CN114975886A - Lithium foil surface passivation method and application thereof in lithium metal battery - Google Patents

Lithium foil surface passivation method and application thereof in lithium metal battery Download PDF

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Publication number
CN114975886A
CN114975886A CN202210680517.4A CN202210680517A CN114975886A CN 114975886 A CN114975886 A CN 114975886A CN 202210680517 A CN202210680517 A CN 202210680517A CN 114975886 A CN114975886 A CN 114975886A
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lithium foil
lithium
lithium metal
passivated
foil
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Inventor
李林森
朱迎迎
周罗增
吴勇民
郭瑞
何雨石
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Shanghai Jiaotong University
Shanghai Institute of Space Power Sources
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Shanghai Jiaotong University
Shanghai Institute of Space Power Sources
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • 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)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a surface-passivated ultrathin lithium foil and a preparation method thereof. The ultrathin lithium metal foil with the uniform and passivated surface is obtained by performing surface treatment on the ultrathin lithium metal foil by using argon plasma in the atmosphere containing a small amount of carbon dioxide. The ultrathin lithium foil obtained by the invention has better stability in air, and the lithium metal battery assembled with the oxide anode has longer cycle life.

Description

Lithium foil surface passivation method and application thereof in lithium metal battery
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a surface-passivated ultrathin lithium foil, a preparation method thereof and application thereof in a lithium metal battery.
Background
Lithium metal batteries, which are capable of providing higher energy densities than current lithium ion batteries, are one of the hot spots in current battery technology research. The high energy density battery needs to use a metal lithium foil with a smaller thickness to reduce the overall weight of the battery and improve the overall energy density of the battery. However, lithium metal is very active and requires a surface passivation treatment for better air stability and cycle stability.
Some lithium metal surface passivation methods have been disclosed only for preparing passivated lithium powders (particles), such as CN108176859B and CN105762328B, but the lithium reactivity is too strong, the passivation of thin lithium foil by conventional methods has a large defect, the lithium used as the active material of the battery is easily consumed too much, and the produced passivation layer is also not pure, which affects the performance of the battery. The conventional method cannot be applied to passivation of ultra-thin lithium metal foils. In order to solve the problem, the invention uses argon plasma to carry out surface treatment on the ultrathin lithium metal foil in the atmosphere containing a small amount of carbon dioxide to obtain the ultrathin lithium foil with a uniformly passivated surface. The ultrathin lithium foil obtained by the invention has better stability in air, and the lithium metal battery assembled with the oxide anode has longer cycle life.
The invention content is as follows:
the present invention has been made to solve the problems of the prior art, and an object of the present invention is to prepare a surface-passivated ultra-thin lithium foil, which improves its air stability and cycle stability in a lithium metal battery.
Characteristics of surface-passivated ultra-thin lithium foil:
1. the thickness of the metal lithium layer is not more than 50 microns;
2. the surface of the material is mainly Li 2 CO 3 The thickness is 10-30 nm.
The preparation method comprises the following steps:
the lithium metal foil was placed in a plasma cleaner (Diener, Femto model) inside an argon-protected glove box with a power of 25-75W and a treatment time of 10-20 min.
Drawings
FIG. 1 is a lithium foil after plasma treatment;
FIG. 2 shows XPS results of plasma-treated lithium foil surfaces(surface is mainly Li) 2 CO 3 ）；
FIG. 3 shows XPS results for lithium foil surfaces that were not plasma treated (surfaces with predominantly C-C, C-H organic contaminants).
Compared with the prior art, the surface of the ultrathin lithium foil with passivated surface, prepared by the invention, uniformly forms pure Li with the particle size of 10-30 nm 2 CO 3 The air stability of the lithium foil and the cycle stability in the lithium metal battery are improved, and the lithium metal battery assembled with the oxide positive electrode has longer cycle life.
Detailed Description
Example 1
3 lithium metal foils having a diameter of 12 mm and a thickness of 50 μm were placed in a chamber of a plasma cleaner (model Femto from Diener) placed inside an argon-protected glove box, and argon gas (containing 100 ppm of CO) was introduced into the chamber 2 ) And 3 samples 1 were obtained by treating for 20 min at a plasma power of 25W. 1 of these sheets was placed in 30% humidity air for 30min, and air stability evaluation was performed. Another 1 slice adopts X-ray photoelectron spectrum-depth analysis technique to measure Li 2 CO 3 The thickness of the layer. Example 2: 2 lithium metal foils having a diameter of 12 mm and a thickness of 30 μm were placed in a chamber of a plasma cleaner (model Femto from Diener) placed inside an argon-shielded glove box, and argon gas (containing 100 ppm of CO) was introduced into the chamber 2 ) Sample 2 was obtained by treating for 12 min at a plasma power of 50W. 1 of these tablets was placed in air of 30% humidity for 30min for air stability evaluation. Another 1 slice adopts X-ray photoelectron spectrum-depth analysis technique to measure Li 2 CO 3 The thickness of the layer.
Example 3
2 lithium metal foils having a diameter of 12 mm and a thickness of 20 μm were placed in a chamber of a plasma cleaner (model Femto from Diener) placed inside an argon-shielded glove box, and argon gas (containing 100 ppm of CO) was introduced into the chamber 2 ) Treating at a plasma power of 75WFor 10 min, sample 3 was obtained. 1 of these sheets was placed in 30% humidity air for 30min, and air stability evaluation was performed. Another 1 slice adopts X-ray photoelectron spectrum-depth analysis technique to measure Li 2 CO 3 The thickness of the layer.
Example 4
The preparation method was the same as example 1, and the obtained surface-passivated lithium metal foil and 811-type ternary cathode material (LiNi) were used 0.8 Mn 0.1 Co 0.1 O 2 ) A separator, and an electrolytic solution (1M lithium hexafluorophosphate dissolved in a volume ratio of 1: 1 dimethyl carbonate and fluoroethylene carbonate) were assembled into button cells in an argon-protected glove box and the test was terminated by charging and discharging at 0.2C rate over a voltage range of 4.3-2.8V until the capacity dropped to 80% of the initial capacity.
Comparative example 1
Lithium metal foil 2 sheets having a diameter of 12 mm and a thickness of 50 μm were purchased without surface treatment. 1 of these sheets was placed in 30% humidity air for 30min, and air stability evaluation was performed. The other 1 piece adopts X-ray photoelectron spectroscopy-depth analysis technique to measure the surface composition and the existing depth.
Comparative example 2
The surface-passivated lithium metal foil was replaced with a commercially available lithium metal foil having a diameter of 12 mm and a thickness of 50 μm without surface treatment, as in example 4
TABLE 1 comparison of surface lithium carbonate layer thickness and air stability
Figure DEST_PATH_IMAGE002
TABLE 2 lithium Metal Battery cycle Life
Cycle life of lithium metal batteryLife (number of cycles when capacity drops to 80% of initial value)
Example 4 285
Comparative example 2 153

Claims (6)

1. A method for passivating a surface of a lithium foil, comprising: the method comprises the steps of putting the lithium foil into a plasma cavity protected by inert gas containing 50-200ppm of carbon dioxide, and carrying out plasma treatment, wherein the plasma treatment power is 25-75W, and the treatment time is 10-20 min, so that the ultrathin lithium foil with the uniform and passivated surface is obtained.
2. The lithium foil surface passivation method of claim 1, characterized in that: the lithium foil is no greater than 50 microns thick.
3. The lithium foil surface passivation method according to claim 2, characterized in that: the main component of the passivated lithium foil surface is Li 2 CO 3 The thickness is 10-30 nm.
4. The lithium foil surface passivation method of claim 1, characterized in that: the inert gas is argon.
5. The lithium foil surface passivation method of claim 1, characterized in that: and putting the lithium foil into a plasma cleaning machine inside a glove box protected by inert gas for passivation, wherein the model of the plasma cleaning machine is Diener and Femto, the power is 25-75W, and the treatment time is 10-20 min.
6. Use of a surface-passivated lithium foil prepared according to any of claims 1-5 in a lithium metal battery.
CN202210680517.4A 2022-06-16 2022-06-16 Lithium foil surface passivation method and application thereof in lithium metal battery Pending CN114975886A (en)

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Application Number Priority Date Filing Date Title
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06124700A (en) * 1992-10-08 1994-05-06 Matsushita Electric Ind Co Ltd Non-aqueous electrolytic solution secondary battery and manufacturing method thereof
JPH1167208A (en) * 1997-08-13 1999-03-09 Ricoh Co Ltd Electrode for secondary battery and its manufacture
US20020012846A1 (en) * 1999-11-23 2002-01-31 Skotheim Terje A. Lithium anodes for electrochemical cells
US20050008938A1 (en) * 2003-07-08 2005-01-13 Samsung Sdi Co., Ltd. Negative electrode for rechargeable lithium battery, method of producing same and rechargeable lithium battery comprising same
CN1585163A (en) * 2003-08-19 2005-02-23 三星Sdi株式会社 Preparation of lithium anodes
CN101126668A (en) * 2007-09-20 2008-02-20 复旦大学 Discharging gas environment ion vacuum gauge auxiliary instrument
CN105762328A (en) * 2014-12-15 2016-07-13 比亚迪股份有限公司 Passivation lithium powder and preparing method thereof, positive electrode material with addition of passivation lithium powder and battery
CN108176859A (en) * 2017-12-05 2018-06-19 天齐锂业股份有限公司 The preparation method of passivation of lithium powder
CN109088065A (en) * 2018-08-21 2018-12-25 成都新柯力化工科技有限公司 A kind of preparation method of the negative electrode material of lithium-air battery
CN109461886A (en) * 2018-11-19 2019-03-12 江西迪比科股份有限公司 A kind of composite metal lithium titanate cathode material and preparation method

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06124700A (en) * 1992-10-08 1994-05-06 Matsushita Electric Ind Co Ltd Non-aqueous electrolytic solution secondary battery and manufacturing method thereof
JPH1167208A (en) * 1997-08-13 1999-03-09 Ricoh Co Ltd Electrode for secondary battery and its manufacture
US20020012846A1 (en) * 1999-11-23 2002-01-31 Skotheim Terje A. Lithium anodes for electrochemical cells
US20050008938A1 (en) * 2003-07-08 2005-01-13 Samsung Sdi Co., Ltd. Negative electrode for rechargeable lithium battery, method of producing same and rechargeable lithium battery comprising same
CN1585163A (en) * 2003-08-19 2005-02-23 三星Sdi株式会社 Preparation of lithium anodes
CN101126668A (en) * 2007-09-20 2008-02-20 复旦大学 Discharging gas environment ion vacuum gauge auxiliary instrument
CN105762328A (en) * 2014-12-15 2016-07-13 比亚迪股份有限公司 Passivation lithium powder and preparing method thereof, positive electrode material with addition of passivation lithium powder and battery
CN108176859A (en) * 2017-12-05 2018-06-19 天齐锂业股份有限公司 The preparation method of passivation of lithium powder
CN109088065A (en) * 2018-08-21 2018-12-25 成都新柯力化工科技有限公司 A kind of preparation method of the negative electrode material of lithium-air battery
CN109461886A (en) * 2018-11-19 2019-03-12 江西迪比科股份有限公司 A kind of composite metal lithium titanate cathode material and preparation method

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