KR101957707B1 - Manufacturing method of lithium hydroxide from lithium compound - Google Patents

Manufacturing method of lithium hydroxide from lithium compound Download PDF

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Publication number
KR101957707B1
KR101957707B1 KR1020180113532A KR20180113532A KR101957707B1 KR 101957707 B1 KR101957707 B1 KR 101957707B1 KR 1020180113532 A KR1020180113532 A KR 1020180113532A KR 20180113532 A KR20180113532 A KR 20180113532A KR 101957707 B1 KR101957707 B1 KR 101957707B1
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South Korea
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lithium
amp
step
lithium hydroxide
carbon
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KR1020180113532A
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Korean (ko)
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류태공
박인수
홍혜진
김병수
서창열
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한국지질자원연구원
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00Lithium compounds
    • C01D15/02Oxides; Hydroxides

Abstract

An embodiment of the present invention relates to a method of manufacturing a lithium secondary battery, comprising the steps of: (a) mixing a lithium compound and a carbon raw material and firing in an inert atmosphere; And (b) hydrothermally hydrolyzing the calcined product to prepare a lithium hydroxide solution. The present invention also provides a process for producing lithium hydroxide from a lithium compound.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing lithium hydroxide from a lithium compound,

The present invention relates to a process for preparing lithium hydroxide from a lithium compound.

Considering the characteristics of stability, capacity and output, the secondary battery for electric automobile mainly contains a cathode material such as NCA (nickel-cobalt-aluminum) and high-nickel (NC) 811 having a nickel content of 80 mol% or more It is a trend to use. The NCA and NCM 811 cathode materials are prepared by using lithium hydroxide instead of lithium carbonate as a lithium source, unlike conventional cathode materials. When the nickel content in the cathode material manufacturing process is 80 mol% or more, lithium hydroxide which is relatively excellent in reactivity and can be fired at a low temperature should be used to easily realize an electrical storage capacity characteristic.

Lithium hydroxide is generally prepared by a natural process of evaporation / concentration using a solar heat in a brine, followed by an impurity refining process to produce lithium carbonate, and then a conversion process. In general, lithium carbonate is converted to lithium hydroxide according to the following reaction formula.

(1) CaO + H 2 O → Ca (OH) 2 + heat

(2) Li 2 CO 3 + Ca (OH) 2 ? 2 LiOH (aq) + CaCO 3

(3) 2LiOH (aq) → 2LiOH · H 2 O

First, the lime (CaO) is dispersed in an aqueous solution to convert it into a calcium hydroxide (Ca (OH) 2 ) having a high solubility, and then a lithium hydroxide solution can be formed through a calcination reaction between lithium carbonate and calcium hydroxide. When the saturated concentration is reached, lithium hydroxide can be produced through crystallization.

As a related prior art, there is a "method for producing lithium hydroxide " disclosed in Korean Patent Registration No. 10-1835038.

Korean Registered Patent No. 10-1835038 (issued on Aug. 20, 2018)

It is an object of the present invention to provide a method of manufacturing a lithium compound from a lithium hydroxide through a simplified and highly efficient process.

In order to achieve the above object, one aspect of the present invention is a method for manufacturing a lithium secondary battery, comprising the steps of: (a) mixing a lithium compound and a carbon raw material and firing in an inert atmosphere; And (b) hydrothermally hydrolyzing the calcined product to prepare a lithium hydroxide solution. The present invention also provides a process for producing lithium hydroxide from a lithium compound.

According to another aspect of the present invention, there is provided a method of manufacturing a lithium secondary battery, comprising the steps of: (a) mixing a lithium compound and a carbon material and firing the mixture in an inert atmosphere; (b) hydrothermally hydrolyzing the calcined product to prepare a lithium hydroxide solution; And (c) crystallizing the lithium hydroxide solution by vacuum evaporation and concentration to obtain a lithium hydroxide solid phase, followed by drying to obtain lithium hydroxide from the lithium compound.

According to one aspect of the present invention, lithium hydroxide can be efficiently produced by mixing a lithium compound such as lithium carbonate with a carbon raw material and performing a firing reaction.

In addition, it is simpler than the conventional wet process, has no use of a chemical solvent, is environmentally friendly, and can minimize the amount of reactants that are lost in the process by recycling unreacted materials after the reaction is completed.

It should be understood that the effects of the present invention are not limited to the above effects and include all effects that can be deduced from the detailed description of the present invention or the configuration of the invention described in the claims.

1 is a flowchart showing an example of a method for producing lithium hydroxide from a lithium compound according to an embodiment of the present invention.
2 is a graph showing the XRD analysis results of the fired product according to the firing temperature performed in Experimental Example 1 of the present invention.
3 is a graph showing the XRD analysis results of the fired product according to the firing time performed in Experimental Example 2 of the present invention.
4 is a graph showing the XRD analysis results of the calcination product according to the mixing molar ratio under the vacuum condition performed in Experimental Example 3 of the present invention.

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

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving it will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings.

It should be understood, however, that the present invention is not limited to the disclosed embodiments, but may be embodied in many different forms and should not be construed as limited to the exemplary embodiments set forth herein. To fully inform the inventor of the category of invention. Further, the present invention is only defined by the scope of the claims.

Further, in the following description of the present invention, if it is determined that related arts or the like may obscure the gist of the present invention, detailed description thereof will be omitted.

According to an aspect of the present invention,

(a) a step (S10) of mixing a lithium compound and a carbon raw material and firing in an inert atmosphere; And

(b) hydrothermally hydrolyzing the calcined product to prepare a lithium hydroxide solution (S20).

In the method for producing lithium hydroxide from a lithium compound according to an embodiment of the present invention, the lithium compound and the carbon raw material are mixed in the step (a) and the inert gas having a predetermined flow rate is charged and fired.

The lithium compound of step (a) may be lithium carbonate.

The lithium compound of step (a) is preferably a compound capable of generating lithium oxide (Li 2 O) form through reaction with a carbon source.

The carbon source of step (a) may include one selected from the group consisting of graphite, activated carbon, carbon nanotube, carbon black, graphene, amorphous carbon, and combinations thereof.

When the lithium compound of the step (a) is lithium carbonate, the mixing is preferably performed so that the carbon-to-carbon ratio of the lithium carbonate: carbon raw material is 1: 0.95 to 1: 2. If the carbon source is added at a molar ratio of less than 1: 0.95, lithium carbonate conversion of lithium carbonate may not be achieved sufficiently. If the molar ratio is more than 1: 2 and the carbon source is added, There is a fear of increase, and unnecessary resource waste can occur.

The calcination in step (a) may be performed at a temperature of 700 ° C to 900 ° C for 2 hours to 12 hours, and preferably at a temperature of 800 ° C to 900 ° C for 4 hours to 12 hours. If the calcination temperature is lower than 700 ° C, the formation efficiency of lithium oxide may be lowered. If the calcination temperature is higher than 900 ° C, excessive energy loss may occur in forming lithium oxide, There is a risk of loss. The lithium compound can be easily formed into lithium oxide at the above-mentioned firing temperature and time range.

The firing in the step (a) is preferably carried out at a pressure of 1 atm or less. Lithium oxide can be formed from a lithium compound with excellent reaction efficiency in the above-described pressure range.

In the method for producing lithium hydroxide from a lithium compound according to an embodiment of the present invention, in step (b) (S20), the calcined product is hydrolyzed to prepare a lithium hydroxide solution.

If the lithium compound in step (a) is lithium carbonate, the hydrothermal treatment in step (b) is preferably carried out under the following conditions.

The hydrothermal treatment in step (b) may be performed by adding water at 60 ° C to 100 ° C. Water at the above temperature can be added to form lithium oxide in the fired product as a lithium hydroxide solution to separate out some unreacted lithium carbonate and carbon raw materials. The unreacted lithium carbonate and carbonaceous material can be reused in the step (a).

In another aspect of the present invention,

(a) mixing a lithium compound and a carbon raw material and firing in an inert atmosphere; And

and (b ') adding steam to the fired product to produce lithium hydroxide hydrate.

The steam treatment in the step (b ') is preferably carried out in the case where the fired product in the step (a) does not contain lithium carbonate and carbon raw materials which are unreacted materials.

According to another aspect of the present invention,

(a) mixing a lithium compound and a carbon raw material and firing in an inert atmosphere;

(b) hydrothermally hydrolyzing the calcined product to prepare a lithium hydroxide solution; And

(c) crystallizing the lithium hydroxide solution by vacuum evaporation and concentration to obtain a lithium hydroxide solid phase, followed by drying to obtain lithium hydroxide from the lithium compound.

In the method for preparing lithium hydroxide according to an embodiment of the present invention, in the step (c), lithium hydroxide crystals are obtained by evaporating and concentrating the lithium hydroxide solution prepared by heating in the step (b).

In the case of the lithium hydroxide hydrate prepared by adding steam to the calcination product of the step (b '), it is dried.

The drying treatment in the step (c) may also be carried out by a steam drying treatment.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following examples and experimental examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

≪ Example 1 > Preparation of lithium hydroxide / molar ratio 1: 1.3 / 800 DEG C 4 h

(a) Lithium carbonate (purity: 99.8 wt%) and carbon powder were mixed in a molar ratio of 1: 1.3, charged into a muffle furnace, and fired at 800 ° C for 4 hours in a nitrogen atmosphere at normal pressure.

(b) The calcined product was washed with water at 80 DEG C to prepare a lithium hydroxide solution.

(c) The lithium hydroxide solution was concentrated by evaporation to obtain crystals, which were then steam-dried to obtain a lithium hydroxide solid.

≪ Example 2 > Preparation of lithium hydroxide / molar ratio 1: 1.3 / 850 DEG C 4 h

The procedure of Example 1 was repeated except that the firing temperature was changed to 850 ° C in the step (a) of Example 1.

≪ Example 3 > Preparation of lithium hydroxide / molar ratio 1: 1.3 / 900 DEG C 4 h

In the step (a) of Example 1, the same procedure as in Example 1 was performed except that the firing temperature was changed to 900 캜.

≪ Example 4 > Preparation of lithium hydroxide / molar ratio 1: 1.3 / 700 DEG C 4 h

In the step (a) of Example 1, the same procedure as in Example 1 was performed except that the firing temperature was changed to 700 캜.

≪ Comparative Example 1 > Preparation of lithium hydroxide / molar ratio 1: 1.3 / 600 DEG C 4 h

In the step (a) of Example 1, the same procedure as in Example 1 was performed except that the firing temperature was changed to 600 캜.

≪ Example 5 > Preparation of lithium hydroxide / molar ratio 1: 1.1 / 800 DEG C 4 h

The procedure of Example 1 was repeated except that the mixing molar ratio was changed to 1: 1.1 in the step (a) of Example 1.

≪ Example 6 > Preparation of lithium hydroxide / molar ratio 1: 1.1 / 800 DEG C 6 h

The procedure of Example 1 was repeated except that the mixing molar ratio was changed to 1: 1.1 and the firing time was changed to 6 hours in the step (a) of Example 1.

≪ Example 7 > Preparation of lithium hydroxide / molar ratio 1: 1.1 / 800 DEG C 8 h

Example 1 was carried out in the same manner as in Example 1, except that in the step (a) of Example 1, the mixing molar ratio was changed to 1: 1.1 and the firing time was changed to 8 hours.

≪ Example 8 > Preparation of lithium hydroxide / molar ratio 1: 1.1 / 800 DEG C 10 h

The procedure of Example 1 was repeated except that the mixing molar ratio was changed to 1: 1.1 and the firing time was changed to 10 hours in the step (a) of Example 1.

≪ Example 9 > Preparation of lithium hydroxide / molar ratio 1: 1.1 / 800 DEG C 12 h

The procedure of Example 1 was repeated except that the mixing molar ratio was changed to 1: 1.1 and the firing time was changed to 12 hours in the step (a) of Example 1.

≪ Example 10 > Preparation of lithium hydroxide / molar ratio 1: 1.3 / 900 DEG C 2 h

Example 1 was carried out in the same manner as in Example 1 except that the pressure was changed to 1 Torr and the firing temperature was changed to 900 ° C. and the firing time was changed to 2 hours in the step (a) of Example 1

≪ Example 11 > Preparation of lithium hydroxide / mol ratio 1: 1.6 / 900 DEG C 2 h

Example 1 was repeated except that the pressure was changed to 1 Torr, the mixing molar ratio was set to 1: 1.6, the sintering temperature was set to 900 ° C, and the sintering time was set to 2 hours in the step (a) .

≪ Example 12 > Preparation of lithium hydroxide / molar ratio 1: 2.0 / 900 DEG C 2 h

Example 1 was repeated except that the pressure was changed to 1 Torr, the mixing molar ratio was set to 1: 2.0, the firing temperature was set to 900 ° C, and the firing time was set to 2 hours in the step (a) .

<Experimental Example 1> XRD analysis of calcined product according to calcination temperature

XRD analysis of the fired products of Examples 1 to 4 and Comparative Example 1 was carried out, and the results are shown in Fig.

Referring to FIG. 2, peaks of lithium carbonate and graphite remained at a temperature of 600 ° C., and lithium oxide peak was generated at 700 ° C., and peaks of lithium carbonate and graphite disappeared at a temperature of 800 ° C. or higher Can be confirmed.

&Lt; Experimental Example 2 > XRD analysis of calcined product according to sintering time

XRD analysis of the fired products of Examples 5 to 9 was carried out, and the results are shown in Fig.

Referring to FIG. 3, it was found that almost all the lithium carbonate and carbon were reacted with each other over 6 hours, and that the main peak was lithium oxide for 12 hours.

&Lt; Experimental Example 3 > XRD analysis of sintered product by pressure

XRD analysis of the fired products of Examples 10 to 12 was carried out, and the results are shown in FIG.

Referring to FIG. 4, when the pressure was reduced to a vacuum of 1 Torr, the reaction time similar to that of the normal pressure condition was similar to that of the normal pressure condition.

As a result of the experiment, it was confirmed that the highest conversion of lithium oxide was observed under the condition of calcination at 800 ° C. for 12 hours, and the reaction product, lithium carbonate, was vaporized at a calcination temperature of 1000 ° C. or higher.

Although a specific example of the method for producing lithium hydroxide from a lithium compound according to an embodiment of the present invention has been described so far, it is apparent that various modifications can be made without departing from the scope of the present invention.

Therefore, the scope of the present invention should not be limited by the described embodiments, but should be determined by the equivalents of the appended claims, as well as the appended claims.

It is to be understood that the foregoing embodiments are illustrative and not restrictive in all respects and that the scope of the present invention is indicated by the appended claims rather than the foregoing description, It is intended that all changes and modifications derived from the equivalent concept be included within the scope of the present invention.

Claims (9)

  1. (a) mixing lithium carbonate and a carbon raw material and calcining the mixture in an inert atmosphere at a temperature of 800 ° C to 900 ° C; And
    (b) hydrothermally hydrolyzing the calcined product to prepare a lithium hydroxide solution,
    Wherein the unreacted lithium carbonate and the carbonaceous raw material are separated and reused in the step (a) after the hot water washing in the step (b).
  2. delete
  3. The method according to claim 1,
    The carbon source of the step (a)
    A process for producing lithium hydroxide from a lithium compound, characterized by comprising one selected from the group consisting of graphite, activated carbon, carbon nanotubes, carbon black, graphene, amorphous carbon, and combinations thereof.
  4. The method according to claim 1,
    The lithium compound of step (a) is lithium carbonate,
    Wherein the mixing is carried out so that the carbon-to-carbon ratio of the lithium carbonate: carbon raw material is 1: 0.95 to 1: 2.
  5. delete
  6. The method according to claim 1,
    The firing in the step (a)
    &Lt; / RTI &gt; is carried out for from 2 hours to 12 hours.
  7. The method according to claim 1,
    The hot water count in the step (b)
    &Lt; RTI ID = 0.0 &gt; 60 C &lt; / RTI &gt; to &lt; RTI ID = 0.0 &gt; 100 C. &lt; / RTI &gt;
  8. delete
  9. (a) mixing lithium carbonate and a carbon raw material and calcining the mixture in an inert atmosphere at a temperature of 800 ° C to 900 ° C;
    (b) hydrothermally hydrolyzing the calcined product to prepare a lithium hydroxide solution; And
    (c) crystallizing the lithium hydroxide solution by vacuum evaporation and concentration, and drying to obtain a lithium hydroxide solid phase,
    Wherein the unreacted lithium carbonate and the carbonaceous raw material are separated and reused in the step (a) after the hot water washing in the step (b).
KR1020180113532A 2018-09-21 2018-09-21 Manufacturing method of lithium hydroxide from lithium compound KR101957707B1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4221775A (en) * 1978-12-26 1980-09-09 Research Dynamics, Inc. Method of producing porous lithium oxide
US4732751A (en) * 1986-04-11 1988-03-22 Lithium Corporation Of America High purity lithium oxide process
KR20120066534A (en) * 2010-12-14 2012-06-22 서강대학교산학협력단 Preparation of lithium hydroxide monohydrate from lithium carbonate
JP2012121780A (en) * 2010-12-10 2012-06-28 Sumitomo Metal Mining Co Ltd Method for manufacturing lithium oxide
JP2016216349A (en) * 2015-05-22 2016-12-22 日本化学工業株式会社 Manufacturing method of lithium sulfide and manufacturing method of inorganic solid electrolyte
KR101835038B1 (en) 2017-12-15 2018-03-08 한국지질자원연구원 Method of preparing lithium hydroxide

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4221775A (en) * 1978-12-26 1980-09-09 Research Dynamics, Inc. Method of producing porous lithium oxide
US4732751A (en) * 1986-04-11 1988-03-22 Lithium Corporation Of America High purity lithium oxide process
JP2012121780A (en) * 2010-12-10 2012-06-28 Sumitomo Metal Mining Co Ltd Method for manufacturing lithium oxide
KR20120066534A (en) * 2010-12-14 2012-06-22 서강대학교산학협력단 Preparation of lithium hydroxide monohydrate from lithium carbonate
JP2016216349A (en) * 2015-05-22 2016-12-22 日本化学工業株式会社 Manufacturing method of lithium sulfide and manufacturing method of inorganic solid electrolyte
KR101835038B1 (en) 2017-12-15 2018-03-08 한국지질자원연구원 Method of preparing lithium hydroxide

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