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EP1652253A1 - Procede pour traiter des composants electriques contenant des cations organiques, des solvants non aqueux et du carbone - Google Patents

Procede pour traiter des composants electriques contenant des cations organiques, des solvants non aqueux et du carbone

Info

Publication number
EP1652253A1
EP1652253A1 EP04762598A EP04762598A EP1652253A1 EP 1652253 A1 EP1652253 A1 EP 1652253A1 EP 04762598 A EP04762598 A EP 04762598A EP 04762598 A EP04762598 A EP 04762598A EP 1652253 A1 EP1652253 A1 EP 1652253A1
Authority
EP
European Patent Office
Prior art keywords
components
edlc
separation
aqueous solvents
carbon
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.)
Withdrawn
Application number
EP04762598A
Other languages
German (de)
English (en)
Inventor
Andree Schwake
Christoph J. Weber
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.)
TDK Electronics AG
Original Assignee
Epcos AG
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 Epcos AG filed Critical Epcos AG
Publication of EP1652253A1 publication Critical patent/EP1652253A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/52—Reclaiming serviceable parts of waste cells or batteries, e.g. recycling
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the invention relates to a method for treating electrical components which contain organic cations, non-aqueous solvents and carbon.
  • Such materials with organic cations, non-aqueous solvents and carbon are contained, for example, in electrochemical double layer capacitors (EDLC - Electrochemical Double Layer Capacitors).
  • EDLC Electrochemical Double Layer Capacitors
  • Electrochemical double layer capacitors based on carbon electrodes and electrolytes, consisting of conductive salts with organic cations, such as.
  • conductive salts with organic cations such as.
  • B. quaternary ammonium, phosphonium, pyrolidinium, pyridinium or imidazolium salts, in non-aqueous solvents, will find access to the automotive industry in the next few years, but also in industrial applications, the
  • the anode material of Li-ion batteries consists of a graphitic, lithium-containing, carbon modification, which is at least the same chemical element as the activated carbon of EDLC.
  • Cathode material e.g. cobalt, manganese, titanium,
  • nickel oxides with lithium ion deposits separator (PP, PE), drain (e.g. copper, nickel, aluminum) and housing (usually steel or aluminum) differ significantly from the materials, the structure and the resulting ones Separation tasks in recycling compared to EDLC.
  • Li ion batteries A method for the disposal of Li ion batteries is described in the literature reference DE4424825A1. After a freezing step, the batteries are shredded at room temperature in an inert atmosphere. The released solvent of the battery electrolyte is supplied to a device for rendering the exhaust gases harmless, ie it is not used. The solid components of the battery are flotated into a light fraction (mainly made of plastic) and a heavy one
  • Non-ferrous metals are separated from each other in a subsequent step. A recovery of the conductive salts is not described.
  • the US4637928 describes a method and an apparatus for neutralizing lithium batteries with high energy density, e.g. B. lithium sulfur and lithium thionyl chloride.
  • the single cell is opened in one step, liquid (water or sodium hydroxide solution) is introduced into the battery and gas is released from the inside of the cell.
  • liquid water or sodium hydroxide solution
  • gas is released from the inside of the cell.
  • WO 94/07277 describes a method for recycling metal-containing electronic components, which include batteries and capacitors, in particular with lithium.
  • the claimed process comprises the comminution of the metal-containing electronic components, the subsequent washing out of the metal-containing solids and the solvent contained in the electrolyte with an aqueous solution.
  • This aqueous solution is then distilled to recover the electrolyte solvent and the water-soluble metal-containing residues.
  • the solid residue from the aqueous washout is washed with an acidic solution in order to dissolve further metal-containing solids.
  • the metal-containing solids are precipitated out of this solution with suitable chemicals and in a subsequent step further converted to metal oxides, which are then used to produce new ones
  • Batteries are to be used.
  • the solid residue from the acid washout is either discarded or burned. During the combustion, the carbon contained in the residue is removed, leaving only free
  • No. 5,888,463 claims a recycling process for Li from waste containing Li, in particular from Li batteries.
  • the batteries are first cooled to temperatures below -320 ° F with liquid nitrogen or argon
  • the cooled Li batteries are then comminuted and reacted with an aqueous LiOH solution, the pH of which is> 10. As a result, the Li salts contained in the batteries are dissolved.
  • This aqueous solution containing the Li salts is brought into contact with further comminuted batteries until the solubility product of the salts is exceeded, so that they precipitate out again.
  • the precipitate is then filtered off.
  • this filter cake it is dissolved again in dilute sulfuric acid and transferred to an “electrolytic hybrid cell”, which is not described further, in which the Li ions selectively migrate from the sulfuric acid solution through a membrane into a basic aqueous solution, where LiOH is then formed can either be used for the previously described leaching of the cooled and shredded batteries or for the production of LiC0 3 be used.
  • electrolytic hybrid cell which is not described further, in which the Li ions selectively migrate from the sulfuric acid solution through a membrane into a basic aqueous solution, where LiOH is then formed can either be used for the previously described leaching of the cooled and shredded batteries or for the production of LiC0 3 be used.
  • WO 99/34473 describes a process for the treatment of Li-containing, electrochemical cells consisting of binder-containing cathode and anode materials and an electrolyte, both the cathode and the anode containing intercalated ions.
  • the process is divided into the steps of shredding in an inert gas atmosphere with absolute exclusion of water, dissolving the electrolyte from the shredded parts with an organic, absolutely anhydrous solvent (acetonitrile), then dissolving the binder in a second organic solvent (NMP) and then reducing the the cathode intercalated ions (electrochemical).
  • This process is primarily intended for the reprocessing of Li-ion batteries. For the separation of the solid parts, only the separation via density differences or via magnetism are mentioned.
  • the invention is intended to provide a way of recycling materials with organic cations, non-aqueous solvents and carbon.
  • the invention achieves this aim with the features of patent claim 1. Further developments of the inventions are characterized in the subclaims.
  • the invention describes a method for recycling materials (waste), the solutions of organic
  • Cations such as B. quaternary ammonium, phosphonium,
  • a method for unloading EDLC and EDLC modules using a particulate carbon bed is described. This medium is variable for all geometrical connection configurations of the EDLC and EDLC modules, allows safe discharge via the electrically conductive particles without melting connections, is inexpensive and does not lead to contamination of the product to be recycled.
  • the invention describes a technically and also economically very advantageous process for separating the electrolyte components from the rest of the waste by Use of non-aqueous solvents, which correspond to the type of solvent used in the electrolyte.
  • the subsequent separation step into the individual solvents can be omitted. If the solvents contained in the waste and the solvents used for washing out were different, such a separation would have to take place.
  • the washing process allows the use of less expensive materials, atmospheres and containers and does not need to be carried out with complete exclusion of moisture, as described in WO 99/34473.
  • a two-stage float / sink separation is used based on the different density of the materials.
  • the materials are very pure.
  • the carbon in particular can be used again for EDLC.
  • an aeroclassification or hydrocassification is used to separate the solids from waste with organic cations and non-aqueous solvents.
  • Metal fraction used. This process can allow the plastic fraction to be separated from the carbon / paper fraction even when there is less flow onto the material to be separated.
  • the materials are very pure.
  • the carbon in particular can be used again for EDLC.
  • an electrostatic separation with a subsequent separation over different densities is proposed for separating the solids from waste with organic cations and non-aqueous solvents.
  • the materials are very pure.
  • the carbon in particular can be used again for EDLC.
  • a two-stage melting process is used to separate the solid components from waste with organic cations and non-aqueous solvents, in which the plastic components (PP, PE, PU) are melted at -200 ° C and aluminum at ⁇ 700 ° C.
  • the infusible fraction is sieved off or filtered.
  • the materials are very pure.
  • the carbon in particular can be used again for EDLC.
  • a process for the separation of carbon coating and Al carrier foil is used. This can be done, also inexpensively, by removing the same in water or an aqueous solution.
  • Process remaining carbon / paper / residual plastics material is possible. This material offers itself as raw material for the production of further activated carbon, e.g. for the use of EDLC, and thus closes the material cycle.
  • Fig. 1 is a flowchart of the process steps including the optional steps and
  • Fig. 2 is a schematic representation of the separation options after process step 6 for the separation of the dried residue or mixture
  • the electrical components consist, in particular the EDLC modules consist of individual cells that are interconnected with aluminum cell connectors and are located in a plastic module housing (PP, PE). Furthermore, an assembled printed circuit board for managing the state of charge of the individual cells and fixing material of the individual cells, e.g. Potting plastic (PU), steel or Al plates and screws.
  • the individual cells consist of an electrolyte-impregnated coil, which is essentially made up of activated carbon, aluminum foil and paper, and optionally a core tube made of plastic (PP, PE).
  • the wraps are in an aluminum housing, which is sealed gas-tight with an aluminum cover and a sealing ring made of rubber-like material.
  • the electrolyte consists of a quaternary
  • Electrode components that have arisen during the life of the capacitor There is also the possibility that short-chain organic compounds, CO, CO 2 , CH, H 2, etc. are present in small amounts as a gas.
  • the targeted discharge can take place via ionic or electrical conductors.
  • Discharge via electrical conductors can be done by connecting electrical loads or by contacting the modules in an electrically conductive medium, e.g. Metal balls, granules, powders, wadding, nets or carbon ulvers, pellets, granules or the like can be realized.
  • This method of discharge is also very advantageously applicable to all other electrochemical cells. Carbon-based discharge media in particular have a sufficiently high discharge resistance and cannot weld to the cells to be discharged.
  • Process step 2 separating the single cell strand from the rest of the module
  • Module separately.
  • module housings, printed circuit boards, fixing elements can be sorted out according to type and sent for further material recycling. If possible, the individual cells should not be damaged. If this cannot be avoided, this process should be carried out in an inert atmosphere.
  • Process step 3 shredding the EDLC lines or the EDLC module
  • the EDLC strands or, if process step 2 was omitted, the complete EDLC modules are shredded with the aid of shredder or grinding processes (eg using hammer, ball, cutting or impact mills) , preferably until particle sizes less than 5 mm can be achieved.
  • shredder or grinding processes eg using hammer, ball, cutting or impact mills
  • the particles produced in this shredding process should be of the same size and shape as possible and should be as uniform as possible
  • Process step 4 washing with a non-aqueous solvent
  • the comminuted EDLC components are washed with a non-aqueous solvent, preferably with the one which was used as the solvent of the electrolyte in the EDLC.
  • This process is also preferably run in a sealed container under an inert gas from which need not necessarily be dried in the EDLC 'conducting salts used are more stable to hydrolysis than in Li
  • Ion cells contain salts and electrode materials.
  • the solvent quality used for washing e.g. water content, purity, impurities
  • the solvent quality used for washing can therefore be lower than the solvents used in the electrochemical cells and capacitors.
  • the washing process can be carried out in a batch process or under continuous circulation with a non-aqueous solvent.
  • the conductive salt and the solvent of the electrolyte dissolve out of the crushed EDLC particles.
  • this process takes place at high speed.
  • this can be carried out with stirring and / or at temperatures above room temperature.
  • the temperature does not necessarily have to be limited to a maximum of 60 ° C since the conductive salts are more stable than Li-ion cells.
  • the use of ultrasonic waves can also accelerate the dissolution rate of the conductive salt and the electrolyte solvent.
  • the washing solution can then be concentrated by increasing the temperature and / or exposure to negative pressure.
  • Washing solution is collected, e.g. with a cold trap. If the solvent used for washing is identical to the solvent of the EDLC electrolyte, the solvent obtained here can be returned to the chemical industry as a raw material or used again for washing the crushed EDLC particles. If solvent mixtures are used as the electrolyte component in the EDLC or if the solvent used for washing differs from the solvent used in the electrolyte of the EDLC, these can be separated, for example, by distillation or extraction.
  • the recovered conductive salt is further purified, for example by means of recrystallization from non-aqueous solvents or chromatographic methods, and for the
  • waste to be processed consists of EDLC with different conductive salts
  • pre-sorting can be done, for example, using appropriate markings in EDLC of the different ones already attached to the EDLC during manufacture
  • the EDLC with the different conductive salts can also be fed together to the recycling process Washing process Leitsalzgemische be isolated.
  • Conductive salt mixtures can then be separated from one another via their different chemical and / or physical properties, for example their solubility products or interactions with chromatographic separation phases.
  • Process step 5 drying the residue from process step 4
  • the components remaining in process step 4 are dried by heating and / or vacuum.
  • the escaping non-aqueous solvents are collected, e.g. B. with a cold trap.
  • an additional shredding step can also be added, depending on the requirements of the following separation steps.
  • Process step 6 separation of AI, C, plastics, paper
  • the different mechanical, physical and / or chemical properties of the individual waste components can be used to separate the EDLC components from process step 5 into AI, C, plastics and paper.
  • the processes flotation exploitation of different water wettability of dispersed material grains
  • aeroclassification or wind sifting separation via different density buoyancy in the air flow
  • hydrocassification separation via different density buoyancy in the water flow
  • electrostatic separation separation via different conductivities
  • Melting separation via different melting points
  • floating-sink sorting subparation via different densities in liquids
  • ballistic separation ballistic separation according to density and piece shape
  • the residue from process step 5 is mixed in a container with a liquid which has a density of 1.5 to 2.6 g / cm 3 , for example an aqueous salt solution or a mixture of water with other solvents. Since apart from aluminum (density 2.7 g / cm 3 ), all other ingredients have a lower density than the added liquid (paper: 0.5 g / cm 3 , plastics approx. 1.4 g / cm 3 , C: 0 , 7 g / cm 3 ), only the AI remains at the bottom of the container and can be separated there.
  • the plastics are separated from the carbon / paper residues.
  • water, aqueous salt solutions and / or mixtures with other solvents or a combination of salt solutions and mixtures are suitable as release agents.
  • the separation by density can be accelerated by centrifugation.
  • Electrostatic separation of electrical conductors and non-conductors This separation process is suitable for the dry recovery of metal particles from different conductor-non-conductor mixtures.
  • the waste mixture to be separated is transferred to a rotating, earthed one via a vibration conveyor Given metal roller and in the area of a
  • the carbon coating can generally be easily removed in water from the Al carrier film, provided that this has not yet been done completely by the comminution process.
  • the material to be separated is flown from below.
  • it is located on a sieve, for example.
  • the inflowing air drives parts with high air resistance (paper and carbon chips) and low density upwards, while the other parts (plastics and especially aluminum) remain on the sieve.
  • the plastics are separated from the aluminum according to the same principle under changed process parameters. The fractions are: 1. aluminum, 2. plastics, 3
  • the material to be separated is heated in a suitable oven to a homogeneous temperature, which is below the melting point of AI, but above the melting point of all types of plastic contained in the material to be separated.
  • the plastics that melt out of the material to be separated are collected and fed to the common methods of plastics processing.
  • the remaining residue of Al, C and paper is then further heated to a homogeneous temperature above the melting point of Al so that it can be melted out of the material to be separated and collected.
  • the AI can finally be further processed using the usual methods of Al recycling.
  • a mixture of coal and paper can be added to the carbonization stage of the activated carbon production process and is thus e.g. used for the production of new EDLC.
  • the remaining Al, C, and paper mixture can be further separated using the other methods mentioned.
  • a separation into the individual fractions aluminum, plastics, paper and carbon is possible.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Processing Of Solid Wastes (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un procédé pour traiter des composants électriques, notamment des cellules électrochimiques à deux éléments contenant des cations organiques, des solvants non aqueux et du carbone. Ce procédé consiste à fractionner les composants, à laver les composants ainsi fractionnés avec des solvants non aqueux, à sécher ce mélange et à séparer les constituants du mélange.
EP04762598A 2003-08-08 2004-08-04 Procede pour traiter des composants electriques contenant des cations organiques, des solvants non aqueux et du carbone Withdrawn EP1652253A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2003136762 DE10336762A1 (de) 2003-08-08 2003-08-08 Verfahren zum Behandeln von organischen Kationen, nicht wässrige Lösungsmittel und Kohlenstoff enthaltenden elekrischen Komponenten
PCT/DE2004/001753 WO2005015668A1 (fr) 2003-08-08 2004-08-04 Procede pour traiter des composants electriques contenant des cations organiques, des solvants non aqueux et du carbone

Publications (1)

Publication Number Publication Date
EP1652253A1 true EP1652253A1 (fr) 2006-05-03

Family

ID=34129531

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04762598A Withdrawn EP1652253A1 (fr) 2003-08-08 2004-08-04 Procede pour traiter des composants electriques contenant des cations organiques, des solvants non aqueux et du carbone

Country Status (3)

Country Link
EP (1) EP1652253A1 (fr)
DE (1) DE10336762A1 (fr)
WO (1) WO2005015668A1 (fr)

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CN101570867A (zh) * 2008-03-27 2009-11-04 霍尼韦尔国际公司 从用于生产气态氟的电解池中回收污染的电解质的方法

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CL2010000487A1 (es) * 2010-05-13 2011-04-08 Univ Santiago Chile Procedimiento para obtener electrodo de carbono desde desechos de pilas acidos que comprende extraer carbon de la pila, sacar recubrimiento, hervir, lavar, lijar y lavar hasta no obtener residuo, sonicar, lavar con solvente altamente apolar, sonicar y lavar con solventes organicos, hervir a ph acido y pulir.
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DE102013011470B4 (de) * 2013-07-10 2015-07-23 Technische Universität Bergakademie Freiberg Verfahren zur Sortierung von Batteriezellen mit Restladung in Wärmeemissions- oder Gefährdungsklassen entsprechend der Restladung
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CN105618459B (zh) * 2015-12-30 2018-03-27 山东精工电子科技有限公司 一种废旧超级电容器的回收方法
CN106252772B (zh) * 2016-08-24 2019-04-19 合肥国轩高科动力能源有限公司 一种废旧锂离子电池的放电方法
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Also Published As

Publication number Publication date
DE10336762A1 (de) 2005-03-10
WO2005015668A1 (fr) 2005-02-17

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