Patent Application
20230361270
This application claims the benefit of Korean Patent Application No. 10-2021-0091135 filed on Jul. 12, 2021 with the Korean Intellectual Property Office, the content of which is incorporated herein by reference in its entirety.
The present disclosure relates to a negative electrode for secondary battery including an active material layer having different composition, an electrode assembly and a secondary battery including same.
Along with the technology development and increased demand for mobile devices, demand for secondary batteries as energy sources has been increasing rapidly. Among such secondary batteries, a lithium secondary battery exhibiting energy density and operating potential, and having long cycle life and low self-discharge rate is now commercialized and widely used.
Also, as interest in environmental issues grows in recent years, studies are frequently conducted on an electric vehicle (EV), a hybrid electric vehicle (HEV) and the like which can replace a vehicle using fossil fuels such as a gasoline vehicle and a diesel vehicle, which are one of the main causes of air pollution. As a power source for such electric vehicle (EV) and hybrid electric vehicle (HEV), lithium secondary batteries with high energy density, high discharge voltage, and output stability are mainly studied and used.
Such lithium secondary batteries are being developed as a model that can perform rapid charging in response to the needs of consumers, and for this purpose, design of the battery is performed in the direction of high energy density, long life, and low swelling.
However, as the charge rate of rapid charging increases, lithium precipitation occurs on the negative electrode of the battery, which occurs locally at first, but eventually causes problems that worsen the battery life retention and swelling.
By the way, the electrodes for secondary battery have different coating amounts for each position due to the sliding phenomenon caused by the coating of the electrode active material slurry during the manufacturing process, and accordingly, the electrodes are different in the charge/discharge characteristics, so that the negative electrode has a difference in the lithium deposition rate, which will affect the long-term performance of the battery.
Therefore, there is a need to develop a technology capable of solving these problems.
It is an object of the present disclosure to provide a negative electrode for secondary battery that can solve the lithium precipitation imbalance problem caused by the difference in the loading amount on a plane caused by the sliding phenomenon during the manufacture of the electrode active material layer, thereby preventing rapid deterioration of battery performance, an electrode assembly and a secondary battery including the same.
According to one aspect of the present disclosure, there is provided a negative electrode for secondary battery in which a negative electrode active material layer is formed on at least one surface of a negative electrode current collector,
Wherein, the negative electrode includes a first inclined portion on one end side, a second inclined portion on the other end side, and a flat portion located between the first inclined portion and the second inclined portion in the planar, and a first negative electrode active material layer may be formed on the flat portion, and a second negative electrode active material layer may be formed on the first inclined portion and the second inclined portion.
The graphite of the first negative electrode active material and the second negative electrode active material may be artificial graphite or natural graphite, and carbon of the second negative electrode active material may be low-crystalline carbon, amorphous carbon, or a mixture thereof.
Wherein, the carbon may be coated in an amount of 5 to 20% by weight based on the total weight of the carbon-coated graphite.
Further, the first negative electrode active material layer and the second negative electrode active material layer include at least one selected from the group consisting of a binder and a conductive material, in which the types thereof may be different, or the content ratios of constituents may be different.
Specifically, the first negative electrode active material may include uncoated graphite as an active material:styrene-butadiene rubber (SBR) as a binder:carbon black or carbon nanotubes (CNT) as a conductive material in a weight ratio of 93-97:1-5:0.1-5, and
Meanwhile, the volume ratio of the first negative electrode active material layer and the second negative electrode active material layer may be 6:4 to 4:6.
According to another aspect of the present disclosure, there is provided an electrode assembly for secondary battery comprising the negative electrode for secondary battery,
Wherein, the positive electrode active material layer may include a first positive electrode active material layer, and a second positive electrode active material layer formed on one side or both sides of the first positive electrode active material layer in a planar and having a composition different from that of the first positive electrode active material layer.
Wherein, the first positive electrode active material layer and the second positive electrode active material layer include at least one selected from the group consisting of a positive electrode active material, a binder, and a conductive material included in each layer, in which the types thereof may be different, or the content ratios of components may be different.
According to yet another aspect of the present disclosure, there is provided a secondary battery in which the electrode assembly for secondary battery, and an electrolyte are incorporated in a battery case.
Hereinafter, the present disclosure will be described in detail based on preferred embodiments of the present disclosure with reference to the accompanying drawings.
Terms or words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the present disclosure should be construed with meanings and concepts that are consistent with the technical idea of the present disclosure based on the principle that the inventors may appropriately define concepts of the terms to appropriately describe their own disclosure in the best way. Therefore, the embodiments described herein and the configuration shown in the accompanying drawings are merely preferred embodiments of the present disclosure, and are not intended to represent all the technical idea of the present disclosure, whereby there may be various equivalents and modifications that can substitute them at the time of filing and the scope of the present disclosure is not limited to the embodiments described below.
According to one embodiment of the present disclosure, there is provided a negative electrode for secondary battery in which a negative electrode active material layer is formed on at least one surface of a negative electrode current collector,
Wherein, the negative electrode current collector may be one selected from the group consisting of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper that is surface-treated with dissimilar metal, stainless steel that is surface-treated with dissimilar metal, and an aluminum-cadmium alloy, and specifically, it may be a metal containing copper as the negative electrode current collector.
Meanwhile, in the related art, the negative electrode active material layer formed on the negative electrode current collector is formed as a single layer or as a multilayer with different compositions. However, when the negative electrode active material layer is produced, a sliding phenomenon appears at one end and the other end in a direction perpendicular to the coating direction depending on the process in which the a negative electrode active material slurry is coated, which thus leads to lack of recognition of the problem that the charge/discharge characteristics appear differently depending on the position.
Thus, the present inventors have attempted to recognize and solve these problems. In particular, the inventors confirmed that as the demand for rapid charging increases in recent years, a lithium precipitation phenomenon appearing during the progress of rapid charging greatly affects the performance of secondary batteries, and such lithium precipitation also appears differently depending on the position in the negative electrode active material layer due to the sliding phenomenon.
Thus, the present inventors have repeated in-depth studies to solve these problems because the sliding phenomenon inevitably appears on the active material layer during the coating process, and as a result, confirmed that in the case where the active material layers are formed differently so as to include mutually different active materials on a plane, and the active material and the like are appropriately selected so as to prevent lithium precipitation imbalance, it is possible to solve these problems and improve the performance of the secondary battery, and completed the present disclosure.
Therefore, the negative electrode active material layer in the negative electrode for secondary battery of the present disclosure is divided into a first negative electrode active material layer, and a second negative electrode active material layer formed on one side or both sides of the first negative electrode active material layer in a planar, wherein the first negative electrode active material layer includes uncoated graphite as a first negative electrode active material, and the second negative electrode active material layer includes carbon-coated graphite as a second negative electrode active material, thereby eliminating the lithium precipitation imbalance problem according to the position and the loading amount.
In order to describe its configuration more specifically,
Referring to
That is, during slurry coating for forming the negative electrode active material layer, a sliding phenomenon appears at both ends in the coating direction, and a first inclined portion 121 and a second inclined portion 122 are provided according to the sliding.
Therefore, the first inclined portion 121 and the second inclined portion 122 and the flat portion 123 are different in the loading amounts and have different charge/discharge characteristics, whereby the lithium precipitation mode also appears differently, which difference results in deterioration of battery performance.
Therefore, the present disclosure solves the above problems by forming a negative electrode active material layer capable of occluding and releasing more lithium on the first inclined portion 121 and the second inclined portion 122 unlike the flat portion 123.
That is, the second negative electrode active material layer includes carbon-coated graphite as a second negative electrode active material, and thus strengthens the particle strength by carbon coating, properly distributes pores on the surface even after electrode rolling, and increases the surface conductivity, so that the rate characteristics of the negative electrode active material can be improved and thus, the lithium deposition rates of the flat portion, the first inclined portion, and the second inclined portion are made uniform.
At this time, for the first negative electrode active material and the second negative electrode active material, graphite is used as a base. In this case, for the first negative electrode active material and the second negative electrode active material, artificial graphite or natural graphite can be applied as the graphite. Specifically, both the first negative electrode active material and the second negative electrode active material may be artificial graphite that improves the rapid charging characteristics of the battery so as to meet the purpose of preventing deterioration of battery performance during rapid charging. At this time, the artificial graphite may be secondary particles formed by agglomeration of primary particles.
The artificial graphite as such secondary particles may have a porosity of 10% to 30%, specifically, a porosity of 15% to 20%. When this range is satisfied, the contact area with lithium ions becomes wider and thus, capacity characteristics and life characteristics can be improved.
Further, the artificial graphite may have a specific surface area of 0.5 m2/g to 1.5 m2/g, specifically, 0.8 m2/g to 1.2 m2/g. Artificial graphite particles having a specific surface area (BET) within this range may have excellent rapid charging characteristics, and cycle life characteristics.
The natural graphite may be a spherical single particle, and in this case, the rolling performance and high temperature storage characteristics can be improved.
Such natural graphite may also have a porosity of 10% to 30%, specifically, a porosity of 15% to 20%. When the porosity satisfies this range, the contact area with lithium ions becomes wider, and thus, the capacity characteristics and life characteristics can be improved.
Further, the natural graphite may have a specific surface area of 0.5 m2/g to 5 m2/g, preferably 1.5 m2/g to 2.5 m2/g, When the specific surface area is within the above range, the rolling performance during rolling is improved, which is preferable in terms of minimizing changes in the electrode structure.
The specific surface area of the graphite can be measured by a BET (Brunauer-Emmett-Teller) method. For example, the specific surface area can be measured by a 6-point BET method according to a nitrogen gas adsorption-flow method using a porosimetry analyzer (Belsorp-II mini by Bell Japan Inc.). Meanwhile, the carbon coating of the carbon-coated graphite used as the second negative electrode active material may be performed by a conventionally known method, but is not limited thereto. For example, it can be formed by providing carbon or a precursor thereof onto the graphite surface and pyrolyzing it. That is, it can be formed by heat treatment. At this time, the heat treatment temperature can be in the range of 1000° C. to 4000° C.
Alternatively, the carbon material may be provided on the graphite surface and then formed by applying a shear force such as simple dry mixing or mechanofusion process.
In this case, specifically, the carbon may be low-crystalline carbon, amorphous carbon, or a mixture thereof.
Specifically, the low crystalline carbon or amorphous carbon may be formed from a carbon precursor including at least one selected from the group consisting of sucrose, methylene diphenyl diisocyanate, polyurethane, phenolic resin, naphthalene resin, polyvinyl alcohol, polyvinyl chloride, furfuryl alcohol, polyacrylonitrile, polyamide, furan resin, cellulose, styrene, polyimide, epoxy resin, vinyl chloride resin, coal-based pitch, petroleum-based pitch, mesophase pitch, tar and low-molecular weight heavy oil, but the present disclosure is not limited thereto.
In addition, the carbon may be coated in an amount of 5 to 20% by weight, specifically 10 to 20% by weight, based on the total weight of the carbon-coated graphite.
If the carbon is coated in a too small content outside the above range, it is difficult to exhibit the effect according to the present disclosure, and when the content is too large, the resistance to movement of lithium ions increases, which is not preferable.
Meanwhile, the average particle diameter (D50) of the uncoated graphite as the first negative electrode active material may be 6 μm to 20 μm, specifically 8 μm to 18 μm, and more specifically 10 μm to 18 μm. When the above range is satisfied, the battery performance such as capacity and storage characteristics is excellent as a whole.
The average particle diameter (D50) of the carbon-coated graphite as the second negative electrode active material may be 10 μm to 25 μm, specifically, 12 μm to 20 μm. When the above range is satisfied, it is preferable from the viewpoint of realizing excellent rapid charging characteristics of the battery.
The average particle diameter (D50) is the particle diameter corresponding to a point of 50% in the cumulative distribution of the number of particles relative to the particle diameter, and can be measured using a laser diffraction method. Specifically, the powder to be measured is dispersed in a dispersion medium, and then introduced into a commercially available laser diffraction particle size analyzer (e.g., Microtrac S3500). When the particles pass through the laser beam, the diffraction pattern difference according to the particle size is measured to calculate the particle size distribution. D50 can be measured by calculating the particle diameter corresponding a point of 50% in the cumulative distribution of the number of particles relative to the particle diameter in the analyzer.
Meanwhile, each of the first negative electrode active material layer and the second negative electrode active material layer may further include a binder and/or a conductive material. The types and contents of these binders and conductive materials may be the same for each layer, but specifically, any one or more selected from the group consisting of a binder and a conductive material may have different types. That is, the type of binder used in each layer may be different, the type of the conductive material may be different, or both may be different.
Alternatively, even if the types are the same, the content ratios of components contained in the first negative electrode active material layer and the second negative electrode active material layer may be different. That is, the content ratio of the negative electrode active material, the binder, and the conductive material may be different in the first negative electrode active material layer and the second negative electrode active material layer.
The binder is a type of binder known in the art, and is not limited as long as it is a type capable of improving the adhesion strength of the electrode components, and for example, it may be at least one selected from the group consisting of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyvinyl alcohol, starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, fluororubber, polyacrylic acid (PAA) as a water-based binder, styrene-butadiene rubber (SBR), and carboxymethylcellulose (CMC). Further, the binder of the first negative electrode active material layer and the binder of the second negative electrode active material layer can be selected from the above-mentioned examples and can be selected to be equal to each other or different from each other.
When the binder is included, it may be included in each active material layer in an amount of 0.1 to 30% by weight, specifically 1 to 10% by weight, and more specifically 1 to 5% by weight. Of course, the content of each layer may be different.
Similarly, the conductive material is not particularly limited as long as it has high conductivity without causing a chemical change in the corresponding battery, and for example, graphite such as natural graphite and artificial graphite; carbon blacks such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; conductive fibers such as carbon fiber and metal fiber; metal powders such as carbon fluoride powder, aluminum powder, and nickel powder; conductive whiskey such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; conductive materials such as polyphenylene derivatives can be used. Further, the conductive material of the first negative electrode active material layer and the conductive material of the second negative electrode active material layer can be selected from the above-mentioned examples and can be selected to be equal to each other or different from each other.
When the conductive material is included, each active material layer may be included in an amount of 0.1 to 30% by weight, specifically 1 to 10% by weight, and more specifically 1 to 5% by weight. Of course, the content of each layer may be different.
Most specifically, the first negative electrode active material includes uncoated graphite as an active material:styrene-butadiene rubber (SBR) as a binder:carbon black or carbon nanotubes (CNT) as a conductive material in a weight ratio of 93-97:1-5:0.1-5, and
Meanwhile, the volume ratio of the first negative electrode active material layer and the second negative electrode active material layer is not limited in that they are formed to correspond to the inclined portion and the flat portion, but when determined based on a conventional process, it may be, for example, 4:6 to 9:1, or 4:6 to 8:2, or 4:6 to 7:3, and most specifically, 4:6 to 6:4.
Meanwhile, according to another embodiment of the present disclosure, there is provided an electrode assembly for secondary battery comprising the negative electrode for secondary battery,
A cross-sectional view of the electrode assembly according to one embodiment is schematically shown in
Meanwhile, the positive electrode active material layer may include a first positive electrode active material layer, and a second positive electrode active material layer formed on one side or both sides of the first positive electrode active material layer in a planar and having a composition different from that of the first positive electrode active material layer.
Here, “having different composition” means that the first positive electrode active material layer and the second positive electrode active material layer include at least one selected from the group consisting of a positive electrode active material, a binder, and a conductive material included in each layer, in which the types thereof are different, or the content ratios of constituents may be different.
A cross-sectional view of such a structure is schematically shown in
Here, similarly to the negative electrode 100, the positive electrode 310 has a flat portion 301 and inclined portions 302 and 303 at both ends of the flat portion 301 according to the sliding phenomenon of the slurry during manufacturing for the formation of the positive electrode active material layer. A first positive electrode active material layer 312 is formed on the flat portion 301 on the positive electrode current collector 311, and a second positive electrode active material layer 313 is formed on the inclined portions.
The positive electrode active material contained in the first positive electrode active material layer and the second positive electrode active material layer may be a layered compound such as lithium cobalt oxide (LiCoO2) or lithium nickel oxide (LiNiO2) or a compound substituted with one or more transition metals; lithium manganese oxides such as chemical formula Li1+xMn2−xO4 (where x is 0˜0.33), LiMnO3, LiMn2O3, LiMnO2; lithium copper oxide (Li2CuO2); vanadium oxides such as LiV3O8, LiV3O4, V2O5, and Cu2V2O7; a Ni-site type lithium nickel oxide represented by chemical formula LiNi1−xMxO2 (where, M=Co, Mn, Al, Cu, Fe, Mg, B or Ga, and x=0.01˜0.3); lithium manganese composite oxide represented by chemical formula LiMn2−xMxO2 (where, M=Co, Ni, Fe, Cr, Zn or Ta, and x=0.01˜0.1) or Li2Mn3MO8 (where, M=Fe, Co, Ni, Cu or Zn); a lithium manganese composite oxide having a spinel structure represented by LiNixMn2−xO4; lithium iron phosphate represented by LiMn2O4; LiFePO4 with a Li portion of the chemical formula substituted with an alkaline earth metal ion; a disulfide compound; Fe2(MoO4)3 and the like, but is not limited thereto.
The type of the positive electrode active material contained in each layer may be the same or different. Examples of the binder and the conductive material contained in the positive electrode active material layer are the same as described in the negative electrode active material layer, and these can also include the same type or different types in each layer.
Further, the content ratio of the active material, the binder, and the conductive material may be the same or different in each layer.
Meanwhile, according to yet another embodiment of the present disclosure, there is also provided a secondary battery in which the electrode assembly for secondary battery and an electrolyte are incorporated in a battery case.
Specific details of the components other than the electrode assembly in the secondary battery are well known in the art, and thus, detailed description thereof will be omitted herein.
Below, the present disclosure will be described in more detail by way of examples.
A needle coke was pulverized using a jet mill and then sieved to obtain a powder. The powder was heat-treated (graphitized) at 3,000° C. for 20 hours under an inert (Ar) gas atmosphere to prepare primary artificial graphite particles having an average particle diameter (D50) of 2.5 μm. After that, the artificial graphite primary particles and petroleum-based pitch were added at a ratio of 92:10, and then heat-treated at 1,500° C. for 10 hours, and the artificial graphite primary particles were agglomerated into secondary particles, granulated, and at the same time, carbon-coated to prepare carbon-coated artificial graphite (carbon content: 3 wt %, average particle diameter (D50): about 15 μm).
A mixture of the carbon-coated artificial graphite prepared in Preparation Example 1 as an active material, SBR as a binder, and carbon black as a conductive material in a weight ratio of 95:3.5:1.5, and water as a dispersion medium were used, and the mixture and the dispersion medium were mixed at a weight ratio of 1:2 to prepare a slurry for the active material layer. Using a slot die, the slurry for the active material layer was coated onto one surface of a copper (Cu) thin film with a thickness of 10 μm, which is a negative electrode current collector, and dried at 130° C. under vacuum for 1 hour to form an active material layer. The active material layer thus formed was rolled by a roll pressing process to produce a negative electrode having an active material layer with a thickness of 80 μm.
A negative electrode was produced in the same manner as in Comparative Example 1, except that in Comparative Example 1, a mixture of uncoated artificial graphite (average particle diameter (D50): 18 μm) instead of carbon-coated artificial graphite as an active material, SBR as a binder and carbon black as a conductive material in a weight ratio of 95:3.5:1.5, and water as a dispersion medium were used, and a slurry for an active material layer in which the mixture and dispersion medium were mixed in a weight ratio of 1:2 was used to form an active material layer.
The negative electrodes produced in Comparative Examples 1 and 2 were used, and Li metal was used as the positive electrode, and an electrolyte solution in which lithium hexafluorophosphate (LiPF6) with a concentration of 1.15 M was dissolved in an organic solvent consisting of ethylene carbonate/dimethyl carbonate/ethyl methyl carbonate (mixed volume ratio of EC/DMC/EMC=3/4/3) was used to produce a coin-type half-cell.
After rotating the coin-type half-cell at CHC 0.1 C for 3 cycles, the 3 C-rate current value was calculated and charged at 3 C for 28 minutes to determine the inflection point at the time of primary differentiation and dQ/dV of the profile, and Li-plating SOC (%) was quantified. The results are shown in Table 1 below.
Referring to Table 1, it can be seen that the rapid charging characteristics of Comparative Example 1 are superior to the rapid charging characteristics of Comparative Example 2. Therefore, when the active material of Comparative Example 1 was used for the inclined portion, it is expected that the lithium precipitation non-uniformity can be eliminated.
Those of ordinary skill in the art will be able to make various applications and modifications within the scope of the present disclosure based on the above contents.
In the negative electrode for secondary battery according to the present disclosure, a first negative electrode active material layer and a second negative electrode active material layer are formed in a planar so as to contain mutually different active materials, whereby the difference in lithium deposition rate caused by sliding during electrode coating can be alleviated, and deterioration of the charge/discharge characteristics of secondary batteries due to deposition imbalance can be prevented.
In addition, when the positive electrode also similarly forms the first positive electrode active material layer and the second positive electrode active material layer in a planar so as to include mutually different active materials, it is possible to more effectively solve such problems and exhibit more improved secondary battery performance.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2021-0091135 | Jul 2021 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2022/009475 | 6/30/2022 | WO |
