Patent Application
20250201849
This application relates to the field of batteries, and specifically to an electrode plate and a related battery cell, battery, and electric apparatus.
Battery cells have characteristics such as high capacity and long service life, and thus are widely used in electronic devices such as mobile phones, laptop computers, electric bicycles, electric vehicles, electric aircrafts, electric ships, electric toy cars, electric toy ships, electric toy aircrafts, and electric tools.
As the application of batteries continues to expand, the requirements for the performance of battery cells have become increasingly stringent. To improve the safety performance of the battery cell, the performance of the electrode plate in the battery cell is usually optimized and improved. However, the active material in the electrode plate currently has poor electrolyte absorption performance, resulting in poor cycling performance of the battery cell when the active material is applied to the battery cell.
This application is conducted in view of the foregoing problems, aiming to provide an electrode plate and a related battery cell, battery, and electric apparatus.
A first aspect of this application provides an electrode plate, where the electrode plate includes a current collector and an active material layer arranged on at least one surface of the current collector, the active material layer includes an active material and an ester polymer, and the active material layer meets:
Therefore, the ester polymer of this application is introduced during preparation of the active material layer, and can form uniform high-infiltration points within the active material layer, which equably improves the infiltration performance of the active material layer, thereby increasing the overall electrolyte absorption rate of the active material layer, and improving the cycling performance of the battery cell using the electrode plate.
In some embodiments, the active material includes a positive electrode active material, and the active material layer meets 1.00<v/λ<4.00, and optionally, 1.20≤v/λ≤3.80.
In some embodiments, the active material includes a positive electrode active material, and based on a mass of the active material layer, a mass percentage of the ester polymer is A %; where 0.1≤A≤1.5. With the mass percentage of the ester polymer falling within the foregoing range, the electrolyte absorption capacity of the positive electrode active material layer can be significantly improved.
In some embodiments, the active material includes a negative electrode active material, and the active material layer meets 3.00<v/λ<50.00, and optionally, 3.40≤v/λ≤30.00.
In some embodiments, the active material includes a negative electrode active material, and based on a mass of the active material layer, a mass percentage of the ester polymer is B %; where 0.2≤B≤5.0. With the mass percentage of the ester polymer falling within the foregoing range, the electrolyte absorption capacity of the negative electrode active material layer can be significantly improved.
In some embodiments, the ester polymer is made into a sheet structure, and the sheet structure undergoes dynamic frequency scanning testing at (Tm+20°) C to obtain an elastic modulus G′-energy loss modulus G″ curve, wherein a slope of the elastic modulus G′-energy loss modulus G″ curve is K, 1<K<∞, optionally, 1<K≤100, and further optionally, 1<K≤10, and Tm° C. represents a melting temperature of the ester polymer.
Therefore, with the polymer of this application meeting the foregoing range, the molecular chains in entangled state can be further reduced, which is conducive to the diffusion of solvent molecules in the electrolyte solution between the molecular chains. Moreover, the polymer still maintains a certain entangled state of molecular chains, which can lock the solvent molecules in situ inside the polymer, reduce the risk of the polymer dissolving in the electrolyte solution, and improve the stability of the performance of the polymer. Additionally, it is favorable for the polymer to form a protective layer on the surface of the active material, improves the solid-liquid interface performance, reduces the side reactions between the active material and the electrolyte solution, and improves the cycling performance and storage performance of the battery cell.
In some embodiments, a glass transition temperature of the ester polymer is Tg, in ° C., where −100≤Tg≤50, and optionally, −80≤Tg≤30. The glass transition temperature of the ester polymer is relatively low, resulting in better flexibility of the molecular chain segments, and making it easier to open adjacent molecular chains and form in situ gels more easily, thereby improving the wetting performance of the electrolyte solution with respect to the active material layer and improving the cycling performance of the battery cell.
In some embodiments, the ester polymer includes a structural unit shown in formula (I),
In some embodiments, the ester polymer includes at least one of structural units shown in formula (I-1) to formula (I-15):
In some embodiments, the ester polymer includes a structural unit shown in formula (II),
In some embodiments, the ester polymer includes at least one of structural units shown in formula (II-1) to formula (II-5):
In some embodiments, n is selected from positive integers from 800 to 20000; and/or a molecular weight of the ester polymer is 1.2×105 g/mol to 1.0×106 g/mol. With the molecular weight of the polymer falling within the foregoing range, it can ensure that the polymer exhibits a certain solubility in the electrolyte solution, while not being easily completely dissolved and dispersed by the electrolyte solution, which helps control the distribution and dispersion of the polymer on the surface of the active material; furthermore, it can further improve the flexibility between the molecular chains of the polymer and ensure a relatively weak interaction force between the molecular chains, which is favorable for the solvent molecules in the electrolyte solution to open the molecular chains to enter between the molecular chains and be wrapped by the molecular chains, thereby facilitating the entry of active ions through the solvent into the active material, and enabling smooth and rapid migration of active ions.
A second aspect of this application provides a battery cell, where the battery cell includes the electrode plate according to any embodiment of the first aspect of this application.
A third aspect of this application provides a battery, including the battery cell according to the second aspect of this application.
A fourth aspect of this application provides an electric apparatus, including the battery according to the third aspect of this application.
To describe the technical solutions of the embodiments of this application more clearly, the following briefly describes the accompanying drawings required for describing the embodiments of this application. Apparently, the accompanying drawings described below show merely some embodiments of this application, and persons of ordinary skill in the art may still derive other drawings from the accompanying drawings without creative efforts.
The figures are not necessarily drawn to scale.
Embodiments that specifically disclose an electrode plate and a related battery cell, battery, and electric apparatus in this application are described in detail below. However, there may be cases in which unnecessary detailed descriptions are omitted. For example, detailed descriptions of well-known matters and repeated descriptions of actually identical structures have been omitted. This is to avoid unnecessarily prolonging the following descriptions, for ease of understanding by persons skilled in the art. In addition, the accompanying drawings and the following descriptions are provided for those skilled in the art to fully understand this application and are not intended to limit the subject described in the claims.
“Ranges” disclosed in this application are defined in the form of lower and upper limits. A given range is defined by one lower limit and one upper limit selected, where the selected lower and upper limits define boundaries of that special range. Ranges defined in this way may or may not include end values, and any combination may be used, meaning that any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are provided for a specific parameter, it is understood that ranges of 60-110 and 80-120 can also be envisioned. In addition, if low limit values of a range are given as 1 and 2, and upper limit values of the range are given as 3, 4, and 5, the following ranges can all be envisioned: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, a value range of “a-b” is a short representation of any combination of real numbers between a and b, where both a and b are real numbers. For example, a value range of “0-5” means that all real numbers in the range of “0-5” are listed herein and “0-5” is just a short representation of combinations of these values. In addition, a parameter expressed as an integer greater than or equal to 2 is equivalent to disclosure that the parameter is, for example, an integer among 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, and so on.
Unless otherwise stated, all the embodiments and optional embodiments of this application can be combined with each other to form new technical solutions. Unless otherwise stated, all the technical features and optional technical features of this application can be combined with each other to form new technical solutions.
Unless otherwise specified, all the steps in this application can be performed sequentially or randomly, in some embodiments, performed sequentially. For example, a method including steps (a) and (b) indicates that the method may include steps (a) and (b) performed in order or may include steps (b) and (a) performed in order. For example, the foregoing method may further include step (c), which indicates that step (c) may be added to the method in any ordinal position, for example, the method may include steps (a), (b), and (c), steps (a), (c), and (b), steps (c), (a), and (b), or the like.
Unless otherwise specified, “include” and “contain” mentioned in this application are non-exclusive. For example, the terms “include” and “contain” can mean that other unlisted components may or may not also be included or contained.
Unless otherwise specified, in this application, the term “or” is inclusive. For example, a phrase “A or B” means “A, B, or both A and B”. More specifically, any one of the following conditions meets the condition “A or B”: A is true (or present) and B is false (or not present); A is false (or not present) and B is true (or present); or both A and B are true (or present). In this disclosure, unless otherwise specified, phrases like “at least one of A, B, and C” and “at least one of A, B, or C” both mean only A, only B, only C, or any combination of A, B, and C.
In this application, the term “a plurality of” means two or more than two and the term “a plurality of types” means two types or more than two types.
The term “alkyl group” covers linear and branched alkyl groups. For example, the alkyl group may be C1-C5 alkyl group, C1-C4 alkyl group, C1-C3 alkyl group, C1-C2 alkyl group. In some embodiments, the alkyl group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and the like. In addition, the alkyl group may be randomly substituted. When substituted, the substituent includes fluorine atoms.
The term “alkoxy group” is an alkyl group bonded to an oxygen atom by a single bond. For example, the alkoxy group may be a C1 to C5 alkoxy group, a C1 to C3 alkoxy group, or a C1 to C2 alkoxy group. In some embodiments, the alkoxy group may include a methoxy group, an ethoxy group, and a propoxy group. In addition, the alkoxy group may be randomly substituted.
The term “hydroxyalkyl group” is a group in which a hydroxyl group is bonded to an alkyl group by a single bond. For example, the hydroxyalkyl group may be a C1 to C8 hydroxyalkyl group, a C1 to C5 hydroxyalkyl group, a C1 to C3 hydroxyalkyl group, or a C1 to C2 hydroxyalkyl group. In some embodiments, the hydroxyalkyl group includes hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxybutyl groups. In addition, the hydroxyalkyl group may be randomly substituted.
The term “halogen atom” refers to fluorine, chlorine, bromine, and the like.
The term “hydrogen” refers to 1H (protium, H), 2H (deuterium, D), or 3H (tritium, T). In some embodiments, “hydrogen” may be 1H (protium, H).
The battery cell includes an electrode assembly and an electrolyte solution, where the electrode assembly includes a positive electrode plate, a negative electrode plate, and a separator arranged between the positive electrode plate and the negative electrode plate. The electrode assembly is a gap-porous structure. The electrolyte solution wets the electrode assembly, and the driving force for wetting is mainly a capillary force, a spontaneous imbibition process. Due to the barrier of the current collector in the electrode plate, the electrolyte solution permeates from an end face of the electrode assembly through the separator and into the interior of the electrode assembly. Therefore, the interlayer gaps of the electrode assembly act as flow guides, and the separator acts as a diverter. The step of wetting within the electrode assembly by the electrolyte solution includes: (1) the electrolyte solution is transported through the gaps between the electrode plate and the separator under the action of capillary force; (2) the electrolyte solution preferentially permeates through pores of the separator (wetting rate of the electrolyte solution is much greater in the separator than in the active material layer of the electrode plate); and (3) the electrolyte solution diffuses through the separator to surfaces of the positive electrode plate and the negative electrode plate on two sides and permeates into the pores of the active material layer.
In the related art, the affinity between the electrode plate and the electrolyte solution is poor, and the wettability of the electrode plate is poor, resulting in a slow diffusion rate of the electrolyte solution from the surface to the interior of the active material layer and poor electrolyte absorption performance of the active material, thereby deteriorating the cycling performance of the battery cell.
In view of this, in the embodiments of this application, from the perspective of increasing the electrolyte absorption rate of the active material layer, materials such as ester polymers within the active material layer are improved so as to increase the electrolyte absorption rate, thereby improving the cycling performance of the battery cell.
According to a first aspect, this application proposes an electrode plate. The electrode plate includes a current collector and an active material layer arranged on at least one surface of the current collector, where the active material layer includes an active material and an ester polymer. The electrode plate may be a positive electrode plate and/or a negative electrode plate. Accordingly, the positive electrode plate includes a positive electrode current collector and a positive electrode active material layer; and the negative electrode plate includes a negative electrode current collector and a negative electrode active material layer.
The electrode plate may be formed by applying a slurry onto the current collector, followed by drying and cold pressing. Alternatively, the electrode plate may be derived from a battery cell, by disassembling the battery cell, taking out the electrolyte solution-infiltrated electrode plate from the battery cell, placing the electrolyte solution-infiltrated electrode plate under vacuum drying conditions at 100° C. for 12 h, to obtain the electrode plate, and using it for tests such as electrolyte absorption rate.
The ester polymer may be synthesized by methods such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization. Alternatively, the ester polymer may be derived from a battery cell, by disassembling the battery cell, taking out the electrolyte solution-infiltrated electrode plate from the battery cell, using external force to strip the active material from the obtained electrode plate to prepare a powder sample, adding the powder sample to dimethyl carbonate DMC, stirring the resulting mixture at 80° C. for 8 h at 500 rpm, after finishing stirring, allowing the resulting mixture to be left standing at room temperature for 10 min, and taking the upper clear liquid and drying it at 80° C. for 12 h to obtain the ester polymer. The resulting ester polymer may contain a small amount of lithium salt, but it does not significantly affect infrared testing and precipitation value testing. To ensure the accuracy of the ester polymer, further washing with DMC at room temperature may be used to remove the lithium salt.
The active material layer meets:
In this application, the actual compacted density P1 refers to a ratio of the mass of the active material layer per unit area to the thickness of the electrode plate, and the actual compacted density is determined by the force applied during rolling after the electrode plate is coated, in a unit of g/cm3. The specific testing steps are as follows: taking an electrode plate with a certain area S, weighing a mass M of the active material layer, and measuring a thickness D of the active material layer. The actual compacted density is equal to M/(S×D).
In this application, the true compacted density P2 is a density of the active material itself in the active material layer. For example, when the active material is a negative electrode active material such as graphite, the density of graphite is 2.25 g/cm3, so the true compacted density of the active material is 2.25 g/cm3.
For example, when the active material is a positive electrode active material, it specifically refers to the mass per unit “actual volume of solid material (excluding open and closed pores as well as inter-particle pores)” in a dense state, the true volume V is measured, and the true compacted density is calculated as P=m/V, which can be tested in accordance with GB/T24586-2009. Specifically, the testing steps are as follows:
(1) Pre-treatment: A clean and dry sample beaker is placed on the balance, zeroing is performed for the balance, a powder sample is added into the sample beaker and occupies approximately half of the volume of the sample beaker, and a mass of the sample is recorded.
(2) The sample beaker containing the sample is placed in a true density tester, the test system is closed, the helium gas is introduced according to the procedure, pressures of gases in the sample chamber and an expansion chamber are measured, a true volume is calculated based on Bohr's law (PV=nRT), and then a true compacted density is calculated.
A volume of the sample beaker is 3.5 cm3; and the analysis gas is helium.
Formula (1) can calculate the porosity λ of the active material layer based on the actual compacted density and the true compacted density.
Specifically,
Formula (2) can characterize the rate at which a certain point on the electrode plate essentially completely absorbs the liquid (for example, electrolyte solution) in the capillary tube per unit time. In this application, the certain point on the electrode plate refers to a region with a certain surface area on the electrode plate, and its area corresponds to the cross-sectional area of the capillary tube.
In this application, the method for measuring the electrolyte absorption rate of the electrode plate includes the following steps:
For example, d is in a range of 0.2 to 1, for example, 0.2; and h is in a range of 3 to 5, for example, 3.
The capillary tube has capillary channels, allowing the capillary tube to directly absorb the electrolyte solution by capillarity, without requiring an external driving unit to provide absorption force. In this way, the amount absorbed may be controlled more precisely when the electrolyte solution is absorbed through capillarity. In addition, the electrode plate absorbs the electrolyte solution through its own capillarity, when the capillary tube is in contact with the electrode plate under test, the electrode plate absorbs the electrolyte solution from the capillary tube, and when the capillary tube is out of contact with the electrode plate under test, the electrolyte solution in the capillary tube no longer flows out. Thus, the amount of electrolyte solution absorbed in the capillary tube can precisely reflect the corresponding volume of electrolyte solution absorbed by the electrode plate, thereby further improving the accuracy of test results and achieving the quantitative calculation of the electrolyte solution absorption rate of the electrode plate.
In this application, a standard electrolyte solution is used as the test sample for testing. For specific formulation of the electrolyte solution, refer to the electrolyte solution formulation in the examples.
Formula (3) indicates the electrolyte absorption rate of the electrode plate at porosity k, which can be used to characterize the electrolyte absorption speed of the electrode plate.
The ester polymer of this application is introduced during preparation of the active material layer, and can form uniform high-infiltration points within the active material layer, which equably improves the infiltration performance of the active material layer, thereby increasing the overall electrolyte absorption rate of the active material layer, and improving the cycling performance of the battery cell using the electrode plate.
Optionally, 1.00<v/λ<50.00.
In some embodiments, the ester polymer is made into a sheet structure. The sheet structure undergoes dynamic frequency scanning testing at (Tm+20°) C to obtain an elastic modulus G′-energy loss modulus G″ curve, where a slope of the elastic modulus G′-energy loss modulus G″ curve is K, 1<K<∞, 1<K≤100, and optionally, 1<K≤10; and Tm° C. represents a melting temperature of the ester polymer.
For example, K may be 1.01, 1.1, 1.2, 1.5, 2, 5, 10, 15, 20, 30, 50, 100, 200, 500, 1000, 5000, 10000, or in a range defined by any two of these values.
Specifically, the process of preparing the sheet structure is as follows: drying a polymer under vacuum at 80° C. for 12 h; hot pressing the dried polymer into sheets using a flat vulcanizing machine, with a hot pressing temperature of (Tm+20°) C, a rolling thickness of 1 mm to 2 mm, a rolling time of 2 min, and a pressure of 8 MPa; after rolling for 2 min, taking out the sample and placing it on another vulcanizing machine of the same model for cold pressing, with a cold pressing pressure of 10 MPa; and obtaining a polymer circular sheet (sheet structure) of fixed size using a circular mold with a diameter of 25 mm. For example, the sheet structure may be a circular sheet with a thickness of 1 mm to 2 mm and a diameter of 25 mm; or may be prepared according to the sample standard required by the test equipment.
According to the conclusions of classical linear viscoelasticity, for polymers, especially linear polymers, the terminal region of the elastic modulus G′-energy loss modulus G″ curve (the interval range approaching the maximum angular velocity) shows that the elastic modulus G′-energy loss modulus G″ conforms to frequency dependence, and the longest chain of the polymer affects the viscoelastic behavior.
The specific steps of the dynamic frequency scanning testing are as follows: performing dynamic frequency scanning testing with a TA-AR2000EX rotational rheometer (TA Instruments, USA), with a parallel plate diameter of 25 mm and a thickness of 0.9 mm; and to ensure testing in the linear viscoelastic region, setting the strain during dynamic frequency scanning testing to 2%, the testing temperature to Tm+20° C., and the frequency scanning range to 500 rad/s≤w2≤0.05 rad/s, so as to obtain data in the low frequency region as possible.
Dynamic frequency scanning testing may characterize the degree of entanglement of molecular chains in the solid phase melting (melt state), compared to linear structures or short-branched structures, long branched structures, mesh structures, and low cross-linked structures have higher degrees of entanglement, showing deviations from linear terminal behavior, with the polymer exhibiting solid-phase behavior. With the polymer of this application meeting the foregoing range, the molecular chains in entangled state can be further reduced, which is conducive to the diffusion of solvent molecules in the electrolyte solution between the molecular chains. Moreover, the polymer still maintains a certain entangled state of molecular chains, which can lock the solvent molecules in situ inside the polymer, reduce the risk of the polymer dissolving in the electrolyte solution, and improve the stability of the performance of the polymer. Additionally, it is favorable for the polymer to form a protective layer on the surface of the active material, improves the solid-liquid interface performance, reduces the side reactions between the active material and the electrolyte solution, and improves the cycling performance and storage performance of the battery cell.
In some embodiments, a glass transition temperature of the ester polymer is Tg, in ° C., where −100≤Tg≤50, and optionally, −80≤Tg≤30.
The glass transition temperature is a transition temperature at which the chain segments of the ester polymer change from a frozen state to a mobile state, and the glass transition temperature has a certain impact on the flexibility of the molecular chains of the ester polymer. A lower glass transition temperature means better flexibility of molecular chains of the ester polymer at room temperature, and a higher glass transition temperature means worse the flexibility of the molecular chains at room temperature. The glass transition temperature may be measured by differential scanning calorimetry DSC. Specifically, the test steps are as follows: taking 0.5 g to 0.8 g of the sample and place the sample in a carrier crucible; performing heating and cooling treatment on the sample in a nitrogen atmosphere, with a heating rate of 10° C./min, from an initial temperature 20° C. lower than an intrinsic temperature Tg of the material to a cutoff temperature 20° C. higher than an intrinsic temperature Tm of the material; and determining an actual glass transition temperature Tg and a melting temperature Tm of the material based on endothermic and exothermic peaks or transition points during the process.
The glass transition temperature of the ester polymer is relatively low, resulting in better flexibility of the molecular chain segments, and making it easier to open adjacent molecular chains and form in situ gels more easily, thereby improving the wetting performance of the electrolyte solution with respect to the active material layer and improving the cycling performance of the battery cell. For example, the glass transition temperature of the ester polymer may be −100° C., −90° C., −80° C., −60° C., −30° C., 0° C., 30° C., 50° C., or in a range defined by any two of these values.
In some embodiments, the ester polymer includes a structural unit shown in formula (I),
For example, the ester polymer includes at least one of structural units shown in formula (I-1) to formula (I-15):
In some embodiments, the ester polymer includes a structural unit shown in formula (II),
For example, the ester polymer includes at least one of structural units shown in formula (II-1) to formula (II-5):
The degree of entanglement of the molecular chains of the ester polymer is relatively low, facilitating the improvement of the flexibility of the molecular chains, and allowing the molecular chains to fully extend in the electrolyte solution, thereby further improving the interface performance of the active material.
The foregoing polymers are only examples of the structural groups of the main molecular chains. In the embodiments of this application, the polymers may also be obtained by copolymerizing the foregoing structural groups with other types of structural groups (such as olefin structural units and acrylonitrile structural units).
The groups of the polymers in this application may be detected with infrared spectroscopy IR. Specifically, the polymer is tested using a Thermo Nicolet Nexus 670 attenuated total reflectance Fourier transform infrared spectrometer (FTIR-ATR), and then tested in accordance with the standard GB/T6040-2002, with a testing range of 600 cm−1 to 4000 cm−1 by ATR method, a repeatability of ±2 cm−1, a resolution of better than 4 cm−1, and a transmission depth of 0.2 μm to 0.6 μm.
The structures of the polymers of this application may be tested through nuclear magnetic resonance NMR. Specifically, 1H NMR and 13C NMR are performed with a Varian Mercury Plus-400 nuclear magnetic resonance instrument, with a testing temperature of 20° C., TMS as the internal standard, CDCl3 as the solvent, and a proton resonance frequency of 400 MHz.
The monomer types of the polymers of this application (especially for monomers that account for a small proportion of the polymer) may be tested by pyrolysis-gas chromatography-mass spectrometry. The specific test steps are as follows: 0.5 mg of the sample is accurately weighed and put into a sample beaker, the beaker is fixed on the injection rod, the injection rod is loaded into the pyrolyzer installed near the GC (gas chromatography) injection port, after the temperature of the pyrolyzer reaches the predetermined temperature, the injection button is pressed so that the sample beaker quickly falls into the core of the pyrolysis furnace by free fall, the volatile components instantly gasify in an inert gas N2 atmosphere, are carried by the carrier gas into the gas chromatography column for separation, and finally are detected by a flame ionization detector FID or a mass spectrometer MS. In this way, a gas chromatogram or a total ion chromatogram is obtained.
When the foregoing groups are substituted, the substituents may include one or more of cyano, nitro, sulfonyl, carboxyl, ester, chlorine, fluorine, and bromine atoms. The foregoing substituents are high-pressure-resistant substituents, which are more conducive to stabilizing the structure of the polymer.
In some embodiments, n is selected from positive integers from 800 to 20000.
Optionally, n is selected from positive integers from 1000 to 15000.
In some embodiments, a molecular weight of the polymer is 1.2×105 g/mol to 10×106 g/mol.
With the molecular weight of the polymer falling within the foregoing range, it can ensure that the polymer exhibits a certain solubility in the electrolyte solution, while not being easily completely dissolved and dispersed by the electrolyte solution, which helps control the distribution and dispersion of the polymer on the surface of the active material; furthermore, it can further improve the flexibility between the molecular chains of the polymer and ensure a relatively weak interaction force between the molecular chains, which is favorable for the solvent molecules in the electrolyte solution to open the molecular chains to enter between the molecular chains and be wrapped by the molecular chains, thereby facilitating the entry of active ions through the solvent into the active material, and enabling smooth and rapid migration of active ions. For example, the molecular weight of the polymer may be 1.2×105 g/mol, 2×105 g/mol, 5×105 g/mol, 8×105 g/mol, 1×106 g/mol, 1.5×106 g/mol, or in a range defined by any two of these values.
The molecular weight of the ester polymer is well known in the art and can be measured using equipment and methods commonly used in the art. Gel permeation chromatography GPC testing can be used. The specific testing steps are as follows: An appropriate amount of the sample under test is weighed (where a sample concentration ensures 8% to 12% opacity), 20 ml of deionized water is added in the sample, external ultrasonication is performed for 5 min (at 53 kHz/120 W) to ensure the sample is fully dispersed, and then the sample is measured in accordance with the standard GB/T 19077-2016/ISO13320:2009.
Alternatively, a multi-angle laser light scattering instrument MALLS may be used for testing. Specifically, GPC, a Dawn Heleos II multi-angle laser light scattering device are used, an Optilab T-rEX refractive index (RI) detector, and a ViscoStar II viscometer (Wyatt Technology Corporation, USA) are used. The testing is conducted at 30° C., tetrahydrofuran is used as the mobile phase, with a flow rate of 1.0 ml/min, and a commercial software ASTRA 6 is used to process SEC-SAMLL data to obtain molecular weight parameters.
When the ester polymer in the embodiments of this application also meets one or more of the following conditions, the cycling performance of the battery cell can be further improved.
In some embodiments, the ester polymer is added to a first solvent at 45° C. to prepare an ester polymer system; the ester polymer system is left standing at 45° C. for 8 h and then at 25° C. for ≥24 h; after undergoing two stages of standing treatment, the ester polymer system partially or completely transforms in situ into a gel state material, and then the ester polymer system is filtered with a 200-mesh filter screen to obtain a remaining first material. A mass of the ester polymer is n, in g; a mass of the first material is m, in g; and the polyester polymer and the first material meet 5≤m/n≤1000, optionally, 10≤m/n≤1000, and further optionally, 10≤m/n≤50. For example, m/n may be 5, 10, 20, 25, 28, 30, 32, 35, 40, 50, 80, 100, 200, 500, 1000, or in a range defined by any two of these values.
For example, based on a mass of the ester polymer system, a ratio of a mass percentage of the ester polymer to a mass percentage of the first solvent is in a range of 1:100 to 1:10, for example, 3:50.
For example, the first solvent is the same as or similar to a solvent of the electrolyte solution, and the first solvent may include a carbonate solvent. For example, the carbonate solvent includes a cyclic carbonate solvent and/or a linear carbonate solvent.
As examples of the cyclic carbonate solvent, the cyclic carbonate solvent includes one or more of ethylene carbonate EC, vinylene carbonate VC, fluoroethylene carbonate FEC, difluoroethylene carbonate DFEC, vinyl ethylene carbonate VEC, and dioctyl carbonate CC.
As examples of the linear carbonate solvent, the linear carbonate solvent includes one or more of dimethyl carbonate DMC, diethyl carbonate DEC, ethyl methyl carbonate EMC, diphenyl carbonate DPC, methyl allyl carbonate MAC, and polycarbonate VA.
Optionally, the first solvent may also contain both a lithium salt and an electrolyte solution additive, for example, lithium hexafluorophosphate, vinylene carbonate VC, and fluoroethylene carbonate FEC.
In this application, m/n is also referred to as a precipitation value, which characterizes the ability of the ester polymer and the solvent to transition into a gel state material.
The first material mainly includes the gel state material formed by the ester polymer and the first solvent, and in this type of gel state material, the molecular structure of the ester polymer essentially does not change.
In some embodiments, the first material is dried at 80° C. for 12 h to remove the first solvent from the first material, and after being detected with infrared spectroscopy IR or being tested through nuclear magnetic resonance NMR, the main component of the dried first material is the ester polymer described above.
In this application, the molecular chains of the ester polymer are extended within the safe operating temperature range of the battery cell by increasing the temperature, which promotes the mutual attraction and physical bonding between the molecular chains of the ester polymer and the solvent, thereby improving the electrolyte absorption capacity. At room temperature, the activity of the molecular chain segments of the ester polymer decreases, so the ester polymer is attached to the surface of the active material and locks the electrolyte solution in the spatial environment of the ester polymer to form a gel-like in situ state, which improves the electrolyte-locking capacity and improves the cycling performance.
The positive electrode plate includes a positive electrode current collector and a positive electrode active material layer arranged on at least one surface of the positive electrode current collector, where the positive electrode active material layer includes a positive electrode active material and an ester polymer. In this application, the ester polymer includes the ester polymer described above.
For example, the positive electrode current collector has two opposite surfaces in its thickness direction, and the positive electrode active material layer is arranged on either or both of the two opposite surfaces of the positive electrode current collector.
In some embodiments, 1.00<v/λ<4.00; optionally, 1.20<v/λ3.80; and further optionally, 1.4<v/λ3.6. For example, v/λ may be 1.20, 1.40, 1.80, 2.00, 2.50, 3.00, 3.50, 3.60, 3.80, 3.90, or in a range defined by any two of these values.
In some embodiments, based on a mass of the positive electrode active material layer, a mass percentage of the ester polymer is A %, where 0.1≤A≤1.5.
With the mass percentage of the ester polymer falling within the foregoing range, the electrolyte absorption capacity of the positive electrode active material layer can be significantly improved. For example, the mass percentage A % of the ester polymer may be 0.1%, 0.2%, 0.5%, 0.8%, 1.0%, 1.2%, 1.5%, or in a range defined by any two of these values.
The positive electrode active material layer includes a positive electrode active material, and the positive electrode active material may use a positive electrode active material known in the art for battery cells. In an example, the positive electrode active material may include at least one of the following materials: a layered structure positive electrode active material (for example, ternary, lithium/sodium nickel oxide, lithium/sodium cobalt oxide, lithium/sodium manganese oxide, lithium/sodium-rich layered and rocksalt-type layered materials), an olivine-type phosphate active material, and a spinel structure positive electrode active material (for example, spinel lithium manganate, spinel lithium nickel manganese oxide, lithium-rich spinel lithium manganate, and lithium nickel manganese oxide).
For example, the general formula of the layered structure positive electrode active material is LixAyNiaCobMncM(1-a-b-c)Yz, where 0≤x≤2.1, 0≤y≤2.1, and 0.9≤x+y≤2.1; 0≤a≤1, 0≤b≤1, 0≤c≤1, and 0.1≤a+b+c≤1; 1.8≤z≤3.5; A is selected from one or more of Na, K, and Mg; M is selected from one or more of B, Mg, Al, Si, P, S, Ca, Sc, Ti, V, Cr, Fe, Cu, Zn, Sr, Y, Zr, Nb, Mo, Cd, Sn, Sb, Te, Ba, Ta, W, Yb, La, and Ce; and Y is selected from one or more of O and F. Optionally, y=0. Specifically, the layered structure positive electrode active material may include one or more of lithium cobalt oxide LCO, lithium nickel oxide LNO, lithium manganese oxide LMO, LiNi1/3Co1/3Mn1/3O2(NCM333), LiNi0.8Co0.1Mn0.1O2 (NCM811), and LiNi0.5Co0.2Mn0.3O2 (NCM523).
For example, the general formula of the olivine-type phosphate active material is LixAyMeaMbP1-cXcYz, where 0≤x≤1.3, 0≤y≤1.3, and 0.9≤x+y≤1.3; 0.9≤a≤1.5, 0≤b≤0.5, and 0.9≤a+b≤1.5; 0≤c≤0.5; 3≤z≤5; A is selected from one or more of Na, K, and Mg; Me is selected from one or more of Mn, Fe, Co, and Ni; M is selected from one or more of B, Mg, Al, Si, P, S, Ca, Sc, Ti, V, Cr, Cu, Zn, Sr, Y, Zr, Nb, Mo, Cd, Sn, Sb, Te, Ba, Ta, W, Yb, La, and Ce; X is selected from one or more of S, Si, Cl, B, C, and N; and Y is selected from one or more of O and F. Specifically, the olivine-type phosphate active material includes one or more of LiFePO4, LiMnPO4, LiNiPO4, and LiCoPO4.
For example, the general formula of the spinel structure positive electrode active material is LixAyMnaM2-aYz, where 0≤x≤2, 0≤y≤1, and 0.9≤x+y≤2; 0.5≤a≤2; 3≤z≤5; A is selected from one or more of Na, K, and Mg; M is selected from one or more of Ni, Co, B, Mg, Al, Si, P, S, Ca, Sc, Ti, V, Cr, Fe, Cu, Zn, Sr, Y, Zr, Nb, Mo, Cd, Sn, Sb, Te, Ba, Ta, W, Yb, La, and Ce; and Y is selected from one or more of O and F. Specifically, the spinel structure positive electrode active material includes one or more of LiMn2O4, LiNi0.5Mn1.5O4, LiCr0.3Mn1.7O4, Li1.1Al0.1Mn1.9O4, Li2Mn2O4, and Li1.5Mn2O4.
In some embodiments, the positive electrode current collector may be a metal foil or a composite current collector. As examples of the metal foil, aluminum foil or aluminum alloy foil may be used. The composite current collector may include a polymer material matrix and a metal material layer formed on at least one surface of the polymer material matrix. For example, the metal material may include a combination selected from one or more of aluminum, aluminum alloys, nickel, nickel alloys, titanium, titanium alloys, silver, and silver alloys, and the polymer material matrix may include a combination selected from one or more of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), and polyethylene (PE).
In some embodiments, the positive electrode active material layer optionally includes a positive electrode conductive agent. The positive electrode conductive agent is not specifically limited to any particular type in this application. For example, the positive electrode conductive agent includes a combination of one or more selected from superconducting carbon, conductive carbon black, conductive graphite, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofiber. In some embodiments, based on a total mass of the positive electrode active material layer, a mass percentage of the positive electrode conductive agent is below 5%.
In some embodiments, the positive electrode active material layer optionally includes a positive electrode binder. The positive electrode binder is not specifically limited to any particular type in this application. In an example, the positive electrode binder may include polyvinylidene fluoride (PVDF). In some embodiments, based on the total mass of the positive electrode active material layer, a mass percentage of the positive electrode binder is below 5%. The degree of crystallinity of the positive electrode binder is higher than that of the ester polymer described earlier in this application. The melting temperature of the positive electrode binder is higher than that of the ester polymer described earlier in this application.
The positive electrode active material layer is typically formed by applying a positive electrode slurry onto the positive electrode current collector, followed by drying and cold pressing. The positive electrode slurry is usually prepared by dispersing the positive electrode active material, the ester polymer, an optional conductive agent, an optional positive electrode binder, and any other components in a solvent, and stirring them into uniformity. The solvent may be N-methylpyrrolidone (NMP), but is not limited thereto.
The negative electrode plate includes a negative electrode current collector and a negative electrode active material layer arranged on at least one surface of the negative electrode current collector, where the negative electrode active material layer includes a negative electrode active material and an ester polymer. In this application, the ester polymer includes the ester polymer described above.
For example, the negative electrode current collector has two opposite surfaces in its thickness direction, and the negative electrode active material layer is arranged on either or both of the two opposite surfaces of the negative electrode current collector.
In some embodiments, 3.00<v/λ<50.00, and optionally 3.40≤v/λ≤30.00. For example, v/λ may be 3.20, 3.40, 3.50, 4.00, 4.50, 5.00, 5.50, 6.00, 6.50, 7.00, 8.00, 9.00, 9.50, 10.00, 10.50, 11.00, 12.00, 13.00, 14.00, or in a range defined by any two of these values.
In some embodiments, based on a mass of the negative electrode active material layer, a mass percentage of the ester polymer is B %, where 0.2≤B≤5.0. With the mass percentage of the ester polymer falling within the foregoing range, the electrolyte absorption capacity of the negative electrode active material layer can be significantly improved. For example, the mass percentage B % of the ester polymer may be 0.2%, 0.5%, 0.8%, 1.0%, 1.2%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0% or in a range defined by any two of these values.
In some embodiments, the negative electrode current collector may be a metal foil or a composite current collector. For example, for the metal foil, a copper foil may be used. The composite current collector may include a polymer material matrix and a metal layer formed on at least one surface of the polymer material matrix. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver, silver alloy, or the like) on a polymer material matrix (for example, matrices of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), and polyethylene (PE)).
In some embodiments, the negative electrode active material may be a negative electrode active material known in the art and used for batteries. In an example, the negative electrode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, a silicon-based material, a tin-based material, and lithium titanate. The silicon-based material may be selected from at least one of elemental silicon, silicon-oxygen compound, silicon-carbon composite, silicon-nitrogen composite, and silicon alloy. The tin-based material may be selected from at least one of elemental tin, tin-oxygen compound, and tin alloy. However, this application is not limited to these materials, and may alternatively use other conventional materials that can be used as the negative electrode active material of the battery. One of these negative electrode active materials may be used alone, or two or more of them may be used in combination.
In some embodiments, the negative electrode active material layer further optionally includes a negative electrode binder. The negative electrode binder may be selected from at least one of styrene-butadiene rubber (SBR), polyacrylic acid (PAA), polyacrylic acid sodium (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS). The degree of crystallinity of the negative electrode binder is higher than that of the ester polymer described earlier in this application. The melting temperature of the negative electrode binder is higher than that of the ester polymer described earlier in this application.
In some embodiments, the negative electrode active material layer further optionally includes a conductive agent. The conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofiber.
In some embodiments, the negative electrode active material layer further optionally includes other promoters such as a thickener (for example, sodium carboxymethyl cellulose (CMC-Na)).
In some embodiments, the negative electrode plate may be prepared in the following manner: the foregoing constituents used for preparing the negative electrode plate, for example, the negative electrode active material, the ester polymer, the conductive agent, the negative electrode binder, and any other constituent, are dispersed in a solvent (for example, deionized water) to prepare a negative electrode slurry; and the negative electrode slurry is applied onto the negative electrode current collector, followed by processes such as drying and cold pressing to obtain the negative electrode plate.
According to a second aspect, this application provides a battery cell, where the battery cell includes a positive electrode plate, a negative electrode plate, a separator arranged between the positive electrode plate and the negative electrode plate, and an electrolyte. The battery cell may be a lithium-ion battery or the like.
In some embodiments, the positive electrode plate may use the positive electrode plate according to any embodiment of the first aspect of this application, thereby improving the cycling performance of the battery cell. The negative electrode plate may use a conventional electrode plate.
In some embodiments, the negative electrode plate may use the negative electrode plate according to any embodiment of the first aspect of this application, thereby improving the cycling performance of the battery cell. The positive electrode plate may use a conventional electrode plate.
In some embodiments, the positive electrode plate may use the positive electrode plate according to any embodiment of the first aspect of this application, and the negative electrode plate may use the negative electrode plate according to any embodiment of the first aspect of this application, thereby improving the cycling performance of the battery cell.
The battery cell further includes an electrolyte, where the electrolyte conducts ions between the positive electrode plate and the negative electrode plate. The electrolyte is not specifically limited to any particular type in this application, and may be selected depending on needs. For example, the electrolyte may be in a liquid state, a gel state, or an all-solid state.
In some embodiments, the electrolyte is an electrolyte solution. The electrolyte solution includes an electrolytic salt and a solvent.
For example, the electrolyte lithium salt may include a combination of one or more selected from lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium perchlorate (LiClO4), lithium hexafluoroarsenate (LiAsF6), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bistrifluoromethanesulfonimide (LiTFSI), lithium trifluoromethanesulfonate (LiTFS), lithium difluoro(oxalato)borate (LiDFOB), lithium dioxalate borate (LiBOB), lithium difluorophosphate (LiPO2F2), lithium difluoro(dioxalato)phosphate (LiDFOP), and lithium tetrafluoro oxalato phosphate (LiTFOP).
For example, the organic solvent may include a combination of one or more selected from ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), butylene carbonate (BC), methyl formate (MF), methyl acetate (MA), ethyl acetate (EA), propyl acetate (PA), methyl propionate (MP), ethyl propionate (EP), propyl propionate (PP), methyl butyrate (MB), ethyl butyrate (EB), gamma-butyrolactone (GBL), sulfolane (SF), methyl sulfonyl methane (MSM), methyl ethyl sulfone (EMS), and diethyl sulfone (ESE).
In some embodiments, the electrolyte solution further optionally includes an additive. For example, the additive may include a negative electrode film-forming additive or a positive electrode film-forming additive, or may include an additive capable of improving some performance of the battery, for example, an additive for improving overcharge performance of the battery, or an additive for improving high-temperature or low-temperature performance of the battery.
In some embodiments, the battery cell further includes a separator. The separator is not specifically limited to any particular type in this application, and may select any well-known porous separator with good chemical stability and mechanical stability.
In some embodiments, the material of the separator may be selected from one or more of glass fiber, non-woven fabric, polyethylene, polypropylene, and polyvinylidene fluoride. The separator may be a single-layer thin film or a multi-layer composite thin film. When the separator is a multi-layer composite thin film, each layer is made of the same or different materials.
In some embodiments, the positive electrode plate, separator, and negative electrode plate may be made into an electrode assembly through a winding process or a lamination process.
The battery cell is not specifically limited to any particular shape in this application, and may be cylindrical, rectangular, or in any other shapes.
In some embodiments, as shown in
The preparation method for the battery cell of this application is known. In some embodiments, the positive electrode plate, separator, negative electrode plate, and electrolyte solution may be assembled to form a battery cell. For example, the positive electrode plate, separator, and negative electrode plate may be made into an electrode assembly through a winding process or a lamination process; and the electrode assembly is placed into an outer package, followed by drying, and the electrolyte solution is injected, followed by processes such as vacuum packaging, standing, formation, and shaping, to obtain a battery cell.
In some embodiments of this application, the battery cells of this application may be assembled into a battery module, where the battery module contains a plurality of battery cells, and the specific number may be adjusted based on the application and capacity of the battery module.
Optionally, the battery module 4 may further include a shell with an accommodating space, and the plurality of battery cells 5 are accommodated in the accommodating space.
In some embodiments, the battery modules may be further assembled into a battery pack, and a quantity of battery modules included in the battery pack may be adjusted based on application and capacity of the battery pack.
Both battery modules and battery packs may be used as examples of batteries for this application.
According to a third aspect, this application provides an electric apparatus, where the electric apparatus includes at least one of the battery cell, battery module, and battery pack of this application. The battery cell, battery module, and battery pack may be used as the power source of the electric apparatus, or may be used as an energy storage unit of the electric apparatus. The electric apparatus may be but is not limited to a mobile device (for example, a mobile phone or a laptop computer), an electric vehicle (for example, a battery electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf vehicle, or an electric truck), an electric train, a ship, a satellite, or an energy storage system.
The electric apparatus may select the battery cell, battery module, or battery pack according to its usage requirements.
The following describes examples of this application. The examples described below are illustrative and only used to explain this application, and cannot be construed as limitations on this application. Examples whose technical solutions or conditions are not specified are made in accordance with technical solutions or conditions described in literature in the field, or made in accordance with product instructions. The reagents or instruments used are all conventional products that are commercially available if no manufacturer is indicated.
A 12 μm thick aluminum foil was used as a positive electrode current collector.
An ester polymer, a positive electrode active material LiFePO4, a conductive agent carbon black, a binder polyvinylidene fluoride (PVDF), and N-methylpyrrolidone (NMP) were made into a positive electrode slurry. In the positive electrode slurry, a mass ratio of the ester polymer, LiFePO4, conductive carbon black, PVDF, and N-methylpyrrolidone (NMP) was 0.5:96.8:2:0.7:29. The positive electrode slurry was applied onto the current collector aluminum foil, and the resulting current collector was dried at 85° C., followed by cold pressing, trimming, cutting, and slitting, and dried under vacuum at 85° C. for 4 h to prepare a positive electrode plate.
A copper foil with a thickness of 8 m was used as a negative electrode current collector.
An ester polymer, a negative electrode active material artificial graphite, a conductive agent carbon black, a binder styrene-butadiene rubber (SBR), a thickener sodium carboxymethyl cellulose (CMC-Na), and deionized water were mixed into uniformity at a weight ratio of 2.5:94:0.5:2:1:100 to prepare a negative electrode slurry. The negative electrode slurry was applied on the current collector copper foil, and the resulting current collector was dried at 85° C., followed by cold pressing, trimming, cutting, slitting, and drying under vacuum at 120° C. for 12 h, to prepare a negative electrode plate.
In an environment with a water content of less than 10 ppm, the non-aqueous organic solvents ethylene carbonate EC and ethyl methyl carbonate (EMC) were mixed at a volume ratio of 3:7 to prepare an electrolyte solution solvent, then the lithium salt LiPF6 was mixed with the mixed solvent to prepare an electrolyte solution with a lithium salt concentration of 1 mol/L.
A polyethylene (PE) film with a thickness of 16 m was used as a separator. The positive electrode plate, the separator, and the negative electrode plate were sequentially stacked so that the separator was located between the positive electrode plate and negative electrode plate to provide separation. Then the resulting stack was wound to obtain an electrode assembly. The electrode assembly was placed into an outer package and dried, and the electrolyte solution was then injected. Processes such as vacuum packaging, standing, formation, and shaping were performed to obtain a lithium-ion battery.
The lithium-ion battery was prepared using a method similar to that of Example 1. The difference from Example 1 was that no ester polymer was added to the positive electrode plate of Comparative Example 1; and no ester polymer was added to the negative electrode plate of Comparative Example 1.
The lithium-ion battery was prepared using a method similar to that of Example 1. The difference from Example 1 was that the materials of the ester polymers of the positive electrode plate and the negative electrode plate of Comparative Example 2 were replaced.
Lithium-ion batteries were prepared using methods similar to that of Example 1. The difference from Example 1 was that the materials of the ester polymers of the positive electrode plate and the negative electrode plate of Example 2 to Example 4 were replaced.
The lithium-ion battery was prepared using a method similar to that of Example 1. The difference from Example 1 was that the ester polymer was added to the positive electrode plate of Example 5, and no ester polymer was added to the negative electrode plate of Example 5.
Lithium-ion batteries were prepared using methods similar to that of Example 1. The difference from Example 1 was that the percentages of the ester polymers in the positive electrode plates of Example 6 to Example 9 were adjusted.
Lithium-ion batteries were prepared using methods similar to that of Example 1. The difference from Example 1 was that the percentages of the ester polymers in the negative electrode plates of Example 10 to Example 12 were adjusted.
The lithium-ion batteries prepared in the examples and comparative examples were charged at a constant current of 1C to 4.25 V in a 45° C. environment, next charged at this constant voltage of 4.25 V until the current was 0.05C, left standing for 5 min, and then discharged at 1C to 2.8 V. The resulting capacity was recorded as the initial capacity C0. The preceding steps were repeated for the same battery and the discharged capacity Cn of the battery after the n-th cycle was recorded, then the capacity retention rate of the battery after each cycle was calculated according to Pn=Cn/C0×100%. A graph of the battery capacity retention rate against the number of cycles was plotted with values of 1200 points of P1, P2, . . . , P1200 as the vertical coordinates and the corresponding numbers of cycles as the horizontal coordinates.
In this test, the first cycle corresponds to n=1, the second cycle corresponds to n=2, . . . , and the 1200-th cycle corresponds to n=1200. For example, the capacity retention rate data of the battery of Example 1 in Table 1 was the data measured after 1200 cycles under the foregoing test conditions, which was the value of P1200. The testing procedures of Comparative Example 1 and other examples are the same as above.
The lithium-ion batteries prepared in the examples and comparative examples were charged at a constant current of 1C to 4.25 V at 45° C., next charged at this constant voltage of 4.25 V until the current was 0.05C, and left standing for 5 min. The voltage V1 at this point was recorded. Then the lithium-ion batteries were discharged at 1C for 30 s, and the voltage V2 was recorded, and then the internal resistance DCR1 of the battery after the first cycle was calculated based on (V2−V1)/1/3C. The foregoing steps were repeated for the same battery, and the internal resistance DCRn of the battery after the n-th cycle (n=1, 2, 3 . . . 1200) was recorded, and a graph of battery discharge DCIR corresponding to the ester polymers of the examples and comparative examples against the number of cycles was plotted with values of 1200 points of DCR1, DCR2, DCR3 . . . DCR1200 as the vertical coordinates and the corresponding number of cycles as the horizontal coordinates.
In this test, the first cycle corresponds to n=1, the second cycle corresponds to n=2, . . . , and the 1200-th cycle corresponds to n=1200. For example, the internal resistance increase ratio of the battery in Example 1 in Table 1 was calculated based on (DCRn−DCR1)/DCR1×100%. The testing procedures of Comparative Example 1 and other examples were the same as above. Data in Table 1 is data measured after 1200 cycles under the foregoing test conditions.
In Table 1, 100% methyl methacrylate means that the mass percentage of methyl methacrylate is 100% based on the total mass of monomer 1, monomer 2, and monomer 3.
85% vinyl acetate means that the mass percentage of vinyl acetate is 85% based on the total mass of monomer 1, monomer 2, and monomer 3; and 15% ethylene means that the mass percentage of ethylene is 15% based on the total mass of monomer 1, monomer 2, and monomer 3.
As shown in Table 1, compared to Comparative Example 1, in the embodiments of this application, the ester polymer of this application is added to the positive electrode plate and/or the negative electrode plate, which can form uniform high-infiltration points within the active material layer, and equably improve the infiltration performance of the active material layer, thereby increasing the overall electrolyte absorption rate of the active material layer, and improving the cycling performance of the battery cell using the electrode plate.
Compared to Comparative Example 2, in the embodiments of this application, when v/λ>1 is met, the cycling performance of the lithium-ion battery can be more significantly improved.
Although this application has been described with reference to some embodiments, various modifications to this application and replacements of the components therein with equivalents can be made without departing from the scope of this application. In particular, as long as there is no structural conflict, the various technical features mentioned in the embodiments can be combined in any manner. This application is not limited to the specific embodiments disclosed in this specification but includes all technical solutions falling within the scope of the claims.
This application is a continuation of International Application No. PCT/CN2023/076811, filed on Feb. 17, 2023, the entire content of which is incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/CN2023/076811 | Feb 2023 | WO |
| Child | 19071461 | US |
