Patent Application
20250105289
The present disclosure claims priority to Chinese Patent Application No. 202310030037.8, filed on Jan. 9, 2023, entitled “Secondary Batteries and Battery Packs”, the content of which is incorporated herein by reference in its entirety.
The present disclosure relates to the field of batteries, and more particularly, to a secondary battery and a battery pack.
With the rapid development of electric automobiles and digital electronics, there is a need for power-type secondary batteries with higher power density and energy density and suitable for rapid charging and discharging to be applied to the electric automobiles and electronic products. For the secondary battery, such as a lithium-ion battery, increasing the energy density of the lithium-ion battery is one of the direct and effective ways to increase the life of the lithium-ion battery.
The secondary battery with high energy density requires a higher material press density and fewer auxiliary materials to provide space for active materials. However, the secondary battery with high rate discharge performance requires a lower material press density, more conductive materials, and a thicker current collector to ensure the high rate discharge performance, and to avoid the decline in cycle performance caused by high temperature and lithium precipitation.
Therefore, there is a need to provide a secondary battery that has high rate capability without affecting the energy density thereof.
A first aspect of the present disclosure provides a secondary battery including a negative electrode plate, wherein the negative electrode plate includes a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector, the negative electrode active material layer includes a negative electrode active material, the negative electrode active material includes a carbon material, wherein a grain size of the negative electrode active material is XS nm; a non-Faraday capacitance of the negative electrode plate is Cdl nF, satisfying 0.05≤Cdl≤10; 0.1≤√{square root over (Cdl−XS)}≤3.
In some embodiments, XS satisfies 0.01≤XS≤6.
In some embodiments, the negative electrode active material has a pore volume of α cm3/g, satisfying 0.5≤Cdl+10×α≤8.
In some embodiments, the negative electrode active material has a pore volume of a cm3/g, satisfying 0.001≤α≤0.5.
In some embodiments, the negative electrode active material has a powder resistivity of R Ω·cm at 20 KN, satisfying 0.01≤10R/Cdl≤5.
In some embodiments, the negative electrode active material has a powder resistivity of R Ω·cm at 20KN, satisfying 0.002≤R≤2.
In some embodiments, the secondary battery further includes a positive electrode plate, the positive electrode plate includes a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector, and the positive electrode active material layer includes a positive electrode active material.
In some embodiments, the negative electrode active material has a particle dispersion degree A, the positive electrode active material has a particle dispersion degree B, and the A and B satisfy at least one of the following: (a) 0.5≤A≤2.5; (b) 1.0≤B≤5.0; (c) 0.5≤B/A≤2.5.
In some embodiments, the negative electrode active material layer has a thickness of C μm, the positive electrode active material layer has a thickness of D μm, and the C and D satisfy at least one of the following: (i) 99≤C≤160; (ii) 80≤D≤130; (iii) 0.1≤1−(D/C)≤0.5.
In some embodiments, a surface of the negative electrode active material is coated with a first coating layer having a thickness of H1 nm, 5≤H1≤200, 10≤Cdl×H1≤250.
In some embodiments, a surface of the positive electrode active material is coated with a second coating layer having a thickness of H2 nm, 5≤H2≤60.
Meanwhile, a second aspect of the present disclosure further provides a battery pack including the secondary battery as described above.
The present disclosure provides a secondary battery and a battery pack. To make the objective, technical solutions, and effect of the present disclosure clear and explicit, the present disclosure will be described in further detail below with reference to the accompanying drawings and embodiments. It is to be understood that the specific embodiments described herein are merely illustrative of the present disclosure and are not intended to limit the present disclosure.
Embodiments of the present disclosure provide a secondary battery and a battery pack having the same. By controlling the non-Faraday capacitance of a negative electrode plate to be within a predetermined range, and simultaneously controlling the grain size of a negative electrode active material and the non-Faraday capacitance of the negative electrode plate to be within the predetermined range, the number of electrochemical active sites on the surface of the negative electrode plate in the secondary battery is increased, which facilitates the contact of the negative electrode active material with an electrolyte, accelerates the conduction rate of ions and electrons, reduces the charge transmission resistance, increases the actual contact area of the negative electrode plate with the electrolyte, shortens the ion-electron transmission distance, increases the number of reactive sites on the surface of the negative electrode plate, and improves the non-Faraday reaction strength, so that the secondary battery has a less charge transmission resistance, thereby greatly improving the rate capability of the secondary battery.
An embodiment of the present disclosure provides a secondary battery including a positive electrode plate, a negative electrode plate, a separator, an electrolyte, and a housing.
The negative electrode plate includes a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector. The negative electrode active material layer comprises a negative electrode active material. The negative electrode active material includes a carbon material.
The negative electrode plate may be a single-sided electrode plate or a double-sided electrode plate. When the negative electrode plate is a single-sided electrode plate, the negative electrode active material layer is provided on one surface of the negative electrode current collector, and when the negative electrode plate is a double-sided electrode plate, the negative electrode active material layer is provided on both surfaces of the negative electrode current collector. Further, the negative electrode plate may have both a region of single-sided negative electrode plate and a region of double-sided negative electrode plate.
In some embodiments, the negative electrode active material includes graphite. In some embodiments, the grain size XS of the negative electrode active material and the non-Faraday capacitance Cdl of the negative electrode plate satisfy: 0.1 √{square root over (Cdl−XS)}≤3. Specifically, the value of √{square root over (Cdl−XS)} may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.96, 1.0, 1.5, 2.0, 2.5, 3.0, or a range of any two of these numerical values. When the negative electrode plate satisfies the above relationship, the negative electrode plate may have a short ion transmission path and a fast electrochemical reaction, thereby achieving a high-rate discharge capability. When the negative electrode plate satisfies the above relationship, the electrolyte infiltration, surface impedance, and high-rate charge/discharge capability of the negative electrode plate are all in a desired state, and the expansion of the negative electrode plate during cycling may be reduced.
In some embodiments, a relationship of XS and Cdl is: 0.5≤√{square root over (Cdl−XS)}≤2.2. When the negative electrode plate satisfies the above relationship, the morphology of the negative electrode active material and the internal structure of the negative electrode plate can be further optimized, so that the overall performance of the secondary battery is improved.
In some embodiments, the relationship of XS and Cdl is: 0.7≤√{square root over (Cdl−XS)}≤2. When the negative electrode plate satisfies the above relationship, the actual contact area between the negative electrode plate and the electrolyte may be further adjusted, the ion-electron transmission distance is shortened, the number of reactive sites on the surface of the negative electrode plate is increased, the non-Faraday reaction strength is increased, and the charge transmission resistance is reduced, so that the overall performance of the secondary battery is improved.
In some embodiments, the non-Faraday capacitance of the negative electrode plate is Cdl nF in a range of 0.05≤Cdl≤10. Specifically, Cdl is 0.05, 0.1, 0.15, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10, or a range of any two of these numerical values. The Faraday reaction in the secondary battery refers to a process in which the oxidation state of an active material is changed, and charge is transferred to the inside of the active material through an electrode interface across two charge layers. The non-Faraday reaction refers to a reaction in which ions are physically adsorbed or detached from the electrode surface to store and release charges, without a charge moving across the electrode interface. The non-Faraday capacitance Cdl indicates the number of electrochemical active sites in the negative electrode plate. In a certain range, the increase of Cdl and the number of electrochemical active sites may facilitate the contact of the negative electrode active material with the electrolyte, accelerate the ion-electron conduction rate, reduce the charge transport resistance, and effectively improve the rate capability of the secondary battery.
In some embodiments, it satisfies 0.1≤Cdl≤10. When the non-Faraday capacitance value of the negative electrode plate is in the above range, the overall performance of the secondary battery is further improved.
In some embodiments, it satisfies 0.5≤Cdl≤9. When the non-Faraday capacitance value of the negative electrode plate is in the above range, the internal structure of the negative electrode plate can be further optimized so that the number of electrochemical active sites on the surface of the negative electrode plate is in a desired range, thereby further improving the overall performance of the secondary battery.
In some embodiments, it satisfies 1.5≤Cdl≤8.0. When the non-Faraday capacitance value of the negative electrode plate is in the above range, the overall performance of the secondary battery can be better balanced, thereby achieving a better performance thereof.
In some embodiments, the grain size of the negative electrode active material is XS nm in a range of 0.01≤XS≤6. Specifically, XS is 0.01, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, or a range of any two of these numerical values. The grain size XS can be obtained by refining XRD pattern of the negative electrode active material, and the conditions for testing XRD are as follows: step scanning is performed with a step size of ≤0.02°, a residence time of ≥2 s, and a scanning range of 10° to 90°.
The conduction characteristics of electrons affect the rate capability of the secondary battery, and the grain size XS can affect cycling of the secondary battery at high voltage and high temperature, and capacity exertion at high current. It is found that when the charge transfer activation energy and ion diffusion activation energy of the negative electrode active material increase, the reaction between the negative electrode plate and the electrolyte at the interface may be inhibited to some extent, affecting the performance of the negative electrode active material. Controlling the grain size XS of the negative electrode active material can affect the actual contact area between the negative electrode plate and the electrolyte, shorten the ion-electron transmission distance, increase the number of reactive active sites on the surface, increase the non-Faraday reaction strength, and have a lower charge transfer resistance, thereby greatly improving the rate capability of the secondary battery. The grain size may be regulated by controlling the particle size of the negative electrode active material, graphitization temperature, graphitization time, doping modification, or other means. Therefore, a relationship between the grain size XS of a non-negative electrode active material of the negative electrode plate and the non-Faraday capacitance Cd1 thereof may be controlled to be: 0.1√{square root over (Cdl−XS)}≤3. When 0.01≤XS≤6, the grain size of the negative electrode active material and the number of reactive sites on the negative electrode plate are in a preferable range, which can make the contact state between the negative electrode plate and the electrolyte better, so that the electrochemical reaction in the secondary battery is in a better state, and the overall performance of the secondary battery can be further improved. Furthermore, it is possible to alleviate a defect that in the secondary battery, due to the increase in the temperature during use, the pore size of the surface of the negative electrode active material increases, the specific surface area decreases, the contact area between the electrolyte and the negative electrode active material decreases, and the number of reaction sites on the surface decreases, so that the non-Faraday reaction strength on the surface of the negative electrode plate decreases, the diffusion capacity and surface reaction decrease, and thus the overall electrochemical performance of the electrode material decreases.
In some embodiments, the grain size of the negative electrode active material is XS nm in a range of 0.1≤XS≤5.5. When the grain size of the negative electrode active material satisfies the above range, the cycling under high voltage and high temperature and the capacity exertion under high current of the negative electrode active material is in a preferable state, and the actual contact area between the electrolyte and the particles of the negative electrode active material is in a more reasonable range, so that the overall performance of the secondary battery is better.
In some embodiments, the grain size of the negative electrode active material is XS nm in a range of 0.2≤XS≤5. When the grain size of the negative electrode active material satisfies the above range, the overall performance of the secondary battery can be further improved.
In some embodiments, the grain size of the negative electrode active material is XS nm in a range of 0.4≤XS≤4.5.
In some embodiments, the grain size of the negative electrode active material is XS nm in a range of 0.4≤XS≤4.2.
In some embodiments, the grain size of the negative electrode active material is XS nm in a range of 0.52≤XS≤3.9.
In some embodiments, a relationship between a pore volume α cm3/g of the negative electrode active material and the non-Faraday capacitance Cdl nF of the negative electrode plate is: 0.5≤Cdl+10×α≤8. Specifically, the value of Cdl+10×α is 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, or a range of any two of these numerical values. Pore volume α cm3/g refers to the total pore volume per unit mass of porous solid. When Cdl+10×α is in the above range, the pore structure of the negative electrode active material is rich, which improves the contact area between the negative electrode plate and the electrolyte, and shortens the transmission path of lithium ions, so that the electrolyte can rapidly infiltrates, and lithium ions can be quickly embedded or detached from the surface of the negative electrode material, thereby accelerating the reaction kinetics, and reducing the polarization of the negative electrode surface. Therefore, the current distribution is more uniform, and more negative electrode active materials participate in accepting Lit at the time of high-rate rapid charging, thereby effectively avoiding lithium precipitation on the negative electrode surface.
In some embodiments, the relationship between the pore volume α cm3/g of the negative electrode active material and the non-Faraday capacitance Cdl nF of the negative electrode plate is 0.8≤Cdl+10×α≤6.8. When Cdl+10×α is in the above range, the negative electrode plate can provide sufficient electrochemical reactive sites in the electrochemical process, accelerate the non-Faraday reaction process of the negative electrode, facilitate the transmission of electrons and ions between a solid phase and a liquid phase, improve the electrochemical reaction kinetics, and further improve the rate capability of the material.
In some embodiments, the relationship between the pore volume α cm3/g of the negative electrode active material and the non-Faraday capacitance Cdl nF of the negative electrode plate is 1.1≤Cdl+10×α≤6.2.
In some embodiments, the relationship between the pore volume α cm3/g of the negative electrode active material and the non-Faraday capacitance Cdl nF of the negative electrode plate is 1.3≤Cdl+10×α≤5.9. When Cdl+10×α is in the above range, the pore structure of the negative electrode active material can be further optimized, the non-Faraday reaction of the negative electrode plate can be enhanced, and the overall performance of the secondary battery can be further improved.
In some embodiments, the pore volume of the negative electrode active material is a cm3/g in a range of 0.001≤α≤0.5. Specifically, α is 0.001, 0.005, 0.01, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, or a range of any two of these numerical values. When the pore volume of the negative electrode active material is within the above range, the pore structure of the particles of the negative electrode active material is rich, which not only increases the contact area between the negative electrode plate and the electrolyte, but also shortens the transmission path of lithium ions, so that the electrolyte can rapidly infiltrates to provide a smooth charge transmission path for the solid-liquid interface, the diffusion energy barrier is reduced, and thus lithium ions can be quickly embedded into and detached from the surface of the negative electrode active material, and thus the reaction kinetics is accelerated.
In some embodiments, the pore volume of the negative electrode active material is α cm3/g in a range of 0.005≤α≤0.45.
In some embodiments, the pore volume of the negative electrode active material is α cm3/g in a range of 0.008≤α≤0.42.
In some embodiments, the pore volume of the negative electrode active material is α cm3/g in a range of 0.01≤α≤0.38. When the pore volume of the negative electrode active material is within the above range, the pore structure of the particles of the negative electrode active material can be further optimized, and the overall performance of the secondary battery can be improved.
In some embodiments, the pore volume of the negative electrode active material is α cm3/g in a range of 0.05≤α≤0.38.
In some embodiments, the pore volume of the negative electrode active material is α cm3/g in a range of 0.08≤α≤0.38.
In some embodiments, the pore volume of the negative electrode active material is α cm3/g in a range of 0.1≤α≤0.38.
In some embodiments, the pore volume of the negative electrode active material is α cm3/g in a range of 0.12≤α≤0.38. When the pore volume α of the negative electrode active material is in the above range, the active sites on the surface of the negative electrode plate are rich, which facilitates charge exchange of lithium ions on the surface of the negative electrode active material and improves the rate capability of the lithium ion battery. Moreover, the diffusion of lithium ions into the cathode active material is facilitated, the solid-state conductivity of lithium ions is improved, the impedance of the secondary battery is reduced, and the service life of the secondary battery is prolonged.
In some embodiments, the negative electrode active material has a powder resistivity of R Ω·cm at 20 KN. In some embodiments, a relationship between R and Cdl is: 0.01≤10R/Cdl≤5. Specifically, the value of 10R/Cdl is 0.01, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, or a range of any two of these numerical values. When the negative electrode plate satisfies the above relationship, the electron conductivity of the negative electrode active material is high, the interface resistance between the electrolyte and the negative electrode active material is low, and the polarization of the secondary battery is less, so that the cycle performance and the rate capability of the secondary battery can be improved.
In some embodiments, the powder resistivity of the negative electrode active material is R Ω·cm at 20 KN. In some embodiments, the relationship between R and Cdl is:
In some embodiments, the powder resistivity of the negative electrode active material is R Ω·cm at 20 KN. In some embodiments, the relationship between R and Cdl is:
In some embodiments, the powder resistivity of the negative electrode active material is R Ω·cm at 20 KN, 0.002≤R≤2. Specifically, R is 0.002, 0.005, 0.01, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.5, 2.0, or a range of any two of these numerical values. When the powder resistivity of the negative electrode active material at 20 KN satisfies the above range, the negative electrode plate can have better conductive performance, and to some extent, influence the performance of the negative electrode plate, so that the overall performance of the secondary battery is better.
In some embodiments, the powder resistivity of the negative electrode active material is R Ω·cm at 20 KN, 0.008≤R≤1.8.
In some embodiments, the powder resistivity of the negative electrode active material is R Ω·cm at 20 KN, 0.011≤R≤1.4.
In some embodiments, the powder resistivity of the negative electrode active material is R Ω·cm at 20 KN, 0.021≤R≤1.4.
The powder resistivity R of the negative electrode active material can be measured by a four-probe method described in GB/T 39978-2021.
In some embodiments, the negative electrode active material has a particle dispersion degree of A, and in some embodiments, 0.5≤A≤2.5. Specifically, A is 0.5, 0.8, 1.0, 1.2, 1.5, 1.8, 2.0, 2.3, 2.5, or a range of any two of these numerical values.
In some embodiments, the negative electrode active material has a particle dispersion degree of A, and in some embodiments, 0.7≤A≤2.
In some embodiments, the negative electrode active material has a particle dispersion degree of A, and in some embodiments, 0.7≤A≤1.9. The particle dispersion is equal to (D99-D10)/D50, where D99 denotes the particle size of active material particles having a cumulative volume distribution of 99%, D10 denotes the particle size of active material particles having a cumulative volume distribution of 10%, and D50 denotes the particle size of active material particles having a cumulative volume distribution of 50%. The particle dispersion degree is used for characterizing the dispersion degree of components with various particle sizes. Small particle dispersion degree indicates that the particle size distribution is centralized, the powder disperses well during a stirring process, the slurry is not prone to settling, and the obtained slurry has a good uniformity and stability, which may effectively regulate the uniformity degree of the coating weight of the electrode plate, enhance the stability of the electrode plate, achieve the purpose of regulating the non-Faraday reaction process, improve the transmission efficiency of lithium ions between the positive electrode plate and the negative electrode plate, and thus improve the rate capability of the secondary battery. Excessive particle dispersion degree indicates that the particle size distribution is too wide, which may cause that small particles of the negative electrode active material may be prone to be embedded between large particles of the negative electrode active material, resulting in that the particles of the negative electrode active material are too dense, which affects the embedding and detaching of lithium ions, and thus the cycle and kinetic performance of the negative electrode plate are reduced. In addition, the preparation of the slurry is also more difficult.
When the particle dispersion degree A of the negative electrode active material on the negative electrode plate satisfies the above range, the stability of the negative electrode plate is enhanced, and the rate capability of the secondary battery is improved.
The particle dispersion degree A of the negative electrode active material can be obtained by measuring D99, D10, D50 of the negative electrode active material using a laser particle size analyzer and then calculating. Specifically, a method for obtaining the negative electrode active material from the negative electrode plate may include discharging the secondary battery at a constant current of 0.04 C to a lower voltage limit, disassembling to obtain the negative electrode plate, soaking and cleaning the negative electrode plate with a DMC (dimethyl carbonate) solution, washing with deionized water for a plurality of times, pouring the upper liquid layer, standing and drying the lower solution layer, and finally heat-treating at 800° C. for 2 hours under an argon atmosphere to obtain the above test sample.
The negative electrode active material layer has a thickness of C μm, and in some embodiments, C is in the range of 99≤C≤160. Specifically, C is 99, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, or a range of any two of these numerical values. If the thickness of the negative electrode active material layer is in the above range, the tortuosity and length of migration paths of lithium ions and electrons are less, and thus the lithium ions and electrons have a strong diffusion ability in the negative electrode plate, which further improves the rate capability of the secondary battery. Moreover, the thickness of the negative electrode active material layer may also affect the adhesion between the negative electrode active material layer and the negative electrode current collector, thereby affecting the performance of the negative electrode plate.
In some embodiments, the thickness of the negative electrode active material layer is C μm in a range of 116≤C≤155.
In some embodiments, the thickness of the negative electrode active material layer is C μm in a range of 116≤C≤149. When the thickness C of the negative electrode active material layer satisfies the above range, the diffusion ability of lithium ions in the negative electrode active material layer can be enhanced, so that the secondary battery has high rate capability and energy density.
In some embodiments, the negative electrode active material layer is disposed on one surface of the negative electrode current collector.
In some embodiments, the negative electrode active material layer is disposed on both surfaces of the negative electrode current collector.
When the negative electrode plate has both a region of the single-sided negative electrode active material layer and a region of the double-sided negative electrode active material layer, the thickness of the negative electrode plate is a thickness of the region of the double-sided negative electrode active material layer. The thickness of the negative electrode active material layer can be measured using a micrometer.
In some embodiments, the surface of the negative electrode active material is provided with a first coating layer having a thickness of H1 nm. In some embodiments, a relationship between H1 and Cdl is 10≤Cdl×H1≤250. Specifically, the value of Cdl×H1 is 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, or a range of any two of these numerical values.
In some embodiments, the surface of the negative electrode active material is provided with a first coating layer having a thickness of H1 nm. In some embodiments the relationship between H1 and Cdl is 20≤Cdl×H1≤230.
In some embodiments, the surface of the negative electrode active material is provided with a first coating layer having a thickness of H1 nm. In some embodiments the relationship between H1 and Cdl is 31≤Cdl×H1≤210.
In some embodiments, the thickness of the first coating layer is H1 nm, 5≤H1≤200. Specifically, H1 is 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, or a range of any two of these numerical values.
In some embodiments, the thickness of the first coating layer is H1 nm, 11≤H1≤180.
In some embodiments, the thickness of the first coating layer is H1 nm, 21≤H1≤165.
In some embodiments, the first coating layer is a carbon coating layer, which can be formed from any of organic resins, asphalt, citric acid, glucose, and hard carbon by a heat treatment process such as sintering.
The preparation of the secondary battery involves a heat treatment process, in which the negative electrode active material is subjected to different degrees of centrifugal extrusion pressure, resulting in, under the action of external force in each direction, internal defect occurring in the negative electrode active material, for example, the interior is relatively loose and easily collapsible. The first coating layer can be used for uniformly coating the particles of the negative electrode active material, and thus the obtained negative electrode active material has strong structural stability. The external coating structure formed by the first coating layer can eliminate the internal defect, improve the diffusion performance of lithium ions therein, reduce the material expansion, and facilitate to improve the electrochemical performance of the secondary battery, such as rate capability and cycle. Furthermore, the carbon coating layer can provide more active sites, reduce the transmission resistance and transmission paths of lithium ions on the surface of the negative electrode active material, facilitate the embedding and detaching of lithium ions, reduce the impedance of the negative electrode active material, and improve the liquid absorption performance, thereby improving the rate capability.
In some embodiments, referring to
The method of assembling the button battery is as follows: the obtained negative electrode plate is dried and cut into small round pieces, weighted, transferred to a vacuum oven, dried at 100° C. for 8 hours, and then transferred to a glove box filled with argon for half battery assembly. The assembly mode is a conventional assembly mode in the art. The non-Faraday potential interval is confirmed using a cyclic voltammetry curve. Then, the current values at different sweep speeds are determined using a linear voltammetry sweep curve in the potential interval, and finally the non-Faraday capacitance Cdl is obtained by fitting.
In some embodiments, the negative electrode current collector includes, but is not limited to, a metal foil, a metal cylinder, a metal winding, a metal plate, a metal film, a metal plate mesh, a stamped metal, a foamed metal, or the like. In some embodiments, the negative electrode current collector is a metal foil. In some embodiments, the negative electrode current collector is aluminum foil or copper foil. As used herein, the term “copper foil” includes copper alloy foils.
In some embodiments, the negative electrode current collector is a composite current collector including a conductive resin.
In some embodiments, the negative current collector is a film obtained by evaporating copper on a polypropylene film.
In some embodiments, the negative electrode active material layer includes a negative electrode active material, a conductive agent, a binder, and a dispersant.
In some embodiments, the negative electrode active material includes at least one of natural graphite, artificial graphite, hard carbon, soft carbon, mesocarbon microspheres.
In some embodiments, the method of preparing the negative electrode active material comprises the steps of:
In some embodiments, the conductive agent includes one or more of carbon black, graphite, carbon fibers, carbon nanotubes, or graphene.
The binder may enhance adhesion between the negative electrode active materials. The type of the binder is not particularly limited as long as it is a material stable to the electrolyte or the solvent used in the preparation of electrodes.
In some embodiments, the binder includes sodium carboxymethyl cellulose and styrene butadiene rubber.
In some embodiments, the binder includes sodium carboxymethyl cellulose, oxidized starch, and styrene butadiene rubber.
The positive electrode plate includes a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector. The positive electrode active material layer comprises a positive electrode active material.
The positive electrode plate may be a single-sided plate or a double-sided plate. When the positive electrode plate is a single-sided plate, the positive electrode active material layer is provided on one surface of the positive electrode current collector, and when the positive electrode plate is a double-sided plate, the positive electrode active material layer is provided on both surfaces of the positive electrode current collector. Further, the positive electrode plate may have both a region of single-sided positive electrode active material layer and a region of double-sided positive electrode active material layer.
When the positive electrode plate has both the region of the single-sided positive electrode active material layer and the region of the double-sided positive electrode active material layer, the thickness of the positive electrode plate is a thickness of the region of the double-sided positive electrode active material layer.
In some embodiments, the positive electrode active material has a particle dispersion degree of B, 1.0≤B≤5.0. Specifically, B is 1.0, 1.2, 1.5, 1.8, 2.0, 2.3, 2.5, 2.8, 3.0, 3.2, 3.5, 3.8, 4.0, 4.2, 4.5, 4.8, 5.0, or a range of any two of these numerical values.
In some embodiments, the positive electrode active material has a particle dispersion degree of B in the range of 1.3≤B≤4.5.
In some embodiments, the positive electrode active material has a particle dispersion degree of B in the range of 1.9≤B≤3.9.
In some embodiments, the positive electrode active material has a particle dispersion degree of B in the range of 2.1≤B≤3.9.
The particle dispersion degree is equal to (D99-D10)/D50, where D99 denotes the particle size of active material particles having a cumulative volume distribution of 99%, D10 denotes the particle size of active material particles having a cumulative volume distribution of 10%, and D50 denotes the particle size of active material particles having a cumulative volume distribution of 50%. The particle dispersion degree is used for characterizing the dispersion degree of components with various particle sizes. Small particle dispersion degree indicates that the particle size distribution is centralized, the powder disperses well during a stirring process, the slurry is not prone to settling, and the obtained slurry has a good uniformity and stability, which may effectively regulate the uniformity degree of the coating weight of the positive electrode plate, enhance the stability of the positive electrode plate, achieve the purpose of regulating the non-Faraday reaction process, improve the transmission efficiency of lithium ions between the positive electrode plate and the negative electrode plate, and thus improve the rate capability of the secondary battery. Excessive particle dispersion degree indicates that the particle size distribution is too wide, which may cause that small particles of the negative electrode active material may be prone to be embedded between large particles of the negative electrode active material, resulting in that the particles of the negative electrode active material are too dense, which affects the embedding and detaching of lithium ions, and thus the cycle and kinetic performance of the positive electrode plate are reduced. In addition, the preparation of the slurry is also more difficult.
When the particle dispersion degree B of the positive electrode active material on the positive electrode plate satisfies the above range, the stability of the positive electrode plate is enhanced, and the rate capability of the secondary battery is improved.
In some embodiments, a relationship between the particle dispersion degree A of the negative electrode active material and the particle dispersion degree B of the positive electrode active material is 0.1≤A/B≤2.5. Specifically, the value of A/B is 0.1, 0.2, 0.3, 0.5, 0.7, 0.8, 1.0, 1.2, 1.5, 1.8, 2.0, 2.3, 2.5, or a range of any two of these numerical values. When the particle dispersion degree A of the negative electrode active material and the particle dispersion degree B of the positive electrode active material satisfy the above range, the negative electrode plate and the positive electrode plate with high tap density can be obtained, and the positive electrode plate and the negative electrode plate both have high transmission performance of electrons and lithium ions, and the transmission efficiency of electrons and lithium ions on the positive electrode plate and the negative electrode plate are more matched, so that the secondary battery has high charging and discharging performance at high rate capability and has high energy density.
In some embodiments, the relationship between the particle dispersion degree A of the negative electrode active material and the particle dispersion degree B of the positive electrode active material satisfies 0.3≤A/B≤2.2.
In some embodiments, the relationship between the particle dispersion degree A of the negative electrode active material and the particle dispersion degree B of the positive electrode active material satisfies 0.5≤A/B≤1.9.
The particle dispersion degree B of the positive electrode active material on the positive electrode plate can be obtained by directly measuring the particle size of the particles of the positive electrode active material using a laser particle size analyzer and then calculating. Alternatively, the secondary battery may be discharged at a constant current of 0.04 C to a lower voltage limit, disassembled to obtain the positive electrode plate, and soaked and washed with a DMC (dimethyl carbonate) solution, and the positive electrode plate is burned in a muffle furnace at 400° C. for 5 hours. The powder is peeled off, washed with deionized water for 2 to 3 times, and left to stand after each washing. The supernatant liquid is poured out, and the lower solution is left to stand, and then dried to obtain a test sample.
In some embodiments, the positive electrode active material layer has a thickness of D μm in the range of 80≤D≤130. Specifically, D is 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, or a range of any two of these numerical values. When both surfaces of the positive electrode current collector are provided with the positive electrode active material layer, D μm is the total thickness of two positive electrode active material layers.
If the thickness of the positive electrode active material layer is in the above range, the tortuosity and length of migration paths of lithium ions and electrons are in a desired range, and thus the lithium ions and electrons have a good diffusion ability in the positive electrode plate, so that the secondary battery has a good rate capability, and it is possible to ensure that the specific capacity and energy density of the secondary battery are in a desired range. The adhesion between the positive electrode active material layer and the positive electrode current collector can be in a desired range, so that the performance of the positive electrode plate is well realized.
In some embodiments, the thickness of the positive electrode active material layer is D μm in the range of 91≤D≤125. When the thickness D of the positive electrode active material layer satisfies the above range, the diffusion ability of lithium ions in the positive electrode active material layer can be enhanced, so that the secondary battery has high rate capability and energy density.
In some embodiments, the thickness of the positive electrode active material layer is D μm in the range of 101≤D≤125.
In some embodiments, a relationship between the thickness C μm of the negative electrode active material layer and the thickness D μm of the positive electrode active material layer is 0.1≤1−(D/C)≤0.5. Specifically, the value of 1−(D/C) is 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, or a range of any two of these numerical values. When the thickness C of the negative electrode active material layer and the thickness D of the positive electrode active material layer satisfy the above range, the electrolyte can sufficiently diffuse in the positive electrode plate and the negative electrode plate, thereby reducing the ohmic impedance of the electrode plate, avoiding lithium precipitation in the negative electrode plate, and ensuring high energy density while improving the kinetic performance of the secondary battery.
In some embodiments, the relationship between the thickness C μm of the negative electrode active material layer and the thickness D μm of the positive electrode active material layer is 0.13≤1−(D/C)≤0.45.
In some embodiments, the relationship between the thickness C μm of the negative electrode active material layer and the thickness D μm of the positive electrode active material layer is 0.17≤1−(D/C)≤0.40.
The surface of the positive electrode active material is provided with a second coating layer having a thickness of H2 nm, and in some embodiments, 5≤H2≤60. Specifically, H2 is 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, or a range of any two of these numerical values.
In some embodiments, the second coating layer contains a coating element including at least one of F, Al, Mg, Ti, or Zr.
In some embodiments, the second coating layer is selected from any one of organic polymers, inorganic metal fluorides, oxides, or lithiated materials.
By coating and modifying the positive electrode active material, the side reaction between the positive electrode active material and the electrolyte can be prevented, thereby avoiding the chemical erosion by the electrolyte, reducing the dissolution of the transition metal, improving the stability of the structure of the positive electrode active material layer, increasing the conductivity of the positive electrode active material layer, and improving the cycle stability and rate capability of the secondary battery.
The positive electrode active material layer may be a single-layer structure or a multiple-layer structure. The multiple positive electrode active material layers may comprise the same or different positive electrode active materials with each other. The positive electrode active material is any substance capable of reversibly embedding and detaching metal ions such as lithium ions.
In some embodiments, the positive electrode active material includes a ternary material, which may include lithium nickel cobalt manganese oxide and/or lithium nickel cobalt aluminum oxide.
In some embodiments, the positive electrode active material includes lithium nickel cobalt manganese oxide, in which the content of the nickel element is greater than or equal to 0.5, based on the mole amounts of the nickel element, the cobalt element, and the manganese element being 1.
In some embodiments, the positive electrode active material includes lithium nickel cobalt manganese oxide, in which the content of the nickel element is less than or equal to 0.85, based on the mole amounts of the nickel element, the cobalt element, and the manganese element being 1.
In some embodiments, the positive electrode active material includes a doping element and/or a coating element.
In addition, the positive electrode active material layer further includes a positive electrode conductive agent and a positive electrode binder.
The type of the positive electrode conductive agent is not limited, and any known conductive agent may be used. Examples of positive electrode conductive agents may include, but are not limited to, carbon materials such as natural graphite, artificial graphite, acetylene black, needle coke; carbon nanotubes; graphene; and the like. The positive electrode conductive agent may be used alone or in any combination.
The type of the solvent used to form the positive electrode material slurry is not limited, as long as the solvent can dissolve or disperse the positive electrode active material, the positive electrode conductive agent, and the positive electrode binder. Examples of the solvent used to form the positive electrode material slurry may include any of an aqueous solvent and an organic solvent. The type of the positive electrode current collector is not particularly limited, and may be any material known to be desirable for use as a positive electrode current collector. Examples of positive electrode current collectors may include, but are not limited to, metals such as aluminum, stainless steel, nickel plating, titanium, tantalum, and other metal materials; carbon materials such as carbon cloth and carbon paper; composite materials formed by polymers and metal layers. In some embodiments, the positive electrode current collector is a metal material. In some embodiments, the positive electrode current collector is aluminum.
The form of the positive electrode current collector is not particularly limited. In some embodiments, the positive electrode current collector is a metal foil. The thickness of the metal foil is not particularly limited. In some embodiments, the thickness of the metal foil is greater than 1 μm, greater than 3 μm, or greater than 5 μm. In some embodiments, the thickness of the metal foil is less than 1 mm, less than 50 μm, or less than 20 μm. In some embodiments, the thickness of the metal foil is in the range of any two of the above values.
The electrolyte includes a lithium salt, an organic solvent, and an additive.
In some embodiments, the lithium salt includes at least one of lithium hexafluorophosphate, lithium organoborate, lithium perchlorate, or lithium sulfonimide. The content of the lithium salt is not particularly limited as long as it does not impair the effect of the present disclosure.
In some embodiments, the organic solvent includes a cyclic carbonate and a linear carbonate.
Specifically, the organic solvent is one of ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), propylene carbonate (PC), ethyl methyl carbonate (EMC), or a combination thereof.
In some embodiments, the additive includes at least one of vinylene carbonate, 1,3-propane sultone, lithium difluorophosphate, fluoroethylene carbonate (FEC), lithium difluoro (oxalato) borate, tripropynyl phosphate, triallyl phosphate, or triallyl isocyanurate.
In order to prevent a short circuit, the separator is generally provided between the positive electrode and the negative electrode. In this case, the electrolyte of the present disclosure is generally infiltrated into the separator for use.
An embodiment of the present disclosure further provides a battery pack including the secondary battery described above. As a typical application, the battery pack may be used in, but is not limited to, electronic toys, electronic tools, electromobile, electric automobile, energy storage devices, ships, spacecraft, and other application.
The method of preparing the secondary battery according to the present disclosure is described as follows in connection with specific examples:
Ternary positive electrode active material LiNi0.8Co0.1Mn0.1O2(NCM811) was added into an aluminum chloride solution, and ammonia water was added to keep the pH of the solution stable. Hydrolysis was performed for 8 h, and then the solution was filtered, washed repeatedly with deionized water and alcohol, dried, and heat-treated in a horizontal kettle at 600° C. for 5 h to obtain a positive electrode active material coated with aluminum oxide, with a thickness H2 of 30 nm. The coated ternary positive electrode active material NCM811 was baked at 85° C. for 8 hours, mixed with conductive carbon black Super P and polyvinylidene fluoride (PVDF) as a binder at a weight ratio of 96:2:2, and added to N-methyl pyrrolidone (NMP) for high-speed dispersion for 4 hours, and peeled off from the kettle. Then, another NMP was added again therein to adjust the viscosity of the slurry while defoaming, so that the viscosity of the slurry was finally in the range of 2500 to 5000 mPa·s. The obtained positive electrode slurry was uniformly coated on both surfaces of the aluminum foil as the positive electrode current collector, and then dried at 120° C., rolled and cut to obtain the positive electrode plate. The thickness D of the positive electrode active material layer was controlled at 90 μm.
Preparation of the negative electrode active material comprises the following steps. Petroleum coke was subjected to a pretreatment process such as crushing and premixing in a roller mill, and the crushed particles had a particle size of 9 μm. The crushed product was subjected to a high-temperature graphitization treatment in a protective atmosphere (which is argon) at a temperature of 2900° C., and then left at 3000° C. for 48 hours. The product was then polished and shaped in a continuous shaping system for 8 h to smooth the surface of the product particles to obtain an artificial graphite having a particle size D50 of 13 μm and a grain size XS of 0.5 nm as the negative electrode active material.
The artificial graphite as the negative electrode active material and asphalt as the first coating material were added to a thermal reactor for stirring and mixing for 6 h, and then heat-treated for 2 h at 1200° C. under an inert gas atmosphere to obtain the negative electrode active material coated with the first coating layer, in which a thickness H1 of the first coating layer is 77 nm. Then, the negative electrode active material, conductive carbon black Super P, sodium carboxymethyl cellulose as the binder, oxidized starch, and styrene-butadiene rubber were mixed at a weight ratio of 96.5:1.2:1.1:0.2:1.0 to prepare the negative electrode material slurry. Specifically, graphite, carbon black, and 80% of sodium carboxymethyl cellulose were mixed uniformly at a low speed, then the remaining 20% of sodium carboxymethyl cellulose, 50% of oxidized starch, and deionized water were added and dispersed with high-speed stirring for 2 h, and then 50% of oxidized starch and styrene-butadiene rubber were added and stirred at a low speed. The viscosity of the slurry was controlled to be in the range of 2500 mPa·s to 4000 mPa·s. and then the slurry was passed through a 200 mesh screen to prepare the negative electrode material slurry. The prepared negative electrode material s slurry was uniformly coated on one side or both sides of the copper foil as the negative electrode current collector, dried in five step at 90° C. to 110° C., rolled and cut to obtain the negative electrode plate, and the thickness C of the negative electrode active material layer was controlled at 110 μm.
Ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (EDC) were mixed at a volume ratio of 1:1:1, and 1 mol/L of LiPF6 was added into the mixture and mixed uniformly to prepare the electrolyte.
The negative electrode plate and the positive electrode plate prepared by the above steps, after drying, were used to prepare a wound electric core together with a separator by using a winding machine. A positive electrode aluminum tab and a negative electrode nickel-plated copper tab were welded to the electric core, and then the welded electric core was placed into an aluminum-plastic film which has been pouched for packaging, wherein the separator is made of a PP film. Then, a process such as electrolyte injection, formation and grading was performed to prepare the secondary battery.
The curve of linear sweep voltammetry (LSV) in the non-Faraday reaction interval at different sweep speeds, in which the current varies linearly with the sweep speed, can be used to evaluate the non-Faraday capacitance (Cdl), which plays an important role in characterizing the number of active sites. In a certain range, the Cdl is increased, the number of electrochemical active sites is increased, so that the contact of the negative electrode active material with the electrolyte is facilitated, the ion-electron conduction rate is accelerated, the charge transmission resistance is low, and the rate capability of the secondary battery can be effectively improved.
The “overhang” region of the negative electrode plate refers to a portion of the negative electrode plate that extends beyond the positive electrode plate in the length and width directions.
The secondary battery was prepared by the method as described in Example 1, in which the particle size of crushed petroleum coke, the graphitization treatment temperature, the heating temperature, the holding time, and the polishing and shaping time were controlled to control the characteristics of the negative electrode plate and the negative electrode active material to be the values as shown in
The secondary battery was prepared by the method as described in Example 1, in which the particle size of crushed petroleum coke, the graphitization treatment temperature, the heating temperature, the holding time, and the polishing and shaping time were controlled to control the parameters of the positive electrode plate and the negative electrode plate to be the values as shown in
The secondary battery was prepared using the method as described in Example 1, with differences as shown in
The performance test of the prepared secondary battery was as follows:
Grain size XS nm test for the negative electrode active material:
The negative electrode active material prepared in the Examples and Comparative Examples was determined by X-ray diffraction using CuKα-rays. The (002) peak attributed to the negative electrode active material in the range of 25° to 27° was analyzed for the diffraction angle 2θ, and then the grain size of the negative electrode active material was calculated by the Scherrer formula. The test results are shown in
Pore volume α cm3/g test for the cathode active material:
The shapes of the negative electrode active materials prepared in the Examples and the Comparative Examples were observed using a scanning electron microscope (SEM), and the pore volumes of the negative electrode active materials prepared in the Examples and the Comparative Examples were measured by a BET 6 point method according to a nitrogen adsorption flow method using a porosity measurement analyzer (Bell Japan Inc, Belsorp-II mini). The test results are shown in
Powder Resistivity R Ω·Cm Test for the Negative Electrode Active Material:
The secondary battery was charged at a large rate at 25° C. Specifically, the secondary battery was discharged at constant current of 1C, left standing for 10 minutes, and charged at constant current of 4C. A discharge capacity of the first time was recorded, and the charge capacity was divided by the discharge capacity of the first time under the charge/discharge of the lithium ion battery at 1C/1C at 25° C. to obtain the 4C-rate capability of the secondary battery. The test results are shown in
To facilitate understanding of the present disclosure, the relevant data in Examples 1 to 30 and Comparative Examples 1 to 4 are listed in the present disclosure, as shown in
The value of the non-Faraday capacitance Cdl of the negative electrode plate of the secondary battery affects the number of electrochemical active sites, and in turn affects the contact of the negative electrode active material with the electrolyte. The value of the non-Faraday capacitance Cdl of the negative electrode plate affects the conduction rate of ions and electrons and the charge transmission resistance, which can effectively affect the rate capability of the secondary battery. The grain size XS of the negative electrode active material influences the cycle performance thereof at high voltage and high temperature and the capacity exertion at high current, and this mainly because the grain size of the negative electrode active material influences the actual contact area between the electrode and the electrolyte, influences the transmission distance of ions and electrons and the number of surface reactive active sites, and further influences the non-Faraday reaction strength of the negative electrode plate and the charge transmission resistance, thereby influencing the rate capability of the secondary battery.
Therefore, referring to
Referring to Comparative Example 1, the difference between the value of the non-Faraday capacitance Cdl of the secondary battery and the grain size XS is excessively large, and √{square root over (Cdl−XS)} is 3.15, which exceeds the range of 0.1√{square root over (Cdl−XS)}≤3 defined in the present disclosure, so that the cycle performance of the secondary battery corresponding to Comparative Example 1 is only 70% at 25° C., and the 4C-rate capability is only 78%. Referring to Comparative Example 2, the difference between the non-Faraday capacitance Cdl of the secondary battery and the grain size XS was negative, resulting in that the cycle performance of the secondary battery corresponding to Comparative Example 2 is only 73% at 25° C. and the 4C-rate capability is only 75%. Referring to Comparative Example 3, the value of the non-Faraday capacitance Cdl of the secondary battery is 12 nF, which exceeds the upper limit of the range of 0.05 nF to 10 nF defined in the present disclosure, so that the cycle performance of the secondary battery corresponding to Comparative Example 3 is only 75% at 25° C., and the 4C-rate capability is only 70%.
Referring to Example 11 and Example 16, when the value of the non-Faraday capacitance of the negative electrode plate is 0.05 nF to 10 nF, 0.1≤√{square root over (Cdl−XS)}≤3, and the pore volume α is 0.001 cm3/g to 0.5 cm3/g, there are many active sites on the surface of the negative electrode active material, which facilitates charge exchange of lithium ions on the surface of the negative electrode active material and improves the rate capability of the secondary battery. Moreover, the diffusion of lithium ions into the negative electrode active material is facilitated, the solid-phase conductivity of lithium ions is improved, the impedance of the secondary battery is reduced, and the service life of the secondary battery is prolonged.
Referring to Examples 5 and 10, the value of Cdl+10×α in the secondary battery prepared in Example 5 is 9.5, which exceeds the upper limit of the range of 0.5≤Cdl+10×α≤8 defined in the present disclosure, so that the cycle performance of the secondary battery prepared in Example 5 is 87% at 25° C. and the 4C-rate capability is 85%. The value of Cdl+10×α of the secondary battery prepared in Example 10 is 5.9, which is in the range of 0.5≤Cdl+10×α≤8 provided in the present disclosure, and the cycle performance of the secondary battery prepared in Example 10 at 25° C. is 90% and the 4C-rate capability is 89%.
Referring to
Further, when the thickness C of the negative electrode active material layer and the thickness D of the positive electrode active material layer are in the range of 0.1≤1−(D/C)≤0.5, the electrolyte can sufficiently diffuse in the positive electrode plate and the negative electrode plate, thereby reducing the ohmic impedance of the electrode plates, avoiding lithium precipitation in the negative electrode, and ensuring high energy density while improving the kinetic performance.
Referring to
Referring to Example 15 and Example 1, the second coating layer is not coated on the surface of the positive electrode active material in Example 15, that is, H2 is 0, and B/A=1.5 in the secondary battery prepared in Example 15, and thus the secondary battery prepared in Example 15 has a cycle performance of 82% at 25° C. and a 4C-rate capability of 85%. In addition, referring to Comparative Example 1 and Example 30, the first coating layer is not coated on the surface of the negative electrode active material in Example 30, that is, H1 is 0, and thus the secondary battery prepared in Example 30 has a cycle performance of 80% at 25° C., and a 4C-rate capability of 80%. These indicate that the coating layer disposed on the negative electrode active material can improve the cycle performance and rate capability of the secondary battery to some extent.
The above embodiments of the present disclosure provides a detailed description of the secondary battery and battery pack. Specific examples are used herein to illustrate the principles and implements of the present disclosure. The description of the above embodiments is merely provided to assist in understanding the method of the present disclosure and the core concepts thereof. Changes will be made to those skilled in the art in both the implements and the scope of application in accordance with the teachings of the present disclosure. In view of the foregoing, the present description should not be construed as limiting the application.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202310030037.8 | Jan 2023 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2023/115701 | 8/30/2023 | WO |
