EX 1001
`EX 1001
`
`

`

`I 1111111111111111 111111111111111 11111 1111111111 1111111111111111 IIII IIII IIII
`
`
`
`
`
`US012119463B2
`
`c12) United States Patent
`Hanisch
`
`(IO) Patent No.: US 12,119,463 B2
`(45) Date of Patent:
`*Oct. 15, 2024
`
`(54) RECYCLING METHOD FOR TREATING
`USED BATTERIES, IN PARTICULAR
`RECHARGEABLE BATTERIES, AND
`BATTERY PROCESSING INSTALLATION
`
`(71) Applicant: DUESENFELD GMBH, Wendeburg
`(DE)
`
`(72)
`
`Inventor: Christian Hanisch, Braunschweig (DE)
`
`(52) U.S. Cl.
`CPC ............. H0lM 10154 (2013.01); C22B 11005
`(2013.01); C22B 7100 (2013.01); C22B 71001
`(2013.01);
`
`(Continued)
`(58) Field of Classification Search
`CPC ......... H0lM 10/54; H0lM 6/52; C22B 1/005;
`C22B 7/00; C22B 7/001; Y02P 10/20;
`Y02W 30/84
`See application file for complete search history.
`
`(73) Assignee: DUESENFELD GMBH, Wendeburg
`(DE)
`
`(56)
`
`References Cited
`
`( *) Notice:
`
`Subject to any disclaimer, the term ofthis
`patent is extended or adjusted under 35
`U.S.C. 154(b) by 593 days.
`
`This patent is subject to a terminal dis(cid:173)
`claimer.
`
`(21)
`
`Appl. No.:
`
`16/343,224
`
`(22)
`
`PCT Filed:
`
`Oct. 12, 2017
`
`(86)
`
`PCT No.:
`
`PCT/EP2017/076113
`
`§ 371 (c)(l),
`(2) Date:
`
`Apr. 18, 2019
`
`(87)
`
`PCT Pub. No.: WO2018/073101
`PCT Pub. Date: Apr. 26, 2018
`
`(65)
`
`Prior Publication Data
`
`US 2019/0260101 Al
`
`Aug. 22, 2019
`
`(30)
`
`Foreign Application Priority Data
`
`Oct. 20, 2016
`
`(DE) ..................... 10 2016 120 046.8
`
`(51)
`
`Int. Cl.
`H0lM 10154
`C22B 1100
`
`(2006.01)
`(2006.01)
`(Continued)
`
`U.S. PATENT DOCUMENTS
`
`3,671,318 A
`4,118,219 A
`
`6/1972 Moe
`10/ 1978 Elmore et al.
`(Continued)
`
`FOREIGN PATENT DOCUMENTS
`
`CA
`CN
`
`11/2016
`2983768 Al
`8/2003
`1438729 A
`(Continued)
`
`OTHER PUBLICATIONS
`
`Dehnert et al: "Vacuum Distillation", Allgemeine Chemie, 14.3, p.
`14, 1979.
`
`(Continued)
`
`Primary Examiner - Stephen J Yanchuk
`(74) Attorney, Agent, or Firm - WC&F IP
`
`ABSTRACT
`(57)
`The invention relates to a method for treating used lithium
`batteries (10) containing the steps: comminuting the batter(cid:173)
`ies (10) such that comminuted material (24) is obtained, and
`(b) inactivating of the comminuted material (24) such that an
`inactive comminuted material ( 42) is obtained. According to
`the invention, the drying is conducted at a maximum pres(cid:173)
`sure of 300 hPa and a maximum temperature of 80° C. and
`the deactivated comminuted material (42) is not filled into a
`transport container and/or said deactivated comminuted
`(Continued)
`
`12
`
`32
`
`•
`
`30
`
`:
`: I
`!
`:
`:
`
`~29
`
`r;,;mlainer
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`liqwdcleot
`
`tocomponent,;,
`
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`oonlainer
`
`t
`
`•
`
`LI
`gasbottje
`
`50
`
`Ascend Elements EX1001 Page 1
`
`

`

`US 12,119,463 B2
`Page 2
`
`material is immediately further processed after the drying
`process.
`
`14 Claims, 4 Drawing Sheets
`
`(51)
`
`Int. Cl.
`C22B 7100
`H0JM6/52
`(52) U.S. Cl.
`CPC ............... H0JM 6152 (2013.01); Y02P 10/20
`(2015.11); Y02W 30/84 (2015.05)
`
`(2006.01)
`(2006.01)
`
`(56)
`
`References Cited
`
`U.S. PATENT DOCUMENTS
`
`CN
`DE
`DE
`DE
`DE
`DE
`DE
`EP
`EP
`EP
`EP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`JP
`KR
`KR
`KR
`WO
`WO
`WO
`WO
`WO
`
`105552470 A
`4424825 Al
`10ll8961 B4
`60 2005 001 937 T2
`10 20ll
`llO 083 Al
`10 2012 024 876 Al
`10 2015 207 843 Al
`0794587 A2
`1041659 Al
`1760821 Al
`2741357 Al
`H06338352 A
`2000243396 A
`2001012704 A
`20050ll698 A
`2005515605 A
`2005197149 A
`2007531977 A
`2008204755 A
`2013004299 A
`2013229326 A
`2015028928 A
`2016512165 A
`20040071776 A
`20060101683
`10-0665626 Bl
`2010/102377 Al
`2010/1496ll Al
`2013023640 Al
`2016/164752 Al
`2016174156 Al
`
`5/2016
`1/1996
`8/2006
`5/2008
`2/2013
`6/2014
`11/2016
`9/1997
`10/2000
`3/2007
`6/2014
`12/1994
`9/2000
`1/2001
`1/2005
`5/2005
`7 /2005
`11/2007
`9/2008
`1/2013
`11/2013
`2/2015
`4/2016
`8/2004
`3/2005
`1/2007
`9/2010
`12/2010
`2/2013
`10/2016
`11/2016
`
`OTHER PUBLICATIONS
`
`und
`Herausgeber: "Florke/WolffKursthemen Chemis-Allgemeine
`Phsyikalische Chemie", "(Course Issues Chemisty----General and
`Physical Chemistry)", 1985.
`Higgelke: "Infinite Power Solutions stellt papierdunnen Akku vor",
`"(Infinite Power Solution presents paper-thin Battery)", Jun. 6,
`2012.
`24351 Trocknungstechnik (VDMA~German Engi(cid:173)
`VDMA-Norm
`neering Federation; VDMA Standared 24351-Drying Technology(cid:173)
`Basic terms and definitions), Sep. 1999.
`Wolf et al: Allgemeine und Physikalische Chemie, Chemie, 1985.
`Carolo-Wilhelmina University of Technology in Braunschweig Final
`report "Joint project as part of the "Renewably Mobile funding
`program of the Federal Ministry for the Environment, Nature
`Conservation, Building and Nuclear Safety, Jul. 1, 2012-Mar.31,
`2016.
`Kwade, A. et al., "LithoRec Recycling von Lithium-Ionen(cid:173)
`Batterien" LithoRec, 2012.
`Perry, R. & Green, D., "Perry's Chemical Engineer's Handbook,
`Seventh Edition", 1997.
`Vacuum Technology; Terms and Definitions; General Terms. DIN
`28400-1, German Institute for Standards e.V., 1990.
`
`* cited by examiner
`
`11/1982 Goodenough
`4/1994 Milewits ................... B09B 3/00
`241/100
`
`5/1997 Meador
`9/2002 Hanisch et al.
`2/2003 Tanii et al.
`9/2006 Kiss
`3/2007 Cardarelli
`
`7/2012 Stevens
`9/2016 Dunagan et al.
`11/2016 Iida
`10/2017 Hanisch
`12/2017 Hayashi et al.
`8/2019 Shin et al.
`6/2021 Hanisch et al.
`10/2003 Sloop
`11/2005 Kakuta et al.
`9/2010 Ewles et al.
`1/2014 Iida .
`
`HOlM 6/52
`75/693
`
`HOlM 10/54
`432/13
`
`4,357,215 A
`5,303,872 A *
`
`5,632,863 A
`6,447,669 Bl
`6,524,737 Bl
`7,101,425 B2
`7,192,564 B2 *
`
`8,210,456 B2
`9,450,277 B2
`9,509,025 B2
`9,780,419 B2
`9,843,077 B2
`10,396,408 B2
`ll,050,097 B2
`2003/0186ll0 Al
`2005/0241943 Al
`2010/0230518 Al
`2014/0017621 Al*
`
`2014/0290438 Al
`2016/0043450 Al
`2016/0045841 Al*
`
`2016/0049699 Al*
`
`10/2014 Hanisch
`2/2016 Sloop
`2/2016 Kaplan
`
`2/2016 Hayashi
`
`B01D3/06
`429/49
`COlF 11/22
`44/387
`HOlM 6/52
`HOlM 10/0525
`.................... C22B47/00
`
`2016/0372802 Al*
`2018/0013181 Al*
`2018/0366740 Al*
`
`12/2016 Chiang
`1/2018 Ho
`12/2018 Muska
`
`FOREIGN PATENT DOCUMENTS
`
`CN
`CN
`CN
`CN
`
`101394015 A
`102496752 A
`103959553 A
`103259062 B
`
`3/2009
`6/2012
`7/2014
`9/2015
`
`Ascend Elements EX1001 Page 2
`
`

`

`~;ot 10.2
`jfl cr10.3
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`battery modules/-cells
`~ t s.i----18
`., X ,_ __
`'
`•
`24
`•
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`28 ,.rb
`.
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`
`Ascend Elements EX1001 Page 3
`
`

`

`U.S. Patent
`
`Oct. 15, 2024
`
`Sheet 2 of 4
`
`US 12,119,463 B2
`
`44
`
`58
`
`26
`
`56
`
`18
`
`54
`
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`
`42
`
`46
`
`42
`
`Fig. 2
`
`Ascend Elements EX1001 Page 4
`
`

`

`U.S. Patent
`
`Oct. 15, 2024
`
`Sheet 3 of 4
`
`US 12,119,463 B2
`
`88
`
`80
`
`76
`
`62
`
`68
`
`86
`
`78
`
`72
`
`42
`
`Fig. 3
`
`Ascend Elements EX1001 Page 5
`
`

`

`U.S. Patent
`
`Oct. 15, 2024
`
`Sheet 4 of 4
`
`US 12,119,463 B2
`
`10.1
`
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`Ascend Elements EX1001 Page 6
`
`

`

`US 12,119,463 B2
`
`1
`RECYCLING METHOD FOR TREATING
`USED BATTERIES, IN PARTICULAR
`RECHARGEABLE BATTERIES, AND
`BATTERY PROCESSING INSTALLATION
`
`2
`installation is connected to the drying device in order to
`generate a vacuum of at least 300 hPa in the drying device,
`and the drying device is configured to dry at a maximum
`temperature of 80° C.
`The advantage of the invention is that the amount of
`electrolyte that can be obtained from the comminuted mate(cid:173)
`rial through drying is such that an electrochemical reaction
`is no longer possible, or only to a negligibly small extent. In
`addition, no flammable or explosive gas phase forms above
`10 the battery fragments, as the organic carbonates of the
`electrolyte that have a low boiling point have been removed
`[from the fragments]. The comminuted material is therefore
`largely inert and can be safely transported or processed
`further, especially if it is packed under vacuum.
`A further advantage is that no additional material has to be
`added to deactivate the comminuted material. This decreases
`the complexity of the battery processing, reduces the weight
`of the deactivated comminuted material and increases the
`purity in the subsequent separation and recycling steps. In
`particular, in potential subsequent hydrometallurgical pro(cid:173)
`cessing steps, a high degree of product purity without
`foreign ions is advantageous.
`It is also advantageous that the formation of relevant
`quantities of fluorophosphates, hydrogen fluoride, carbon
`monoxide, polyfluorinated dibenzodioxins and dibenzo(cid:173)
`furans, nitrogen oxides, carbonyl fluoride and/or hydrogen
`cyanide can be ruled out. Fluorophosphates are often strong
`neurotoxins, the formation of which must be reliably pre(cid:173)
`vented. Furthermore, due to the low electrolyte content, it is
`guaranteed that a self-amplifying and intensifying build-up
`of heat triggered by an electrochemical reaction cannot
`occur. It has been proven that hydrogen fluoride and fluo(cid:173)
`rophoshate can form in significant quantities at compara(cid:173)
`tively low temperatures of over 80° C.
`Furthermore, it is advantageous that the removal of the
`electrolyte is possible without expending a considerable
`amount of energy. The electrolyte can also be largely reused.
`The condensation of the vaporised electrolyte, as intended
`according to a preferred embodiment, also leads to a low-
`40 emission recycling of lithium batteries.
`The battery processing installation according to the inven(cid:173)
`tion enables material recycling rates of over 80%, which is
`not possible with current installations.
`Within the scope of the present description, the term
`45 drying should be understood particularly
`to mean the
`removal of at least one solvent in the conducting salt. In
`particular, the drying is executed such that at least 90 percent
`by weight of dimethyl carbonate and/or ethyl methyl car(cid:173)
`bonate is removed.
`A lithium battery should to understood particularly to
`mean a rechargeable battery whose electrochemical reaction
`involves lithium and/or lithium ions and/or a lithium com(cid:173)
`pound.
`A battery processing installation should also be under-
`55 stood particularly to mean a rechargeable battery processing
`installation for processing rechargeable batteries.
`The transport container should also be understood par(cid:173)
`ticularly to mean transport packaging. The transport pack(cid:173)
`aging is preferably sealed by way of a vacuum seal. Alu-
`60 minium composite foil is especially well-suited as transport
`packaging.
`The comminution unit should be understood especially to
`mean a device which, when operating, comminutes the
`batteries. For example, the comminution unit (i) is a pressure
`65 comminution unit whereby the batteries are crushed between
`two tool surfaces, (ii) a striking comminution unit whereby
`the batteries lie on a tool surface and are smashed by striking
`
`25
`
`The invention refers to a method for the treatment of used
`batteries, in particular used lithium batteries, such as lithium
`ion batteries, with the steps (a) comminuting the batteries
`such that comminuted material is obtained, (b) inactivating
`of the comminuted material such that an inactive commi(cid:173)
`nuted material is obtained.
`According to a second aspect, the invention refers to a
`battery processing installation for the treatment of used
`batteries, in particular for the treatment of used lithium
`batteries with (a) a comminuting device for comminuting the 15
`batteries such that comminuted material is obtained, and (b)
`an inactivation device for inactivating the comminuted
`material.
`US 2005/0241943 Al describes a method for processing
`used batteries in which the batteries are heated prior to a 20
`comminuting step, thereby destroying plastic components in
`the batteries. The disadvantage of this type of procedure is
`that the remaining components of the batteries may be
`contaminated with degradation products of the plastic.
`DE 10 2012 024 876 Al describes a system for transfer-
`ring transport-critical electrolyte cells, in which they are
`initially comminuted under inert gas and then dusted with a
`deactivation powder so as to prevent the electrochemically
`active material from spontaneously combusting. The disad(cid:173)
`vantage of this is that the resulting material still poses a 30
`comparatively high hazard potential and that the dusting
`power itself poses a risk of exposure and that the formation
`of a flammable and explosive atmosphere in the transport
`container cannot be ruled out.
`DE 10 2011 110 083 Al describes a method for recov-
`ering active material from a galvanic cell, in which the
`galvanic cells are initially mechanically comminuted, then
`pre-dried and subsequently sifted. Finally, the binder is
`broken down in an oven.
`This type of device is very well-suited to the efficient
`recycling of larger amounts of galvanic elements. However,
`for partial load operation, the construction of this installation
`is comparatively complex. It has also been proven that
`highly toxic fluoroorganic compounds and hydrogen fluo(cid:173)
`ride may form, the disposal of which is highly complex.
`WO 2010/102377 Al describes a method in which the
`batteries to be recycled, such as lithium batteries, are heated
`in a rotary kiln and the resulting gases are sucked away. The
`disadvantage of this method is that it is difficult to reuse the
`electrolyte and it produces large quantities of hydrogen 50
`fluoride and fluoro-organic compounds.
`The post-published publication WO 2016/174156 Al
`describes a method in which used batteries are first locally
`deactivated and placed in a transport container. Following
`the transport of the comminuted material to a central pro(cid:173)
`cessing plant, the deactivated cell fragments are processed
`further.
`The invention aims to reduce disadvantages of the prior
`art.
`The invention solves the problem by way of a method
`according to the preamble in which the drying is conducted
`at a maximum pressure of 300 hPa, preferably at least in part
`at 50 hPa, and at a maximum of 80° C. In particular, the
`deactivation is conducted at least also by drying the com(cid:173)
`minuted material. According to a second aspect, the inven(cid:173)
`tion solves the problem by way of a battery processing
`installation according to the preamble, wherein a vacuum
`
`35
`
`Ascend Elements EX1001 Page 7
`
`

`

`US 12,119,463 B2
`
`5
`
`3
`them with a second moveable tool, (iii) a cropping commi(cid:173)
`nution unit whereby the batteries are comminuted by two
`tool surfaces that move in opposite directions, (iv) a cutting
`comminution unit whereby the batteries are cut into two
`parts by means of two blades and/or (v) an impact commi-
`nution whereby the batteries are thrown against a wall,
`impact against a moving tool or two particles collide. Of
`course, the comminution unit may also work by way of two
`or more of the named comminution mechanisms.
`According to a preferred embodiment, the comminution 10
`unit forms part of a comminuting device which comprises a
`container in which the comminution unit is arranged.
`The given temperatures and pressures always relate to the
`atmospheric temperature in the respective device. In this
`way, the characteristic that the drying occurs at a maximum 15
`pressure of 300 hPa and at a maximum of 80° C. should be
`understood particularly to mean that the temperature of the
`atmosphere in the dryer is a maximum of 80° C. It is
`irrelevant that the local temperature may be higher.
`It is beneficial if the drying occurs after the comminuting 20
`of the batteries. It is indeed possible and represents a
`preferred embodiment that the batteries are exposed to a
`vacuum when in an uncomminuted state such that at least
`parts of the electrolyte vaporise, wherein the resulting gas
`either escapes through a safety valve in the rechargeable 25
`battery or the battery is destroyed by the pressure difference
`between the external environment and the internal pressure,
`enabling the vaporising electrolyte to escape. However,
`since the electrolyte
`is predominantly
`located between
`tightly wound or stacked and pressed layers of electrodes 30
`and separators and in their pores, and it is connected to other
`components of the batteries, this procedure can be very
`time-consuming. It is thus often more beneficial and repre(cid:173)
`sents a preferred embodiment of the invention for the
`batteries to be mechanically comminuted, for example 35
`through cutting, cropping, impact, cutting and/or crushing.
`This means that a larger interface is available for the
`transition of materials into the gas phase.
`The drying process is preferably conducted at a maximum
`pressure of 30 hPa for at least 50% of the drying time. 40
`Alternatively or additionally, a minimum pressure during the
`drying process is at most 50 hPa. This allows for the removal
`of a very large proportion of the electrolyte. The minimum
`pressure should be understood especially to mean the lowest
`atmospheric pressure in the drying device that is maintained 45
`for at least one minute.
`According to a preferred embodiment, it is also possible
`for the drying to occur at the same time as the comminuting.
`In other words, a vacuum with a maximum pressure of 300
`hPa is attached to a comminuting device in which the 50
`batteries are comminuted. The advantage of this is that the
`mechanical energy introduced during comminuting supports
`the vaporising of the electrolyte. It is therefore not necessary
`to introduce additional thermal energy into the comminuted
`material in order to vaporise the electrolyte (although this is 55
`possible and included in the invention). Furthermore, it is
`not necessary to cool the comminuted material during com(cid:173)
`minuting (although this is possible and included in the
`invention). The comminution unit also effects a circulation
`of the comminuted material, which accelerates the drying 60
`process.
`It is favourable if the drying occurs while the comminuted
`material is being agitated and/or circulated. This results in
`the separation of the galvanic elements, which consist of
`anode, separator and cathode. An obstruction of the vaporis(cid:173)
`ing process by way of foils which stick together is pre(cid:173)
`vented. Mechanical energy is introduced for the separation
`
`4
`of current collector foil and coating, and the resulting
`frictional heat feeds the vaporising heat into the system.
`Prior to being comminuted, the used batteries are prefer(cid:173)
`ably dismantled. This means that larger battery systems are
`dismantled into their smaller subcomponents, the modules
`or stacks, or even that the cells which contain the electro-
`chemically active material are separated from the control
`electronics. The control electronics comprise, for example,
`semiconductor elements and/or sensors and are responsible
`for the charge control of the batteries.
`The drying occurs under a vacuum. According to its most
`general configuration, the invention solves the problem by
`means of a method according to the preamble, wherein the
`vacuum is selected to be so large that the pressure is below
`the vapour pressure of dimethyl carbonate at 80° C., in
`particular at 70° C. However, it is especially beneficial if the
`drying occurs at a maximum pressure of 300 hPa, in
`particular a maximum of 100 hPa. At such low pressures,
`considerable parts of most electrolytes vaporise, especially
`dimethyl carbonate and ethyl methyl carbonate, and do so at
`temperatures of less than 80° C. The advantage of low
`temperatures is that the formation of hydrogen fluoride and
`fluoro-organic compounds is hindered. Both pose a potential
`risk for the battery processing installation and the surround(cid:173)
`ings. It is therefore beneficial to prevent their development.
`The drying preferably occurs at a temperature that is
`lower than a decomposition temperature. The decomposition
`temperature should be understood particularly to mean the
`lowest temperature at which at least 80 percent by mass of
`the binder of the lithium batteries has decomposed into
`gaseous components after keeping the comminuted material
`at this temperature for an hour. The decomposition tempera(cid:173)
`ture can be measured by successively increasing the tem(cid:173)
`perature of the comminuted material and recording when a
`loss of mass occurs, especially through the build-up of gas
`due to a decomposition of the binder, and the specified
`criteria is fulfilled. If necessary, the experiment must be
`conducted several times, each time using a new sample of
`comminuted material at an increased temperature.
`According to a preferred embodiment, the method com(cid:173)
`prises the condensation of the gases which result from the
`drying process. This preferably occurs at ambient pressure,
`whereby a deviation of ±50 hPa is possible. It is beneficial
`if the temperature during condensation is at least 0° C. This
`reduces the required cooling capacity and prevents the
`formation of ice. The cooling capacity is preferably at least
`4 kilowatts and at most 40 kilowatts relative to one tonne of
`processed batteries per hour. Alternatively, the temperature
`upon condensation is lower than 0° C., such that water is
`removed from the atmosphere through the formation of ice.
`It is possible that the condenser has two or more zones of
`varying temperature. In this case, the temperature in one of
`the two zones is so high that no ice forms and so low in
`another zone that water is separated as ice.
`It is favourable if the maximum temperature upon con(cid:173)
`densation is at most 50° C., preferably a maximum of30° C.,
`in particular a maximum of 20° C. This means that the
`organic carbonates in the batteries can be almost completely
`recovered. Moreover, virtually no emissions are produced
`and the amount of energy required for condensation is low.
`The comminuting of the batteries is preferably executed
`such that at least 90% by weight of the components of the
`comminuted material has a maximum sieve size of 50 mm,
`in particular a maximum of 30 mm, preferably a maximum
`65 of 20 mm. This should be understood to mean that 90% by
`weight of the components fall through a sieve which has a
`mesh width of 50 mm (or the respective given width). This
`
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`5
`type of comminuting avoids micro short circuits, thereby
`increasing the level of safety of transport, storage and further
`processing.
`It is favourable if the drying occurs under an atmosphere
`in which the partial pressure of the water is lower than 50 Pa,
`in particular lower than 10 Pa. A low partial pressure of the
`water leads to a low reaction rate of lithium compounds to
`lithium hydroxide and thus only to a low build-up of
`hydrogen. This prevents the formation of flammable hydro(cid:173)
`gen-oxygen mixtures and contributes to the safety of the
`installation.
`In addition, it is favourable if the partial pressure of
`oxygen upon drying has a maximum value of 30 millibars,
`especially a maximum value of 10 millibars. This largely
`inhibits the reaction of oxygen with oxidisable components
`of the batteries. It is possible to achieve the low partial
`pressure of oxygen by means of drying at a low pressure.
`Alternatively or additionally, the drying may occur in an
`inert gas atmosphere.
`According to a preferred embodiment, the method com(cid:173)
`prises the steps of a continuous recording of a water vapour
`concentration during comminuting and/or drying, and a
`reduction of the water vapour concentration when a pre(cid:173)
`determined threshold value is exceeded. The water vapour
`concentration should be understood especially to mean a
`proportion of water vapour in relation to the entirety of the
`atmospheric components. In particular, the water vapour
`concentration should also be understood to mean a partial
`water vapour pressure. For instance, the reduction of the
`water vapour concentration may comprise a decrease in the
`pressure and/or a supply of inert gas. The threshold value for
`the water vapour concentration is preferably selected such
`that, below the threshold value, a formation of significant
`quantities of hydrogen fluoride through decomposition of
`the conducting salt, such as LiPF 6 , and a significant reaction
`of the water with metallic lithium is impossible. These
`criteria are met at a dew point of -40° C. It is possible, but
`not necessary, for the water vapour concentration to be
`measured directly, for instance by spectroscopy, especially
`infrared spectroscopy. It is also possible, for example, to
`identify the sum of the concentrations of inert gas, oxygen
`and organic compounds and assume that the rest is made up
`of water vapour.
`According to a preferred embodiment, the method com(cid:173)
`prises the steps of a continuous recording of a oxygen
`concentration during comminuting and/or drying, and a
`reduction of the oxygen concentration when a pre-deter(cid:173)
`mined threshold value is exceeded. The oxygen concentra(cid:173)
`tion should be understood especially to mean a proportion of
`oxygen in relation to the entirety of the atmospheric com(cid:173)
`ponents. In particular, the oxygen concentration should also
`be understood to mean a partial oxygen pressure. The
`reduction of the oxygen concentration may comprise, for
`example, a decrease in the pressure and/or a supply of inert
`gas. The threshold value for the oxygen concentration is
`preferably selected such that an explosion is impossible
`below the threshold value. It is possible, but not necessary,
`for the oxygen concentration to be measured directly, for
`instance using a Nernst probe, a lambda probe, paramagnetic
`sensors or a resistive probe. It is also possible, for example,
`to determine the concentration of the oxygen by measuring
`gases in air that are accompanied by oxygen, such as carbon
`dioxide by assuming that the same mixing ratio of oxygen is
`present in the measured gas as in the air.
`In particular, the method comprises the steps (i) continu(cid:173)
`ous monitoring of a concentration of organic carbonates in
`the atmosphere of the drying device during drying and (ii)
`
`6
`completion of the drying when a lower explosion limit is no
`longer reached. The lower explosion limit is the concentra(cid:173)
`tion of organic components for which the following applies:
`following the filling of a container with the comminuted
`5 material in air with a temperature of 23° C., under 1013 hPa
`and at 80% humidity, an ignition does not cause an explo(cid:173)
`sion but does lead to a higher concentration. If this lower
`explosion limit is still reached, the drying continues.
`The concentration of inert gas is preferably set at at least
`10 90% by weight, in particular at least 95% by weight,
`preferably at least 97% by weight. The measurement of the
`concentration is preferably done, for example, spectroscopi(cid:173)
`cally.
`Alternatively or additionally, a progress parameter is
`15 recorded which describes the progress of the drying, and the
`drying is completed when the progress parameter reaches a
`pre-determined progress parameter threshold value. The
`progress parameter is small at the beginning of the drying
`and increases with the progression of the drying. An equiva-
`20 lent situation is for the progress parameter to be large at the
`beginning of the drying and to decrease with the progression
`of the drying.
`For instance, the progress parameter is the concentration
`of a gaseous electrolyte in the gas which has been sucked
`25 out. In this situation, it is possible, but not necessary, to
`directly measure the concentration of a gaseous electrolyte,
`in particular organic carbonates, for instance by spectros(cid:173)
`copy, especially infrared spectroscopy. Alternatively or addi(cid:173)
`tionally, it is possible that the progress parameter is the
`30 condensate flow (measured, for example, in volume, mass,
`weight or quantity of substance per time unit) of condensed
`gas components in an available condenser. Alternatively, the
`progress parameter is the pressure in the drying container or
`the gas flow out of the drying container. If a pump output is
`35 constant, the pressure only depends, in good approximation,
`on the drying progress and the temperature of the commu(cid:173)
`nited material. If the electrolyte has largely been vaporised,
`the pressure decreases. The gas flow also reduces.
`According to a preferred embodiment, the comminuted
`40 material is further processed immediately after the drying
`process. In particular, the comminuted material is not put in
`a transport container after drying. In particular, the commi(cid:173)
`nuted material is transported after drying by means of a
`continuously or discontinuously feeding conveyor for fur-
`45 ther processing, for example a separating device. In particu(cid:173)
`lar, the conveyor is connected to the dryer such that it is
`dust-tight. Examples of a continuously feeding conveyor are
`dust-tight tube chain conveyors, preferably with two adjust(cid:173)
`able outlet slides, conveyors, conveyor troughs, screw con-
`50 veyors, bucket conveyors or semi-continuous conveyors.
`A method is preferred in which the drying of the com(cid:173)
`minuted material is only completed if, after the completion
`of the drying process, no flammable or explosive gas mix(cid:173)
`ture can form above the comminuted material that has been
`55 filled [in the container] and/or when the comminuted mate(cid:173)
`rial is so dry that no flanimable or explosive gas mixture can
`emerge in the transport container or during the subsequent
`processing. The property that the drying is completed if,
`after the completion of the drying process, no flammable or
`60 explosive gas mixture can form above the comminuted
`material that has been filled [in the container] should be
`understood particularly to mean that, within the space of one
`week at 50° C. and 1013 hPa, no flanimable gas mixture
`forms in a transport container in the form of a 50 litre
`65 container that has been half-filled (relative to its volume)
`with the comminuted material. Preliminary tests determine
`whether the criteria has been fulfilled. If a flammable gas
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`US 12,119,463 B2
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`15
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`7
`mixture does form, the drying must be conducted for a
`longer time and/or at a lower pressure. The preliminary tests
`are repeated until a drying time and/or drying pressure has
`been identified at which, in a set of tests of three transport
`containers, the requirements for the property have been
`fulfilled for all three transport containers.
`The comminuted material is preferably dried until an
`electrolyte content in the comminuted material is so low that
`an electrochemical reaction is impossible. In other words,
`the electrolyte content is lower than a threshold value, the 10
`threshold value being selected such that, if this threshold
`value is not achieved, the cell voltage is reduced to a
`maximum of one quarter. This threshold value is deter(cid:173)
`mined, for example, by defining the cell voltage of a battery
`in relation to the electrolyte content. Shortly before achiev-
`ing the threshold value, the cell voltage collapses, i.e. it
`decreases by at least 75%. If the threshold value is not
`achieved, the battery contains so little electrolyte that, to a
`good approximation, an electrochemical reaction is no lon(cid:173)
`ger possible.
`The comminuted material is preferably dried for so long
`that a 50 kg amount of comminuted material, which is
`contained in a compacted form in a 50 litre drum, does not
`experience a build-up of heat, or the build-up of heat is so
`lo