EX1010
`EXI1010
`
`

`

`THI NA MADINI DI MI TO AT MAN UNITATE
`
`US009843077B2
`
`US 9 , 843 , 077 B2
`Dec . 12 , 2017
`
`( 10 ) Patent No . :
`( 45 ) Date of Patent :
`( 52 ) U . S . CI .
`CPC . . . . . . . . . . . . . HOIM 10 / 54 ( 2013 . 01 ) ; COIF 11 / 22
`( 2013 . 01 ) ; CIOL 1 / 02 ( 2013 . 01 ) ; CIOL
`2290 / 06 ( 2013 . 01 ) ;
`( Continued )
`Field of Classification Search
`CPC . . . . CIOL 1 / 02 ; CIOL 2290 / 06 ; CIOL 2290 / 54 ;
`CIOL 2290 / 541 ; C10F 11 / 22 ; YO2W
`30 / 84 ; HO1M 10 / 54 ; HOTM 2300 / 0034
`See application file for complete search history .
`References Cited
`U . S . PATENT DOCUMENTS
`2008 / 0050295 AL
`2 / 2008 Uchida et al .
`5 / 2015 Boll . . . . . . . . . . . . . . . . . . . . . . . C01D 15 / 04
`2015 / 0140332 A1 *
`428 / 402
`2015 / 0246827 A1 *
`9 / 2015 Izawa . . . . . . . . . . . . . . . . . . . . CO2F 1 / 001
`210 / 252
`
`( 58 )
`
`( 56 )
`
`( 12 ) United States Patent
`Hayashi et al .
`
`( * ) Notice :
`
`( 54 ) METHOD FOR PROCESSING
`FLUORINE - CONTAINING ELECTROLYTE
`SOLUTION
`( 71 ) Applicant : MITSUBISHI MATERIALS
`CORPORATION , Tokyo ( JP )
`( 72 ) Inventors : Hiroshi Hayashi , Iwaki ( JP ) ; Koichiro
`Hirata , Iwaki ( JP ) ; Hidenori
`Tsurumaki , Iwaki ( JP ) ; Hisashi
`Hoshina , Tokyo ( JP )
`( 73 ) Assignee : MITSUBISHI MATERIALS
`CORPORATION , Tokyo ( JP )
`Subject to any disclaimer , the term of this
`patent is extended or adjusted under 35
`U . S . C . 154 ( b ) by 0 days .
`( 21 ) Appl . No . :
`14 / 778 , 701
`Sep . 26 , 2013
`( 22 ) PCT Filed :
`@ events
`( 86 ) PCT No . :
`PCT / JP2013 / 076083
`$ 371 ( C ) ( 1 ) ,
`Sep . 21 , 2015
`( 2 ) Date :
`( 87 ) PCT Pub . No . : W02014 / 155784
`PCT Pub . Date : Oct . 2 , 2014
`Prior Publication Data
`US 2016 / 0049699 A1 Feb . 18 , 2016
`Foreign Application Priority Data
`( 30 )
`( JP ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2013 - 071367
`Mar . 29 , 2013
`
`( 65 )
`
`( 51 ) Int . CI .
`HOIM 10 / 54
`COIF 11 / 22
`CIOL 1 / 02
`
`( 2006 . 01 )
`( 2006 . 01 )
`( 2006 . 01 )
`
`CN
`CN
`
`FOREIGN PATENT DOCUMENTS
`1819326 A
`8 / 2006
`100530813 C
`8 / 2009
`( Continued )
`OTHER PUBLICATIONS
`International Search Report dated Dec . 3 , 2013 , issued for PCT /
`JP2013 / 076083 .
`( Continued )
`Primary Examiner — Cephia D Toomer
`( 74 ) Attorney , Agent , or Firm — Locke Lord LLP
`ABSTRACT
`( 57 )
`A method for processing a fluorine - containing electrolyte
`solution including a gasification step of gasifying a volatile
`component of an electrolyte solution including a fluorine
`compound by heating the electrolyte solution under reduced
`pressure , a fluorine immobilization step of immobilizing the
`fluorine component included in the gasified gas as calcium
`fluoride by allowing the fluorine component to react with
`calcium , and an organic solvent component collection step
`( Continued )
`
`van groep
`
`- - EXHAUST
`
`15
`
`10
`
`U
`
`OIL PHASE
`( ORGANIC PHASE ) * *
`
`OIL AND WATER
`SEPARATION
`
`WATER PHASE
`Ca COMPOUND - - -
`PHS . 5 - 7 NEUTRALIZATION
`
`SOLID AND LIQUID
`SEPARATION
`
`PROCESSED
`WATER
`
`CaF ,
`
`Ascend Elements EX1010 Page 1
`
`

`

`US 9 , 843 , 077 B2
`Page 2
`
`of collecting an organic solvent component included in the
`gasification gas , in which , preferably , after a small amount
`of water , aqueous mineral acid solution , or the like is added
`to the electrolyte solution , the volatile component of the
`electrolyte solution is gasified by heating the electrolyte
`solution under reduced pressure .
`15 Claims , 3 Drawing Sheets
`
`( 52 )
`
`( 56 )
`
`A see
`
`JP
`WO
`
`U . S . CI .
`CPC . . . . CIOL 2290 / 54 ( 2013 . 01 ) ; CIOL 2290 / 541
`( 2013 . 01 ) ; HOIM 2300 / 0034 ( 2013 . 01 ) ; YO2W
`30 / 84 ( 2015 . 05 )
`
`References Cited
`
`FOREIGN PATENT DOCUMENTS
`2721467 B2
`3 / 1998
`8 / 2000
`3079285 B2
`2005 - 026089 A
`1 / 2005
`2006 - 004884 A
`1 / 2006
`3935594 B2
`6 / 2007
`2012 / 127291 AL
`9 / 2012
`
`OTHER PUBLICATIONS
`Office Action dated Dec . 16 , 2016 , issued for the Chinese patent
`application No . 201380074377 . 5 and English translation thereof .
`* cited by examiner
`
`Ascend Elements EX1010 Page 2
`
`

`

`U . S . Patent
`
`Dec . 12 , 2017
`
`Sheet 1 of 3
`
`US 9 , 843 , 077 B2
`
`1
`
`w
`
`1
`
`1
`
`1
`
`KLUXU
`
`.
`
`15
`
`10
`
`- - - EXHAUST
`
`NYERTEN
`
`WWW
`
`wwwwwwwwwwwwwwwwwwwwwwwwww
`
`*
`
`*
`
`wanne
`
`OIL PHASE
`( ORGANIC PHASE )
`
`OIL AND WATER
`SEPARATION
`
`WANAWw wwwwwwwwww
`
`WATER PHASE
`
`pH5 . 5 - w7 NEUTRAL IZATION
`
`SOLID AND LIQUID
`SEPARATION
`
`the
`
`
`
`
`
`maintain them when
`
`PROCESSED
`WATER
`
`www
`
`Cars
`
`Ascend Elements EX1010 Page 3
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`

`

`U . S . Patent
`
`Dec . 12 , 2017
`
`Sheet 2 of 3
`
`US 9 , 843 , 077 B2
`
`nadinas
`
`ADDITIVE
`SOLVENT
`( WATER . ACID )
`
`PODO paona
`
`1
`
`moyon EXHAUST
`
`NEUTRALIZATION
`
`Ca COMPOUND
`SOLID AND LIQUID
`SEPARATION
`mwomb ORGANIC SOLVENT
`Caf ,
`
`FIG . 3
`
`ADDITIVE
`( WATER , ACID )
`
`15
`
`10
`
`KRONE
`
`-
`
`wwwwwwwyo EXHAUST
`
`1 JOK * * * DA
`
`1
`
`ORGANIC SOLVENT
`
`Ascend Elements EX1010 Page 4
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`

`

`U . S . Patent
`
`Dec . 12 , 2017
`
`Sheet 3 of 3
`
`US 9 , 843 , 077 B2
`
`FIG . 4
`1
`
`1
`
`1 1
`
`rayna
`
`Ca FILLIT
`STAVER
`
`CaF ,
`
`KANAKA
`
`
`
`
`
`more than one
`
`15
`
`10
`
`ORGANIC PHASE
`
`Ascend Elements EX1010 Page 5
`
`

`

`US 9 , 843 , 077 B2
`
`TECHNICAL FIELD
`
`METHOD FOR PROCESSING
`FLUORINE - CONTAINING ELECTROLYTE
`SOLUTION
`
`the processing method in which the lithium battery is
`roasted , fluorine is processed as combustion gas . Therefore ,
`fluorine cannot be recycled since it cannot be collected as
`fluorine component having high purity . In the processing
`method of collecting the electrolyte solution by using the
`organic solvent , it is difficult to process the collected elec
`trolyte solution . As indicated above , the flammable organic
`The present invention relates to a safe method for pro -
`solvent is included in the electrolyte solution , and the
`cessing a nonaqueous electrolyte solution which is used in a
`lithium ion battery or the like .
`fluorine compound in the electrolyte solution reacts with
`Priority is claimed on Japanese Patent Application No . 10 water and generates toxic hydrogen fluoride , and thus safe
`2013 - 071367 , filed Mar . 29 , 2013 , the content of which is
`processing is required .
`incorporated herein by reference .
`An object of the present invention is to solve the problems
`of the processing methods of the related art described above ,
`BACKGROUND ART
`15 and is to provide a method in which a volatile fluorine
`compound ( LiPF6 or the like ) and an electrolyte solution
`A large - sized lithium ion battery for supplying high
`including an organic solvent are processed safely .
`capacity electricity is generally used in an electric vehicle or
`an electronic device , and the processing of the used large
`Means for Solving the Problem
`sized battery which is generated in a large quantity becomes
`a problem due to the prevalence of the electric vehicle or the 20
`The present invention provides a method for processing a
`electronic device .
`fluorine - containing electrolyte solution having the following
`An electrolyte solution used in the lithium ion battery or
`step .
`the like includes a fluorine compound which is an electrolyte
`[ 1 ] A method for processing a fluorine - containing elec
`( LiPF , LiBF4 , or the like ) and a volatile organic solvent ,
`and the organic solvent is a flammable substance which is 25 trolyte solution including a volatile fluorine compound and
`mainly ester carbonates . In addition , when LiPF , reacts with
`an organic solvent , the method including a gasification step
`water , LiPF , is hydrolyzed and generates toxic hydrogen
`of gasifying a volatile component by heating the electrolyte
`solution under reduced pressure ; a fluorine immobilization
`fluoride . For this reason , a safe processing method is
`step of immobilizing the fluorine component included in the
`required .
`As a method for processing the lithium ion battery , and 30 gasified gas as calcium fluoride by allowing the fluorine
`the electrolyte solution thereof , in the related art , the fol
`component to react with calcium ; and an organic solvent
`component collection step of collecting an organic solvent
`lowing methods for processing are known .
`1 . A processing method in which the lithium ion battery
`component in the gasification gas .
`[ 2 ] The method for processing a fluorine - containing elec
`or the like is frozen at a temperature lower than or equal to
`a melting point of the electrolyte solution , the battery is 35 trolyte solution according to [ 1 ] described above , in which ,
`demolished and crushed , the electrolyte solution is separated
`in the gasification step , the volatile component of the elec
`in the organic solvent from a crushed body , and the extracted
`trolyte solution is gasified by heating the electrolyte solution
`electrolyte solution is distilled and is separated into the
`under reduced pressure after adding water or an aqueous
`electrolyte and the organic solvent ( for example , refer to
`mineral acid solution to the electrolyte solution .
`[ 3 ] The method for processing a fluorine - containing elec
`PTL 1 ) .
`2 . A processing method in which the used lithium battery
`trolyte solution according to [ 1 ] or [ 2 ] described above , in
`is roasted , a roasted substance thereof is crushed and is
`which the gas in which the volatile component of the
`sorted into a magnetic substance and a non - magnetic sub
`electrolyte solution is gasified is introduced to a wet pro
`stance , and the substance having a large amount of useful
`cessing step , and in the wet processing step , the fluorine
`metal such as aluminum or copper is collected ( for example , 45 component and the organic solvent component included in
`the gas are subjected to water cooling capture , the captured
`refer to PTL 2 ) .
`3 . A processing method in which the lithium battery is
`liquid is subjected to oil and water separation , the organic
`opened by ultrahigh pressure water , and the electrolyte
`solvent component is collected , a calcium compound is
`added to a separated water phase , and fluorine in the water
`solution is collected by using an organic solvent ( for
`50 phase reacts with calcium , and calcium fluoride is generated .
`example , refer to PTL 3 ) .
`[ 4 ] The method for processing a fluorine - containing elec
`trolyte solution according to [ 1 ] or [ 2 ] described above , in
`CITATION LIST
`which the gas in which the volatile component of the
`electrolyte solution is gasified is introduced to a wet pro
`Patent Literature
`cessing step , and in the wet processing step , the fluorine
`component and the organic solvent component included in
`[ PTL 1 ] Japanese Patent No . 3935594
`the gas are condensed and captured , a calcium compound is
`[ PTL 2 ] Japanese Patent No . 3079285
`added to the captured liquid , fluorine reacts with calcium ,
`[ PTL 3 ] Japanese Patent No . 2721467
`and calcium fluoride is generated .
`SUMMARY OF INVENTION
`5 1 The method for processing a fluorine - containing elec
`trolyte solution according to [ 1 ] or [ 2 ] described above , in
`Problem to be Solved by the Invention
`which the gas in which the volatile component of the
`electrolyte solution is gasified is introduced to a wet pro
`In the processing method of the related art , the processing
`cessing step , and in the wet processing step , the gas is in
`method in which the lithium battery is demolished and 65 contact with the mixed solution , fluorine in the gas is
`crushed while being frozen requires refrigeration equipment ,
`absorbed by a calcium compound mixed solution , calcium
`and thus it is difficult to perform this method . In addition , in
`fluoride is generated by allowing fluorine to react with
`
`40
`
`60
`
`Ascend Elements EX1010 Page 6
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`

`

`US 9 , 843 , 077 B2
`calcium , the gas passing through the mixed solution is
`A method for processing a fluorine - containing electrolyte
`condensed , and the organic solvent component is collected .
`solution of the present invention includes , a gasification step
`[ 6 ] The method for processing a fluorine - containing elec
`of gasifying a volatile component of the electrolyte solution
`trolyte solution according to [ 1 ] or [ 2 ] described above , in
`including a fluorine compound by heating the electrolyte
`which the gas in which the volatile component of the 5 solution under reduced pressure ; a fluorine immobilization
`electrolyte solution is gasified is introduced to a dry pro
`step of immobilizing the fluorine component included in the
`cessing step , and in the dry processing step , the gasification
`gasified gas as calcium fluoride by allowing the fluorine
`gas passes through a filling layer of the calcium compound ,
`component to react with calcium ; and an organic solvent
`fluorine in the gas reacts with calcium , calcium fluoride is
`10 component collection step of collecting an organic solvent
`generated , the gas passing through the filling layer is con - 10 €
`component in the gasification gas .
`densed , and the organic solvent component is collected .
`com
`In the electrolyte solution used in a lithium ion battery or
`[ 7 ] The method for processing a fluorine - containing elec
`the like , a fluorine compound of the electrolyte and an
`trolyte solution according to any one of [ 3 ] to [ 6 ] described
`organic solvent are included . The fluorine compound is
`above , in which the electrolyte solution is heated at 80° C .
`to 150° C . under reduced pressure of 5 kPa to ordinary 13 mainly lithium hexafluorophosphate ( LiPF ) , and the
`organic solvent is ester carbonates such as dimethyl carbon
`pressure , the volatile component is gasified , and the gasified
`018
`ate ( DMC ) , ethyl methyl carbonate ( EMC ) , diethyl carbon
`gas is introduced to the wet processing step or the dry
`processing step .
`ate ( DEC ) , propylene carbonate ( PC ) , and ethylene carbon
`[ 8 ] The method for processing a fluorine - containing elec - 20 ate ( EC ) . Among them , DMC is a flammable substance
`trolyte solution according to [ 1 ] described above , in which
`classified as Japan Fire Service Act ( iv ) Class I petroleum ,
`the electrolyte solution is heated at 80° C . to 150° C . under
`and EMC and DEC are flammable substances classified as
`reduced pressure of less than or equal to 1 kPa , the volatile
`Japan Fire Service Act ( iv ) Class II petroleums .
`component is gasified , and the gasified gas is introduced to
`In this processing method , in order to take the electrolyte
`a dry processing step .
`25 solution out of the lithium ion battery safely , after the used
`[ 9 ] The method for processing a fluorine - containing elec -
`lithium ion battery is discharo
`lithium ion battery is discharged , a packaging sheet is peeled
`trolyte solution according to any one of [ 1 ] to [ 8 ] described
`off , and the electrolyte solution is depressurized and gasified
`above , in which calcium fluoride is collected and recycled ,
`by using a safety valve . In the lithium ion battery , a safety
`and the collected organic solvent component is used as fuel
`valve for decreasing an excessive internal pressure of the
`or alternative fuel .
`battery is disposed . As illustrated in FIG . 1 , the safety valve
`[ 10 ] The method for processing a fluorine - containing
`is opened and a pipe passage 12 is connected to an opening
`electrolyte solution according to any one of [ 1 ] to [ 9 ]
`11 . The volatile component of the electrolyte solution is
`described above , in which a pipe passage is connected to an
`gasified by heating the battery under reduced pressure , and
`opening portion of a used battery which includes the elec
`the used 35 thus the generated gas is introduced to a processing step
`trolyte solution including the fluorine compound , the used »
`through the pipe passage 12 .
`battery is heated under reduced pressure , the volatile com
`[ Gasification Step ]
`ponent of the electrolyte solution is gasified , and the gasified
`gas is introduced to the fluorine immobilization step and the
`Among the organic solvent included in the electrolyte
`organic solvent collection step through the pipe passage and
`solution , a boiling point of DMC is 90° C . , a boiling point
`of EMC is 109° C . , a boiling point of DEC is 127° C . , a
`is processed .
`1111 The method for processing a fluorine - containing
`boiling point of PC is 240° C . , and a boiling point of EC is
`electrolyte solution according to [ 10 ] described above , in
`244° C . The volatile component ( DMC , EMC , DEC , PC ,
`which a safety valve of the used lithium ion battery is
`EC , or the like ) is gasified by heating the electrolyte solution
`opened , the pipe passage is connected to the opening , and 45 to a temperature higher than these boiling points . LiPF , is
`the volatile component of the electrolyte solution is gasified
`decomposed by heating or hydrolysis , and thus the fluorine
`component is gasified .
`by heating the battery under reduced pressure .
`Specifically , each electrolyte solution at 0° C . , 10° C . , 20°
`[ 12 ] The method for processing a fluorine - containing
`electrolyte solution according to 1101 described above , in
`C . , 80° C . , and 150° C . under atmospheric pressure ( 101 . 3
`which a safety valve of a plurality of used lithium ion
`kPa ) is in
`a state of an atmospheric pressure conversion
`batteries is opened , the batteries are contained in a hermetic
`temperature shown in Table 1 under reduced pressure con
`ditions of 15 kPa , 10 kPa , 5 kPa , 1 kPa , and 0 . 1 kPa .
`container , the pipe passage is connected to the container , and
`the volatile component of the electrolyte solution is gasified
`Accordingly , under the reduced pressure conditions which
`55 are selected , the electrolyte solution is heated such that the
`by heating the batteries under reduced pressure .
`[ 13 ] The method for processing a fluorine - containing
`atmospheric pressure conversion temperature of the electro
`electrolyte solution according to [ 2 ] described above , in
`lyte solution , for example , is higher than or equal to 244° C . ,
`which an amount of the water or the aqueous mineral acid
`and thus it is possible to volatilize DMC , EMC , DEC , PC ,
`solution which is added to the electrolyte solution is 5 % to
`EC , or the like .
`For example , when the inside of the battery is depressur
`20 % with respect to a weight of the electrolyte solution .
`ized to be 5 kPa and is heated at 80° C . to 150° C . , the
`DESCRIPTION OF EMBODIMENTS
`electrolyte solution is in a state of 170° C . to 251° C . at the
`atmospheric pressure conversion temperature , and thus
`Hereinafter , the present invention will be specifically 65 DMC , EMC , DEC , PC , and EC included in the electrolyte
`described . Furthermore , " % ” described later indicates “ mass
`solution , and the thermally decomposed fluorine compound
`are able to be volatilized . Furthermore , the inside of the
`% ” .
`
`Ascend Elements EX1010 Page 7
`
`

`

`Actual
`Tem -
`perature
`0° C .
`10° C .
`20° C .
`80° C .
`150° C .
`
`Atmospheric
`Pressure
`101 . 3 kPa
`0° C .
`10° C .
`20° C .
`80° C .
`150° C .
`
`0
`
`0
`
`0
`
`0
`
`TABLE 1
`Atmospheric Pressure Conversion Temperature ]
`
`Pressure
`
`10
`
`1 kPa 0 . 1 kPa
`5 kPa
`15 kPa 10 kPa
`74° C . 108° C . 152° C .
`49° C .
`58° C .
`86° C . 120° C . 166° C .
`60° C . 70° C .
`98° C . 134° C . 180° C .
`71° C . 81°C .
`139° C . 151° C . 170° C . 210° C . 262° C .
`217° C . 230° C . 251° C . 297° C . 354° C .
`
`US 9 , 843 , 077 B2
`battery may be depressurized to be less than 5 kPa , for
`[ One Example of Wet Processing )
`example , 1 kPa to 0 . 1 kPa and may be heated at 80° C . to
`One example of a wet processing step ( water cooling
`capture ) is illustrated in FIG . 1 . As illustrated , a battery 10
`120° C .
`is contained in heating equipment 15 , the pipe passage 12
`extending from the opening 11 of the battery 10 is connected
`to
`a vacuum pump 13 through a cooler 16 and a water
`cooling trap 14 . In an illustrated example , a two - stage water
`cooling trap is provided . Water is put into the water cooling
`trap , and a water temperature is maintained at 0° C . to 10°
`C . In a state where the battery 10 is heated by the heating
`equipment 15 and is depressurized by the vacuum pump 13 ,
`the electrolyte solution is gasified . The gasification gas is
`sucked into the vacuum pump 13 , is introduced to the cooler
`16 through the pipe passage 12 and is cooled to be a
`15 condensed solution . The condensed solution is introduced to
`the water cooling trap 14 . At this time , the reduced pressure
`conditions inside the pipe may be maintained at a constant
`pressure , the pressure may decrease at a constant speed , or
`By heating the electrolyte solution under reduced pressure
`a change of alternately repeating atmospheric pressure and
`after a small amount of water is added thereto , the volatile 20 reduced pressure at regular time intervals , or the like may be
`component of the electrolyte solution is gasified . And then ,
`performed . A depressurizing degree is able to be easily
`as denoted by the following expression , LiPF , sequentially
`adjusted by controlling the operation of the vacuum pump .
`reacts with water and is hydrolyzed to phosphoric acid and
`The fluorine compound ( HF or the like ) and the organic
`hydrogen fluoride . Therefore , it is possible to accelerate
`solvent component ( the organic component : DMC , EMC ,
`gasification due to decomposition of LiPFG .
`DEC , PC , EC , or the like ) are subjected to water cooling
`capture by the water cooling trap 14 .
`LiPF6 + H20 - LiF + 2HF ( 1 ) + POF3
`Thus , the organic solvent and the hydrogen fluoride are
`captured by the water cooling trap 14 , and are separated into
`POF3 + H20 - > HPO2F2 + HF ( 1 )
`a water phase and an organic phase . The separated water
`HPO2F2 + H20 - H2PO3F + HF ( 1 )
`30 phase is collected . In such a water phase , the fluorine
`component of the gasification gas is included . A plurality of
`H2PO3F + H20 - > H3PO4 + HF ( 1 )
`stages of the water cooling trap 14 may be disposed in series
`or in parallel , or may be disposed by combining both
`According to the method of performing the gasification by
`dispositions in series and in parallel .
`the addition of water , it is possible to gasify fluorine in a
`large quantity as HF . In addition , as denoted by the expres - 35
`The water phase ( fluorine - containing water ) is acidic
`sion described above , fluorine is gasified as HF , and phos -
`water of less than or equal to pH 2 . A calcium compound
`phorous becomes H3PO4 and remains in solution , and thus
`( calcium carbonate , lime hydrate , calcined lime , or the like )
`fractional efficiency of fluorine and phosphorous is excel -
`is added to the fluorine - containing water , the fluorine
`lent . It is preferable that an added amount of water is 5 % to
`containing water is neutralized to be pH 5 . 5 to pH 7 . 0 ,
`20 % with respect to the weight of the electrolyte solution . 40 fluorine reacts with calcium in the solution , and thus calcium
`The state of the added water may be either liquid or gas
`fluoride is precipitated . The calcium fluoride is subjected to
`( moisture vapor ) . A method of adding water may be any one
`solid and liquid separation and is collected .
`of a method of adding water to the electrolyte solution in
`[ Another Example of Wet Processing ]
`advance , a method of sequentially adding water during the
`Another example ( condensing capture ) of the wet pro
`reaction , a method of continuously supplying water , and a 45 cessing step is illustrated in FIG . 2 . As illustrated , the battery
`10 is contained in the heating equipment 15 , and the pipe
`method combined thereof .
`It is possible to accelerate the decomposition of LiPF in
`passage 12 extending from the opening 11 of the battery 10
`the same way by adding a small amount of dilute aqueous
`is connected to the vacuum pump 13 through the cooler 16
`mineral acid ( inorganic acid ) solution to the electrolyte
`and the trap 14 . In a state where the battery 10 is heated by
`solution . Sulfuric acid , hydrochloric acid , nitric acid , a 50 the heating equipment 15 and is depressurized by the
`mixture of two or more thereof , and the like are able to be
`vacuum pump 13 , the electrolyte solution is gasified . The
`used as mineral acid . The concentration of the mineral acid
`gasification gas is sucked into the vacuum pump 13 , is
`in the aqueous mineral acid solution is suitably 0 . 1 M to 5
`introduced to the cooler 16 through the pipe passage 12 and
`M , and the added amount of the aqueous mineral acid
`is cooled to be a condensed solution . The condensed solution
`solution is preferably 5 % to 20 % with respect to the weight 55 is introduced to the trap 14 . The fluorine compound ( HF or
`of the electrolyte solution . When the concentration of the
`the like ) and the organic solvent component ( the organic
`aqueous mineral acid solution is greater than the range
`component : DMC , EMC , DEC , PC , EC , or the like ) is
`described above or the added amount is greater than the
`captured by the trap 14 .
`range described above , sulfuric acid , hydrochloric acid , and
`The solution collected by the trap 14 has an organic
`nitric acid are simultaneously volatilized and collected at the 60 solvent component as a main component . When water , an
`time of being depressurized and distilled . Therefore , a
`aqueous mineral acid solution , or the like is added at the
`harmful effect of decreasing purity or the like is caused at the
`beginning , moisture is also included . However , since the
`time of collecting fluorine as calcium fluoride .
`organic solvent component has high solubility in water , a
`The gas of the gasified volatile component is introduced
`small amount of moisture is dissolved in the organic solvent
`to a wet processing step or a dry processing step , fluorine is 65 component . Therefore , only the organic phase is able to be
`immobilized as calcium fluoride , and thus an organic solvent
`obtained without separating the water phase . The solution
`collected by the trap 14 is a fluorine - containing solution
`( an oil phase ) is collected .
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`Ascend Elements EX1010 Page 8
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`US 9 , 843 , 077 B2
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`5
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`moisture is dissolved in the organic solvent component , and
`( water + an organic solvent ) of less than or equal to pH 2 . A
`thus only the organic phase is able to be obtained without
`calcium compound ( lime hydrate , calcined lime , or the like )
`separating the water phase .
`is added to the fluorine - containing solution , the fluorine
`[ Dry Processing ]
`containing solution is neutralized to be pH 5 . 5 to pH 7 . 0 ,
`A dry processing step is illustrated in FIG . 4 . As illus
`fluorine reacts with calcium in the solution , and thus calcium
`trated , the gasification gas passes through a filling layer of
`fluoride is precipitated . The calcium fluoride is subjected to
`the calcium compound , fluorine in the gas reacts with
`the solid and liquid separation , and each of the organic
`calcium , and thus calcium fluoride is generated . This cal
`solvent of a liquid phase and calcium fluoride of a solid
`cium fluoride is extracted from the filling layer , and the
`content is collected .
`filling layer is filled with a new calcium compound and is
`Still another example ( calcium absorbing capture ) of the
`used . Meanwhile , the gas passing through the filling layer is
`wet processing step is illustrated in FIG . 3 . As illustrated , the
`introduced to a condensation trap , and the organic solvent
`battery 10 is contained in the heating equipment 15 , and the
`component is collected . A plurality of filling layers of the
`pipe passage 12 extending from the opening 11 of the battery
`10 is connected to a vacuum pump 13 through a container 16 calcium compound may be disposed in series or in parallel ,
`for a Ca mixed solution 17 , the cooler 16 , and the trap 14 .
`or may be disposed by combining both dispositions in series
`In a state where the battery 10 is heated by the heating
`and in parallel .
`equipment 15 and is depressurized by the vacuum pump 13 ,
`In the aggregation trap of the dry processing , water is not
`the electrolyte solution is gasified . The gasification gas is
`necessary , and it is possible for the captured gas to be used
`sucked into the vacuum pump 13 and is introduced to the 20 as fuel of combustion equipment or a combustion improver
`container for a Ca mixed solution 17 through the pipe
`since it is condensed only to be an organic solvent phase . In
`passage 12 . The fluorine component is absorbed in a Ca
`addition , the operation of the dry processing is simple , and
`mixed solution at the container 17 , reacts with a calcium
`a drainage treatment is not necessary .
`compound , and is immobilized as calcium fluoride . The
`In the gasification step , when the gasification is performed
`gasification gas passing through the container 17 is intro - 25 at a pressure higher than a vapor pressure of water , the
`duced to the cooler 16 , is cooled to be a condensed solution ,
`gasification gas is able to be introduced to the wet processing
`and is introduced to the trap 14 . The organic solvent com
`step or the dry processing step and is able to be processed .
`In contrast , when the gasification is performed at a pressure
`ponent ( an organic component : DMC , EMC , DEC , PC , EC ,
`lower than a vapor pressure of water , the gasification gas is
`or the like ) is captured by the trap 14 .
`Thus , the fluorine component reacts with the calcium 30 introduced to the dry processing step and is processed
`compound in the container for a Ca mixed solution 17 , and
`The gasification gas is cooled by the cooler 16 up to
`calcium fluoride is generated . Calcium carbonate , calcium
`reduced pressure of approximately 5 kPa . When the gasifi
`hydroxide , calcium oxide , calcium sulfate , calcium chloride ,
`cation gas is generated by heating the electrolyte solution in
`and calcium nitrate are able to be used as the calcium
`25 35 a depressurized state stronger than the reduced pressure , for
`compound of the Ca mixed solution , and calcium carbonate
`example , in a depressurized state of 1 kPa and 0 . 1 kPa , the
`which is able to perform granulation of collected calcium
`water cooling trap is not suitable because the pressure of the
`fluoride at low cost is preferable . As a liquid of the Ca mixed
`gasification gas is lower than the vapor pressure of water
`solution , water or an organic solvent is able to be used .
`even when it is cooled to 10° C . by the cooler 16 . In this
`When the liquid is the organic solvent , an electrolyte solu - 40 case , the gasification gas is introduced to the dry processing
`tion component ( DMC , EMC , DEC , PC , EC , or the like )
`step and is processed .
`may be used . When the organic solvent of the electrolyte
`In contrast , when the electrolyte solution is heated and the
`volatile component is gasified in a depressurized state of 5
`solution is used , a part of the gasified gas may be cooled and
`condensed , and may be captured in the container for a Ca
`kPa to ordinary pressure , the pressure is higher than the
`mixed solution 17 . In this case , it is advantageous to the cost . 45 vapor pressure of water when the gasification gas is cooled
`When a liquid temperature of the Ca mixed solution
`to be lower than or equal to 10° C . by the cooler 16 .
`decreases , the gasified organic solvent is condensed in a
`Therefore , the gasification gas is able to be introduced to the
`large quantity , and thus a liquid amount increases . In order
`wet processing step and is able to be processed . Further
`to stabilize the liquid amount of the Ca mixed solution , it is
`more , the gasification gas may be introduced to a dry step .
`preferable that the solution is kept warm or heated and is 50
`Advantageous Effects of Invention
`gasified so that the liquid amount is adjusted . Furthermore ,
`a plurality of containers for a Ca mixed solution 17 may be
`disposed in series or in parallel , or may be disposed by
`According to the processing method of the present inven
`combining both dispositions in series and in parallel .
`tion , fluorine is able to be recycled as a hydrofluoric acid
`The generated calcium fluoride in the container for a Ca 55 manufacturing raw material or a cement raw material
`mixed solution 17 is able to be collected by volatilizing a
`because fluorine is collected from the electrolyte solution as
`liquid component and by drying a solid material or by
`calcium fluoride having high purity . According to the pro
`performing the solid and liquid separation with respect to
`cessing method of the present invention , it i