Polymers, plates and related battery cells, batteries and power consumption devices
A sheet-like ether-based polymer with specific properties forms a protective layer on electrode plates, addressing interfacial performance issues to improve battery cell cycle and storage performance by stabilizing the solid-liquid interface and reducing side reactions.
Patent Information
- Application Number
- JP2025516098
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2023-02-17
- Publication Date
- 2025-09-19
AI Technical Summary
The interfacial performance of active materials in current electrode plates is poor, leading to poor cycle performance and storage performance of battery cells.
A sheet-like ether-based polymer is used in electrode plates, characterized by a specific storage modulus G'-loss modulus G'' curve slope (1 < K < ∞) and glass transition temperature (-100 ≤ Tg ≤ 50 °C), which forms a protective layer on the active material surface, reducing side reactions and improving stability.
The polymer enhances the cycle and storage performance of battery cells by forming a stable solid-liquid interface, reducing side reactions and maintaining normal lithium ion transport.
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Figure 2025531269000001_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of batteries, specifically to polymers, electrode plates, related battery cells, batteries and power consumption devices.
Background Art
[0002] Battery cells have characteristics such as high capacity and long life, so they are widely applied to power consumption devices, such as mobile phones, notebook computers, battery vehicles, electric vehicles, electric airplanes, electric ships, electric toy cars, electric toy ships, electric toy airplanes and electric tools, etc.
[0003] As the application range of batteries is becoming increasingly wide, the requirements for the performance of battery cells are also becoming gradually stricter. In order to improve the safety performance of battery cells, generally, the performance of the electrode plates in the battery cells is optimized and improved. However, the interfacial performance of the active materials in the current electrode plates is relatively poor, and when they are used in battery cells, the cycle performance and storage performance of the battery cells are relatively poor.
Summary of the Invention
[0004] This application is made in view of the above problems, and aims to provide a polymer, an electrode plate, a related battery cell, a battery and a power consumption device.
[0005] The first aspect of this application provides a polymer used in a battery cell, the polymer includes an ether-based polymer, here, the ether-based polymer is fabricated as a sheet-like structure, the sheet-like structure undergoes a dynamic frequency scanning test at (Tm + 20) °C to obtain a storage modulus G'-loss modulus G" curve, the slope of the storage modulus G'-loss modulus G" curve is K, 1 < K < ∞, and Tm °C represents the melting temperature of the ether-based polymer.
[0006] Thus, when the polymer of the present application meets the above range, the entanglement state of the molecular chains can be further reduced, which is beneficial to the diffusion of solvent molecules between the molecular chains in the electrolyte. Moreover, the polymer still maintains a certain entanglement state of the molecular chains, can retain the solvent molecules inside the polymer in situ, reduce the risk of the polymer dissolving in the electrolyte, improve the stability of the polymer performance, and is beneficial for the polymer to form a protective layer on the surface of the active material and improve the solid-liquid interface performance, reduce the side reaction between the active material and the electrolyte, and improve the cycle performance and storage performance of the battery cell.
[0007] In some embodiments, 1 < K ≤ 100, and optionally, 1 < K ≤ 10.
[0008] In some embodiments, the glass transition temperature of the ether-based polymer is Tg, with the unit of °C, and -100 ≤ Tg ≤ 50, and optionally, -80 ≤ Tg ≤ 30. The glass transition temperature of the polymer is relatively low, the flexibility of the chain segments of the molecular chains is better, and the adjacent molecular chains are more likely to be opened.
[0009] In some embodiments, the ether-based polymer contains a structural unit shown in formula (I). In formula (I) of JPEG2025531269000002.jpg29157, R1 and R2 each independently contain a hydrogen atom, a substituted or unsubstituted C1-C3 alkyl group or a substituted or unsubstituted C1-C3 alkoxy group, R3 contains a substituted or unsubstituted C1-C5 methylene group, and optionally, R1 and R2 each independently contain a hydrogen atom, a substituted or unsubstituted C1-C2 alkyl group, and / or R3 contains a single bond, a substituted or unsubstituted C1-C4 methylene group.
[0010] In some embodiments, the ether-based polymer contains at least one of the structural units shown in formula (I-1) to formula (I-8). Of JPEG2025531269000003.jpg105170.
[0011] In some embodiments, the ether-based polymer comprises a structural unit shown in formula (II): JPEG2025531269000004.jpg35170In formula (II), R4 to R7 each independently comprise a hydrogen atom, a substituted or unsubstituted C1 to C3 alkyl group, a substituted or unsubstituted C1 to C3 alkoxy group, or an ether group, and at least one of R4 to R7 comprises a substituted or unsubstituted C1 to C3 alkoxy group or ether group, and optionally R4 to R7 each independently comprise a hydrogen atom, a substituted or unsubstituted C1 to C2 alkyl group, a substituted or unsubstituted C1 to C2 alkoxy group or ether group, and at least one of R4 to R7 comprises a substituted or unsubstituted C1 to C2 alkoxy group or ether group.
[0012] In some embodiments, the ether-based polymer comprises a structural unit represented by formula (II-1) to a structural unit represented by formula (II-7): Contains at least one of JPEG2025531269000005.jpg121170.
[0013] In some embodiments, n is a positive integer selected from 1500 to 25000, and / or the molecular weight of the ether-based polymer is 1.2×10 5 g / mol ~ 1.0 × 10 6 g / mol. When the molecular weight of the polymer is in the above range, it can ensure that the polymer has a certain solubility in the electrolyte, and is not easily completely dissolved and dispersed by the electrolyte, which is favorable for adjusting the distribution and dispersion of the polymer on the surface of the active material, and can further improve the flexibility between the molecular chains of the polymer, and the interaction force between the molecular chains is relatively weak, which is favorable for the solvent molecules in the electrolyte to open the molecular chains, enter between the molecular chains, and be wrapped by the molecular chains, which is favorable for the active ions to enter the active material through the solvent, and realize the smooth and fast movement of the active ions.
[0014] In some embodiments, the polymer is added to a first solvent at 45° C. to form a polymer system, the polymer system is allowed to stand at 45° C. for 8 hours, and then allowed to stand at 25° C. for ≥ 24 hours, after which the polymer system is filtered through a 200 mesh filter to leave a first substance, wherein the mass of the polymer is n in grams, the mass of the first substance is m in grams, and the ratio of the polymer and the first substance satisfies 5≦m / n≦1000.
[0015] Therefore, the present application achieves polymer chain elongation within the safe operating temperature range of the battery cell by increasing the temperature, promoting mutual attraction and physical bonding between the polymer chain and the solvent. At room temperature, the activity of the polymer chain segments decreases, and they adhere to the active material surface, maintaining the electrolyte in the spatial environment where the polymer is located, forming an in-situ gel-like state, protecting the active material interface while maintaining normal lithium ion transport, thereby achieving interface protection, reducing surface side reactions, and improving cycle performance and storage performance.
[0016] A second aspect of the present application provides a positive electrode plate, the positive electrode plate including a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector, the positive electrode active material layer including a positive electrode active material and a polymer, and the polymer including the polymer described in any one of the embodiments of the first aspect of the present application.
[0017] A third aspect of the present application provides a negative electrode plate, the negative electrode plate including a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector, the negative electrode active material layer including a negative electrode active material and a polymer, and the polymer including the polymer described in any one of the embodiments of the first aspect of the present application.
[0018] A fourth aspect of the present application provides a battery cell, the battery cell comprising a positive electrode plate and a negative electrode plate, wherein the positive electrode plate comprises the positive electrode plate according to any one of the embodiments of the second aspect of the present application, and / or the negative electrode plate comprises the negative electrode plate according to any one of the embodiments of the third aspect of the present application.
[0019] A fifth aspect of the present application provides a battery, the battery including the battery cell according to the fourth aspect of the present application.
[0020] A sixth aspect of the present application provides a power consuming device, the power consuming device comprising a battery according to the fifth aspect of the present application. [Brief explanation of the drawings]
[0021] In order to more clearly explain the technical solutions of the embodiments of the present application, the following briefly introduces the drawings that need to be used in the embodiments of the present application. It is obvious that the drawings described below are only some embodiments of the present application, and those skilled in the art can obtain other drawings based on the drawings without making any creative efforts. The drawings are not necessarily drawn to scale. [Figure 1] 1 is a schematic diagram of one embodiment of a battery cell of the present application. [Figure 2] FIG. 2 is an exploded schematic view of an embodiment of the battery cell of FIG. 1. [Figure 3] 1 is a schematic diagram of one embodiment of a battery module of the present application. [Figure 4] 1 is a schematic diagram of one embodiment of a battery pack of the present application. [Figure 5] FIG. 5 is an exploded schematic view of the embodiment of the battery pack shown in FIG. 4. [Figure 6] 1 is a schematic diagram of one embodiment of a power consuming device that includes a battery cell of the present application as a power source. DETAILED DESCRIPTION OF THE INVENTION
[0022] Hereinafter, embodiments specifically disclosing the polymer, electrode plate, and related battery cell, battery, and power consumption device of the present application will be described in detail. However, unnecessary details may be omitted. For example, detailed descriptions of well-known matters and redundant descriptions of structures that are actually the same may be omitted. This is to avoid unnecessarily lengthening the following description and to facilitate understanding by those skilled in the art. Note that the drawings and the following description are provided to enable those skilled in the art to fully understand the present application and are not intended to limit the subject matter described in the claims.
[0023] The "ranges" disclosed in this application are defined in the form of lower and upper limits, and a given range is defined by selecting one lower limit and one upper limit, and the selected lower and upper limits define the boundaries of the particular range. Such defined ranges may be inclusive or exclusive of the end values, and any combination is possible; i.e., any lower limit can be combined with any upper limit to form a single range. For example, if ranges of 60 to 120 and 80 to 110 are listed for a particular parameter, it is understood that ranges of 60 to 110 and 80 to 120 are also possible. Furthermore, if 1 and 2 are listed as minimum range values and 3, 4, and 5 are listed as maximum range values, the ranges 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4, and 2 to 5 are all possible. In this application, unless otherwise specified, a numerical range "a to b" is a shorthand notation for any combination of real numbers a to b, where a and b are both real numbers. For example, the numerical range "0-5" represents that the present specification has already listed all real numbers between "0-5," and "0-5" is merely a shorthand representation of combinations of these numbers. Also, expressing a parameter as an integer ≧2 is equivalent to disclosing that this parameter is, for example, the integers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
[0024] Unless otherwise stated, all embodiments and optional embodiments of the present application can be combined with each other to form new technical solutions. Unless otherwise stated, all technical features and optional technical features of the present application can be combined with each other to form new technical solutions.
[0025] Unless otherwise stated, all steps in this application may be performed in order or randomly, preferably in order. For example, a method including steps (a) and (b) means that the method may include steps (a) and (b) performed in order, or may include steps (b) and (a) performed in order. For example, a method that may further include step (c) means that step (c) may be added to the method in any order, e.g., the method may include steps (a), (b), and (c), or may include steps (a), (c), and (b), or may include steps (c), (a), and (b), etc.
[0026] Unless otherwise specified, the terms "comprise" and "comprises" used in this application may be open-ended or closed-ended. For example, "comprise" and "comprises" may indicate that other components not listed may be further included or included, or that only the listed components may be included or included.
[0027] Unless otherwise stated, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B." More specifically, "A or B" is satisfied when A is true (or exists) and B is false (or does not exist), when A is false (or does not exist) but B is true (or exists), or when both A and B are true (or exist).
[0028] As used in this application, the terms "plurality" and "plurality" refer to two or more.
[0029] The term "alkyl group" covers straight-chain and branched-chain alkyl groups. For example, the alkyl group may be a C1-C5 alkyl group, a C1-C4 alkyl group, a C1-C3 alkyl group, or a 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. The alkyl group may also be optionally substituted. When substituted, the substituent may include a fluorine atom.
[0030] The term "alkoxy group" refers to a group in which an alkyl group and an oxygen atom are connected by a single bond. For example, the alkoxy group may be a C1-C5 alkoxy group, a C1-C3 alkoxy group, or a C1-C2 alkoxy group. In some embodiments, the alkoxy group may include a methoxy group, an ethoxy group, or a propoxy group. Additionally, the alkoxy group may be optionally substituted.
[0031] The term "halogen atom" refers to fluorine atom, chlorine atom, bromine atom, and the like.
[0032] The term "hydrogen" refers to 1H (protium, H), 2H (deuterium, D), or 3H (tritium, T). In some embodiments, "hydrogen" may be 1H (protium, H).
[0033] A battery cell includes a positive electrode plate, a negative electrode plate, and an electrolyte. A solid-liquid contact interface exists between the electrode plate and the electrolyte, and side reactions may occur at this contact interface, deteriorating the performance of the battery cell. Taking a positive electrode plate as an example, a solid-liquid contact interface exists between the positive electrode active material contained in the positive electrode plate and the electrolyte. At this interface, side reactions may occur between the positive electrode active material and the electrolyte, resulting in loss of the positive electrode active material and potentially reducing the cycle performance of the battery cell. Furthermore, the side reactions may produce products that are unfavorable to the cycle of the battery cell, potentially deteriorating the storage performance of the battery cell.
[0034] In view of this, an embodiment of the present application improves the cycle performance and storage performance of a battery cell from the perspective of improving the interfacial performance of a solid-liquid contact interface. An embodiment of the present application proposes a polymer. When the polymer is used in a positive electrode plate and / or a negative electrode plate, an in-situ gel can be formed on the surface of a solid-phase active material, that is, a stable solid-liquid interface is formed on the surface of the active material, and the risk of side reactions occurring at the solid-liquid interface is reduced, thereby improving the cycle performance and storage performance of the battery cell.
[0035] polymer According to a first aspect, the present application proposes a polymer. The polymer is used in a battery cell. The polymer includes an ether-based polymer. Here, the ether-based polymer is fabricated as a sheet-like structure. The sheet-like structure undergoes a dynamic frequency scanning test at (Tm + 20) °C to obtain a storage modulus G’ - loss modulus G’’ curve. The slope of the storage modulus G’ - loss modulus G’’ curve is K, where 1 < K < ∞. Tm °C represents the melting temperature of the ether-based polymer.
[0036] Specifically, the manufacturing process of the sheet-like structure is as follows: that is, the polymer is vacuum dried at 80 °C for 12 h. The dried polymer is hot pressed into a sheet using a flat vulcanizer. The hot pressing temperature is set to (Tm + 20) °C, the rolling thickness is 1 - 2 mm, the pressure delay time is 2 min, and the pressure is 8 MPa. After rolling for 2 min, the sample is taken out and placed on another vulcanizer of the same model number for cold pressing, and the cold pressing pressure is 10 MPa. When a circular mold with a diameter of 25 mm is adopted, a polymer wafer (sheet-like structure) with a fixed size can be obtained. Exemplarily, the sheet-like structure may be a wafer with a thickness of 1 - 2 mm and a diameter of 25 mm, or samples may be fabricated according to the sample specifications required by the test equipment.
[0037] According to the conclusion of classical linear viscoelasticity, for polymers, especially linear polymers, the storage modulus G’ - loss modulus G’’ in the terminal region (the interval range approaching the maximum angular velocity value) of the storage modulus G’ - loss modulus G’’ curve conforms to frequency dependence, and the longest chain of the polymer acts on the viscoelastic behavior.
[0038] The specific steps of the dynamic frequency scanning test are as follows: namely, a TA-AR2000EX rotational rheometer (TA Instruments, USA) is used to perform the dynamic frequency scanning test. The diameter of the parallel plates is 25 mm, and the thickness is 0.9 mm. To ensure that the test is in the linear elastic region, the strain during the dynamic frequency scanning test is 2%, the test temperature is Tm + 20 °C, and the frequency scanning range of the test is 500 rad / s ≤ ω 2 ≤ 0.05 rad / s, so as to obtain data in the low-frequency region as much as possible.
[0039] The dynamic frequency scanning test can characterize the entanglement degree of molecular chains in the solid-phase melting (melting state). Compared with the linear structure or short-branched structure, the long-branched structure, network structure and low-crosslinked structure have a high entanglement degree, show a behavior deviating from the linear end, and the polymer shows a solid-phase behavior. When the polymer of the present application satisfies the above range, the entanglement state of the molecular chains can be further reduced, which is beneficial to the diffusion of solvent molecules between the molecular chains in the electrolyte, and the polymer still maintains a certain entanglement state of the molecular chains, can retain the solvent molecules in situ inside the polymer, reduce the risk of the polymer dissolving in the electrolyte, improve the stability of the polymer performance, and is beneficial for the polymer to form a protective layer on the surface of the active material and improve the solid-liquid interface performance, reduce the side reaction between the active material and the electrolyte, and improve the cycle performance and storage performance of the battery cell.
[0040] In some embodiments, 1 < K ≤ 100, and optionally, 1 < K ≤ 10.
[0041] In some embodiments, the glass transition temperature of the ether-based polymer is Tg, the unit is °C, -100 ≤ Tg ≤ 50, and optionally, -80 ≤ Tg ≤ 30.
[0042] The glass transition temperature is the temperature at which a polymer chain segment transitions from freezing to motion. The glass transition temperature has a certain effect on the flexibility of the polymer molecular chain. The lower the glass transition temperature, the better the flexibility of the polymer molecular chain at room temperature. The higher the glass transition temperature, the worse the flexibility of the molecular chain at room temperature. The glass transition temperature can be measured by differential scanning calorimetry (DSC). Specifically, the test steps are as follows: take a sample of 0.5g-0.8g, place the sample in a crucible, and heat the sample in a nitrogen gas atmosphere. The temperature is increased at a rate of 10°C / min from an initial temperature 20°C lower than the intrinsic Tg of the material to a cutoff temperature 20°C higher than the intrinsic Tm of the material. The actual glass transition temperature (Tg) and melting temperature (Tm) of the material are determined based on the endothermic peak or transition point of the material during the process.
[0043] The glass transition temperature of the polymer is relatively low, the chain segments of the molecular chain are more flexible, and adjacent molecular chains are more likely to open. For example, the glass transition temperature of the ether-based polymer may be −100° C., −80° C., −60° C., −30° C., 0° C., 30° C., 50° C., or a range consisting of any two of the above values.
[0044] In some embodiments, the ether-based polymer comprises a structural unit according to formula (I): JPEG2025531269000006.jpg32170In formula (I), R1 and R2 each independently comprise a hydrogen atom, a substituted or unsubstituted C1-C3 alkyl group, or a substituted or unsubstituted C1-C3 alkoxy group, and R3 comprises a substituted or unsubstituted C1-C5 methylene group; optionally, R1 and R2 each independently comprise a hydrogen atom, a substituted or unsubstituted C1-C2 alkyl group, and / or R3 comprises a single bond, a substituted or unsubstituted C1-C4 methylene group.
[0045] For example, the ether-based polymer may include structural units represented by formula (I-1) to (I-8): Contains at least one of JPEG2025531269000007.jpg105170.
[0046] In some embodiments, the ether-based polymer comprises a structural unit shown in formula (II): JPEG2025531269000008.jpg36170In formula (II), R4 to R7 each independently comprise a hydrogen atom, a substituted or unsubstituted C1 to C3 alkyl group, a substituted or unsubstituted C1 to C3 alkoxy group or an ether group, and at least one of R4 to R7 comprises a substituted or unsubstituted C1 to C3 alkoxy group or an ether group.
[0047] Optionally, R4 to R7 each independently comprise a hydrogen atom, a substituted or unsubstituted C1 to C2 alkyl group, a substituted or unsubstituted C1 to C2 alkoxy group or an ether group, and at least one of R4 to R7 comprises a substituted or unsubstituted C1 to C2 alkoxy group or an ether group.
[0048] In some embodiments, the ether-based polymer comprises a structural unit represented by formula (II-1) to a structural unit represented by formula (II-7): Contains at least one of JPEG2025531269000009.jpg122170.
[0049] The monomers used in the above ether-based polymers are multi-membered rings, such as six-membered rings or shorter-chain monomers, which are advantageous for polymerizing a high content of -O- structures. The degree of entanglement of such structural types is relatively low, which is advantageous for improving the flexibility of the molecular chains, allowing the molecular chains to fully extend in the electrolyte, thereby further improving the interfacial performance of the active material.
[0050] The above polymers are merely examples of structural groups in the main molecular chain, and in embodiments of the present application, the polymers may be obtained by copolymerizing the above structural groups with other types of structural groups (e.g., olefin-based structural units, acrylonitrile-based structural units, etc.).
[0051] The groups of the polymer of the present application can be detected by infrared spectrophotometry (IR). Specifically, the polymer is tested using a ThermoNicolet Nexus 670 attenuated total reflectance Fourier transform infrared spectrometer (FTIR-ATR) and is tested in accordance with the standard GB / T6040-2002. The test range is ATR 600-4000 cm -1 , Reproducibility: ±2cm -1 , Resolution: 4cm -1 It has a better penetration depth of 0.2-0.6 μm.
[0052] The structure of the polymers of the present application can be tested by nuclear magnetic resonance NMR, specifically, 1H NMR and 13C NMR were performed on a Varian MercuryPlus-400 nuclear magnetic resonance instrument, with a test temperature of 20°C, TMS as the internal standard, CDCl3 as the solvent, and a proton resonance frequency of 400 MHz.
[0053] The polymer monomer type of this application (especially applicable to monomers with a relatively small proportion in the polymer) can be carried out by decomposition-gas chromatography-mass spectrometry. The specific test steps are as follows: 0.5 mg of sample is accurately weighed and placed in a sample cup, and then attached to a sample injection rod, and then placed in a cracker installed near the GC (gas chromatography) sample injection port. After the temperature of the cracker reaches the set temperature, the sample injection button is pressed, and the sample cup falls rapidly into the core of the decomposition furnace by free fall. In the inert gas N2 atmosphere, the volatile components are instantly gasified and carried by the carrier gas into the gas chromatography column for separation, and finally detected by a flame ionization detector FID or a mass spectrometer MS, thereby obtaining a gas chromatograph or total ion current graph.
[0054] In the above-mentioned group substitution, the substituent may include one or more of a nitrile group (-CN), a nitro group, a sulfonic acid group, a sulfonyl group, an amide group, a carboxyl group, an ester group, and a halogen atom. The above-mentioned substituent is a high-pressure-resistant substituent, which is further advantageous for stabilizing the polymer structure. The halogen atom may include a fluorine atom, a chlorine atom, a bromine atom, etc.
[0055] In some embodiments, n is a positive integer selected from the range of 1500 to 25000.
[0056] Optionally, n is a positive integer selected from 3,000 to 18,000.
[0057] In some embodiments, the molecular weight of the polymer is 1.2×10 5 g / mol ~ 1.0 × 10 6 g / mol.
[0058] When the molecular weight of the polymer is within the above range, it can ensure that the polymer exhibits a certain solubility in the electrolyte, and is not easily completely dissolved and dispersed by the electrolyte, which is advantageous for adjusting the distribution and dispersion of the polymer on the surface of the active material, and can further improve the flexibility between the molecular chains of the polymer, and the force between the molecular chains is relatively weak, which is advantageous for the solvent molecules in the electrolyte to open the molecular chains, enter between the molecular chains, and be wrapped by the molecular chains, thereby advantageous for the active ions to enter the active material through the solvent, and realize the smooth and fast movement of the active ions. For example, the molecular weight of the polymer is 1.2×10 5 g / mol, 2 × 10 5 g / mol, 5 × 10 5 g / mol, 8 × 10 5 g / mol, 1×10 6 g / mol, 1.5 × 10 6 It may be g / mol or a range consisting of any two of the above values.
[0059] The molecular weight of a polymer is a known term in the art and can be measured using instruments and methods commonly used in the art. It can be tested using gel permeation chromatography (GPC). The specific test steps are as follows: take an appropriate amount of sample to be measured (the sample concentration should ensure a light shielding rate of 8%-12%), add 20ml of deionized water, and wait for more than 5 minutes (53KHz / 120W) to ensure the sample is completely dispersed. Then, measure the sample in accordance with GB / T19077-2016 / ISO13320:2009 standards.
[0060] Alternatively, a multi-angle laser scattering analyzer (MALLS) was used for the test, specifically, a GPC with a DawnHeleos II multi-angle laser light scattering device, an OptilabT-rEX refractive index (RI) detector, and a ViscoStar II viscometer (Wyatt Technology Corporation, USA). The test was conducted at 30°C using tetrahydrofuran as the flow phase at a flow rate of 1.0 ml / min. The commercial software ASTRA6 was used to process the SEC-SAMLL data and obtain molecular weight parameters.
[0061] Further research has revealed that the cycle performance and storage performance of the battery cell can be further improved if the polymer further satisfies one or more of the following conditions:
[0062] In some embodiments, the polymer is added to a first solvent at 45° C. to form a polymer system, the polymer system is allowed to stand at 45° C. for 8 hours and at 25° C. for ≥ 24 hours, and then a portion of the polymer system is in situ transformed into a gel-state material after two-stage settling treatments, and the polymer system is filtered through a 200-mesh filter to leave a first material, wherein the first temperature is greater than the second temperature, the mass of the polymer is n in grams, the mass of the first material is m in grams, and the ratio of the polymer and the first material satisfies 5≦m / n≦1000, optionally 10≦m / n≦1000, and further optionally 10≦m / n≦50. Illustratively, m / n may be 5, 10, 20, 25, 28, 30, 32, 35, 40, 50, 80, 100, 200, 500, 1000, or a range consisting of any two of the above values.
[0063] Exemplarily, based on the mass of the polymer system, the ratio range of the mass content of the polymer to the mass content of the first solvent is 1:100 to 1:10, for example 3:50.
[0064] For example, the first solvent and the solvent of the electrolyte may be the same or similar, and the first solvent may include a carbonate-based solvent, such as a cyclic carbonate solvent and / or a chain carbonate solvent.
[0065] Examples of cyclic carbonate solvents include one or more of ethylene carbonate EC, vinylene carbonate VC, fluoroethylene carbonate FEC, difluoroethylene carbonate DFEC, vinylethylene carbonate VEC, and dioctyl carbonate CC.
[0066] Examples of the linear carbonate solvent include one or more of dimethyl carbonate DMC, diethyl carbonate DEC, ethyl methyl carbonate EMC, diphenyl carbonate DPC, methyl allyl carbonate MAC, and polycarbonate VA.
[0067] Alternatively, the first solvent may contain both a lithium salt and an electrolyte additive, such as lithium hexafluorophosphate, vinylene carbonate (VC), or fluoroethylene carbonate (FEC).
[0068] In this application, m / n is also referred to as the sedimentation value, which characterizes the ability of a polymer and solvent to transform into a gel-state material.
[0069] The first substance includes a gel-state substance formed mainly by a polymer and a first solvent, and in such a gel-state substance, the molecular structure of the polymer hardly changes.
[0070] In some embodiments, the first material is dried at 80° C. for 12 hours to remove the first solvent in the first material, and then subjected to infrared spectroscopy (IR) or nuclear magnetic resonance (NMR) testing, and the main component of the first material after drying is the polymer.
[0071] The present invention achieves polymer chain elongation within the safe operating temperature range of a battery cell by increasing the temperature, promoting mutual attraction and physical bonding between the polymer chain and the solvent. At room temperature, the activity of the polymer chain segments decreases, allowing them to adhere to the surface of the active material and maintain the electrolyte in the spatial environment where the polymer is located, forming an in-situ gel-like state, protecting the active material interface while maintaining normal lithium ion transport, thereby achieving interface protection, reducing surface side reactions, and improving cycle performance and storage performance.
[0072] positive electrode plate According to a second aspect, the present application proposes a positive electrode plate, the positive electrode plate including a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector, the positive electrode active material layer including a positive electrode active material and a polymer, and the polymer including the polymer described in any one of the embodiments of the first aspect of the present application.
[0073] For example, the positive electrode current collector has two surfaces facing each other in the thickness direction thereof, and the positive electrode active material layer is disposed on either one or both of the two facing surfaces of the positive electrode current collector.
[0074] The electrode plate may be prepared by applying the slurry onto a current collector, drying it, and cold pressing it. Alternatively, the electrode plate may be derived from a battery cell, and may be prepared by disassembling the battery cell, removing the electrode plate that is immersed in the electrolyte from the battery cell, and subjecting the electrode plate to vacuum drying at 100°C for 12 hours to obtain the electrode plate, which is then used for electrode plate tests such as liquid absorption rate.
[0075] Polymers can be synthesized using methods such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization. Alternatively, polymers can be derived from battery cells. The battery cells can be disassembled, and the electrodes immersed in the electrolyte can be removed. The active material from the electrodes can be peeled from the current collectors by external force to form powder samples. These samples can then be added to DMC and stirred at 500 rpm for 8 hours at 80°C. After stirring, the samples are allowed to stand at room temperature for 10 minutes. The supernatant liquid is then dried at 80°C for 12 hours to obtain the polymer. The resulting polymer may contain a small amount of lithium salt, but this has little effect on infrared and sedimentation tests. To ensure the accuracy of the polymer, the lithium salt can be separated by further washing with DMC at room temperature.
[0076] In some embodiments, the positive electrode active material layer satisfies the following: JPEG2025531269000010.jpg49170In equations (1) to (3), λ represents the porosity of the positive electrode active material layer, P1 represents the actual compaction density of the positive electrode active material layer, and its unit is g / cm 3 and P2 represents the true compaction density of the positive electrode active material, and its unit is g / cm 3 and v represents the liquid absorption rate of the positive electrode active material layer, and its unit is mg / s, d represents the diameter of a capillary in a capillary test of the positive electrode active material layer, and its unit is mm; h represents the liquid level in the capillary tube, and its unit is mm; ρ represents the density of the electrolyte in the capillary test, and its unit is g / cm 3 and t represents the time taken for the electrolyte in the capillary to be absorbed, and its unit is s.
[0077] In the present application, the actual compaction density P1 is the ratio of the mass of the positive electrode active material layer per unit area of the electrode plate to the thickness. The actual compaction density is determined by the force applied by the roller after coating the electrode plate, and is expressed in units of g / cm. 3 The specific test steps are to take an electrode plate with a certain area S, measure the mass M of its positive electrode active material layer, and measure the thickness D of the positive electrode active material layer, and the actual compaction density = M / (S × D).
[0078] In this application, the true packed density P2 refers to the density of the positive electrode active material itself in the positive electrode active material layer, and specifically refers to the mass of the unit "actual volume of the solid material (excluding open pores, closed pores, and inter-particle voids)" in a dense state. It is obtained by testing the true volume V, and then calculating the true packed density based on P=m / V. This can be tested with reference to GB / T24586-2009. Specifically, the test steps are as follows:
[0079] 1) Pretreatment: Take a clean and dry sample cup and place it on the balance, clear it, add the powder sample to the sample cup, occupying about 1 / 2 of the volume of the sample cup, and record the sample mass; 2) Place the sample cup containing the sample in the true density tester, seal the test system, pass helium gas through it according to the procedure, detect the gas pressure in the sample chamber and the expansion chamber, and then calculate the true compacted density by calculating the true volume based on Bohr's law (PV=nRT).
[0080] Here, the sample cup volume is 3.5 cm 3, analysis gas: helium gas.
[0081] Equation (1) can calculate the porosity λ of the active material layer based on the actual compaction density and the true compaction density.
[0082] in particular, JPEG2025531269000011.jpg22170.
[0083] Here, V1 represents the volume of the positive electrode active material layer per mass m, and its unit is cm 3 and V2 represents the volume occupied by the active particles in the positive electrode active material layer in mass m, and its unit is cm 3 and m represents the mass of the positive electrode active material layer, and its unit is g.
[0084] Equation (2) can characterize the rate at which a point on a plate nearly completely absorbs the liquid (e.g., electrolyte) in the capillary per unit time. In this application, a point on a plate refers to a region of the plate having a certain area, which corresponds to the cross-sectional area of the capillary.
[0085] In this application, the method for detecting the liquid absorption rate of the electrode plate is as follows: Aspirating a predetermined amount of electrolyte using a capillary tube; Bringing the capillary tube into contact with the electrode plate, the electrode plate to be measured absorbs the electrolyte in the capillary tube by capillary action; and a step of recording the liquid level h at which the electrolyte in the capillary is absorbed after a predetermined time t has elapsed, calculating the amount of electrolyte absorbed based on the liquid level h, diameter d, and density ρ of the electrolyte in the capillary, and quantitatively calculating the liquid absorption rate v of the electrode plate based on the ratio of the absorbed amount to the predetermined time t.
[0086] Illustratively, the d value is between 0.2 and 1, for example, the value is 0.2, and the h value is between 3 and 5, for example, the value is 3.
[0087] The capillary has a capillary channel, whereby the capillary does not need to be provided with a liquid suction power by an external driving unit and can directly suck the electrolyte by capillary action. Thus, when sucking the electrolyte by capillary action, the suction amount can be more accurately controlled. On the other hand, since the electrode plate absorbs the electrolyte by its own capillary action, only when the capillary contacts the electrode plate to be measured, the electrode plate sucks the electrolyte out of the capillary, and when it detaches from the contact, the electrolyte in the capillary does not flow out, so that the amount of the electrolyte absorbed in the capillary accurately reflects that the electrode plate has absorbed the corresponding volume of the electrolyte, further improving the accuracy of the test result and enabling the quantitative calculation of the absorption rate at which the electrode plate absorbs the electrolyte.
[0088] In this application, a standard electrolyte is used as a test sample for testing, and for the specific formulation of the electrolyte, reference may be made to the formulation of the electrolyte in the examples.
[0089] Equation (3) represents the liquid suction rate of the electrode plate at the porosity λ and may be used to characterize the liquid suction speed of the electrode plate.
[0090] By introducing the polymer of this application in the manufacturing process of the active material layer, a uniform high wetting point is formed inside the active material layer, and by uniformly enhancing the wetting performance of the active material layer, the liquid suction speed of the entire active material layer is increased, thereby improving the cycle performance of the battery cell employing the electrode plate.
[0091] Optionally, 1.00 < v / λ < 50.00.
[0092] In some embodiments, 1.00 < v / λ < 4.00, optionally, 1.20 ≤ v / λ ≤ 3.80, and further optionally, 1.4 ≤ v / λ ≤ 3.6. Exemplarily, 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 a range composed of any two of the above numerical values.
[0093] In some embodiments, the mass content of the polymer is A %, based on the mass of the positive electrode active material layer, where 0.1≦A≦1.5.
[0094] When the mass content of the polymer is within the above range, the interfacial performance of the positive electrode active material layer can be significantly improved. For example, the mass content of the polymer may be 0.1%, 0.2%, 0.5%, 0.8%, 1.0%, 1.2%, 1.5%, or a range consisting of any two of the above values.
[0095] The positive electrode active material layer includes a positive electrode active material, which may be a positive electrode active material known in the art and used in battery cells. For example, the positive electrode active material may include at least one of a layered positive electrode active material (e.g., a ternary material, a lithium / sodium nickelate, a lithium / sodium cobaltate, a lithium / sodium manganate, a lithium / sodium-rich layered material, and a rock salt layered material), an olivine-type phosphate active material, and a spinel-type positive electrode active material (e.g., a spinel lithium manganate, a spinel lithium nickel manganate, a lithium-rich spinel lithium manganate, and a lithium nickel manganate).
[0096] For example, the general formula of the layered positive electrode active material is Li x A y Ni a Co b Mn c M (1-a-b-c) Y zwhere 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, and 1.8≦z≦3.5; A is one or more selected from Na, K, and Mg; M is one or more selected from 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 one or more selected from O and F. Optionally, y=0. Specifically, the layered positive electrode active material may be lithium cobalt oxide (LCO), lithium nickel oxide (LNO), lithium manganese oxide (LMO), or LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2(NCM333), LiNi 0.8 Co 0.1 Mn 0.1 O2(NCM811) and LiNi 0.5 Co 0.2 Mn 0.3 O2 (NCM523) may be included.
[0097] For example, the general formula of the olivine-type phosphate active material is Li x A y Me a M b P 1-c X c Y zwherein 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 one or more selected from Na, K, and Mg; Me is one or more selected from Mn, Fe, Co, and Ni; M is one or more selected from 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 one or more selected from S, Si, Cl, B, C, and N; and Y is one or more selected from O and F. Specifically, the olivine-type phosphate active material includes one or more of LiFePO4, LiMnPO4, LiNiPO4, and LiCoPO4.
[0098] For example, the general formula of the positive electrode active material having a spinel structure is Li x A y Mn a M 2-a Y z where 0≦x≦2, 0≦y≦1, and 0.9≦x+y≦2, 0.5≦a≦2, 3≦z≦5, A is one or more selected from Na, K, and Mg, M is one or more selected from 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 one or more selected from O and F. Specifically, the positive electrode active material having a spinel structure is LiMn2O4, LiNi 0.5 Mn 1.5 O4, LiCr 0.3 Mn 1.7 O4, Li 1.1 Al 0.1 Mn 1.9 O4, Li2Mn2O4 and Li 1.5 Mn2O4.
[0099] In some embodiments, the positive electrode current collector may be a metal foil sheet or a composite current collector. Examples of the metal foil sheet include aluminum foil or aluminum alloy foil. The composite current collector may include a polymer base layer and a metal layer formed on at least one surface of the polymer base layer. For example, the metal layer may include one or more combinations selected from aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver, and silver alloy. The polymer base layer may include one or more combinations selected from polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), and polyethylene (PE).
[0100] In some embodiments, the positive electrode active material layer further optionally includes a positive electrode conductive agent. The present application is not particularly limited by the type of positive electrode conductive agent, and examples of the positive electrode conductive agent include one or a combination of superconducting carbon, conductive carbon black, conductive graphite, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers. In some embodiments, the mass content of the positive electrode conductive agent is 5% or less, based on the total mass of the positive electrode active material layer.
[0101] In some embodiments, the positive electrode active material layer optionally further includes a positive electrode adhesive. The present application is not particularly limited to the type of positive electrode adhesive. For example, the positive electrode adhesive may include one or more combinations selected from polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and a fluorine-containing acrylate resin. In some embodiments, the mass content of the positive electrode adhesive is 5% or less, based on the total mass of the positive electrode active material layer. The positive electrode adhesive has a higher crystallinity than the ether-based polymer of the present application. The positive electrode adhesive has a higher melting temperature than the ether-based polymer of the present application.
[0102] The positive electrode active material layer is generally obtained by applying a positive electrode slurry to a positive electrode current collector, drying, and cold pressing. The positive electrode slurry is generally formed by dispersing a positive electrode active material, an optional conductive agent, an optional adhesive, and any other optional components in a solvent and stirring the mixture uniformly. The solvent may be, but is not limited to, N-methylpyrrolidone (NMP).
[0103] Negative electrode plate According to a third aspect, the present application provides a negative electrode plate, the negative electrode plate including a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector, the negative electrode active material layer including a negative electrode active material and a polymer, the polymer including any one of the examples of the first aspect of the present application.
[0104] For example, the negative electrode current collector has two surfaces facing each other in the thickness direction thereof, and the negative electrode active material layer is disposed on either one or both of the two facing surfaces of the negative electrode current collector.
[0105] In some embodiments, the negative electrode active material layer satisfies formula (4): v / λ>1.00; In equation (4), λ represents the porosity of the negative electrode active material layer. v represents the liquid absorption rate of the negative electrode active material layer, and its unit is mg / s.
[0106] The detection methods of λ and v are the same as those of the positive electrode active material layer, and will not be further described here.
[0107] In some embodiments, 3.00 < v / λ < 50.00, and optionally, 3.40 ≤ v / λ ≤ 30.00. Exemplarily, 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 a range consisting of any two of the above numerical values.
[0108] In some embodiments, based on the mass of the negative electrode active material layer, the mass content of the polymer is B%, where 0.2 ≤ B ≤ 5.0.
[0109] When the mass content of the polymer is within the above range, the interfacial performance of the negative electrode active material layer can be significantly improved. Exemplarily, the mass content of the 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 a range consisting of any two of the above numerical values.
[0110] In some embodiments, the negative electrode current collector may employ a metal foil sheet or a composite current collector. For example, as the metal foil sheet, a copper foil may be employed. The composite current collector may include a metal layer formed on at least one surface of a polymer material base layer and a polymer material substrate. The composite current collector can be formed by forming a metal material (such as copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as substrates like polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
[0111] In some embodiments, the negative electrode active material may be any negative electrode active material known in the art. For example, the negative electrode active material may include at least one of artificial graphite, natural graphite, soft carbon, hard carbon, a silicone-based material, a tin-based material, and lithium titanate. The silicone-based material may be selected from at least one of a silicone element, a silicone oxide, a silicone carbon composite, a silicone nitrogen composite, and a silicone alloy. The tin-based material may be selected from at least one of a tin element, a tin oxide, and a tin alloy. However, the present application is not limited to these materials, and other conventional materials usable as battery negative electrode active materials may also be used. These negative electrode active materials may be used alone or in combination.
[0112] In some embodiments, the negative electrode active material layer optionally further comprises a negative electrode adhesive, which may be selected from at least one of styrene butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
[0113] In some embodiments, the negative electrode active material layer further optionally includes a conductive agent, which may be selected from at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
[0114] In some embodiments, the negative electrode active material layer optionally further includes other additives, such as a thickener (eg, sodium carboxymethyl cellulose (CMC-Na)).
[0115] In some embodiments, the negative electrode plate can be manufactured in the following manner: Components for manufacturing the negative electrode plate, such as the negative electrode active material, the polymer, the conductive agent, the adhesive, and any other components, are dispersed in a solvent (e.g., deionized water) to form a negative electrode slurry, which is then coated onto a negative electrode current collector, and the negative electrode plate is obtained after processes such as drying and cold pressing.
[0116] Battery cell According to a fourth aspect, the present application provides a battery cell, the battery cell including a positive electrode plate, a negative electrode plate, a separator disposed between the positive electrode plate and the negative electrode plate, and an electrolyte, the battery cell being a lithium ion battery.
[0117] In some embodiments, the positive electrode plate may be the positive electrode plate of any one of the embodiments of the second aspect of the present application, thereby improving the cycle performance and storage performance of the battery cell, and the negative electrode plate may be a conventional negative electrode plate.
[0118] In some other embodiments, the negative electrode plate may be the negative electrode plate according to any one of the embodiments of the third aspect of the present application, thereby improving the cycle performance and storage performance of the battery cell, and the positive electrode plate may be a conventional positive electrode plate.
[0119] In some further embodiments, the positive electrode plate may be the positive electrode plate according to any one of the embodiments of the second aspect of the present application, and the negative electrode plate may be the negative electrode plate according to any one of the embodiments of the third aspect of the present application, thereby improving the cycle performance and storage performance of the battery cell.
[0120] [Electrolyte] The battery cell further includes an electrolyte, which serves to conduct ions between the positive and negative electrodes. The present application does not specifically limit the type of electrolyte, and the electrolyte may be selected as needed. For example, the electrolyte may be liquid, gel, or all-solid.
[0121] In some embodiments, the electrolyte is an electrolytic solution, which includes an electrolyte salt and a solvent.
[0122] By way of example, the lithium salt may include one or more combinations selected from lithium hexafluorophosphate (LiPF), lithium tetrafluoroborate (LiBF), lithium perchlorate (LiClO), lithium hexafluoroarsenate (LiAsF), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium trifluoromethanesulfonate (LiTFS), lithium difluoro(oxalato)borate (LiDFOB), lithium bis(oxalato)borate (LiBOB), lithium difluorophosphate (LiPOF), lithium difluorobis(oxalato)phosphate (LiDFOP), and lithium tetrafluoro(oxalato)phosphate (LiTFOP).
[0123] By way of example, the organic solvent may comprise one or more combinations 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), 1,4-butyrolactone (GBL), sulfolane (SF), dimethyl sulfone (MSM), ethyl methyl sulfone (EMS), and diethyl sulfone (ESE).
[0124] In some embodiments, the electrolyte solution may further optionally contain additives, such as an additive for forming a negative electrode film or a positive electrode film, and may further include additives that can improve some battery performance, such as an additive for improving the overcharge performance of the battery or an additive for improving the high-temperature or low-temperature performance of the battery.
[0125] [Separator] In some embodiments, the battery cell further includes a separator. The present application does not particularly limit the type of separator, and any known porous separator with good chemical and mechanical stability may be selected.
[0126] In some embodiments, the separator may be made of one or more of glass fiber, nonwoven fabric, polyethylene, polypropylene, and polyvinylidene fluoride. The separator may be a single-layer film or a multi-layer composite film. When the separator is a multi-layer composite film, the materials of each layer may be the same or different.
[0127] In some embodiments, the positive electrode plate, separator, and negative electrode plate can be fabricated into an electrode assembly by a winding process or a stacking process.
[0128] The present application does not particularly limit the shape of the battery cell, which may be cylindrical, rectangular, or any other shape. Figure 1 shows a battery cell 5 with a rectangular structure as an example.
[0129] In some embodiments, as shown in FIGS. 1 and 2 , the exterior body may include a case 51 and a cover plate 53. Here, the case 51 may include a bottom plate and side plates connected to the bottom plate, which together form a surrounding accommodating cavity. The case 51 has an opening communicating with the accommodating cavity, and the cover plate 53 is used to cover the opening to seal the accommodating cavity. The positive electrode plate, the negative electrode plate, and the separator may be formed into an electrode assembly 52 by a winding process or a stacking process. The electrode assembly 52 is packaged in the accommodating cavity. An electrolyte is impregnated into the electrode assembly 52. The number of electrode assemblies 52 included in the battery cell 5 may be one or more and can be adjusted as needed.
[0130] The manufacturing method of the battery cell of the present application is well known. In some embodiments, a battery cell may be formed by assembling a positive electrode plate, a separator, a negative electrode plate, and an electrolyte. For example, the positive electrode plate, the separator, and the negative electrode plate may be formed into an electrode assembly by a winding process or a stacking process, the electrode assembly may be placed in an outer package, dried, and then the electrolyte may be injected. The battery cell may be obtained through processes such as vacuum packaging, standing, chemical conversion, and shaping.
[0131] In some embodiments of the present application, the battery cells according to the present application may be assembled into a battery module, and the number of battery cells included in the battery module may be multiple, and the specific number may be adjusted according to the application and capacity of the battery module.
[0132] Fig. 3 is a schematic diagram of an example battery module 4. As shown in Fig. 3, in the battery module 4, a plurality of battery cells 5 may be arranged in order along the longitudinal direction of the battery module 4. Of course, they may be arranged in any other manner. Furthermore, the plurality of battery cells 5 may be fixed by fasteners.
[0133] Optionally, the battery module 4 may further include a housing having an accommodating space, and the plurality of battery cells 5 are accommodated in this accommodating space.
[0134] In some embodiments, the battery modules may be further assembled into a battery pack, and the number of battery modules included in the battery pack may be adjusted according to the application and capacity of the battery pack.
[0135] Both the battery module 4 and the battery pack may be specific examples of the battery of the present application.
[0136] 4 and 5 are schematic diagrams of an example battery pack 1. As shown in FIGS. 4 and 5, the battery pack 1 may include a battery box and a plurality of battery modules 4 installed in the battery box. The battery box includes an upper housing 2 and a lower housing 3, and the upper housing 2 covers the lower housing 3 and is used to form a sealed space for accommodating the battery modules 4. The plurality of battery modules 4 may be arranged in the battery box in any manner.
[0137] power consumption equipment According to a fifth aspect, the present application provides a power consuming device, the power consuming device including at least one of the battery cell, battery module, and battery pack of the present application. The battery cell, battery module, and battery pack may be used as a power source for the power consuming device or as an energy storage unit for the power consuming device. The power consuming device may be, but is not limited to, a mobile device (e.g., a mobile phone, a laptop, etc.), an electric vehicle (e.g., a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck, etc.), an electric train, a ship, a satellite, an energy storage system, etc.
[0138] A power consuming device may select a battery cell, a battery module, or a battery pack depending on its usage needs. FIG. 6 is a schematic diagram of an example power consuming device. The power consuming device 6 may be a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle. To meet the demand for high power output and high energy density, the power consuming device may employ a battery pack 1 or a battery module. Another example power consuming device may be a mobile phone, a tablet computer, a laptop computer, etc. The power consuming device generally requires a thin design and may employ a battery cell as a power source.
[0139] Example The following describes the examples of this application. The examples described below are illustrative and are intended to help interpret this application, but should not be understood as limitations on this application. If specific techniques or conditions are not specified in the examples, they are carried out according to techniques or conditions described in literature in the field or according to the product instructions. The reagents or equipment used do not indicate the manufacturers, and are all conventional products that are commercially available.
[0140] Example 1 (1) Manufacturing of positive electrode plates: A 12 μm thick aluminum foil was used as the positive electrode current collector.
[0141] A positive electrode slurry was prepared using an ether-based polymer, the positive electrode active material LiFePO4, the conductive agent carbon black, and an adhesive such as polyvinylidene fluoride and N-methylpyrrolidone (NMP). The mass ratio of the ether-based polymer, LiFePO4, the conductive agent carbon black, PVDF, and N-methylpyrrolidone (NMP) in the positive electrode slurry was 0.5:96.8:2:0.7:29. The positive electrode slurry was applied to an aluminum foil current collector, dried at 85°C, cold-pressed, trimmed, cut, and slit, and then dried in a vacuum at 85°C for 4 hours to prepare a positive electrode plate.
[0142] (2) Manufacturing of negative electrode plates: A copper foil with a thickness of 8 μm was used as the negative electrode current collector.
[0143] The negative electrode slurry was prepared by uniformly mixing an ether polymer, artificial graphite as the negative electrode active material, carbon black as the conductive agent, styrene butadiene rubber (SBR) as the adhesive, sodium carboxymethyl cellulose (CMC-Na) as the thickener, and deionized water in a weight ratio of 2.5:94:0.5:2:1:100. The negative electrode slurry was applied to a copper foil current collector, dried at 85°C, and then cold-pressed, trimmed, cut, and slit. The negative electrode plate was then dried at 120°C under vacuum for 12 hours.
[0144] (3) Electrolyte production: 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 in a volume ratio of 3:7 to obtain an electrolyte solvent, which was then mixed with lithium salt LiPF6 to prepare an electrolyte with a lithium salt concentration of 1 mol / L.
[0145] (4) Lithium-ion battery manufacturing: A 16 μm polyethylene film (PE) was used as a separator. The positive electrode plate, separator, and negative electrode plate were stacked in this order, with the separator positioned between the positive and negative electrodes to provide isolation, and then wound up to obtain an electrode assembly. The electrode assembly was placed in an outer case, dried, and then an electrolyte was injected. After vacuum packaging, standing, chemical formation, and shaping, a lithium-ion battery was obtained.
[0146] Comparative Example 1 A lithium ion battery was manufactured using a method similar to that of Example 1, but the difference from Example 1 is that no ether-based polymer was added to the positive electrode plate of Comparative Example 1, and no ether-based polymer was added to the negative electrode plate of Comparative Example 1.
[0147] Comparative Example 2 A lithium ion battery was manufactured using a method similar to that of Example 1, but the difference from Example 1 is that the positive electrode plate and the negative electrode plate of Comparative Example 2 were made of ether-based polymer materials.
[0148] Examples 2 to 4 The lithium ion batteries were manufactured using a method similar to that of Example 1, but the difference from Example 1 is that the positive electrode plate and the negative electrode plate of Examples 2 to 4 were made of ether-based polymer materials.
[0149] Example 5 A lithium ion battery was manufactured using a method similar to that of Example 1, but the difference from Example 1 is that an ether-based polymer was added to the positive electrode plate of Example 5, and no ether-based polymer was added to the negative electrode plate of Example 5.
[0150] Example 6 A lithium ion battery was manufactured using a method similar to that of Example 1, but the difference from Example 1 is that an ether-based polymer was added to the negative electrode plate of Example 6, but no ether-based polymer was added to the positive electrode plate of Example 6.
[0151] The data for the examples and comparative examples are shown in Table 1.
[0152] Test part 1. Lithium-ion battery capacity retention rate test The lithium-ion batteries fabricated in the examples and comparative examples were charged to 4.25 V at a constant current of 1 / 3 C at room temperature, then charged to 0.05 C at a constant voltage of 4.25 V, left for 5 minutes, and then discharged to 2.8 V at 1 / 3 C. The resulting capacity was designated as the initial capacity C0. The batteries were then adjusted to 97% SOC and stored at 60°C. The same batteries were repeatedly charged and the discharge capacity Cn was recorded every 30 days. The battery capacity retention Pn after each 30 day was calculated as Cn / C0 * 100%. A dot graph of the battery capacity retention versus storage days was created by plotting the values of five points P1, P2...P5 as the ordinate and the corresponding storage time as the abscissa. The battery capacity retention data in Table 1 is the data measured after 120 days of storage under the above test conditions, i.e., the P5 value.
[0153] 2. DC impedance test for lithium-ion batteries The lithium-ion batteries manufactured in the examples and comparative examples were charged at 25°C to 4.25V at a constant current of 1 / 3C, then further charged to a current of 0.05C at a constant voltage of 4.25V, and allowed to stand for 5 minutes. The voltage V1 was recorded. After a further 30 seconds at 1 / 3C, the voltage V2 was recorded. The voltage was calculated as (V2 - V1) / 1 / 3C, giving the battery's internal resistance (DCR1) after the first cycle. These batteries were charged at a constant current of 1 / 3C to 4.25V at room temperature, then further charged to a current of 0.05C at a constant voltage of 4.25V, allowed to stand for 5 minutes, and then discharged to 2.8V at 1 / 3C. The resulting capacity was designated as the initial capacity (C0). The batteries were then adjusted to 97% state of charge (SOC) and stored at 60°C. The above steps were repeated for the same battery every 30 days, and the internal resistance DCRn (n = 1, 2, 3, 4, 5) of the battery at the nth time was recorded at the same time. The values of the five points DCR1, DCR2, DCR3, DCR4, and DCR5 were taken as the ordinate and the corresponding number of cycles as the abscissa to obtain a curve diagram of the battery discharge DCIR versus the number of days of storage.
[0154] The battery internal resistance increase rate in Table 1 is (DCRn-DCR1) / DCR1*100%, and the data in Table 1 is measured after storing for 120 days under the above test conditions.
[0155] Test Results
[0156] [Table 1]
[0157] In Table 1, 100% ethylene oxide means that the mass content of ethylene oxide is 100% based on the total mass of Monomer 1 and Monomer 2.
[0158] 80% ethylene oxide means that based on the total mass of monomer 1 and monomer 2, the mass content rate of ethylene oxide is 80%, and 20% 2-ethyl ethylene oxide means that based on the total mass of monomer 1 and monomer 2, the mass content rate of 2-ethyl ethylene oxide is 20%.
[0159] As can be seen from Table 1, compared with Comparative Example 1, the examples of the present application improved the cycle performance and storage performance of the lithium-ion battery by adding the polymer of the present application to the positive electrode plate and / or the negative electrode plate. Compared with Comparative Example 2, in the examples of the present application, when 1 < K < ∞, especially when 1 < K ≤ 100 is satisfied, and further when 1 < K ≤ 10 is satisfied, its molecular chain arrangement tends to loosen, the interaction force between molecular chains is relatively small, adjacent molecular chains are easily opened, and chain segment movement is realized by intramolecular rotation, forming a molecular chain structure with relatively high flexibility, and the cycle performance and storage performance of the lithium-ion battery can be more significantly improved.
[0160] The present application has been described with reference to the preferred embodiments, but various improvements may be made thereto without departing from the scope of the present application, and members thereof may be replaced with equivalents. In particular, as long as there is no structural conflict, each technical feature mentioned in each embodiment may be combined in any manner. The present application is not limited to the specific embodiments disclosed herein, but includes all technical solutions included within the scope of the claims.
Explanation of Reference Signs
[0161] The explanation of the reference signs is as follows: 1, battery pack; 2, upper housing; 3, lower housing; 4, battery module; 5, battery cell; 51, case; 52, electrode assembly; 53, cover plate; 6, power consumption device.
Claims
1. A polymer including an ether-based polymer for use in a battery cell, The ether-based polymer is prepared as a sheet-like structure, The sheet-like structure is subjected to a dynamic frequency scanning test at (Tm+20)°C to obtain an elastic modulus G'-loss modulus G" curve, the slope of the elastic modulus G'-loss modulus G" curve is K, where 1<K<∞, and Tm°C represents the melting temperature of the ether-based polymer.
2. 2. The polymer of claim 1, wherein 1<K≦100, and optionally 1<K≦10.
3. The polymer according to claim 1 or 2, wherein the glass transition temperature of the ether-based polymer is Tg, and its unit is ° C., and −100≦Tg≦50, and optionally −80≦Tg≦30.
4. The ether-based polymer comprises a structural unit represented by formula (I): In formula (I), R 1 and R 2 each independently contains a hydrogen atom, a substituted or unsubstituted C1 to C3 alkyl group, or a substituted or unsubstituted C1 to C3 alkoxy group, R 3 contains a substituted or unsubstituted C1-C5 methylene group, Optionally, R 1 and R 2 each independently contain a hydrogen atom, a substituted or unsubstituted C1-C2 alkyl group, and / or R 3 The polymer of any one of claims 1 to 3, wherein comprises a single bond, a substituted or unsubstituted C1 to C4 methylene group.
5. The ether-based polymer comprises structural units represented by formula (I-1) to (I-8): The polymer of claim 4 comprising at least one of:
6. The ether-based polymer comprises a structural unit represented by formula (II): In formula (II), R 4 ~R 7 each independently contains a hydrogen atom, a substituted or unsubstituted C1 to C3 alkyl group, a substituted or unsubstituted C1 to C3 alkoxy group, or an ether group, and R 4 ~R 7 at least one of contains a substituted or unsubstituted C1-C3 alkoxy group or ether group, Optionally, R 4 ~R 7 each independently contains a hydrogen atom, a substituted or unsubstituted C1-C2 alkyl group, a substituted or unsubstituted C1-C2 alkoxy group, or an ether group, and R 4 ~R 7 The polymer according to any one of claims 1 to 5, wherein at least one of comprises a substituted or unsubstituted C1-C2 alkoxy group or ether group.
7. The ether-based polymer comprises a structural unit represented by formula (II-1) to a structural unit represented by formula (II-7): The polymer of claim 6, comprising at least one of:
8. n is a positive integer selected from 1500 to 25000, and / or The molecular weight of the ether polymer is 1.2×10 5 g / mol~1.0×10 6 8. The polymer of claim 4, wherein the molecular weight is 1000 or more.
9. adding the polymer to a first solvent at 45°C to form a polymer system; The polymer system is allowed to stand at 45°C for 8 hours, and then allowed to stand at 25°C for ≥ 24 hours, after which the polymer system is filtered through a 200 mesh filter to leave a first substance; wherein the mass of the polymer is n and its unit is g, the mass of the first substance is m and its unit is g, and the polymer and the first substance satisfy 5≦m / n≦1000.
10. 10. A positive electrode plate comprising: a positive electrode current collector; and a positive electrode active material layer disposed on the positive electrode current collector, wherein the positive electrode active material layer comprises a positive electrode active material and a polymer, and the polymer comprises the polymer according to any one of claims 1 to 9.
11. 10. A negative electrode plate comprising: a negative electrode current collector; and a negative electrode active material layer disposed on the negative electrode current collector, wherein the negative electrode active material layer comprises a negative electrode active material and a polymer, and the polymer comprises the polymer according to claim 1.
12. A battery cell including a positive electrode plate and a negative electrode plate, The positive electrode plate comprises the positive electrode plate according to claim 10; and / or A battery cell, wherein the negative electrode plate comprises the negative electrode plate of claim 11.
13. A battery comprising the battery cell of claim 12.
14. 14. A power consuming device comprising the battery of claim 13.
Citation Information
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