KR101659800B1 - Method for producing metallic lithium - Google Patents

Method for producing metallic lithium Download PDF

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KR101659800B1
KR101659800B1 KR1020150125812A KR20150125812A KR101659800B1 KR 101659800 B1 KR101659800 B1 KR 101659800B1 KR 1020150125812 A KR1020150125812 A KR 1020150125812A KR 20150125812 A KR20150125812 A KR 20150125812A KR 101659800 B1 KR101659800 B1 KR 101659800B1
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South Korea
Prior art keywords
powder
lithium
parts
weight
reducing
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KR1020150125812A
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Korean (ko)
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박재신
한길수
최국선
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재단법인 포항산업과학연구원
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10Obtaining alkali metals
    • C22B26/12Obtaining lithium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/14Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24Binding; Briquetting ; Granulating
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00General methods of reducing to metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00General methods of reducing to metals
    • C22B5/02Dry methods smelting of sulfides or formation of mattes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/001Dry processes

Abstract

More particularly, the present invention relates to a process for producing metal lithium, comprising the steps of: adding iron powder, a reducing agent powder and a reducing promoter powder to a lithium phosphate powder to prepare a mixed powder; And a method for producing the metal lithium, which comprises the steps of:

Description

[0001] METHOD FOR PRODUCING METALLIC LITHIUM [0002]

And a method for producing metallic lithium.

Generally, metallic lithium is widely used in various industries such as lithium batteries, glass, ceramics, alloys, lubricants, and pharmaceuticals.

As a method of producing such metal lithium, a process by heat reduction or electrolysis (electrolysis) is known, and among these methods, electrolysis is widely used.

Generally, a raw material used in the production of metallic lithium by electrolysis is lithium chloride (LiCl), which is mixed with potassium chloride (KCl) and dissolved at a high temperature to prepare a eutectic mixture, and installing the anode, and then - Applying a voltage and a current density of about 2A / cm 2 of 3.6V, the metal lithium is generated at the cathode.

At this time, since it takes about 35 kWh of electricity to produce 1 kg of Li, it is pointed out that the energy consumption is excessive and the production cost of metal lithium increases. Further, there is a problem that metallic lithium is generated in the cathode and harmful chlorine gas is generated in the cathode.

In addition, in the case of lithium chloride, which is a raw material for electrolysis, since it is common to prepare lithium carbonate from brines, spodumene, etc., and then reacting such lithium carbonate with hydrochloric acid, There is a problem that hydrochloric acid, which is a harmful substance, is used in the production process of the material.

On the other hand, in the case of the method for producing metal lithium by thermal reduction, a method of using lithium oxide as a raw material, mixing it with calcium oxide and a reducing agent and then reducing in a high-temperature vacuum atmosphere has been proposed. However, There is an expensive problem.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a method for producing metal lithium by reducing lithium phosphate by a thermal reduction method at a relatively low cost.

In one aspect, the present invention provides a method for preparing a lithium metal phosphate, comprising: preparing a mixed powder by adding iron powder, a reducing agent powder, and a reducing promoter powder to a lithium phosphate powder; and thermally reducing the mixed powder to obtain metal lithium And a manufacturing method thereof.

At this time, the amount of the iron powder may be 100 to 150 parts by weight based on 100 parts by weight of the lithium phosphate powder.

Meanwhile, the reducing agent powder may be at least one powder selected from the group consisting of aluminum, silicon, ferrosilicon, and combinations thereof.

At this time, the amount of the silicon powder may be 40 to 60 parts by weight based on 100 parts by weight of the lithium phosphate powder.

The average diameter of the silicon powder may be 100 mesh or less.

Here, the amount of the reducing promoter powder may be 350 parts by weight to 500 parts by weight based on 100 parts by weight of the silicon powder.

The amount of the aluminum powder to be added may be 80 to 100 parts by weight based on 100 parts by weight of the lithium phosphate powder.

The average diameter of the aluminum powder may be 20 mesh or less.

Here, the amount of the reduction promoter powder may be 70 parts by weight to 85 parts by weight based on 100 parts by weight of the aluminum powder.

In the present invention, the average diameter of the lithium phosphate powder may be 100 mesh or less.

Also, the reduction promoter powder may be at least one selected from the group consisting of calcium oxide, aluminum oxide, and combinations thereof.

The average diameter of the reduction promoter powder may be 100 mesh or less.

Meanwhile, in the method for producing metallic lithium according to the present invention, the step of thermally reducing the mixed powder to obtain metallic lithium may be performed at a temperature ranging from 1000 ° C to 1400 ° C.

Further, the step of thermally reducing the mixed powder to obtain metal lithium may be performed in a pressure range of 0.001 atm or less.

More specifically, the step of thermally reducing the mixed powder to obtain metal lithium may include the steps of producing monochromatic light by applying pressure to the mixed powder, heating the monochromatic light to generate lithium vapor, And condensing the lithium vapor.

According to the method for producing metallic lithium according to one embodiment of the present invention, relatively low cost lithium phosphate is used as a raw material, and the production cost is reduced by reducing the process ratio by the heat reduction method, It is possible to provide a method for producing metal lithium which is environmentally safe because it can be effectively removed.

1 shows the state diagram of Fe and P (Fe-P phase diagram).
2 schematically shows a reduction system used in an embodiment of the present invention.
FIG. 3 is a photograph showing the state of the crucible after the metal lithium was produced according to Example 1. FIG.
FIG. 4 is a photograph showing the state of a crucible after preparing metallic lithium according to Comparative Example 1. FIG.
5 is a SEM photograph taken using a reducing slag remaining after the preparation of metallic lithium according to Example 1. Fig.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs. Whenever a component is referred to as "including" an element throughout the specification, it is to be understood that the element may include other elements, not the exclusion of any other element, unless the context clearly dictates otherwise. Also, singular forms include plural forms unless the context clearly dictates otherwise.

The inventors of the present invention have conducted research to develop a method for producing metal lithium which can reduce the production cost while using relatively inexpensive lithium phosphate as a raw material. As a result, they have found that the lithium phosphate powder, the reducing agent powder and the reducing promoter powder are mixed , It has been found that the above objects can be achieved when metal lithium is produced using a thermal reduction process. In this case, however, as the reaction as shown in the following [Formula 1] proceeds in the course of the reduction process after mixing the raw powders, phosphorus (P) gas which is toxic due to lithium phosphate powder as a raw material is generated Still remained.

[Formula 1]

Li 3 PO 4 + 4 CaO + 2 Si? 3 Li (g) + 0.5 P 2 (g) + 2 (2 CaO.SiO 2 )

Accordingly, the inventors of the present invention have made various attempts to solve such problems, and have found that when iron (Fe) powder is added together when raw material powders are mixed together, iron (Fe) and phosphorus (P) (Fe-P) compound can be induced by using the phosphorus (Fe-P) compound. Therefore, the present invention has been completed based on the finding that phosphorus, which is a toxic gas, can be removed.

Accordingly, a method for producing metallic lithium according to an embodiment of the present invention includes the steps of adding iron powder, reducing agent powder, and reduction promoting agent powder to a lithium phosphate powder to prepare a mixed powder, and heat- , ≪ / RTI >

First, a process for preparing a mixed powder by adding lithium phosphate powder, iron powder, reducing agent powder, and reduction promoter powder will be described.

In the production method according to the present invention, lithium phosphate powder may be used as a raw material. As described above, in the case of producing metallic lithium by the heat reduction process, the production cost can be drastically reduced because lithium phosphate which is inexpensive is used instead of expensive lithium oxide generally used as a raw material.

At this time, the average diameter of the lithium phosphate powder may be 100 mesh or less. When the average diameter of the lithium phosphate exceeds 100 mesh, the reaction surface area of the lithium phosphate powder becomes small, so that the reaction rate is slowed in the reduction process to be described later, and the reactivity may be lowered.

In addition, in the present mixed powder production process, iron powder is added together with the lithium phosphate powder to remove toxic gas generated in a reducing process to be described later.

For ease of understanding, FIG. 1 shows a state diagram of iron (Fe) and phosphorus (P). In Fig. 1, the horizontal axis represents composition and the vertical axis represents temperature. M2P + M3P is a region in which Fe 2 P and Fe 3 P compounds coexist, and FEP + M2P is a region in which FeP and Fe 2 P compounds coexist.

As can be seen from the state diagram of FIG. 1, iron (Fe) and phosphorus (P) readily react at high temperatures to form iron phosphide (Fe-P) compounds.

Therefore, in the metal lithium production method including the high-temperature thermal reduction process as described in the present invention, when iron powder is added together with lithium phosphate to the raw material powder mixing step, iron (Fe) and phosphorus (P) Fe 2 P, and / or Fe 3 P is formed. Therefore, it is possible to easily remove phosphorus, which is a toxic gas, and to provide a method for manufacturing environmentally safe metal lithium.

At this time, the amount of the iron powder may be 100 parts by weight to 150 parts by weight based on 100 parts by weight of the lithium phosphate powder.

When the amount of the iron powder is less than the limited range, the amount of the iron phosphide compound to be produced is reduced, thereby reducing the phosphorus removal rate.

Further, when the amount of iron powder to be added is in excess of the limited range, excessive amount of iron powder is added, which may cause economic damages.

Next, the reducing agent powder is not particularly limited as long as the lithium phosphate powder is capable of reducing metallic lithium to produce metallic lithium. Examples of the reducing agent powder include aluminum (Al), silicon (Si), ferrosilicon ), And a combination of these.

The reduction promoter powder may be at least one selected from the group consisting of calcium oxide, aluminum oxide, and combinations thereof, as long as it is a material capable of promoting the reduction reaction of lithium phosphate. Particularly, in the present invention, the reduction promoter powder is preferably a calcium oxide powder in terms of economy and reactivity.

At this time, the average diameter of the reduction promoter powder may be 100 mesh or less. When the average diameter of the reducing promoter powder is more than 100 mesh, the reaction surface area of the reducing promoter powder becomes small, so that the reaction rate is slowed down and the reactivity may be lowered in a reduction process described later.

Specifically, the kind of the reducing agent powder will be described below.

First, when silicon powder is used as the reducing agent powder together with the lithium phosphate powder and the iron powder, and the calcium carbonate powder is used as the reducing promoter powder, the thermal reduction reaction is represented by the following formulas 2 to 4 .

 [Formula 2]

Li 3 PO 4 + 4 CaO + 2 Si + Fe? 3 Li (g) + 2 ( 2 CaO.SiO 2 ) + FeP

[Formula 3]

Li 3 PO 4 + 4 CaO + 2 Si + 2 Fe? 3 Li (g) + 2 (2 CaO.SiO 2 ) + Fe 2 P

[Formula 4]

Li 3 PO 4 + 4CaO + 2Si + 3Fe → 3Li (g) + 2 (2CaO · SiO 2) + Fe 3 P

At this time, the amount of each powder may be determined in consideration of the reaction molar ratio of the formulas 2 to 4.

Specifically, the charging amount of the silicon powder may be 40 to 60 parts by weight based on 100 parts by weight of the lithium phosphate powder.

In this case, the amount of the reducing promoter powder may be 350 parts by weight to 500 parts by weight based on 100 parts by weight of the silicon powder.

When the amounts of the reducing agent and the reducing accelerator are less than the respective limits, the reduction reaction according to the above formulas 2 to 4 incompletely occurs, so that the yield of the metal lithium is Because it is not economical.

Further, when the respective amounts of the reducing agent and the reducing accelerator are more than the respective limited ranges, they are excessively consumed in the reactions of the above formulas 2 to 4, which may also cause economic damages.

At this time, the average diameter of the silicon powder may be 100 mesh or less. When the average diameter of the silicon powder is more than 100 mesh, the reaction surface area of the silicon powder becomes small, so that the reaction rate is slowed in the reduction process to be described later, and the reactivity may be lowered.

If ferrosilicon is used as the reducing agent, the amount of the filler may be determined based on the weight of silicon contained in the ferrosilicon. Also, at this time, the amount of iron powder may be adjusted based on the weight of iron contained in the ferrosilicon.

Aluminum powder may also be used as the reducing agent powder. At this time, the average diameter of the aluminum powder may be 20 mesh or less. When the average diameter of the aluminum powder exceeds 20 mesh, the reaction surface area of the aluminum powder becomes small, so that the reaction rate is slowed in the reduction process to be described later, and the reactivity can be lowered.

In this case, the amount of the aluminum powder may be 80 to 100 parts by weight based on 100 parts by weight of the lithium phosphate powder.

In this case, the amount of the reduction promoter powder may be 70 parts by weight to 85 parts by weight based on 100 parts by weight of the aluminum powder.

When the amount of each of the reducing agent and the reducing accelerator is less than the respective limits, the reduction reaction is incompletely performed in the reduction step to be described later, and the yield of the metal lithium is lowered.

Further, when the amount of the reducing agent and the amount of the reducing accelerator to be added are in excess of the respective limited ranges, the excessive amount is too large to be consumed in the reducing step to be described later, which can also cause economic damages.

Next, in the method for producing metallic lithium according to the present invention, the step of obtaining metallic lithium by thermally reducing the mixed powder prepared as described above will be described.

FIG. 2 schematically shows a reduction system used in an embodiment of the present invention. In the present invention, for example, the reduction reaction according to Formula 2 or Formula 3 can be performed using a reduction system. Hereinafter, a case where the reduction system shown in FIG. 2 schematically illustrated is used will be described as an example.

The reducing system of FIG. 2 comprises a reducing furnace 100, a retort 110, a condenser 120, and the like.

The litter 110 has a lid on the upper part thereof, which can be opened to introduce the reaction materials of the above formula (2). For example, the reaction materials of Formula 2 or 3 may be prepared in the form of a briquette 130 to be described later and then introduced.

At this time, in order to induce the reduction reaction of the formula 2, the temperature of the reducing furnace 100 may be maintained in a temperature range of 1000 ° C to 1400 ° C. That is, the thermal reduction may be performed at a temperature ranging from 1000 ° C to 1400 ° C.

The reason for limiting the temperature range as described above is that the reduction reaction of the above formulas 2 to 4 can be incompletely performed at a temperature lower than 1000 캜, and at a high temperature exceeding 1400 캜, And it is possible that sticking between the single beams 130 may occur.

Independently, the upper portion of the retort 110 is connected by a vacuum pump, so that the interior of the retort 110 can be maintained in a vacuum. Also, there is a lid which can maintain a vacuum in the lower portion of the retort 110. After the reduction process is completed, the slag can be opened by opening the lid.

That is, independently of this, the thermal reduction may be performed in a pressure range of 0.001 atm or less. The pressure range corresponds to a pressure range near the vacuum, and if it exceeds 0.001 atm, the reduction rate of metal lithium may be lowered.

On the other hand, a portion of the upper portion of the return 110 is out of the reducing furnace 100, and a portion thereof can be made into a low temperature portion by using cooling water. By placing the condenser 120 at the low temperature portion, the metallic lithium gas (vapor) generated in the inside of the Ritor 110 can be condensed according to the Equations 2 to 4 above.

In the above description, the vertical reduction system in which the lithot 110 of FIG. 2 is positioned in the vertical direction is taken as an example, but a horizontal type reduction system in which the lithot 110 is positioned in the horizontal direction may be used.

More specifically, the step of thermally reducing the mixed powder to obtain metal lithium may include the steps of producing monochromatic light by applying pressure to the mixed powder, heating the monochromatic light to generate lithium vapor, And condensing.

This means that in the above-mentioned reduction step, the mixed powder is put into a short-circuiting machine to produce a single-phase form, and then the single-phase light is injected into the above-mentioned reduction system to finally obtain metal lithium.

As described above, in the present invention, metal lithium is produced by a thermal reduction process instead of an electrolysis process in which energy consumption is excessive, but lithium phosphate which is inexpensive compared to expensive lithium oxide used in a general heat reduction process is used as a raw material, The cost can be remarkably reduced.

In addition, since it is not necessary to add a separate apparatus or process to remove toxic fumes generated in the manufacturing process by adding iron powder in the preparation of the mixed powder, it is possible to improve the production efficiency, A manufacturing method can be provided.

Hereinafter, preferred embodiments of the present invention and experimental examples therefor will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited to the following examples.

Example  One

Lithium phosphate powders, calcium oxide, silicon and iron powders were prepared and ball milled to an average diameter of about 100 mesh each. Next, the powders were uniformly mixed so that the weight ratio of the lithium phosphate powder: calcium oxide powder: silicon powder: iron powder = 20.5: 39.8: 10.0: 29.7 was uniformly mixed to prepare a mixed powder.

The mixed powder was prepared by applying a pressure of 100 MPa using a single-light production press to monochromatic light.

On the other hand, a crucible made of mild steel having excellent phosphorus reactivity was separately prepared to confirm the removal of phosphorus from the reduction reaction.

Next, put the Briquetting 50g degree in the furnace, 1200 ℃ to lead to a reduction reaction, 10 - 2 torr was reacted for 2 hours under the conditions to obtain a condensed metal lithium. .

Comparative Example  One

The metallic lithium was prepared in the same manner as in Example 1, except that the mixed powder was uniformly mixed in a weight ratio of lithium phosphate powder: calcium oxide powder: silicon powder = 29.2: 56.6: 14.2 to prepare a single powder.

Experimental Example  One

The metal crucible was photographed in order to confirm the removal of phosphorus (P) generated in the reduction process after the metal lithium was produced according to Example 1 and Comparative Example 1, and is shown in FIGS. 3 and 4, respectively.

Referring to the portions indicated by arrows in FIG. 3, it can be seen that, in the case where metallic lithium was prepared by mixing iron powder according to Example 1, even after the reduction process, the edges of the crucible were clean and there was no trace of damage have. Therefore, it can be seen that the phosphorus generated in the reduction process reacts with iron to form iron (Fe-P) compound, and most of it is removed.

On the other hand, in the case of producing metallic lithium without adding iron powder according to Comparative Example 1, it can be seen that the corners of the crucible can not maintain its shape and all are damaged as shown by the arrows in FIG. 4 . This is probably due to the local melting of the corner parts due to the reaction of phosphorus and crucible during the reduction process.

Experimental Example  2

In order to confirm the presence of the iron (Fe-P) compound, the reduction slag remaining after the metal lithium was produced according to Example 1 was analyzed by SEM. The result is shown in FIG.

Referring to FIG. 5, it can be seen that a large amount of iron (Fe-P) compound was observed in the reducing slag after the metal lithium was produced according to Example 1. Accordingly, it can be confirmed that, when the iron powder is mixed with the iron powder as in the present invention, poisonous phosphorus is effectively removed.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

100: reduction furnace
110: Ritoru
120: condenser
130: Single light

Claims (15)

  1. Adding iron powder, a reducing agent powder and a reducing promoter powder to a lithium phosphate powder to prepare a mixed powder; And
    Thermally reducing the mixed powder to obtain metal lithium;
    ≪ / RTI >
  2. The method according to claim 1,
    The amount of the iron powder to be charged is,
    And 50 parts by weight to 150 parts by weight based on 100 parts by weight of the lithium phosphate powder.
  3. The method according to claim 1,
    Wherein the reducing agent powder is at least one powder selected from the group consisting of aluminum, silicon, ferrosilicon, and combinations thereof.
  4. The method of claim 3,
    The amount of the silicon powder to be charged is,
    Wherein the lithium phosphate powder is 40 to 60 parts by weight per 100 parts by weight of the lithium phosphate powder.
  5. The method of claim 3,
    Wherein the silicon powder has an average diameter of 100 mesh or less.
  6. 5. The method of claim 4,
    The amount of the reduction promoter powder to be added is,
    Wherein the amount of lithium is from 350 parts by weight to 500 parts by weight based on 100 parts by weight of the silicon powder.
  7. The method of claim 3,
    The amount of the aluminum powder to be charged is,
    Wherein the lithium phosphate powder is 80 to 100 parts by weight based on 100 parts by weight of the lithium phosphate powder.
  8. The method of claim 3,
    Wherein the average diameter of the aluminum powder is 20 mesh or less.
  9. 8. The method of claim 7,
    The amount of the reduction promoter powder to be added is,
    Wherein the aluminum powder is 70 to 85 parts by weight based on 100 parts by weight of the aluminum powder.
  10. The method according to claim 1,
    Wherein the lithium phosphate powder has an average diameter of 100 mesh or less.
  11. The method according to claim 1,
    Wherein the reduction promoter powder is at least one selected from the group consisting of calcium oxide, aluminum oxide, and combinations thereof.
  12. The method according to claim 1,
    Wherein the reduction promoter powder has an average diameter of 100 mesh or less.
  13. The method according to claim 1,
    The step of thermally reducing the mixed powder to obtain metallic lithium includes:
    Is carried out in a temperature range of 1000 ° C to 1400 ° C.
  14. The method according to claim 1,
    The step of thermally reducing the mixed powder to obtain metallic lithium includes:
    Lt; RTI ID = 0.0 > 0.001 < / RTI > atm.
  15. The method according to claim 1,
    The step of thermally reducing the mixed powder to obtain metallic lithium includes:
    Applying a pressure to the mixed powder to produce a single light;
    Heating the single light to generate lithium vapor; And
    Condensing the lithium vapor;
    ≪ / RTI >
KR1020150125812A 2015-09-04 2015-09-04 Method for producing metallic lithium KR101659800B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019198949A1 (en) * 2018-04-10 2019-10-17 주식회사 엘지화학 Method of producing iron phosphide, positive electrode for lithium secondary battery comprising iron phosphide, and lithium secondary battery comprising same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100092355A (en) * 2009-02-12 2010-08-20 포세이지 인크. Method for the preparation of a lithium phosphate compound with an olivine crystal structure
KR20130061666A (en) * 2010-04-22 2013-06-11 하루오 우에하라 Device and method for recovering lithium
KR20140084476A (en) * 2012-12-26 2014-07-07 주식회사 포스코 Method for manufacturing magnesium

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100092355A (en) * 2009-02-12 2010-08-20 포세이지 인크. Method for the preparation of a lithium phosphate compound with an olivine crystal structure
KR20130061666A (en) * 2010-04-22 2013-06-11 하루오 우에하라 Device and method for recovering lithium
KR20140084476A (en) * 2012-12-26 2014-07-07 주식회사 포스코 Method for manufacturing magnesium

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019198949A1 (en) * 2018-04-10 2019-10-17 주식회사 엘지화학 Method of producing iron phosphide, positive electrode for lithium secondary battery comprising iron phosphide, and lithium secondary battery comprising same

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