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Reintroduction of Lithium Into Recycled Electrode

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Reintroduction of Lithium Into Recycled Electrode (19) TZZ Z_T (11) EP 2 248 220 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: H01M 10/052 (2010.01) H01M 10/42 (2006.01) 04.11.2015 Bulletin 2015/45 H01M 10/54 (2006.01) H01M 4/485 (2010.01) H01M 4/505 (2010.01) H01M 4/525 (2010.01) (2010.01) (21) Application number: 09713108.0 H01M 4/58 (22) Date of filing: 20.02.2009 (86) International application number: PCT/US2009/034779 (87) International publication number: WO 2009/105713 (27.08.2009 Gazette 2009/35) (54) REINTRODUCTION OF LITHIUM INTO RECYCLED ELECTRODE MATERIALS FOR BATTERY WIEDEREINFÜGUNG VON LITHIUM IN VERWERTETE ELEKTRODENMATERIALIEN FÜR BATTERIEN RÉINTRODUCTION DE LITHIUM DANS DES MATÉRIAUX D’ÉLECTRODES RECYCLÉS POUR BATTERIES (84) Designated Contracting States: (56) References cited: AT BE BG CH CY CZ DE DK EE ES FI FR GB GR EP-A1- 1 009 058 CN-A- 1 585 187 HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL JP-A- 11 054 159 US-A- 5 628 973 PT RO SE SI SK TR US-A- 5 679 477 US-A- 6 150 050 US-A1- 2003 180 604 US-A1- 2004 175 618 (30) Priority: 22.02.2008 US 30916 US-A1- 2005 003 276 US-A1- 2005 175 877 US-A1- 2005 244 704 US-A1- 2007 134 546 (43) Date of publication of application: US-A1- 2007 224 508 US-B1- 6 261 712 10.11.2010 Bulletin 2010/45 US-B2- 6 844 103 (73) Proprietor: Sloop, Steven E. • D.I. RA ET AL: "Used lithium ion rechargeable Bend, OR 97701 (US) battery recycling using Etoile-Rebatt technology", JOURNAL OF POWER SOURCES, (72) Inventor: Sloop, Steven E. vol. 163, no. 1, 7 December 2006 (2006-12-07), Bend, OR 97701 (US) pages 284-288, XP027938467, ISSN: 0378-7753 [retrieved on 2006-12-07] (74) Representative: Herrmann, Uwe et al Lorenz - Seidler - Gossel Remarks: Widenmayerstrasse 23 Thefile contains technical information submitted after 80538 München (DE) the application was filed and not included in this specification Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 248 220 B1 Printed by Jouve, 75001 PARIS (FR) 1 EP 2 248 220 B1 2 Description lithium in the lithium-deficient electrode material. [0012] In another example, a method for refurbishing Technical Field an electrode material in a cell of an energy-storage device is provided. The method comprises breaching an enclo- [0001] The present application relates to the field of 5 sure of the cell, replenishing at least some lithium in a lithium-based energy-storage devices, and more partic- lithium-deficientelectrode material ofthe cell, andsealing ularly, to recycling lithium-based energy-storage devic- the enclosure of the cell. es. [0013] It will be understood that the summary above is provided to introduce in simplified form a selection of con- Background 10 cepts that are further described in the detailed descrip- tion, which follows. It is not meant to identify key or es- [0002] Lithium-based energy-storage devices are sential features of the claimed subject matter, the scope used in a variety of consumer products. Such devices of which is defined by the claims that follow the detailed include supercapacitors, ultracapacitors, and more com- description. Further, the claimed subject matter is not monly lithium cells and lithium-ion cells. These devices 15 limited to implementations that solve any disadvantages are often referred to as ’lithium batteries’ both individually noted above or in any part of this disclosure. and as an ensemble. Some lithium-based energy-stor- age devices are rechargeable and have a relatively long Brief Description of the Drawings useful lifetime. Nevertheless, they eventually fail or are discarded prior to failure, and therefore contribute to a 20 [0014] significant and growing waste stream. In view of this sit- uation, environmental regulations, industry standards, FIG. 1 illustrates aspects of an example method for and collection services have arisen to promote the recy- making a recycled electrode material for an energy- cling of lithium-based energy storage devices. storage device, in accordance with the present dis- [0003] The Journal of Power Sources, vol. 163, no. 1, 25 closure. 7 December 2006, pages 284-288, XP027938467, de- scribes a method for recycling a lithium-ion rechargeable FIG. 2 illustrates an example method for harvesting battery using the Etoile-Rebatt technology. a lithium-deficient electrode material from a waste [0004] CN 1 585 187 A discloses a method for regen- or recycling stream, in accordance with the present erating anode materials of used lithium-ion secondary 30 disclosure. battery. [0005] US 6 150 050 A discloses a method for making FIG. 3 illustrates an example of a solid-state method a recycled electrode material according to the pre-char- for replenishing at least some lithium in a lithium- acterising portion of claim 1. deficient electrode material. [0006] US 6 261 712 B1 discloses a method of reclaim- 35 ing cathodic active material of lithiumion secondary bat- FIG. 4 illustrates an example embodiment of a hy- teries. drothermal method for replenishing at least some [0007] EP 1 009 058 A1 discloses a method of treating lithium in a lithium-deficient electrode material, in ac- a waste lithium battery to recycle its materials. cordance with the present disclosure. [0008] JP 11 054159 A discloses a process for recy- 40 cling anode waste material of a lithium battery. FIG. 5 illustrates an example of a reductive method [0009] US 2007/134546 A1 discloses a method for re- for replenishing at least some lithium in a lithium- cycling a battery that includes a plurality of lithium cells deficient electrode material. removing from one another. [0010] US 6 844 103 B2 discloses an apparatus and 45 FIG. 6 illustrates an example of a lithium or lithium- a method for recovering lithium cobalt oxide from spent ion cell refurbishment method. lithium batteries. Detailed Description Summary 50 [0015] FIG. 1 illustrates aspects of an example embod- [0011] The inventors herein have recognized that an iment of a method 10 for making a recycled electrode economically robust recycling or refurbishing strategy is material for an energy-storage device. It will be under- one that preserves and enhances the value of the elec- stood that the example method may be part of a more trode material. Therefore, in one embodiment, a method extensive method for recycling batteries and/or process- for making a recycled electrode material for an energy- 55 ing waste streams that include battery-derived wastes. storage device is provided. The method comprises har- Further, the example method may be part of a more ex- vesting a lithium-deficient electrode material from a re- tensive method for making a recycled electrode for an cycling or waste stream, and replenishing at least some energy-storage device or for making an energy storage 2 3 EP 2 248 220 B1 4 device. Accordingly, in some embodiments, one or more carbon dioxide, with a controlled amount of an oxidant actions may be taken prior to the first illustrated step, and such as air or water added to the carbon dioxide. In these one or more actions may follow the final illustrated step. and other embodiments, the controlled environment in [0016] At 12, a lithium-deficient electrode material is which the breached cells are passivated may be config- harvested from a recycling or waste stream. The recy- 5 ured to accommodate a release of dihydrogen or other cling or waste stream from which the lithium-deficient gas-phase products that may be released when the lith- electrode material is harvested may be a dedicated bat- ium-containing negative electrodes of the one or more tery recycling or waste stream, or more particularly, a breached cells are passivated. lithium-battery recycling or waste stream. Further, the [0019] The harvesting method then advances to 22, lithium-deficient electrode material may be harvested 10 where a lithium-deficient electrode material is separated from the waste or recycling stream in any suitable man- from the one or more breached cells of the battery. In ner. However, one example harvesting method is illus- one embodiment, the lithium-deficient electrode material trated in FIG. 2. separated from the one or more breached cells may com- [0017] Referring now to FIG. 2, harvesting method 14 prise a lithium-deficient form of lithium cobalt oxide 15 begins at 16, where the cells of a spent battery (if the (LiCoO2), viz., Li1-xCoO2 where 0 < x < 1. Thus, the lith- battery comprises more than one cell) are separated. ium-deficient electrode material may be a positive elec- Separating the cells of the spent battery may comprise trode material used in a lithium or lithium-ion cell of the removing or opening an envelope of the battery, for ex- battery. Accordingly, the lithium-deficient electrode ma- ample. The harvesting method then advances to 18, terial may further comprise various other materials, in- where the enclosures of the one or more cells of the bat- 20 cluding graphitic and/or amorphous carbon. In these and tery are breached. Breaching the enclosures may involve other embodiments, the lithium-deficient electrode ma- drilling or cutting the enclosures, for example.
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