CN108538642A - A kind of preparation method stabilizing metallic lithium powder - Google Patents
A kind of preparation method stabilizing metallic lithium powder Download PDFInfo
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- CN108538642A CN108538642A CN201810076532.1A CN201810076532A CN108538642A CN 108538642 A CN108538642 A CN 108538642A CN 201810076532 A CN201810076532 A CN 201810076532A CN 108538642 A CN108538642 A CN 108538642A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 44
- 239000000843 powder Substances 0.000 title claims abstract description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 230000000087 stabilizing effect Effects 0.000 title claims 2
- 239000010453 quartz Substances 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052786 argon Inorganic materials 0.000 claims abstract description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 4
- 239000002923 metal particle Substances 0.000 claims abstract description 3
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 210000001787 dendrite Anatomy 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000006138 lithiation reaction Methods 0.000 abstract description 2
- 239000005486 organic electrolyte Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011888 foil Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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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
- 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
- Y02E60/13—Energy storage using capacitors
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- Power Engineering (AREA)
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- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
一种稳定化金属锂粉的制备方法，其特征是按如下步骤：取适量的全氟树脂和金属锂粉，分别放置在两个石英杯中，再将两个石英杯一起放入管式炉中，在持续通入氩气的氛围下，加热到350℃保温2小时，再降温到175℃保温12小时，使锂金属颗粒表面生成氟化锂，从而制得稳定化金属锂粉。表面氟化的稳定金属锂粉可以在空气中长时间稳定保存，当应用于电极材料时，可以有效的阻止有机电解液对锂粉的腐蚀作用和防止锂金属枝状晶体的形成。不仅为锂粉的储存带来便利，而且为锂离子电容器的预锂化过程带来方便，大大提高锂离子电容器的性能。本发明方法简单可行。
A preparation method of stabilized lithium metal powder is characterized in that the following steps are taken: take an appropriate amount of perfluororesin and lithium metal powder, place them in two quartz cups respectively, and put the two quartz cups into a tube furnace together In the process, under the atmosphere of continuous feeding of argon gas, heat to 350°C for 2 hours, then cool down to 175°C for 12 hours, so that lithium fluoride is formed on the surface of lithium metal particles, so as to obtain stabilized lithium metal powder. The surface fluorinated stable metal lithium powder can be stored stably in the air for a long time. When applied to electrode materials, it can effectively prevent the corrosion of the organic electrolyte on the lithium powder and prevent the formation of lithium metal dendrites. It not only brings convenience to the storage of lithium powder, but also brings convenience to the pre-lithiation process of lithium ion capacitors, greatly improving the performance of lithium ion capacitors. The method of the invention is simple and feasible.
Description
技术领域technical field
本发明涉及一种稳定化金属锂粉的制备工艺。The invention relates to a preparation process of stabilized lithium metal powder.
背景技术Background technique
锂离子电容器中的锂源主要来源于电解液中的锂离子，但在充放电过程中负极表面形成固体电解质界面（SEI）膜消耗的锂以及嵌入负极材料中难以脱嵌的不可逆锂会造成锂离子大量的流失，势必影响电容器的容量和循环性能，因此对负极的预先补锂尤为重要。实践证明，稳定金属锂粉补锂是锂离子电容器负极预锂化的一个简单有效的方式。过去常用的稳定金属锂粉是通过锂粉外包一层聚合物保护层来达到隔绝水分和氧气的目的，然而这种方式形成的稳定金属锂粉在空气中稳定存在的时间较短，当应用于电极材料时，在循环的过程中过多的锂粉会形成枝状晶体，会破坏隔膜和电极表面，造成电池的损坏。The lithium source in lithium-ion capacitors mainly comes from lithium ions in the electrolyte, but the lithium consumed by the formation of a solid electrolyte interface (SEI) film on the surface of the negative electrode during charge and discharge and the irreversible lithium embedded in the negative electrode material that is difficult to deintercalate will cause lithium The loss of a large number of ions will inevitably affect the capacity and cycle performance of the capacitor, so it is particularly important to pre-supplement lithium to the negative electrode. Practice has proved that lithium supplementation with stable metal lithium powder is a simple and effective way to pre-lithiate the negative electrode of lithium ion capacitors. In the past, the commonly used stable lithium metal powder was coated with a polymer protective layer to achieve the purpose of isolating moisture and oxygen. However, the stable lithium metal powder formed in this way has a short time of stable existence in the air. When applied to When using electrode materials, too much lithium powder will form dendrites during the cycle, which will damage the separator and electrode surface, causing damage to the battery.
发明内容Contents of the invention
本发明的目的在于提出一种稳定化金属锂粉的制备方法，通过锂粉表面氟化的方式提高金属锂粉的稳定性，解决电容器循环过程中锂枝晶的形成，提高锂离子电容器的倍率、容量和循环性能。The purpose of the present invention is to propose a preparation method of stabilized lithium metal powder, improve the stability of lithium metal powder by fluorinating the surface of lithium powder, solve the formation of lithium dendrites in the capacitor cycle process, and increase the rate of lithium ion capacitors , capacity and cycle performance.
本发明是通过以下技术方案实现的。The present invention is achieved through the following technical solutions.
本发明所述的一种稳定化金属锂粉的制备方法，按如下步骤：取适量的全氟树脂（CYTOP）置于石英杯中，再加入一定量的金属锂粉，为避免二者混合，金属锂粉和全氟树脂分别放置在两个石英杯中，再将石英杯一起放入管式炉中，在持续通入氩气的氛围下，加热到350℃保温2小时，再降温到175℃保温12小时，使锂金属颗粒表面生成氟化锂，从而制得稳定化金属锂粉。The preparation method of a kind of stabilized lithium metal powder of the present invention, according to the following steps: take an appropriate amount of perfluororesin (CYTOP) and place it in a quartz cup, and then add a certain amount of lithium metal powder, in order to avoid mixing the two, Lithium metal powder and perfluororesin were placed in two quartz cups respectively, and then the quartz cups were placed together in a tube furnace, heated to 350°C for 2 hours in an atmosphere of continuous argon gas, and then cooled to 175°C. ℃ for 12 hours, so that lithium fluoride is generated on the surface of lithium metal particles, thereby preparing stabilized lithium metal powder.
表面氟化的稳定金属锂粉可以在空气中长时间稳定保存，当应用于电极材料时，可以有效的阻止有机电解液对锂粉的腐蚀作用和防止锂金属枝状晶体的形成。不仅为锂粉的储存带来便利，而且为锂离子电容器的预锂化过程带来方便，大大提高锂离子电容器的性能。本发明方法简单可行。The surface fluorinated stable metal lithium powder can be stored stably in the air for a long time. When applied to electrode materials, it can effectively prevent the corrosion of the organic electrolyte on the lithium powder and prevent the formation of lithium metal dendrites. It not only brings convenience to the storage of lithium powder, but also brings convenience to the pre-lithiation process of lithium ion capacitors, greatly improving the performance of lithium ion capacitors. The method of the invention is simple and feasible.
附图说明Description of drawings
图1 为本发明制备工艺示意图。Figure 1 is a schematic diagram of the preparation process of the present invention.
具体实施方式Detailed ways
本发明将通过以下实施例作进一步说明。但本发明并不限于以下实施例。The invention will be further illustrated by the following examples. However, the present invention is not limited to the following examples.
实施例1。Example 1.
在充满氩气的手套箱中，量取10ml全氟树脂（CYTOP）置于石英杯底部，将多微孔箔片固定在石英杯顶部，再称取0.5g金属锂粉置于箔片上，将石英杯在密封的情况下转移至持续通入氮气的管式炉中，加热到350℃保温2小时，再降温到175℃保温12小时，即得到表面氟化的稳定金属锂粉。In a glove box filled with argon, measure 10ml of perfluororesin (CYTOP) and place it on the bottom of the quartz cup, fix the microporous foil on the top of the quartz cup, then weigh 0.5g of metallic lithium powder and place it on the foil, place The quartz cup was transferred to a tube furnace that was continuously fed with nitrogen under sealed conditions, heated to 350°C for 2 hours, and then cooled to 175°C for 12 hours to obtain stable metal lithium powder with fluorinated surface.
实施例2。Example 2.
在充满氩气的手套箱中，量取10ml全氟树脂（CYTOP）置于石英杯底部左侧，再称取0.5g金属锂粉置于石英杯底部右侧，石英杯加盖，将石英杯在密封的情况下转移至持续通入氮气的管式炉中，加热到350℃保温2小时，再降温到175℃保温12小时，即得到表面氟化的稳定金属锂粉。In a glove box filled with argon, measure 10ml of perfluororesin (CYTOP) and place it on the left side of the bottom of the quartz cup, then weigh 0.5g of lithium metal powder and place it on the right side of the bottom of the quartz cup, cover the quartz cup, and place the quartz cup In the sealed condition, transfer to a tube furnace continuously fed with nitrogen, heat to 350°C for 2 hours, and then cool down to 175°C for 12 hours to obtain stable metal lithium powder with fluorinated surface.
实施例3。Example 3.
在充满氩气的手套箱中，称取0.5g金属锂粉和10ml全氟树脂（CYTOP）置于石英杯中，用多孔隔层将CYTOP和金属锂粉上下隔开放置，将石英杯在密封的情况下转移至持续通入氮气的管式炉中，加热到350℃保温2小时，再降温到175℃保温12小时，即得到表面氟化的稳定金属锂粉。In a glove box filled with argon gas, weigh 0.5g metal lithium powder and 10ml perfluororesin (CYTOP) and place them in a quartz cup, separate CYTOP and metal lithium powder up and down with a porous partition, and place the quartz cup in a sealed transfer to a tube furnace continuously fed with nitrogen, heated to 350°C for 2 hours, and then cooled to 175°C for 12 hours to obtain stable metal lithium powder with fluorinated surface.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101213039A (en) * | 2005-07-05 | 2008-07-02 | Fmc公司 | The preparation method of the stabilized metal lithium powder applied to lithium ion |
| US20130122318A1 (en) * | 2009-12-18 | 2013-05-16 | Chemetall Gmbh | Surface-passivated lithium metal and method for the production thereof |
| CN104185522A (en) * | 2012-01-13 | 2014-12-03 | 罗克伍德锂有限责任公司 | Stabilized lithium metal impressions coated with alloy-forming elements and method for production thereof |
| CN104393267A (en) * | 2014-10-24 | 2015-03-04 | 上海四驱新能源科技有限公司 | Preparation method of high-stability lithium metal microsphere powder |
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- 2018-01-26 CN CN201810076532.1A patent/CN108538642A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101213039A (en) * | 2005-07-05 | 2008-07-02 | Fmc公司 | The preparation method of the stabilized metal lithium powder applied to lithium ion |
| US20130122318A1 (en) * | 2009-12-18 | 2013-05-16 | Chemetall Gmbh | Surface-passivated lithium metal and method for the production thereof |
| CN104185522A (en) * | 2012-01-13 | 2014-12-03 | 罗克伍德锂有限责任公司 | Stabilized lithium metal impressions coated with alloy-forming elements and method for production thereof |
| CN104393267A (en) * | 2014-10-24 | 2015-03-04 | 上海四驱新能源科技有限公司 | Preparation method of high-stability lithium metal microsphere powder |
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Application publication date: 20180914 |