collector with a layer of conductive paste comprises:
and coating a conductive slurry layer on the current collector by means of gravure coating.
9. The coating method for a positive electrode sheet according to claim 7, wherein the thickness of the conductive paste layer is 1 to 3 μm.
10. The positive electrode sheet coating method according to claim 7, wherein the conductive paste layer is coated with the following components: 7-12% of conductive agent, 23-38% of binder and 55-65% of solvent.
11. The positive electrode sheet coating method according to claim 7, wherein a first active material layer is coated on the electroconductive paste layer; the method specifically comprises the following steps:
detecting the thickness of the first active material layer;
when the thickness of the first active material layer is smaller than a first set value, the power of a first supply pump for supplying the first active material is adjusted.
12. The positive electrode sheet coating method according to claim 7, wherein a second active material layer is coated on the first active material layer; the method specifically comprises the following steps:
detecting the thickness of the second active material layer;
when the thickness of the second active material layer is smaller than a second set value, the power of a second feed pump for feeding the second active material is adjusted.
13. The positive electrode sheet coating method according to claim 12, wherein a second active material layer is coated on the first active material layer; the method specifically comprises the following steps:
and determining the coating thickness of the second active material layer according to the detected thickness of the first active material layer and the set total thickness of the active material layers.
14. The positive electrode sheet coating method according to any one of claims 7 to 13, wherein the first active material layer to be coated comprises:
95-97% of active substance, 1.5-3% of binder and 1.5-2% of conductive agent.
15. The positive electrode sheet coating method according to claim 14, wherein the second active material layer to be coated comprises:
92-97% of active substance, 1.5-4.5% of binder and 1.5-3.5% of conductive agent.
16. The positive electrode sheet coating method according to claim 7, further comprising: the thickness of the first active material layer applied is equal to or greater than the thickness of the second active material layer.
17. The positive electrode sheet coating method according to claim 16, wherein the thickness of the first active material layer is between: 1/2 to 2/3 of the total thickness of the active material layer;
the thickness of the second active material layer is 1/3 to 1/2 of the total thickness of the active material layer; wherein the content of the first and second substances,
the total thickness of the set active material layers is the sum of the thicknesses of the first active material layer and the second active material layer.
18. The positive electrode sheet coating method according to claim 17, wherein the thickness of the first active material layer is 150 to 350 μm.
19. The positive electrode sheet coating method according to claim 15, wherein the proportion of the active material in the first active material layer is equal to the proportion of the active material in the second active material layer; and the thickness of the first active material layer applied is greater than the thickness of the second active material layer.
20. A positive plate is characterized by comprising a current collector, a conductive slurry layer covering the current collector, a first active material layer covering the conductive slurry layer, and a second active material layer covering the first active material layer; wherein a content of the active material in the first active material layer is larger than a content of the active material in the second active material layer.
21. The positive electrode sheet according to claim 20, wherein the first active material layer comprises the following components:
95-97% of active substance, 1.5-3% of binder and 1.5-2% of conductive agent.
22. The positive electrode sheet according to claim 21, wherein the second active material layer comprises the following components:
92-97% of active substance, 1.5-4.5% of binder and 1.5-3.5% of conductive agent.
23. The positive electrode sheet according to claim 22, wherein the thickness of the first active material layer is equal to or greater than the thickness of the second active material layer.
24. The positive electrode sheet according to claim 23, wherein the thickness of the first active material layer is between: 1/2 to 2/3 of the total thickness of the active material layer;
the thickness of the second active material layer is 1/3 to 1/2 of the total thickness of the active material layer; wherein the content of the first and second substances,
the total thickness of the set active material layers is the sum of the thicknesses of the first active material layer and the second active material layer.
25. The positive electrode sheet according to claim 23, wherein the thickness of the first active material layer is 150 to 350 μm.
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