WO2019198972A1 - Method for producing lithium hydroxide monohydrate by using waste cathode material of lithium ion secondary battery - Google Patents

Abstract

The present invention relates to a method for producing lithium hydroxide monohydrate by using a waste cathode material of a lithium ion secondary battery and, more specifically, to a method for producing lithium hydroxide monohydrate by using a waste cathode material of a lithium ion secondary battery, wherein the waste cathode material containing lithium is pretreated by injection of steam in an inert atmosphere, and then subjected to water leaching, whereby lithium ions can be recovered at a high recovery rate and high-purity lithium hydroxide monohydrate can be produced.

Description

Method for manufacturing lithium hydroxide monohydrate using waste cathode material of lithium ion secondary battery

The present invention relates to a method for producing lithium hydroxide monohydrate using a waste cathode material of a lithium ion secondary battery, and more specifically, by injecting water vapor in an inert atmosphere and pre-treating the waste cathode material containing lithium by water leaching The present invention relates to a method for producing lithium hydroxide monohydrate using a waste cathode material of a lithium ion secondary battery capable of recovering lithium ions at a high recovery rate and producing high purity lithium hydroxide monohydrate.

Recently, the lithium ion secondary battery market has been increasing in demand as the market for electric vehicles, energy storage devices (ESS), etc. has expanded beyond the IT battery market.

Lithium-ion secondary battery has the advantage of having a small size and high-density energy, and is manufactured for each product use is used in various ways as well as smart phones, battery cars.

The lithium ion secondary battery battery includes a cathode material, an anode material, a separator, an electrolyte, and the cathode material contains valuable metals such as lithium, nickel, cobalt, and manganese.

Of these, lithium is the main raw material that enables the storage or release of electrical energy in the battery.

In recent years, as the prices of lithium carbonate and lithium hydroxide for batteries soar, demand for technology development for efficiently recovering lithium by recycling waste lithium ion batteries is increasing.

The existing technology of recycling lithium using waste lithium ion secondary battery is to recover valuable metals such as nickel and cobalt first through sulfuric acid leaching and solvent extraction process, and then recover lithium with residual impurities. have.

However, conventional technologies for recycling lithium using waste lithium ion secondary batteries have a problem in that they are recovered as low purity lithium compounds by containing a large amount of impurities, and the recovery rate is lowered.

The present invention has been made to solve such a problem, an object of the present invention is to recover the lithium ion with a high recovery rate by using the waste cathode material of the lithium ion secondary battery, high-purity lithium hydroxide work by minimizing impurities It is to provide a method for producing lithium hydroxide monohydrate using the waste cathode material of a lithium ion secondary battery capable of producing a hydrate.

The objects of the present invention are not limited to the above-mentioned objects, and other objects that are not mentioned will be clearly understood by those skilled in the art from the following description.

In order to achieve the above object, the present invention provides a waste cathode material preparation step of preparing a waste cathode material of a lithium ion secondary battery; A waste cathode material pretreatment step of pretreating the prepared waste cathode material by injecting water vapor in an inert atmosphere; A water leaching step of adding water to the pretreated pretreatment result and stirring; Solid-liquid separation step of separating the water-leached mixture into a solid solution to separate the leachate and the residue; A crystallization step of concentrating and crystallizing the leachate; It provides a method for producing lithium hydroxide monohydrate using the waste cathode material of a lithium ion secondary battery comprising a; washing and drying step of washing and drying the crystallized lithium hydroxide monohydrate.

In a preferred embodiment, the waste cathode material of the lithium ion secondary battery is lithium nickel cobalt aluminum oxide (LiNiCoAlO ₂ , NCA), lithium nickel cobalt manganese oxide (LiNiCoMnO ₂ , NCM), oxides of lithium iron (LiFePO ₄ , LFP), Group consisting of lithium manganese iron oxides (LiMnFePO ₄ , LMFP), lithium manganese oxides (LiMn ₂ O ₄ , LMO), lithium nickel manganese spinel (LiNi _0.5 Mn _1.5 O ₄ , LNMO), lithium cobalt oxide (LiCoO ₂ , LCO) At least one selected from.

In a preferred embodiment, the waste cathode material pretreatment step is reacted by Scheme 1 shown below.

Scheme 1

2LiMeO ₂ + H ₂ O → 2LiOH + MeOMeO ₂

Here, Me is at least one selected from the group consisting of Ni, Co, Mn, Al.

In a preferred embodiment, the waste cathode material pretreatment step is nitrogen, carbon dioxide or hydrogen is injected at 0.1 to 1,000 LPM (Liter per minute) per 1g of the waste cathode material to form the inert atmosphere, the water vapor is the waste anode It is injected at 0.1 to 1,000 LPM (Liter per minute) per 1 g of ash, and is heat-treated at 500 ° C. to 1,000 ° C. for 100 to 600 minutes.

In a preferred embodiment, the water leaching step is mixed with 1 to 10 times the water based on the weight of the pretreatment result to the pretreatment result is stirred for 1 to 5 hours at a temperature of 20 ℃ to 100 ℃ .

In a preferred embodiment, the residue is used to separate Ni, Co, Mn or Al.

In a preferred embodiment, the crystallization step is concentrated by evaporation in a vacuum at a temperature of 60 ℃ to 120 ℃ for 30 minutes to 10 hours.

The present invention has the following excellent effects.

First, according to the method for producing lithium hydroxide monohydrate using the waste cathode material of the lithium ion secondary battery of the present invention, lithium is discharged by pre-treating the waste cathode material containing lithium in an inert atmosphere and then pre-treated with water There is an effect that can be recovered at a high recovery rate.

In addition, according to the method for producing lithium hydroxide monohydrate using the waste cathode material of the lithium ion secondary battery of the present invention, by leaching without using an acid, lithium ions are removed without nickel, cobalt, manganese or aluminum ions. Bay can be selectively extracted has the advantage of producing a high purity lithium hydroxide monohydrate.

In addition, according to the manufacturing method of lithium hydroxide monohydrate using the waste cathode material of the lithium ion secondary battery of the present invention, by using the residue separated from the water-leached mixture to separate nickel, cobalt, manganese or aluminum elements There is an advantage that can be recycled as a precursor of the secondary battery cathode material.

1 is a step for explaining a method of manufacturing lithium hydroxide monohydrate using the waste cathode material of a lithium ion secondary battery according to an embodiment of the present invention.

2 is an XRD analysis result of lithium nickel cobalt oxide (NCA) as a waste cathode material according to an embodiment of the present invention.

3 is an XRD analysis result of the pretreatment result after the pretreatment step according to an embodiment of the present invention.

The terms used in the present invention are selected as general terms as widely used as possible, but in some cases, the terms arbitrarily selected by the applicant, in which case, the meanings described or used in the detailed description of the present invention, rather than simply the names of the terms, are considered. The meaning should be grasped.

Hereinafter, with reference to the preferred embodiments shown in the accompanying drawings will be described in detail the technical configuration of the present invention.

However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Like numbers refer to like elements throughout the specification.

1 is a step for explaining a method for producing lithium hydroxide monohydrate using the waste cathode material of a lithium ion secondary battery according to the present invention.

Referring to FIG. 1, a method of manufacturing lithium hydroxide monohydrate using waste cathode materials of a secondary battery according to an embodiment of the present invention recovers lithium from waste cathode materials of a lithium ion secondary battery and converts the lithium hydroxide into lithium hydroxide monohydrate. As a technology for manufacturing, first, a waste cathode material of a lithium ion secondary battery is prepared (S100).

Here, the waste cathode material is not limited as long as it is a cathode material containing lithium element, preferably lithium nickel cobalt aluminum oxide (LiNiCoAlO ₂ , NCA), lithium nickel cobalt manganese oxide (LiNiCoMnO ₂ , NCM), lithium iron oxide (LiFePO ₄ , LFP), lithium manganese oxides (LiMnFePO ₄ , LMFP), lithium manganese oxides (LiMn ₂ O ₄ , LMO), lithium nickel manganese spinel (LiNi _0.5 Mn _1.5 O ₄ , LNMO), lithium cobalt oxide (LiCoO ₂ , LCO) may be any one or more selected from the group consisting of.

Next, a pretreatment step of pre-treating the prepared waste cathode material by injecting water vapor in an inert atmosphere is performed (S200).

The pretreatment step (S200) is a process for deforming the structure of the waste cathode material to transform lithium into the form of a water-soluble material, and is reacted by Scheme 1 shown below.

Scheme 1

2LiMeO ₂ + H ₂ O → 2LiOH + M _e OMeO ₂

Here, Me is at least one selected from the group consisting of Ni, Co, Mn, Al.

At this time, in order to form an inert atmosphere, nitrogen, carbon dioxide or hydrogen may be injected at 0.1 to 1,000 LPM (Liter per minute) per 1g of the waste cathode material.

 In addition, the water vapor is injected at 0.1 to 1,000 LPM (Liter per minute) per 1g of the waste cathode material, and induces physicochemical decomposition of the waste cathode material through a hydrolysis reaction by high temperature saturated steam.

At this time, the temperature is maintained in the range of 500 ℃ to 1,000 ℃, heat treatment for 100 minutes to 600 minutes.

Next, a water leaching step of adding and stirring water to the pretreated pretreatment result is performed (S300).

In the water leaching step (S300), it is preferable to extract lithium by adding water to the pretreatment result without using an acid.

The reason is that when acid is used, it is difficult to produce high purity lithium products by leaching metal materials such as nickel, cobalt, manganese, and aluminum in addition to lithium to be extracted, but when using water, nickel, cobalt manganese aluminum, etc. This is because only lithium can be selectively extracted to produce a high purity lithium product.

At this time, the water is added 1 to 10 times on the basis of the weight of the pretreatment result, it is stirred at 200rpm to 1,000rpm for 1 to 5 hours at a temperature of 20 ℃ to 100 ℃.

That is, in the water leaching step (S300), the lithium hydroxide formed through the pretreatment step (S200) is reacted as in Scheme 2 below.

Scheme 2

^{_{LiOH + H 2 O → Li +}} + OH - + H 2 O

Next, a solid-liquid separation step (S400) of separating the water-leached mixture into solids and separating the leachate and residues is performed.

Here, metallic elements, such as nickel, cobalt, manganese, and aluminum, are separated into a cake residue, and lithium is dissolved and separated in a leach solution.

Thereafter, the residue is separated separately and recovered as elements such as nickel, cobalt, manganese, aluminum through sulfuric acid leaching or solvent extraction process, and synthesized as a precursor of a secondary battery cathode material using this as a raw material. Can be recycled.

Next, a crystallization step (S500) of concentrating and crystallizing the leaching solution in which lithium is dissolved is performed.

In the crystallization step (S500), the leachate is concentrated by evaporation at a temperature of 60 ° C to 120 ° C for 30 minutes to 10 hours in a vacuum to form lithium hydroxide monohydrate crystals.

That is, as water is evaporated, crystals are formed by concentrating lithium to a concentration higher than the solubility of lithium hydroxide.

Next, the resulting lithium hydroxide monohydrate crystals are washed with water and dried to obtain a final lithium hydroxide monohydrate (S600).

EXAMPLE

Waste cathode material preparation stage

150 g of lithium nickel cobalt aluminum oxide (LiNiCoAlO ₂ , NCA) was used as a waste cathode material of a secondary battery.

On the other hand, Table 1 shows the results of ICP chemical component content analysis of the lithium nickel cobalt aluminum oxide, Figure 2 shows the lithium nickel cobalt aluminum oxide XRD analysis results.

division	Mg	Na	Li	Co	Ni	Zn	Al	S
Content (wt%)	0.02	0.07	6.67	6.65	54.37	0.22	0.4	0.14

After the pretreatment step , the prepared waste cathode material powder was introduced into a tube kiln, and then heated to 800 ° C. ± 10 ° C. at a temperature rising rate of 10 ° C. per minute, and then maintained for 120 minutes.

At this time, in order to maintain an inert atmosphere, nitrogen gas was injected at 30cc per minute, and steam was injected at 650cc per minute. After the end of the isothermal period, natural cooling was performed to obtain a pretreatment result, and nitrogen and steam were not injected in the cooling section.

FIG. 3 shows the XRD analysis results of the pretreatment result. Referring to FIGS. 2 and 3, since the steam is injected and pretreated in an inert atmosphere by nitrogen gas, the intensity value is reduced at 19 degrees. It was observed that the deformation of the intermolecular bonding structure in the waste cathode material was confirmed.

Water leaching stage

Thereafter, 10 g of the pretreatment product was mixed with 198.82 g of water, and stirred at 500 rpm for 120 minutes using a magnetic stirrer at room temperature to recover lithium.

Solid-liquid Separation Step

Thereafter, the water-leached mixture was separated into a solid solution and separated into a leach solution and a residue, and the components of the leach solution were shown in Table 2 below.

division	Li	S	Na	Si	Ni	Co	Mn	Al
Leachate (ppm)	3212	3	7	2	N / D	N / D	N / D	N / D

Referring to Table 2, it was confirmed that the recovery of lithium is about 80%, nickel, cobalt, manganese, aluminum was not detected in the immersion liquid.

Thereafter, the leachate was concentrated by evaporation and crystallization, and the obtained crystals were washed with water and dried to obtain lithium hydroxide monohydrate that can be used in a secondary battery battery.

Comparative example

Lithium nickel cobalt aluminum oxide was prepared as a waste cathode material in the same manner as in Example, and the prepared waste cathode material powder was introduced into a tube kiln, and then heated up to 800 ° C. ± 10 ° C. at a temperature rising rate of 10 ° C. per minute, and then 5. After cooling for an hour, it was naturally cooled.

At this time, nitrogen and water vapor were reacted without injecting, 50g of the pretreatment result was obtained, mixed with 232.57g of water, and water leaching was performed to recover lithium. Stirring was performed at 500 rpm using a magnetic stirrer at 70 ° C., and the reaction time was 120 minutes.

The lithium concentration in the leachate obtained by solid-liquid separation of the solution from which the water leach was completed was analyzed, and the result confirmed that the lithium recovery was 11.6%.

From this, it was found that the pretreatment process according to the present invention, in which nitrogen gas is injected to form an inert atmosphere and steam is pretreated by injecting steam, decomposes the structure of the cathode material and transforms lithium into a water-soluble material. .

As described above, in the method for producing lithium hydroxide monohydrate using the waste cathode material of the lithium ion secondary battery according to the present invention, by pre-treating the waste cathode material containing lithium in an inert atmosphere by pre-treatment with water vapor and then leaching water, Lithium component can be recovered with high recovery rate, and by leaching water without using acid, only lithium ions can be selectively extracted without nickel, cobalt, manganese or aluminum ions, thereby producing high purity lithium hydroxide monohydrate. It has the advantage to do it.

At the same time, nickel, cobalt, manganese, or aluminum can be separated by using the residue separated from the water-leached mixture and recycled as a precursor of the secondary battery cathode material.

As described above, the present invention has been illustrated and described with reference to preferred embodiments, but is not limited to the above-described embodiments, and is provided to those skilled in the art without departing from the spirit of the present invention. Various changes and modifications will be possible.

Recovering lithium from the waste cathode material, it can be used as a raw material of the lithium ion secondary battery, it can be applied to various fields using lithium hydroxide monohydrate as a raw material.

Claims (7)

1. A waste cathode material preparation step of preparing waste cathode material of a lithium ion secondary battery;

   A waste cathode material pretreatment step of pretreating the prepared waste cathode material by injecting water vapor in an inert atmosphere;

   A water leaching step of adding water to the pretreated pretreatment result and stirring;

   Solid-liquid separation step of separating the water-leached mixture into a solid solution to separate the leachate and the residue;

   A crystallization step of concentrating and crystallizing the leachate;

   The washing and drying step of washing and drying the crystallized lithium hydroxide monohydrate; Method for producing lithium hydroxide monohydrate using the waste cathode material of a lithium ion secondary battery.
2. The method of claim 1,

   The waste cathode material of the lithium ion secondary battery is lithium nickel cobalt aluminum oxide (LiNiCoAlO ₂ , NCA), lithium nickel cobalt manganese oxide (LiNiCoMnO ₂ , NCM), lithium iron oxide (LiFePO ₄ , LFP), lithium manganese iron oxide (LiMnFePO ₄ , LMFP), lithium manganese oxide (LiMn ₂ O ₄ , LMO), lithium nickel manganese spinel (LiNi _0.5 Mn _1.5 O ₄ , LNMO), at least one selected from the group consisting of lithium cobalt oxide (LiCoO ₂ , LCO) A method for producing lithium hydroxide monohydrate using the waste cathode material of a lithium ion secondary battery, characterized in that.
3. The method of claim 1,

   The waste cathode material pretreatment step is a method for producing lithium hydroxide monohydrate using the waste cathode material of a lithium ion secondary battery, characterized in that the reaction by reaction 1 shown below.

   Scheme 1

   2LiMeO ₂ + H ₂ O → 2LiOH + M _e OMeO ₂

   Here, Me is at least one selected from the group consisting of Ni, Co, Mn, Al.
4. The method of claim 1,

   The waste cathode material pretreatment step

   Nitrogen, carbon dioxide, or hydrogen is injected at 0.1 to 1,000 LPM (Liter per minute) per 1g of the waste cathode material to form the inert atmosphere, and the water vapor is 0.1 to 1,000 LPM (Liter per minute) per 1g of the waste cathode material. A method of manufacturing lithium hydroxide monohydrate using the spent positive electrode material of a lithium ion secondary battery, which is injected and heat treated at 500 ° C. to 1,000 ° C. for 100 to 600 minutes.
5. The method of claim 4, wherein

   The water leaching step

   1 to 10 times of water is mixed with the pretreatment result on the basis of the weight of the pretreatment result, which is then agitated for 1 to 5 hours at a temperature of 20 ° C to 100 ° C. Method for producing lithium hydroxide monohydrate using a cathode material.
6. The method of claim 3, wherein

   A method for producing lithium hydroxide monohydrate using the waste cathode material of a lithium ion secondary battery, characterized in that to separate Ni, Co, Mn or Al using the residue.
7. The method of claim 1,

   The crystallization step is a lithium hydroxide monohydrate manufacturing method using a waste cathode material of a lithium ion secondary battery, characterized in that the evaporation and concentration for 30 minutes to 10 hours at a temperature of 60 ℃ to 120 ℃ in a vacuum state.

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