Patent Application
20240413311
Pursuant to 35 U.S.C. § 119, the present application claims priority from Chinese patent application No. 202310681756.6 filed on Jun. 9, 2023, which is incorporated herein by reference in its entirety.
The present application relates to the field of energy storage, and in particular, to a composite positive electrode sheet with high compacted density for energy storage devices, a method for preparing the same, and energy storage devices comprising the same.
Along with the progress of the times, high energy density is increasingly pursued for lithium batteries. At present, the main positive electrode material used in batteries is lithium iron phosphate, which has a theoretical gram capacity of only 170 mAh/g, which is relatively low as a positive electrode material. Therefore, it is expected to develop a positive electrode material with a high theoretical gram capacity or a high operating voltage in order to develop lithium batteries with high energy densities. Lithium iron manganese phosphate is similar to lithium iron phosphate in the safety property and theoretical gram capacity, but has an energy density which is 20% higher than that of lithium iron phosphate because of its voltage platform at 4.1V.
The method currently used in scientific research or commercially for preparing a positive electrode sheet from lithium iron manganese phosphate comprises: (1) premixing of raw materials: adding main raw materials into a mixer for stirring and premixing to obtain a mixture; (2) wetting: stirring to disperse the mixture with an organic solvent under vacuum; (3) high speed dispersing: adding an organic solvent and performing high-speed stirring to disperse under vacuum to obtain a mixed slurry; (4) sieving: sieving the mixed slurry prepared in the high-speed dispersing step to remove large particles to obtain an positive electrode slurry; (5) coating: coating the positive electrode slurry onto an aluminum foil, and then drying thoroughly to form a coating layer, thereby obtaining the positive electrode sheet.
In a first aspect, the present application provides a composite positive electrode sheet for energy storage devices, comprising a current collector, a coating layer and inserts, wherein:
In another aspect, the present application provides a method for preparing the composite positive electrode sheet of the present application, comprising the steps of:
In another aspect, the present application provides an energy storage device, comprising the composite positive electrode sheet of the present application.
In the present application, a new type of composite positive electrode sheet with a high compacted density is designed.
In a first aspect, the present application provides a composite positive electrode sheet for energy storage devices, comprising a current collector, a coating layer and inserts, wherein:
In a specific embodiment, the current collector is aluminum foil, which may have a thickness ranging from 10 μm to 20 μm.
In a specific embodiment, the coating layer has a thickness ranging from 70 μm to 120 μm.
In a specific embodiment, the coating layer and the inserts are both made from lithium iron manganese phosphate.
In a specific embodiment, the coating layer has a mean particle size Dv50 ranging from 0.6 μm to 0.8 μm, and the inserts have a mean particle size Dv50 ranging from 1.1 μm to 1.3 μm.
In a specific embodiment, the inserts have a width D along a length direction of the composite positive electrode sheet ranging from 14 μm to 18 μm, or about 16 μm.
In a specific embodiment, the distance L between two adjacent inserts is less than or equal to 30 μm.
In a specific embodiment, the depth h of the portion of each insert inserted into the coating layer is about 45 μm, taking the outer surface of the coating layer facing away from the current collector as a reference plane.
In a specific embodiment, as shown in graph c) of
In another aspect, the present application provides a method for preparing the composite positive electrode sheet of the present application. The method includes the steps of:
In a specific embodiment, the method of the present application further includes a post-treatment step. In the post-treatment step, the composite positive electrode sheet obtained in step (2) is pressed on a press machine, so that the compacted density is larger than or equal to 2.3 g/cm3.
A specific process for preparing the composite positive electrode sheet of the present application is shown in
(1) Corresponding amounts of lithium iron manganese phosphate (mean particle size Dv50 ranging from 0.6 to 0.8 μm), conductive carbon black and polyvinylidene fluoride are weighed and added into a mixing tank according to a mass ratio of 95%:2%:3%, followed by adding an appropriate amount of N-methylpyrrolidone (NMP). The mixture is stirred for 6 h to give a uniform slurry with an appropriate viscosity.
(2) The slurry is evenly coated on an aluminum foil by extrusion coating to form a coating layer, which is subjected to rapid pre-shaping in an oven (70 to 90° C., 3 to 5 min).
(1) Corresponding amounts of lithium iron manganese phosphate (mean particle size Dv50 ranging from 1.1 to 1.3 μm), conductive carbon black and polyvinylidene fluoride are weighed and added into a mixing tank according to a mass ratio of 95%:2%:3%, followed by adding an appropriate amount of N-methylpyrrolidone (NMP). The mixture is stirred for 6 h to give a uniform slurry with an appropriate viscosity.
(2) The slurry is loaded into a special device such as a syringe. The slurry is inserted into the coating layer with the syringe, while controlling the injection volume, movement displacement, frequency, etc. The width of the inserts along a length direction of the composite positive electrode sheet is illustrated as D. The distance between two adjacent inserts is illustrated as L. Taking the outer surface of the coating layer facing away from the current collector as a reference plane, the depth of the portion of each insert inserted into the coating layer is illustrated as h. After sufficient drying in an oven, a composite positive electrode sheet is formed.
The cross-section and the surface of the composite positive electrode sheet obtained in the present application are respectively shown in graphs c) and d) in
The composite positive electrode sheet obtained in step 2 is placed on a press machine and pressed at a pressure of 30 MPa, so that the compacted density of the composite positive electrode sheet is larger than or equal to 2.3 g/cm3.
In a specific embodiment, the ends of the inserts form protrusions on the surface of the positive electrode sheet. By forming a regular array of protrusions on the outermost surface of the positive electrode sheet, a tiny gap is formed between the positive electrode sheet and the separator after the positive electrode sheet is rolled into an electrode assembly. This facilitates the flow of the electrolyte between the positive electrode sheet and the separator, reduces the fluid resistance of the electrolyte flow, and makes the electrolyte infiltration more effective and more uniform.
In another aspect, the present application provides an energy storage device, which comprises the composite positive electrode sheet of the present application.
In an embodiment of the present application, the energy storage device is a lithium-ion battery.
In a specific embodiment, the lithium-ion battery of the present application is prepared as follows:
(1) Corresponding amounts of artificial graphite, conductive carbon black and carboxymethyl cellulose sodium are weighed and added into a mixing tank according to a mass ratio of 95%:2.5%:2.5%, followed by adding an appropriate amount of deionized water. The mixture is stirred for 5 h to give a uniform slurry with an appropriate viscosity. The slurry is coated onto a copper foil with a thickness of 10 μm, placed in a vacuum oven, and dried at 150° C. for 15 h to give a negative electrode sheet.
(2) The negative electrode sheet is placed into a press machine and pressed. A negative electrode disc of Φ18 mm is cut with a puncher.
(3) A positive electrode disc of Φ15 mm is cut with a puncher from the composite positive electrode sheet of the present application.
(4) The positive electrode disc and the negative electrode disc are placed into a glove box which has been filled with an argon protective atmosphere for battery assembly, using a solution of 1 mol/L lithium hexafluorophosphate dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate with a molar ratio of 1:1 as the electrolyte. The positive electrode disc, the negative electrode disc, a polyethylene separator and other components are assembled together, followed by injection of the electrolyte, thereby obtaining the lithium-ion battery.
The technical solution of the present application will be further described in detail below with reference to specific examples.
Using the process shown in
(1) Corresponding amounts of lithium iron manganese phosphate, conductive carbon black and polyvinylidene fluoride were weighed and added into a mixing tank according to a mass ratio of 95%:2%:3%, followed by adding an appropriate amount of N-methylpyrrolidone (NMP). The mixture was stirred for 6 h to give a uniform slurry with an appropriate viscosity. The morphology of the lithium iron manganese phosphate particles used is shown in graph a) in
(2) The slurry is evenly coated on an aluminum foil by extrusion coating to form a coating layer, which is subjected to rapid pre-shaping in an oven (70 to 90° C., 3 to 5 min). The coating layer has a thickness of about 70 μm. The particle size distribution of lithium iron manganese phosphate particles in the coating layer is shown in
(1) Corresponding amounts of lithium iron manganese phosphate, conductive carbon black and polyvinylidene fluoride were weighed and added into a mixing tank according to a mass ratio of 95%:2%:3%, followed by adding an appropriate amount of N-methylpyrrolidone (NMP). The mixture was stirred for 6 h to give a uniform slurry with an appropriate viscosity. The morphology of the lithium iron manganese phosphate particles used is shown in graph b) in
(2) The slurry was loaded into a syringe. The slurry was inserted into the coating layer with the syringe, while controlling the injection volume, movement displacement, frequency, etc., to form the inserts. The width D of the inserts along a length direction of the composite positive electrode sheet was about 10 μm. The distance L between two adjacent inserts was about 30 μm. Taking the outer surface of the coating layer facing away from the current collector as a reference plane, the depth h of the portion of each insert inserted into the coating layer was about 30 μm.
After sufficient drying in an oven, a composite positive electrode sheet was formed, in which the particle size distribution of lithium iron manganese phosphate particles in the inserts is shown in
The distributions of particles and coatings in a partial cross-section of the composite positive electrode sheet are shown in
The aforementioned composite positive electrode sheet was placed on a press machine and pressed at a pressure of 30 MPa, so that the compacted density of the composite positive electrode sheet was 2.3 g/cm3.
The same method and materials as in Example 1 were used to prepare a composite positive electrode sheet, except that the width D of the inserts along a length direction of the composite positive electrode sheet was 12 μm.
The same method and materials as in Example 1 were used to prepare a composite positive electrode sheet, except that the width D of the inserts along a length direction of the composite positive electrode sheet was 14 μm.
The same method and materials as in Example 1 were used to prepare a composite positive electrode sheet, except that the width D of the inserts along a length direction of the composite positive electrode sheet was 16 μm.
The same method and materials as in Example 1 were used to prepare a composite positive electrode sheet, except that the width D of the inserts along a length direction of the composite positive electrode sheet was 18 μm.
The same method and materials as in Example 1 were used to prepare a composite positive electrode sheet, except that the width D of the inserts along a length direction of the composite positive electrode sheet was 20 μm.
The same method and materials as in Example 1 were used to prepare a composite positive electrode sheet, except that the distance L between two adjacent inserts was 40 μm.
The same method and materials as in Example 1 were used to prepare a composite positive electrode sheet, except that the distance L between two adjacent inserts was 50 μm.
The same method and materials as in Example 1 were used to prepare a composite positive electrode sheet, except that the depth h of the portion of each insert inserted into the coating layer was 35 μm.
The same method and materials as in Example 1 were used to prepare a composite positive electrode sheet, except that the depth h of the portion of each insert inserted into the coating layer was 40 μm.
The same method and materials as in Example 1 were used to prepare a composite positive electrode sheet, except that the depth h of the portion of each insert inserted into the coating layer was 45 μm.
The same method and materials as in Example 1 were used to prepare a composite positive electrode sheet, except that the depth h of the portion of each insert inserted into the coating layer was 50 μm.
The same method and materials as in step 1 of Example 1 were used to prepare a coating layer on an aluminum foil, thereby forming a composite positive electrode sheet with a coating layer.
The aforementioned composite positive electrode sheet was placed on a press machine and pressed at a pressure of 30 MPa, so that the compacted density of the positive electrode sheet was 2.1 g/cm3.
The same method and materials as in Comparative Example 1 were used to prepare a composite positive electrode sheet, except that the compacted density of the positive electrode sheet was 2.2 g/cm3.
The same method and materials as in Comparative Example 1 were used to prepare a composite positive electrode sheet, except that the compacted density of the positive electrode sheet was 2.3 g/cm3.
Lithium-ion batteries were prepared as follows using the composite positive electrode sheets prepared in the above examples and comparative examples.
(1) Corresponding amounts of artificial graphite, conductive carbon black and carboxymethyl cellulose sodium were weighed and added into a mixing tank according to a mass ratio of 95%:2.5%:2.5%, followed by adding an appropriate amount of deionized water. The mixture was stirred for 5 h to give a uniform slurry with an appropriate viscosity. The slurry was coated onto a copper foil with a thickness of 10 μm, placed in a vacuum oven, and dried at 150° C. for 15 h to give a negative electrode sheet.
(2) The negative electrode sheet was placed into a press machine and pressed. A negative electrode disc of Φ18 mm was cut with a puncher.
(3) A positive electrode disc of Φ15 mm was cut with a puncher from one of the composite positive electrode sheets prepared in the above examples and comparative examples.
(4) The positive electrode disc and the negative electrode disc were placed into a glove box which has been filled with an argon protective atmosphere for battery assembly, using a solution of 1 mol/L lithium hexafluorophosphate dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate with a molar ratio of 1:1 as the electrolyte. The positive electrode disc, the negative electrode disc, a polyethylene separator and other components were assembled together, followed by injection of the electrolyte, thereby producing the lithium-ion battery.
The composite positive electrode sheets or the lithium-ion batteries produced above were subjected to the following tests.
A laser diffraction particle size distribution measuring instrument (Malvern Mastersizer 3000) was used to measure the particle size distribution according to the particle size distribution laser diffraction method illustrated in GB/T19077-2016 to give Dv50 values.
At 25° C., a lithium battery was charged to 4.3V at a rate of 0.5 C, and then discharged to 3V at a rate of 0.5 C, and the discharge capacity under these conditions was recorded as 0.5 C discharge capacity. The lithium battery was then charged to 4.3V at a rate of 1 C, and then discharged to 2.5V at a rate of 1 C, and the discharge capacity under these conditions was recorded as 1 C discharge capacity.
At 25° C., a lithium battery was charged to 4.3V at a rate of 1 C, and then discharged to 2.5V at a rate of 1 C. Taking the capacity of the first cycle as the initial capacity, the retention rate value was obtained by dividing the capacity of the 200th cycle by the initial capacity.
It can be seen from Comparative Examples 1, 2 and 3 in Table 1 that increasing the compacted density of the composite positive electrode sheet will lead to increased degree of squeeze between the particles, thereby making the voidage smaller. Consequently, the liquid holding capacity of the positive electrode sheet becomes worse, which directly deteriorates the electrochemical performances of the lithium battery.
It can be seen from Example 3 and Comparative Example 1 in Table 1 that, on the basis that the compacted density of the positive electrode sheet is 2.3 g/cm3, the specially distributed inserts designed in the present application are beneficial for the electrolyte to infiltrate into the positive electrode sheet, leading to better electrochemical performances of the lithium battery.
It can be seen from Examples 1, 2, 3, 4, 5 and 6 in Table 1 that when the width D of the inserts along a length direction of the composite positive electrode sheet gradually increases (from 10 μm to 20 μm), the electrochemical performances of the lithium batteries first increase and then decrease. The reason is that when the insert is too large, the proportion of large particles is too high, causing insufficient realization of the material properties. Therefore, in the method for preparing the composite positive electrode sheet of the present application, the optimal width D of the inserts along a length direction of the composite positive electrode sheet is about 16 μm.
It can be seen from Examples 1, 7 and 8 in Table 1 that when the distance L between two adjacent inserts increases (from 30 μm to 50 μm), the number of channels for electrolyte infiltration decreases, which worsens the electrochemical performances of the lithium battery. Therefore, in the method for preparing the composite positive electrode sheet of the present application, the distance L between two adjacent inserts is less than or equal to 30 μm.
It can be seen from Examples 1, 9, 10, 11 and 12 in Table 1 that when the depth h of the portion of each insert inserted into the coating layer gradually increases (from 30 μm to 50 μm), the electrochemical performances of the lithium batteries first increase and then decrease for the same reason as indicated above. Therefore, in the method for preparing the composite positive electrode sheet of the present application, the optimal depth h of the portion of each insert inserted into the coating layer is about 45 μm.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202310681756.6 | Jun 2023 | CN | national |
