KR20140071541A - Method for Recovering of Lithium Hydroxide from Spent Liquor from Manufacturing of Lithium Iron Phosphate and Lithium Hydroxide Prepared Therefrom - Google Patents

Abstract

The present invention relates to a method for recovering a lithium hydroxide (LiOH) solution, comprising producing lithium iron phosphate (LiFePO_4) by a hydrothermal method or a supercritical hydrothermal method, inducing precipitation in a remaining liquid waste after producing lithium iron phosphate, and removing the precipitate to recover a lithium hydroxide (LiOH) solution; and to a lithium hydroxide (LiOH) solution prepared therefrom.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a method for recovering a lithium hydroxide solution from a waste solution of a lithium iron phosphate and a lithium hydroxide solution prepared therefrom,

The present invention relates to a method for recovering a lithium hydroxide (LiOH) solution from a waste liquid for production of lithium iron phosphate (LiFePO ₄ ) and a lithium hydroxide solution prepared therefrom.

As information technology (IT) technology has developed remarkably, various portable information and communication devices have been spreading, so that the 21st century is being developed into a "ubiquitous society" capable of providing high quality information services regardless of time and place.

As a development base for such a ubiquitous society, a lithium secondary battery occupies an important position.

The lithium secondary battery has a higher operating voltage and energy density than other secondary batteries and can be used for a long time, so that it can meet the complex requirements for diversification and combination of devices.

2. Description of the Related Art [0002] Recently, efforts have been actively made worldwide to expand the application field of lithium secondary battery technology by further developing the conventional lithium secondary battery technology, as well as an environmentally friendly transportation system such as an electric vehicle.

Among the components of the lithium secondary battery, the cathode material plays an important role in determining the capacity and performance of the battery in the battery.

LiCoO _{2, the} first to be adopted, has been able to apply its charge characteristics to the recent charge voltage of 4.3 V, while continuing to develop it by adopting a technique called doping or surface modification.

On the other hand, the complexity of the application equipment has further strengthened the required characteristics. Research and development of new materials have begun with high operating voltage as well as high capacity. Among them, LiNi _{1? X} M _x O ₂ , Li [Ni _x Mn _y Co _z ] O ₂ , Li [Ni _0.5 Mn _0.5 ] O _{2 and} so on.

In recent years, development of electric vehicles has become more active due to high oil prices, and new materials with high safety have become necessary. In response to these demands, highly safe materials such as LiMn ₂ O ₄ and LiFePO ₄ have been developed.

The most widely known method for producing such cathode materials is a solid phase reaction method. The solid-phase reaction method is advantageous in that it is easy to approach because it is a technique that has been conventionally used to manufacture metal oxides. However, since the synthesis is performed at a high temperature, the particle size of the sample is rapidly increased to decrease the surface area and the diffusion of lithium ions, And the performance is deteriorated.

Specifically, when LiFePO ₄ is produced by a solid-phase reaction method, Fe ₂ O ₃ , Li ₃ Fe ₂ (PO ₄ ) ₃ and Fe ₂ O ₃ produced by an Fe ³⁺ ion are reacted with an excessive amount of nitrogen gas or by using a homogeneous starting material The same impurity formation should be minimized.

As another method for producing LiFePO ₄ , a hydrothermal method or supercritical water heating method is known in the art.

However, when LiFePO ₄ is produced by the hydrothermal method or the supercritical hydrothermal method, an excessive amount of lithium source should be supplied, while lithium ions other than lithium ions participating in the synthesis of LiFePO ₄ are dissolved in the manufacturing waste liquid It is true.

Lithium metal is a rare metal of high price, and it is a recent situation that the entire amount is imported from abroad. Recently, a lot of techniques for recovering lithium metal from seawater have been researched, but the technology of recovering lithium ions from the waste liquid for manufacturing LiFePO ₄ has not been known to date.

Therefore, the inventors of the present application intend to provide a technique for recovering lithium ions from a waste liquid for producing LiFePO ₄ and a recovered lithium hydroxide solution according to the method of the present invention.

The lithium hydroxide solution according to the present invention is characterized in that the content of metal cations having +1 oxidation or +2 oxidation number which makes it an insoluble salt which is combined with anions provided from a salt of iron (Fe) 0.01 to 30%.

Specifically, the salt of iron (Fe) may be at least one selected from the group consisting of iron sulfate, iron carbonate (FeCO ₃ ) and iron chloride. More specifically, iron sulfate is ferrous sulfate (FeSO ₄ ) hydrate, It may be a ferrous chloride (FeCl ₂₎ hydrate. In this case, the anion provided from the salt of iron (Fe) may be at least one selected from the group consisting of sulfate ion (SO ₄ ^2- ), carbonate ion (CO ₃ ^2- ) or chloride ion (Cl ^- ).

The metal cation having an oxidation number of +1 or +2 is selected from the group consisting of a transition metal having an oxidation number of +1 valence, an alkaline earth metal, a transition metal having an oxidation number of +2 or a metal having a valence of +2 The transition metal having the oxidation number of +1 valence may be silver (Ag), and the alkaline earth metal may be barium (Ba), calcium (Ca), or strontium (Sr) The metal having an oxidation number of +2 valence may be lead (Pb).

Such a lithium hydroxide solution can be obtained from a manufacturing waste liquid of lithium iron phosphate (LiFePO ₄ ) produced by hydrothermal method or supercritical hydrothermal method.

In one specific embodiment, LiFePO ₄ is prepared by premixing an aqueous solution of an iron (Fe) precursor compound, an alkalizing agent and a lithium precursor compound and adding to the mixture a supercritical charge in the range of 200 to 700 ° C under a pressure of 180 to 550 bar And secondary mixing and drying of the subcomponent.

In some cases, the synthesized lithium metal composite oxide may be continuously calcined or calcined in the range of 600 to 1200 ° C, followed by calcination. The above-mentioned calcination after the continuous calcination or granulation, followed by calcination, can improve the degree of contact between the crystals by growing crystals of the lithium composite oxide particles.

The iron (Fe) precursor compound, non-limiting examples of the alkali agent, ferrous sulfate, and can be at least one selected from the group consisting of carbon steel (FeCO ₃₎ and iron chloride, as described above, is an alkali metal hydroxide (NaOH, KOH and the like), alkaline earth metal hydroxides (Ca (OH) ₂ , Mg (OH) ₂ and the like), ammonia compounds (ammonia water and ammonium nitrate), and mixtures thereof. Possible water-soluble salts include, but are not limited to, lithium nitrate, lithium acetate, lithium hydroxide, lithium sulfate, and the like. In particular, lithium hydroxide can serve not only as a lithium source but also to enhance alkalinity.

Excessive lithium ions are present in the waste liquid for manufacturing LiFePO ₄ produced through the above process. This can be confirmed from the following Reaction Scheme 1.

_{3LiOH + FeX + H 3 PO 4} → LiFePO 4 + 2Li + + X + 3H 2 O (1)

In the above formula, X is an anion forming an insoluble salt by ionic bonding with the +1 + or 2 + -valent metal ion. Specifically, sulfate ion (SO ₄ ^2- ), carbonate ion (CO ₃ ^2- ) ion (Cl ^-) may be at least one selected from the group consisting of.

(A) an evaporation process for increasing the concentration of lithium ions by heating and / or reducing pressure in a waste aqueous solution or lithium ion in which anions provided from salts of lithium ions and iron (Fe) are dissolved;

(b) a precipitation process in which a hydroxide of a metal having an oxidation number of +1 or +2 is added to a solution having a higher lithium ion concentration to precipitate the insoluble salt of the metal; And

(c) separating the precipitate and obtaining a filtrate; And a method for producing the lithium hydroxide solution. After the step (c), a distillation step for concentrating the filtrate containing lithium hydroxide may be further included.

The method may further include a step of preparing a lithium transition metal oxide or a lithium transition metal phosphate using the recovered lithium hydroxide solution as a lithium source.

Specifically, the evaporation process in step (a) is performed to increase the concentration of lithium ions dissolved in the aqueous solution, and proceeds until the concentration of dissolved lithium ions in the aqueous solution becomes 1 wt% or more of the aqueous solution. More specifically, the evaporation process may be performed by heating at a temperature ranging from 100 to 200 ° C, or simultaneously performing reduced pressure and heating at a temperature and a vacuum condition ranging from 40 to 90 ° C.

Hydroxide of the process (b) is specifically, hydroxide (AgOH) hydroxide and lead (Pb (OH) _2), barium hydroxide (Ba (OH) _2), calcium hydroxide (Ca (OH) _2), strontium hydroxide ( Sr (OH) ₂ ), or a mixture thereof. These hydroxides may be added in the form of a liquid aqueous solution or in the form of a solid solid powder, and may be added at a concentration equal to or more than the equivalent amount of lithium ions. Particularly, in the case of barium hydroxide, the higher the temperature, the higher the solubility. Therefore, it can be added at a temperature of 70 ° C or higher.

The equivalent ratio of the hydroxide to lithium ion may be in the range of 1: 1 to 3: 1.

The present invention also provides a lithium secondary battery using a lithium transition metal oxide or a lithium transition metal phosphate produced by using the lithium hydroxide solution recovered by the above method as a lithium source as a cathode active material.

Examples of the lithium transition metal oxide or lithium transition metal phosphorus oxide include a layered compound such as lithium cobalt oxide (LiCoO ₂ ) and lithium nickel oxide (LiNiO ₂ ), or a compound substituted with one or more transition metals; Lithium manganese oxides such as Li _{1 + y} Mn _2-y O ₄ (where y is 0 to 0.33), LiMnO ₃ , LiMn ₂ O ₃ and LiMnO ₂ ; Lithium copper oxide (Li ₂ CuO ₂ ); Vanadium oxides such as LiV ₃ O ₈ , LiFe ₃ O ₄ , V ₂ O ₅ and Cu ₂ V ₂ O ₇ ; Formula _{LiNi 1-y M y O 2} ( where, the M = Co, Mn, Al, Cu, Fe, Mg, B or Ga, y = 0.01 ~ 0.3 Im) Ni site type lithium nickel oxide which is represented by; Formula _{LiMn 2-y M y O 2} ( where, M = Co, Ni, Fe , Cr, and Zn, or Ta, y = 0.01 ~ 0.1 Im) or Li ₂ Mn ₃ MO ₈ (where, M = Fe, Co, Ni, Cu, or Zn); LiMn ₂ O _{4 in} which a part of Li in the formula is substituted with an alkaline earth metal ion; Disulfide compounds; Fe ₂ (MoO ₄ ) ₃ , and the like. However, the present invention is not limited to these.

The lithium secondary battery has a structure in which an electrolyte assembly is impregnated with an electrode assembly including a positive electrode, a separator, and a negative electrode. The positive electrode is formed by mixing a positive electrode mixture containing the positive electrode active material with a solvent such as NMP, Applying it on a current collector, followed by drying and rolling.

In addition to the cathode active material, the cathode mixture may optionally include a conductive material, a binder, a filler, and the like.

The cathode current collector generally has a thickness of 3 to 500 mu m. Such a positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery, and examples thereof include copper, stainless steel Surface-treated with carbon, nickel, titanium, silver or the like, aluminum-cadmium alloy, or the like can be used. The positive electrode current collector may be formed into various shapes such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven fabric, or the like by forming fine irregularities on the surface to enhance the bonding force of the positive electrode active material.

The conductive material is usually added in an amount of 1 to 30% by weight based on the total weight of the mixture including the cathode active material. Such a conductive material is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery, for example, graphite such as natural graphite or artificial graphite; Carbon black such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fiber and metal fiber; Metal powders such as carbon fluoride, aluminum, and nickel powder; Conductive whiskey such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.

The binder is added to the binder in an amount of 1 to 30% by weight, based on the total weight of the mixture containing the cathode active material, as a component that assists in bonding between the active material and the conductive agent and bonding to the current collector. Examples of such binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene , Polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butylene rubber, fluorine rubber, and various copolymers.

The filler is optionally used as a component for suppressing expansion of the anode, and is not particularly limited as long as it is a fibrous material without causing a chemical change in the battery. Examples of the filler include olefin-based polymerizers such as polyethylene and polypropylene; Fibrous materials such as glass fibers and carbon fibers are used.

Typical examples of the dispersion include isopropyl alcohol, N-methyl pyrrolidone (NMP), and acetone.

The method of uniformly applying the paste of the cathode material to the metal material can be selected from known methods or a new appropriate method in view of the characteristics of the material and the like. For example, the paste can be uniformly dispersed by using a doctor blade or the like after being distributed on the current collector. In some cases, a method of performing the distribution and dispersion processes in a single process may be used. In addition, a die casting method, a comma coating method, a screen printing method, or the like may be used. Alternatively, the resin may be formed on a separate substrate, and then pressed or laminated by a pressing or laminating method. .

It is preferable that the paste applied on the metal plate is dried in a vacuum oven at 50 to 200 DEG C within one day.

The negative electrode may be formed by coating a negative electrode active material on a negative electrode collector and drying the negative electrode active material. If necessary, the negative electrode may further include components such as a conductive agent, a binder, and a filler as described above.

The negative electrode collector is generally made to have a thickness of 3 to 500 mu m. Such an anode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery, and may be formed of a material such as copper, stainless steel, aluminum, nickel, titanium, fired carbon, surface of copper or stainless steel A surface treated with carbon, nickel, titanium, silver or the like, an aluminum-cadmium alloy, or the like can be used. In addition, like the electrode current collector, fine unevenness may be formed on the surface to enhance the bonding force of the negative electrode active material, and it may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.

The negative electrode active material may include, for example, carbon such as non-graphitized carbon or graphite carbon; _{Li x Fe 2 O 3 (0≤x≤1} ), Li x WO 2 (0≤x≤1), Sn x Me 1-x Me 'y O z (Me: Mn, Fe, Pb, Ge; Me' : Metal complex oxides such as Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, Halogen, 0 < x < Lithium metal; Lithium alloy; Silicon-based alloys; Tin alloy; _{SnO, SnO 2, PbO, PbO} 2, Pb 2 O 3, Pb 3 O 4, Sb 2 O 3, Sb 2 O 4, Sb 2 O 5, GeO, GeO 2, Bi 2 O 3, Bi 2 O 4, Bi ₂ O ₅ and the like; Conductive polymers such as polyacetylene; Li-Co-Ni-based material, and the like.

The separation membrane is interposed between the electrode and the cathode, and an insulating thin film having high ion permeability and mechanical strength is used. The pore diameter of the separator is generally 0.01 to 10 mu m and the thickness is generally 5 to 300 mu m. Such separation membranes include, for example, olefinic polymers such as polypropylene, which are chemically resistant and hydrophobic; A sheet or nonwoven fabric made of glass fiber, polyethylene or the like; Kraft paper and the like are used. Representative examples currently on the market include the Celgard ^R 2400, 2300 (from Hoechest Celanese Corp.), polypropylene separator (from Ube Industries Ltd. or Pall RAI), and polyethylene series (from Tonen or Entek).

In some cases, a gel polymer electrolyte may be coated on the separation membrane to increase the stability of the cell. Representative examples of such a gel polymer include polyethylene oxide, polyvinylidene fluoride, and polyacrylonitrile.

When a solid electrolyte such as a polymer is used as an electrolyte, the solid electrolyte may also serve as a separation membrane.

The lithium salt-containing non-aqueous electrolyte is composed of a nonaqueous electrolyte and lithium. As the non-aqueous electrolyte, a non-aqueous electrolyte, a solid electrolyte, an inorganic solid electrolyte and the like are used.

Examples of the nonaqueous electrolyte include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate , Gamma -butyrolactone, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydroxyfuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, Diethyl ether, formamide, dimethyl formamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid triester, trimethoxymethane, dioxolane A non-protonic organic solvent such as an ether, a methyl pyrophosphate, or an ethyl propionate is used as the solvent, a sulfone, a methyl sulfolane, a 1,3-dimethyl-2-imidazolidinone, a propylene carbonate derivative, a tetrahydrofuran derivative, .

Examples of the organic solid electrolyte include a polymer electrolyte such as a polyethylene derivative, a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, an agitation lysine, a polyester sulfide, a polyvinyl alcohol, a polyvinylidene fluoride, Polymers containing ionic dissociation groups, and the like can be used.

Examples of the inorganic solid electrolyte include Li ₃ N, LiI, Li ₅ NI ₂ , Li ₃ N-LiI-LiOH, LiSiO ₄ , LiSiO ₄ -LiI-LiOH, Li ₂ SiS ₃ , Li ₄ SiO ₄ , Nitrides, halides and sulfates of Li such as Li ₄ SiO ₄ -LiI-LiOH and Li ₃ PO ₄ -Li ₂ S-SiS ₂ can be used.

The lithium salt is a material that is readily soluble in the non-aqueous electrolyte, for example, LiCl, LiBr, LiI, LiClO 4, LiBF 4, LiB 10 Cl 10, LiPF 6, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF _{6, LiSbF 6, LiAlCl 4,} CH 3 SO 3 Li, CF 3 SO 3 Li, LiSCN, LiC (CF 3 SO 2) 3, (CF 3 SO 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, 4-phenylborate, imide, and the like can be used.

For the purpose of improving the charge / discharge characteristics and the flame retardancy, the electrolytic solution is preferably mixed with an organic solvent such as pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylenediamine, glyme, Benzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrrole, 2-methoxyethanol, . In some cases, halogen-containing solvents such as carbon tetrachloride and ethylene trifluoride may be further added to impart nonflammability. In order to improve the high-temperature storage characteristics, carbon dioxide gas may be further added. FEC (fluoro-ethylene carbonate, PRS (propene sultone), FPC (fluoro-propylene carbonate), and the like.

The secondary battery according to the present invention can be used not only in a battery cell used as a power source for a small device but also as a unit cell in a middle or large battery module including a plurality of battery cells.

Also, the present invention provides a battery pack including the battery module as a power source of a middle- or large-sized device, wherein the middle- or large-sized device is an electric vehicle (EV), a hybrid electric vehicle (HEV) An electric vehicle including a plug-in hybrid electric vehicle (PHEV), a power storage device, and the like, but the present invention is not limited thereto.

The method for manufacturing the lithium transition metal oxide or lithium transition metal phosphate, the method for manufacturing the lithium secondary battery, the battery module, and the method for manufacturing the battery pack are well known in the art, and therefore, detailed description thereof will be omitted.

As described above, the present invention provides a method of recovering lithium hydroxide from a waste liquid of lithium iron phosphate produced by a hydrothermal method or a supercritical hydrothermal method, thereby recovering lithium hydroxide by using a recovered lithium hydroxide as a lithium transition metal oxide or lithium transition metal There is an advantage that the manufacturing cost of the phosphorus oxide can be lowered.

In addition, the recovery method according to the present invention has an advantage of enabling the implementation of a circulating system in which the recovered lithium hydroxide solution is reintroduced for the production of lithium iron phosphate or a continuous process system in the lithium transition metal oxide production process . That is, there is an advantage that it can exhibit improved fairness due to the implementation of the circulation system or the continuous process system described above.

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

≪ Example 1 >

An aqueous solution prepared by mixing 21.32 parts by weight of iron sulfate (FeSO ₄ .7H ₂ O) and 8.84 parts by weight of phosphoric acid (85 wt%) was pumped at a rate of 4.8 ml / min at room temperature to 250 bar. A mixed solution of aqueous ammonia and lithium hydroxide NH ₃ 1.3 wt%, LiOH.H ₂ O 6.43 wt%) was pumped under pressure at a rate of 4.8 ml / min in a first mixer. At this time, sucrose (C ₁₂ H ₂₂ O ₁₁ ) was mixed with iron sulfate aqueous solution in an amount of 10 wt% based on the weight of iron sulfate. The NH ₃ / SO ₄ molar ratio was 1.0 and the Li / Fe molar ratio was 2.0. The mixture was pressurized at 250 bar with ultrapure water heated to about 450 ° C at a rate of 96 ml / min to meet in a second mixer. The resulting mixture was allowed to stand in a reactor maintained at 405 DEG C for 12 seconds, then cooled and concentrated. The concentrate was dried at 120 DEG C using a spray drier and calcined in a nitrogen atmosphere at 600 DEG C for 12 hours to obtain lithium iron phosphate (LiFePO ₄ ).

The waste aqueous solution was heated to concentrate the lithium ion concentration to 1 wt% relative to the waste aqueous solution. The waste aqueous solution concentrate and 0.72 M aqueous solution of barium hydroxide (Ba (OH) ₂ ) Was mixed at a volume ratio of 1: 1, and the mixture was heated at 80 DEG C for 4 hours while stirring, and then filtered using a vacuum filter to obtain a lithium hydroxide solution.

≪ Example 2 >

Except that 0.86 M of a barium hydroxide (Ba (OH) ₂ ) aqueous solution (reaction with an aqueous solution of 1 weight% of lithium ions at an equivalent ratio of 1: 1.2) was used in Example 1, Lithium solution was obtained.

<Experimental Example 1>

The recovery of lithium (Li) and the concentration of barium ions (Ba ²⁺ ) and sulfate ions (SO ₄ ^2- ) were measured using the lithium hydroxide solution prepared in Example 1, and the results are shown in Table 1.

Li recovery rate Concentration of Li ⁺ Concentration of Ba ²⁺ Concentration of SO ₄ ^2- Example 1 90.2% 0.55 wt% 1550 ppm &Lt; 10 ppm

As can be seen in Table 1, the method according to the present invention has a recovery of Li of 90.2% and a concentration of Ba ²⁺ to Li ⁺ of 28.1%. Since the concentration of sulfate ions in the aqueous solution of the waste solution is at least half of the lithium ion concentration in the formula (1), the detection concentration of sulfate ions (10) is about 10% (0.2750 wt%) corresponding to 50% ppm), it can be seen that the removal rate of sulfate ion is 95% or more.

Those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

Claims (23)

Characterized in that the concentration of metal cations having a +1 or +2 oxidation number which is combined with anions provided from the salts of iron (Fe) to make the insoluble salts is 30% based on the concentration of lithium ions relative to the concentration of lithium ions . The lithium hydroxide solution according to claim 1, wherein the salt of iron (Fe) is at least one selected from the group consisting of iron sulfate, iron carbonate (FeCO ₃ ) and iron chloride. The lithium hydroxide solution according to claim 2, wherein the iron sulfate is ferrous sulfate (FeSO ₄ ). The lithium hydroxide solution according to claim 3, wherein the iron chloride is ferrous chloride (FeCl ₂ ). The metal cation according to claim 1, wherein the metal cation having an oxidation number of +1 or +2 is selected from the group consisting of a transition metal having an oxidation number of +1 valence, an alkaline earth metal, a transition metal having an oxidation number of +2 or a transition metal having a +2 oxidation number &Lt; / RTI &gt; lithium hydroxide solution. 6. The lithium hydroxide solution according to claim 5, wherein the transition metal having the oxidation number of + 1 is silver (Ag). The lithium hydroxide solution according to claim 5, wherein the alkaline earth metal is barium (Ba), calcium (Ca) or strontium (Sr). 6. The lithium hydroxide solution according to claim 5, wherein the metal having an oxidation number of +2 valence is lead (Pb). (a) an evaporation process for increasing the concentration of lithium ions by heating and / or reducing pressure in a waste aqueous solution in which anions provided from salts of lithium ions and iron (Fe) are dissolved;
(b) a precipitation process in which a hydroxide of a metal having an oxidation number of +1 or +2 is added to a solution having a higher lithium ion concentration to precipitate the insoluble salt of the metal; And
(c) separating the precipitate and obtaining a filtrate;
&Lt; / RTI &gt; by weight based on the total weight of the lithium hydroxide solution. The method according to claim 9, wherein the waste aqueous solution in step (a) is a by-product aqueous solution generated in the process of producing lithium iron phosphate represented by the following reaction formula (1)
_{3LiOH + FeX + H 3 PO 4} → LiFePO 4 + 2Li + + X + 3H 2 O (1)
In the above formula, X is an anion which forms an insoluble salt by ionic bonding with the +1 + or 2 + -valent metal ion. The process for producing a lithium hydroxide solution according to claim 10, wherein X is at least one selected from the group consisting of sulfate ions (SO ₄ ^2- ), carbonate ions (CO ₃ ^2- ) and chloride ions (Cl ^- Way. The method according to claim 9, wherein the evaporation process of the step (a) is carried out until the concentration of lithium ions dissolved in the waste aqueous solution is 1 wt% or more based on the weight of the waste aqueous solution . 10. The method according to claim 9, wherein the heating process is performed at a temperature ranging from 100 to 200 &lt; 0 &gt; C. 10. The method of claim 9, wherein the heating and depressurization are performed at a temperature ranging from 40 to 90 &lt; 0 &gt; C and a vacuum condition. The method for producing a lithium hydroxide solution according to claim 9, wherein the hydroxide of the step (b) is in a liquid phase or a solid phase. The method of claim 15, wherein the hydroxide is hydroxide (AgOH), hydroxide, lead (Pb (OH) _2), barium hydroxide (Ba (OH) _2), calcium (Ca (OH) ₂₎ hydroxide or strontium hydroxide (Sr ( OH) ₂ ). &Lt; / _RTI &gt; The method according to claim 9, wherein the hydroxide of the step (b) is added at a concentration equal to or more than the equivalent amount of the lithium ion. 18. The method of claim 17, wherein the equivalent ratio of hydroxide to lithium ion is 1: 1 to 3: 1. The method according to claim 9, wherein the precipitation process of step (b) is performed at a temperature of 70 ° C or higher. The method for producing a lithium hydroxide solution according to claim 1, further comprising a distillation step for concentrating the filtrate containing lithium hydroxide after the step (c). The method for producing a lithium hydroxide solution according to claim 9, wherein the removal rate of the sulfate ion is 95% or more. A process for producing a lithium transition metal oxide, wherein the lithium hydroxide solution according to claim 1 is used as a lithium source. Characterized in that the lithium hydroxide solution according to claim 1 is used as a lithium source to produce a lithium transition metal phosphate.