KR101238898B1 - Method for recovering with high purity lithium, lithium carbonate, lithium hydroxide and synthetic method of cathod material for lithium secondary battery from sea water - Google Patents

Method for recovering with high purity lithium, lithium carbonate, lithium hydroxide and synthetic method of cathod material for lithium secondary battery from sea water Download PDF

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KR101238898B1
KR101238898B1 KR20100077945A KR20100077945A KR101238898B1 KR 101238898 B1 KR101238898 B1 KR 101238898B1 KR 20100077945 A KR20100077945 A KR 20100077945A KR 20100077945 A KR20100077945 A KR 20100077945A KR 101238898 B1 KR101238898 B1 KR 101238898B1
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lithium
seawater
solution
cathode
purity
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KR20120015658A (en
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전웅
김기홍
송창호
한기천
김기영
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재단법인 포항산업과학연구원
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/02Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/42Treatment of water, waste water, or sewage by ion-exchange
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/42Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/425Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The present invention relates to a method for recovering lithium from seawater, comprising: a first step of introducing an adsorbent into the seawater; Adsorbing lithium in the seawater to an adsorbent; A third step of taking out lithium adsorbent from the sea water; Provided is a method for economically recovering lithium from seawater comprising a fourth step of immersing the adsorbent taken out in the third step in an aqueous solution of phosphoric acid to precipitate lithium as lithium phosphate. According to the present invention, the dissolved lithium of seawater is adsorbed to the adsorbent. It is possible to recover a large amount of lithium contained in seawater in a large amount by easily depositing it into lithium phosphate having low solubility after immersing in an aqueous solution of phosphoric acid, and it is possible to economically and efficiently extract lithium by greatly saving time and energy of the recovery process. .

Description

METHOD FOR RECOVERING WITH HIGH PURITY LITHIUM, LITHIUM CARBONATE, LITHIUM HYDROXIDE AND SYNTHETIC METHOD OF CATHOD MATERIAL FOR LITHIUM SECONDARY BATTERY FROM SEA WATER}

The present invention relates to a method for recovering lithium, lithium carbonate and lithium hydroxide from seawater with high purity and to a method for producing a lithium secondary battery cathode material, and more particularly, to adsorb lithium in the seawater into lithium phosphate after adsorption. The present invention relates to a method for recovering lithium carbonate and lithium hydroxide with high purity by separating lithium through electrolysis after precipitation, and directly manufacturing a lithium secondary battery cathode material.

Lithium is widely used in various industries such as secondary batteries, glass, ceramics, alloys, lubricants, and pharmaceuticals. In particular, lithium secondary batteries have recently attracted attention as a major power source for hybrid and electric vehicles. The battery cell is expected to grow into a huge market 100 times larger than the existing small battery market such as mobile phones and laptops.

In addition, due to the global movement to strengthen environmental regulations, its application fields will be expanded not only to the hybrid and electric vehicle industries, but also to electronics, chemicals, and energy. Domestic and overseas demand is expected to surge.

Conventionally, the production of lithium and lithium compounds has been mainly used ore or brine, but most of the reserves are concentrated in the South American continent such as Chile and Bolivia, and the price is continuously rising due to the insufficient supply compared to the rapidly increasing demand. Due to the problem, seawater, which is presently present in trace amounts but abundantly, has attracted attention as a source of lithium.

It is estimated that about 250 billion tons of lithium is dissolved in seawater, but its concentration is very low at 0.17mg per liter of seawater, so considering the economical efficiency of lithium recovery, a method of recovering lithium at a low cost is required. have.

As a method for recovering lithium from seawater, coprecipitation, solvent extraction, bioconcentration, and adsorption are known, but among these methods, adsorption is considered to be the most realistic way because of high selectivity to lithium. Adsorbed lithium in seawater by ion exchange of and lithium, and then the adsorbent adsorbed lithium recovers lithium through the exchange of hydrogen and lithium in acid aqueous solution, and such manganese oxide inorganic adsorbent can be used repeatedly Has

At this time, the lithium contained in the seawater is mainly extracted in the form of lithium carbonate, the solubility of the lithium carbonate is about 13g / L, so that most of the lithium contained in the seawater is re-dissolved even if most of it is converted to lithium carbonate There is a problem that it is difficult to recover lithium from seawater.

Therefore, conventionally, in order to extract lithium contained in seawater in the form of lithium carbonate, the acid treatment of the adsorbent to desorb the lithium, remove impurities, and then concentrated the lithium solution to a high concentration through a concentrator lithium carbonate more than the solubility of lithium carbonate Since this method has been used, such a conventional method takes a lot of time and energy for lithium concentration, which lowers the industrial productivity, and the lithium recovers in the form of a salt such as sodium to reduce the recovery rate of lithium. there is a problem.

In addition, as a method of manufacturing lithium, electrolysis is generally known. In this method, a bipoly membrane, an anion exchange membrane, and a cation exchange membrane are installed between an anode and a cathode to make three cells of a salt chamber, an acid chamber, and an alkali chamber. A lithium chloride aqueous solution is supplied to the salt chamber, and hydrochloric acid is recovered from the acid chamber, and a lithium hydroxide aqueous solution is recovered from the alkali chamber. However, by using deliquescent lithium chloride, moisture must be cut off during storage, transport and handling, which leads to complicated work, reduced productivity and considerable cost, and a large amount of toxic corrosive chlorine gas from the anode. Therefore, there is a problem that the manufacturing cost is expensive due to the introduction of equipment for recovering the chlorine and performing the detoxification treatment. In addition, due to the complex structure using three cells, such as a salt chamber, an acid chamber, and an alkali chamber, there is a problem in that the distance between the electrodes is widened, the resistance is increased, and the power consumption required for electrolysis is greatly increased.

And, blowing the conventional CO 2 gas in the lithium-containing solution as shown in constituting the anode of the and that leg of the conventional lithium secondary is composed of a lithium composite oxide cathode and a carbon anode common, double lithium secondary battery positive electrode material 5 After lithium carbonate is prepared to produce lithium carbonate, the lithium carbonate is mixed with one or more materials selected from Co, Ni, Fe, Mg, phosphate, and the like, dried at a low temperature, and then heat-treated at a high temperature to obtain LiCoO. 2 , LiNiO 2 , LiFeO 2 , LiMnO 2 , LiFePO 4 and the like has been prepared and used, but there are a number of processes, such as the production of lithium carbonate, there is a problem that the process is complicated and takes a lot of manufacturing cost and time.

The present invention has been made to solve the above problems, by adsorbing a small amount of lithium dissolved in seawater and then precipitated with low solubility lithium phosphate, simplifying the structure of the conventional complex electrolytic device to lower the electrolytic voltage and the power of Low consumption, easy handling, high purity manufacturing method of lithium, lithium carbonate and lithium hydroxide which does not require the introduction of equipment for detoxification treatment due to no generation of chlorine gas, and various lithium processes by omitting lithium carbonate manufacturing process It is an object of the present invention to provide a method in which a lithium secondary battery cathode material can be easily manufactured at low cost by mass synthesis of a secondary battery cathode material.

The present invention comprises the first step of injecting the adsorbent into the sea water; Adsorbing lithium in the seawater to an adsorbent; A third step of dipping the adsorbed lithium into the acid aqueous solution to desorb the adsorbed lithium; In the third step, a method of recovering lithium from seawater including a fourth step of depositing lithium into lithium phosphate by adding phosphoric acid or a compound containing phosphoric acid to a solution from which lithium is desorbed is provided.

At this time, the lithium phosphate is filtered to extract the lithium phosphate, which is characterized by further comprising the step.

In addition, the lithium phosphate concentration is characterized by being 0.39 g / L or more.

In addition, the adsorbent is characterized in that the manganese oxide capable of selective ion exchange between lithium and hydrogen.

In addition, the present invention is prepared by dissolving the lithium phosphate in a solution containing phosphoric acid to produce a lithium phosphate aqueous solution, and after preparing the electrolytic apparatus partitioned by the cation exchange membrane, the anode cell and the cathode cell containing the cathode, Supplying the aqueous lithium phosphate solution to the positive cell, supplying the aqueous solution to the negative electrode cell, and then applying current to transfer lithium ions separated from the positive cell to the negative electrode cell to obtain a lithium hydroxide aqueous solution. It provides a method for recovering lithium from the high purity.

At this time, the electrolytic electrolytic conditions are characterized in that the current density is 1 ~ 200A / cm 2 , the electrolysis temperature is 15 ~ 25 ℃.

In addition, the cation exchange membrane is porous, and its characteristic is that the porosity is 10 to 50%.

In addition, the positive electrode and the negative electrode cells are controlled in an inert gas atmosphere during the reduction of the electrolysis.

Furthermore, the cation exchange membrane is characterized in that it is a polymer membrane capable of passing a cation having one valence.

In addition, the pH of the solution in which the lithium ions of the negative electrode cells are concentrated after the electrolysis is characterized by more than 7.

The present invention also provides a method for recovering lithium carbonate from seawater, characterized by depositing lithium carbonate by reacting a lithium hydroxide aqueous solution obtained by the lithium recovery method according to any one of claims 5 to 10 with CO 2 gas. Provide a method.

The present invention provides a method for recovering lithium hydroxide from seawater with high purity, wherein the lithium hydroxide solution is heated by heating the aqueous lithium hydroxide obtained by the lithium recovery method of any one of claims 5 to 10. .

In addition, the present invention is to prepare a lithium hydroxide aqueous solution by the lithium recovery method of any one of claims 5 to 10, and one or more substances selected from Co, Ni, Fe, Mn is dissolved in the aqueous lithium hydroxide solution. It provides a method for producing a lithium secondary battery positive electrode material from seawater comprising a dissolving step of making a mixed solution by mixing and hot spraying the mixed solution in a chamber to synthesize a lithium secondary battery positive electrode material powder.

At this time, the hot spraying is characterized in that the temperature is 500 ~ 800 ℃.

In addition, after the dissolving step, a chelating and polymerization step of adding and heating a chelating agent and a polymerization aid to the mixed solution, and a pyrolysis step of heating and decomposing the mixed solution having undergone the chelation and polymerization step There is also a feature included in it.

In addition, the chelating agent is citric acid, the polymerization aid is characterized in that the ethylene glycol.

In addition, the present invention comprises a dissolution step of mixing and dissolving the lithium phosphate precipitated by the lithium recovery method of any one of claims 1 to 4, the iron feed material and the phosphoric acid-containing material in an acid; A chelating and polymerization step of adding a chelating agent and a polymerization aid to the solution of the dissolving step and then heating to form a chelating polymer; Pyrolysis step of decomposing the chelated polymer in which the solvent is volatilized by heating in a reducing atmosphere; It provides a method for producing a LiFePO 4 cathode material for lithium secondary batteries from seawater comprising a reduction heat treatment step of heat-treating the material decomposed by the thermal decomposition in a reducing atmosphere.

Here, the chelating agent is citric acid, the polymerization aid is also characterized in that the ethylene glycol.

In addition, the reduction heat treatment step is characterized in that it is made at a temperature of 700 ~ 1,000 ℃.

In addition, the reducing atmosphere is characterized in that the volume ratio of CO / CO 2 is 1: 1 atmosphere.

According to the present invention, after adsorbing a small amount of lithium dissolved in seawater, it precipitates as lithium phosphate having low solubility, and simplifies the structure of the conventional complex electrolytic apparatus, thereby lowering the electrolytic voltage, lowering power consumption, and easy to handle and chlorine. Since there is no gas generation, it is not necessary to introduce a facility for the detoxification process, and thus it is possible to economically manufacture high purity lithium, lithium carbonate and lithium hydroxide, and to omit the manufacturing process of lithium carbonate, and to simplify the various lithium secondary batteries. By directly synthesizing the cathode material, mass production is easy and there is an effect that a lithium secondary battery cathode material can be manufactured at low cost.

1 is a graph showing the concentration of lithium in a lithium-containing solution according to the reaction time when lithium is precipitated with lithium carbonate.
2 is a graph showing the concentration of lithium in a lithium-containing solution according to the reaction time when the lithium is precipitated with lithium phosphate.
3 is a block diagram of an electrolysis device of a lithium manufacturing method according to the present invention.
Figure 4 (a) is a graph showing a change in Li concentration with time when using the lithium manufacturing method according to the present invention, Figure 4 (b) is a graph showing a change in P concentration with time.
5 is a flow chart of a conventional lithium secondary battery cathode material manufacturing method.
6 is a flow chart of a method for producing a LiFePO 4 cathode material for a lithium secondary battery according to the present invention.
7 is an electron micrograph of the LiFePO 4 cathode material powder synthesized by the production method of the present invention.
8 is a graph showing the results of X-ray diffraction analysis (XRD) of the LiFePO 4 cathode material powder prepared according to the present invention.

Hereinafter, the lithium recovery method of the present invention will be described in detail with reference to the drawings.

[How to recover lithium from seawater with high purity]

The present invention first performs a first step of introducing an adsorbent into the seawater in which trace amounts of lithium are dissolved. In this case, the adsorbent is preferably manganese oxide capable of selective ion exchange between lithium and hydrogen, or manganese peroxide having excellent selective adsorption capacity to lithium. The manganese oxide is a spinel manganese oxide, that is, manganese oxide represented by the formula H n Mn 2-x O 4 (wherein 1≤n≤1.33, 0≤x≤0.33, n≤1 + x) is preferred, but Without limitation, manganese peroxide such as MnO 4 may also be used in the present invention.

In the first step, the adsorbent may be introduced into the seawater, or the seawater may be supplied into the chamber using the supply pipe and the supply pump, and the adsorbent may be introduced to adsorb lithium.

After performing the first step, a second step of adsorbing lithium in the seawater to the adsorbent is performed. In this case, when the manganese oxide is used as an adsorbent, lithium is adsorbed by selective ion exchange between hydrogen and lithium, and when the manganese peroxide is used as the adsorbent, lithium in seawater preferentially adsorbs by the following reaction. Is adsorbed on manganese peroxide.

Li + + MnO 4 - → LiMnO 4

In the case where the adsorbent is introduced into the seawater, the adsorbent is kept in the seawater until sufficient time elapses, and when the seawater is supplied into the chamber and adsorbed, the remaining seawater after the adsorption process is discharged through the outlet pipe by the discharge pump. Drain it.

After performing the second step, a third step of taking out the adsorbent with lithium adsorbed from the sea water is performed. That is, it is a process of recovering the adsorbent added after sufficient time for adsorbing the trace dissolved lithium of seawater to an adsorbent.

After performing the third step, a fourth step of depositing lithium into lithium phosphate is performed by immersing the taken out adsorbent in an aqueous solution of phosphoric acid. That is, lithium carbonate (Li 2 CO 3 ) has a solubility of about 13 g / L and is a substance that is dissolved in a relatively large amount, whereas lithium has a small amount of dissolved water in the seawater, so sodium carbonate and the like are added to the seawater to generate lithium carbonate. Most of them are redissolved again, which makes it difficult to extract lithium. Acid treatment of the adsorbent to remove lithium, remove impurities, and then concentrate the lithium solution to a high concentration through a concentrator to precipitate lithium carbonate above the solubility of lithium carbonate. However, this method takes a lot of time and energy for the lithium concentration, the industrial productivity is lowered, there is a problem that the recovery rate of lithium is reduced by the precipitation of lithium in the form of a salt, such as sodium.

However, since lithium phosphate (Li 3 PO 4 ) has a solubility of about 0.39 g / L and is very low solubility compared to lithium carbonate, lithium phosphate adsorbed on the adsorbent is eluted when an aqueous phosphate solution is immersed in the aqueous phosphate solution. The precipitate is easily precipitated and separated into solid lithium phosphate. Here, it is natural that the concentration should be 0.39 g / L or more in order for the lithium phosphate to be precipitated in a solid state without being re-dissolved.

After performing the fourth step, the precipitated lithium phosphate is filtered and extracted from the aqueous solution.

EMBODIMENT OF THE INVENTION Hereinafter, the Example of the method of collect | recovering lithium with high purity from seawater of this invention is described in detail with reference to drawings. However, the following examples are only described to illustrate the present invention, but the present invention is not limited thereto.

The following Comparative Examples and Examples are the results of experiments in the lithium-containing solution, but those skilled in the art will readily know that it is also applicable to the present invention in which lithium is adsorbed into an aqueous solution of phosphoric acid to precipitate lithium as lithium phosphate. Could be.

[Comparative Example]

Sodium carbonate was added at a concentration of 7 g / L to a lithium-containing solution in which lithium ions were dissolved at a concentration of 0.917 g / L, and the temperature of the lithium-containing solution was raised to 90 ° C. and maintained for 15 to 60 minutes.

After the reaction was completed, the lithium-containing solution was filtered to separate the precipitated lithium carbonate, and the remaining filtrate was collected to measure the concentration of lithium, and the results are shown in FIG. 1.

As shown in FIG. 1, even when sodium carbonate was added to the lithium-containing solution and reacted for 15 to 60 minutes, the concentration of lithium in the filtrate was almost the same as that of lithium in the lithium-containing solution before the reaction.

That is, the solubility of lithium carbonate is about 13 g / L, which corresponds to a substance in which a relatively large amount is dissolved in water. Thus, by evaporating and concentrating the lithium-containing solution, the lithium carbonate solution can be added to the lithium-containing solution without significantly increasing the amount of lithium carbonate. It can be confirmed that it is difficult to extract a small amount of dissolved lithium in the form of lithium carbonate. However, when evaporating the lithium-containing solution, a lot of energy and time is required for evaporation, thereby lowering productivity and reducing a recovery rate of lithium.

[Example 1]

After adding sodium phosphate to a concentration of 7.217g / L in a lithium-containing solution in which lithium ions were dissolved at a concentration of 0.917g / L, the temperature of the lithium-containing solution was raised to 90 ° C. and maintained for 15 to 60 minutes. .

After the reaction was completed, the lithium-containing solution was filtered to separate the precipitated lithium phosphate, and the remaining filtrate was collected to measure the concentration of lithium, and the results are shown in FIG. 2.

As shown in FIG. 2, the initial concentration of sodium phosphate in the lithium-containing solution rapidly decreased the concentration of lithium in the filtrate, and after 15 minutes of reaction time, the concentration of lithium in the filtrate was less than 50 mg / L. It can be seen that more than 95% of the lithium dissolved in the lithium-containing solution is precipitated and separated by lithium phosphate.

That is, the solubility of lithium phosphate is about 0.39 g / L, which is very low solubility compared to lithium carbonate. Thus, a small amount of lithium dissolved in a lithium-containing solution is added to a lithium-containing solution by adding a phosphorus supply material such as sodium phosphate to the lithium-containing solution. It can be confirmed that the lithium phosphate can be easily precipitated and separated.

Therefore, the above embodiment is also applied to the present invention relating to seawater, and after adsorbing lithium dissolved in a small amount in seawater to an adsorbent, it is immersed in an aqueous solution of phosphate, and lithium is precipitated with lithium phosphate instead of lithium carbonate and filtered to remove lithium from seawater. It can be seen that it can recover economically and efficiently.

[Method of recovering lithium with high purity from seawater by electrolysis]

An embodiment of the electrolysis device used in the present invention will be described with reference to FIG. 3, by dissolving lithium phosphate in an aqueous solution containing phosphoric acid to increase the solubility to produce a high concentration of lithium phosphate aqueous solution, the anode cell and the cathode in which the positive electrode is installed The negative electrode cell is partitioned by a cation exchange membrane, and thus the complex structure using three cells of a conventional salt chamber, an acid chamber, and an alkali chamber increases the spacing between electrodes, thereby increasing resistance and greatly increasing power consumption required for electrolysis. The increasing problem was solved.

In addition, by supplying lithium phosphate instead of lithium chloride to the anode cell and electrolyzing, there is no need for cumbersome work during storage, transportation and handling by using lithium chloride, and no toxic corrosive chlorine gas is generated from the anode. No introduction of equipment for performing the detoxification process is required.

Here, since the anode can be dissolved in the electrolytic bath of the anode cell as a consuming electrode, it is possible to form an alloy with lithium ions, and it is preferable to use a material having less reactivity with lithium ions. For example, carbon is used for the anode. As a result, the carbon consumed becomes CO 2 gas and is discharged to suppress the reaction with lithium ions.

In addition, it is preferable to use a material that is less reactive with lithium ions in order to increase the recovery rate of lithium, and the negative electrode material is composed of one metal selected from iron, nickel, stainless steel or on the surface of the selected metal. It is preferable that the plating layer is formed.

In addition, the cation exchange membrane is made of a porous material that is in contact with the aqueous lithium phosphate solution of the positive electrode and the aqueous solution of the negative electrode cell, and allows the movement of lithium ions, the porosity is 10 to 50 It is preferable that it is%. When the porosity of the cation exchange membrane exceeds 50%, the lithium phosphate aqueous solution may move from the positive electrode cell to the negative electrode cell, resulting in a decrease in electrolytic efficiency. When the porosity is less than 10%, it becomes difficult to conduct current. This is because the mobility of lithium ions decreases.

The cation exchange membrane is preferably a polymer membrane containing at least one selected from sulfonic acid group, carboxylic acid group, phosphonic acid group, sulfuric acid ester group, and phosphate ester group, wherein the polymer membrane is a lithium cation having one valency. By improving the permeability, it is possible to suppress the passage of polyvalent cations such as calcium and magnesium, or to suppress or exclude the passage of phosphate ions which are anions.

In addition, in the electrolysis device according to the present invention, it is preferable to provide a tank for supplying an aqueous lithium phosphate solution and an aqueous solution to the anode cell and the cathode cell, respectively, to circulate each electrolyte solution. That is, the tank is connected to a circulation line and the electrolyte discharged from each cell is electrolyzed while circulating back to each cell through the tank. When the measured voltage of the anode cell exceeds the preset cell voltage, the concentration of the lithium phosphate solution supplied to the anode cell is reduced to an unsuitable level for electrolysis. Thus, a new lithium phosphate solution is supplied. Supply via line.

In the electrolysis method according to the present invention, as shown in FIG. 1, when a lithium phosphate aqueous solution is added to an anode cell, an aqueous solution is added to an anode cell, and a current is applied to the electrolysis device, the lithium phosphate aqueous solution is used in the anode cell. The decomposition is separated into lithium ions and phosphate ions, wherein the lithium ions separated from the positive cell are transferred to the negative electrode cell through a cation exchange membrane and recovered as lithium metal.

In this case, the electrolytic conditions of the electrolysis is preferably a current density of 10 ~ 200A / cm 2 , an electrolysis temperature of 15 ~ 25 ℃, when the current density is less than 10A / cm 2 , the recovery rate of metal lithium in the negative electrode is low, If the current density exceeds 200 A / cm 2 , there is a problem that the calorific value of the cathode becomes excessive and the temperature management of the electrolytic bath becomes difficult, and the electrolytic bath does not solidify in the range of 15 to 25 ° C. where the electrolytic temperature is room temperature. This is because the current is excellently energized.

In addition, it is preferable to control the anode cell and the cathode cell in an inert gas atmosphere during the reduction of electrolysis. Thus, the atmosphere is controlled by the generation of metallic lithium and hydrogen gas at the cathode of the anode cell, and oxygen in the cathode cell. Gas or, in some cases, carbon dioxide gas is discharged. By controlling the atmosphere of the upper atmosphere inside the anode cell and the cathode cell with an inert gas atmosphere, the contact reaction between each other can be suppressed, thereby eliminating the factor of lowering the electrolytic efficiency. . At this time, the inert gas is preferably argon.

In addition, at the anode, the oxygen ions of the aqueous solution become oxygen gas, and the electrons are given out. At the cathode, the hydrogen ions of the aqueous solution receive the electrons to generate hydrogen gas, and the generated oxygen and hydrogen gas are externally discharged through the upper outlet. Is discharged.

A positive electrode (+): 2O 2- → O 2 (g) + 4e -

A negative electrode (-): 4H + + 4e - → 2H 2 (g)

As described above, since the lithium phosphate aqueous solution is electrolyzed and lithium ions are selectively permeated through the cation exchange membrane in the positive electrode cell, the concentration of lithium ions is gradually lowered and the concentration of phosphate ions is increased, thereby lowering the pH of the electrolyte solution.

On the other hand, in the cathode cell, the concentration of lithium ions transmitted through the cation exchange membrane gradually increases, and as the hydrogen ions in the aqueous solution are released into the hydrogen gas, the pH of the electrolyte is gradually increased, and the lithium cells are highly concentrated in the cathode cell. An aqueous lithium hydroxide solution is produced.

In addition, it is preferable that the pH of the solution in which the lithium ions of the negative electrode cell are concentrated after electrolysis is maintained to be basic, which is 7 when the lithium is carbonated to produce lithium carbonate (Li 2 CO 3 ). If less than lithium carbonate due to the high solubility of lithium carbonate there is a problem that redissolved again, so it is necessary to add an alkali such as NaOH to adjust the pH, in the present invention lithium ion of the negative electrode cell by electrolysis Since the pH of the concentrated solution is more than 7 to maintain basicity, there is an effect of simplifying and facilitating the carbonation process of lithium.

Hereinafter, an embodiment of a method for recovering lithium with high purity from seawater of the present invention will be described in detail with reference to the drawings. However, the following examples are only described to illustrate the present invention, but the present invention is not limited thereto.

[Example 2]

An electrolytic chamber having a positive electrode cell and a negative electrode cell partitioned by a cation exchange membrane was prepared, a positive electrode made of carbon was installed in the positive electrode cell, an iron negative electrode was installed in the negative electrode cell, and the cation exchange membrane had a porosity of 40%. A fluorine cation exchange membrane having a sulfonic acid group was used. Then, as a cathode electrolytic bath, a lithium phosphate aqueous solution having a Li concentration of 15.77 g / L and a P concentration of 89.23 g / L was supplied to the anode cell, and the aqueous solution was supplied to the anode cell. After setting the atmosphere to dry argon atmosphere, electrolysis was performed under electrolytic conditions at an electrolysis temperature of 20 ° C. and a current density of 20 A / cm 2 . As a result, the pH of the final solution of the anode cell was 12.5, no toxic chlorine gas was generated, and metallic lithium with a purity of 99% or more was obtained in a yield of 95% or more.

In addition, as shown in FIGS. 4 (a) and 4 (b), changes in Li concentration and P concentration in the anode cell with time of electrolysis were performed. At pH 12.5 the concentration of lithium was 25.56 g / L and the concentration of P was 0.015 g / L. As described above, P was hardly moved by the method of manufacturing lithium by electrolysis of the present invention, but it was confirmed that lithium was selectively permeated through the cation exchange membrane and mostly moved to the cathode cell.

[Method for recovering lithium carbonate or lithium hydroxide from seawater with high purity]

The method of recovering lithium carbonate with high purity from seawater according to the present invention is characterized by depositing lithium carbonate by carbonizing a lithium hydroxide aqueous solution in which lithium obtained by the lithium recovery method is highly concentrated with CO 2 gas. Since the lithium hydroxide aqueous solution is a high purity solution without impurities such as B, Mg, Ca, and SO 4 , the lithium carbonate may be carbonized with CO 2 gas to obtain high purity lithium carbonate.

In addition, the method of recovering lithium hydroxide from the seawater according to the present invention with high purity is characterized by depositing lithium hydroxide by heating the lithium hydroxide aqueous solution obtained by the above-described lithium recovery method. Since the lithium hydroxide aqueous solution is a solution containing high purity lithium in which impurities are purified, high purity lithium hydroxide may be obtained by evaporating the solvent through heating.

[Manufacturing Method of Lithium Secondary Battery Cathode Material from Sea Water]

The present invention first performs a step of preparing a concentrated lithium solution. The lithium concentrated solution is a solution in which impurities such as Mg, Ca, B, and SO 4 are removed and lithium is concentrated at a high concentration, and the lithium concentrated solution may be any solution in which lithium is highly concentrated by various methods. It is preferred that the high purity lithium separated by decomposition be a concentrated solution.

That is, as an example, as shown in FIG. 3, a cathode cell having a cathode partitioned by a cation exchange membrane and a cathode cell provided with a cathode are prepared, and a high concentration of aqueous lithium phosphate solution is supplied to the anode cell as a cathode electrolytic bath. After supplying the aqueous solution to the cathode cell, by electrolysis to selectively separate the lithium ions through a cation exchange membrane can be obtained a lithium hydroxide (LiOH) aqueous solution of high purity lithium free of impurities.

Then, a dissolution step of dissolving a material containing at least one selected from Co, Ni, Fe, and Mn in the lithium concentrated solution to form a mixed solution is performed. That is, one material selected from Co, Ni, Fe, and Mn is mixed and dispersed in the lithium concentrated solution to prepare a liquid mixed solution.

At this time, a chelating and polymerization step of heating by adding a chelating agent and a polymerization agent to the mixed solution, and pyrolysis to heat and decompose the mixed solution after the chelating and polymerization step. A pyrolysis step may be further included.

That is, by adding a chelating agent to the mixed solution, hydrogen (H) attached to the outermost part becomes H + to be dissolved, and soon combines with metal ions dissolved in the solution. Here, the chelating agent is citric acid (C 6 H 8 O 7 , citric acid), adipic acid (C 6 H 10 O 4 , adipic acid), methacrylic acid (C 4 H 6 O 2 , methacrylic acid), glyco Although it may be composed of one or more selected from lactic acid (C 2 H 4 O 3 , glycolic acid), it is particularly preferable to use citric acid, which is low in price and excellent in chelating reactivity.

Then, the polymerization aid is added together and heated to form a polymer by esterification. In this case, it is preferable to use ethylene glycol having excellent polymerization reactivity as the polymerization aid.

Here, the polymerization reaction is preferably heated to a temperature range of 100 ~ 250 ℃, less than 100 ℃ polymerization reactivity is lower, if it exceeds 250 ℃ is a lot of polymerization heat is generated to remove the heat effectively difficult to control the reaction Losing is a problem.

Thereafter, a pyrolysis step of heating and decomposing the mixed solution having undergone the chelation and polymerization steps may be performed. The pyrolysis step may be performed by heating and decomposing the polymer to evaporate elements such as C and H. It's a process. At this time, the heating is preferably made at a temperature of 400 ~ 550 ° C, the decomposition of the chelate polymer is not smooth at a temperature below 400 ° C, since the effect of pyrolysis is saturated at a temperature exceeding 550 ° C. to be.

Thereafter, a synthesis step of synthesizing the lithium secondary battery positive electrode material by hot spraying the mixed solution into the chamber. That is, lithium secondary battery cathode materials such as LiCoO 2 , LiNiO 2 , LiFeO 2 , and LiMnO 2 , which are composite oxides, may be synthesized by hot spraying the liquid mixed solution in the chamber while the chamber is heated with a burner.

The hot spraying is performed by spraying a mixed solution of lithium mixed with at least one material selected from Co, Ni, Fe, and Mn prepared in a liquid state while heating the chamber to a high temperature.

At this time, the temperature during the hot spray is preferably 500 ~ 800 ℃ bar, if the temperature exceeds 800 ℃ the synthesis reaction proceeds so fast that the abnormal growth particles are formed in a non-uniform phase life of the secondary battery This is because there is a problem that can be lowered, and if the temperature is less than 500 ° C., the desired final composite oxide structure may not be formed.

As such, when the lithium secondary battery cathode material used as the cathode active material of the lithium secondary battery is omitted, a complicated lithium carbonate manufacturing process is omitted, and a mixture of lithium and one or more materials selected from Co, Ni, Fe, and Mn is mixed. By hot-spraying the melt and synthesizing it directly into various composite oxides, mass production is easy and a lithium secondary battery cathode material can be manufactured at low cost.

That is, as shown in FIG. 5 and then conventionally produced lithium carbonate by blowing a CO 2 gas to a lithium concentration solution precipitated, filtered and washed and then producing a lithium carbonate, which Co, Ni, Fe, Mn 1 After mixing and pulverizing with more than one species and drying, the lithium secondary battery cathode material manufactured through high-temperature heat treatment was required to undergo a complicated process, but in the present invention, as shown in FIG. 3, Co, Ni, Fe, and Mn were selected. By hot-spraying a mixed solution of one or more materials and lithium into the chamber by directly spraying a variety of lithium secondary battery cathodes, the process can be drastically reduced to produce a lithium secondary battery cathode material at low cost.

In particular, in the case of using a high concentration lithium hydroxide aqueous solution in which the lithium phosphate aqueous solution is supplied to the anode cell as shown in Figure 3 and selectively permeate the electrolyzed lithium ions through the cation exchange membrane, a concentrated solution containing high purity lithium It is possible to obtain a high-quality lithium secondary battery positive electrode material directly without a separate manufacturing process of lithium carbonate.

The lithium secondary battery positive electrode material may be finally obtained by performing the step of recovering the synthesized lithium secondary battery positive electrode material powder. Here, the recovery means uses known means that are commonly used.

EMBODIMENT OF THE INVENTION Hereinafter, the Example of the manufacturing method of the lithium secondary battery positive electrode material from seawater of this invention is described in detail. However, the following examples are only described to illustrate the present invention, but the present invention is not limited thereto.

[Example 3]

As shown in FIG. 2, a cathode cell having a cathode partitioned by a cation exchange membrane and a cathode cell provided with a cathode are prepared, a high concentration lithium phosphate aqueous solution is supplied to the anode cell as an anode electrolytic bath, and an aqueous solution is supplied to the cathode cell. Thereafter, electrolysis was performed to selectively separate lithium ions through a cation exchange membrane into a cathode cell, thereby preparing a lithium hydroxide (LiOH) aqueous solution in which lithium of high purity was concentrated.

In addition, Co (NO 3 ) 2 6H 2 O, which is a cathode material, is mixed with the lithium hydroxide aqueous solution to form a mixed solution, and the mixed solution is heated in the chamber for 3 hours while the chamber is heated at a temperature of 700 ° C. Hot sprayed.

Example 4

After preparing a lithium hydroxide (LiOH) aqueous solution by the same process as in Example 1, Co (NO 3 ) 2 6H 2 O as a cathode material raw material was mixed with the aqueous lithium hydroxide solution to form a mixed solution, the mixture Citric acid and ethylen glycol were added to the solution, and the mixture was heated at 130 ° C. for 2 hours, and then heated to 200 ° C. to concentrate. The polymer was then pyrolyzed by heating to a temperature of 450 ° C. and then the mixed solution was hot sprayed into the chamber for 3 hours while the chamber was heated at a temperature of 700 ° C.

As a result of the above Example 3 and Example 4, it was possible to obtain a homogeneous LiCoO 2 cathode material powder by a simplified process.

Therefore, the present invention can omit a complicated process for producing lithium carbonate, and hot-spray a mixed solution of lithium and one or more substances selected from Co, Ni, Fe, and Mn, which are raw materials for lithium secondary battery cathode materials, into the chamber. By synthesizing various lithium secondary battery cathode materials, it is possible to manufacture high quality lithium secondary battery cathode materials at a low cost with easy mass production.

LiFePO for Lithium Secondary Batteries from Seawater 4  Manufacturing Method of Cathode Material]

As shown in FIG. 6, the present invention first performs a dissolution step of dissolving the iron feed material, lithium phosphate and phosphoric acid containing material by mixing in an acid (S1 step). That is, the iron feed material, lithium phosphate, and phosphoric acid containing material are mixed and dissolved in an acid at a constant molar ratio.

At this time, the iron feed material is most preferably electrolytic iron (electroltic iron) that is well soluble in acid, iron-containing compounds of various metal iron salts (hydrates such as FeNO 3 , FeCl 2 , FeCl 3 ) that can be dissolved in acid is also used. Can be.

In addition, the lithium phosphate is preferably used lithium phosphate powder in consideration of solubility, and the lithium phosphate powder is mainly used by precipitating a phosphorus supply material in a lithium-containing solution.

In addition, the phosphoric acid-containing material may be one or more selected from phosphoric acid, sodium phosphate, potassium phosphate, ammonium phosphate.

After the dissolving step, a chelating agent and a polymerization step are added to the dissolved solution in which the raw materials are mixed and dissolved, followed by chelating and polymerization to form a chelate polymer by heating. (Step S2). That is, by adding a chelating agent to the solution, hydrogen (H) attached to the outermost layer becomes H + to be dissolved, and soon combines with metal ions dissolved in the solution.

Here, the chelating agent is citric acid (C 6 H 8 O 7 , citric acid), adipic acid (C 6 H 10 O 4 , adipic acid), methacrylic acid (C 4 H 6 O 2 , methacrylic acid), glyco Although it may be composed of one or more selected from lactic acid (C 2 H 4 O 3 , glycolic acid), it is particularly preferable to use citric acid, which is low in price and excellent in chelating reactivity.

In addition, a polymerization aid is added together with the chelating agent and heated to form a chelating polymer by esterification. In this case, it is preferable to use ethylene glycol having excellent polymerization reactivity as the polymerization aid.

Here, it is preferable to heat to the temperature range of 100 ~ 250 ℃ in the polymerization reaction, the polymerization reactivity is less than below 100 ℃, if it exceeds 250 ℃ a lot of polymerization heat is generated to remove the heat effectively difficult to control the reaction Losing is a problem.

After the chelation and polymerization steps, a solvent volatilization step may be performed to volatilize the solvent. Here, as for heating temperature, the temperature of 300-400 degreeC is preferable.

Next, a pyrolysis step of decomposing the chelate polymer by heating in a reducing atmosphere is performed (step S3). That is, it is preferable to thermally decompose in a reducing atmosphere to prevent oxidation of iron (Fe 2+ ), and to inject argon (Ar) gas for controlling such a reducing atmosphere.

The pyrolysis step is a process of evaporating and removing elements such as C and H by heating and decomposing the chelate polymer to prepare LiFePO 4 cathode material. At this time, the heating is preferably made at a temperature of 400 ~ 550 ℃, there is a problem that the decomposition of the chelate polymer is not smooth at a temperature below 400 ℃, because the effect of pyrolysis is saturated at a temperature exceeding 550 ℃. to be.

After the pyrolysis step, a reduction heat treatment step of heat-treating the material decomposed by pyrolysis in a reducing atmosphere is performed (step S4). In this case, the reducing atmosphere may be H 2 atmosphere or CO, CO 2 atmosphere, in particular, the atmosphere of the volume ratio of CO / CO 2 is 1: 1 is preferred. As such, the oxygen partial pressure may be further lowered under an atmosphere having a volume ratio of CO / CO 2 of 1: 1 to prevent oxidation of iron (Fe 2+ ).

In addition, the reduction heat treatment step is preferably carried out at a temperature of 700 ~ 1,000 ℃, less than 700 ℃ has a problem in that the crystalline material is difficult to form a low degree of synthesis of LiFePO 4 single phase having Fe 2+ , 1,000 ℃ If it exceeds, there is a problem that the degree of synthesis is saturated and the energy is excessively consumed.

Then, the synthesized LiFePO 4 cathode material powder for lithium secondary battery is recovered by a conventional recovery means.

With reference to the drawings an embodiment of the lithium secondary battery positive electrode LiFePO 4 preparation material from the water the inventors will be described in detail. However, the following examples are intended to illustrate the present invention, but the present invention is not limited thereto.

[Example 5]

The raw materials electrolytic iron, lithium phosphate powder, and phosphoric acid were quantified in a molar ratio of 1: 1: 1, dissolved in aqua regia mixed with hydrochloric acid and nitric acid in a volume ratio of 3: 1, and citric acid and ethylin glycol were dissolved in the mixed solution. Was added and heated at 130 ° C. for 2 hours, and heated to 200 ° C. to form a chelate polymer. After heating at 350 ° C. to volatilize the solvent, and pyrolyzing the chelating polymer by maintaining heating at 450 ° C. under Ar atmosphere, the final reduction heat treatment is performed at 900 ° C. under an atmosphere having a volume ratio of CO / CO 2 of 1: 1. Heat treatment for 30 minutes to prepare a LiFePO 4 powder.

The LiFePO 4 powder prepared in Example was analyzed by electron microscopy and X-ray diffraction (XRD), and the results are shown in FIGS. 7 and 8. As shown in Figure 7, the LiFePO 4 powder synthesized according to the production method of the present invention can be confirmed that the particles are fine and homogeneous, as shown in Figure 8 synthesized as a single-phase cathode material powder without an impurity peak (peak) there was.

As a result, the present invention can significantly reduce the number of existing complex processes and directly manufacture LiFePO 4 cathode material without the synthesis process of lithium hydroxide or lithium carbonate, which enables easy mass production and low cost, and also provides fine and non-powder particles. It has a large surface area and excellent battery characteristics.

Claims (20)

  1. A first step of introducing an adsorbent into seawater;
    Adsorbing lithium in the seawater to an adsorbent;
    A third step of dipping the adsorbed lithium into the acid aqueous solution to desorb the adsorbed lithium;
    A method for recovering lithium from seawater comprising a fourth step of depositing lithium into lithium phosphate by adding a phosphoric acid or a compound containing phosphoric acid to the solution in which the lithium is desorbed in the third step.
  2. The method of claim 1,
    And recovering lithium from the seawater with high purity, further comprising filtering the precipitated lithium phosphate to extract lithium phosphate.
  3. The method of claim 1,
    The lithium phosphate concentration is 0.39g / L or more method for recovering lithium from sea water, characterized in that high purity.
  4. The method of claim 1,
    The adsorbent is a manganese oxide capable of selective ion exchange between lithium and hydrogen, the method of recovering lithium from seawater with high purity.
  5. 5. The method according to any one of claims 1 to 4,
    After dissolving the lithium phosphate in a solution containing phosphoric acid to prepare a lithium phosphate aqueous solution, and after preparing an electrolytic device partitioned by a cation exchange membrane, a cathode cell containing a cathode and a cathode cell containing a cathode,
    Supplying the aqueous lithium phosphate solution to the positive electrode cell, supplying the aqueous solution to the negative electrode cell, and then applying a current to transfer lithium ions separated from the positive electrode cell to the negative electrode cell to obtain a lithium hydroxide aqueous solution. A high purity recovery of lithium from seawater.
  6. The method of claim 5,
    Electrolytic conditions of the electrolysis is a method for recovering lithium from the sea water, characterized in that the current density is 1 ~ 200A / cm 2 , the electrolysis temperature is 15 ~ 25 ℃.
  7. The method of claim 5,
    The cation exchange membrane is porous, the method of recovering lithium from the sea water with high purity, characterized in that the porosity of 10 to 50%.
  8. The method of claim 5,
    A method for recovering lithium from seawater with high purity, characterized in that for controlling the cathode and anode cells in an inert gas atmosphere during the reduction of the electrolysis.
  9. The method of claim 5,
    The cation exchange membrane is a method for recovering lithium from the seawater with high purity, characterized in that the polymer membrane capable of passing a cation having one valence.
  10. The method of claim 5,
    After the electrolysis, the method of recovering lithium from the sea water with a high purity, characterized in that the pH of the solution of the concentrated lithium ion of the negative electrode cell exceeds 7.
  11. A method of recovering lithium carbonate from seawater with high purity, wherein the aqueous lithium hydroxide solution obtained by the lithium recovery method of claim 5 is reacted with CO 2 gas to precipitate lithium carbonate.
  12. The lithium hydroxide aqueous solution obtained by the lithium recovery method of Claim 5 is heated, and lithium hydroxide is precipitated, The method of recovering lithium hydroxide from seawater with high purity.
  13. Preparing an aqueous lithium hydroxide solution by the lithium recovery method of claim 5;
    A dissolution step of dissolving at least one material selected from Co, Ni, Fe, and Mn in the aqueous lithium hydroxide solution to form a mixed solution;
    The method of manufacturing a lithium secondary battery cathode material from seawater comprising the step of hot spraying the mixed solution to the chamber to synthesize a lithium secondary battery cathode material powder.
  14. The method of claim 13,
    Temperature during the hot spray is a method of manufacturing a lithium secondary battery cathode material from sea water, characterized in that 500 ~ 800 ℃.
  15. The method of claim 13,
    After the dissolution step, a chelating and polymerization step of heating by adding a chelating agent and a polymerization aid to the mixed solution;
    A method for producing a lithium secondary battery cathode material from seawater, characterized in that it further comprises a pyrolysis step of heating and decomposing the mixed solution having undergone the chelation and polymerization steps.
  16. 16. The method of claim 15,
    Wherein said chelating agent is citric acid and said polymerization aid is ethylene glycol.
  17. A dissolving step of mixing lithium phosphate precipitated by the lithium recovery method according to any one of claims 1 to 4 with an iron supply material and a phosphoric acid-containing material by dissolving it in an acid;
    A chelating and polymerization step of adding a chelating agent and a polymerization aid to the solution of the dissolving step and then heating to form a chelating polymer;
    Pyrolysis step of decomposing the chelated polymer in which the solvent is volatilized by heating in a reducing atmosphere;
    Method for producing a lithium secondary battery LiFePO 4 cathode material from seawater comprising a reduction heat treatment step of heat-treating the material decomposed by the thermal decomposition in a reducing atmosphere.
  18. 18. The method of claim 17,
    Said chelating agent is citric acid, and said polymerization aid is ethylene glycol, The manufacturing method of the LiFePO 4 positive electrode material for lithium secondary batteries from seawater.
  19. 18. The method of claim 17,
    The reduction heat treatment step is a method of manufacturing a LiFePO 4 cathode material for lithium secondary batteries from sea water, characterized in that at a temperature of 700 ~ 1,000 ℃.
  20. 18. The method of claim 17,
    The reducing atmosphere is a method for producing a LiFePO 4 cathode material for lithium secondary batteries from sea water, characterized in that the volume ratio of CO / CO 2 is 1: 1.
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