CN112157557A - Surface treatment device and surface treatment method for metal lithium belt and lithium metal battery - Google Patents
Surface treatment device and surface treatment method for metal lithium belt and lithium metal battery Download PDFInfo
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- CN112157557A CN112157557A CN202011165330.8A CN202011165330A CN112157557A CN 112157557 A CN112157557 A CN 112157557A CN 202011165330 A CN202011165330 A CN 202011165330A CN 112157557 A CN112157557 A CN 112157557A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 228
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 93
- 239000002184 metal Substances 0.000 title claims abstract description 93
- 238000004381 surface treatment Methods 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims description 32
- 230000001681 protective effect Effects 0.000 claims abstract description 21
- 238000004804 winding Methods 0.000 claims abstract description 16
- 239000000428 dust Substances 0.000 claims description 17
- -1 polypropylene Polymers 0.000 claims description 16
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 12
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 12
- 238000005096 rolling process Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 210000004209 hair Anatomy 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- 238000005086 pumping Methods 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 230000001680 brushing effect Effects 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 241001465754 Metazoa Species 0.000 claims description 5
- 239000004677 Nylon Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920001778 nylon Polymers 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 claims description 3
- 229910018957 MClx Inorganic materials 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 238000002161 passivation Methods 0.000 abstract description 22
- 230000007547 defect Effects 0.000 abstract description 10
- 210000001787 dendrite Anatomy 0.000 abstract description 7
- 239000010410 layer Substances 0.000 description 20
- 239000007789 gas Substances 0.000 description 15
- 238000007667 floating Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011241 protective layer Substances 0.000 description 7
- 238000009776 industrial production Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 210000002268 wool Anatomy 0.000 description 4
- 238000012545 processing Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229920000572 Nylon 6/12 Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B27/00—Other grinding machines or devices
- B24B27/033—Other grinding machines or devices for grinding a surface for cleaning purposes, e.g. for descaling or for grinding off flaws in the surface
-
- A—HUMAN NECESSITIES
- A46—BRUSHWARE
- A46D—MANUFACTURE OF BRUSHES
- A46D1/00—Bristles; Selection of materials for bristles
- A46D1/02—Bristles details
- A46D1/0207—Bristles characterised by the choice of material, e.g. metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B1/00—Processes of grinding or polishing; Use of auxiliary equipment in connection with such processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B29/00—Machines or devices for polishing surfaces on work by means of tools made of soft or flexible material with or without the application of solid or liquid polishing agents
- B24B29/005—Machines or devices for polishing surfaces on work by means of tools made of soft or flexible material with or without the application of solid or liquid polishing agents using brushes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B29/00—Machines or devices for polishing surfaces on work by means of tools made of soft or flexible material with or without the application of solid or liquid polishing agents
- B24B29/02—Machines or devices for polishing surfaces on work by means of tools made of soft or flexible material with or without the application of solid or liquid polishing agents designed for particular workpieces
- B24B29/06—Machines or devices for polishing surfaces on work by means of tools made of soft or flexible material with or without the application of solid or liquid polishing agents designed for particular workpieces for elongated workpieces having uniform cross-section in one main direction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B41/00—Component parts such as frames, beds, carriages, headstocks
- B24B41/005—Feeding or manipulating devices specially adapted to grinding machines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B41/00—Component parts such as frames, beds, carriages, headstocks
- B24B41/04—Headstocks; Working-spindles; Features relating thereto
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B55/00—Safety devices for grinding or polishing machines; Accessories fitted to grinding or polishing machines for keeping tools or parts of the machine in good working condition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B55/00—Safety devices for grinding or polishing machines; Accessories fitted to grinding or polishing machines for keeping tools or parts of the machine in good working condition
- B24B55/06—Dust extraction equipment on grinding or polishing machines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D13/00—Wheels having flexibly-acting working parts, e.g. buffing wheels; Mountings therefor
- B24D13/02—Wheels having flexibly-acting working parts, e.g. buffing wheels; Mountings therefor acting by their periphery
- B24D13/10—Wheels having flexibly-acting working parts, e.g. buffing wheels; Mountings therefor acting by their periphery comprising assemblies of brushes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of lithium metal batteries, and particularly relates to a lithium metal strip surface treatment device which comprises an unreeling assembly, a first brush roller pair, a second brush roller pair and a reeling assembly, wherein the unreeling assembly, the first brush roller pair, the second brush roller pair and the reeling assembly are sequentially arranged in the conveying direction of a lithium metal strip; the surface of the first brush roll pair is provided with a plurality of first bristles; the surface of the second brush roll is provided with a plurality of second bristles; the winding assembly is used for winding the metal lithium belt. According to the device for treating the surface of the metal lithium belt, the metal lithium belt sequentially passes through the first brush roll pair and the second brush roll pair to be mechanically polished, the first brush roll pair is used for removing the passivation layer on the surface of the metal lithium belt, the second brush roll pair is used for further removing the passivation layer on the surface of the metal lithium belt and removing the surface defects of the metal lithium belt to increase the flatness of the surface of the metal lithium belt, so that a uniform protective film can be attached to the surface of the metal lithium belt subsequently, the protective effect of the protective film is improved, lithium dendrite is prevented from being generated, a superior SEI film can be formed after the surface defects are removed, and the cycle performance of a lithium metal battery is improved.
Description
Technical Field
The invention belongs to the technical field of lithium metal batteries, and particularly relates to a surface treatment device and a surface treatment method for a metal lithium belt and a lithium metal battery.
Background
Nowadays, green, high-efficiency secondary batteries are vigorously developed in various countries. The lithium battery as a novel secondary battery has the advantages of high energy density and power density, high working voltage, light weight, small volume, long cycle life, good safety, environmental protection and the like, and has wide application prospect in the aspects of portable electric appliances, electric tools, large-scale energy storage, electric traffic power supplies and the like.
Among the numerous negative electrode materials for lithium batteries, metallic lithium is considered to be the most desirable negative electrode material for lithium batteries due to its low density, high theoretical capacity and low potential. However, in the cycle process of the lithium metal negative electrode, on one hand, because the lithium metal is unevenly deposited, dendrite is easily generated on the surface, which brings a safety hazard, and on the other hand, because the volume expansion causes the repeated generation of a Solid Electrolyte Interface (SEI), the electrolyte and the lithium metal are consumed, and meanwhile, the impedance of the battery is remarkably increased. In the last decades, there have been continuously studied and reported the treatment of the surface of lithium metal, and the principle of the treatment is that a uniform protective layer is formed on the surface of lithium metal, which can help to solve the above-mentioned problems of lithium metal and improve the cycle performance of lithium metal batteries.
However, because the chemical activity of the metallic lithium is high, a passivation layer is easily formed on the surface of the metallic lithium in the rolling, transportation and storage processes, and the passivation layer easily causes the unevenness of a protective layer formed by the metallic lithium, and particularly, in the process of protecting the surface of the metallic lithium by a chemical method, a grain boundary, a defect or insufficient film formation is easily formed in the protective layer, so that the protective effect of the protective layer is seriously affected. Therefore, a flat lithium metal surface is also important for forming a lithium metal protective layer.
The passivation layer on the surface of the lithium sheet is removed by knife cutting in the literature to form a bright and flat surface, however, the method cannot be applied to the surface treatment of ultra-thin lithium strips (thickness <200 μm). Chinese patent publication No. CN107815724A discloses that a large-scale atomically flat lithium surface can be obtained by polishing a lithium metal surface by an electrochemical method, however, this method is only suitable for a laboratory stage and cannot be used for large-scale continuous production. Therefore, it is highly desirable to develop an industrialized method that can remove the passivation layer on the surface of the lithium metal without affecting the application of the lithium metal in the lithium ion battery.
In view of the above, it is necessary to provide a technical solution to solve the above technical problems.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the device for treating the surface of the metal lithium strip is provided, the passivation layer on the surface of the metal lithium strip can be removed, the flatness of the surface of the metal lithium strip is increased, and the industrial production is easy to realize.
In order to achieve the purpose, the invention adopts the following technical scheme:
a surface treatment device for a lithium metal strip comprises an unreeling assembly, a first brush roller pair, a second brush roller pair and a reeling assembly which are sequentially arranged in the conveying direction of the lithium metal strip; a plurality of first brush bristles are arranged on the surface of the first brush roll pair; a plurality of second brush bristles are arranged on the surface of the second brush roll pair; the rolling component is used for rolling the metal lithium belt.
The improved lithium metal strip surface treatment device further comprises guide rollers, wherein the guide rollers comprise a first guide roller group, a second guide roller group and a third guide roller group, the first guide roller group is arranged between the unreeling assembly and the first brush roller pair, the second guide roller group is arranged between the first brush roller pair and the second brush roller pair, and the third guide roller group is arranged between the second brush roller pair and the reeling assembly. The guide rollers are used for receiving and releasing the metal lithium strips, and the number of the guide rollers can be set according to actual conditions.
The improved lithium metal strip surface treatment device further comprises a floating roller, and the floating roller is arranged between the guide rollers of the second guide roller group. The floating roller can float up and down, automatically controls the tension, and prevents the lithium metal strip from breaking, blocking and the like in the surface treatment process.
The improved surface treatment device for the metal lithium belt further comprises a release film winding assembly and a release film unwinding assembly, wherein the release film winding assembly is arranged between the unwinding assembly and the first brush roller pair and is used for receiving a release film separated from the metal lithium belt. When the metal lithium belt comes, the surface is attached with a release film for protecting the metal lithium belt, the release film winding assembly is used for tearing the release film, and the metal lithium belt is conveyed to the first brush roller for surface treatment. The release film unreeling assembly is arranged between the second brush roll pair and the reeling assembly and used for releasing the release film to cover the metal lithium belt. After the passivation layer is removed and the flatness is increased, the surface of the metal lithium strip is covered with a release film, so that dust is prevented from being attached to the surface of the metal lithium strip, and the internal short circuit is prevented when the lithium metal battery is assembled.
As an improvement of the lithium metal strip surface treatment device, the first brush bristles are made of nylon, polypropylene, polyethylene terephthalate or polybutylene terephthalate, and the number of the first brush roller pairs is at least one. The material of the first bristles is preferably a polyethylene terephthalate (PET) material, which has low water absorption and does not adhere to lithium metal, compared to other materials. Wherein the nylon can adopt nylon 612 brush filaments with the diameter of 0.5 mm.
As an improvement of the lithium metal strip surface treatment device, the second brush bristles are made of polyethylene terephthalate or animal hair, and the number of the second brush roller pairs is at least one. The second bristles are preferably made of existing materials, wherein the animal hair is wool or horsehair, the raw materials of the wool or horsehair are easy to obtain and low in price, static electricity is not easy to generate, and the flatness of the surface of the metal lithium strip can be increased. Preferably, the second bristles are made of horse hair or polyethylene terephthalate and have a diameter of less than 0.1 mm. It is further preferred that the second bristles have a density greater than that of the first bristles for further increasing the flatness of the surface of the lithium metal strip.
The improved lithium metal strip surface treatment device further comprises a vacuum-pumping assembly and a dust collecting assembly, wherein the vacuum-pumping assembly is arranged corresponding to the gaps between the first brush roller pair and the second brush roller pair respectively, and the dust collecting assembly is connected with the vacuum-pumping assembly. Specifically, evacuation subassembly includes pump-line and vacuum pump, and the collection dirt subassembly is the dust removal sack, and the mouth of pipe of pump-line corresponds the setting with the clearance of first brush roller pair, and corresponds the setting with the clearance of second brush roller pair, and when the metal lithium area carried out surface treatment, the passivation layer that the brush roller brushed out was taken out the dust removal sack from pump-line, prevents that the metal lithium dust from burning and exploding.
The improved lithium metal strip surface treatment device further comprises a positive pressure gas input assembly, and the positive pressure gas input assembly is connected with a dryer and/or an inert gas storage tank. Wherein the inert gas comprises nitrogen, argon or helium. The dryer is used for drying air to a dew point below-40 ℃. Specifically, the positive pressure gas input assembly comprises a gas compressor and a gas output pipeline, the pipe orifice of the gas output pipeline is correspondingly arranged with the gap between the first brush roller pair and the second brush roller pair, positive pressure control is realized on the environment where the metal lithium strip is located by the positive pressure gas input assembly, and the contact between the outside air containing moisture and the metal lithium strip can be prevented.
The second purpose of the invention is: provided is a surface treatment method of a lithium metal strip, comprising the following operations:
preparing a metallic lithium strip surface treatment device as described in any one of the preceding specifications;
brushing the surface of the lithium metal strip by using a first brush roll;
and brushing the surface of the metal lithium belt by using a second brush roller to obtain the treated metal lithium belt.
Compared with the surface treatment method of the electrolytic metal lithium belt, the method provided by the invention is easier to realize large-scale industrial production, the surface treatment time is short, and the technology is mature.
As an improvement of the surface treatment method of the metal lithium strip, the method is realized in a dry environment with the dew point below < -40 ℃ or in an oxygen-free and water-free inert gas environment, wherein the inert gas comprises nitrogen, helium or argon; the metal lithium belt comprises a copper-lithium composite belt, a carbon-lithium composite belt or a lithium metal belt, and the thickness of the metal lithium belt is less than 200 mu m. Since lithium metal is chemically active and is easily exploded by exposure to moisture in the air, the dew point needs to be strictly limited. The invention is mainly suitable for ultrathin metal lithium belts with the thickness of less than 200 mu m, is particularly suitable for metal lithium belts with the thickness of 100-120 mu m, especially 110 mu m, and is convenient for realizing industrial production.
The improvement of the surface treatment method of the lithium metal strip further comprises the steps of immersing the lithium metal strip in a protective solution and drying; the protective solution comprises fluoroethylene carbonate, ethyl orthosilicate, silicone oil, 1, 3-dioxolane, tetrahydrofuran, AgF solution and CuF2At least one of a solution and a MClx solution, wherein M is As, In, Bi or Zn. Wherein the soaking time is 4-6 h and is set according to the actual condition. The metal lithium belt is soaked in the protective solution, a compact protective layer can be formed on the surface of the metal lithium belt, the generation of lithium dendrites is avoided, and the cycle performance of the lithium metal battery is improved.
The third purpose of the invention is that: the lithium metal battery comprises a positive plate, a diaphragm, a negative plate and electrolyte, wherein the negative plate is a metal lithium belt treated by the metal lithium belt surface treatment method in any one of the specifications.
Compared with the prior art, the invention at least has the following beneficial effects: the invention provides a surface treatment device for a lithium metal belt, which comprises an unreeling assembly, a first brush roller pair, a second brush roller pair and a reeling assembly, wherein the unreeling assembly, the first brush roller pair, the second brush roller pair and the reeling assembly are sequentially arranged in the conveying direction of the lithium metal belt; a plurality of first brush bristles are arranged on the surface of the first brush roll pair; a plurality of second brush bristles are arranged on the surface of the second brush roll pair; the rolling component is used for rolling the metal lithium belt. According to the device for treating the surface of the metal lithium belt, the metal lithium belt sequentially passes through the first brush roll pair and the second brush roll pair to be mechanically polished, the first brush roll pair is used for removing the passivation layer on the surface of the metal lithium belt, the second brush roll pair is used for further removing the passivation layer on the surface of the metal lithium belt and removing the surface defects of the metal lithium belt to increase the flatness of the surface of the metal lithium belt, so that a uniform protective film can be attached to the surface of the metal lithium belt subsequently, the protective effect of the protective film is improved, lithium dendrite is prevented from being generated, a superior SEI film can be formed after the surface defects are removed, and the cycle performance of a lithium metal battery is improved. In addition, the surface treatment device for the metal lithium strip provided by the invention can realize industrial mass production compared with the treatment of the metal lithium strip through chemical and electrolytic treatment.
Drawings
Fig. 1 is a schematic structural view of a surface treatment apparatus for a lithium metal strip in example 1.
FIG. 2 is a Scanning Electron Micrograph (SEM) of # 1 metallic lithium band in example 2.
Fig. 3 is a Scanning Electron Micrograph (SEM) of # 2 metallic lithium tape in comparative example 1.
Fig. 4 is a graph showing the cycle profiles of the 3# lithium metal battery and the 4# lithium metal battery.
The device comprises a metal lithium belt 1, a metal lithium belt 2, an unreeling assembly 3, a first brush roller pair 4, a second brush roller pair 5, a reeling assembly 6, a guide roller 61, a first guide roller set 62, a second guide roller set 63, a third guide roller set 7, a floating roller 8, a release film reeling assembly 9, a release film unreeling assembly 10, a vacuum pumping assembly 11, a dust collecting assembly 12 and a positive pressure gas input assembly.
Detailed Description
As used in the specification and in the claims, certain terms are used to refer to particular components. As one skilled in the art will appreciate, manufacturers may refer to a component by different names. This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. "substantially" means within an acceptable error range, within which a person skilled in the art can solve the technical problem to substantially achieve the technical result.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", horizontal ", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
In the present invention, unless otherwise expressly specified or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
The present invention will be described in further detail below with reference to the accompanying drawings, but the present invention is not limited thereto.
Example 1
As shown in fig. 1, a lithium metal strip surface treatment device comprises an unreeling assembly 2, a first brush roller pair 3, a second brush roller pair 4 and a reeling assembly 5 which are sequentially arranged according to the transmission direction of a lithium metal strip 1; a plurality of first brush bristles are arranged on the surfaces of the first brush roll pairs 3; a plurality of second brush bristles are arranged on the surface of the second brush roller pair 4; the winding component 5 is used for winding the lithium metal strip 1.
According to the device for treating the surface of the metal lithium belt, the metal lithium belt 1 sequentially passes through the first brush roll pair 3 and the second brush roll pair 4 to be mechanically polished, the first brush roll pair 3 is used for removing a passivation layer on the surface of the metal lithium belt 1, the second brush roll pair 4 is used for further removing the passivation layer on the surface of the metal lithium belt 1 and removing surface defects of the metal lithium belt 1 to increase the flatness of the surface of the metal lithium belt 1, so that a uniform protective film can be attached to the surface of the metal lithium belt 1 subsequently, the protective effect of the protective film is improved, lithium dendrite is prevented from being generated, a superior SEI film can be formed after the surface defects are removed, and the cycle performance of a lithium metal battery is improved.
Compared with the device for processing the surface of the metal lithium strip 1 by chemical and electrolytic processing, the device for processing the surface of the metal lithium strip provided by the invention can realize industrialized mass production.
Further, the roller winding device further comprises a guide roller 6, wherein the guide roller 6 comprises a first guide roller group 61, a second guide roller group 62 and a third guide roller group 63, the first guide roller group 61 is arranged between the unwinding assembly 2 and the first brush roller pair 3, the second guide roller group 62 is arranged between the first brush roller pair 3 and the second brush roller pair 4, and the third guide roller group 63 is arranged between the second brush roller pair 4 and the winding assembly 5. The guide rollers 6 are used for receiving and releasing the lithium metal strip 1, and the number of the guide rollers 6 can be set according to actual conditions.
Further, the guide roll device also comprises a floating roll 7, and the floating roll 7 is arranged between the guide rolls 6 of the second guide roll group 62. The floating roller 7 can float up and down, automatically control the tension, and prevent the lithium metal strip 1 from breaking, blocking and the like in the surface treatment process. Further preferably, the floating roller 7 is further arranged between the unwinding assembly 2 and the release film winding assembly 8, and the floating roller 7 is further arranged between the winding assembly 5 and the release film unwinding assembly 9.
Further, still including from type membrane rolling subassembly 8, set up between unreeling subassembly 2 and first brush roll pair 3 from type membrane rolling subassembly 8, be used for receiving from the type membrane with the separation of lithium metal strip 1 from type membrane rolling subassembly 8. When the metal lithium belt 1 comes, the surface is attached with the release film for protecting the metal lithium belt 1, the release film winding assembly 8 is used for tearing the release film, and the metal lithium belt 1 is conveyed to the first brush roll for surface treatment of the first brush roll pair 3.
Further, still including unreeling the subassembly 9 from the type membrane, unreeling the subassembly 9 from the type membrane and set up between second brush roller pair 4 and rolling subassembly 5, unreeling the subassembly 9 from the type membrane and being used for releasing to cover lithium metal strip 1 from the type membrane. After the passivation layer of the metal lithium belt 1 is removed and the flatness is increased, the surface of the metal lithium belt 1 is covered with a release film, so that dust is prevented from adhering to the surface of the metal lithium belt 1, and internal short circuit is prevented when the lithium metal battery is assembled.
Further, the first brush bristles are made of nylon, polypropylene, polyethylene terephthalate or polybutylene terephthalate, and the number of the first brush roller pairs 3 is at least one. The material of the first bristles is preferably a polyethylene terephthalate (PET) material, which has low water absorption and does not adhere to lithium metal, compared to other materials. Wherein the nylon can adopt nylon 612 brush filaments with the diameter of 0.5 mm.
Further, the second brush bristles are made of polyethylene terephthalate or animal hair, and the number of the second brush roller pairs 4 is at least one. The second bristles are preferably made of an existing material, wherein the animal hair is wool or horse hair, the raw materials of the wool or the horse hair are easy to obtain and low in price, static electricity is not easy to generate, and the flatness of the surface of the metal lithium strip 1 can be increased. Preferably, the second bristles are made of horse hair or polyethylene terephthalate and have a diameter of less than 0.1 mm. It is further preferable that the density of the second bristles is greater than that of the first bristles for further increasing the flatness of the surface of the lithium metal strip 1.
Furthermore, the brush roller cleaning device further comprises a vacuum-pumping assembly 10 and a dust collecting assembly 11, wherein the vacuum-pumping assembly 10 is arranged corresponding to the gaps between the first brush roller pair 3 and the second brush roller pair 4 respectively, and the dust collecting assembly 11 is connected with the vacuum-pumping assembly 10. Specifically, evacuation subassembly 10 includes pump-line and vacuum pump, and collection dirt subassembly 11 is the dust removal sack, and the mouth of pipe of pump-line corresponds the setting with the clearance of first brush roll to 3, and corresponds the setting with the clearance of second brush roll to 4, and when metal lithium area 1 carried out surface treatment, the passivation layer that the brush roll brushed out was taken out the dust removal sack from pump-line, prevents that the metal lithium dust from burning and exploding.
Further, the device also comprises a positive pressure gas input assembly 12, and a dryer and/or an inert gas storage tank are connected to the positive pressure gas input assembly 12. Wherein the inert gas comprises nitrogen, argon or helium. The dryer is used for drying air to a dew point below-40 ℃. Specifically, malleation gas input assembly 12 includes gas compressor and gaseous output pipeline, and the mouth of pipe of gaseous output pipeline sets up with the clearance correspondence of first brush roller pair 3 and second brush roller pair 4, and malleation gas input assembly 12 realizes malleation control to the environment that lithium metal strip 1 was located, can prevent that the external air that contains moisture from taking 1 contact with lithium metal.
The working process of the device is as follows:
s1, the unwinding assembly 2 unwinds the metal lithium strip 1 coil; the release film winding assembly 8 winds the release film attached to the surface of the lithium metal strip 1, the lithium metal strip 1 is transmitted to a gap between the first brush roller pair 3 through the guide roller 6, the first brush brushes on the surface of the first brush roller pair 3 rub the surface of the lithium metal strip 1, and the passivation layer on the surface of the lithium metal strip 1 is removed; an air exhaust pipeline of the vacuumizing assembly 10 is aligned with a gap of the first brush roll pair 3, passivation layer powder removed from the surface of the metal lithium belt 1 is absorbed into a dust removal cloth bag, positive pressure gas is input into the assembly 12 to work, and the operation space is ensured to be dry air or inert atmosphere;
s2, the metal lithium belt 1 is conveyed to a gap between a second brush roller pair 4 after the tension is adjusted through a second guide roller group 62 and a floating roller 7, a second brush hair on the surface of the second brush roller pair 4 is used for rubbing the surface of the metal lithium belt 1, a passivation layer on the surface of the metal lithium belt 1 is further removed, the flatness of the surface of the metal lithium belt 1 is increased, an air suction pipeline of the vacuumizing assembly 10 is also aligned to the gap between the second brush roller pair 4, passivation layer powder removed on the surface of the metal lithium belt 1 is absorbed into a dust removal cloth bag, the positive pressure gas input assembly 12 works, and the operation space is guaranteed to be dry air or inert atmosphere;
s3, after the lithium metal strip 1 passes through the second brush roller pair 4, the release film unreeling component 9 unreels the release film, attaches to the surface of the processed lithium metal strip 1, and is reeled by the reeling component 5.
Example 2
A surface treatment method of a lithium metal strip comprises the following operations:
s1, preparing the lithium metal strip surface treatment device of example 1;
s2, brushing the surface of the lithium metal strip 1 by using the first brush roller pair 3;
and S3, brushing the surface of the lithium metal strip 1 by using the second brush roller pair 4 to obtain the treated lithium metal strip.
Compared with the surface treatment method of the electrolytic metal lithium belt, the method provided by the invention is easier to realize large-scale industrial production, the surface treatment time is short, and the technology is mature.
Further, the above method is implemented in a dry environment with dew point below-40 deg.C or in an oxygen-free and water-free inert gas environment, wherein the inert gas comprises nitrogen, helium or argon; the metallic lithium strip 1 comprises a copper-lithium composite strip, a carbon-lithium composite strip or a lithium metal strip, and the thickness of the metallic lithium strip is less than 200 mu m. Since lithium metal is chemically active and is easily exploded by exposure to moisture in the air, the dew point needs to be strictly limited. The invention is mainly suitable for ultrathin metal lithium belts with the thickness of less than 200 mu m, is particularly suitable for metal lithium belts with the thickness of 100-120 mu m, especially 110 mu m, and is convenient for realizing industrial production.
Further, S4, immersing the lithium metal strip 1 in a protective solution, and drying; the protective solution comprises fluoroethylene carbonate, ethyl orthosilicate, silicone oil, 1, 3-dioxolane, tetrahydrofuran, AgF solution and CuF2At least one of a solution and a MClx solution, wherein M is As, In, Bi or Zn. Wherein the soaking time is 4-6 h and is set according to the actual condition. The metal lithium belt 1 is immersed in the protective solution, a compact protective layer can be formed on the surface of the metal lithium belt 1, the generation of lithium dendrites is avoided, and the circulation of the lithium metal battery is improvedRing performance.
Comparative example 1
This comparative example provides a surface treatment method of a lithium metal strip 1, which is different from example 2 in that it does not include S1 to S3, and is the same as example 2 in the rest, and thus, the description thereof is omitted.
Example 3
The present embodiment provides a lithium metal battery, which includes a positive electrode sheet, a separator, a negative electrode sheet, and an electrolyte, wherein the negative electrode sheet is the lithium metal strip 1 treated by the surface treatment method of the lithium metal strip 1 in embodiment 2.
Comparative example 2
This comparative example provides a lithium metal battery, and unlike example 3, the negative electrode sheet was the metallic lithium strip 1 treated by the metallic strip surface treatment method in comparative example 1.
And (3) performance testing:
the metallic lithium ribbon 1 obtained after the treatment in example 2 was recorded as a # 1 lithium ribbon, the metallic lithium ribbon 1 obtained after the treatment in comparative example 1 was recorded as a # 2 lithium ribbon, and scanning electron micrographs of the # 1 lithium ribbon and the # 2 lithium ribbon were respectively obtained, as shown in FIGS. 2 to 3, in which the length of the white space in the drawings was 50 μm. As can be seen from the figure, the surface of the No. 1 lithium ribbon is smoother and flatter, while the surface of the No. 2 lithium ribbon has a plurality of protrusions, which indicates that the surface of the No. 2 lithium ribbon has a passivation layer.
The 1# lithium tape and the 2# lithium tape were assembled as a negative electrode tab with a positive electrode tab and a separator into a lithium metal battery, which were recorded as a 3# battery and a 4# battery in this order.
The cycle performance test was performed on the 3# battery and the 4# battery, respectively, and the test results are shown in fig. 4. As can be seen from fig. 4, the cycle performance of the 3# battery is better because the 1# metallic lithium strip 1 sequentially passes through the first brush roller pair 3 and the second brush roller pair 4 for mechanical polishing, the first brush roller pair 3 is used for removing the passivation layer on the surface of the metallic lithium strip 1, the second brush roller pair 4 is used for further removing the passivation layer on the surface of the metallic lithium strip 1, and removing the surface defects of the metallic lithium strip 1 to increase the flatness of the surface of the metallic lithium strip 1, so that a uniform protective film can be attached to the surface of the metallic lithium strip 1 subsequently, the protective effect of the protective film is improved, the generation of lithium dendrites is prevented, and a superior SEI film can be formed after the surface defects are removed, thereby improving the cycle performance of the lithium metal battery.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope 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 surface treatment device for a lithium metal strip is characterized by comprising an unreeling assembly, a first brush roller pair, a second brush roller pair and a reeling assembly which are sequentially arranged in the conveying direction of the lithium metal strip; a plurality of first brush bristles are arranged on the surface of the first brush roll pair; a plurality of second brush bristles are arranged on the surface of the second brush roll pair; the rolling component is used for rolling the metal lithium belt.
2. The lithium metal strip surface treatment device of claim 1, further comprising guide rollers including a first guide roller set disposed between the unwinding assembly and the first pair of brush rollers, a second guide roller set disposed between the first pair of brush rollers and the second pair of brush rollers, and a third guide roller set disposed between the second pair of brush rollers and the winding assembly.
3. The lithium metal strip surface treatment device according to claim 2, further comprising a dancer roll disposed between the plurality of guide rolls of the second guide roll group.
4. The device for surface treatment of the metal lithium belt according to claim 1, further comprising a release film winding assembly and a release film unwinding assembly, wherein the release film winding assembly is disposed between the unwinding assembly and the first pair of brush rollers, and is configured to receive a release film separated from the metal lithium belt; the release film unreeling assembly is arranged between the second brush roll pair and the reeling assembly and used for releasing the release film to cover the metal lithium belt.
5. The lithium metal strip surface treatment device according to claim 1, wherein the first bristles are made of nylon, polypropylene, polyethylene terephthalate or polybutylene terephthalate, and the number of the first brush roller pairs is at least one; the second brush bristles are made of polyethylene terephthalate or animal hair, and the number of the second brush roller pairs is at least one pair.
6. The lithium metal strip surface treatment device according to claim 1, further comprising a vacuum-pumping assembly and a dust collecting assembly, wherein the vacuum-pumping assembly is disposed corresponding to gaps of the first pair of brush rollers and the second pair of brush rollers, respectively, and the dust collecting assembly is connected to the vacuum-pumping assembly.
7. A surface treatment method of a lithium metal strip comprises the following operations:
preparing a surface treatment device for the lithium metal strip according to any one of claims 1 to 6;
brushing the surface of the lithium metal strip by using a first brush roll;
and brushing the surface of the metal lithium belt by using a second brush roller to obtain the treated metal lithium belt.
8. The lithium metal strip surface treatment process of claim 7, wherein the process is carried out in a dry environment below dew point < -40 ℃ or in an oxygen-free and water-free inert gas environment, the inert gas comprising nitrogen, helium, or argon; the metal lithium belt comprises a copper-lithium composite belt, a carbon-lithium composite belt or a lithium metal belt, and the thickness of the metal lithium belt is less than 200 mu m.
9. The method for surface treatment of a lithium metal strip according to claim 7, further comprising immersing the lithium metal strip in a protective solution and drying; the protective solution comprises fluoroethylene carbonate, ethyl orthosilicate, silicone oil, 1, 3-dioxolane, tetrahydrofuran, AgF solution and CuF2At least one of a solution and a MClx solution, wherein M is As, In, Bi or Zn.
10. A lithium metal battery, which is characterized by comprising a positive plate, a diaphragm, a negative plate and electrolyte, wherein the negative plate is a metal lithium belt treated by the metal lithium belt surface treatment method according to any one of claims 7 to 9.
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