CN111987278B - Composite diaphragm for lithium metal secondary battery and preparation method and application thereof - Google Patents
Composite diaphragm for lithium metal secondary battery and preparation method and application thereof Download PDFInfo
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- CN111987278B CN111987278B CN202010753375.0A CN202010753375A CN111987278B CN 111987278 B CN111987278 B CN 111987278B CN 202010753375 A CN202010753375 A CN 202010753375A CN 111987278 B CN111987278 B CN 111987278B
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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
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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
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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
- H01M10/42—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
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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
- H01M4/624—Electric conductive fillers
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- Y02E60/10—Energy storage using batteries
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- 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
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Abstract
The invention provides a composite diaphragm for a lithium metal secondary battery, and a preparation method and application thereof. The coating is transferred to the surface of a lithium metal cathode in the assembly process of the battery, and in-situ conversion reaction occurs in the subsequent battery circulating electrochemical process to generate a mixed electron ion conductor layer, and meanwhile, the distribution of ions and electrons on an interface is adjusted, so that the ion concentration gradient is relieved, uniform lithium deposition is guided, and the generation of lithium dendrites is inhibited. The lithium metal secondary battery using the composite diaphragm shows excellent cycle and rate performance. The composite diaphragm of the invention avoids the complex procedures and harsh operating environment of the prior art for directly modifying lithium metal, has simple preparation technology, easily obtained raw materials and extremely high practical and large-scale prospects.
Description
Technical Field
The invention belongs to the field of electrochemical power sources, and particularly relates to a functional composite diaphragm of a lithium metal secondary battery, a preparation method of the functional composite diaphragm, the lithium metal secondary battery assembled by using the functional composite diaphragm, and application of the functional composite diaphragm in an energy storage device.
Background
Lithium ion secondary batteries have been widely used in the fields of consumer electronics and communications. But due to its limited theoretical capacity, exploitation has been approaching its limit. With the rapid development in the fields of hybrid electric vehicles, smart power grids and the like in the future, people put forward higher and higher performance requirements, such as high energy density, high safety and the like, on lithium ion batteries in the energy storage link.
The metal lithium is paid much attention due to the fact that the metal lithium has high theoretical specific capacity (3860mAh/g) and the lowest cathode electrochemical potential (-3.04V, hydrogen standard potential), and has wide development prospects. Lithium metal secondary batteries, which can provide much higher energy density than conventional batteries, are considered as one of the most important energy storage technologies of the next generation.
However, during the battery cycling process, the metal lithium on the surface of the lithium metal negative electrode is unevenly deposited, so that lithium dendrites are generated, the separator is easily punctured, and great potential safety hazards are caused. On the other hand, the reaction activity between the lithium metal cathode and the electrolyte is extremely high, new Solid Electrolyte Interphase (SEI) is formed again after the SEI is broken down continuously, the electrolyte is consumed continuously, harmful byproducts are generated, and the cycle life of the battery is shortened. Therefore, protecting the metallic lithium negative electrode becomes a key challenge for the commercial development of the metallic lithium battery.
At present, the most common means for protecting the metallic lithium cathode is to add an electrolyte additive, or modify a protective layer on the lithium cathode to prevent the continuous reaction of the electrolyte and the lithium metal and to uniform the deposition of lithium; or the lithium negative electrode is made into a three-dimensional current collector, so that the specific surface area is increased, the current density is reduced, and the uniform deposition of lithium is guided. However, these approaches involve complicated preparation processes and harsh manufacturing environments, which are not conducive to scale-up practical production.
Therefore, it is urgently needed to develop a method for protecting a lithium metal negative electrode, which has a simple process and a low cost, so as to achieve the effect of inhibiting the dendrite of the lithium metal in the negative electrode circulation process, improve the safety and the circulation stability of the battery, and promote the practicability of the lithium metal battery.
Disclosure of Invention
Therefore, the invention aims to solve the problems that lithium dendrites are easily generated on the lithium metal negative electrode and pierce a diaphragm to cause serious potential safety hazards in the conventional secondary battery, and provides a simple and easy-to-operate functional composite diaphragm which can be used for uniformly depositing lithium ions, inhibiting the generation of lithium dendrites, improving the cycling stability and safety of the battery and avoiding the complicated process and harsh operating environment for directly modifying the lithium metal in the prior art.
In one aspect, the present invention provides a composite separator for a lithium metal secondary battery, comprising a separator base layer and a functional coating layer coated on at least one surface of the separator base layer, wherein the functional coating layer comprises material particles capable of reacting with lithium metal.
According to the present invention, there is provided a composite separator, wherein the particles of the substance capable of reacting with lithium metal comprise at least one metal nitride and/or metal fluoride. Wherein the metal nitride may be selected from one or more of magnesium nitride, copper nitride, strontium nitride, dysprosium nitride, lanthanum nitride, cerium nitride, ytterbium nitride, iron nitride, manganese nitride, titanium nitride, vanadium nitride, cobalt nitride, nickel nitride, molybdenum nitride, germanium nitride, and aluminum nitride. The metal fluoride may be selected from one or more of magnesium fluoride, copper fluoride, strontium fluoride, dysprosium fluoride, lanthanum fluoride, cerium fluoride, ytterbium fluoride, iron fluoride, manganese fluoride, titanium fluoride, vanadium fluoride, cobalt fluoride, nickel fluoride, molybdenum fluoride, germanium fluoride, and aluminum fluoride.
According to the composite diaphragm provided by the invention, the thickness of the functional coating can be 0.1-30 μm, and preferably 0.5-5 μm.
In a preferred embodiment, the particles of the substance have a particle size of 5nm to 5 μm, preferably 200 to 500 nm.
The composite separator according to the present invention is not particularly limited, and a separator commonly used in secondary batteries in the art may be used as the separator base layer. For example, the separator base layer may be selected from a polyethylene separator, a polypropylene separator, a polyethylene/polypropylene separator, an alumina polyethylene separator, and a ceramic fiber paper separator.
The composite separator provided by the invention is a functional separator, and can transfer a coating compound coated on the separator in advance to the surface of lithium metal in the assembly process of a battery so as to protect the lithium metal. Therefore, the traditional complicated lithium metal protection scheme is greatly avoided, the steps are simple, the production is facilitated, and the cost is saved. More importantly, the coating can generate a mixed electron ion conductor layer through in-situ conversion in the electrochemical reaction process, and meanwhile, the electron and ion distribution at the lithium cathode interface is adjusted, the ion concentration gradient is relieved, the deposition of lithium is uniform, the generation of lithium dendrites is avoided, and the safety and the cycling stability of the battery are improved.
On the other hand, the invention also provides a preparation method of the composite diaphragm, which comprises the following steps:
(1) dispersing active substance particles and a binder in an organic solvent to obtain coating slurry;
(2) and (2) coating the coating slurry prepared in the step (1) on at least one surface of the diaphragm base layer, and drying to obtain the composite diaphragm.
According to the preparation method provided by the invention, the active material particles comprise at least one metal nitride and/or metal fluoride, preferably, the metal nitride is selected from one or more of magnesium nitride, copper nitride, strontium nitride, dysprosium nitride, lanthanum nitride, cerium nitride, ytterbium nitride, iron nitride, manganese nitride, titanium nitride, vanadium nitride, cobalt nitride, nickel nitride, molybdenum nitride, germanium nitride and aluminum nitride; the metal fluoride may be selected from one or more of magnesium fluoride, copper fluoride, strontium fluoride, dysprosium fluoride, lanthanum fluoride, cerium fluoride, ytterbium fluoride, iron fluoride, manganese fluoride, titanium fluoride, vanadium fluoride, cobalt fluoride, nickel fluoride, molybdenum fluoride, germanium fluoride, and aluminum fluoride.
According to the preparation method provided by the invention, the binder is selected from one or more of polyvinylidene fluoride, carboxymethyl cellulose, sodium carboxymethyl cellulose, styrene butadiene rubber, sodium alginate, polyethylene oxide, polyvinyl alcohol, polytetrafluoroethylene and polyamide; preferably, the solvent is selected from one or more of dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, diethyl ether, acetonitrile, cyclohexane, dichloromethane, acetone, ethanol and methanol.
The content of the active material particles and the binder in the coating slurry in the production method of the present invention is not particularly limited. In some embodiments, the mass fraction of active material particles in the coating slurry is 1 to 50 wt.%, preferably 10 to 20 wt.%. In some embodiments, the mass fraction of binder in the coating slurry is 0.1 to 20 wt.%, preferably 1 to 10 wt.%.
In a preferred embodiment of the invention, the coating slurry is uniformly mixed by high-energy ball milling, and the ball milling speed is 300-800 rpm, preferably 400-600 rpm; the ball milling time is 3 to 10 hours, preferably 4 to 8 hours.
According to the preparation method provided by the invention, the drying temperature can be 10-80 ℃, and preferably 30-60 ℃.
In still another aspect, the present invention also provides a lithium metal secondary battery comprising a positive electrode, a lithium negative electrode, an electrolyte and a separator, wherein the separator is the above composite separator, and a surface of the composite separator facing the lithium negative electrode is coated with a coating layer.
According to the lithium metal secondary battery provided by the present invention, the positive electrode may be a conventional positive electrode for a lithium metal secondary battery, and may include, for example, a positive electrode active material, a conductive additive, a binder, and the like.
The positive electrode active material is not particularly limited, and any positive electrode active material may be used for a general lithium metal secondary battery, such as one or more of nickel cobalt lithium manganate, lithium cobaltate, lithium manganate, lithium nickel manganese manganate, lithium nickel cobalt aluminate, sulfur-ketjen black composite, sulfur-Super P composite, sulfur-carbon nanotube composite, sulfur-acidified carbon nanotube composite, selenium-ketjen black composite, selenium-Super P composite, selenium-carbon nanotube composite, and selenium-acidified carbon nanotube composite.
The conductive additive used for the positive electrode can be one or more of Super P, Ketjen black, graphene and conductive carbon nanotubes; the binder can be one or more of polyvinylidene fluoride, sodium carboxymethylcellulose, styrene butadiene rubber/sodium carboxymethylcellulose and sodium alginate.
In some embodiments of the invention, the mass of the positive active material in the positive electrode accounts for 70-90% of the total mass of the positive electrode, the conductive additive accounts for 5-20% of the total mass of the positive electrode, and the binder accounts for 5-20% of the total mass of the positive electrode.
According to the lithium metal secondary battery provided by the present invention, the negative electrode is a metallic lithium negative electrode.
According to the lithium metal secondary battery provided by the present invention, the electrolyte includes a solvent and a lithium salt. Wherein, the solvent can be selected from at least one of 1,3 dioxolane, 1,4 dioxane, tetrahydrofuran, trimethylolpropane triglycidyl ether, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methyl carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate; the lithium salt may be at least one of lithium hexafluorophosphate, lithium dioxalate borate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonate) imide and lithium perchlorate. Preferably, the concentration of the lithium salt is 0.5-3M.
In still another aspect, the present invention also provides an energy storage device comprising the above lithium metal secondary battery.
Compared with the prior art, the functional composite diaphragm of the lithium metal secondary battery provided by the invention has the following advantages:
1. the complex procedure of conventional modification of the lithium metal cathode or lithium metal interface and harsh environmental conditions are avoided.
2. The coating layer is coated on a separator, which is stored and used as a conventional component of a battery. After the obtained functional composite diaphragm is assembled as a lithium metal secondary battery diaphragm, a coating can be transferred to the surface of lithium metal, the process is simplified, the cost is saved, and the method has a very high commercialization prospect.
3. The coating and lithium metal generate in-situ conversion reaction in the electrochemical cycle process to generate an electron conductor and a fast ion conductor. The electron conductor can be evenly distributed, and simultaneously, the fast ion conductor part can conduct lithium ions rapidly, alleviates concentration gradient, promotes the even deposit of lithium, effectively improves the dendrite problem of metal negative pole, promotes battery security and stability.
Drawings
Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
fig. 1(a) is a SEM image of the coating surface of the composite separator prepared in example 1 of the present invention;
FIG. 1(b) is a sectional SEM photograph of a composite separator prepared in example 1 of the present invention;
fig. 2(a) is a graph of coulombic efficiency and cycle performance at 0.5C rate for the cell made in example 1 of the present invention;
fig. 2(b) is a first-turn charge-discharge curve of the battery prepared in example 1 of the present invention at a 0.5C rate;
fig. 3(a) is a graph of coulombic efficiency and cycle performance at 0.5C rate for the cell made in comparative example 1;
fig. 3(b) is a first-turn charge and discharge curve at a 0.5C rate of the battery prepared in comparative example 1.
FIG. 4: the invention discloses a schematic diagram of a composite diaphragm for a lithium metal secondary battery.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, and the examples are given only for illustrating the present invention and not for limiting the scope of the present invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available.
Example 1
This example illustrates the preparation of a composite separator of the present invention and its application in nickel cobalt lithium manganate (NCM622) batteries
(1) Polyvinylidene fluoride (mass fraction: 2 wt.%), magnesium nitride particles (particle size: about 200nm, mass fraction: 20 wt.%) and N-methylpyrrolidone were mixed and subjected to high energy ball milling at a speed of 450rpm for a period of 4 hours. After mixing was complete, the solution was drawn down on the surface of a commercial polyethylene separator with a doctor blade having a gap of 1 μm. And placing the diaphragm at 50 ℃ for drying treatment to obtain the composite diaphragm coated with the magnesium nitride on the surface.
Fig. 1(a) is a scanning image of the morphology of the magnesium nitride-coated side, and fig. 1(b) is a scanning image of a cross section of the composite diaphragm. As can be seen from fig. a, the magnesium nitride particles are uniformly coated on the surface of the diaphragm, and as can be seen from the sectional view b, the magnesium nitride particles are thin and uniform, and are tightly decorated on the diaphragm base layer.
(2) Under high-purity argon, NCM622 is used as a positive active material (200mg), Super P is used as a conductive additive (25mg), PVDF is used as a binder (25mg), and the positive plate is prepared according to the mass ratio of 8:1: 1. After the above-mentioned electrode sheets were obtained, a composite separator, an electrolyte (1M LiPF6 dissolved in EC: DEC: DMC ═ 1:1:1) and a lithium negative electrode were stacked in this order.
(3) The battery case was completely sealed, left to stand for 6 hours, and battery performance tests were performed.
Battery performance testing
The electrochemical performance of the cells was tested in a cell test system. The test temperature is 25 ℃, the test voltage interval is a cycle test under the conditions of 0.5C and 2.8-4.3V voltage, wherein 1C is 200mA h g-1。
Fig. 2 is a graph of coulombic efficiency and cycle performance at 0.5C rate (fig. 2a) and a first-turn charge-discharge curve at 0.5C rate (fig. 2b) of the NCM622 battery prepared in example 1. It can be seen that the NCM622 battery using the composite diaphragm is stable in cycle, the initial discharge capacity is 170.1mAh/g, after 100 cycles, the capacity is still 159.1mAh/g, and the retention rate is 93.5%, which indicates that the cycle stability and the capacity retention rate of the battery are improved by using the composite diaphragm.
Example 2
A composite separator and a battery were produced in the same manner as in example 1, except that the particle diameter of the coated active material particles used in step (1) was about 50 nm.
Example 3
A composite separator and a battery were produced in the same manner as in example 1, except that the coated active material used in step (1) had a particle size of about 1 μm.
Example 4
A composite separator and a battery were fabricated in the same manner as in example 1, except that the particle size of the coated active material used in step (1) was about 2 μm.
Example 5
A composite separator and a battery were fabricated in the same manner as in example 1, except that the particle size of the coated active material used in step (1) was about 500 nm.
As can be seen from comparison of examples 1 to 5, the particle size of the coating active material has an influence on the battery performance, and 200 to 500nm is preferred.
Example 6
A composite separator and a battery were produced in the same manner as in example 1, except that the coating blade gap used in step (1) was about 5 μm.
Example 7
A composite separator and a battery were produced in the same manner as in example 1, except that the coating blade gap used in step (1) was about 0.5 μm.
Example 8
A composite separator and a battery were produced in the same manner as in example 1, except that the coating blade gap used in step (1) was about 8 μm.
As can be seen from comparison of examples 6-8, the thickness of the coating layer also has a certain influence on the battery performance, and the thickness is preferably 0.5-5 μm, wherein 0.5-5 μm is more preferred.
Example 9
A composite separator and a battery were produced in the same manner as in example 1, except that the active material in step (1) was copper nitride.
Example 10
A composite separator and a battery were fabricated in the same manner as in example 1, except that the active material in step (1) was magnesium fluoride.
Comparison of examples 1, 9, and 10 shows that many nitrides and fluorides can achieve the effect of the comparative example.
Example 11
A composite separator and a battery were produced in the same manner as in example 1, except that the mass fraction of the active material in the slurry in step (1) was 5%.
Example 12
A composite separator and a battery were produced in the same manner as in example 1, except that the mass fraction of the active material in the slurry in step (1) was 15%.
Example 13
A composite separator and a battery were produced in the same manner as in example 1, except that the mass fraction of the active material in the slurry in step (1) was 25%.
A comparison of examples 11, 12, 13 and example 1 shows that the mass fraction of active material in the slurry has some, but less, effect on the battery performance.
Example 14
A composite separator and a battery were produced in the same manner as in example 7, except that the slurry solvent in step (1) was acetone.
Example 15
A composite separator and a battery were produced in the same manner as in example 7, except that the slurry solvent in step (1) was dimethyl sulfoxide.
Example 16
A composite separator and a battery were produced in the same manner as in example 7, except that the base film used in step (1) was a polypropylene separator.
Example 17
A composite separator and a battery were produced in the same manner as in example 1, except that the positive electrode material used in step (2) was NCM 811.
Comparative example 1
A battery was fabricated in the same manner as in step (2) of example 1, except that a commercial polyethylene separator was used.
Fig. 3(a) and 3(b) are graphs of cycle performance and corresponding charge and discharge curves for the first cycle, respectively. It can be seen that the initial discharge capacity is normal and is 168.1mAh/g, after 100 cycles, the discharge capacity is only 147.1mAh/g, the capacity retention rate is 87.5%, which is much lower than that of the composite diaphragm battery. The compound diaphragm has obvious effect on adjusting the uniform deposition of lithium ions and stabilizing the interface of the lithium cathode.
The lithium batteries obtained in the examples and comparative examples were subjected to electrochemical performance tests, and the results are shown in table 1 below:
the invention creatively transfers the modification protection of lithium metal to the modification of the diaphragm, directly transfers the protective layer to the surface of the lithium metal cathode in the assembly process, and carries out in-situ conversion reaction in the subsequent electrochemical cycle process to form a mixed conductor layer, and simultaneously regulates and controls the electron ions to be uniformly distributed and guide the uniform deposition of lithium. And further improves the cycling stability and the dynamic performance of the battery. The cycling specific capacity of the full battery matched with the NCM622 anode at 0.5 ℃ is obviously higher than that of an unmodified common diaphragm, the capacity attenuation is obviously and effectively inhibited, and the polarization after modification is obviously reduced in a charging and discharging platform curve. This shows that the formed mixed conductor layer effectively promotes interfacial ion transport, and guides uniform lithium deposition, thereby inhibiting side reactions, reducing polarization, stabilizing the interface structure, and improving coulombic efficiency, cycling stability, and rate capability of the battery. The method is simple and convenient to operate, good in uniformity, remarkable in effect and suitable for large-scale production.
The specific embodiments described above are merely illustrative of the present disclosure and do not represent limitations of the present disclosure. The specific structure of the application can be modified by those skilled in the art according to the main idea of the invention and the actual research system. The protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (4)
1. A method of preparing a composite separator for a lithium metal secondary battery, the composite separator comprising a separator base layer and a functional coating layer coated on at least one surface of the separator base layer, wherein the functional coating layer comprises active material particles capable of reacting with lithium metal, and the functional coating layer has a thickness of 0.5 to 1 μm, the method comprising the steps of:
(1) dispersing active substance particles and a binder in an organic solvent to obtain coating slurry, wherein the active substance particles comprise magnesium nitride or copper nitride, the particle size is 200-500 nm, and the organic solvent is N-methylpyrrolidone;
(2) and (2) coating the coating slurry prepared in the step (1) on at least one surface of the diaphragm base layer, and drying to obtain the composite diaphragm.
2. The production method according to claim 1, wherein the binder is one or more selected from polyvinylidene fluoride, carboxymethyl cellulose, sodium carboxymethyl cellulose, styrene-butadiene rubber, sodium alginate, polyethylene oxide, polyvinyl alcohol, polytetrafluoroethylene, and polyamide.
3. A lithium metal secondary battery comprising a positive electrode, a lithium negative electrode, an electrolyte and a separator, wherein the separator is the composite separator obtained by the preparation method according to claim 1, and the surface of the composite separator facing the lithium negative electrode is coated with a functional coating.
4. An energy storage device comprising the lithium metal secondary battery of claim 3.
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| CN112430832A (en) * | 2020-12-04 | 2021-03-02 | 金川集团股份有限公司 | Electrolytic diaphragm bag |
| CN114628849A (en) * | 2020-12-14 | 2022-06-14 | 宁波大学 | Preparation method and application of super-hydrophobic and super-hydrophilic organic electrolyte diaphragm |
| CN113314801B (en) * | 2021-05-21 | 2022-08-30 | 中南大学 | Slow-release functional diaphragm, preparation method thereof and lithium battery |
| CN113451580A (en) * | 2021-06-30 | 2021-09-28 | 珠海冠宇电池股份有限公司 | Interface layer and lithium ion battery comprising same |
| CN116120766B (en) * | 2021-11-12 | 2024-06-14 | 钢研工程设计有限公司 | Hot galvanizing shielding paint, preparation method and use method |
| CN114242942B (en) * | 2021-11-30 | 2023-05-02 | 厦门大学 | Composite buffer layer with stable anode interface and solid-state lithium metal battery thereof |
| CN116606574A (en) * | 2023-05-22 | 2023-08-18 | 山东锌派新能源科技有限公司 | Coating material for improving ion transfer-diffusion effect on battery interface, preparation method and application thereof |
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| CN110783554A (en) * | 2019-11-27 | 2020-02-11 | 江苏红东科技有限公司 | High-magnification low-temperature-resistant long-life lithium ion battery negative electrode material |
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