CN112151727B - Lithium-containing diaphragm, preparation method thereof and lithium ion battery - Google Patents
Lithium-containing diaphragm, preparation method thereof and lithium ion battery Download PDFInfo
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- CN112151727B CN112151727B CN202011097809.2A CN202011097809A CN112151727B CN 112151727 B CN112151727 B CN 112151727B CN 202011097809 A CN202011097809 A CN 202011097809A CN 112151727 B CN112151727 B CN 112151727B
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 214
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 208
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 39
- 230000001681 protective effect Effects 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 239000012159 carrier gas Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000005507 spraying Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 88
- 239000010410 layer Substances 0.000 claims description 35
- 239000011241 protective layer Substances 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 239000002356 single layer Substances 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 230000007613 environmental effect Effects 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000011368 organic material Substances 0.000 claims description 6
- 229920000767 polyaniline Polymers 0.000 claims description 5
- 229920000123 polythiophene Polymers 0.000 claims description 5
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- 239000011147 inorganic material Substances 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000012788 optical film Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000013589 supplement Substances 0.000 abstract description 8
- 238000004804 winding Methods 0.000 abstract description 7
- 238000007599 discharging Methods 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 3
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- 230000000052 comparative effect Effects 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 230000001502 supplementing effect Effects 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
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- 230000001276 controlling effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
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- 230000003116 impacting effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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 lithium-containing diaphragm, a preparation method thereof and a lithium ion battery. The preparation method provided by the invention comprises the following steps: and (3) taking protective gas as carrier gas, and spraying the lithium-containing powder subjected to load heating onto the surface of the base film to obtain the lithium-containing diaphragm. The preparation method provided by the invention can spray on the surface of the base film to quickly form the lithium-containing film, and can supplement the lithium loss in the battery charging and discharging process. The thickness of the formed lithium film can be controlled, and the unwinding and winding speed of the diaphragm can be regulated and controlled by adjusting the gas flow rate, the lithium-containing powder amount and the unwinding and winding speed of the diaphragm. The protective gas is used as the carrier gas, so that the requirement of the lithium-containing material on the environment can be ensured, and the sealing property can be ensured by selecting a drying room for reaction.
Description
Technical Field
The invention belongs to the technical field of batteries, relates to a diaphragm and a preparation method thereof and a lithium ion battery, and particularly relates to a lithium-containing diaphragm and a preparation method thereof and a lithium ion battery.
Background
During the first charge of the battery, an SEI film is formed and consumed in the battery, thereby causing loss of lithium, lowering the capacity of the battery, and causing first efficiency reduction. In order to reduce the decrease in battery capacity due to irreversible capacity during charging, some lithium needs to be supplemented in the material.
The lithium supplementing method in the prior art comprises the following steps:
1. the lithium powder is directly scattered on the diaphragm and then cold-pressed to form the composite diaphragm (dry method), the diaphragm is compounded by the lithium belt dry method, the requirement on the environment is high, the content of metal lithium compounded on the surface of the diaphragm is difficult to accurately control, the excessive metal lithium on the diaphragm can more easily cause lithium precipitation, the flexibility of the diaphragm can be reduced, and inconvenience is brought to pole piece winding.
2. The lithium powder is prepared into slurry to be coated on the surface of the diaphragm, a large amount of organic solvent is required to be added for preparing the slurry, the coating and drying are carried out, the process time is long, and the energy consumption is high.
3. The lithium ribbon and the diaphragm are compounded together by a cold pressing method (compounding of the lithium ribbon), and the lithium in a molten state is compounded with the diaphragm, so that the requirement on the environment is high, and the thickness of the lithium film cannot be controlled.
CN111312966a discloses a lithium-containing diaphragm, a lithium battery cell, a lithium battery and their preparation methods. The lithium-containing separator includes: web form the separator of (4); one or more lithium-containing regions distributed along the length of the web on one surface of the separator, wherein the length of the separator is equal to or greater than the length of the lithium-containing regions in the length direction of the web, and the width of the separator is greater than the width of the lithium-containing regions in the width direction of the web, and the thickness of the lithium-containing regions is 0.1 to 100 μm, preferably 0.1 to 30 μm.
CN110459723A discloses a battery diaphragm, which comprises a diaphragm body and a lithium-containing coating, wherein the diaphragm body and the lithium-containing coating are arranged in a laminated manner, the lithium-containing coating comprises a lithium-containing compound and a binder, and the mass fraction of the lithium-containing compound in the lithium-containing coating is 80-98%. The preparation method comprises the following steps: providing a lithium-containing compound slurry comprising the lithium-containing compound, the binder, and a dispersant uniformly mixed; coating the lithium-containing compound slurry on the separator body; and drying the separator coated with the lithium-containing compound slurry to remove the dispersant.
CN105206777A discloses a lithium battery diaphragm containing lithium ion conductive porous inorganic oxide and a preparation method thereof. The surface of the lithium battery diaphragm is coated with a coating, the coating comprises a binder, a stabilizer and a porous inorganic oxide capable of conducting lithium ions, and the porous inorganic oxide is formed by compounding and crystallizing a polymer capable of conducting lithium ions and an inorganic oxide precursor; the preparation method is characterized in that a lithium ion conducting polymer and an inorganic oxide precursor are compounded under the action of a surfactant, then crystallized under a hydrothermal condition to form a porous inorganic oxide capable of conducting lithium ions, and then the porous inorganic oxide is mixed with a binder, a stabilizer and an alkyl chain ultraviolet crosslinking agent to prepare slurry, and finally the slurry is coated on the surface of a lithium ion battery diaphragm, irradiated by ultraviolet rays and dried.
However, the above solutions all have the problems of troublesome preparation, high environmental requirements, incapability of controlling the thickness of the lithium thin film, and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a lithium-containing diaphragm, a preparation method thereof and a lithium ion battery. The preparation method provided by the invention can form the lithium film with controllable thickness on the diaphragm, the lithium supplement effect is good.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a lithium-containing separator, the method comprising the steps of:
and (3) taking protective gas as carrier gas, and spraying the lithium-containing powder after load heating onto the surface of the base film to obtain the lithium-containing diaphragm.
In the invention, the protective gas is adopted to load the lithium-containing powder to quickly form the lithium-containing film on the surface of the basal film, so that the lithium loss in the charging and discharging processes of the battery can be supplemented.
The thickness of the lithium-containing film formed by the method can be controlled, and the thickness of the lithium-containing film can be controlled by adjusting the gas flow rate; in addition, the amount of the lithium-containing powder and the unreeling and reeling speed of the diaphragm can also regulate and control the thickness of the lithium-containing film.
And protective gas is used as carrier gas, so that the requirement of the lithium powder on the environment can be ensured.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
As a preferred technical scheme of the invention, the lithium-containing powder comprises metallic lithium and an inert protective layer positioned on the surface of the metallic lithium.
By adopting the structure, the lithium-containing powder can become softer through heating, can deform to expose the metal lithium when impacting the base film, and can form a film through the direct affinity action of the metal lithium.
If the inert protective layer is a high molecular polymer, the inert protective layer can interact with the base film under the impact heat to form a film.
Preferably, in the lithium-containing powder, the weight part of the metallic lithium is 60 to 99 parts, such as 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts or 99 parts, and the like, and the weight part of the inert protective layer is 1 to 40 parts, such as 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts or 40 parts, and the like.
In the invention, if the metallic lithium in the lithium-containing powder is too much relative to the inert protective layer, the lithium supplementing efficiency is low, and the polarization of the battery is increased; if the lithium-containing powder contains too little metallic lithium relative to the inert protective layer, the metallic lithium is unstable, and the use process has safety risk.
The shape of the lithium-containing powder includes any one of a linear shape, a flake shape, or a spherical shape, or a combination of at least two thereof.
Preferably, the lithium powder is contained in a particle size range of 5nm to 10 μm, for example, 5nm, 10nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm, and the like, preferably 1 to 5 μm.
Preferably, the inert protective layer comprises an inorganic protective monolayer, an organic protective monolayer, or an organic-inorganic composite layer.
Preferably, the material of the inorganic protective monolayer comprises LiF, li 2 O or Li 2 CO 3 Any one or a combination of at least two of them.
Preferably, the material of the organic protective monolayer includes polyaniline and/or polythiophene.
Preferably, the organic-inorganic composite layer has a structure in which an inner layer is made of an inorganic material and an outer layer is made of an organic material, the inner layer is located on the surface of the metal lithium, and the outer layer is located on the surface of the inner layer.
The outer layer is made of organic materials, and the organic materials on the outer layer can interact with the base film under the impact heat to form a film.
Preferably, the inorganic material of the inner layer comprises LiF, li 2 O or Li 2 CO 3 Any one or a combination of at least two of them.
Preferably, the organic material of the outer layer comprises polyaniline and/or polythiophene.
As a preferred embodiment of the present invention, the protective gas comprises argon. But not limited to argon, other dry gases that provide protection and have a dew point < -45 c may be used in the present invention. In the present invention, nitrogen gas cannot be used as the protective gas because nitrogen gas reacts with metallic lithium.
Preferably, the flow rate of the protective gas is 200-2000m/s, such as 200m/s, 300m/s, 400m/s, 500m/s, 600m/s, 700m/s, 800m/s, 900m/s, 1000m/s, 1100m/s, 1200m/s, 1300m/s, 1400m/s, 1500m/s, 1600m/s, 1700m/s, 1800m/s, 1900m/s or 2000m/s, etc. In the invention, if the flow rate of the protective gas is too high, the excessive extrusion deformation of the diaphragm can be caused, the polarization of the battery is too large, and the lithium precipitation risk exists; if the flow rate of the protective gas is too low, the adhesion of lithium may be insufficient. By adjusting the gas flow rate, the amount of the lithium-containing powder sprayed onto the base film can be controlled to some extent, because the lithium-containing powder is sprayed by the gas flow, the larger the flow rate, the more the lithium-containing powder adheres to the base film in the same time.
In a preferred embodiment of the present invention, the heated lithium-containing powder is obtained by bringing the lithium-containing powder into a heating device with the protective gas as a carrier gas and heating the lithium-containing powder. The heating device may be a heating chamber.
Preferably, the temperature of the heating means is 130-150 ℃, such as 130 ℃, 135 ℃, 140 ℃, 145 ℃ or 150 ℃ and the like. The temperature range can ensure that the temperature carried by the lithium-containing material has no influence on the base film. In the invention, if the temperature of the heating device is too high, the diaphragm can deform and wrinkle; if the temperature of the heating device is too low, the deformation of the lithium metal particles is insufficient, and the adhesion is insufficient
As a preferable embodiment of the present invention, the base film includes any one of a dry separator, a wet separator, an optical film, and a ceramic separator.
Preferably, the thickness of the lithium-containing film formed on the base film by the lithium-containing powder is 1 to 100 μm, for example, 1 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, or 100 μm, etc., preferably 1 to 3 μm.
As a preferable technical solution of the present invention, the base film is wound in a process of spraying heated lithium-containing powder onto a surface of the base film.
Preferably, the base film is wound at a rate of 1 to 120m/min, such as 1m/min, 5m/min, 10m/min, 25m/min, 50m/min, 75m/min, 100m/min, 110m/min, 120m/min, or the like. According to the invention, the thickness of the lithium-containing film can be controlled to a certain extent through the winding rate of the base film, and the faster the base film is wound, the shorter the time of contact with lithium-containing powder is, and the thinner the lithium-containing film is; the slower the winding rate of the base film, the longer the time of contact with the lithium-containing powder, the thicker the lithium-containing film.
As a preferred embodiment of the present invention, the operation of spraying the heated lithium-containing powder onto the surface of the base film is performed in a drying room.
Preferably, the drying room comprises an environment box provided with a base film inlet and a base film outlet, a nozzle positioned at the top of the environment box and a porous flat plate arranged inside the environment box and used for supporting the base film.
The drying room with the structure has good sealing performance, and can prevent the dust of the lithium-containing material from diffusing. Wherein, the nozzle is used for spraying, and a high-pressure nozzle can be selected; the porous flat plate is used for adsorption support. The environmental chamber is preferably one with dew point < -45 deg.C.
Preferably, the porous plate is connected to a vacuum pump.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) Taking protective gas as carrier gas, and carrying the lithium-containing powder into a heating device with the temperature of 130-150 ℃ at the flow rate of 200-2000m/s for heating to obtain heated lithium-containing powder;
wherein the lithium-containing powder comprises metallic lithium and an inert protective layer positioned on the surface of the metallic lithium; in the lithium-containing powder, by weight, the weight part of metal lithium is 60-99 parts, and the weight part of the inert protective layer is 1-40 parts; the particle size range of the lithium powder is 5nm-10 mu m; the inert protective layer comprises an inorganic protective single layer, an organic protective single layer or an organic-inorganic composite layer;
(2) Loading the heated lithium-containing powder in the step (1) onto the surface of a base film at a flow rate of 200-2000m/s by using protective gas as carrier gas, and rolling the base film at a speed of 1-120m/min to obtain the lithium-containing diaphragm;
the thickness of the lithium-containing film formed on the base film by the lithium-containing powder is 1-100 μm.
In a second aspect, the present invention provides a lithium-containing separator obtained by the preparation method according to the first aspect.
The lithium-containing separator includes a base film and a lithium-containing film formed on the base film.
In a third aspect, the present invention provides a lithium ion battery comprising the lithium-containing separator of the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method provided by the invention can spray on the surface of the base film to quickly form the lithium-containing film, and the prepared lithium-containing diaphragm can supplement the lithium loss in the battery charging and discharging process. The thickness of the formed lithium-containing film can be controlled, and the unwinding and winding speed of the diaphragm can be regulated and controlled by adjusting the gas flow rate, the lithium-containing powder amount and the unwinding and winding speed of the diaphragm. The protective gas is used as the carrier gas, so that the requirement of the lithium-containing material on the environment can be ensured, and the drying room is selected for reaction, so that the good sealing property can be ensured. The first efficiency of the lithium ion battery using the lithium-containing diaphragm provided by the invention can reach 97.0%, the capacity retention rate can be 100% after 1000 times of charge and discharge cycles at the temperature of 25 ℃ under the 1C/1C multiplying power, and the capacity retention rate can be 100% after 800 times of charge and discharge cycles at the temperature of 45 ℃ under the 1C/1C multiplying power.
Drawings
FIG. 1 is a schematic view of the drying chamber and the base film used in example 1, wherein 1-nozzle, 2-environmental chamber, 3-base film, 4-perforated plate.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1
This example prepares a lithium-containing separator as follows:
(1) Taking argon as carrier gas and taking the lithium-containing powder into a heating device with the temperature of 140 ℃ at the flow rate of 1100m/s for heating to obtain heated lithium-containing powder;
the lithium-containing powder is in a shape of a sheet, and consists of metal lithium and an inert protective layer positioned on the surface of the metal lithium, wherein the particle size of the lithium-containing powder is 50nm-1 mu m, and the inert protective layer is a LiF single layer. In the lithium-containing powder, by weight, the weight part of the metal lithium is 80 parts, and the weight part of the inert protective layer is 20 parts;
(2) And (2) inserting a base film into a drying room, using argon gas as carrier gas to load the heated lithium-containing powder in the step (1) at the flow rate of 1100m/s to spray the lithium-containing powder onto the surface of the base film (dry polypropylene base film), rolling the base film at the speed of 60m/min, and forming a lithium-containing film with the thickness of 1 mu m on the base film to obtain the lithium-containing diaphragm.
The structure of the drying room in the step (2) is as shown in fig. 1, and comprises an environment box 2 provided with a base film 3 inlet and outlet, a nozzle 1 positioned at the top of the environment box 2, and a porous flat plate 4 arranged inside the environment box 2 and used for supporting the base film 3. The nozzle 1 is a high-pressure nozzle and is used for spraying; the environmental chamber 2 is an environmental chamber with dew point less than minus 45 ℃; the porous flat plate 4 is connected with a vacuum pump and plays a role of adsorption and support.
Example 2
This example prepares a lithium-containing separator as follows:
(1) Taking argon as carrier gas and carrying the lithium-containing powder into a heating device with the temperature of 130 ℃ at the flow rate of 200m/s for heating to obtain heated lithium-containing powder;
the particle size of the lithium-containing powder is 1-5 mu m, the lithium-containing powder is spherical, the lithium-containing powder consists of metal lithium and an inert protective layer positioned on the surface of the metal lithium, and the inert protective layer is a polyaniline single layer. In the lithium-containing powder, the weight part of metal lithium is 99 parts, and the weight part of the inert protective layer is 1 part;
(2) The base film was inserted into the same drying chamber as in example 1, the heated lithium-containing powder of step (1) was sprayed onto the surface of the base film (dry polypropylene base film) with argon as a carrier gas at a flow rate of 200m/s, and the base film was wound at a rate of 120m/min to form a lithium-containing film having a thickness of 2 μm on the base film, thereby obtaining the lithium-containing separator.
Example 3
This example prepares a lithium-containing separator as follows:
(1) Taking argon as carrier gas, and taking the lithium-containing powder into a heating device with the temperature of 150 ℃ at the flow rate of 2000m/s for heating to obtain heated lithium-containing powder;
the lithium-containing powder has the granularity of 5-10 mu m, is flaky and spherical, consists of metal lithium and an inert protective layer positioned on the surface of the metal lithium, and is an organic-inorganic composite layer, and the inner layer of the inert protective layer is Li 2 O, the outer layer is polythiophene (the mass ratio of the inner layer to the outer layer is 1:2), the inner layer is positioned on the surface of the metal lithium, and the outer layer is positioned on the surface of the metal lithiumA surface of the inner layer. In the lithium-containing powder, by weight, the weight part of the metal lithium is 60 parts, and the weight part of the inert protective layer is 40 parts;
(2) The base film was inserted into the same drying chamber as in example 1, the heated lithium-containing powder of step (1) was sprayed onto the surface of the base film (wet-process polyethylene base film) with argon gas as a carrier gas at a flow rate of 2000m/s, and the base film was wound at a rate of 1m/min to form a lithium-containing film having a thickness of 3 μm on the base film, thereby obtaining the lithium-containing separator.
Example 4
This example is different from example 1 in that lithium-containing powder is introduced into a heating device having a temperature of 100 c to be heated.
Example 5
This example is different from example 1 in that lithium-containing powder is introduced into a heating apparatus having a temperature of 180 c to be heated.
Comparative example 1
This comparative example a lithium-containing separator was prepared according to the method of example two of CN110571391 a:
(1) Preparing glue coating layer glue solution: adding 200g of Polyacrylonitrile (PAN) powder into 800g of deionized water, and mixing and stirring uniformly at 60 ℃ to obtain a glue coating layer;
(2) Preparing lithium supplement slurry: mixing 100g Li 2 CO 3 Adding lithium carbonate into 700g of deionized water solvent, stirring for 30min, adding 200g of sodium carboxymethylcellulose (CMC), continuously stirring for 3h, and uniformly mixing to obtain lithium supplement slurry;
(3) Coating: coating the glue coating solution prepared in the first step on one side of a dry-method polypropylene-based film layer with the thickness of 12 microns, coating the glue coating solution with the thickness of 1 micron, drying the glue coating solution in an oven with the temperature set to 80 ℃, coating the lithium supplementing slurry prepared in the second step on the polypropylene-based film layer with the thickness of 1 micron, and drying the lithium supplementing layer in the oven with the temperature set to 80 ℃ to obtain the lithium supplementing composite diaphragm.
Test method
The lithium-containing separators provided in examples and comparative examples were used in combination with positive and negative electrode sheets and electricityAnd assembling the electrolyte into a test battery for performance test. The preparation method of the negative plate comprises the following steps: preparing a negative electrode material graphite, a conductive agent acetylene black and a binder SBR into slurry according to the mass percentage of 94; the preparation method of the positive plate comprises the following steps: preparing a positive electrode material NCM811, a conductive agent acetylene black and a binder PVDF into slurry according to a mass ratio of 94; the electrolyte is LiPF 6 EC + DEC + DMC (volume ratio of EC, DEC and DMC of 1.
And performing first-effect test, 25 ℃ cycle life test and 45 ℃ cycle life test on the test battery prepared by the method under the condition of 1C/1C charge and discharge by using Land charge and discharge equipment.
The test results are shown in the following table
TABLE 1
By combining the above examples and comparative examples, the preparation method provided by the invention can rapidly form a lithium-containing film by spraying on the surface of the base film, and can supplement the lithium loss in the battery charging and discharging process. The thickness of the formed lithium film can be controlled, and the gas flow rate, the lithium-containing powder amount and the unreeling and reeling speed of the diaphragm are regulated and controlled.
Example 4 lithium was easily peeled from the separator because the heating temperature of the lithium-containing powder was too low.
Example 5 the heating temperature of the lithium-containing powder was too high, which resulted in the membrane being wrinkled and not being used normally.
Comparative example 1 since a paste layer was coated on one side of the base film and then a lithium supplement paste was coated on the paste layer, the lithium supplement efficiency was decreased and the battery impedance was increased.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (22)
1. A method for preparing a lithium-containing separator, comprising the steps of:
spraying the lithium-containing powder subjected to load heating to the surface of the base film by taking dry protective gas with dew point < -45 ℃ as carrier gas to obtain the lithium-containing diaphragm;
the lithium-containing powder comprises metal lithium and an inert protective layer positioned on the surface of the metal lithium;
in the lithium-containing powder, by weight, the weight part of metal lithium is 60-99 parts, and the weight part of the inert protective layer is 1-40 parts;
the flow rate of the protective gas is 200-2000m/s;
the heated lithium-containing powder is obtained by taking the lithium-containing powder into a heating device by using the protective gas as a carrier gas and heating;
the temperature of the heating device is 130-150 ℃.
2. The production method according to claim 1, wherein the shape of the lithium-containing powder includes any one of a linear shape, a flake shape, or a spherical shape, or a combination of at least two kinds.
3. The method of claim 1, wherein the lithium powder is contained to have a particle size ranging from 5nm to 10 μm.
4. The method of claim 3, wherein the lithium powder is contained in a particle size range of 1 to 5 μm.
5. The method according to claim 1, wherein the inert protective layer comprises an inorganic protective monolayer, an organic protective monolayer, or an organic-inorganic composite layer.
6. The method according to claim 5, wherein the material of the inorganic protective monolayer comprises LiF, li 2 O or Li 2 CO 3 Any one or a combination of at least two of them.
7. The method according to claim 5, wherein the material of the organic protective monolayer comprises polyaniline and/or polythiophene.
8. The preparation method according to claim 5, wherein the organic-inorganic composite layer has a structure in which an inner layer is an inorganic material and an outer layer is an organic material, the inner layer is located on the surface of the lithium metal, and the outer layer is located on the surface of the inner layer.
9. The method according to claim 8, wherein the inorganic material of the inner layer comprises LiF, li 2 O or Li 2 CO 3 Any one or a combination of at least two of them.
10. The method according to claim 8, wherein the organic material of the outer layer includes polyaniline and/or polythiophene.
11. The method of claim 1, wherein the protective gas comprises argon.
12. The production method according to claim 1, wherein the base film comprises any one of a dry separator, a wet separator, an optical film, or a ceramic separator.
13. The method according to claim 1, wherein the lithium-containing film formed on the base film from the lithium-containing powder has a thickness of 1 to 100 μm.
14. The method according to claim 13, wherein the lithium-containing film formed on the base film by the lithium-containing powder has a thickness of 1 to 3 μm.
15. The method of manufacturing according to claim 1, further comprising: and rolling the base film in the process of spraying the heated lithium-containing powder to the surface of the base film.
16. The production method according to claim 15, wherein the take-up rate of the base film is 1 to 120m/min.
17. The method of claim 1, wherein the spraying of the heated lithium-containing powder onto the surface of the base film is performed in a drying room.
18. The method as claimed in claim 17, wherein the drying room comprises an environmental chamber having an inlet and an outlet for the base film, a nozzle disposed at a top of the environmental chamber, and a perforated plate disposed inside the environmental chamber for supporting the base film.
19. The method of claim 18, wherein the porous plate is connected to a vacuum pump.
20. The method for preparing according to claim 1, characterized in that it comprises the following steps:
(1) Taking protective gas as carrier gas, and carrying the lithium-containing powder into a heating device with the temperature of 130-150 ℃ at the flow rate of 200-2000m/s for heating to obtain heated lithium-containing powder;
wherein the lithium-containing powder comprises metallic lithium and an inert protective layer positioned on the surface of the metallic lithium; in the lithium-containing powder, by weight, the weight part of metal lithium is 60-99 parts, and the weight part of the inert protective layer is 1-40 parts; the particle size range of the lithium powder is 5nm-10 mu m; the inert protective layer comprises an inorganic protective single layer, an organic protective single layer or an organic-inorganic composite layer;
(2) Loading the heated lithium-containing powder in the step (1) onto the surface of a base film at a flow rate of 200-2000m/s by using protective gas as carrier gas, and rolling the base film at a speed of 1-120m/min to obtain the lithium-containing diaphragm;
the thickness of the lithium-containing film formed on the base film by the lithium-containing powder is 1-100 μm.
21. A lithium-containing separator obtained by the production method according to any one of claims 1 to 20.
22. A lithium ion battery comprising the lithium-containing separator of claim 21.
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| CN110707267A (en) * | 2018-07-10 | 2020-01-17 | 中国科学院大连化学物理研究所 | Composite diaphragm for alkali metal battery and preparation and application thereof |
| CN111613759A (en) * | 2020-05-27 | 2020-09-01 | 湖北亿纬动力有限公司 | Diaphragm slurry, preparation method thereof, diaphragm and lithium ion battery |
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| US5705292A (en) * | 1995-06-19 | 1998-01-06 | Sony Corporation | Lithium ion secondary battery |
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| US8470468B2 (en) * | 2010-02-12 | 2013-06-25 | GM Global Technology Operations LLC | Lithium-ion batteries with coated separators |
| CN106299214A (en) * | 2015-06-05 | 2017-01-04 | 东莞市亿顺新材料有限公司 | A kind of lithium ion battery and ceramic diaphragm thereof |
| KR102488677B1 (en) * | 2017-05-12 | 2023-01-16 | 주식회사 엘지에너지솔루션 | Method for preparing lithium secondary battery |
| CN107275550B (en) * | 2017-06-20 | 2020-07-07 | 深圳市星源材质科技股份有限公司 | Ceramic and polymer composite coating lithium ion diaphragm and preparation method thereof |
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| CN110707267A (en) * | 2018-07-10 | 2020-01-17 | 中国科学院大连化学物理研究所 | Composite diaphragm for alkali metal battery and preparation and application thereof |
| CN111613759A (en) * | 2020-05-27 | 2020-09-01 | 湖北亿纬动力有限公司 | Diaphragm slurry, preparation method thereof, diaphragm and lithium ion battery |
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