CN209822779U - Ultrathin lithium foil and device for preparing ultrathin lithium foil - Google Patents
Ultrathin lithium foil and device for preparing ultrathin lithium foil Download PDFInfo
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- CN209822779U CN209822779U CN201920341275.XU CN201920341275U CN209822779U CN 209822779 U CN209822779 U CN 209822779U CN 201920341275 U CN201920341275 U CN 201920341275U CN 209822779 U CN209822779 U CN 209822779U
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
Provided are an ultra-thin lithium foil and a device for preparing the same. The ultra-thin lithium foil is a continuous, self-supporting strip foil. The ultrathin lithium foil has a uniform thickness of 20 μm or less, a thickness tolerance of ± 1.5 μm, and a width of 10 to 500 mm. The surface of the ultrathin lithium foil is bright and is silvery; the surface is smooth, and no holes and damages can be detected visually; the edge is neat and has no defects.
Description
Technical Field
The utility model relates to an energy storage technology field especially relates to an ultra-thin lithium foil that can be used to secondary cell and preparation method thereof.
Background
The lithium battery is widely applied to the fields of aerospace, computers, mobile communication equipment, robots, electric automobiles and the like due to the advantages of high energy density, long cycle life and wide applicable temperature range. With the development of society and the progress of science and technology, the requirement on the energy density of a lithium battery is higher and higher, but the current lithium ion battery taking graphite as a negative electrode is difficult to meet the social expectation, so that the development of novel positive and negative electrode materials with higher specific capacity is needed. For the negative electrode material, lithium metal has a high specific capacity (3860mAh/g, 10 times that of graphite negative electrode) and the lowest redox potential (-3.04V VS standard hydrogen potential). The lithium metal is adopted to replace the existing graphite cathode, so that the working voltage of the battery can be improved on one hand, and the using amount of the cathode can be reduced on the other hand, so that the energy density of the lithium ion battery can be greatly improved. Meanwhile, as the negative electrode contains metallic lithium and is used as a lithium source of the battery, the material of the positive electrode is more widely selected, and an electrochemical energy system with higher energy is formed, such as a lithium-sulfur battery and a lithium-air battery. At present, the energy density of lithium batteries is expected to reach 500wh/kg or more in various countries internationally.
Although lithium metal has such advantages, its amount in the battery, including the thickness of the lithium metal negative electrode, is precisely controlled. Because the anode materials adopted by the existing lithium ion batteries are lithium-containing materials (such as lithium cobaltate, lithium iron phosphate, ternary materials and the like), the lithium contained in the anode can meet the charge and discharge requirements of the lithium ion batteries, and the lithium foil material of the cathode only needs to provide a very small amount of lithium to make up for the lithium loss in the circulating process. In addition, the metal lithium has very good conductivity and can be used as a current collector of a negative electrode, the density of the metal lithium is 1/16 of the density of metal copper, and the energy density of the battery can be greatly improved by directly adopting an ultrathin lithium metal foil with accurately controlled thickness. For example, researchers have reported that when a lithium nickel manganese cobalt oxide system is used for the positive electrode and a lithium metal with a double-sided thickness of 100 microns is compounded on a copper foil current collector of 8 microns for the negative electrode, the energy of the battery just reaches 300wh/kg (Joule 3, 1-12, March 20, 2019), and as mentioned earlier, the positive electrode contains lithium ions, and if the negative electrode can be thinner, for example, 20 microns, and does not contain copper foil, the energy density of the battery can reach as high as 500 wh/kg.
The tensile strength limit of the metallic lithium is 11.8kg/mm2The belt breakage condition exists in the production of the ultrathin lithium foil; the lithium metal is easy to adhere, has strong self-weldability and is easy to stick to the roller. It is difficult to produce uniform defect-free rolled lithium foil of 20 microns thickness by current techniques. In view of this, in order to achieve high energy density of the battery, it is necessary to develop a rolled ultra-thin lithium foil product having a thickness of 20 μm or less.
SUMMERY OF THE UTILITY MODEL
The utility model aims at providing an ultra-thin lithium foil that thickness that can practical application is below 20 microns to and be used for preparing this ultra-thin lithium foil's industrial production equipment.
In one aspect, the present invention provides an ultra-thin lithium foil, said lithium foil being a self-supporting continuous strip foil having a uniform thickness of less than 20 μm with a thickness tolerance within ± 1.5 μm.
Optionally, the thickness of the lithium foil is in the range of 10-20 μm; the width is 10-500 mm; the length of the lithium foil exceeds 0.1 m.
Optionally, the lithium foil is flat surfaced with no visible holes, tears, and wrinkles.
Optionally, the lithium foil has clean edges and no crack defects.
Optionally, the surface of the lithium foil is bright and is silvery white.
Optionally, the lithium foil is a coiled strip.
Optionally, the lithium content of the lithium foil is 99.90-99.99%, and the content of the surface lithium element is 99.90-99.95%.
In another aspect, the present invention provides an apparatus for preparing the above ultra-thin lithium foil, the apparatus is a roll-to-roll production apparatus, comprising: the metal lithium strip unwinding device, the rolling mill and the winding device are characterized in that the rolling mill comprises a roller and an anti-sticking layer on the surface of the roller.
Optionally, the release layer is 0.005mm-2mm thick.
Optionally, the device further comprises a thickness measuring device arranged at the outlet side of the rolling mill, and the thickness measuring device is used for performing online thickness measurement on the rolled lithium foil.
Optionally, the unwinding device comprises an unwinding roller and an unwinding support roller; the winding device comprises a supporting roller, a tension control roller and a winding roller.
Optionally, the support rollers are themselves powered.
The utility model discloses select the metal lithium strip of utmost point high purity as the raw materials, set up antiseized material on the roll surface to tension when further accurate control roll gap interval and rolling has solved the metal lithium and has taken easy roller that glues, easy fracture, easy corrugating or damaged problem, through rolling many times, has obtained ultra-thin (below 20 mu m) even (thickness tolerance is in
Within ± 1.5 μm). The utility model discloses an ultra-thin lithium foil material can be through the preparation of roll-to-roll technology, is fit for the continuous production of industrialization.
Drawings
Fig. 1 shows a schematic diagram of the apparatus for producing ultra-thin lithium foil according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail with reference to the accompanying drawings and the following detailed description. It should be understood that the detailed description and specific examples, while indicating the invention, are given by way of illustration only. Furthermore, the technical features mentioned in the embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.
According to certain embodiments, the present invention provides an ultra-thin lithium foil, which is a continuous, self-supporting strip, without the need for a support, such as a metal (copper) foil or plastic carrier, that can be prepared and wound by a roll-to-roll process, and when in use, can be used directly by unreeling. Of course, the ultra-thin lithium foil may be wound after being combined with a protective film before the final winding, so as to protect the ultra-thin lithium foil during storage and transportation of the coil.
The ultrathin lithium foil has a thickness of 20 μm or less, and is uniform in thickness with a thickness tolerance within. + -. 1.5. mu.m, preferably within. + -. 1.0. mu.m. The thickness of the lithium foil is in the range of 10 to 20 μm, for example, the thickness may be 20 μm, 18 μm, 16 μm, 12 μm or 10 μm.
The width of the ultrathin lithium foil can be 10-500 mm, such as 50mm, 100mm, 200mm, and the like. The width tolerance may be within 0.4 mm. The length of the lithium foil may exceed 0.1m, for example 0.1-1000 m.
The surface of the metal lithium foil is flat, and holes, damages and folds which can be detected visually are avoided; and the surface is bright and is silvery white. And the edges of the lithium foil are neat without crack defects.
The lithium content of the ultrathin lithium foil is 99.90-99.99%. The utility model discloses the people finds that when the lithium content of lithium area is 99.9% below, in the preparation process of ultra-thin lithium foil, the damage and the wrinkle of lithium area appear easily, especially when rolling, and when improving lithium content to the high purity more than 99.90%, even through rolling many times, damage and wrinkle also rarely appear on lithium foil surface. Although the mechanism is still not completely understood, it is presumed that the impurities contained in the lithium ribbon cause local stress unevenness and are liable to cause breakage and wrinkling. When rolling is performed, since a considerable force is applied to the lithium ribbon, if there is a case where the force is unevenly applied, breakage and wrinkles are more easily generated. It should be noted that the thinner the thickness of the lithium foil, the more easily the breakage and wrinkling occur, and the lithium content of the ultra-thin lithium foil should be controlled. The content of elements other than lithium in the lithium ribbon can be determined by Inductively Coupled Plasma (ICP) monitoring techniques.
Generally, the surface of the lithium foil has a passivation film, which results in a surface lithium content lower than the lithium content of the bulk lithium foil. However, the surface lithium content of the ultra-thin lithium foil of the present invention can reach 99.90% -99.95%, (the surface lithium content can be detected by the X-ray photoelectron spectroscopy analysis technique, and the test thickness is several nanometers), and the difference between the surface lithium content and the lithium content of the lithium foil main body is almost the same. The reason for this is that the passivation film on the surface of the ultra-thin lithium foil of the present invention is very thin.
According to other embodiments, a method for manufacturing the ultrathin lithium foil is provided, wherein the method is a roll-to-roll production method, and a rolled thin metal lithium foil is obtained by unwinding, rolling and then rolling a raw material metal lithium strip. The rolling is repeated several times, for example 2-10 times, preferably 3-4 times, to finally obtain the ultra-thin lithium foil with the thickness of less than 20 microns.
The metal lithium strip with the thickness of 100-300 microns (the thickness tolerance is +/-4 microns) can be used as a raw material, and the metal lithium strip is rolled by a rolling mill after unreeling. The roller of the rolling mill is provided with the anti-sticking layer, and the anti-sticking layer can effectively prevent the lithium strip from sticking the roller, so that the lithium strip can be rolled to be thinner. The anti-sticking layer can be made of one or more of polyethylene, polyformaldehyde, organic silicon polymer, ceramic and the like; polyethylene, polyoxymethylene, silicone polymers are preferred because these organic layers have some flexibility to help reduce or eliminate the potential for uneven stress induced breakage or wrinkling of the rolled lithium strip surface. The thickness of the anti-sticking layer can be 0.005mm-2 mm. And a thickness measuring device is arranged at the outlet side of the rolling mill, so that the rolled lithium strip can be measured on line, and when the thickness deviation exceeds +/-1 mu m of a set value, the rolling mill can finely adjust the roll gap of the roller according to the measured thickness, thereby ensuring the uniform thickness of the lithium strip at the outlet side of the rolling mill. The thickness measuring device can adopt a laser thickness gauge, an X-ray thickness gauge and the like. Rolling the rolled lithium belt by using rolling equipment, wherein the rolling equipment at least comprises a supporting roller, a tension control roller and a rolling roller, and the maximum tension range of the rollers is 0.1-10N; the supporting roller is preferably a powered supporting roller which can draw the lithium belt forward by utilizing micro-pulling force; the tension control roller can move up and down or swing, so that the tension of the lithium strip can be controlled, and the winding speed can be controlled according to the height or the swing angle of the tension control roller. The rolling process is repeated for 2-5 times, and the rolling compression ratio of each time is controlled to be 2-15 (preferably 2-6), so that the uniform lithium foil with any thickness of more than 10 micrometers can be prepared by the process method.
According to other embodiments, the present invention provides an apparatus for preparing the above ultra-thin lithium foil. The device is roll-to-roll production equipment and comprises metal lithium strip unreeling equipment, a rolling mill and reeling equipment.
Fig. 1 shows a schematic diagram of the apparatus for producing ultra-thin lithium foil according to the present invention. As shown in fig. 1, a lithium metal strip is used as a raw material, and is unreeled by an unreeling apparatus 10, where the unreeling apparatus 10 at least includes an unreeling roller 11 and an unreeling supporting roller 12; the raw material lithium belt enters a rolling mill 20 after passing through an unwinding roller 11 and an unwinding support roller 12; the rolling mill 20 at least comprises a roller 21 and an anti-sticking layer 22 on the roller 21, and the rolling pressure of the rolling mill 20 and the roll gap between the rollers 21 can be finely adjusted; the outlet side of the rolling mill 20 is provided with a thickness measuring device 30 which can perform online thickness measurement on the rolled lithium strip, the rolling mill 20 can perform fine adjustment on a roll gap according to the measured thickness, so that the thickness of the lithium strip on the outlet side of the rolling mill is uniform and consistent, and the thickness measuring device 30 can adopt a laser thickness gauge, an X-ray thickness gauge and the like; the rolled lithium strip is rolled by using a rolling device 40, wherein the rolling device 40 at least comprises a supporting roller 41, a tension control roller 42 and a rolling roller 43; the support roller 41 is provided with power, and can pull the lithium belt to advance by utilizing micro pulling force; the tension control roller 42 can move up and down or swing, so that the tension of the lithium strip can be controlled, and the winding speed of the winding roller 43 can be controlled according to the height or the swing angle of the tension control roller 42.
Hereinafter, the present invention will be described in more detail by way of examples using the above-described process equipment. The following embodiments employ various product structure parameters, various reaction participants and process conditions, which are typical examples, but a great number of experiments prove that the invention is applicable to other different structure parameters, other types of reaction participants and other process conditions listed above, and can achieve the claimed technical effects.
Example 1
Adopting a metal lithium strip with 99.95 percent of lithium content and 160 microns of thickness, assisting an unreeling and reeling device, rolling to thin by a roller with an organic silicide coating, rolling for the first time, and controlling a rolling compression ratio to be 2 to obtain the lithium strip with the thickness of 80 microns; performing secondary rolling, and controlling the rolling compression ratio to be 2 to prepare a metal lithium strip with the thickness of 40 microns; and (3) rolling for the third time, and controlling the rolling compression ratio to be 2 to obtain the ultrathin lithium foil with the thickness of 20 micrometers, wherein the thickness tolerance is +/-1 micrometer.
Example 2
Adopting a metal lithium strip with 99.93 percent of lithium content and 130 microns of thickness, assisting an unreeling and reeling device, rolling to thin by a polyethylene coating roller, rolling for the first time, and controlling a rolling compression ratio to be 2 to obtain a lithium strip with 65 microns of thickness; performing secondary rolling, and controlling the rolling compression ratio to be 2 to prepare a metal lithium strip with the thickness of 32 microns; and rolling for the third time, and controlling the rolling compression ratio to be 2 to obtain the ultrathin lithium foil with the thickness of 16 microns, wherein the thickness tolerance is +/-1 micron.
Comparative example 1
Adopting a metal lithium strip with 99.95 percent of lithium content and 160 microns of thickness to assist an unreeling and reeling device, rolling the metal lithium strip by a roller with an organic silicide coating, and controlling a rolling compression ratio to be 8 in a primary rolling process, wherein due to too large deformation of the primary rolling, the ultrathin lithium foil with cracked edges can not be prepared into a coiled metal lithium foil with the thickness of 20 microns; cutting a section of lithium foil product with the thickness of 20 microns and paving the lithium foil product, wherein the phenomenon of irregular edge and crack exists; the surface of the lithium foil is provided with wrinkles.
Comparative example 2
The method comprises the steps of adopting a metal lithium strip with the lithium content of 98.30% and the thickness of 100 microns, assisting an unreeling and reeling device, rolling to be thin through a roller with an organic silicide coating, rolling for the first time, controlling the rolling compression ratio to be 2, obtaining the lithium foil material with the thickness of 50 microns, wherein the lithium foil material with the thickness of 50 microns has cracked edges and folds, cannot be rolled again, and cannot obtain coiled ultrathin lithium foil materials with the thickness of 20 microns or less.
Comparative example 3
The method is characterized in that a metal lithium strip with 99.95 percent of lithium content and 160 microns of thickness is adopted, an unreeling and reeling device is assisted, the lithium strip with the thickness of 80 microns is obtained by rolling through a roller without an anti-sticking coating, the first rolling is carried out, the rolling compression ratio is controlled to be 2, the problems of edge cracking and holes on the surface of a lithium foil with the thickness of 80 microns are solved, the lithium strip cannot be rolled again, and the coiled ultrathin lithium foil with the thickness of 20 microns or less cannot be obtained.
It should be understood that the above-described embodiments are merely exemplary of the present invention, and are not intended to limit the present invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. An ultra-thin lithium foil, wherein the lithium foil is a self-supporting continuous strip foil having a uniform thickness of 20 μm or less with a thickness tolerance within ± 1.5 μm.
2. The ultra-thin lithium foil as claimed in claim 1, wherein the thickness of the lithium foil is in the range of 10 to 20 μm; the width is 10-500 mm; the length of the lithium foil exceeds 0.1 m.
3. The ultra-thin lithium foil of claim 1, wherein the lithium foil is flat surfaced with no visible holes, tears, and wrinkles; and/or the lithium foil has neat edges and no crack defects.
4. The ultra-thin lithium foil as claimed in claim 1, wherein the surface of the lithium foil is bright and is silver-white.
5. The ultra-thin lithium foil of claim 1, wherein the lithium foil is a coiled strip.
6. An apparatus for preparing the ultra-thin lithium foil as claimed in any one of claims 1 to 5, wherein the apparatus is a roll-to-roll production facility comprising: the metal lithium strip unwinding device, the rolling mill and the winding device are characterized in that the rolling mill comprises a roller and an anti-sticking layer on the surface of the roller.
7. The device of claim 6 wherein the release layer is 0.005mm-2mm thick.
8. The apparatus of claim 6, further comprising a thickness measuring device disposed at an outlet side of the rolling mill, wherein the thickness measuring device performs on-line thickness measurement on the rolled lithium strip.
9. The apparatus of claim 6, wherein the unwinding device comprises an unwinding roller and an unwinding support roller; the winding device comprises a supporting roller, a tension control roller and a winding roller.
10. The device of claim 9, wherein the support rollers are themselves powered.
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| CN201920341275.XU CN209822779U (en) | 2019-03-18 | 2019-03-18 | Ultrathin lithium foil and device for preparing ultrathin lithium foil |
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| CN201920341275.XU CN209822779U (en) | 2019-03-18 | 2019-03-18 | Ultrathin lithium foil and device for preparing ultrathin lithium foil |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111299321A (en) * | 2020-03-06 | 2020-06-19 | 重庆天齐锂业有限责任公司 | Processing device and processing method of ultrathin lithium foil |
| CN111725496A (en) * | 2019-03-18 | 2020-09-29 | 天津中能锂业有限公司 | Ultrathin lithium foil and preparation method thereof |
| CN113732058A (en) * | 2021-08-13 | 2021-12-03 | 奉新赣锋锂业有限公司 | Preparation method of ultra-wide and ultra-thin metal lithium and alloy strip thereof |
| CN114583312A (en) * | 2022-03-07 | 2022-06-03 | 华中科技大学 | Processing and recycling method of ultrathin lithium foil and product |
| CN116967285A (en) * | 2023-09-22 | 2023-10-31 | 江苏铭丰电子材料科技有限公司 | Copper foil calendering device |
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2019
- 2019-03-18 CN CN201920341275.XU patent/CN209822779U/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111725496A (en) * | 2019-03-18 | 2020-09-29 | 天津中能锂业有限公司 | Ultrathin lithium foil and preparation method thereof |
| CN111299321A (en) * | 2020-03-06 | 2020-06-19 | 重庆天齐锂业有限责任公司 | Processing device and processing method of ultrathin lithium foil |
| CN111299321B (en) * | 2020-03-06 | 2022-05-10 | 重庆天齐锂业有限责任公司 | Processing method of ultrathin lithium foil |
| CN113732058A (en) * | 2021-08-13 | 2021-12-03 | 奉新赣锋锂业有限公司 | Preparation method of ultra-wide and ultra-thin metal lithium and alloy strip thereof |
| CN114583312A (en) * | 2022-03-07 | 2022-06-03 | 华中科技大学 | Processing and recycling method of ultrathin lithium foil and product |
| CN114583312B (en) * | 2022-03-07 | 2023-08-29 | 华中科技大学 | Processing and recycling method of ultrathin lithium foil and product |
| CN116967285A (en) * | 2023-09-22 | 2023-10-31 | 江苏铭丰电子材料科技有限公司 | Copper foil calendering device |
| CN116967285B (en) * | 2023-09-22 | 2023-12-15 | 江苏铭丰电子材料科技有限公司 | Copper foil calendering device |
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