CN113206217A - Anti-tensile ultrathin lithium foil and preparation method thereof - Google Patents
Anti-tensile ultrathin lithium foil and preparation method thereof Download PDFInfo
- Publication number
- CN113206217A CN113206217A CN202110445386.7A CN202110445386A CN113206217A CN 113206217 A CN113206217 A CN 113206217A CN 202110445386 A CN202110445386 A CN 202110445386A CN 113206217 A CN113206217 A CN 113206217A
- Authority
- CN
- China
- Prior art keywords
- lithium
- porous
- ultra
- stretch
- thin
- 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.)
- Pending
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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
- H01M4/806—Nonwoven fibrous fabric containing only fibres
-
- 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
Abstract
The invention provides a stretch-resistant ultrathin lithium foil, which comprises the following components in percentage by weight: an electrically conductive porous tensile layer formed from an inorganic fibrous material, wherein the porous tensile layer has a pore size of from 1 nanometer to 200 microns and a porosity of from 10% to 85%; and a discontinuous lithium metal material disposed in the pores of the porous tensile layer, wherein the discontinuous lithium metal material is dispersed as a discrete lithium metal material in the pores of the porous tensile layer; and optionally a surface protective layer on the porous stretch resistant layer.
Description
Technical Field
The invention belongs to the field of metal lithium processing, and particularly relates to an anti-tensile ultrathin lithium foil and a preparation method thereof.
Background
Metallic lithium, as the metal material with the lowest density, has been the key material for manufacturing light alloys and metallic lithium batteries. Particularly in the field of new energy, the lithium metal has high specific capacity (3860mAh/g) and most negative chemical potential (-3.04V vs H/H)+) And the like, and the lithium ion battery has the potential to be a single component, namely, the lithium ion battery is used as a metal lithium cathode, and plays a decisive role in improving the energy density of the battery. However, lithium metal is soft and when processed into ultra-thin foil (thickness < 20 microns), the edges and interior of the foil are prone to cracking. Therefore, the ultra-thin lithium metal foil cannot be continuously formed. To increase the energy density of the battery, however, the lithium metal foil is required to be less than 20 microns thick, and sometimes even less than 5 microns thick. Therefore, at the current processing level, if the ultra-thin lithium foil is not subjected to stretch-proof treatment, the above goal cannot be achieved, and the application of the lithium metal cathode in the new energy field is also greatly hindered.
In addition, conventional lithium metal anodes also suffer from volume expansion and dendrite deposition during battery cycling. Which may lead to an impact on the stability and cycle life of the battery.
In addition, the lithium metal has active chemical properties, and is easy to have harmful reactions in the processes of processing, storing and using. The quality guarantee period of the foil material can be shortened rapidly due to a large amount of impurities such as lithium hydroxide, lithium nitride and lithium carbonate existing on the surface of the metal lithium foil, and the performance of the metal lithium negative electrode can be influenced due to the existence of the impurities, so that the side reactions of the metal lithium battery are increased, and the cycle life of the electrode is shortened.
With the refinement and expansion of the application field of lithium batteries, the application of ultra-thin lithium foils in the battery field also faces many challenges. In the field of energy storage, batteries are required to have longer cycle life and high and low temperature performance. In the field of power batteries, batteries are required to have high rate performance and safety performance besides high and low temperature performance, and the requirement on the cycle life of the batteries is not high. Therefore, ultra-thin lithium foil products must be functionally designed to meet such diverse market demands.
In summary, the industrial application of ultra-thin lithium foil is still important and far.
Disclosure of Invention
It is an object of the present invention to provide a stretch-resistant ultra-thin lithium foil that overcomes the above-mentioned problems of the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect of the present invention, there is provided a stretch-resistant ultra-thin lithium foil, including:
an electrically conductive porous tensile layer formed from an inorganic fibrous material, wherein the porous tensile layer has a pore size of from 1 nanometer to 200 microns and a porosity of from 10% to 85%;
a discontinuous lithium metal material disposed in the pores of the porous tensile layer, wherein the discontinuous lithium metal material is dispersed as a discrete lithium metal material in the pores of the porous tensile layer; and
optionally a surface protective layer on the porous stretch resistant layer.
Preferably, the porous stretch resistant layer has a pore size of from 5nm to 100 microns, more preferably from 10 nm to 50 microns.
Preferably, the porosity of the porous tensile layer is from 15% to 80%, more preferably from 25% to 70%.
In some embodiments, the inorganic fiber material includes at least one selected from the group consisting of carbon nanotubes, carbon fibers, metal fibers, semiconductor fibers, and inorganic oxide fibers. For example, the metal fibers may comprise Ni, Pt, Au, Al or stainless steel fibers, the semiconductor fibers may comprise InP, Si or GaN fibers, and the inorganic oxide fibers may comprise SiO2Or TiO2A fiber.
In some embodiments, the inorganic fiber material is an inorganic fiber material modified by vapor deposition, magnetron sputtering, electroplating, atomic doping, atomic etching, or a combination thereof. For example, the surface treatment may include surface graphitization, amination, acid etching, coating polyethylene oxide, or deposition of nano-alumina, and the atomic doping may include nano-silver particle doping, graphene doping, or conductive graphite doping.
In some embodiments, the inorganic fiber material has a diameter of 1 nanometer to 30 micrometers, preferably 5 nanometers to 10 micrometers.
In some embodiments, the inorganic fiber material has a length of 10 nanometers or more, preferably 50 nanometers or more.
In some embodiments, the average thickness of the stretch resistant ultra-thin lithium foil is from 0.1 microns to 200 microns, preferably from 1 micron to 50 microns, more preferably from 5 microns to 20 microns.
In some embodiments, the surface roughness of the stretch resistant ultra-thin lithium foil is 5 microns or less.
In some embodiments, the tensile modulus of the ultra-thin lithium foil is in the range of 1MPa to 300MPa, preferably in the range of 10MPa to 300MPa, and more preferably in the range of 100MPa to 300 MPa.
In some embodiments, the metallic lithium material is metallic lithium or an alloy of lithium with at least one selected from: ag. Al, Au, B, Ba, Be, Bi, C, Ca, Cd, Co, Cr, Cs, Fe, Ga, Ge, Hf, Hg, In, Ir, K, Mg, Mn, Mo, N, Na, Nb, Ni, Pt, Pu, Rb, Rh, S, Se, Si, Sn, Sr, Ta, Te, Ti, V, Y, Zn, Zr, Pb, Pd, Sb and Cu.
In some embodiments, the surface protection layer has a thickness of 5nm to 100 microns, more preferably 10 nm to 50 microns.
In some embodiments, the material of the surface protective layer includes at least one selected from an organic polymer and an inorganic compound. For example, the organic polymer may include polyethylene oxide, oleic acid, or PVDF, and the inorganic compound may include lithium phosphate, lithium carbide, lithium fluoride, an oxide solid electrolyte, or glass ceramic.
In some embodiments, the surface protective layer may be disposed on one surface of the porous tensile layer, or may be disposed on both surfaces of the porous tensile layer.
According to another aspect of the present invention, there is provided a method of preparing a stretch-resistant ultra-thin lithium foil as described above, comprising the steps of:
step 1: mixing an inorganic fiber material, a binder, a pore-forming agent and an optional inorganic filler to prepare slurry, coating the slurry and carrying out high-temperature carbonization treatment on the slurry at the temperature of 300-3000 ℃ to form a conductive porous anti-stretching layer, wherein the pore size of the porous anti-stretching layer is 1 nanometer to 200 micrometers, and the porosity is 10 to 85 percent;
step 2: attaching a metallic lithium material to the pores of the porous tensile layer to form a discontinuous metallic lithium material, the discontinuous metallic lithium material being dispersed as a discrete metallic lithium material within the pores of the porous tensile layer; and
and step 3: optionally, a surface protective layer is applied over the porous stretch resistant layer.
In some embodiments, the pore former comprises at least one of ammonium bicarbonate, naphthalene, polystyrene, and ammonium carbonate.
In some embodiments, the pore former has a size of 10 nanometers to 10 micrometers, more preferably 20 nanometers to 5 micrometers.
In some embodiments, the binder comprises at least one of polymethylmethacrylate, polytetrafluoroethylene, styrene-butadiene rubber, polyvinylidene fluoride, polyepoxy, polystyrene, carboxymethylcellulose, polyvinylpyrrolidone, polyvinyl alcohol, sucrose, polyphenylene sulfide, and polyphenylene oxide resin.
In some embodiments, the inorganic filler comprises at least one of conductive graphite, carbon black, ketjen black, graphene, metal nanoparticles, metal oxides, and inorganic solid state electrolytes.
In some embodiments, the temperature of the high temperature carbonization treatment is preferably 400-.
In some embodiments, the method further comprises the step of modifying the inorganic fiber material by vapor deposition, magnetron sputtering, electroplating, atomic doping, atomic etching, or combinations thereof prior to step 1.
In some embodiments, attaching a lithium metal material to the pores of the porous tensile layer includes attaching a lithium metal material to the pores of the porous tensile layer by melt impregnation, melt infiltration, or powder adsorption.
Compared with the prior art, the stretch-resistant ultrathin lithium foil provided by the invention has the following advantages:
(1) the framework material for forming the porous stretch-resistant layer is optional, the mechanical strength is good, and the prepared ultrathin lithium foil is high in strength and light in weight and can be used for preparing a battery device with high energy density;
(2) the specific surface of the adopted conductive framework material is large, so that the current density can be effectively dispersed, and the growth of dendritic crystals is relieved when metal lithium is deposited;
(3) the framework material is surrounded around the discontinuous metal lithium material and forms a stable structure, so that the expansion of the metal lithium can be effectively inhibited, the stable electrode structure is maintained, and the cycle performance of the battery is improved;
(4) compared with planar lithium or blocky lithium, discontinuous metal lithium has irregular surface and larger specific surface area, so that the current density on the surface of the metal lithium can be effectively reduced, the ion and electron contact interface is increased, and the rate capability of the electrode is favorably improved;
(5) compared with organic polymers, the ultrathin metal lithium foil mainly comprises metal lithium and inorganic materials, and has better heat resistance;
(6) the ultrathin lithium foil surface protective layer can effectively relieve the side reaction of the metal lithium with the electrolyte and air, and reduce the occurrence of safety accidents;
(7) the binding capacity between the lithium metal and the porous tensile layer can be improved by modifying the inorganic fiber material, and the electronic conductivity of the product can be improved.
(8) The stretch-resistant ultrathin lithium foil can be produced in batch.
Drawings
Fig. 1 is a photograph of a stretch resistant ultra thin lithium foil according to one embodiment of the present invention.
Fig. 2 is a schematic structural view of a stretch-resistant ultra-thin lithium foil (including a protective layer) according to an embodiment of the present invention.
Fig. 3 shows cycle performance test curves of batteries using the ultra-thin lithium foils of example 7 of the present application and comparative example 2 as electrode sheets.
Detailed Description
The present invention will be described with reference to the accompanying drawings and specific embodiments. It should be understood, however, that the following specific examples are merely illustrative of embodiments of the present invention, and the scope of the present invention is not limited thereto.
Examples
Example 1
The preparation method comprises the steps of adopting a carbon nano tube (model GT-300, Shandong Dachang, diameter: 12-15nm) as an inorganic fiber material, mixing the carbon nano tube, polymethyl methacrylate and ammonium bicarbonate powder as a pore forming agent to obtain carbon nano tube slurry, coating the slurry to prepare a stretch-proof layer film, and placing the film in a tubular furnace protected by nitrogen atmosphere to carry out high-temperature carbonization treatment for 8 hours to obtain the porous stretch-proof layer.
And (3) soaking the porous stretch-proofing layer in molten metal lithium liquid, taking out the porous stretch-proofing layer, rolling and leveling the porous stretch-proofing layer, and thus obtaining a stretch-proofing ultrathin lithium foil product with the thickness of 5 micrometers.
Fig. 1 shows a photograph of a stretch resistant ultra thin lithium foil product according to this example, where the bright spots indicate discontinuous lithium metal and the dark areas indicate the framework material of the porous stretch resistant layer. As can be seen in fig. 1, the discrete lithium metal is dispersed in the pores of the porous tensile layer in the form of discrete lithium metal.
Example 2
The preparation method comprises the steps of adopting carbon nanotubes (the formation is organic, the diameter is 30-50nm) as inorganic fiber materials, mixing the carbon nanotubes, polystyrene serving as a pore-forming agent and molten polytetrafluoroethylene to obtain carbon nanotube slurry, coating the obtained slurry to prepare an anti-stretching layer film, placing the film in a tubular furnace protected by argon atmosphere, and carrying out high-temperature carbonization treatment for 12 hours to obtain the porous anti-stretching layer.
And spreading molten metal lithium on the porous stretch-resistant layer in a negative pressure inert atmosphere, and cooling after the lithium liquid permeates into pores to obtain a stretch-resistant ultrathin lithium foil product with the thickness of 5 micrometers.
Example 3
Carbon fibers (from east of Japan) having a diameter of 8 μm, ammonium bicarbonate powder as a pore-forming agent, and nano silver particles were added to molten polyethylene oxide, mixed uniformly, and coated to form a film. And carrying out high-temperature carbonization treatment on the cooled membrane to obtain the porous stretch-resistant layer.
Lithium metal was attached to the porous tensile layer in the same manner as in example 1, resulting in a tensile ultra-thin lithium foil with a thickness of 10 μm.
Example 4
Tensile ultra-thin lithium foil having a thickness of 10 μm was manufactured in a similar manner to example 1, except that aluminum fiber having a diameter of 6 μm was used as the inorganic fiber material.
Example 5
Tensile ultra-thin lithium foil having a thickness of 20 μm was prepared in a similar manner to example 3, except that silicon fiber having a diameter of 15 μm was used as the inorganic fiber material.
Example 6
A tensile ultra-thin lithium foil having a thickness of 50 μm was prepared in a similar manner to example 2, except that silica fibers having a diameter of 10 μm were used as the inorganic fiber material and graphene was used as the filler.
Example 7
A tensile ultra-thin lithium foil having a thickness of 10 μm was prepared in a similar manner to example 3, except that the carbon fiber was surface-modified by depositing a 3 nm-thick silver plating layer on the surface of the carbon fiber used in example 3 through vapor deposition.
Example 8
After a tensile-resistant ultra-thin lithium foil having a thickness of 10 μm was prepared in a similar manner to example 3, a protective layer of aluminum oxide having a thickness of 3nm was applied to the surface of the ultra-thin lithium foil by vacuum thermal evaporation.
Comparative example 1
The polypropylene and the carbon nano tube (the diameter is 12-15nm, the mass percent of the carbon nano tube is 10%) are melted and mixed evenly, and a porous membrane with the thickness of 50 mu m and the porosity of 80% is prepared on lithium battery diaphragm production equipment by adopting a known dry method double-pulling method. And plating a layer of metal lithium with the thickness of 0.1 mu m on the surface of the porous membrane by adopting an electroplating method (the upper surface and the lower surface of the porous membrane are plated with the metal lithium with the thickness of 0.1 mu m) to obtain the composite lithium belt with the thickness of 50 mu m.
For convenience of explanation, the preparation conditions of the ultra-thin lithium foil of each example are summarized in table 1.
Table 1: preparation conditions of ultrathin lithium foil
The results of the testing of the performance of the tensile ultra-thin lithium foils in each example are set forth in table 2.
The porosity of the porous tensile layer is measured by the BET method and calculated.
And calculating the mass ratio of the lithium metal of the tensile ultra-thin lithium foil according to the porosity, the density of the framework material of the porous tensile layer and the density of the lithium metal.
The specific capacity of the tensile ultrathin lithium foil is measured by adopting the following method: the tensile ultra-thin lithium foil prepared in the above examples was punched into disks and the quality of the punched disks was weighed. Assembling a button type half cell by taking the metal lithium as a negative electrode and the punched wafer as a positive electrode; setting a charge and discharge program: the charging current is 0.1mA, the cut-off voltage is 1V, and the mass of the active substance is the mass of the punched wafer; after the charging is finished, the specific capacity of the stretch-resistant ultrathin lithium foil in each embodiment is calculated.
The tensile modulus of the tensile ultra-thin lithium foil was measured by the following method: test specimens of the same width, 5 specimens per example, were prepared using the ultra-thin lithium foil in each example, and the tensile test was performed on a tensile strength tester. The tensile strength of the ultrathin lithium foil of each example was the average of the tensile strengths of 5 bars.
The conductivity of the tensile ultra-thin lithium foil was measured by the following method: the ultra-thin lithium foil in each example was punched into a disk, the resistance of the disk was measured, and the conductivity was then calculated using the following formula: conductivity is sample thickness/(contact area resistance).
The softening deformation temperature of the tensile ultra-thin lithium foil is measured by the following method: placing the stretch-resistant ultrathin lithium foil in each embodiment on a heating table in a glove box, controlling the temperature rise speed to be 10 ℃/min, and recording the softening deformation temperature of the ultrathin lithium foil.
The discoloration time of the tensile ultra-thin lithium foil was measured by the following method: and (3) placing the stretch-resistant ultrathin lithium foil in dry air with a dew point of-50 ℃, and recording the color change time of the ultrathin lithium foil.
Table 2: performance of ultra-thin lithium foil
As can be seen from table 1 above, the ultra-thin lithium foil prepared in the example of the present invention is superior to the composite lithium tape of comparative example 1 in specific capacity, tensile modulus, electron conductivity, and softening deformation temperature.
As can be seen from example 3, the electron conductivity of the ultra-thin lithium foil can be improved to some extent by adding the conductive filler. The ultra-thin lithium foil of example 7 in which the carbon fiber was surface-modified had the highest electron conductivity. The ultra-thin lithium foil of example 8 having the surface protective layer did not undergo discoloration in the discoloration test.
Comparative example 2
As a test sample, a commercially available 10 μm thick ultra-thin lithium foil (manufactured by Tianjin lithium industries, Ltd.) was directly used.
Cycle performance test
Cycle performance testing was performed by the following method: the ultra-thin lithium foils of example 7 and comparative example 2 were cut into pole pieces, respectively, and assembled into pouch cells. The battery was subjected to charge-discharge cycling under the following conditions: the electrolyte contains 1mol/L LiPF6And a two-component mixed solvent EC: EMC of 1: 1 (volume ratio v/v), and the diaphragm is dry-process double-drawing polyThe propylene film is tested at 25 ℃, and the circulating process steps are as follows: standing for 5 hr, constant current charging for 0.5 hr, constant current discharging for 0.5 hr, and circulating current of 0.4mA/cm2The circulation capacity is 0.2mAh/cm2. The voltage and cycle time during the cycle were recorded and plotted, and the results are shown in fig. 3.
As can be seen from fig. 3, the cell using the ultra-thin lithium foil of comparative example 2 as a pole piece started to increase in overpotential for charge and discharge after less than 100 hours of charge and discharge cycles, while the cell using the ultra-thin lithium foil of example 7 as a pole piece maintained stable voltage during about 350 hours of charge and discharge cycles. This indicates that the use of the ultra-thin lithium foil according to the present invention as a battery pole piece can improve the cycle stability of the battery, probably because the ultra-thin lithium foil of the present invention alleviates the problems of lithium expansion and dendrite deposition during charge and discharge cycles.
It is to be understood that in the embodiments of the present invention, although the ultra-thin lithium foil with tensile resistance of the present invention is described in detail in conjunction with the specific porous tensile resistant layer composition and structure, protective layer composition, etc., the above description is made only for the sake of satisfying legal requirements, and the present invention is not limited to the given embodiments. The replication of the stretch resistant ultra thin lithium foil can be accomplished by suitable operations by those skilled in the art in light of the disclosure and teachings of the specification.
Appropriate changes and modifications to the embodiments described above will become apparent to those skilled in the art from the disclosure and teachings of the foregoing description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. A stretch-resistant ultra-thin lithium foil, comprising:
an electrically conductive porous tensile layer formed from an inorganic fibrous material, wherein the porous tensile layer has a pore size of from 1 nanometer to 200 microns and a porosity of from 10% to 85%;
a discontinuous lithium metal material disposed in the pores of the porous tensile layer, wherein the discontinuous lithium metal material is dispersed as a discrete lithium metal material in the pores of the porous tensile layer; and
optionally a surface protective layer on the porous stretch resistant layer.
2. The stretch-resistant ultra-thin lithium foil of claim 1, wherein the inorganic fiber material comprises at least one selected from carbon nanotubes, carbon fibers, metal fibers, semiconductor fibers, and inorganic oxide fibers, wherein the inorganic fiber material is optionally modified by vapor deposition, magnetron sputtering, electroplating, atomic doping, atomic etching, or a combination thereof.
3. The ultra-thin tensile lithium foil in accordance with claim 1, wherein the inorganic fiber material has a diameter of 1 nm to 30 μm and a length of 10 nm or more.
4. The ultra-thin, stretch-resistant lithium foil of claim 1, wherein the average thickness of the ultra-thin, stretch-resistant lithium foil is between 0.1 microns and 200 microns.
5. The ultra-thin lithium foil with tensile resistance of claim 1, wherein the tensile strength of the ultra-thin lithium foil with tensile resistance is in a range of 1MPa to 300 MPa.
6. The stretch-resistant ultra-thin lithium foil of claim 1, wherein the metallic lithium material is metallic lithium or an alloy of lithium with at least one selected from the group consisting of: ag. Al, Au, B, Ba, Be, Bi, C, Ca, Cd, Co, Cr, Cs, Fe, Ga, Ge, Hf, Hg, In, Ir, K, Mg, Mn, Mo, N, Na, Nb, Ni, Pt, Pu, Rb, Rh, S, Se, Si, Sn, Sr, Ta, Te, Ti, V, Y, Zn, Zr, Pb, Pd, Sb and Cu.
7. A method of making the stretch resistant ultra thin lithium foil of any one of claims 1 to 6, comprising the steps of:
step 1: mixing an inorganic fiber material, a binder, a pore former, and optionally an inorganic filler to make a slurry, and coating the slurry and subjecting it to a high temperature carbonization treatment at a temperature of 300 to 3000 ℃ to form a conductive porous tensile layer having a pore size of 1 nm to 200 μm and a porosity of 10% to 85%, wherein the inorganic fiber material is optionally modified by vapor deposition, magnetron sputtering, electroplating, atomic doping, atomic etching, or a combination thereof;
step 2: attaching a metallic lithium material to the pores of the porous tensile layer to form a discontinuous metallic lithium material, the discontinuous metallic lithium material being dispersed as a discrete metallic lithium material within the pores of the porous tensile layer; and
and step 3: optionally, a surface protective layer is applied over the porous stretch resistant layer.
8. The method of claim 7, wherein the pore former comprises at least one of ammonium bicarbonate, naphthalene, polystyrene, and ammonium carbonate, and wherein the pore former has a size of 10 nanometers to 10 micrometers.
9. The method of claim 7, wherein the binder comprises at least one of polymethylmethacrylate, polytetrafluoroethylene, styrene-butadiene rubber, polyvinylidene fluoride, polyepoxy, polystyrene, carboxymethylcellulose, polyvinylpyrrolidone, polyvinyl alcohol, sucrose, polyphenylene sulfide, and polyphenylene oxide resin; and the inorganic filler includes at least one of conductive graphite, carbon black, ketjen black, graphene, metal nanoparticles, metal oxide, and inorganic solid electrolyte.
10. The method of claim 7 wherein attaching a lithium metal material to the pores of the porous tensile layer includes attaching a lithium metal material to the pores of the porous tensile layer by melt impregnation, melt infiltration, or powder adsorption.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110445386.7A CN113206217A (en) | 2021-04-23 | 2021-04-23 | Anti-tensile ultrathin lithium foil and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110445386.7A CN113206217A (en) | 2021-04-23 | 2021-04-23 | Anti-tensile ultrathin lithium foil and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113206217A true CN113206217A (en) | 2021-08-03 |
Family
ID=77028356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110445386.7A Pending CN113206217A (en) | 2021-04-23 | 2021-04-23 | Anti-tensile ultrathin lithium foil and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113206217A (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274386A (en) * | 2013-05-24 | 2013-09-04 | 厦门大学 | Aperture-controllable porous electrode and preparation method thereof |
| CN104409674A (en) * | 2014-12-08 | 2015-03-11 | 清华大学 | Composite diaphragm material and preparation method and application thereof |
| CN104425134A (en) * | 2014-11-11 | 2015-03-18 | 超威电源有限公司 | High-porosity and high-conductivity porous electrode, batch manufacturing process of porous electrode and super pseudo-capacitor using porous electrode |
| CN108172761A (en) * | 2017-12-30 | 2018-06-15 | 中南大学 | It a kind of composite negative pole for lithium secondary battery and its prepares and application |
| CN108565407A (en) * | 2018-01-09 | 2018-09-21 | 苏州氟特电池材料股份有限公司 | A kind of lithium battery electrode material and preparation method thereof |
| CN109256548A (en) * | 2018-09-06 | 2019-01-22 | 珠海光宇电池有限公司 | A kind of ultralight complex lithium band of high intensity and preparation method thereof |
| CN109273704A (en) * | 2017-07-18 | 2019-01-25 | 中国科学院上海硅酸盐研究所 | A kind of lithium anode and preparation method thereof with high-ratio surface protective layer |
| CN109713224A (en) * | 2018-12-28 | 2019-05-03 | 蜂巢能源科技有限公司 | Compound lithium an- ode and preparation method, lithium ion battery |
| CN110010852A (en) * | 2018-01-05 | 2019-07-12 | 中南大学 | A kind of secondary cell lithium anode, preparation method and applications |
| CN111180673A (en) * | 2020-01-21 | 2020-05-19 | 天齐锂业股份有限公司 | Preparation process of metal lithium cathode with surface protection layer |
| CN111490250A (en) * | 2020-04-26 | 2020-08-04 | 上海汽车集团股份有限公司 | Lithium metal negative electrode, preparation method thereof and lithium metal battery |
-
2021
- 2021-04-23 CN CN202110445386.7A patent/CN113206217A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274386A (en) * | 2013-05-24 | 2013-09-04 | 厦门大学 | Aperture-controllable porous electrode and preparation method thereof |
| CN104425134A (en) * | 2014-11-11 | 2015-03-18 | 超威电源有限公司 | High-porosity and high-conductivity porous electrode, batch manufacturing process of porous electrode and super pseudo-capacitor using porous electrode |
| CN104409674A (en) * | 2014-12-08 | 2015-03-11 | 清华大学 | Composite diaphragm material and preparation method and application thereof |
| CN109273704A (en) * | 2017-07-18 | 2019-01-25 | 中国科学院上海硅酸盐研究所 | A kind of lithium anode and preparation method thereof with high-ratio surface protective layer |
| CN108172761A (en) * | 2017-12-30 | 2018-06-15 | 中南大学 | It a kind of composite negative pole for lithium secondary battery and its prepares and application |
| CN110010852A (en) * | 2018-01-05 | 2019-07-12 | 中南大学 | A kind of secondary cell lithium anode, preparation method and applications |
| CN108565407A (en) * | 2018-01-09 | 2018-09-21 | 苏州氟特电池材料股份有限公司 | A kind of lithium battery electrode material and preparation method thereof |
| CN109256548A (en) * | 2018-09-06 | 2019-01-22 | 珠海光宇电池有限公司 | A kind of ultralight complex lithium band of high intensity and preparation method thereof |
| CN109713224A (en) * | 2018-12-28 | 2019-05-03 | 蜂巢能源科技有限公司 | Compound lithium an- ode and preparation method, lithium ion battery |
| CN111180673A (en) * | 2020-01-21 | 2020-05-19 | 天齐锂业股份有限公司 | Preparation process of metal lithium cathode with surface protection layer |
| CN111490250A (en) * | 2020-04-26 | 2020-08-04 | 上海汽车集团股份有限公司 | Lithium metal negative electrode, preparation method thereof and lithium metal battery |
Non-Patent Citations (1)
| Title |
|---|
| 宗亚宁、张海霞: "《纺织材料学》", 东华大学出版社, pages: 65 - 69 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101103841B1 (en) | Metal ions-assisted electroless etching method for the bundle type silicon nano-rod composite and its application as anode materials for lithium secondary batteries | |
| CN110061191B (en) | Three-dimensional metal lithium cathode and preparation method and application thereof | |
| TWI521773B (en) | Porous silicon-based anode active material, method of preparing the same, and lithium secondary battery including the anode active material | |
| JP5535158B2 (en) | Negative electrode for lithium ion secondary battery, lithium ion secondary battery, and method for producing negative electrode for lithium ion secondary battery | |
| US9831500B2 (en) | Porous electrode active material and secondary battery including the same | |
| US20090186267A1 (en) | Porous silicon particulates for lithium batteries | |
| JP5927710B2 (en) | Negative electrode active material, negative electrode, lithium secondary battery, and method for producing porous composite | |
| WO2013141230A1 (en) | Porous silicon particles and porous silicon-composite particles | |
| EP3598526A1 (en) | Network of metal fibers, method for producing a network of metal fibers, electrode and battery | |
| KR20130040198A (en) | Submicron sized silicon powder with low oxygen content | |
| KR101665099B1 (en) | Anode materials for lithium rechargeable batteries including natural graphite and metal and a preparation method thereof | |
| TW200941802A (en) | Mesoporous materials for electrodes | |
| TW201640719A (en) | Powder, electrode and battery comprising such a powder | |
| CN112928238B (en) | Ultrathin metal lithium electrode, preparation thereof and application of ultrathin metal lithium electrode as negative electrode of secondary lithium battery | |
| KR20170117036A (en) | Powder, an electrode including the powder, and a battery | |
| KR101226245B1 (en) | Negative active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR101392388B1 (en) | Carbon nanofibers composite and method for preparing the same and anode active materials for lithium secondary batteries comprising the same | |
| KR102081772B1 (en) | Electrode and Lithium Secondary Battery Comprising the Same | |
| KR101737197B1 (en) | Porous silicon based anode active material, preparation method thereof, and lithium secondary battery comprising the same | |
| CN215118948U (en) | Stretch-proof ultrathin lithium foil | |
| CN113206217A (en) | Anti-tensile ultrathin lithium foil and preparation method thereof | |
| US20200262707A1 (en) | Hybrid structure, sulfur-hybrid complex comprising the same, and method for producing hybrid structure and sulfur-hybrid complex | |
| JP2020009754A (en) | Active material powder for use in negative electrode of battery and battery including such active material powder | |
| EP4207366A1 (en) | Positive electrode active material for secondary battery, method for preparing same, free-standing film comprising same, dry positive electrode, and secondary battery comprising dry positive electrode | |
| JP6720762B2 (en) | Negative electrode material for lithium-ion secondary battery, and lithium-ion secondary battery |
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 |