CN108220607A - A kind of method that lithium is recycled from waste material containing lithium electrode - Google Patents
A kind of method that lithium is recycled from waste material containing lithium electrode Download PDFInfo
- Publication number
- CN108220607A CN108220607A CN201810155120.7A CN201810155120A CN108220607A CN 108220607 A CN108220607 A CN 108220607A CN 201810155120 A CN201810155120 A CN 201810155120A CN 108220607 A CN108220607 A CN 108220607A
- Authority
- CN
- China
- Prior art keywords
- lithium
- atmosphere
- waste
- roasting
- reduction
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Secondary Cells (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention provides a kind of methods that lithium is recycled from waste material containing lithium electrode.It the described method comprises the following steps：(1) it is roasted under reducing atmosphere to containing lithium electrode waste material, the material after cooling is restored under protective atmosphere after roasting leaches the material after the reduction with leaching agent, separation of solid and liquid obtains lithium-containing solution and solid slag；(2) step (1) described lithium-containing solution is prepared into product containing lithium.Method provided by the invention carries out reduction roasting using reducibility gas, calcination temperature is low, less energy consumption, efficiently separating for lithium and other metallic elements can be realized through step leaching after reduction, the concentration of lithium is high in leachate, the rate of recovery of lithium greatly improves, and recycles the obtained height of product purity containing lithium, can additionally recycle other transition metal elements in waste and old electrode.The method flow of the present invention is short, at low cost, it is easy to accomplish industrial applications.
Description
Technical field
The invention belongs to secondary resource recycling and circular economy technical fields, are related to one kind from waste material containing lithium electrode
The method for recycling lithium.
Background technology
Natural reserves of the lithium in the earth's crust are 11,000,000 tons, account for about the 0.0065% of crustal elements, main in nature
Exist in the form of salt lake bittern, spodumene, lepidolite and peganite ore deposit.Lithium is mainly extracted from containing lithium ore and salt lake bittern,
It applies in lithium ion battery, ceramics, glass and lubricant.China's spodumene ore deposit grade is low, quality is unstable, picks up cost
Height, ore rely primarily on import；Lithium from Salt Lake Brine content is low, and Mg/Li ratio is high, and removal of impurities is complicated.With the exploitation of primary lithium resource
It utilizes, the recycling of secondary lithium resource will be more and more important because of its degree of enrichment height.
Lithium ion battery is with energy density is high, cycle performance is superior, charge efficiency is high, self discharge is small, memory-less effect
Many advantages, such as, it is widely used on power battery and other energy storage materials, for producing new energy electric car and current consumption
Electronic product.Lithium ion battery yield and demand constantly increase severely in recent years, 2005 to 2015 lithium ion batteries it is complete
Ball annual output increases 1200%.Wherein, power-type lithium ion battery will welcome after the growth of new energy electric car burst and scrap
Peak, the recycling market of waste and old lithium ion battery will increase rapidly.Lithium, nickel, cobalt are usually contained in lithium ion cell anode waste
With the valuable metals such as manganese, cannot such as be effectively treated will cause potential threat to environment and human health.On the other hand, these are valuable
Metal has strategic status in following sustainability material and technology.Therefore, slave lithium-ion electric of the exploitation with economic benefit
The technology path of these valuable metals of selective recovery in the anode waste of pond, not only can be to avoid its potential risk, moreover it is possible to realize
Valuable metal recovery utilizes, and lithium ion battery industry is promoted to realize the sustainable development under the new era.
At present lithium ion battery selective extraction recycling mainly using substep recycling method, respectively obtain nickel, cobalt, manganese,
The valuable elements such as lithium.PCT/JP2011/078153 reports a kind of recovery method of high-temperature roasting-liquid agitation-screening separation,
The different salvage material of size is obtained after screening, cobalt and impurity element (such as iron) are efficiently separated.CN101818251A is disclosed
The method of a kind of Call Provision from waste and old lithium ion battery and lithium, by old and useless battery positive pole powder and alkali metal salt in this method
It is roasted after mixing, product obtains leachate after water logging, then respectively obtains cobalt oxalate and lithium carbonate through precipitation.
CN106916955A is disclosed is separately recovered nickel cobalt mixed powder by waste and old lithium ion battery through acidleach, electro-deposition and precipitation, electricity
Product manganese and lithium carbonate.For the universality for the route that develops skill, CN104124487A discloses a kind of utilization liquid phase reactor substep
Recycle cobalt in waste lithium ion batteries, copper, aluminium, lithium method, incorporate alkali leaching, acidleach, have agent extraction method realize electricity
The full constituent recycling of valuable element in pond.
It can be seen that study at present the lithium ion cell anode waste being related to can be separately recovered using nickel, cobalt, manganese and
The recovery process of lithium, especially nickel, cobalt and manganese relative maturity.But it since the selectivity that valuable metal is separately recovered is not strong, leads
It causes recovery process cumbersome, and has secondary pollution governing problem.In addition, the recycling of lithium is often isolating nickel cobalt in studying before
After manganese, lead to lithium loss seriously, the rate of recovery is low, and obtained low concentration lithium-containing solution limits its industrial application value.
The method that CN106129511A discloses comprehensively recovering valuable metal in a kind of material from waste and old lithium ion battery, should
Method (including one kind in lignite, bituminous coal, anthracite or mixes waste lithium ion cell anode material with carbon containing reducer
Object) it mixes or mixes the whole battery of simple crushing with carbonaceous reducing agent, it is carried out at reduction roasting at a temperature of 500~750 DEG C
Reason, product of roasting use CO first2Be carbonized water logging, lithium bicarbonate aqueous solution is obtained, available for producing Li2CO3Product；Water logging slag
Using the valuable elements such as oxidation acid leaching or oxidation ammonia leaching leaching cobalt therein, nickel, manganese, correspondingization is produced after extracting, purifying
Composition powder.This method is that the rate of recovery of lithium is low using traditional carbon thermal reduction, deficiency, and the concentration of lithium is low in leachate.
In view of flourishing for lithium ion old and useless battery recycling industry, it is badly in need of developing a kind of new selective recycling lithium
Technology path realizes the Short-range efficient recycling of lithium.
Invention content
For above-mentioned deficiency in the prior art, the purpose of the present invention is to provide one kind from waste material containing lithium electrode
The method for recycling lithium.Method provided by the invention carries out high-temperature roasting reduction using reducibility gas, and with reference to leaching operation, makes
The rate of recovery of lithium greatly improves, do not introduce secondary pollution, and can also obtain in addition to lithium other transition metal elements simple substance,
Alloy or oxide, technological process is short, and industrial applications prospect is good.
In order to achieve the above object, the present invention uses following technical scheme：
The present invention provides a kind of method that lithium is recycled from waste material containing lithium electrode, the described method comprises the following steps：
(1) it is roasted under reducing atmosphere to containing lithium electrode waste material, cools down and gone back under protective atmosphere after roasting
Material after original leaches the material after the reduction with leaching agent, and separation of solid and liquid obtains lithium-containing solution and solid slag；
(2) step (1) described lithium-containing solution is prepared into product containing lithium.
It is provided by the invention from waste material containing lithium electrode recycle lithium method in, by the use of reducing atmosphere as reducing agent into
Row roasting reduction, because carrying out carbon thermal reduction compared to carbonaceous solids reducing agent, the reduction temperature of gaseous reducing agent is relatively low, leaching
The lithium concentration for going out liquid is higher, and extraction time is short, and the rate of recovery of lithium greatly improves.
In the present invention, lithium-containing solution that step (1) separation of solid and liquid obtains is rich lithium solution, lithium it is dense；And it obtains
Solid slag in, simple substance, alloy or oxide rich in other transition metal elements in electrode waste material in addition to lithium (such as nickel
Cobalt alloy and manganese oxide), it can be separated by simple magnetic separation.
Method flow provided by the invention is short, at low cost, realizes the Short-range efficient selective recovery of lithium, it is easy to accomplish work
Industry application.
Below as currently preferred technical solution, but not as the limitation to technical solution provided by the invention, lead to
Following preferred technical solution is crossed, can preferably reach and realize the technical purpose and advantageous effect of the present invention.
As currently preferred technical solution, in step (1), the reducing atmosphere includes CO atmosphere, H2Atmosphere, SO2
Atmosphere, NO2Atmosphere or NH3In atmosphere any one or at least two combination, it is typical but be non-limiting combination and have：CO
Atmosphere and H2The combination of atmosphere, SO2Atmosphere and NO2The combination of atmosphere, NO2Atmosphere and NH3Combination of atmosphere etc., preferably H2Gas
Atmosphere.Use H2Reduction effect well, and H can be not only played as reducing agent2Accessory products are water after reduction, will not be to ring
Cause any pollution in border.
Preferably, the flow of the reducing atmosphere is 0.1-10L/min, such as 0.1L/min, 0.5L/min, 2L/min,
4L/min, 6L/min, 8L/min or 10L/min etc., it is not limited to cited numerical value, interior other of the numberical range do not arrange
The numerical value of act is equally applicable, preferably 0.2-3L/min.
As currently preferred technical solution, in step (1), the waste material containing lithium electrode gives up for lithium ion cell positive
Material.
Preferably, the lithium ion cell anode waste includes nickle cobalt lithium manganate battery waste, lithium manganate battery waste material, cobalt
In acid lithium battery waste material, lithium nickelate battery waste or iron manganese phosphate for lithium battery waste any one or at least two combination,
It is typical but be non-limiting combination and have：The combination of nickle cobalt lithium manganate battery waste and lithium manganate battery waste material, cobalt acid lithium battery
The combination of waste material and lithium nickelate battery waste, the combination of lithium nickelate battery waste and iron manganese phosphate for lithium battery waste etc..
As currently preferred technical solution, in step (1), the temperature of the roasting is 300-1200 DEG C, such as 300
DEG C, 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C or 1200 DEG C etc., it is not limited to institute
The numerical value enumerated, other interior unrequited numerical value of the numberical range are equally applicable, preferably 400-800 DEG C.In the present invention, use
The benefit of 400 DEG C of -800 DEG C of this preferable temperatures is the reduction that can have not only realized to material, but also is avoided that the energy that excessive temperature is brought
Consume is lost.
Preferably, in step (1), time of the roasting is 0.1-10h, for example, 0.1h, 0.5h, 1h, 2h, 3h, 4h,
5h, 7h, 9h or 10h etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally suitable
With preferably 0.5-4h.
Preferably, in step (1), the roasting carries out in tube furnace.
As currently preferred technical solution, in step (1), the protective atmosphere includes N2Atmosphere and/or Ar atmosphere.
In the present invention, the N2Atmosphere and/or Ar atmosphere refer to that protective atmosphere can be N2Atmosphere, or Ar atmosphere can also be
N2The combination of atmosphere and Ar atmosphere.
As currently preferred technical solution, in step (1), the leaching agent is neutral leaching agent, acid lixiviant
Or alkaline leaching agent, preferably neutral leaching agent.
Preferably, the neutral leaching agent is water.In the present invention, the water as neutral leaching agent can use deionization
Water, to reduce influence of other heteroions to product purity.
As currently preferred technical solution, in step (1), the quality of the material after the reduction and the body of leaching agent
Long-pending solid-to-liquid ratio is 0.1-10000gL-1, such as 0.1gL-1、1g·L-1、10g·L-1、50g·L-1、100g·L-1、
150g·L-1、200g·L-1、250g·L-1、300g·L-1、350g·L-1、400g·L-1、450g·L-1、500g·L-1、
550g·L-1、600g·L-1、650g·L-1、700g·L-1、750g·L-1、800g·L-1、1000g·L-1、5000g·L-1
Or 10000gL-1Deng, it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally applicable,
Preferably 100-800gL-1.Here, using 100-800gL-1The benefit of this preferred solid-to-liquid ratio is that the height of material can be achieved
Effect enrichment, obtains the higher leachate of lithium concentration.
Preferably, in step (1), the temperature of the leaching is 20-100 DEG C, for example, 20 DEG C, 40 DEG C, 60 DEG C, 80 DEG C or
100 DEG C etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally applicable, preferably
40-80℃。
Preferably, in step (1), time of the leaching is 1-600min, for example, 1min, 10min, 50min,
100min, 200min, 300min, 400min, 500min or 600min etc., it is not limited to cited numerical value, the numerical value
In the range of other unrequited numerical value it is equally applicable, preferably 10-200min.
As currently preferred technical solution, in step (1), the separation of solid and liquid is divided to be separated by filtration and/or centrifuge
From being preferably separated by filtration.It is described to be separated by filtration and/or centrifuge refer to be to be separated by filtration in the present invention, it can also
Can also be the combination for being separated by filtration and centrifuging to centrifuge.
As optimal technical scheme of the present invention, in step (2), the product containing lithium is lithium carbonate and/or a hydrated hydroxide
Change lithium.In the present invention, the lithium carbonate and/or a hydronium(ion) lithia refer to can be lithium carbonate, or a hydronium(ion)
Lithia can also be the combination of lithium carbonate and a hydronium(ion) lithia.
Preferably, when in step (2), when the product containing lithium is lithium carbonate, the method for preparing the product containing lithium is heavy for addition
Shallow lake agent and/or carbonaceous gas is passed through, is preferably passed through carbonaceous gas.It is described to add precipitating reagent and/or be passed through carbon containing in the present invention
Gas refers to can be addition precipitating reagent, or is passed through carbonaceous gas, can also be to add precipitating reagent and be passed through carbon containing gas
The combination of body had not only added precipitating reagent but also had been passed through carbonaceous gas.
Preferably, the precipitating reagent includes ammonium hydrogen carbonate and/or sodium carbonate.In the present invention, the ammonium hydrogen carbonate and/or carbon
Sour sodium refers to can be ammonium hydrogen carbonate, or sodium carbonate can also be the combination of ammonium hydrogen carbonate and sodium carbonate.
Preferably, the carbonaceous gas includes carbon dioxide.
Preferably, when being passed through carbonaceous gas, the flow of carbonaceous gas is 0.01-10Lmin-1, such as 0.01L
min-1、0.1L·min-1、0.5L·min-1、1L·min-1、1.5L·min-1、2L·min-1、4L·min-1、6L·min-1、
8L·min-1Or 10Lmin-1Deng it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range
It is equally applicable, preferably 0.1-2Lmin-1。
Preferably, when in step (2), when the product containing lithium is a hydronium(ion) lithia, the method for preparing the product containing lithium
For distillation and concentration.Method provided by the invention can obtain purity when using distillation and concentration one hydronium(ion) lithia of preparation and be more than
A 99% hydronium(ion) lithia.
Preferably, the distillation and concentration carries out in crystallizing evaporator.
As the further preferred technical solution of the method for the invention, the described method comprises the following steps：
(1) in the H of 0.1-10L/min2Lithium ion cell anode waste is roasted under atmosphere, calcination temperature 300-
1200 DEG C, roasting time 0.1-10h, the material after cooling is restored under protective atmosphere after roasting, after the reduction
Material leached at 25-100 DEG C with water, extraction time 10-200min is separated by filtration to obtain lithium-containing solution and solid
Slag；Wherein, the solid-to-liquid ratio of the volume of the quality and water of the material after the reduction is 100-800gL-1；
(2) step (1) described lithium-containing solution is placed in crystallizing evaporator and carries out distillation and concentration, obtain hydronium(ion) oxidation
Lithium.
Compared with the prior art, the present invention has the advantages that：
(1) method provided by the invention that lithium is recycled from waste material containing lithium electrode carries out reduction roasting using reducing atmosphere
It burns, calcination temperature is low, less energy consumption, and efficiently separating for lithium and other metallic elements, leaching can be realized through step leaching after reduction
The concentration of lithium is high in liquid, and the rate of recovery of lithium greatly improves, and reaches more than 95%, and recycles obtained product purity containing lithium and be up to
More than 99%；
(2) in the method provided by the invention that lithium is recycled from waste material containing lithium electrode, what separation of solid and liquid obtained after leaching consolidates
Body slag is rich in the simple substance of other transition metal elements in addition to lithium in electrode waste material, alloy or oxide (such as nickel cobalt (alloy)
And manganese oxide), it can be separated by simple magnetic separation；
(3) method flow provided by the invention that lithium is recycled from waste material containing lithium electrode is short, can be to avoid using soda acid band
The secondary pollution come and liquid waste processing, it is at low cost, realize the Short-range efficient selective recovery of lithium, it is easy to accomplish industrialization should
With.
Description of the drawings
Fig. 1 is the process flow chart for the method that lithium is recycled from waste material containing lithium electrode that the embodiment of the present invention 1 provides.
Specific embodiment
For the present invention is better described, technical scheme of the present invention is easy to understand, below to the present invention further specifically
It is bright.But following embodiments is only the simple example of the present invention, does not represent or limit the scope of the present invention, this
Invention protection domain is subject to claims.
But non-limiting example typical for the present invention below：
Embodiment 1
The present embodiment provides a kind of method that lithium is recycled from waste material containing lithium electrode, specific method is：
Lithium ion cell anode waste (cobalt acid lithium battery anode waste) is placed in tube furnace, being passed through gas flow is
1.0L·min-1H2, the furnace cooling after reduction roasting 1 hour at 800 DEG C, gas uses 0.2Lmin instead during cooling-1Ar.
Material after restoring in right amount is taken, by 200gL-1Solid-to-liquid ratio adds in deionized water, is placed in 50 DEG C of water-baths and leaches 60min, passes through
Filter obtains rich lithium aqueous solution and filter residue.
Rich lithium aqueous solution is distilled using crystallizing evaporator and prepares product containing lithium, obtains a hydronium(ion) lithia.
The technological process of the method provided in this embodiment that lithium is recycled from waste material containing lithium electrode is as shown in Figure 1.
In the present embodiment, detected through inductive coupling plasma emission spectrograph (ICP-OES), rich lithium aqueous solution lithium concentration
For 16.9gL-1.It is analyzed through X-ray diffraction (XRD), the main object of filter residue is mutually metallic cobalt.The hydronium(ion) oxidation finally obtained
Lithium purity is 99.6% (mass fraction), and the rate of recovery of lithium is 97.8%.
It is detected with inductive coupling plasma emission spectrograph (ICP-OES), the cobalt acid lithium battery anode that this implementation uses
Waste material is as shown in table 1 into being grouped as.
1. waste and old cobalt acid lithium battery positive electrode metallic element of table
| Metal | Li | Al | Ni | Co | Mn |
| Content, wt% | 6.81 | 0.52 | 0.03 | 59.23 | 0.01 |
Embodiment 2
The present embodiment provides a kind of method that lithium is recycled from waste material containing lithium electrode, specific method is：
Nickle cobalt lithium manganate anode waste is placed in tube furnace, is passed through gas flow as 0.5Lmin-1H2, at 700 DEG C
Furnace cooling after lower roasting 4 hours, gas uses 0.2Lmin instead during cooling-1Ar.Material after restoring in right amount is taken, by 100g
L-1Solid-to-liquid ratio adds in deionized water, is placed in 60 DEG C of water-baths and leaches 20min, filtered to obtain rich lithium aqueous solution and filter residue.
At room temperature 0.1Lmin is passed through into rich lithium aqueous solution-1Carbon dioxide, Precipitation lithium carbonate.
It in the present embodiment, is detected through ICP-OES, rich lithium aqueous solution lithium concentration is 8.3gL-1.Through XRD analysis, filter residue master
It is mutually metal nickel cobalt (alloy) and manganese oxide to want object.The lithium carbonate purity finally obtained is 99.8%, and the rate of recovery of lithium is 96.2%.
It is detected through ICP-OES, the nickle cobalt lithium manganate battery (LiNi that the present embodiment uses0.5Co0.2Mn0.3O2) anode waste
Ingredient is as shown in table 2.
2. waste and old nickle cobalt lithium manganate (LiNi of table0.5Co0.2Mn0.3O2) cell positive material metallic element
| Metal | Li | Al | Ni | Co | Mn |
| Content, wt% | 6.69 | 0.20 | 28.64 | 12.10 | 16.45 |
Embodiment 3
The present embodiment provides a kind of method that lithium is recycled from waste material containing lithium electrode, specific method is：
Nickle cobalt lithium manganate cell anode waste is placed in tube furnace, is passed through gas flow as 1.5Lmin-1H2,
Furnace cooling after being roasted 1 hour at 700 DEG C, gas uses 0.1Lmin instead during cooling-1Ar.Material after restoring in right amount is taken, is pressed
300g·L-1Solid-to-liquid ratio add in deionized water, be placed in 60 DEG C of water-baths and leach 100min, it is filtered obtain rich lithium aqueous solution and
Filter residue.
At room temperature 0.5Lmin is passed through into rich lithium aqueous solution-1Carbon dioxide, Precipitation lithium carbonate.
It in the present embodiment, is detected through ICP-OES, rich lithium aqueous solution lithium concentration is 20.8gL-1.Through XRD analysis, filter residue master
It is mutually metal nickel cobalt (alloy) and manganese oxide to want object.The lithium carbonate purity finally obtained is 99.7%, and the rate of recovery of lithium is 97.5%.
It is detected through ICP-OES, the nickle cobalt lithium manganate battery (LiNi that the present embodiment uses0.3Co0.3Mn0.3O2) anode waste
Ingredient is as shown in table 3.
3. waste and old nickle cobalt lithium manganate (LiNi of table0.3Co0.3Mn0.3O2) cell positive material metallic element
| Metal | Li | Al | Ni | Co | Mn |
| Content, wt% | 6.71 | 0.19 | 20.64 | 20.10 | 18.45 |
Embodiment 4
The present embodiment provides a kind of method that lithium is recycled from waste material containing lithium electrode, specific method is：
Anode waste is placed in tube furnace, is passed through gas flow as 2Lmin-1H2, it is small that 1.5 are roasted at 450 DEG C
When after furnace cooling, gas uses 0.2Lmin instead during cooling-1Ar.Material after restoring in right amount is taken, by 400gL-1Solid-to-liquid ratio
Deionized water is added in, is placed in 30 DEG C of water-baths and leaches 200min, it is filtered to obtain rich lithium aqueous solution and filter residue.
Rich lithium aqueous solution is distilled using crystallizing evaporator, obtains a hydronium(ion) lithia.
It in the present embodiment, is detected through ICP-OES, rich lithium aqueous solution lithium concentration is 21.9gL-1.Through XRD analysis, filter residue master
It is mutually metal nickel cobalt (alloy) and manganese oxide to want object.The hydronium(ion) lithia purity finally obtained is 99.3%, the rate of recovery of lithium
It is 97.8%.
It is detected through ICP-OES, the nickle cobalt lithium manganate battery (LiNi that the present embodiment uses0.8Co0.1Mn0.1O2) anode waste
Ingredient is as shown in table 4.
4. waste and old nickle cobalt lithium manganate (LiNi of table0.3Co0.3Mn0.3O2) cell positive material metallic element
| Metal | Li | Al | Ni | Co | Mn |
| Content, wt% | 6.88 | 0.12 | 44.64 | 6.01 | 5.64 |
Embodiment 5
The present embodiment provides a kind of method that lithium is recycled from waste material containing lithium electrode, specific method is：
Anode waste is placed in tube furnace, is passed through gas flow as 0.8Lmin-1H2, it is small that 3 are roasted at 500 DEG C
When after furnace cooling, gas uses 0.2Lmin instead during cooling-1N2.Material after restoring in right amount is taken, by 100gL-1Solid-to-liquid ratio adds
Enter deionized water, be placed in 20 DEG C of water-baths and leach 100min, it is filtered to obtain rich lithium aqueous solution and filter residue.
At room temperature 1Lmin is passed through into rich lithium aqueous solution-1Carbon dioxide, Precipitation lithium carbonate.
It in the present embodiment, is detected through ICP-OES, rich lithium aqueous solution lithium concentration is 8.9gL-1.Through XRD analysis, filter residue master
It is mutually manganese oxide to want object.The lithium carbonate purity finally obtained is 99.6%, and the rate of recovery of lithium is 95.8%.
It is detected through ICP-OES, the lithium manganate cell positive electrode waste material ingredient that the present embodiment uses is as shown in table 5.
5. anode material of wasted lithium manganate battery metallic element of table
| Metal | Li | Al | Ni | Co | Mn |
| Content, wt% | 3.55 | 0.08 | 0.02 | 0.01 | 58.89 |
Embodiment 6
The present embodiment provides a kind of method that lithium is recycled from waste material containing lithium electrode, specific method is：
Anode waste is placed in tube furnace, is passed through gas flow as 3Lmin-1H2, it is small that 0.5 is roasted at 500 DEG C
When after furnace cooling, gas uses 0.2Lmin instead during cooling-1Ar.Material after restoring in right amount is taken, by 500gL-1Solid-to-liquid ratio
Deionized water is added in, is placed in 50 DEG C of water-baths and leaches 30min, it is filtered to obtain rich lithium aqueous solution and filter residue.
Rich lithium aqueous solution is distilled using crystallizing evaporator, obtains a hydronium(ion) lithia.
It in the present embodiment, is detected through ICP-OES, rich lithium aqueous solution lithium concentration is 23.8gL-1.Through XRD analysis, filter residue master
It is mutually metal nickel cobalt (alloy) and manganese oxide to want object.The hydronium(ion) lithia purity finally obtained is 99.5%, the rate of recovery of lithium
It is 96.9%.
It is detected through ICP-OES, the nickle cobalt lithium manganate battery (LiNi that the present embodiment uses0.5Co0.2Mn0.3O2) anode waste
Ingredient is as shown in table 6.
6. waste and old nickle cobalt lithium manganate (LiNi of table0.5Co0.2Mn0.3O2) cell positive material metallic element
| Metal | Li | Al | Ni | Co | Mn |
| Content, wt% | 6.69 | 0.20 | 28.64 | 12.10 | 16.45 |
Embodiment 7
The present embodiment provides a kind of method that lithium is recycled from waste material containing lithium electrode, specific method is：
Nickle cobalt lithium manganate anode waste is placed in tube furnace, is passed through gas flow as 0.1Lmin-1H2, at 400 DEG C
Furnace cooling after lower roasting 0.5 hour, gas uses 0.2Lmin instead during cooling-1Ar.Material after restoring in right amount is taken, is pressed
800g·L-1Solid-to-liquid ratio adds in deionized water, is placed in 100 DEG C of water-baths and leaches 1min, filtered to obtain rich lithium aqueous solution and filter
Slag.
At room temperature 0.01Lmin is passed through into rich lithium aqueous solution-1Carbon dioxide, Precipitation lithium carbonate.
It in the present embodiment, is detected through ICP-OES, rich lithium aqueous solution lithium concentration is 26.8gL-1.Through XRD analysis, filter residue master
It is mutually metal nickel cobalt (alloy) and manganese oxide to want object.The lithium carbonate purity finally obtained is 99.2%, and the rate of recovery of lithium is 96.9%.
Nickle cobalt lithium manganate battery (the LiNi that the present embodiment uses0.5Co0.2Mn0.3O2) anode waste ingredient makes with embodiment 2
It is identical.
Embodiment 8
The present embodiment provides a kind of method that lithium is recycled from waste material containing lithium electrode, specific method is：
Nickle cobalt lithium manganate anode waste is placed in tube furnace, is passed through gas flow as 0.2Lmin-1CO, at 300 DEG C
Furnace cooling after lower roasting 10 hours, gas uses 0.2Lmin instead during cooling-1Ar.Material after restoring in right amount is taken, is pressed
1000g·L-1Solid-to-liquid ratio add in deionized water, be placed in 40 DEG C of water-baths and leach 600min, it is filtered obtain rich lithium aqueous solution and
Filter residue.
At room temperature 2Lmin is passed through into rich lithium aqueous solution-1Carbon dioxide, Precipitation lithium carbonate.
It in the present embodiment, is detected through ICP-OES, rich lithium aqueous solution lithium concentration is 26.9gL-1.Through XRD analysis, filter residue master
It is mutually metal nickel cobalt (alloy) and manganese oxide to want object.The lithium carbonate purity finally obtained is 99.1%%, and the rate of recovery of lithium is
95.6%.
Nickle cobalt lithium manganate battery (the LiNi that the present embodiment uses0.5Co0.2Mn0.3O2) anode waste ingredient makes with embodiment 2
It is identical.
Embodiment 9
The present embodiment provides a kind of method that lithium is recycled from waste material containing lithium electrode, specific method is：
Nickle cobalt lithium manganate anode waste is placed in tube furnace, is passed through gas flow as 10Lmin-1NH3, 1200
Furnace cooling after being roasted 0.1 hour at DEG C, gas uses 0.2Lmin instead during cooling-1Ar.Material after restoring in right amount is taken, is pressed
10000g·L-1Solid-to-liquid ratio add in deionized water, be placed in 80 DEG C of water-baths and leach 10min, it is filtered obtain rich lithium aqueous solution and
Filter residue.
At room temperature 10Lmin is passed through into rich lithium aqueous solution-1Carbon dioxide, Precipitation lithium carbonate.
It in the present embodiment, is detected through ICP-OES, rich lithium aqueous solution lithium concentration is 27.1gL-1.Through XRD analysis, filter residue master
It is mutually metal nickel cobalt (alloy) and manganese oxide to want object.The lithium carbonate purity finally obtained is 99.3%, and the rate of recovery of lithium is 96.6%.
Nickle cobalt lithium manganate battery (the LiNi that the present embodiment uses0.5Co0.2Mn0.3O2) anode waste ingredient makes with embodiment 2
It is identical.
Embodiment 10
The present embodiment provides a kind of methods that lithium is recycled from waste material containing lithium electrode, and specific method is with reference to embodiment 2, area
It is not：In step (2), enough precipitating reagent sodium carbonate, Precipitation lithium carbonate are added into rich lithium aqueous solution at room temperature.
It in the present embodiment, is detected through ICP-OES, rich lithium aqueous solution lithium concentration is 8.3gL-1.Through XRD analysis, filter residue master
It is mutually metal nickel cobalt (alloy) and manganese oxide to want object.The lithium carbonate purity finally obtained is 99.8%, and the rate of recovery of lithium is 96.6%.
Comparative example 1
For the specific method of this comparative example with reference to embodiment 1, difference lies in step (1), be not passed through reproducibility H2Atmosphere,
And lignite is used as reducing agent.Other operations are same as Example 1.
As a result, in this comparative example, detected through ICP-OES, rich lithium aqueous solution lithium concentration is 0.5gL-1.Through XRD points
Analysis, the main object of filter residue is mutually metallic cobalt.The lithium carbonate purity finally obtained is 82.5% (mass fraction), and the rate of recovery of lithium is
26.5%.
Comparative example 2
For the specific method of this comparative example with reference to embodiment 4, difference lies in step (1), be not passed through reproducibility H2Atmosphere,
And it is changed to be passed through inert gas Ar atmosphere.Other operations are same as Example 4.
As a result, lithium concentration is 5.2mgL in filtrate-1, through XRD analysis, the main object of filter residue is mutually nickel cobalt mangaic acid respectively
Lithium (LiNi0.8Co0.1Mn0.1O2), significant change does not occur for the nickle cobalt lithium manganate without reducing material roasting, fails to realize lithium
Selective recovery.
Comparative example 3
For the specific method of this comparative example with reference to embodiment 5, difference lies in step (1), be not passed through reproducibility H2Atmosphere,
And it is changed to be passed through inert gas Ar atmosphere.Other operations are same as Example 5.
As a result, as a result, lithium concentration is 3.5mgL in filtrate-1, through XRD analysis, the main object of filter residue is mutually distinguished
It is LiMn2O4, significant change does not occur for the LiMn2O4 without reducing material roasting, fails to realize the selective recovery of lithium.
Comparative example 4
For the specific method of this comparative example with reference to embodiment 6, difference lies in step (1), be not passed through reproducibility H2Atmosphere,
And it is changed to be passed through inert gas Ar atmosphere.Other operations are same as Example 6.
As a result, lithium concentration is 4.5mgL in filtrate-1, through XRD analysis, the main object of filter residue is mutually nickel cobalt mangaic acid respectively
Lithium (LiNi0.5Co0.2Mn0.3O2), significant change does not occur for the nickle cobalt lithium manganate without reducing material roasting, fails to realize lithium
Selective recovery.
Summary embodiment and comparative example it is found that method provided by the invention carries out reduction roasting with reducing atmosphere,
Calcination temperature is low, less energy consumption, efficiently separating for lithium and other metallic elements can be realized through step leaching after reduction, in leachate
The concentration of lithium is high, and the rate of recovery of lithium greatly improves, and it is high to recycle obtained product purity containing lithium.Comparative example does not use this hair
Bright scheme, thus the effect of the present invention can not be obtained.
Applicant states that the present invention illustrates the detailed process equipment of the present invention and technological process by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological processes, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, selection of concrete mode etc. all fall within the present invention's
Within protection domain and the open scope.
Claims (10)
- A kind of 1. method that lithium is recycled from waste material containing lithium electrode, which is characterized in that the described method comprises the following steps：(1) it is roasted under reducing atmosphere to containing lithium electrode waste material, after cooling obtains reduction under protective atmosphere after roasting Material, the material after the reduction is leached with leaching agent, separation of solid and liquid obtains lithium-containing solution and solid slag；(2) step (1) described lithium-containing solution is prepared into product containing lithium.
- 2. according to the method described in claim 1, it is characterized in that, in step (1), the reducing atmosphere includes CO atmosphere, H2 Atmosphere, SO2Atmosphere, NO2Atmosphere or NH3In atmosphere any one or at least two combination, preferably H2Atmosphere；Preferably, the flow of the reducing atmosphere is 0.1-10L/min, preferably 0.2-3L/min.
- 3. method according to claim 1 or 2, which is characterized in that in step (1), the waste material containing lithium electrode for lithium from Sub- cell anode waste；Preferably, the lithium ion cell anode waste includes nickle cobalt lithium manganate battery waste, lithium manganate battery waste material, cobalt acid lithium In battery waste, lithium nickelate battery waste or iron manganese phosphate for lithium battery waste any one or at least two combination.
- 4. according to claim 1-3 any one of them methods, which is characterized in that in step (1), the temperature of the roasting is 300-1200 DEG C, preferably 400-800 DEG C；Preferably, in step (1), the time of the roasting is 0.1-10h, preferably 0.5-4h；Preferably, in step (1), the roasting carries out in tube furnace.
- 5. according to claim 1-4 any one of them methods, which is characterized in that in step (1), the protective atmosphere includes N2 Atmosphere and/or Ar atmosphere.
- 6. according to claim 1-5 any one of them methods, which is characterized in that in step (1), the leaching agent is soaked to be neutral Go out agent, acid lixiviant or alkaline leaching agent, preferably neutral leaching agent；Preferably, the neutral leaching agent is water.
- 7. according to claim 1-6 any one of them methods, which is characterized in that in step (1), material after the reduction The solid-to-liquid ratio of quality and the volume of leaching agent is 0.1-10000gL-1, preferably 100-800gL-1；Preferably, in step (1), the temperature of the leaching is 20-100 DEG C, preferably 40-80 DEG C；Preferably, in step (1), the time of the leaching is 1-600min, preferably 10-200min.
- 8. according to claim 1-7 any one of them methods, which is characterized in that in step (1), the separation of solid and liquid is filtering Separation and/or centrifugation, are preferably separated by filtration.
- 9. according to claim 1-8 any one of them methods, which is characterized in that in step (2), the product containing lithium is carbonic acid Lithium and/or a hydronium(ion) lithia；Preferably, when in step (2), when the product containing lithium is lithium carbonate, the method for preparing the product containing lithium is addition precipitating reagent And/or carbonaceous gas is passed through, preferably it is passed through carbonaceous gas；Preferably, the precipitating reagent includes ammonium hydrogen carbonate and/or sodium carbonate；Preferably, the carbonaceous gas includes carbon dioxide；Preferably, when being passed through carbonaceous gas, the flow of carbonaceous gas is 0.01-10Lmin-1, preferably 0.1-2Lmin-1；Preferably, when in step (2), when the product containing lithium is a hydronium(ion) lithia, the method for preparing the product containing lithium is steaming Evaporate concentration；Preferably, the distillation and concentration carries out in crystallizing evaporator.
- 10. according to claim 1-9 any one of them methods, which is characterized in that the described method comprises the following steps：(1) in the H of 0.1-10L/min2Lithium ion cell anode waste is roasted under atmosphere, calcination temperature 300-1200 DEG C, roasting time 0.1-10h, the material after cooling is restored under protective atmosphere after roasting, by the object after the reduction Material is leached with water at 25-100 DEG C, and extraction time 10-200min is separated by filtration to obtain lithium-containing solution and solid slag； Wherein, the solid-to-liquid ratio of the volume of the quality and water of the material after the reduction is 100-800gL-1；(2) step (1) described lithium-containing solution is placed in crystallizing evaporator and carries out distillation and concentration, obtain a hydronium(ion) lithia.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810155120.7A CN108220607A (en) | 2018-02-23 | 2018-02-23 | A kind of method that lithium is recycled from waste material containing lithium electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810155120.7A CN108220607A (en) | 2018-02-23 | 2018-02-23 | A kind of method that lithium is recycled from waste material containing lithium electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108220607A true CN108220607A (en) | 2018-06-29 |
Family
ID=62662047
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810155120.7A Pending CN108220607A (en) | 2018-02-23 | 2018-02-23 | A kind of method that lithium is recycled from waste material containing lithium electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108220607A (en) |
Cited By (41)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108808155A (en) * | 2018-08-17 | 2018-11-13 | 湖南金凯循环科技有限公司 | A method of by waste lithium ion cell anode material preparation battery-level lithium carbonate |
| CN108977665A (en) * | 2018-08-17 | 2018-12-11 | 湖南金凯循环科技有限公司 | A method of recycling waste and old lithium manganese phosphate |
| CN109133117A (en) * | 2018-08-17 | 2019-01-04 | 湖南金凯循环科技有限公司 | A method of battery-level lithium carbonate is prepared by waste metal lithium battery |
| CN109881013A (en) * | 2019-04-02 | 2019-06-14 | 中国恩菲工程技术有限公司 | The method of valuable metal element is recycled from waste lithium ion cell anode material |
| CN109987617A (en) * | 2019-05-13 | 2019-07-09 | 中国科学院过程工程研究所 | A method of shraff containing lithium prepares lithium hydroxide |
| CN110040751A (en) * | 2019-05-13 | 2019-07-23 | 中国科学院过程工程研究所 | A kind of recycling processing method of the shraff containing lithium |
| CN110304666A (en) * | 2019-03-06 | 2019-10-08 | 清华大学 | A method of recycling valuable element from waste lithium ion cell anode material |
| CN110343864A (en) * | 2019-07-24 | 2019-10-18 | 中国矿业大学 | The method that microwave calcining auxiliary recycles lithium and cobalt in waste and old electrode material |
| CN110371943A (en) * | 2019-06-28 | 2019-10-25 | 湖南邦普循环科技有限公司 | A kind of selective recovery technique of nickle cobalt lithium manganate and LiFePO4 mixing waste |
| CN110408796A (en) * | 2019-08-05 | 2019-11-05 | 江西理工大学 | A kind of flash reduction method that efficient selective mentions lithium from waste lithium cell |
| CN110498434A (en) * | 2019-07-26 | 2019-11-26 | 长沙佳纳锂业科技有限公司 | A kind of recovery method of anode active material of lithium ion battery and its application |
| CN110714124A (en) * | 2019-10-16 | 2020-01-21 | 厦门钨业股份有限公司 | Method for extracting cobalt from tungsten waste recovery slag |
| CN110714125A (en) * | 2019-10-16 | 2020-01-21 | 厦门钨业股份有限公司 | Method for extracting cobalt from tungsten waste smelting slag |
| CN110835693A (en) * | 2019-10-16 | 2020-02-25 | 厦门钨业股份有限公司 | Method for extracting cobalt from tungsten waste smelting slag |
| CN111172396A (en) * | 2019-12-30 | 2020-05-19 | 银隆新能源股份有限公司 | Method for recovering metal elements in lithium battery anode and cathode materials |
| CN111463475A (en) * | 2020-03-11 | 2020-07-28 | 长沙有色冶金设计研究院有限公司 | Method for selectively recycling waste power lithium battery positive electrode material |
| CN111924892A (en) * | 2020-07-24 | 2020-11-13 | 中国科学院过程工程研究所 | Method for selectively recovering lithium ion battery electrode powder |
| CN111994966A (en) * | 2020-07-20 | 2020-11-27 | 中南大学 | Method for recycling waste ternary positive electrode under high-temperature condition of hydrogen sulfide atmosphere |
| CN112259821A (en) * | 2020-10-22 | 2021-01-22 | 中钢集团南京新材料研究院有限公司 | Method for recovering valuable metals from waste lithium ion batteries |
| CN112400029A (en) * | 2018-07-10 | 2021-02-23 | 巴斯夫欧洲公司 | Method for recycling spent lithium ion battery cells |
| CN112481493A (en) * | 2019-09-11 | 2021-03-12 | 荆门市格林美新材料有限公司 | Method for recovering valuable metals from ternary positive electrode materials of waste power batteries |
| CN112582601A (en) * | 2020-12-14 | 2021-03-30 | 中钢集团南京新材料研究院有限公司 | Method for preparing lithium nickel manganese oxide by utilizing waste lithium manganese oxide and lithium nickel manganese oxide |
| CN112575203A (en) * | 2020-12-07 | 2021-03-30 | 金川集团股份有限公司 | Method for recycling lithium in waste power lithium battery |
| CN112680598A (en) * | 2020-12-15 | 2021-04-20 | 中南大学 | Method for low-cost clean treatment of waste lithium ion battery anode material |
| CN113106257A (en) * | 2021-04-12 | 2021-07-13 | 广东佳纳能源科技有限公司 | Recycling method of lithium battery waste and application thereof |
| CN113149039A (en) * | 2021-04-30 | 2021-07-23 | 四川万邦胜辉新能源科技有限公司 | Method for preparing lithium oxide by thermally reducing spodumene |
| CN113186410A (en) * | 2021-04-27 | 2021-07-30 | 中国恩菲工程技术有限公司 | Method for recovering valuable metal lithium from waste lithium ion battery anode material |
| CN113422122A (en) * | 2021-06-28 | 2021-09-21 | 郑州大学 | Waste battery lithium resource recovery method based on solid electrolyte |
| WO2021218510A1 (en) * | 2020-05-01 | 2021-11-04 | XProEM Ltd. | Process for recovering lithium and transition metals from waste cathode of spent lithium ion battery |
| CN113784922A (en) * | 2019-12-16 | 2021-12-10 | 株式会社Lg化学 | Method for separating transition metal from waste positive electrode material |
| CN113832349A (en) * | 2021-09-22 | 2021-12-24 | 荆门市格林美新材料有限公司 | Method for recovering lithium, nickel, cobalt and manganese from battery waste |
| CN113999967A (en) * | 2021-11-02 | 2022-02-01 | 赣州有色冶金研究所有限公司 | Method for recovering lithium in lithium ion battery anode material |
| CN114015881A (en) * | 2021-10-28 | 2022-02-08 | 中国科学院广州能源研究所 | Method for recovering valuable metals by in-situ thermal reduction of waste lithium battery cathode materials |
| CN114207162A (en) * | 2019-07-26 | 2022-03-18 | 巴斯夫欧洲公司 | Method for recovering lithium and other metals from spent lithium ion batteries |
| CN114335781A (en) * | 2021-12-27 | 2022-04-12 | 上海电力大学 | Method for extracting precious metal from waste lithium battery |
| CN114368766A (en) * | 2021-12-22 | 2022-04-19 | 威立雅新能源科技(江门)有限公司 | Method for extracting lithium from waste lithium ion battery and application thereof |
| US20220194806A1 (en) * | 2020-12-22 | 2022-06-23 | Pukyong National University Industry-University Cooperation Foundation | Lithium oxide recovery method from lithium manganese oxide (lmo) |
| CN114867690A (en) * | 2019-12-26 | 2022-08-05 | Sk新技术株式会社 | Method for recovering precursor of positive electrode active material |
| CN115103813A (en) * | 2020-02-10 | 2022-09-23 | Sk新技术株式会社 | Method for recovering active metal of lithium secondary battery |
| CN115175876A (en) * | 2020-02-27 | 2022-10-11 | Sk新技术株式会社 | Method for recovering active metal of lithium secondary battery |
| CN116742173A (en) * | 2023-04-10 | 2023-09-12 | 湖南金凯循环科技有限公司 | Reduction roasting method for recycling ternary lithium battery waste |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004011010A (en) * | 2002-06-11 | 2004-01-15 | Sumitomo Metal Mining Co Ltd | Method for recovering lithium and cobalt from lithium cobaltate |
| CN106129511A (en) * | 2016-06-27 | 2016-11-16 | 北京科技大学 | A kind of method of comprehensively recovering valuable metal from waste and old lithium ion battery material |
| CN106834703A (en) * | 2017-03-30 | 2017-06-13 | 中南大学 | A kind of leaching method of waste lithium ion cell anode active material |
| CN107017443A (en) * | 2017-03-28 | 2017-08-04 | 北京科技大学 | A kind of method of the comprehensively recovering valuable metal from waste and old lithium ion battery |
| CN107611514A (en) * | 2017-09-18 | 2018-01-19 | 库特勒环保科技（苏州）有限公司 | A kind of based lithium-ion battery positive plate regenerative system and its method |
| CN107666022A (en) * | 2017-09-25 | 2018-02-06 | 湖南工业大学 | Lithium, the recovery method of nickel cobalt manganese in a kind of discarded tertiary cathode material |
-
2018
- 2018-02-23 CN CN201810155120.7A patent/CN108220607A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004011010A (en) * | 2002-06-11 | 2004-01-15 | Sumitomo Metal Mining Co Ltd | Method for recovering lithium and cobalt from lithium cobaltate |
| CN106129511A (en) * | 2016-06-27 | 2016-11-16 | 北京科技大学 | A kind of method of comprehensively recovering valuable metal from waste and old lithium ion battery material |
| CN107017443A (en) * | 2017-03-28 | 2017-08-04 | 北京科技大学 | A kind of method of the comprehensively recovering valuable metal from waste and old lithium ion battery |
| CN106834703A (en) * | 2017-03-30 | 2017-06-13 | 中南大学 | A kind of leaching method of waste lithium ion cell anode active material |
| CN107611514A (en) * | 2017-09-18 | 2018-01-19 | 库特勒环保科技（苏州）有限公司 | A kind of based lithium-ion battery positive plate regenerative system and its method |
| CN107666022A (en) * | 2017-09-25 | 2018-02-06 | 湖南工业大学 | Lithium, the recovery method of nickel cobalt manganese in a kind of discarded tertiary cathode material |
Cited By (50)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112400029A (en) * | 2018-07-10 | 2021-02-23 | 巴斯夫欧洲公司 | Method for recycling spent lithium ion battery cells |
| CN108977665A (en) * | 2018-08-17 | 2018-12-11 | 湖南金凯循环科技有限公司 | A method of recycling waste and old lithium manganese phosphate |
| CN109133117A (en) * | 2018-08-17 | 2019-01-04 | 湖南金凯循环科技有限公司 | A method of battery-level lithium carbonate is prepared by waste metal lithium battery |
| CN108808155A (en) * | 2018-08-17 | 2018-11-13 | 湖南金凯循环科技有限公司 | A method of by waste lithium ion cell anode material preparation battery-level lithium carbonate |
| CN110304666B (en) * | 2019-03-06 | 2021-12-28 | 清华大学 | Method for recovering valuable elements from waste lithium ion battery anode material |
| CN110304666A (en) * | 2019-03-06 | 2019-10-08 | 清华大学 | A method of recycling valuable element from waste lithium ion cell anode material |
| CN109881013A (en) * | 2019-04-02 | 2019-06-14 | 中国恩菲工程技术有限公司 | The method of valuable metal element is recycled from waste lithium ion cell anode material |
| CN110040751A (en) * | 2019-05-13 | 2019-07-23 | 中国科学院过程工程研究所 | A kind of recycling processing method of the shraff containing lithium |
| CN109987617A (en) * | 2019-05-13 | 2019-07-09 | 中国科学院过程工程研究所 | A method of shraff containing lithium prepares lithium hydroxide |
| CN110371943A (en) * | 2019-06-28 | 2019-10-25 | 湖南邦普循环科技有限公司 | A kind of selective recovery technique of nickle cobalt lithium manganate and LiFePO4 mixing waste |
| CN110343864A (en) * | 2019-07-24 | 2019-10-18 | 中国矿业大学 | The method that microwave calcining auxiliary recycles lithium and cobalt in waste and old electrode material |
| CN110498434A (en) * | 2019-07-26 | 2019-11-26 | 长沙佳纳锂业科技有限公司 | A kind of recovery method of anode active material of lithium ion battery and its application |
| CN114207162A (en) * | 2019-07-26 | 2022-03-18 | 巴斯夫欧洲公司 | Method for recovering lithium and other metals from spent lithium ion batteries |
| CN110408796B (en) * | 2019-08-05 | 2021-08-10 | 江西理工大学 | Method for efficiently and selectively extracting lithium from waste lithium batteries through flash reduction |
| CN110408796A (en) * | 2019-08-05 | 2019-11-05 | 江西理工大学 | A kind of flash reduction method that efficient selective mentions lithium from waste lithium cell |
| CN112481493A (en) * | 2019-09-11 | 2021-03-12 | 荆门市格林美新材料有限公司 | Method for recovering valuable metals from ternary positive electrode materials of waste power batteries |
| CN110714125A (en) * | 2019-10-16 | 2020-01-21 | 厦门钨业股份有限公司 | Method for extracting cobalt from tungsten waste smelting slag |
| CN110835693A (en) * | 2019-10-16 | 2020-02-25 | 厦门钨业股份有限公司 | Method for extracting cobalt from tungsten waste smelting slag |
| CN110714124A (en) * | 2019-10-16 | 2020-01-21 | 厦门钨业股份有限公司 | Method for extracting cobalt from tungsten waste recovery slag |
| CN113784922A (en) * | 2019-12-16 | 2021-12-10 | 株式会社Lg化学 | Method for separating transition metal from waste positive electrode material |
| EP3951979A4 (en) * | 2019-12-16 | 2022-08-17 | Lg Chem, Ltd. | Method for separating transition metal from waste cathode material |
| CN114867690A (en) * | 2019-12-26 | 2022-08-05 | Sk新技术株式会社 | Method for recovering precursor of positive electrode active material |
| CN111172396A (en) * | 2019-12-30 | 2020-05-19 | 银隆新能源股份有限公司 | Method for recovering metal elements in lithium battery anode and cathode materials |
| CN115103813A (en) * | 2020-02-10 | 2022-09-23 | Sk新技术株式会社 | Method for recovering active metal of lithium secondary battery |
| CN115175876A (en) * | 2020-02-27 | 2022-10-11 | Sk新技术株式会社 | Method for recovering active metal of lithium secondary battery |
| CN111463475A (en) * | 2020-03-11 | 2020-07-28 | 长沙有色冶金设计研究院有限公司 | Method for selectively recycling waste power lithium battery positive electrode material |
| WO2021218510A1 (en) * | 2020-05-01 | 2021-11-04 | XProEM Ltd. | Process for recovering lithium and transition metals from waste cathode of spent lithium ion battery |
| CN113924682A (en) * | 2020-05-01 | 2022-01-11 | XproEM有限公司 | Method for recovering lithium and transition metal from waste positive electrode of waste lithium ion battery |
| CN111994966A (en) * | 2020-07-20 | 2020-11-27 | 中南大学 | Method for recycling waste ternary positive electrode under high-temperature condition of hydrogen sulfide atmosphere |
| CN111924892A (en) * | 2020-07-24 | 2020-11-13 | 中国科学院过程工程研究所 | Method for selectively recovering lithium ion battery electrode powder |
| CN112259821A (en) * | 2020-10-22 | 2021-01-22 | 中钢集团南京新材料研究院有限公司 | Method for recovering valuable metals from waste lithium ion batteries |
| CN112575203A (en) * | 2020-12-07 | 2021-03-30 | 金川集团股份有限公司 | Method for recycling lithium in waste power lithium battery |
| CN112582601A (en) * | 2020-12-14 | 2021-03-30 | 中钢集团南京新材料研究院有限公司 | Method for preparing lithium nickel manganese oxide by utilizing waste lithium manganese oxide and lithium nickel manganese oxide |
| CN112680598A (en) * | 2020-12-15 | 2021-04-20 | 中南大学 | Method for low-cost clean treatment of waste lithium ion battery anode material |
| WO2022127117A1 (en) * | 2020-12-15 | 2022-06-23 | 中南大学 | Method for treating positive electrode material of waste lithium battery |
| US20220194806A1 (en) * | 2020-12-22 | 2022-06-23 | Pukyong National University Industry-University Cooperation Foundation | Lithium oxide recovery method from lithium manganese oxide (lmo) |
| CN113106257A (en) * | 2021-04-12 | 2021-07-13 | 广东佳纳能源科技有限公司 | Recycling method of lithium battery waste and application thereof |
| CN113186410A (en) * | 2021-04-27 | 2021-07-30 | 中国恩菲工程技术有限公司 | Method for recovering valuable metal lithium from waste lithium ion battery anode material |
| CN113149039B (en) * | 2021-04-30 | 2023-03-03 | 四川万邦胜辉新能源科技有限公司 | Method for preparing lithium oxide by thermal reduction of spodumene |
| CN113149039A (en) * | 2021-04-30 | 2021-07-23 | 四川万邦胜辉新能源科技有限公司 | Method for preparing lithium oxide by thermally reducing spodumene |
| CN113422122A (en) * | 2021-06-28 | 2021-09-21 | 郑州大学 | Waste battery lithium resource recovery method based on solid electrolyte |
| CN113422122B (en) * | 2021-06-28 | 2022-05-24 | 郑州大学 | Solid electrolyte-based waste battery lithium resource recovery method |
| CN113832349A (en) * | 2021-09-22 | 2021-12-24 | 荆门市格林美新材料有限公司 | Method for recovering lithium, nickel, cobalt and manganese from battery waste |
| WO2023045646A1 (en) * | 2021-09-22 | 2023-03-30 | 荆门市格林美新材料有限公司 | Method for recycling lithium and nickel-cobalt-manganese from battery waste |
| CN114015881A (en) * | 2021-10-28 | 2022-02-08 | 中国科学院广州能源研究所 | Method for recovering valuable metals by in-situ thermal reduction of waste lithium battery cathode materials |
| CN113999967A (en) * | 2021-11-02 | 2022-02-01 | 赣州有色冶金研究所有限公司 | Method for recovering lithium in lithium ion battery anode material |
| CN114368766A (en) * | 2021-12-22 | 2022-04-19 | 威立雅新能源科技(江门)有限公司 | Method for extracting lithium from waste lithium ion battery and application thereof |
| CN114335781A (en) * | 2021-12-27 | 2022-04-12 | 上海电力大学 | Method for extracting precious metal from waste lithium battery |
| CN116742173A (en) * | 2023-04-10 | 2023-09-12 | 湖南金凯循环科技有限公司 | Reduction roasting method for recycling ternary lithium battery waste |
| CN116742173B (en) * | 2023-04-10 | 2024-01-05 | 湖南金凯循环科技股份有限公司 | Reduction roasting method for recycling ternary lithium battery waste |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108220607A (en) | A kind of method that lithium is recycled from waste material containing lithium electrode | |
| CN107017443B (en) | A method of the comprehensively recovering valuable metal from waste and old lithium ion battery | |
| CN106129511B (en) | A method of the comprehensively recovering valuable metal from waste and old lithium ion battery material | |
| Yang et al. | Selective recovery of lithium from spent lithium iron phosphate batteries: a sustainable process | |
| CN107267759B (en) | A kind of comprehensive recovering process of anode material for lithium-ion batteries | |
| CN106829907B (en) | A kind of method that nickel-contained pig iron prepares nickel sulfate solution and battery-grade iron phosphate | |
| CN108832215A (en) | A kind of method of selective recovery anode material for lithium-ion batteries | |
| CN100595970C (en) | Method for selectively removing copper from waste lithium ion battery | |
| CN111118294A (en) | Method for recycling valuable metals from waste lithium ion battery materials step by step | |
| CN110527835B (en) | Method for recycling soft package full components of waste ternary lithium battery | |
| CN106684489A (en) | Method for recycling valuable metal from waste polybasic lithium ion batteries | |
| CN110129571A (en) | A method of extracting valuable metal from waste and old lithium ion battery material | |
| CN109881008A (en) | A kind of method that reduction roasting-water quenching recycles lithium in waste and old lithium ion battery | |
| CN106611841B (en) | A method of nickel-cobalt-manganese ternary material precursor is prepared using nickel cobalt slag charge | |
| CN109179359A (en) | A method of extracting lithium and ferric phosphate from LiFePO4 waste material | |
| CN108023134A (en) | The recovery method of valuable element in a kind of waste lithium ion battery electrode material | |
| CN106848473A (en) | A kind of selective recovery method of lithium in waste lithium iron phosphate battery | |
| CN107046154B (en) | Method for enhanced reduction leaching of waste ternary lithium battery | |
| CN112111650B (en) | Method for recovering valuable metals of waste lithium ion batteries by selective reduction | |
| CN105244561B (en) | The method that high voltage multicomponent material is prepared as raw material using waste and old polynary dynamic lithium battery | |
| CN105098281A (en) | Method for recycling multi-element anode material from waste multi-element power lithium ion battery | |
| CN111961839A (en) | Method for synchronously leaching valuable metals from positive and negative electrode active materials of waste lithium ion batteries and removing impurities | |
| CN110791668B (en) | Method for recovering manganese from lithium ion battery anode waste containing manganese element | |
| CN111593200A (en) | Method for recovering valuable metals in waste lithium ion batteries | |
| JP6314730B2 (en) | Method for recovering valuable metals from waste nickel metal hydride batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180629 |
|
| RJ01 | Rejection of invention patent application after publication |