WO2004047202A1 - Compositions cathodiques et procede pour la construction de piles aux ions de lithium comprenant un additif de compose de lithium, eliminant la perte de capacite irreversible - Google Patents

Compositions cathodiques et procede pour la construction de piles aux ions de lithium comprenant un additif de compose de lithium, eliminant la perte de capacite irreversible Download PDF

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Publication number
WO2004047202A1
WO2004047202A1 PCT/US2002/036878 US0236878W WO2004047202A1 WO 2004047202 A1 WO2004047202 A1 WO 2004047202A1 US 0236878 W US0236878 W US 0236878W WO 2004047202 A1 WO2004047202 A1 WO 2004047202A1
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WO
WIPO (PCT)
Prior art keywords
lithium
cathode
composition
compound additive
metal
Prior art date
Application number
PCT/US2002/036878
Other languages
English (en)
Inventor
Joseph B. Kejha
W. Novis Smith
Original Assignee
Kejha Joseph B
Smith W Novis
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 Kejha Joseph B, Smith W Novis filed Critical Kejha Joseph B
Priority to US10/534,313 priority Critical patent/US20060121352A1/en
Priority to PCT/US2002/036878 priority patent/WO2004047202A1/fr
Publication of WO2004047202A1 publication Critical patent/WO2004047202A1/fr

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Classifications

    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

  • This invention relates to cathode compositions for lithium-ion cells and other metal ion cells which have a metal compound additive, to eliminate irreversible capacity loss.
  • Prior art patents addressing this problem propose various additives in the liquid electrolyte of the cell. These additives, for example, 2% vinylene carbonate or vinyl acetate create their own passivation layer on carbon, but the preferred additives are very expensive, and do not fully eliminate, but merely reduce the amount of irreversible capacity loss. Additionally, the prior art additives usually negatively affect the cycle life of the cell.
  • Another prior art patent proposes an extra 5% lithiation of manganese oxide spinel in a high temperature chemical process prior to fabricating the cathode; in which LiOH is mked with Mn0 2 and the LiOH is decomposed by heat, resulting in Li 1 . 05 Mn 2 ⁇ 4.
  • the spinel is then used with a binder and carbon black to form the cathode electrodes of a Uthium-ion battery.
  • the extra 5% of lithium is consumed for the anode passivation during the first cycle of the battery, leaving 100% capacity for the consequent cycling.
  • a lithium compound such as a lithium carbonate additive
  • the slurry may comprise, for example, a lithiated metal oxide (such as
  • the slurry is coated, or extruded and pressed onto a metal current collector substrate, and the solvent is evaporated if necessary, to form the cathode electrode, which may be used in a Uthium-ion cell.
  • the principal object of the invention is to provide a cathode composition for lithium-ion cells and other metal-ion cells which eliminates the irreversible capacity loss,
  • a further object of the invention is to provide a cathode composition of the character aforesaid which is particularly suitable for economical mass production.
  • FIG. is a graph of tests of a cell having a cathode composition constructed in accordance with the invention. It should, of course, be understood that the description and drawings herein are merely illustrative and that various modifications and changes can be made in the compositions disclosed without departing from the spirit of the invention,
  • Lithium metal oxides such as lithium cobaltate, lithium manganate, lithium nickelate, or other related lithium transition metal oxides actually store or supply the reversible flow of lithium-ions during charging and discharging in a lithium-ion battery.
  • the irreversible lithium loss from the cathode occurs on the initial charging cycle when it is lost in irreversibly passivating the anode.
  • the cathode composition to be described is useful in lithium-ion cells of well-known type, and eliminates the irreversible capacity loss of approximately 1.0% which results from the passivation layer formed by lithium on the carbon anode surface of the cell.
  • the cathode composition can be any lithium based positive electrode (Cathode) slurry or paste to which the lithium compound additive is added prior to it being coated onto a metal current collector substrate to form a cathode electrode, and then used in a lithium ion cell.
  • Cathode lithium based positive electrode
  • Lithium carbonate contains approximately 19% of lithium by weight
  • Lithiated cobalt oxide contains approximately 7% lithium by weight.
  • the excess CO 2 by-product gas is vented out of the cell, during cycling, and/or the cell is repackaged and sealed.
  • Li 2 CO 3 additive in the range molecularly equivalent to 2% to 40%, and preferably 10% of the lithium atoms contained in the cathode material should be added to the cathode mix prior to coating or formation of the cathode. This depends on the usual irreversible loss of the carbon type used in the anode, or other anodic material type used, Li 2 CO 3 decomposes electrochemically in the cell upon initial charging. After the excess CO 2 is vented out, only 0,7% % of the LiCoO 2 weight is added by this extra 10% of lithium, and it remains in the cell, which is a small weight increase for the benefit of a 10% capacity increase.
  • Lithium carbonate is of relatively low cost which also eliminates the need for expensive additives in the electrolytes.
  • This method can be applied with any lithium-ion cathode type to passivate any lithium-ion anode type, in a cell.
  • the irreversible capacity loss is only reduced, not eliminated. If more Li 2 CO 3 is added than required, the added weight decreases the overall cell energy density, Lithium plating on the anode may also occur, which is dangerous and should be avoided.
  • the cell electrodes should be therefore balanced, which means having approximately the same capacity.
  • lithium compounds may be added to the cathode slurry to function as a lithium source for irreversible loss, providing that these sources have a lithium content substantially greater by weight % than the lithium metal oxide cathode material, In order to be practical, the compatible lithium compound should have a lithium content greater than 10% by weight.
  • the amount of lithium compound to add should contain enough lithium to be approximately equivalent to the amount of lithium irreversibly lost by the lithium metal oxide component of the cathode. Useful range of addition of these lithium compounds is 0.1% to 10% by weight of slurry mix excluding solvent.
  • the cathode slurry was prepared by rmxing with a high speed stirrer for 1 hour in HOg dimethoxyethane (DME) as a solvent, in a closed bottle and containing 1. 11.25 g PNDF/HFP 2801 (Atofina) 14.7% 2. 17.25 g proprietary plasticizer 22.5%
  • the Li 2 CO 3 is useful in the range from 0.1% to 10% by weight,
  • the plasticizer can be also replaced by an electrolyte in the slurry.
  • the weight of the cathode electrode without the current collector was 0.80 g which at 55% loading by LiCoO 2 had 0.44 g of this active material therein.
  • the 100% expected capacity was 60 mAh
  • the cell was tested on MACCOR Tester, Model 2300 at C/5 rate and the capacity is illustrated in the FIG. Charge Cvcle Cap mAh
  • Li 2 CO 3 decomposes electrochemically, and that the balanced Li 2 CO 3 addition to the cathode completely eliminates the irreversible capacity loss, and then n ⁇ iimizes the capacity decline.
  • Other lithium compounds can be similarly used, such as Li 2 SO 3 , LiF, Li 2 0, Li 3 N, lithium oxalate and their mixtures including Li 2 CO 3 and provide similar results.
  • this invention is not limited to lithium-ion cells.
  • Other metal ion type cells may use other metal carbonates or other metal compounds matching the selected chemistry of the cell to eliminate irreversible loss, and/or to reduce capacity decline.
  • sodium-ion cell would use similarly sodium carbonate, or other sodium compounds like Na 2 SO 3> NaF, Na 2 O, Na 3 BO 3 including their mixtures and provide similar results.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention a trait à des compositions cathodiques destinées à être utilisées dans des piles aux ions de lithium et de piles aux ions d'autres métaux, dans lesquelles des additifs d'un composé de lithium ou d'autre composés métalliques, correspondant à la composition chimique choisie pour la pile, lesquels additifs élimine la perte de capacité irréversible.
PCT/US2002/036878 2002-11-18 2002-11-18 Compositions cathodiques et procede pour la construction de piles aux ions de lithium comprenant un additif de compose de lithium, eliminant la perte de capacite irreversible WO2004047202A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US10/534,313 US20060121352A1 (en) 2002-11-18 2002-11-18 Cathode compositions and method for lithium-ion cell construction having a lithum compound additive, eliminating irreversible capacity loss
PCT/US2002/036878 WO2004047202A1 (fr) 2002-11-18 2002-11-18 Compositions cathodiques et procede pour la construction de piles aux ions de lithium comprenant un additif de compose de lithium, eliminant la perte de capacite irreversible

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2002/036878 WO2004047202A1 (fr) 2002-11-18 2002-11-18 Compositions cathodiques et procede pour la construction de piles aux ions de lithium comprenant un additif de compose de lithium, eliminant la perte de capacite irreversible

Publications (1)

Publication Number Publication Date
WO2004047202A1 true WO2004047202A1 (fr) 2004-06-03

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011157958A1 (fr) * 2010-06-17 2011-12-22 Centre National De La Recherche Scientifique Procede pour l'elaboration d'une batterie au lithium ou au sodium
CN103441236A (zh) * 2013-09-11 2013-12-11 东莞新能源科技有限公司 锂离子电池阴极片、锂离子电池及其制备方法
CN105098188A (zh) * 2014-04-28 2015-11-25 比亚迪股份有限公司 一种锂离子电池正极材料添加剂及其制备方法、含有该添加剂的正极材料和锂离子电池
WO2016209571A1 (fr) * 2015-06-22 2016-12-29 SiNode Systems, Inc. Additifs de cathode permettant de fournir une source de lithium en excès pour des batteries au lithium-ion
CN106384808A (zh) * 2016-11-29 2017-02-08 湖南三迅新能源科技有限公司 一种锂离子电池正极片及其制备方法、锂离子电池
US9882219B2 (en) 2010-08-17 2018-01-30 Bloom Energy Corporation Method for solid oxide fuel cell fabrication
CN109728253A (zh) * 2018-12-27 2019-05-07 江西星盈科技有限公司 锂离子电池及其正极片及其制备方法
CN109742324A (zh) * 2018-12-27 2019-05-10 江西星盈科技有限公司 锂离子电池及其正极片及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6022641A (en) * 1996-12-27 2000-02-08 Sony Corporation Non-aqueous electrolyte secondary cell
US20020119375A1 (en) * 2001-02-28 2002-08-29 Meijie Zhang Use of lithium borate in non-aqueous rechargeable lithium batteries

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6022641A (en) * 1996-12-27 2000-02-08 Sony Corporation Non-aqueous electrolyte secondary cell
US20020119375A1 (en) * 2001-02-28 2002-08-29 Meijie Zhang Use of lithium borate in non-aqueous rechargeable lithium batteries

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011157958A1 (fr) * 2010-06-17 2011-12-22 Centre National De La Recherche Scientifique Procede pour l'elaboration d'une batterie au lithium ou au sodium
FR2961634A1 (fr) * 2010-06-17 2011-12-23 Centre Nat Rech Scient Procede pour l'elaboration d'une batterie au lithium ou au sodium
US9882219B2 (en) 2010-08-17 2018-01-30 Bloom Energy Corporation Method for solid oxide fuel cell fabrication
CN103441236A (zh) * 2013-09-11 2013-12-11 东莞新能源科技有限公司 锂离子电池阴极片、锂离子电池及其制备方法
CN105098188B (zh) * 2014-04-28 2017-09-01 比亚迪股份有限公司 一种锂离子电池正极材料添加剂及其制备方法、含有该添加剂的正极材料和锂离子电池
CN105098188A (zh) * 2014-04-28 2015-11-25 比亚迪股份有限公司 一种锂离子电池正极材料添加剂及其制备方法、含有该添加剂的正极材料和锂离子电池
WO2016209571A1 (fr) * 2015-06-22 2016-12-29 SiNode Systems, Inc. Additifs de cathode permettant de fournir une source de lithium en excès pour des batteries au lithium-ion
US10115998B2 (en) 2015-06-22 2018-10-30 SiNode Systems, Inc. Cathode additives to provide an excess lithium source for lithium ion batteries
US10608279B2 (en) 2015-06-22 2020-03-31 Nanograf Corporation Cathode additives to provide an excess lithium source for lithium ion batteries
US11069919B2 (en) 2015-06-22 2021-07-20 Nanograf Corporation Cathode additives to provide an excess lithium source for lithium ion batteries
CN106384808A (zh) * 2016-11-29 2017-02-08 湖南三迅新能源科技有限公司 一种锂离子电池正极片及其制备方法、锂离子电池
CN106384808B (zh) * 2016-11-29 2019-09-06 湖南三迅新能源科技有限公司 一种锂离子电池正极片及其制备方法、锂离子电池
CN109728253A (zh) * 2018-12-27 2019-05-07 江西星盈科技有限公司 锂离子电池及其正极片及其制备方法
CN109742324A (zh) * 2018-12-27 2019-05-10 江西星盈科技有限公司 锂离子电池及其正极片及其制备方法

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