WO2023240681A1 - Matériau d'accélération du transfert de masse et de réduction de la dilatation pour électrode négative et utilisation - Google Patents

Matériau d'accélération du transfert de masse et de réduction de la dilatation pour électrode négative et utilisation Download PDF

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WO2023240681A1
WO2023240681A1 PCT/CN2022/101806 CN2022101806W WO2023240681A1 WO 2023240681 A1 WO2023240681 A1 WO 2023240681A1 CN 2022101806 W CN2022101806 W CN 2022101806W WO 2023240681 A1 WO2023240681 A1 WO 2023240681A1
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mass transfer
negative electrode
lithium
accelerating
component
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PCT/CN2022/101806
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English (en)
Chinese (zh)
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郭立超
王亚
孔令丽
郭纪
张志荣
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天津力神电池股份有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the fields of electrochemical technology and electrochemical energy storage, and specifically relates to a material and application for accelerating mass transfer and improving expansion of a negative electrode.
  • high compaction negative electrodes In order to extend the battery life of electronic devices, it is necessary to increase the energy density of battery cells.
  • the development and application of negative electrodes with high compaction density (referred to as high compaction negative electrodes) can effectively increase the energy density and specific energy of the battery core; however, there are also some problems, such as: high cyclic expansion stress of the negative electrode material, The thickness of the pole piece increases rapidly, causing the thickness of the battery core to exceed the standard; the high-pressure compacted negative electrode has low porosity, large tortuosity, small net liquid volume, poor lithium ion transmission conditions, and large reaction polarization.
  • the high-pressure compacted negative electrode active material has Charging capacity is often poor, and lithium precipitation side reactions are prone to occur, causing capacity attenuation and thickness expansion of the battery core. Therefore, high-energy electrochemical devices containing high-pressure anodes have average rate and cycle performance, and the cell thickness expansion rate is high. In particular, the capacity retention rate and thickness control of low-temperature cycles are not ideal.
  • the purpose of the present invention is to overcome the shortcomings of the prior art and provide a material and application for accelerating mass transfer and improving expansion of the negative electrode;
  • a material for accelerating mass transfer and improving expansion of the negative electrode which is characterized in that it includes at least one component of a mass transfer accelerating component I and a mass transfer accelerating component II;
  • the accelerated mass transfer component I is a multi-component copolymer; the multi-component copolymer is formed by copolymerization of styrene, olefins and mass transfer functional monomers; wherein the molar ratio of styrene:olefin is ⁇ 3.0; the mass transfer functional monomer : The molar ratio of the sum of the amounts of styrene and olefins is 0.05-0.25; the mass transfer functional monomer is one or a combination of an enoate ester monomer and a lithium olefin monomer;
  • the multi-component copolymer in this application can adopt random copolymerization, graft copolymerization or block copolymerization; its preparation method can adopt the existing preparation process, and only needs to meet its molar ratio.
  • the accelerated mass transfer component II is a polymer, and the polymer is carboxymethylcellulose lithium, polyacrylic acid-carboxymethylcellulose lithium copolymer, polybutyric acid-carboxymethylcellulose lithium copolymer One or a combination of polymethacrylic acid-lithium carboxymethyl cellulose copolymer.
  • binders such as styrene-butadiene rubber (containing carboxyl groups), although they have relatively strong interaction with current collectors and have good toughness, do not significantly promote the transmission of electrolyte. Especially when it is applied to a high-pressure anode, the rate and low-temperature performance are poor; another example is styrene-acrylate polymer, although it significantly promotes the transmission of electrolyte and has excellent low-temperature performance, but the adhesive force Poor, with poor deformation resistance, the pole piece is easy to swell, and the cycle expansion at room temperature and high temperature is large.
  • the accelerated mass transfer component I contains both rigid segments and mass transfer functional segments.
  • the rigid segment with the above-mentioned styrene:olefin molar ratio makes the accelerated mass transfer component I have sufficient stiffness and good toughness. , which can suppress the violent expansion of the volume of the negative active material;
  • the mass transfer functional chain segment with the above content has a certain polarity and is well wetted with the electrolyte, which can accelerate the transmission of lithium ions and prevent the lithium evolution reaction. occurrence, improve the capacity retention rate and reduce the thickness expansion rate; in addition, when the accelerating mass transfer chain segment contains removable lithium, the rate and cycle performance of the battery core can be further improved.
  • the polymerized monomer of olefin is butadiene, propylene, or butene.
  • the mass transfer functional segment includes an oxygen-containing mass transfer polymer segment.
  • the polymerized monomer of the oxygen-containing mass transfer polymer segment is one or a combination of acrylate monomers and lithium acrylate monomers, and the above components are used to improve electrolyte infiltration and ion transmission kinetics.
  • the acrylic acid ester monomer is one or a combination of acrylate, crotonic acid ester, methacrylate or derivatives of the above monomers;
  • the acrylic acid lithium monomer is lithium acrylate, butyl acrylate.
  • Lithium enoate monomers contain free lithium, which is beneficial to lithium ion transport.
  • the polymerized monomer of the oxygen-containing mass transfer polymer segment may also include substructural segments containing lone pairs of electrons, such as polyethylene glycol or polyethyleneimine.
  • the medium particle size (D50) range of the accelerated mass transfer component I is 100-250 nm, ensuring that it has sufficient contact points with the negative active material and current collector.
  • Accelerated mass transfer component II is carboxymethyl cellulose lithium, polyacrylic acid-carboxymethyl cellulose lithium copolymer, polybutyric acid-carboxymethyl cellulose lithium copolymer, polymethacrylic acid-carboxymethyl cellulose lithium copolymer One or a combination of copolymers.
  • the accelerated mass transfer component II itself contains freely migrating lithium ions, which promotes the transport of lithium ions.
  • This application also includes an application of the extremely accelerated mass transfer material, which is applied to negative electrode powder;
  • the negative electrode powder includes a negative electrode active material and a binder including the accelerating mass transfer component I in the negative electrode accelerating mass transfer material;
  • the negative electrode powder includes a negative electrode active material and a binder including the accelerated mass transfer component II in the negative electrode accelerated mass transfer material;
  • the negative electrode powder includes a negative electrode active material, a binder including the mass transfer accelerating component I and the mass transfer accelerating component II in the negative electrode accelerating mass transfer material;
  • the negative electrode powder includes a negative electrode active material, a binder including the mass transfer accelerating component I and the mass transfer accelerating component II in the negative electrode accelerating mass transfer material, and a conductive agent;
  • the sum of the mass fractions of the accelerated mass transfer component I and the accelerated mass transfer component II in the negative electrode powder layer is 0.5-3.5%.
  • the mass proportion of mass transfer accelerating component I in the negative electrode powder layer is 0.7-1.3%; the mass proportion of mass transfer accelerating mass transfer component II in the negative electrode powder layer is 0.5-1.0%.
  • the negative active material may include, but is not limited to, graphite, silicon, silicon oxygen, prelithiated silicon oxygen, silicon carbon, and prelithiated silicon carbon. , tin, phosphorus, oxides, prelithiated oxides, sulfides, prelithiated sulfides and other materials.
  • the negative active material must meet the processing requirements of high-pressure compacted pole pieces. The surface of the rolled pole pieces is flat and smooth, without wrinkles or overpressure, and the negative electrode material will not be broken.
  • the conductive agent can include one or a combination of conductive carbon black and one-dimensional carbon nanomaterials.
  • One-dimensional carbon nanomaterials include multi-walled carbon nanotubes, single-walled carbon nanotubes, carbon nanofibers, etc., which can form a long-range continuous conductive network, reduce ohmic voltage drop, and improve the voltage platform; or they can be used with high-capacity negative electrodes such as silicon and tin. , enhance the continuity of the conductive network.
  • This application also includes a negative electrode, including a negative electrode current collector and the negative electrode powder.
  • a negative electrode current collector can include but is not limited to copper foil, coated copper foil, carbon-coated copper foil, lithium-plated copper foil, alloy foil, perforated foil, Foam metal, etc.
  • the rolling process involved in this application can be a single rolling process to reach the specified compaction density, or it can be two or more times of rolling to reach the specified compaction density. It is necessary to ensure that the pole pieces do not over-pressure.
  • the application also includes an electrochemical device, including a positive electrode, the negative electrode, a porous separator, and an electrolyte.
  • the electrochemical device of this application has no special limitations on the positive electrode piece of the positive electrode, as long as it meets the purpose of this application.
  • the positive electrode piece includes a positive electrode powder layer.
  • the positive electrode powder layer includes positive electrode active materials, and the positive electrode active materials include but are not limited to one or more of lithium-transition metal oxides, lithium-transition metal phosphates, lithium-fluorinated transition metal phosphates, etc.; among the above materials, A "transition metal” can be one transition metal element or two or more transition metal elements.
  • the positive electrode powder layer may also include a positive electrode binder.
  • the positive electrode binder includes but is not limited to one or more types of polyvinylidene fluoride, polyacrylic acid, lithium polyacrylate, and the like.
  • the positive electrode powder layer may also include a conductive agent for the positive electrode.
  • the conductive agent for the positive electrode includes but is not limited to one or more types of carbon black, carbon tube, graphene, and carbon fiber.
  • the positive electrode sheet can also include a positive current collector.
  • a positive current collector can be but is not limited to aluminum foil, coated aluminum foil, carbon-coated aluminum foil, Alloy foil, foam metal, etc.
  • the electrochemical device of the present application may also include a porous separator that isolates the positive and negative electrodes and conducts the electrolyte.
  • the electrochemical device of the present application has no special limitations on the separator, as long as it meets the purpose of the present application.
  • the porous separator can be, but is not limited to, PE separator, PP separator, multi-layer composite separator (such as PP/PE/PP), rubber-coated separator, rubber-coated ceramic separator, aramid separator, non-woven separator, etc.
  • the electrochemical device of this application also includes an electrolyte.
  • the electrolyte can be in a liquid state, a semi-gel state, a gel state, etc. This application does not impose special restrictions on the electrolyte solution, as long as it meets the purpose of this application.
  • the electrochemical device of this application also includes a collector ear and a packaging shell. This application does not impose special restrictions on this, as long as it meets the purpose of this application.
  • the structure of the electrochemical device of the present application can be, but is not limited to, any of winding, lamination, etc.
  • the type of electrochemical device is not limited and may be, but is not limited to, primary batteries, secondary batteries, supercapacitors, ion-supercapacitor hybrid devices, etc.
  • the manufacturing process of the electrochemical device of this application is well known in the industry and is not particularly limited.
  • the present application also includes an electronic device including the electrochemical device described above.
  • electronic equipment may include but is not limited to laptop computers, wearable devices, mobile phones, game consoles, cameras, televisions, recording equipment, video equipment, lighting equipment, power tools, energy storage modules, automobiles , unmanned aircraft, etc.
  • the accelerating mass transfer component I of the present application can simultaneously enhance the charge and discharge capacity and control the cyclic expansion of high temperature, medium temperature and low temperature.
  • the main function of the accelerating mass transfer component II is to enhance the charging capacity and control the low temperature cyclic expansion; preferably, when accelerating mass transfer
  • the mass material group contains both accelerated mass transfer components I and accelerated mass transfer components II, which can significantly improve the comprehensive performance of electrochemical devices such as cycle, rate, and low temperature.
  • the accelerating mass transfer component I, accelerating mass transfer component II and one-dimensional carbon nanomaterials are simultaneously applied to the high-pressure anode to build an effective ion and electronic conductive network, further reducing the impedance of electrochemical reactions and mass transfer, and improving power. Learn to reduce the occurrence of side effects.
  • Mass transfer accelerating component I if it only improves expansion at medium and low temperatures, may contain at least one of mass transfer accelerating component I and mass transfer accelerating component II. If you only need to improve the cycle capacity retention rate, it is enough to include at least one of the mass transfer accelerating component I and the mass transfer accelerating component II.
  • This application also proposes a negative electrode, an electrochemical device and an electronic device including the negative electrode.
  • the negative electrode includes a negative electrode accelerating mass transfer material. Each component is flexibly matched.
  • the accelerating mass transfer material can improve material transmission efficiency and prevent lithium precipitation. Improve capacity retention.
  • the technology of this application can significantly improve the low temperature, rate, cycle and other performance of high-energy electrochemical devices.
  • Figure 1 is a schematic diagram of the principle.
  • Figure 3 is a comparison chart of the thickness expansion rates after the 0°C cycle between the Example and the blank control group.
  • Figure 4 is a comparison chart of the thickness expansion rates after the 45°C cycle between the embodiment and the blank control group.
  • electrochemical devices used in the following examples are lithium ion secondary batteries, but the electrochemical devices involved in this application are not limited to lithium ion secondary batteries.
  • the following three tests were performed on the blank control group and example samples.
  • I 0 be the current corresponding to 0.1C
  • I 1 be the current corresponding to 1C.
  • Fresh batteries that have not been tested for electrical performance are placed in a constant temperature box at 25°C for more than 1 hour, discharged to 3V with a constant current of I 0 ; left to stand for 10 minutes; charged with a constant current of I 0 for 5 hours (the final instantaneous voltage is recorded as U 0 ), and then charge with a constant current I 1 for 1 s (the final instantaneous voltage is recorded as U 1 ).
  • I 00 be the current corresponding to 0.1C
  • I 01 be the current corresponding to 0.5C.
  • Fresh batteries that have not been tested for electrical performance are placed in a constant temperature box at 0°C for more than 2 hours, discharged to 3V with a constant current of I 00 ; left to stand for 10 minutes; charged with a constant current of I 00 for 5 hours (the final instantaneous voltage is recorded as U 00 ), and then charge with constant current I 01 for 0.5s (the end instant voltage is recorded as U 01 ).
  • Thickness expansion rate (T 1 /T 0 -1)*100%
  • Thickness expansion rate (T 1 /T 0 -1)*100%
  • Negative electrode production Mix artificial graphite, acetylene black, sodium carboxymethylcellulose, and styrene-butadiene rubber according to the mass ratio of 97.5:0.4:0.8:1.3, add deionized water to adjust the viscosity, and then apply and roll (compacted density 1.75 g/cm 3 ), shearing and other processes to complete the production of pole pieces.
  • Positive electrode production Mix lithium cobalt oxide, conductive carbon black, and polyvinylidene fluoride at a mass ratio of 98:1:1, add NMP to adjust the viscosity, and complete the production of the electrode piece through processes such as coating, rolling, and shearing.
  • Battery core production Use the above-mentioned negative electrode and positive electrode to make a wound battery core. After the battery core is chemically separated and sorted, the electrical performance test is performed.
  • Example 1 except "mix artificial graphite, acetylene black, sodium carboxymethylcellulose, styrene-butadiene rubber, and styrene-butadiene-isobutylene ester in a mass ratio of 97.5:0.4:0.8:0.6:0.7". Same as the blank control group.
  • Example 2 Except for “mixing artificial graphite, acetylene black, sodium carboxymethyl cellulose, and styrene-butadiene-isobutylene ester according to the mass ratio of 97.5:0.4:0.8:1.3", everything else is the same as the blank control group .
  • Example 3 Except for “mixing artificial graphite, acetylene black, sodium carboxymethylcellulose, and styrene-butadiene-propylene ester according to the mass ratio of 97.5:0.4:0.8:1.3", everything else is the same as the blank control group .
  • Example 4 Except for “mixing artificial graphite, acetylene black, sodium carboxymethyl cellulose, and styrene-propylene-isobutylene ester in a mass ratio of 97.5:0.4:0.8:1.3", everything else was the same as the blank control group.
  • Example 5 Except for “mixing artificial graphite, acetylene black, sodium carboxymethylcellulose, and styrene-butadiene-lithium acrylate according to a mass ratio of 97.5:0.4:0.8:1.3", everything else is the same as the blank control group .
  • Example 6 Except for “mixing artificial graphite, acetylene black, sodium carboxymethyl cellulose, styrene-butadiene-methacrylate-acrylonitrile according to the mass ratio of 97.5:0.4:0.8:1.3", all others were mixed with The blank control group was the same.
  • Example 7 Except “mix artificial graphite, acetylene black, sodium carboxymethyl cellulose, styrene-butadiene-isobutylene (n-glycol) lithium diacrylate according to the mass ratio of 97.5:0.4:0.8:1.3" Except for this, everything else was the same as the blank control group.
  • Example 8 Except for “mixing artificial graphite, acetylene black, sodium carboxymethylcellulose, polyacrylic acid-lithium carboxymethylcellulose, and styrene-butadiene rubber in a mass ratio of 97.5:0.4:0.3:0.5:1.3", other All were the same as the blank control group.
  • Example 9 Except for “mixing artificial graphite, acetylene black, polyacrylic acid-lithium carboxymethylcellulose, and styrene-butadiene rubber in a mass ratio of 97.5:0.4:0.8:1.3", everything else was the same as the blank control group.
  • Example 10 Except for “mixing artificial graphite, acetylene black, polyacrylic acid-lithium carboxymethylcellulose, and styrene-butadiene rubber in a mass ratio of 97.5:0.4:1.0:1.1", everything else was the same as the blank control group.
  • Example 11 Except for “mixing artificial graphite, acetylene black, polyacrylic acid-lithium carboxymethyl cellulose, and styrene-butadiene-isobutylene ester according to the mass ratio of 97.5:0.4:0.8:1.3", the others were all with the blank The control group was the same.
  • Example 12 In addition to “mixing artificial graphite, acetylene black, polyacrylic acid-lithium carboxymethyl cellulose, styrene-butadiene-isobutylene ester, and carbon fiber according to the mass ratio of 97.5:0.3:0.8:1.3:0.1", Others were the same as the blank control group.
  • Example 2 53.0 131.1
  • Example 3 53.1 131.4
  • Example 4 53.2 131.0
  • Example 5 52.8 129.4
  • Example 6 53.1 131.8
  • Example 7 52.6 128.9
  • Example 8 53.7 138.3
  • Example 9 53.1 130.8
  • Example 10 53.3 130.5
  • Example 11 52.0 122.7
  • Example 12 51.5 121.0
  • FIG. 1 is a schematic diagram of the principle; as shown in Figures 2 and 3, the blank control sample uses a traditional binder, which has the worst kinetics, the cycle capacity retention rate continues to decay, the thickness after cycles expands by more than 9%, and the dissection found that the battery core analyzed Lithium; the low-temperature cycle performance of sample A (Example 2), sample B (Example 9), and sample C (Example 11) is significantly better than the blank control sample, which shows that the accelerated mass transfer material group can effectively increase the lithium ion transfer rate , inhibiting the occurrence of lithium evolution and improving the low-temperature cycle performance of electrochemical devices containing the above-mentioned high-compact negative electrode.
  • the low-temperature cycle performance of sample C is better than that of sample A and sample B.
  • the accelerated mass transfer component I and the accelerated mass transfer component II have a synergistic effect, and their simultaneous application can further enhance the improvement effect.
  • Figure 4 is a comparison chart of the thickness expansion rates after the 45°C cycle of the embodiment and the blank control group.
  • the cyclic expansion rate of sample A and sample C is less than that of the blank control, and the thickness expansion rate of sample B is similar to that of the blank control. This shows that the accelerated mass transfer component I has the effect of improving high temperature cycle expansion.

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Abstract

La présente invention concerne un matériau d'accélération du transfert de masse et de réduction de la dilatation pour une électrode négative et son utilisation. Le matériau d'accélération du transfert de masse et de réduction de la dilatation pour une électrode négative comprend au moins l'un d'un constituant d'accélération de transfert de masse I et d'un constituant d'accélération de transfert de masse II, le constituant d'accélération de transfert de masse I étant un mélange de polymères, le mélange de polymères comprenant du styrène, une oléfine et des segments fonctionnels de transfert de masse, et le constituant d'accélération de transfert de masse II étant l'un parmi la carboxyméthylcellulose lithiée et un copolymère d'acide polyacrylique/(iso)buténoïque/carboxyméthylcellulose lithiée ou une combinaison de ceux-ci. Lesdits deux constituants peuvent améliorer la capacité de charge d'une électrode négative, supprimer le placage de lithium et réguler le taux de dilatation par cycle, ce qui permet d'améliorer les propriétés de cycle, de vitesse et à basse température d'un dispositif électrochimique à haute énergie. En outre, lorsque le matériau d'accélération du transfert de masse contient simultanément le constituant d'accélération de transfert de masse I ainsi que le constituant d'accélération de transfert de masse II, l'effet d'amélioration sur les propriétés globales du dispositif électrochimique est relativement remarquable.
PCT/CN2022/101806 2022-06-15 2022-06-28 Matériau d'accélération du transfert de masse et de réduction de la dilatation pour électrode négative et utilisation WO2023240681A1 (fr)

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CN105849943A (zh) * 2014-01-29 2016-08-10 日本瑞翁株式会社 锂离子二次电池电极用浆料组合物、锂离子二次电池用电极及锂离子二次电池
CN107925058A (zh) * 2016-03-29 2018-04-17 株式会社Lg化学 二次电池用负极、其制造方法及包含其的二次电池
CN113851608A (zh) * 2020-06-26 2021-12-28 Sk新技术株式会社 用于锂二次电池的负极和包含其的锂二次电池
CN113773510A (zh) * 2021-09-07 2021-12-10 重庆理工大学 一种羧甲基纤维素锂接枝聚丙烯酸锂的生产方法
CN114335422A (zh) * 2021-12-30 2022-04-12 珠海冠宇电池股份有限公司 一种负极片和包括该负极片的锂离子电池

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