CN108376783B - Lithium anode surface protective coating and preparation method thereof - Google Patents

Lithium anode surface protective coating and preparation method thereof Download PDF

Info

Publication number
CN108376783B
CN108376783B CN201810132064.5A CN201810132064A CN108376783B CN 108376783 B CN108376783 B CN 108376783B CN 201810132064 A CN201810132064 A CN 201810132064A CN 108376783 B CN108376783 B CN 108376783B
Authority
CN
China
Prior art keywords
lithium
protective coating
coating
diaphragm
anode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810132064.5A
Other languages
Chinese (zh)
Other versions
CN108376783A (en
Inventor
魏志凯
张�焕
叶长英
黄美灵
闫新秀
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan Huakun Energy Co ltd
Original Assignee
Sichuan Huakun Energy Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sichuan Huakun Energy Co ltd filed Critical Sichuan Huakun Energy Co ltd
Priority to CN201810132064.5A priority Critical patent/CN108376783B/en
Publication of CN108376783A publication Critical patent/CN108376783A/en
Application granted granted Critical
Publication of CN108376783B publication Critical patent/CN108376783B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a lithium anode surface protective coating and a preparation method thereof, wherein the protective coating is mainly formed by stacking nanoparticles, and solid electrolyte is filled in pores formed by stacking the nanoparticles; the protective coating is disposed between the lithium anode and the separator. The protective coating is formed by stacking the nano particles, and the stacking structure formed by stacking the nano particles can effectively inhibit the growth of lithium dendrites on the lithium metal polar plate, so that the problem that the membrane is pierced due to the growth of the lithium dendrites is solved. The solid electrolyte filled in the nano-particle stacking pores has higher lithium ion conductivity, ensures the transmission rate of the lithium metal pole plate, effectively isolates the side reaction of the lithium metal and the electrolyte, greatly prolongs the recycling service life of the lithium metal pole plate, and improves the safety of the lithium metal pole plate.

Description

Lithium anode surface protective coating and preparation method thereof
Technical Field
The invention relates to a protection structure between a diaphragm and a lithium electrode used in a lithium metal battery, in particular to a lithium anode surface protection coating and a preparation method thereof.
Background
In recent years, with the development of scientific technology, the requirement of people on the energy density of energy storage devices is gradually increased, and the energy density development of the lithium ion battery at present basically reaches the theoretical limit of materials of the lithium ion battery, generally is lower than 300Wh/kg, and the space for further improvement is limited. In order to meet the social demands, the development of novel high energy density energy storage systems and energy storage materials is imperative. The lithium metal has small molecular weight, high specific capacity up to 3800mAh/g, and extremely high mass energy density and volume energy density. In the existing lithium ion battery system, a metal lithium anode is used to replace the existing graphite anode; or the lithium metal anode and the sulfur cathode are matched to form the lithium-sulfur battery, so that the energy density of the energy storage device can be greatly improved. However, due to the safety and cycling stability of lithium metal anodes, lithium metal anodes are currently used in primary lithium metal batteries such as lithium iodine, lithium thionyl chloride, lithium manganese dioxide, and the like, and commercial secondary battery systems are rarely used.
Failure of rechargeable lithium metal batteries is mostly due to battery lithium metal anode cycling problems. On one hand, in the repeated charge-discharge cycle process of the lithium metal battery, dendritic crystals on the surface of a lithium metal electrode gradually grow, and the pierced diaphragm is in contact with the cathode of the battery to cause short circuit in the battery, so that the battery cannot be circulated and the safety problem is caused. On the other hand, because lithium metal has high activity and is easy to generate side reaction with liquid organic electrolyte, the lithium metal deposited on the surface of the lithium metal electrode is in a loose deposition state and is easy to separate from the surface of the electrode substrate in the circulation process, so that dead lithium is generated, and the capacity of the battery is attenuated. In order to solve the above problems, researchers have extended the cycle life of lithium metal anodes by forming a protective layer on the surface of the lithium metal anode. The protective layer needs to have high lithium ion conductivity to ensure efficient transmission of lithium ions, high strength to prevent growth and puncture of lithium dendrites, and effective isolation of lithium metal from contacting with electrolyte to reduce side reactions of a metal lithium electrode.
The preparation of the lithium metal electrode surface protective layer can be realized by adding a film forming additive into the electrolyte and utilizing the in-situ reaction of the electrolyte components and the lithium metal, for example, as disclosed by the sialon Power in the chinese patent CN1930725A, by adding an additive containing N-O lithium salt into the electrolyte, a protective layer is generated on the lithium metal surface to improve the cycling stability and capacity utilization rate of the lithium-sulfur battery. However, such a lithium anode protective layer prepared by in-situ film formation through a controlled reaction after the battery is assembled generally has a porous structure, cannot completely prevent the permeation of an electrolyte, is weak in strength, has a weak effect of inhibiting lithium metal dendrites, and is difficult to maintain the effect of the protective layer during the long-term cycling of the battery. Another way to construct the lithium metal anode protection layer is to construct a solid ceramic electrolyte protection layer with higher strength on the lithium metal surface by a pretreatment method, and then to assemble the battery, for example, as disclosed by Polyplus in U.S. Pat. No.5314765, a thin LiPON ceramic solid electrolyte is pre-plated on the lithium metal surface to isolate the lithium from directly contacting with the liquid electrolyte. The pre-plating technology can form a complete and compact ceramic electrolyte protective layer on the surface of lithium metal, has high strength and high lithium ion conductivity, but the technology needs special processes such as evaporation or magnetron sputtering and the like, has high cost and is not suitable for batch production, and the formed ceramic electrolyte protective layer has high brittleness and poor processing performance. In summary, the current lithium metal anode protection layer technology still has difficulty in meeting the long-cycle use requirement and the application requirement of batch preparation of lithium metal anodes.
Disclosure of Invention
The first purpose of the invention is to provide a lithium metal battery which can inhibit the growth of lithium dendrite on a lithium anode of the lithium metal battery and solve the safety problem caused by the fact that the battery is not short-circuited because the dendrite grows and pierces a diaphragm to be in contact with a battery cathode; and the lithium anode surface protective coating can ensure the high-efficiency transmission of lithium ions, effectively isolate the direct contact of lithium metal and electrolyte, reduce the generation of dead lithium and prolong the cycle service life of the electrode.
It is another object herein to provide a method for preparing the above protective coating, which is simple, low in process cost, and suitable for industrial production applications.
The lithium anode surface protective coating provided by the first object of the invention is arranged between a lithium anode and a diaphragm, the protective coating is mainly formed by accumulating nano particles, solid electrolyte materials which have high lithium ion conductivity and are stable to lithium metal are filled among the nano particles, and the solid electrolyte materials are obtained by the in-situ reaction of precursor materials and lithium.
The protective coating provided by the invention is formed by stacking the nano particles, the growth of lithium dendrites on a lithium metal polar plate is effectively inhibited by the high strength characteristic of the nano particle stacking structure, and the safety problem caused by the fact that the battery is not short-circuited due to the fact that the battery is contacted with the cathode after the battery is pierced by the diaphragm due to the growth of the dendrites is solved. Meanwhile, solid electrolyte is filled in pores formed by accumulating the nano particles, so that the direct contact between lithium metal in the lithium metal pole plate and electrolyte is effectively isolated while the high-efficiency transmission of lithium ions in the lithium metal pole plate is ensured, the side reaction of the lithium metal pole plate and the electrolyte is inhibited, the generation of dead lithium is reduced, the cycle service life of the lithium anode is prolonged, and the use safety of the lithium anode is improved.
Specifically, the nano particles are aluminum oxide or silicon dioxide.
Specifically, the particle size of the nanoparticles is 10-150 nm.
Specifically, the solid electrolyte is one or a combination of more of lithium sulfide, lithium iodide, lithium phosphide and lithium nitride.
Specifically, the thickness of the protective coating is 2-100 μm.
Preferably, the thickness of the protective coating is 2-30 μm,
preferably, the thickness of the protective coating is 6-15 μm.
Specifically, the precursor material comprises one or a combination of sulfur, phosphorus, iodine or copper nitride and a simple substance or a compound containing corresponding elements, and the in-situ reaction is a heating composite reaction mode or an in-situ electrochemical reaction mode after being infiltrated by electrolyte, so that the lithium metal reacts with the precursor material.
The preparation method of the lithium anode surface protective coating provided by the second object of the invention comprises the following steps:
step 1: carrying out ball milling or heating compounding on 40-60 parts by weight of one or more substances of sulfur, iodine, phosphorus or copper nitride and 30-60 parts by weight of nanoparticles to obtain a composite material;
step 2: adding 8-10 parts by weight of binder and 350 parts by weight of solvent into the composite material obtained in the step 1, and stirring to obtain a composite coating;
and step 3: uniformly coating the composite coating obtained in the step 2 on the surface of a diaphragm in a spraying, blade coating or transfer coating mode and drying;
and 4, step 4: and (3) placing the side, coated with the composite coating, of the separator on the surface of the lithium anode, and performing the following step A or step B:
step A: pressing the diaphragm coated with the composite coating and the lithium anode at the temperature of 80-180 ℃ in a hot rolling mode, so that substances in the composite coating coated on the diaphragm and lithium elements in the lithium anode generate in-situ reaction, and a protective coating is formed between the diaphragm and the lithium anode;
and B: and pressing the diaphragm coated with the composite coating and the lithium anode in a cold pressing and rolling mode, and infiltrating by using electrolyte, so that substances in the composite coating coated on the diaphragm and lithium elements in the lithium anode are subjected to in-situ reaction, and a protective coating is formed between the diaphragm and the lithium anode.
The preparation method is simple to operate, low in process cost and suitable for industrial production and application.
Specifically, the binder is polyoxyethylene, polyacrylonitrile or polyvinylidene fluoride. The adhesive property is strong, so that the nano particles and the solid electrolyte can be effectively adhered, and the protective property is stronger.
The invention has the beneficial effects that: the protective coating is formed by stacking the nanoparticles, and the stacking structure formed by stacking the nanoparticles can effectively inhibit the growth of lithium dendrites on the lithium metal polar plate, so that the problem that the membrane is pierced due to the growth of the lithium dendrites is solved. The solid electrolyte filled in the nano-particle stacking pores has higher lithium ion conductivity, ensures the transmission rate of a lithium metal polar plate, effectively isolates the side reaction of lithium metal and electrolyte, and the protective coating is arranged on the surface of the lithium anode, so that the cycle service life of the lithium anode can be greatly prolonged, and the safety of the lithium anode is improved.
The preparation method provided by the application is low in process cost, simple to operate and suitable for industrial production and application.
Drawings
FIG. 1 is a schematic structural view of a lithium anode formed using a protective coating provided in the present invention;
FIG. 2 shows a 2mA/cm lithium-sulfur battery assembled by the lithium metal electrode plate of comparative example 1 according to the present invention2The charge-discharge curve diagrams of the first circle and the 49 circles under the current density;
FIG. 3 is an assembly of lithium metal plates provided in comparative example 1 according to the present inventionLithium sulfur battery at 2mA/cm2A plot of cycle retention at current density;
FIG. 4 shows a 2mA/cm lithium sulfur battery assembled with a formed lithium anode according to an embodiment of the present invention2The charge-discharge curve diagrams of the first circle and the 50 circles under the current density;
FIG. 5 shows a 2mA/cm lithium sulfur battery assembled with a formed lithium anode according to an embodiment of the present invention2A plot of cycle retention at current density;
FIG. 6 shows a 2mA/cm lithium sulfur battery assembled by using a lithium anode formed according to the second embodiment of the present invention2The charge-discharge curve diagrams of the first circle and the 50 circles under the current density;
FIG. 7 shows a 2mA/cm lithium sulfur battery assembled by using a lithium anode formed according to the second embodiment of the present invention2A plot of cycle retention at current density;
FIG. 8 shows a 2mA/cm lithium sulfur battery assembled by using a lithium anode formed according to a third embodiment of the present invention2The charge-discharge curve diagrams of the first circle and the 50 circles under the current density;
FIG. 9 shows a 2mA/cm lithium sulfur battery assembled by using a lithium anode formed according to a third embodiment of the present invention2A plot of cycle retention at current density;
in the figure: 1-lithium metal plate, 2-protective coating and 3-diaphragm.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The claimed subject matter is described in further detail with reference to the figures and the detailed description.
To better illustrate the better performance of the electrode provided by the present invention, comparative example 1 is provided herein; the electrode provided in comparative example 1 was prepared from elemental sulfur powder and conductive carbon black in a ratio of 3: 1 mass ratio, placing the mixture in a sealed container at 155 ℃ for heating treatment for 6 hours to obtain the sulfur-carbon composite powder. Mixing the sulfur-carbon composite powder with polyvinylidene fluoride (PVDF) powder according to the weight ratio of 95: 5, mixing and adding the mixture into a Nitrogen Methyl Pyrrolidone (NMP) solution, and performing ball milling and stirring to obtain uniform slurry. And coating the slurry on an aluminum foil current collector, and evaporating the solvent to obtain the sulfur-carbon composite cathode, wherein the sulfur loading capacity on the sulfur-carbon composite cathode is 8mg/cm 2. The sulfur-carbon composite cathode is cut into 2cm2 electrode plates, the electrode plates, a lithium foil anode and a diaphragm are assembled into a laminated simulation battery, 1M LiTFSI and 0.2M LiiNO 3 DME/DOL electrolyte are added, and the capacity of the simulation battery is 16 mAh. The performance test of the battery is shown in the attached figures 2 and 3, the capacity of the first circle is 15.81mAh under 2mA/cm2, the internal short circuit phenomenon caused by lithium dendrite occurs after the battery is circulated for 49 circles only, the battery cannot be charged, the capacity retention rate is 89.07% when the battery fails, and the average capacity per circle is attenuated by 0.218%.
The first embodiment is as follows:
as shown in fig. 1, the lithium anode surface protection coating provided by the present embodiment is formed by stacking nanoparticles having a particle size of 20 to 50nm, and pores between the stacked nanoparticles are filled with solid electrolyte particles; the nano particles are silicon dioxide, and the solid electrolyte can adopt lithium sulfide.
The protective coating 2 is arranged between the lithium anode 1 and the diaphragm 3 of the lithium metal battery and is used for protecting the lithium anode 1; the thickness of the protective coating 2 may be 2 μm, 10 μm, 18 μm, or 30 μm.
The protective coating provided in this example can be prepared by the following method:
step 1: taking 40 parts of silicon dioxide nano particles with the particle size of 20-50 nm, taking 50 parts of elemental sulfur powder, putting the elemental sulfur powder into a ball milling tank, and mixing and ball milling for 2 hours to obtain a uniform composite material;
step 2: adding 8 parts of polyoxyethylene binder into the ball milling tank, mixing with the composite material obtained in the step 1, adding 350 parts of deionized water as a solvent, and continuing ball milling for 6 hours to obtain a uniform mixed coating;
and step 3: scraping the composite coating obtained in the step 2 on a diaphragm by using a 75-micron scraper, and baking the diaphragm at 80 ℃;
and 4, step 4: and (3) placing the surface of the lithium foil coated with the composite coating on the diaphragm on the surface coated with the composite coating, placing the lithium foil coated with the composite coating on the surface of the diaphragm in a roller press with a heating function for rolling, heating to ensure that the diaphragm coated with the composite coating and the lithium foil are pressed by the roller press when the rolling temperature reaches 140 ℃, and enabling substances in the composite coating coated on the diaphragm to react with lithium elements in the lithium foil in situ to obtain the lithium anode with the protective coating.
The lithium anode and the sulfur-carbon composite cathode in the comparative example 1 are used for assembling a simulation battery, the used electrolyte and the assembling process are the same as those in the comparative example 1, and the designed capacity of the simulation battery is 16 mAh. The performance test of the battery is shown in attached figures 4 and 5, the capacity of the first circle is 16.74mAh under 2mA/cm2, the capacity retention rate of the battery after 50 circles of battery circulation is 97.13%, the capacity retention rate of the battery after 100 circles is 91.84%, and the average capacity attenuation of each circle is 0.0816%. The battery does not have a battery short circuit phenomenon caused by lithium dendrites in the circulation process, and the battery capacity exertion and the capacity retention rate are superior to those of the battery in the comparative example 1, which shows that the structural design of the lithium anode protective layer can effectively inhibit the growth of dendrites on the surface of the lithium anode, improve the capacity and the circulation retention rate of the corresponding lithium-sulfur battery and contribute to the improvement of the battery safety.
Example two:
as shown in fig. 1, the lithium anode surface protection coating provided by the present embodiment is formed by stacking nanoparticles having a particle size of 10 to 100nm, and pores between the stacked nanoparticles are filled with solid electrolyte particles; wherein the nano particles are aluminum oxide, and the solid electrolyte can adopt lithium phosphide.
The protective coating 2 is arranged between the lithium anode 1 and the diaphragm 3 of the lithium metal battery and is used for protecting the lithium anode 1; wherein the thickness of the protective coating 2 may be 6 μm, 9 μm, 15 μm or 45 μm.
The protective coating provided in this example can be prepared by the following method:
step 1: taking 60 parts of aluminum oxide nano particles with the particle size of 10-80 nm, taking 30 parts of simple substance red phosphorus powder, and putting the simple substance red phosphorus powder into a heater to heat for 2 hours to obtain a uniform composite material;
step 2: adding 10 parts of polyacrylonitrile binder into a heater, mixing with the composite material obtained in the step 1, adding 350 parts of azomethyl pyrrolidone as a solvent, and continuously heating for 6 hours to obtain a uniform mixed coating;
and step 3: spraying the composite coating obtained in the step 2 on a diaphragm by using a sprayer, and baking the diaphragm at the temperature of 150 ℃;
and 4, step 4: and (3) placing the surface of the diaphragm coated with the composite coating on the lithium foil surface used in the comparative example 1, rolling the lithium foil surface in a rolling machine, and immersing the rolled lithium foil surface in the electrolyte used in the comparative example 1 for 30min to enable substances in the composite coating coated on the diaphragm to react with lithium elements in the lithium foil in situ to obtain the lithium anode with the protective coating.
The lithium anode obtained in the example and the sulfur-carbon composite cathode in the comparative example 1 were used to assemble a simulated battery, the electrolyte and the assembly process used were the same as in the comparative example 1, and the designed capacity of the simulated battery was 16 mAh. The performance test of the battery is shown in the attached figures 6 and 7, the capacity of the first circle is 16.58mAh under 2mA/cm2, the capacity retention rate of the battery after 50 circles of circulation is 94.18%, the capacity retention rate of the battery after 100 circles is 84.86%, and the average capacity attenuation of each circle is 0.151%.
Example three:
as shown in fig. 1, the lithium anode surface protection coating provided by the present embodiment is formed by stacking nanoparticles having a particle size of 100 to 150nm, and pores between the stacked nanoparticles are filled with solid electrolyte particles; wherein the nanoparticles are silicon dioxide, and the solid electrolyte can adopt lithium nitride.
The protective coating 2 is arranged between the lithium anode 1 and the diaphragm 3 of the lithium metal battery and is used for protecting the lithium anode 1; wherein the thickness of the protective coating 2 may be 50 μm, 75 μm, 90 μm or 100 μm.
The protective coating provided in this example can be prepared by the following method:
step 1: taking 60 parts of silicon dioxide nano particles with the particle size of 100-150 nm, taking 60 parts of copper nitride powder, and putting the copper nitride powder into a ball milling tank to heat for 2 hours to obtain a uniform composite material;
step 2: adding 10 parts of polyvinylidene fluoride binder into the ball milling tank, mixing with the composite material obtained in the step (1), adding 350 parts of azomethylpyriolidone serving as a solvent, and continuously heating for 6 hours to obtain a uniform mixed coating; and step 3: scraping the composite coating obtained in the step 2 on a diaphragm by using a 75-micron scraper, and baking the diaphragm at 150 ℃;
and 4, step 4: and (3) placing the surface of the lithium foil coated with the composite coating on the side of the diaphragm coated with the composite coating on the surface of the lithium foil used in the comparative example 1, placing the diaphragm coated with the composite coating and the lithium foil into a roller press, rolling, immersing the diaphragm and the lithium foil into DME/DOL electrolyte of 1M LiTFSI +0.2M LiNO3 for 30min, and then enabling substances in the composite coating coated on the diaphragm to react with lithium elements in the lithium foil in situ to obtain the lithium anode with the protective coating.
The lithium anode obtained in the example and the sulfur-carbon composite cathode in the comparative example 1 were used to assemble a simulated battery, the electrolyte and the assembly process used were the same as in the comparative example 1, and the designed capacity of the simulated battery was 16 mAh. The performance test of the battery is shown in attached figures 9 and 8, the capacity of the first circle is 15.96mAh under 2mA/cm2, the capacity retention rate of the battery after 50 circles of circulation is 94.97%, the capacity retention rate of the battery after 100 circles is 84.82%, and the average capacity attenuation of each circle is 0.152%.
Table 1 also provides a visual comparison of cycling data for a battery assembled from a lithium anode formed using a protective coating as provided herein and a battery assembled from an electrode as provided in comparative example 1, which more visually demonstrates that a battery assembled from an electrode as provided herein performs better and has a longer cycling life.
Table 1 comparison of cycle data for cells assembled from comparative example 1 electrodes and lithium anodes comprising protective coatings provided herein
First circle capacity Retention ratio at 50 weeks% Retention ratio at 100 weeks%
Comparative example 1 15.81 89.07(49 weeks failure) /
Example one 16.74 97.13 91.84
Example two 16.58 94.18 84.86
EXAMPLE III 15.96 94.97 84.82
As can be seen from the data in table 1, the battery assembled by using the protective coating provided in the present application to protect the lithium anode has better performance in terms of first-turn capacity and cycle retention rate.
In addition, the solid electrolyte described in the first, second, and third embodiments is obtained by in-situ reaction of one or more of simple substances or compounds containing corresponding elements, such as sulfur, phosphorus, iodine, or copper nitride, with lithium metal, where the in-situ reaction is a thermal recombination reaction or an in-situ electrochemical reaction after infiltration with an electrolyte.
The above embodiments are only for illustrating the technical solutions of the present invention and are not limited, and modifications or equivalent substitutions made by those skilled in the art to the technical solutions of the present invention are included in the scope of the claims of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (8)

1. A preparation method of a lithium anode surface protective coating is characterized by comprising the following steps: the method comprises the following steps:
step 1: carrying out ball milling or heating compounding on 40-60 parts by weight of one or more substances of sulfur, iodine, phosphorus or copper nitride and 30-60 parts by weight of nanoparticles to obtain a composite material;
step 2: adding 8-10 parts by weight of binder and 350 parts by weight of solvent into the composite material obtained in the step 1, and stirring to obtain a composite coating;
and step 3: uniformly coating the composite coating obtained in the step 2 on the surface of a diaphragm in a spraying, blade coating or transfer coating mode and drying;
and 4, step 4: and (3) placing the side, coated with the composite coating, of the separator on the surface of the lithium anode, and performing the following step A or step B:
step A: pressing the diaphragm coated with the composite coating and the lithium anode at the temperature of 80-180 ℃ in a hot rolling mode, so that one or more substances of sulfur, iodine, phosphorus or copper nitride in the composite coating coated on the diaphragm and lithium elements in the lithium anode are subjected to in-situ reaction, and a protective coating is formed between the diaphragm and the lithium anode;
and B: pressing the diaphragm coated with the composite coating and the lithium anode in a cold pressing and rolling mode, and infiltrating by using electrolyte, so that one or more substances of sulfur, iodine, phosphorus or copper nitride in the composite coating coated on the diaphragm and lithium elements in the lithium anode are subjected to in-situ reaction, and a protective coating is formed between the diaphragm and the lithium anode;
the nano particles in the step 1 are aluminum oxide or silicon dioxide.
2. The method of claim 1, wherein: the binder is polyoxyethylene, polyacrylonitrile or polyvinylidene fluoride.
3. The method of claim 1, wherein: the protective coating is arranged between the lithium anode and the diaphragm, the protective coating is mainly formed by accumulating nano particles, solid electrolyte materials which have high lithium ion conductivity and are stable to lithium metal are filled among the nano particles, and the solid electrolyte materials are obtained by the in-situ reaction of precursor materials and lithium; the precursor material is one or more of sulfur, iodine, phosphorus or copper nitride.
4. The production method according to claim 3, characterized in that: the particle size of the nanoparticles is 10-150 nm.
5. The production method according to claim 3 or 4, characterized in that: the solid electrolyte comprises one or a combination of several of lithium sulfide, lithium iodide, lithium phosphide and lithium nitride.
6. The production method according to claim 3 or 4, characterized in that: the thickness of the protective coating is 2-100 mu m.
7. The production method according to claim 3 or 4, characterized in that: the thickness of the protective coating is 2-30 mu m.
8. The production method according to claim 3 or 4, characterized in that: the thickness of the protective coating is 6-15 mu m.
CN201810132064.5A 2018-02-09 2018-02-09 Lithium anode surface protective coating and preparation method thereof Active CN108376783B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810132064.5A CN108376783B (en) 2018-02-09 2018-02-09 Lithium anode surface protective coating and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810132064.5A CN108376783B (en) 2018-02-09 2018-02-09 Lithium anode surface protective coating and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108376783A CN108376783A (en) 2018-08-07
CN108376783B true CN108376783B (en) 2020-10-23

Family

ID=63017492

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810132064.5A Active CN108376783B (en) 2018-02-09 2018-02-09 Lithium anode surface protective coating and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108376783B (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109216675A (en) * 2018-09-05 2019-01-15 中国科学院物理研究所 A kind of lithium battery material and its preparation method and application that copper nitride is modified
CN109962200A (en) * 2019-02-28 2019-07-02 湖南立方新能源科技有限责任公司 A kind of lithium metal secondary cell
CN110224177B (en) * 2019-05-08 2020-11-17 华中科技大学 Protection method of lithium metal/sodium metal negative electrode and product
CN110137566B (en) * 2019-05-21 2021-06-08 哈尔滨工业大学 Method for inhibiting lithium dendrite on solid electrolyte interface and application
CN110085919B (en) * 2019-05-21 2021-06-22 哈尔滨工业大学 All-solid-state battery electrolyte interface modification method and application thereof
CN112448023B (en) * 2019-08-28 2022-02-18 宁德时代新能源科技股份有限公司 Solid electrolyte membrane and solid lithium metal battery
CN111430668A (en) * 2019-12-31 2020-07-17 蜂巢能源科技有限公司 Negative electrode protection layer, preparation method, negative electrode and lithium ion battery
CN111933888A (en) * 2020-06-30 2020-11-13 国网浙江省电力有限公司湖州供电公司 Fast ion conductor solid-state lithium battery cathode with SEI and preparation method thereof
CN112234185B (en) * 2020-10-28 2022-08-30 珠海冠宇电池股份有限公司 Positive pole piece and application thereof
CN112477451B (en) * 2020-12-03 2023-08-11 安徽维森智能识别材料有限公司 Mixed base heat transfer carbon belt suitable for various printing stock
CN113659282A (en) * 2021-08-17 2021-11-16 哈尔滨工业大学 Oxide coating with oxygen defect for inhibiting lithium dendrite and preparation method thereof
CN113745470B (en) * 2021-08-30 2022-12-09 清华大学 Solid-state lithium battery composite cathode and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1866583A (en) * 2005-04-27 2006-11-22 三星Sdi株式会社 Lithium secondary battery
CN1950968A (en) * 2004-05-14 2007-04-18 松下电器产业株式会社 Lithium ion secondary battery
CN107078343A (en) * 2014-10-29 2017-08-18 株式会社Lg 化学 Lithium-sulfur cell

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6432586B1 (en) * 2000-04-10 2002-08-13 Celgard Inc. Separator for a high energy rechargeable lithium battery
JP2003077462A (en) * 2001-09-03 2003-03-14 Japan Storage Battery Co Ltd Non-aqueous electrolyte secondary battery
CN102315420B (en) * 2010-07-05 2014-09-10 中国科学院上海硅酸盐研究所 Metal cathode structure with protection layer and preparation method thereof
CN106803580A (en) * 2017-01-19 2017-06-06 浙江大学 A kind of negative material for lithium metal battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1950968A (en) * 2004-05-14 2007-04-18 松下电器产业株式会社 Lithium ion secondary battery
CN1866583A (en) * 2005-04-27 2006-11-22 三星Sdi株式会社 Lithium secondary battery
CN107078343A (en) * 2014-10-29 2017-08-18 株式会社Lg 化学 Lithium-sulfur cell

Also Published As

Publication number Publication date
CN108376783A (en) 2018-08-07

Similar Documents

Publication Publication Date Title
CN108376783B (en) Lithium anode surface protective coating and preparation method thereof
CN103746089B (en) A kind of solid lithium battery with gradient-structure and preparation method thereof
CN102394305B (en) Foamy copper oxide/copper lithium ion battery anode and preparation method thereof
CN101420047B (en) Preparation of lithium sulfureous secondary battery
CN110828883A (en) Lithium ion battery, preparation method thereof and electric vehicle
CN106159318A (en) Novel slice type solid-state serondary lithium battery that garnet-type solid electrolyte supports and preparation method thereof
CN101859887A (en) Transition metal phosphate-clad composite lithium ion battery anode material
CN110581253A (en) Electrode pole piece, preparation method thereof and solid-state battery
CN111900485B (en) Slow-release modification method for solid electrolyte/metal lithium interface and solid lithium metal battery
CN110858660B (en) Lithium ion battery, preparation method thereof and electric vehicle
CN109273760A (en) A kind of lithium ion cell electrode piece and coating method with solid-state electrolyte layer
CN112687865A (en) Lithium ion battery cathode slurry, preparation method and application thereof
CN112736245B (en) Lithium ion battery negative electrode material, and preparation method and application thereof
CN103346292B (en) A kind of composite lithium ion battery anode and its preparation method and application
CN114373982B (en) Liquid ether organic electrolyte-based low-negative electrode secondary sodium battery and preparation method thereof
CN104966814A (en) High-security metallic lithium cathode and preparation method thereof
KR101049826B1 (en) A positive electrode for a lithium secondary battery, a manufacturing method thereof, and a lithium secondary battery including the same
CN101587952A (en) Compound lithium cobaltate cathode material, preparing method and application thereof
CN107403907A (en) A kind of lithium battery cathode plate and preparation method thereof
CN112786860B (en) Composite positive electrode material and preparation method thereof, positive electrode slurry, positive electrode plate and all-solid-state battery
CN102332582B (en) Preparation method for novel lithium vanadium phosphate/bamboo charcoal composite cathode material
CN113363427A (en) Preparation method of lithium alloy cathode for sulfide all-solid-state battery and battery thereof
CN114203976A (en) Mixed solution capable of improving stability of metal lithium cathode, preparation method and application
CN108565397A (en) Metal lithium electrode surface oxidation composite protection layer structure and preparation method
WO2013146454A1 (en) Electrode material, all-solid-state lithium secondary battery, and manufacturing method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant