CN111697270B - Method for forming negative electrode protection layer through in-situ transfer - Google Patents
Method for forming negative electrode protection layer through in-situ transfer Download PDFInfo
- Publication number
- CN111697270B CN111697270B CN201910190086.1A CN201910190086A CN111697270B CN 111697270 B CN111697270 B CN 111697270B CN 201910190086 A CN201910190086 A CN 201910190086A CN 111697270 B CN111697270 B CN 111697270B
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- CN
- China
- Prior art keywords
- lithium
- coating
- negative electrode
- reaction
- ion battery
- Prior art date
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Images
Classifications
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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Abstract
The invention provides a method for forming a negative electrode protection layer through in-situ transfer. The initial raw materials form a coating on the diaphragm, the preparation process is simple, and the preparation conditions are loose. The reaction occurs inside the cell and is transferred to the surface of the cathode through the reaction without additional control of the water-oxygen conditions. The protective layer and the surface of the negative electrode form a whole body due to reaction, and the interface impedance between the protective layer and the negative electrode is reduced, so that the cycle life of the corresponding battery is prolonged. The protective layer can effectively influence the lithium deposition behavior in the circulation process on the surface of the negative electrode, and is beneficial to improving the stability of the corresponding negative electrode and the safety of the battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a method for forming a negative electrode protection layer through in-situ transfer.
Background
The lithium ion battery has the advantages of high specific capacity, long cycle life, environmental protection and the like, is one of the main representatives of the high-performance secondary battery at present, and is widely applied to different fields of various electronic devices, electric or hybrid electric vehicles, aerospace and the like. The lithium ion battery mainly comprises four parts, namely an anode, a cathode, a diaphragm and an electrolyte, wherein the cathode material at present mostly adopts a carbon cathode, the theoretical specific capacity of the carbon cathode is relatively low (372mAh/g), and the carbon cathode is difficult to meet the increasing demand. Therefore, novel negative electrode materials such as silicon carbon electrodes and lithium metal electrodes need to replace carbon materials to become novel negative electrodes. The theoretical specific capacity of the lithium metal is 3860mAh/g, and the lithium metal is the negative electrode material with the highest known specific capacity at present, so that the lithium metal is expected to become the optimal negative electrode material of the next-generation lithium battery. However, the lithium metal cathode is very easy to form dendritic lithium deposition in the circulation process, and can pierce through the diaphragm to cause short circuit of the battery, so that thermal runaway is caused, and finally, fire and even explosion occur to bring potential safety hazards. In addition, irregular deposition generated by lithium ions in the circulation process is easy to fall off from the surface of a lithium metal electrode and scatter on the surface of the electrode, so that electrons cannot be lost continuously to participate in reaction to form dead lithium, and the internal interface internal resistance of the battery is increased, so that the coulomb efficiency of the battery is reduced, the specific capacity is attenuated, and the service life is shortened. Similarly, silicon-carbon cathodes and the like also face similar problems, and therefore, how to effectively solve the two problems of safety, cycle capacity and service life of the cathodes becomes a research object of researchers at present.
Currently, research on the negative electrode of the lithium ion battery mainly focuses on the following aspects: firstly, an effective additive is added into a battery electrolyte, so that the deposition behavior of lithium ions on the surface of a negative electrode is reasonably improved, and a stable interface layer is formed in an auxiliary manner; secondly, a coating is added on the battery diaphragm, so that the tolerance degree of the diaphragm to dendritic crystals is increased, and the overall safety performance of the battery is improved; and thirdly, the surface or the structure of the negative electrode is improved, lithium ions are induced to be uniformly deposited or are limited to be deposited in a specific area, and dendritic lithium crystals are reduced. The negative electrode plate, especially the lithium metal plate, is very active and is easy to react with water, oxygen and the like, so in the process of modifying the negative electrode, the experimental conditions need to be strictly controlled, and the difficulty of wide application of the corresponding method is increased. In addition, the increased internal interfacial resistance between the protective layer and the negative electrode is also a concern of researchers, and if the protective layer and the negative electrode cannot be in effective contact with each other, the influence of the protective layer on the deposition behavior of lithium ions may be reduced, and the additionally increased internal interfacial resistance also reduces the cycle performance of the battery.
In addition, the technical means for modifying the diaphragm is relatively mature at present, a large number of polyolefin diaphragms coated with ceramic are available in the market, and the ceramic layer of the polyolefin diaphragm mainly has the function of improving the thermal shrinkage performance of the diaphragm, so that the safety performance of the battery is improved. The coating on the separator, when assembled in a battery, is typically in macroscopic contact with the negative electrode, with interfacial problems between the two, and therefore the coating has a relatively small effect on the lithium ion deposition behavior on the negative electrode.
Disclosure of Invention
In order to overcome the defects in the prior art, the first aspect of the invention provides a method for preparing a lithium ion battery negative electrode protective layer in an in-situ transfer mode, which comprises the following steps:
contacting the diaphragm coated with the coating with the lithium ion battery cathode, reacting, and obtaining a protective layer on the surface of the lithium ion battery cathode; the reactions include, but are not limited to, intercalation reactions and redox reactions; the reaction is carried out under the condition of certain external voltage; the raw material for forming the coating comprises at least one of the following coating materials: phosphates, manganates, carbonates, metal hydroxides, inorganic solid electrolyte materials, inorganic semiconductor materials and transition metal oxides that can react with lithium.
The second aspect of the invention provides a preparation method of a lithium ion battery, which comprises the above method for preparing the lithium ion battery negative electrode protective layer in an in-situ transfer manner.
The third aspect of the invention provides a lithium ion battery, which is prepared by the preparation method of the lithium ion battery.
The invention has the beneficial effects that:
the invention provides a method for preparing a lithium ion battery cathode protective layer in an in-situ transfer mode. The initial raw materials form a coating on the diaphragm, the preparation process is simple, and the preparation conditions are loose. The reaction occurs inside the cell and is transferred to the surface of the cathode through the reaction without additional control of the water-oxygen conditions. The protective layer and the surface of the negative electrode form a whole body due to reaction, and the interface impedance between the protective layer and the negative electrode is reduced, so that the cycle life of the corresponding battery is prolonged. The protective layer can effectively influence the lithium deposition behavior in the circulation process on the surface of the negative electrode, and is beneficial to improving the stability of the corresponding negative electrode and the safety of the battery.
Compared with the modification of the negative electrode which is completed before the negative electrode is assembled into the battery in the prior art, the modification of the negative electrode is completed after the battery is assembled into the battery. The method does not need to consider the influence on the cathode in the modification process, and particularly does not need to strictly control the water oxygen content in the preparation process when aiming at the lithium metal cathode, so that the preparation cost and the preparation difficulty are greatly reduced.
Drawings
Fig. 1 is a scanning electron microscope picture of the coating transfer compounded on the surface of the negative electrode obtained in example 1.
Detailed Description
As mentioned above, the first aspect of the present invention provides a method for preparing a lithium ion battery negative electrode protection layer in an in-situ transfer manner, the method comprising:
contacting the diaphragm coated with the coating with the lithium ion battery cathode, reacting, and obtaining a protective layer on the surface of the lithium ion battery cathode; the reactions include, but are not limited to, intercalation reactions and redox reactions; the reaction is carried out under the condition of certain external voltage; the raw material for forming the coating comprises at least one of the following coating materials: phosphates, manganates, carbonates, metal hydroxides, inorganic solid electrolyte materials, inorganic semiconductor materials and transition metal oxides that can react with lithium.
Taking the intercalation reaction as an example, lithium is ionically intercalated into the coating material to produce a lithium-containing compound that is capable of forming a uniform protective layer on the surface of the negative electrode during the reaction. Illustratively, lithium in the negative electrode is inserted into the crystal lattice of the coating material in the form of ions, resulting in a lithium-containing compound that is capable of forming a uniform protective layer on the surface of the negative electrode during the reaction.
Taking redox reaction as an example, the simple substance lithium reacts with the coating material to generate a corresponding reduction product and a lithium-containing compound, and the reduction product and the lithium-containing compound are integrated with the negative electrode to form a protective layer of the negative electrode. Illustratively, the lithium negative electrode reacts with the coating material to generate a corresponding metal simple substance and a lithium-containing compound, and the metal simple substance and the lithium-containing compound are integrated with the negative electrode to form a protective layer of the negative electrode.
Wherein the cathode is a conventional lithium ion battery cathode known in the art, such as at least one selected from a carbon cathode, a silicon carbon cathode, a lithium metal cathode, a lithium titanate cathode, and the like.
In a specific embodiment, the applied voltage is greater than 0 and equal to or less than 5V, and preferably greater than 0 and equal to or less than 3V; the pressurization time of the applied voltage is more than 0 hour, and preferably more than 0 hour and not more than 24 hours. For example, the applied voltage is 0.5V, 1.0V, 1.5V, 2.0V or 2.5V, and the pressing time is 1h, 3h, 5h, 10h, 12h, 18h or 24 h.
In a specific embodiment, the transition metal oxide that can react with lithium is selected from one or more of nickel oxide, lead oxide, and the like; the phosphate is selected from one or more of ferric phosphate, nickel phosphate and the like; the manganate is selected from one or more of cobalt manganate, zinc manganate and the like; the carbonate is selected from one or more of iron carbonate, zinc carbonate and the like; the metal hydroxide is selected from one or more of nickel hydroxide, magnesium hydroxide and the like; the inorganic solid electrolyte material is selected from one or more of a lithium fast ion conductor, perovskite and the like; the inorganic semiconductor material is selected from one or more of tin oxide, silver sulfide and the like.
Specifically, the coating material is selected from one or more of cobalt manganate, nickel oxide, lead zirconate titanate, zinc carbonate, nickel hydroxide, tin oxide and iron phosphate.
In a particular embodiment, the coating material further comprises a dispersant. The dispersant is selected from water and organic agents. The organic agent is selected from conventional organic solvents known in the art, for example, at least one selected from ethanol, acetone, isopropanol, and chloroform, etc.
In a specific embodiment, the raw material of the coating further comprises an auxiliary agent. Specifically, the auxiliary agent is at least one selected from a surfactant and a dispersing auxiliary agent. Wherein the surfactant comprises one or more of dodecyl benzene sulfonate (such as sodium dodecyl benzene sulfonate), dioctyl succinate sulfonate, fatty alcohol polyoxyethylene ether, oleyl alcohol polyoxyethylene ether, polyoxyethylene fatty acid ester, oleate and stearate. The dispersing aid comprises one or more of polyacrylic acid and salts thereof, copolymerized poly (acrylic acid-methacrylic acid) and salts thereof, castor oil, dodecyl sulfate, triethylhexyl phosphoric acid, methyl amyl alcohol, polyacrylamide, polyoxyethylene ether, oleamide and the like.
In a specific embodiment, the raw material of the coating further comprises a binder. Specifically, the binder comprises one or more of styrene-butadiene rubber, fluorinated rubber, polyvinyl alcohol, hydroxymethyl cellulose salt, polyacrylic acid, polyacrylate and derivatives thereof, polyacrylonitrile, acrylate-acrylonitrile copolymer, polymethyl methacrylate, dimethyl diallyl ammonium chloride, alginate, pectate, deerhorn glue salt and polyvinylidene fluoride.
In a specific embodiment, the method further comprises preparing a separator coated with the coating, the preparing of the separator comprising the steps of:
(1) dispersing a coating material in a dispersing agent, optionally adding an auxiliary agent and/or a binder, and uniformly mixing to prepare mixed slurry of the coating material;
(2) coating the mixed slurry of the step (1) on one side surface of a diaphragm base layer;
(3) and (3) drying the diaphragm base layer coated with the mixed slurry in the step (2), thus preparing the diaphragm coated with the coating.
In step (1), the mass ratio of the coating material to the dispersant is (0.1-50):100, preferably (0.5-33):100, and more preferably (1-15): 100.
In the step (1), the mass ratio of the auxiliary agent to the dispersant is (0.001-20):100, preferably (0.001-10):100, and more preferably (0.005-5): 100.
In the step (1), the mass ratio of the binder to the dispersant is (0.001-20):100, preferably (0.001-15):100, and more preferably (0.005-10): 100.
In the step (2), the coating is at least one selected from spray coating, blade coating, coating roll, coating brush and the like.
In the step (3), the drying time is 0.01-24 h; the drying temperature is 30-80 ℃.
Wherein the thickness of the coating is 0.1-10 μm.
Wherein the coating has a coating areal density of 0.2 to 5g/m2。
As mentioned above, the second aspect of the present invention provides a method for preparing a lithium ion battery, which includes the above method for preparing a lithium ion battery negative electrode protection layer in an in-situ transfer manner.
In a specific embodiment, the method further comprises the steps of contacting the positive electrode and the separator coated with the coating with a negative electrode of the lithium ion battery, and reacting to obtain a protective layer on the surface of the negative electrode of the lithium ion battery; the reaction includes, but is not limited to, intercalation and/or redox reactions; the reaction is carried out under the condition of certain external voltage; the raw material for forming the coating comprises at least one of the following coating materials: phosphates, manganates, carbonates, metal hydroxides, inorganic solid electrolyte materials, inorganic semiconductor materials and transition metal oxides that can react with lithium.
As described above, the third aspect of the present invention provides a lithium ion battery, which is prepared by the above-mentioned method for preparing a lithium ion battery.
Preferably, the lithium ion battery is at least one of a button battery, a stacked battery and a wound battery.
Preferably, the outer package of the lithium ion battery is a soft plastic package or a steel shell package.
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
In this embodiment, when the prepared lithium ion battery is subjected to a cyclic charge and discharge test, the lithium ion battery is subjected to the charge and discharge cycle test at 0.5C, and the discharge specific capacities at 10 th, 100 th, 200 th and 500 th cycles are recorded respectively.
In this embodiment, when the prepared lithium ion battery is used for observing the appearance of the protective layer in-situ transfer, the lithium ion battery is disassembled in a glove box in an argon atmosphere, washed clean with an electrolyte solvent, dried and observed by using a scanning electron microscope.
Preparing a positive plate: and (3) fully mixing 85 parts of lithium iron phosphate serving as a positive active material, 5 parts of acetylene black, 5 parts of conductive graphite and 5 parts of PVDF with N-methylpyrrolidone to obtain positive slurry, and uniformly coating the positive slurry on the surface of the aluminum foil current collector to finish the preparation of the positive plate.
Preparing a negative plate: a lithium metal electrode is selected.
Example 1
Step 1) dissolving 25g of sodium dodecyl benzene sulfonate in 460mL of water to obtain a mixed system, dispersing 160g of nickel oxide in the mixed system, adding 5g of styrene butadiene rubber binder, and fully stirring to obtain mixed slurry;
step 2) coating the mixed slurry scraper in the step 1) on one side of a polypropylene diaphragm base layer;
step 3) drying the diaphragm base layer coated with the mixed slurry in the step 2) in a vacuum drying oven at 40 ℃ for 2h to prepare the diaphragm of the nickel oxide coating; the thickness of the coating was 4 μm.
Step 4), assembling the lithium ion battery:
putting the nickel oxide diaphragm obtained in the step 3) between the positive pole piece and the negative pole piece, enabling the coating direction to face to one side of the negative pole, adding 100 mu L of commercial lithium ion battery electrolyte, putting the commercial lithium ion battery electrolyte into a reed, and sealing the battery by using a hydraulic sealing machine to prepare the button 2032 lithium ion battery.
Step 5) coating in-situ transfer process: and electrifying for 10h under a constant voltage of 1.5V, wherein lithium ions are inserted into nickel oxide lattices in the coating and form a uniform layer in the electrifying process, and the lithium ions are closely contacted with the cathode, namely a protective layer is formed on the surface of the cathode.
The prepared lithium ion battery is subjected to cyclic charge and discharge tests (see table 1) and in-situ transfer protection layer morphology characterization (see table 1).
FIG. 1 is a graph of the in-situ transferred protective layer morphology characterization of example 1. As can be seen, the coating on the separator has been successfully transferred to the lithium metal cathode and promoted a smoother deposition of lithium during cycling.
Example 2
The other steps are the same as example 1, except that:
step 1) dissolving 15g of methylpentanol in 1500mL of water to obtain a mixed system, dissolving 145g of ferric phosphate in the mixed system, adding 14g of polyacrylic acid binder, and fully stirring to obtain a composite slurry;
step 5) coating in-situ transfer process: and electrifying for 10h under a constant voltage of 1.5V, wherein lithium ions are embedded into the iron phosphate crystal lattices in the electrifying process to form compounds such as lithium iron phosphate and the like, and a uniform layer can be formed and is tightly combined with the negative electrode, namely a protective layer is formed on the surface of the negative electrode.
Example 3
The other steps are the same as example 1, except that:
step 1) dissolving 15g of methyl amyl alcohol in 1500mL of acetone to obtain a mixed system, dispersing 200g of cobalt manganate in the mixed system, adding 30g of polyvinylidene fluoride binder, and fully stirring to obtain composite slurry;
step 5) coating in-situ transfer process: and electrifying for 5 hours under the constant voltage of 2.5V, wherein in the electrifying process, the cobalt manganate in the coating and lithium metal generate oxidation-reduction reaction to generate manganese, cobalt metal simple substances and a small amount of low-valence compounds, and the manganese, cobalt metal simple substances can form a uniform layer and are tightly combined with the cathode, namely a protective layer is formed on the surface of the cathode.
Example 4
The other steps are the same as example 1, except that:
step 1) dissolving 35g of castor oil in 1500mL of water to obtain a mixed system, dissolving 300g of zinc carbonate in the mixed system, adding 100g of polyacrylonitrile binder, and fully stirring to obtain a composite slurry;
step 5) coating in-situ transfer process: and electrifying for 10 hours under the constant voltage of 0.5V, wherein in the electrifying process, zinc carbonate in the coating and lithium generate oxidation-reduction reaction to generate a mixture of lithium carbonate and metal zinc and zinc-lithium alloy, and the mixture forms a uniform layer and is tightly combined with the negative electrode, namely a protective layer is formed on the surface of the negative electrode.
Example 5
The other steps are the same as example 1, except that:
step 1) dissolving 5g of sodium oleate in 1500mL of water to obtain a mixed system, dissolving 145g of nickel hydroxide in the mixed system, adding 15g of polyacrylic acid binder, and fully stirring to obtain composite slurry;
step 5) coating in-situ transfer process: electrifying for 5h under a constant voltage of 1.5V, wherein in the electrifying process, the nickel hydroxide in the coating and lithium ions generate oxidation-reduction reaction to generate simple substance nickel and a compound containing lithium, and the simple substance nickel and the compound containing lithium form a uniform layer and are tightly combined with the cathode, namely a protective layer is formed on the surface of the cathode.
Example 6
The other steps are the same as example 1, except that:
step 1) dissolving 5g of castor oil in 1500mL of water to obtain a mixed system, dissolving 200g of lead zirconate titanate in the mixed system, adding 20g of sodium carboxymethylcellulose as a binder, and fully stirring to obtain composite slurry; step 5) coating in-situ transfer process: electrifying for 1h under the constant voltage of 1.5V, wherein in the electrifying process, lead zirconate titanate in the coating and lithium metal generate oxidation-reduction reaction to generate simple substance lead and a lithium-containing compound, and the simple substance lead and the lithium-containing compound form a uniform layer and are tightly combined with the cathode, namely a protective layer is formed on the surface of the cathode.
Example 7
The other steps are the same as example 1, except that:
step 1) dissolving 15g of sodium oleate in 1500mL of water to obtain a mixed system, dissolving 145g of tin oxide in the mixed system, adding 10g of sodium acrylate binder, and fully stirring to obtain composite slurry;
step 5) coating in-situ transfer process: and electrifying for 18h under a constant voltage of 1.5V, wherein in the electrifying process, the tin oxide in the coating and lithium metal generate oxidation-reduction reaction to generate a tin metal simple substance and lithium oxide, and the tin metal simple substance and the lithium oxide form a uniform layer and are tightly combined with the cathode, namely a protective layer is formed on the surface of the cathode.
Comparative example 1
The other steps are the same as example 1, except that:
step 1) dissolving 25g of sodium dodecyl benzene sulfonate in 460mL of water to obtain a mixed system, dispersing 160g of alumina in the mixed system, adding 1g of styrene butadiene rubber binder, and fully stirring to obtain mixed slurry;
step 5) coating in-situ transfer process: electrifying for 10h under a constant voltage of 1.5V, and generating no in-situ transfer in the electrifying process.
Comparative example 2
An uncoated polypropylene diaphragm (commercial polypropylene diaphragm) is placed between the positive pole piece and the negative pole piece, 100 mu L of commercial lithium ion battery electrolyte is added, a reed is placed, then a hydraulic sealing machine is used for sealing, the button 2032 lithium ion battery is prepared, the battery is electrified for 10h under a constant voltage of 1.5V, and no in-situ transfer occurs in the electrifying process. Followed by a cyclic charge and discharge test.
Comparative example 3
The other steps are the same as example 1, except that step 5) is omitted, and the prepared button 2032 lithium ion battery is directly subjected to a cyclic charge and discharge test without an electrifying step.
Examples 1 to 7 and comparative examples 1 to 3 were tested by the above test methods, and the cell performance parameters were as shown in table 1.
Table 1 shows the performance parameters of the lithium ion batteries prepared in examples 1-7 and comparative examples 1-3
As can be seen from the data in Table 1, the cycle stability of the lithium ion battery of the invention is obviously better than that of the comparative example, and especially the performance after 500 cycles is at least improved by 20 percent compared with that of the comparative example, thus the lithium ion battery has a wide application prospect.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
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| CN114142161B (en) * | 2021-11-26 | 2023-09-22 | 吉林大学 | A kind of preparation method of modified lithium-ion battery separator |
| CN115832180B (en) * | 2022-01-05 | 2024-03-22 | 宁德时代新能源科技股份有限公司 | Secondary battery, battery module, battery pack and power utilization device thereof |
| CN114744158B (en) * | 2022-05-18 | 2024-05-03 | 中南大学 | Method for modifying surface of lithium metal electrode by using organic/inorganic composite coating |
| CN118610689B (en) * | 2024-05-24 | 2025-01-24 | 哈尔滨工业大学 | Preparation method and application of protective layer material for suppressing short circuit in lithium battery |
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