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WO2016085363A1 - Matériau pour anode - Google Patents

Matériau pour anode Download PDF

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Publication number
WO2016085363A1
WO2016085363A1 PCT/RU2014/000938 RU2014000938W WO2016085363A1 WO 2016085363 A1 WO2016085363 A1 WO 2016085363A1 RU 2014000938 W RU2014000938 W RU 2014000938W WO 2016085363 A1 WO2016085363 A1 WO 2016085363A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
layer
foil
battery
thickness
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/RU2014/000938
Other languages
English (en)
Russian (ru)
Inventor
Дмитрий Александрович СЕМЕНЕНКО
Петр Анатольевич ЦЫГАНКОВ
Алина Игоревна БЕЛОВА
Даниил Михайлович ИТКИС
Виктор Александрович КРИВЧЕНКО
Никита Александрович РАЦ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Micromash Ou
Obshestvo S Ogranichennoj Otvetstvennost'yu "lition"
Original Assignee
Micromash Ou
Obshestvo S Ogranichennoj Otvetstvennost'yu "lition"
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Micromash Ou, Obshestvo S Ogranichennoj Otvetstvennost'yu "lition" filed Critical Micromash Ou
Publication of WO2016085363A1 publication Critical patent/WO2016085363A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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
    • H01M4/04—Processes of manufacture in general
    • 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
    • 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

Definitions

  • the invention relates to a coated metal anode and can be used in lithium batteries.
  • polymer, ceramic or composite polymer-ceramic coatings can be used as protective coatings for lithium electrodes (US 2013/0236764 A1, publ. 12.09.2013).
  • polymers for such coatings copolymers including hydrophobic (polydimethylsiloxane) and hydrophilic (polyoxymethylene methacrylate or polyoxyethylene acrylate) polymer blocks having a low glass transition temperature can be used.
  • the specific capacity of the lithium battery containing the lithium anode protected in this way does not exceed 150 mA / g, and the drop in capacity for 30 recharge cycles reaches 30%.
  • the closest analogue of the claimed group of the invention is the anode material disclosed in the source EP 0715366 A1, publ. 06/20171996, in which various transition metal oxides (W, Mo, Ti, V, Nb, Zr, Hf, Ta, and Cr) were used as a protective anode coating. Solutions of the precursors of the corresponding metals are applied to the surface of the lithium anode, the solvent is dried, and then annealed at a temperature of 300-500 ° C to form an oxide layer. In addition, oxide films can be formed by sputtering, chemical vapor deposition, and electron beam evaporation.
  • the objective of the proposed technical solution is to develop an anode material for secondary batteries with a protective coating having a low electrochemically inactive mass.
  • the technical result of the invention is to increase the strength of the lithium layer of the anode material and reduce the electrochemically inactive mass.
  • the anode material is made in the form of a metal foil with down conductors, made with the possibility of applying a lithium metal layer to its surface by spraying or rolling lithium foil and then spraying a protective layer on the lithium metal layer.
  • Al As the material of the metal foil, Al, Ni, stainless steel are used.
  • the thickness of the lithium metal layer is from 50 nm to 50 ⁇ m.
  • the thickness of lithium foil is 50-500 microns.
  • the thickness of the protective layer is from 10 nm to 10 ⁇ m.
  • FIG. 1 Discharging curve of a battery manufactured in accordance with EP 0715366 A1.
  • FIG. 2 Discharge curve of a battery containing a lithium anode on nickel foil with deposited layers of lithium 10 ⁇ m thick and 50 nm thick silicon, at a current density of 0.15 mA / cm 2 and a discharge depth of 1.5 mAh / cm 2 .
  • FIG. 3 Discharge curve of a battery containing a lithium anode on aluminum foil, onto the surface of which a lithium foil 500 ⁇ m thick was rolled and then a germanium layer was deposited with a thickness of 10 ⁇ m, at a current density of 0.15 mA / cm 2 and a discharge depth of 1.5 mAh / cm 2 .
  • Anode material made in the form of a metal foil with down conductors made with the possibility of applying a layer of lithium metal onto its surface by spraying or rolling lithium foil and then spraying a protective layer on a lithium metal layer.
  • the material of the metal foil used AI i, stainless steel.
  • the thickness of the lithium metal layer is from 50 nm to 50 ⁇ m.
  • the thickness of the deposited lithium layer less than 50 nm will be insufficient to implement the required depth of discharge of the battery; above 50 microns will be excessive and will lead to an increase in inactive mass of the battery.
  • the thickness of lithium foil is 50-500 microns. A thickness of lithium foil less than 50 microns will not be sufficient to implement the required depth of discharge of the battery; above 500 microns will be excessive and will lead to an increase in inactive mass of the battery.
  • the thickness of the protective layer is from 10 nm to 10 ⁇ m. If the protective layer is more than 10 ⁇ m thick, diffusion of lithium ions from the lithium electrode to the electrolyte is difficult, which can lead to a decrease in the operating voltage of the battery. A layer less than 10 nm may be mechanically destroyed when quoting the battery.
  • the lithium and protective layers are sprayed using magnetron sputtering, temperature-induced and plasma chemical vapor deposition, electron beam sputtering, and cluster ion evaporation.
  • a layer of metallic Li with a thickness of 10 ⁇ m is applied by magnetron sputtering.
  • the resulting electrode can be used as an anode in a lithium battery containing a cathode and an electrolyte. From FIG. 1 it can be seen that when the battery is recharged, the lithium layer of the anode material can be destroyed or dendrites are formed, which leads to deterioration of the battery, therefore, such an anode material has a low strength lithium layer and a high electrochemically inactive mass. As experiments showed (see Fig.
  • the anode of the battery is in the form of a nickel foil with down conductors, the surface of which is sprayed with a 10- ⁇ m thick layer of metallic Li, over which a 50-nm-thick Si protective layer is sprayed, recharged without breaking the lithium layer, i.e. . has a higher strength, which does not lead to deterioration of the battery and the formation of dendrites, and also allows to reduce the electrochemically inactive mass. In this case, the strength of the lithium layer increases by 10 times, and the electrochemically inactive mass decreases by 10 times.
  • a 500 ⁇ m thick lithium foil is rolled onto the surface of the aluminum foil with down conductors.
  • a layer of Ge with a thickness of 10 ⁇ m was deposited over the layer of a metal layer by plasma chemical vapor deposition.
  • the resulting electrode can be used as an anode in a lithium battery containing a cathode and an electrolyte. From FIG. 1 it can be seen that when the battery is recharged, the lithium layer of the anode material can be destroyed or dendrites are formed, which leads to deterioration of the battery, therefore, such an anode material has a low strength lithium layer and a high electrochemically inactive mass. As experiments showed (see Fig.
  • the anode of the battery is in the form of an aluminum foil with down conductors, a lithium foil with a thickness of 500 ⁇ m is rolled onto its surface, on top of which a 10 ⁇ m thick Ge layer is sprayed and recharged without destroying the lithium layer, i.e. has a higher strength, which does not lead to deterioration of the battery and the formation of dendrites, and also allows to reduce the electrochemically inactive mass.
  • the strength of the lithium layer increases by 10 times, and the electrochemically inactive mass decreases by 10 times.
  • the present invention allows to obtain anode material with increased strength of the lithium layer and with a reduced electrochemically inactive mass.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne un matériau pour anode comportant un revêtement, et un accumulateur avec une anode métallique comprenant un revêtement. Le résultat technique de l'invention consiste en une plus grande résistance de la couche de lithium du matériau pou anode et en une diminution de la masse électrochimiquement inactive. Le matériau pour anode se présente sous forme d'une feuille métallique avec des sortie de courant, et sur la surface de laquelle on applique une couche de lithium métallique par pulvérisation ou stratification d'une feuille de lithium, après quoi on pulvérise une couche de protection sur la couche de lithium métallique.
PCT/RU2014/000938 2014-11-28 2014-12-17 Matériau pour anode Ceased WO2016085363A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2014148083 2014-11-28
RU2014148083/07A RU2596023C2 (ru) 2014-12-17 2014-12-17 Анодный материал

Publications (1)

Publication Number Publication Date
WO2016085363A1 true WO2016085363A1 (fr) 2016-06-02

Family

ID=56074757

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/RU2014/000938 Ceased WO2016085363A1 (fr) 2014-11-28 2014-12-17 Matériau pour anode

Country Status (2)

Country Link
RU (1) RU2596023C2 (fr)
WO (1) WO2016085363A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110350202A (zh) * 2019-07-24 2019-10-18 江苏塔菲尔新能源科技股份有限公司 一种集流体及其制备方法和锂离子电池

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2718707C1 (ru) * 2019-01-11 2020-04-14 Сергей Николаевич Максимовский Способ создания наноструктурированного кремниевого анода
GB202000467D0 (en) 2020-01-13 2020-02-26 Sigma Lithium Ltd Alkali metal materials

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060234127A1 (en) * 2003-06-25 2006-10-19 Kim You M Anode material for lithium secondary cell with high capacity
WO2011068767A1 (fr) * 2009-12-03 2011-06-09 Fmc Corporation Poudre métallique de lithium finement déposée
WO2014074332A1 (fr) * 2012-11-06 2014-05-15 Ultora, Inc. Nanotubes de carbone attachés à une feuille de métal

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JP3347555B2 (ja) * 1994-12-01 2002-11-20 キヤノン株式会社 リチウム二次電池の負極の作製方法
RU2105392C1 (ru) * 1995-06-05 1998-02-20 Общество с ограниченной ответственностью "Интергрин" Химический источник тока
CN1885595A (zh) * 2006-05-31 2006-12-27 华南理工大学 一种可集成的全固态锂离子薄膜微电池正极的制备方法
CN100561778C (zh) * 2007-07-31 2009-11-18 北京理工大学 一种提高锂离子电池负极安全性的表面镀膜修饰方法
JP5573408B2 (ja) * 2010-06-23 2014-08-20 ソニー株式会社 導電材料の製造方法および導電材料、並びに電池
CN102054961A (zh) * 2010-07-22 2011-05-11 中信国安盟固利动力科技有限公司 活性负极极片及其制备方法
CN104160544B (zh) * 2012-03-07 2016-08-31 麻省理工学院 用于宽温操作的可充电锂电池
CN103456983B (zh) * 2013-09-09 2016-10-19 桂林电子科技大学 薄膜固体电解质材料及其制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060234127A1 (en) * 2003-06-25 2006-10-19 Kim You M Anode material for lithium secondary cell with high capacity
WO2011068767A1 (fr) * 2009-12-03 2011-06-09 Fmc Corporation Poudre métallique de lithium finement déposée
WO2014074332A1 (fr) * 2012-11-06 2014-05-15 Ultora, Inc. Nanotubes de carbone attachés à une feuille de métal

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110350202A (zh) * 2019-07-24 2019-10-18 江苏塔菲尔新能源科技股份有限公司 一种集流体及其制备方法和锂离子电池

Also Published As

Publication number Publication date
RU2596023C2 (ru) 2016-08-27
RU2014148083A (ru) 2016-07-10

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