CN105870528B - A kind of method that utilization intermediate frequency furnace reclaims lithium metal in lithium ion battery - Google Patents
A kind of method that utilization intermediate frequency furnace reclaims lithium metal in lithium ion battery Download PDFInfo
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- CN105870528B CN105870528B CN201610210890.8A CN201610210890A CN105870528B CN 105870528 B CN105870528 B CN 105870528B CN 201610210890 A CN201610210890 A CN 201610210890A CN 105870528 B CN105870528 B CN 105870528B
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- intermediate frequency
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- 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
Abstract
The invention discloses a kind of utilization intermediate frequency furnace reclaim lithium ion battery in lithium metal method, including battery discharge process, disassemble, battery core slightly break and melting operation；Described melting operation refers to that will be placed in carry out melting in intermediate frequency furnace by thick broken battery core, and concrete operation step is as follows：1) battery core and flux after thick breaking are placed in intermediate frequency furnace；2) intermediate frequency furnace is warming up to 1,300 1400 DEG C, until material all melts, obtains the alloy containing Co and/or Ni, filter residue and flying dust；3) flying dust is collected, adds deionized water dissolving, filtering removal insoluble matter to obtain filtrate；4) to addition saturation Na in filtrate2CO3Solution, obtains product Li2CO3.Present device aspect uses the advantage of intermediate frequency furnace, and high with production efficiency, operating procedure is simple, the few advantage of flue dust, and very notable at energy-saving aspect.
Description
Technical field
It is especially a kind of to reclaim lithium-ion electric using intermediate frequency furnace the present invention relates to resource reclaim and environmental protection technical field
The method of lithium metal in pond.
Background technology
With the rapid growth of World Economics, people are increasing to the demand of automobile, therefore energy crisis and environment are dirty
Dye has turned into the two large problems that countries nowadays generally face, and greatly develop new-energy automobile be solve problem main method it
One, its technological core is exactly electrokinetic cell.Lithium ion battery because of its high security, high-energy-density and environmental protection and low cost and
It is used widely, is particularly even more unique advantage in electric automobile, microelectronic component and aerospace industry field.Currently, China
Battery industry develop rapidly, by 2015, electric automobile cumulative sale was up to 500,000, it is contemplated that the year two thousand twenty up to 5,000,000,
Meanwhile, the pure electric vehicle of China and electrokinetic cell of hybrid powered vehicle scrap cumulative amount and will also reach 12~170,000 tons, but
The rate of recovery of China's battery is but less than 2%, if battery recycling system and advanced recovery technology without specification, these batteries
Certainly will will cause the wasting of resources and huge environmental hazard.
At present, scrap lithium ion battery recycling technology is mainly focused on the recovery of the metals such as nickel, copper and rare earth element,
And the document of lithium metal recovery is relatively fewer, concrete technology has pyrogenic process and the class of wet method two.
Thermal process is then that lithium ion battery and sulfate or other salts are carried out into calcination process, after baking, battery
In lithium can change into soluble-salt, be eventually adding precipitating reagent and reclaimed.It is related to alkali to soak in process route, acidleach, roasting etc.
Step, it is relatively complicated.Wet processing includes disassembling, and sorts, and leaches, the step such as precipitation, and its advantage is that each component is obtained effectively
Reclaim, the purity for processing products obtained therefrom is generally higher.But wet recycling process flow is often excessively complicated, and leachate and residual
Slag has corrosivity and toxicity, if dealing with improperly, easily causes even more serious secondary pollution.In addition, after leaching, can also pass through
Adding ion sieve carries out adsorption recovery, and available adsorption rate higher is reported in such as Chinese patent CN 1451771A, but, its
Ion sieve synthesis is more difficult and high to the quality requirement of ion sieve, and this method is applied to laboratory research, and improper industry is big raw
Produce.
The preparation technology of current lithium carbonate is broadly divided into ore and extracts and salt lake bittern two major classes of extraction, if by reclaiming
Lithium prepares lithium carbonate method, and not only input cost is high, and technical difficulty is big, secondary pollution is easily caused, so being unfavorable for work
The realization of industry.Therefore, seeking a kind of process for preferably reclaiming lithium undoubtedly has good development prospect.
The content of the invention
Present invention aim at a kind of method that utilization intermediate frequency furnace reclaims lithium metal in lithium ion battery is provided, using intermediate frequency
The characteristics of stove, obtain a kind of simple to operate, energy-saving, lithium-ion electric that production efficiency is high, environmental benefit is good, good in economic efficiency
The recovery method of lithium metal in pond.
To achieve these goals, the present invention uses following technical scheme：
A kind of method that utilization intermediate frequency furnace reclaims metal in lithium ion battery, including discharge process, disassemble, battery core slightly break and
Melting operation, comprises the following steps that：
Discharge process：The lithium ion battery of recovery is put into electrolyte, remaining capacity is fully put only in making battery；Due to
The powered cutting of battery is thick broken to be susceptible to blast, thus it is thick it is broken before must carry out discharge process；
Disassemble：Cut less than at 1.5cm along to battery top with cutter, the battery after cutting is opened, separate battery core
And battery container, wherein battery container recycling；
Battery core is slightly broken：Using shearing-crushing, impact grinding, splitting is broken, grinding is broken, bending is broken and perforate in one
Plant or more than one method is processed battery core；Because waste battery is sealing system and inside battery has electrolyte
Deng if battery core directly to be carried out dry melt treatment, there is the danger of blast, accordingly, it would be desirable to using the method for broken or perforate
Treatment battery core, makes battery core to be vented in melting processing procedure, it is to avoid blast；
Melting operation refers to that will be placed in carry out melting in intermediate frequency furnace by thick broken battery core, and concrete operation step is as follows：
1) battery core and flux after thick breaking are placed in intermediate frequency furnace, wherein flux accounts for the 8-12% of total amount；
2) intermediate frequency furnace is warming up to 1300-1400 DEG C, reaction until material all fusings, obtain the conjunction containing Co and/or Ni
Gold, slag and flying dust；
3) flying dust is collected using cyclone dust collectors in fusion process, adds a small amount of deionized water dissolving, filtering removal is not
Molten thing, obtains filtrate；
4) to addition saturation Na in filtrate2CO3Solution, obtains product Li2CO3。
Preferably, described flux is the composition of Fe and MgO, and by weight, 0.4≤Fe/MgO≤0.6.
Preferably, described electrolyte is one or more in NaOH, NaCl, KOH and KCl.
Preferably, step 2) in fusing time be 30~60min.
Beneficial effects of the present invention：
The present invention using intermediate frequency furnace scrap the recovery method of lithium metal in power lithium-ion battery, and equipment aspect is used
Intermediate frequency furnace has production efficiency high, and operating procedure is simple, the few advantage of flue dust, and very notable at energy-saving aspect.Separately
The outer flux for using in the present invention so that can not only reclaim the metals such as nickel cobalt copper, at the same greatly simplify lithium reclaim and
Purifying technique, substantially reduces production cost, realizes the cycling and reutilization of valuable metal in battery.
Brief description of the drawings
Fig. 1 is present invention process schematic flow sheet.
Specific embodiment
Power lithium-ion battery will be scrapped and be placed in the sodium chloride solution that concentration is 10% and soak 48h, it is ensured that lithium electricity
The residual electricity whole discharge off in pond.
Electrokinetic cell of scrapping after electric discharge is transported to the room of disassembling using cutter along cutting at battery top~1.5cm.For
Prevent from being overheated in cutting process, trigger burning or explode, need to cut synchronous with spray cooling.Finally battery core is taken from battery case
Go out, battery case can be recycled directly.
The battery core of extraction is slightly broken, it is therefore an objective to prevent the blast of refuse battery, i.e. refuse battery be sealing system and
Internally there is electrolyte etc., when pyrogenic process melt process is directly carried out in the presence of the danger for being possible to blast.Accordingly, it would be desirable to take
Break process (such as shearing-crushing, impact grinding, splitting is broken, grinding is broken, bending is broken) is in order to be vented, it is also possible to enter
Row perforate is processed, for example, carrying out physics perforate to refuse battery using the point of a knife of needle-like.Additionally, in the present invention, due to later
Pyrogenic attack in by melting operation, therefore do not need each component separation.
Melting is carried out in intermediate frequency furnace by being placed in by thick broken battery core.
Embodiment 1
1) battery core and flux after thick broken are placed in intermediate frequency furnace, and wherein flux accounts for the 10% of total amount, and flux by Fe and
MgO is constituted, and Fe/MgO=0.4；2) intermediate frequency furnace is warming up to 1400 DEG C, and smelting time is 30min, and material all melts, obtains
Alloy, slag and flying dust containing Co and/or Ni；3) using cyclone dust collectors collection flying dust is reclaimed, appropriate deionized water is added
Dissolving, impurity can be removed by insoluble matter filtering, obtain filtrate；4) saturation Na is added in filtrate2CO3Solution is until precipitate not
Regeneration, precipitation is product Li2CO3.The rate of recovery of lithium is 81%, and in the alloy of production, the rate of recovery of nickel and cobalt is respectively
89% and 90%.
Embodiment 2
1) battery core and flux after thick broken are placed in intermediate frequency furnace, and wherein flux accounts for the 12% of total amount, and flux by Fe and
MgO is constituted, and Fe/MgO=0.5；2) intermediate frequency furnace is warming up to 1400 DEG C, and smelting time is 60min, and material all melts, obtains
Alloy, slag and flying dust containing Co and/or Ni；3) using cyclone dust collectors collection flying dust is reclaimed, appropriate deionized water is added
Dissolving, impurity can be removed by insoluble matter filtering, obtain filtrate；4) saturation Na is added in filtrate2CO3Solution is until precipitate not
Regeneration, precipitation is product Li2CO3.The rate of recovery of lithium is 85%, and in the alloy of production, the rate of recovery of nickel and cobalt is respectively
94% and 94%.
Embodiment 3
1) battery core and flux after thick broken are placed in intermediate frequency furnace, and wherein flux accounts for the 8% of total amount, and flux by Fe and
MgO is constituted, and Fe/MgO=0.6；2) 1400 DEG C are warming up to, smelting time is 60min, material all melts, obtain containing Co and/
Or the alloy of Ni, slag and flying dust；3) using cyclone dust collectors collection flying dust is reclaimed, appropriate deionized water dissolving is added, will
Insoluble matter filtering can remove impurity, obtain filtrate；4) saturation Na is added in filtrate2CO3Solution is not regenerated until precipitating,
Precipitation is product Li2CO3.The rate of recovery of lithium is 83%, and in the alloy of production, the rate of recovery of nickel and cobalt is respectively 91% He
92%.
Comparative example 1
1) battery core and flux after thick broken are placed in intermediate frequency furnace, and wherein flux accounts for the 10% of total amount, and flux by Fe and
MgO is constituted, and Fe/MgO=0.3；2) 1400 DEG C are warming up to, smelting time is 60min, material all melts, obtain containing Co and/
Or the alloy of Ni, slag and flying dust；3) using cyclone dust collectors collection flying dust is reclaimed, appropriate deionized water dissolving is added, will
Insoluble matter filtering can remove impurity and obtain filtrate；4) it is last that saturation Na is added in filtrate2CO3Solution is not until precipitation regenerates
Into precipitation is product Li2CO3.The rate of recovery of lithium is 69%, and in the alloy of production, the rate of recovery of nickel and cobalt is respectively 79% He
80%.
Comparative example 2
1) battery core and flux after thick broken are placed in intermediate frequency furnace, and wherein flux accounts for the 10% of total amount, and flux by Fe and
MgO is constituted, and Fe/MgO=0.7；2) 1400 DEG C are warming up to, smelting time is 60min, material all melts, obtain containing Co and/
Or the alloy of Ni, slag and flying dust；3) using cyclone dust collectors collection flying dust is reclaimed, appropriate deionized water dissolving is added, will
Insoluble matter filtering can remove impurity and obtain filtrate；4) saturation Na is added in filtrate2CO3Solution is not regenerated until precipitating, and is sunk
Shallow lake is product Li2CO3.The rate of recovery of lithium is 71%, and in the alloy of production, the rate of recovery of nickel and cobalt is respectively 82% and 80%.
Claims (6)
1. a kind of method that utilization intermediate frequency furnace reclaims metal in lithium ion battery, it is characterised in that the discharge process including battery,
Disassemble, battery core is slightly broken and melting operation；
Described melting operation refers to that will be placed in carry out melting in intermediate frequency furnace by thick broken battery core, and concrete operation step is as follows：
1) battery core and flux after thick breaking are placed in intermediate frequency furnace, wherein flux accounts for the 8-12% of total amount；
2) intermediate frequency furnace is warming up to 1300-1400 DEG C, reaction until material all fusings, obtain alloy, stove containing Co and/or Ni
Slag and flying dust；
3) flying dust is collected using cyclone dust collectors in fusion process, adds deionized water dissolving, filtering removal insoluble matter to obtain
Filtrate；
4) to addition saturation Na in filtrate2CO3Solution, obtains product Li2CO3；
Wherein, described flux is the composition of Fe and MgO, and by weight, 0.4≤Fe/MgO≤0.6.
2. the method that utilization intermediate frequency furnace according to claim 1 reclaims metal in lithium ion battery, it is characterised in that described
Discharge process be that the lithium ion battery of recovery is put into electrolyte, remaining capacity is fully put only in making battery.
3. the method that utilization intermediate frequency furnace according to claim 1 reclaims metal in lithium ion battery, it is characterised in that described
Disassemble be with cutter along to battery top less than 1.5cm locate cutting, by after cutting battery open, separation battery core and battery
Housing, wherein battery container are recycled.
4. the method that utilization intermediate frequency furnace according to claim 1 reclaims metal in lithium ion battery, it is characterised in that described
Battery core slightly it is broken be using shearing-crushing, impact grinding, splitting is broken, grinding is broken, bending is broken and perforate in one kind or
More than one methods.
5. the method that utilization intermediate frequency furnace according to claim 2 reclaims metal in lithium ion battery, it is characterised in that described
Electrolyte be one or more in NaOH, NaCl, KOH and KCl.
6. the method that utilization intermediate frequency furnace according to claim 1 reclaims metal in lithium ion battery, it is characterised in that step
2) fusing time is 30~60min in.
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| CN1172404C (en) * | 2001-08-22 | 2004-10-20 | 财团法人工业技术研究院 | Method for recovering metal from used Li ion cell |
| CN101519726B (en) * | 2009-04-16 | 2011-01-05 | 北京矿冶研究总院 | Method for directly roasting and treating waste lithium ion battery and recycling valuable metal |
| CN101818251B (en) * | 2009-12-09 | 2011-12-14 | 兰州理工大学 | Method for recovering cobalt and lithium from waste lithium ion batteries |
| CN102251097B (en) * | 2011-07-08 | 2012-09-26 | 鞍山鑫普新材料有限公司 | Method for recovering metal from waste lithium battery |
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