WO2019103459A2 - Method for manufacturing positive electrode additive for lithium secondary battery - Google Patents

Abstract

Provided is a method for manufacturing a positive electrode additive for a lithium secondary battery, the method being capable of greatly reducing the amount of gas generated during electrode operation by decreasing the contents of Li-based byproducts generated in a manufacturing process and unreacted lithium oxides.

Description

 2019/103459 1 »(: 1 ^ {2018/014368

Title of the Invention

 Method for preparing positive electrode additive for lithium secondary battery

 TECHNICAL FIELD

 Cross-reference with related application (s)

 This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0156744 dated November 22, 2017, and Korean Patent Application No. 10-2018-0143870 dated November 20, 2018, The entire contents of which are incorporated herein by reference.

The present invention relates to a method for producing a positive electrode additive for a lithium secondary battery, which can reduce byproducts and unreacted materials generated during the production process, thereby significantly reducing the amount of gas generated during operation of the electrode _.

 BACKGROUND ART [0002]

 As technology development and demand for mobile devices increase, the demand for secondary batteries as energy sources is rapidly increasing. Among such secondary batteries, lithium secondary batteries having a high energy density and voltage, a long cycle life, and a low self-discharge rate are commercially available and widely used.

Although graphite is mainly used as a negative electrode material of a lithium secondary battery, the capacity per unit mass of graphite is 372

It is difficult to increase the capacity of the lithium secondary battery. As a result, a material for forming a lithium-metal intercalation compound such as silicon, tin and oxides thereof has been developed and used as a non-carbon anode material exhibiting a higher capacity than graphite, but these cathode materials have low initial efficiency, There is a problem that the irreversible capacity loss is large.

On the other hand, a method of overcoming the irreversible capacity loss of the cathode using a material which can provide a lyrium ion source or a storage material to the cathode material and which exhibits electrochemical activity after the first cycle so as not to deteriorate the performance of the entire battery is studied , Respectively. Specifically, there is a method of using a lithium nickel calcined product containing an excessive amount of lithium, such as Ni ₂ O ₂ , as a sacrificial anode material or an irreversible additive (or an overdischarge preventing agent) for the anode.

However, the lithium-nickel-based oxide is mainly produced by reacting nickel oxide, nickel carbonate and the like with an excess amount of lithium oxide, 2019/103459 1 »(: 1 ^ {2018/014368

Unreacted lithium oxide (Nishi ₂ ⑴, or you (¾, you are by-products such as ₂ ¥ ₃ is left in the Lyrium nickel-containing oxide to be finally manufactured. Lithium oxide, and by-products remaining in the lithium nickel-based oxide are the initial cell cycle And decomposes to generate an excessive amount of gas such as 0 _2, 00 _2, etc. In the case of a by-product such as a ternary system, the viscosity of the composition is increased or gelated by reacting with the binder component in preparing a composition for electrode production, It is difficult to uniformly apply the electrode composition for the formation of the positive electrode active material, and as a result, there is a problem that the characteristics of the battery are deteriorated. .

DETAILED DESCRIPTION OF THE INVENTION

 [Technical Problem]

 The present invention solves the above problems and provides a method for producing a positive electrode additive for a lithium secondary battery capable of reducing a content of a by-product and an unreacted lithium oxide generated during a manufacturing process, The purpose.

 The present invention also relates to a positive electrode additive for a lithium secondary battery, which is produced according to the above-described production method and has a greatly reduced content of Ni byproducts and unreacted materials causing gas generation, and an anode for a lithium secondary battery exhibiting excellent electrochemical characteristics And lyrium provide a secondary battery.

 [Technical Solution]

According to an embodiment of the present invention, there is provided a process for producing a lyrium nickel oxide represented by the following Chemical Formula 1 by mixing a raw material of lyrium, a raw material of a nickel raw material and an element, followed by heat treatment in an inert gas atmosphere, Wherein the heat treatment comprises a first heat treatment at 300 to 500 x; And 550 to 800 after the primary heat treatment

Wherein the first heat treatment is performed for 30 to 50% of the total heat treatment time, wherein the first heat treatment is performed for 30 to 50% of the total heat treatment time :

 [Chemical Formula 1]

₂ ] Total () ₂

In Formula 1, M is selected from the group consisting of a transition metal, an amphoteric element, P, F, and B,

 0 < x < l.

According to another embodiment of the present invention, there is provided a lithium nickel oxide according to the above-described process, which comprises the lithium nickel oxide of Formula 1 and further contains less than 11 wt% of NiO and less than 1 wt% of Li ₂ O Wherein the total amount of NiO and Li ₂₀ is 11% by weight or less.

 According to another embodiment of the present invention, there is provided a positive electrode and a lyrium negative electrode for a lithium secondary battery comprising the positive electrode additive.

 【Effects of the Invention】

 The method for producing a positive electrode additive for a lithium secondary battery according to the present invention can reduce byproducts and unreacted materials generated during the production process, thereby significantly reducing the amount of gas generated during operation of the electrode. Accordingly, the positive electrode and the lithium positive electrode prepared using the positive electrode additive can exhibit better electrochemical characteristics and lifetime characteristics.

 BRIEF DESCRIPTION OF THE DRAWINGS

 1 is a graph showing the results of thermal analysis for a mixture for preparing a positive electrode additive in Test Example 1. Fig.

 2 is a graph showing X-ray diffraction spectroscopy (XRD) results of the positive electrode additives according to Examples 1 to 3 and Comparative Examples 1 to 5.

 FIG. 3 is a graph showing the amount of gas generated during operation of the positive electrode additive-containing battery according to Examples 1 to 3 and Comparative Examples 1 to 3.

 BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention Based on the principle that the present invention is based on the technical concept of the present invention, 2019/103459 1 »(: 1 ^ {2018/014368

It must be interpreted.

 Hereinafter, a method for preparing a positive electrode additive for a lithium secondary battery according to an embodiment of the present invention, a positive electrode additive manufactured thereby, and a positive electrode and a lithium secondary battery including the same will be described.

 The method for preparing a positive electrode additive for a lithium secondary battery according to an embodiment of the present invention comprises mixing a raw material of a lariium raw material, a nickel raw material and an element, and then heat-treating the mixture in an inert gas atmosphere to prepare a lyrium nickel oxide represented by the following formula &Lt; / RTI &gt;

 The heat treatment may include a first heat treatment at 300 to 500 x: And a second heat treatment at 550 to 800 X: after the first heat treatment,

 The primary heat treatment is performed for 30 to 50% of the entire heat treatment time.

 [Chemical Formula 1]

 Nishi Mika

 In Formula 1,

 Is selected from the group consisting of transition metals, amphoteric elements, and grafts, with the proviso that it is not nickel,

 (X <

 As described above, the production method according to one embodiment of the present invention is characterized in that, in the production of the positive electrode additive containing lyrium nickel oxide represented by Formula 1 using the nickel raw material, the raw material of the element, and the lyrium raw material, And mixtures thereof to induce sufficient reaction of the raw materials of lyrium through a multistage heat treatment at a temperature at which the reaction occurs, and thereby, unreacted tritium oxide and byproducts Can be significantly reduced.

Specifically, in the manufacturing method according to one embodiment, the heat treatment process may be performed by performing a primary heat treatment at 300 to 500 in an inert gas atmosphere to form a mixture of lithium source material, nickel source material, and lithium source The raw material and the raw material of the element are reacted to form a lithium-element

Preparing an inclusion compound; And a second order at 550 to 800 X: under an inert gas atmosphere 2019/103459 1 »(: 1 ^ {2018/014368

And a step of reacting the remaining lyrium raw material and the nickel raw material without reacting in the step 1 while preparing the rehomium oxide of the formula 1 through a heat treatment.

The primary heat treatment step is specifically performed at a temperature of 300 to 500 X :. When the first heat treatment is performed within the above temperature range, the reaction between the lithium source material and the raw material of the element is sufficiently performed, and lithium and element-containing compounds can be produced with a high yield. However, if the temperature is lower than 300 ° C during the first heat treatment, the reaction between the lithium raw material and the raw material of the element ¾ does not occur sufficiently, resulting in a large amount of unreacted raw material, May be generated. If it is more than 500 (:), it is not easy to control the reaction rate of the lithium raw material and the raw material of the element, and as a result, there is a fear of formation of an inferred reactant. Another 500

In temperatures above ₂₀ and you and出0

Since the raw material reacts at the same time, the effect of controlling the unreacted Ni ₂₀ in the first heat treatment step becomes insignificant. Control of the formation of unreacted and non-reacted products by temperature control in the first heat treatment step,

Considering that the compound generating effect is excellent, the first heat treatment can be performed at a temperature of 330 to 450 ° C., and more specifically, at a temperature of 400 ° C. to 350 ° C.

In addition, the primary heat treatment may be performed for 30 to 50% of the entire heat treatment time. When the primary heat treatment is performed within the time range described above, the reaction of the raw material of lyrium and the raw material of the element can sufficiently occur. However, if the time for the first heat treatment is less than 30% of the total heat treatment time, the reaction between the larium raw material and the raw material of the element does not sufficiently take place, resulting in a large amount of unreacted raw material, There is a fear that a side reaction product is produced. Also, when the first heat treatment time exceeds 50% of the total heat treatment time, the second heat treatment time is relatively reduced. As Guam, the reaction time between the unreacted lithium raw material and the nickel raw material during the second heat treatment step is not neglected, The amount of unreacted lyrium oxide may increase. Considering that the control of generation of unreacted materials and byproducts by controlling the heat treatment time in the first heat treatment step and the effect of producing lithium and element containing compounds are excellent, the first heat treatment is performed at 35 to 45% of the total heat treatment time, more specifically, Is performed for 40 to 45% 2019/103459 1 »(: 1 ^ {2018/014368

.

 The primary heat treatment may also include a heating step of heating the mixture of reactants to the heat treatment temperature and a maintenance step of maintaining the reaction at a heated temperature for a certain period of time.

Temperature rising stage at the primary heat treatment is specifically 300 to 500 ° (: up to 2-7 / _111, and more specifically, may be performed by heating at a rate of 2 to 5公/ _111. When the temperature is raised at the controlled heating rate, the reaction efficiency can be further increased.

 Also, the holding step may be performed for 40 to 80% of the total time of the first heat treatment step. When the holding step is performed for the above-mentioned time, the diffusion reaction between the particles can be sufficiently performed, so that the completion of the reaction between the element-containing raw material and the lithium raw material can be enhanced. Considering that the improvement effect according to the control of the holding time is excellent, the holding step may be performed for 40 to 70% of the total time of the first heat treatment step.

The first heat treatment including the first heat treatment, specifically the temperature increase and the maintenance step, may be performed in an inert gas atmosphere such as nitrogen, helium, or argon to suppress side reaction formation. Of these, the reaction can be carried out under a nitrogen gas atmosphere in consideration of an increase in the reaction efficiency and an excellent effect of suppressing side reaction formation. On the other hand, in the primary heat treatment, the Lyrium raw materials may have to be used Lyrium-containing oxide, sulfate, nitrate, acetate, carbonate, oxalate, citrate, halide, hydroxide or oxy-hydroxide or the like, specifically, you ₂ 0¾ , needle _03, 11 ^ _2, you 0比Needle (犯- ¾0, you比you kneader, needle, needle 1, 0 _{3 ¥ 01 [, needle _20, needle ^ 0 _4,抑₃ ¥ 0 Needle, or Needle ₃ (: ₆ ¾0 can be ₇ and so on. Any one or a mixture of two or more of them may be used. Considering the reaction efficiency and the effect of reducing byproduct formation during the reaction with the nickel-containing precursor material, the lithium source material may be ₂₀ days.

The nickel raw material may be a nickel-containing oxide or hydroxide such as nickel oxide (0) or nickel hydroxide ((0) ₂ ).

Further, the raw material of the above element

Oxides, sulfates, nitrates, acetates, carbonates, oxalates, citrates, halides, hydroxides or 2019/103459 1 »(: 1 ^ {2018/014368

Oxyhydroxides, phosphates, and the like can be used, and phosphates can be used. At this time, the ¾ the final included by substituting part of nickel contained Lyrium nickel oxide produced thereby that serve to improve the thermal stability and structural stability, specifically, 0 _0, and, bottles, 1, (!!: _11, or a transition metal element having a divalent, trivalent or pentasaccharide number as shown below; An amphoteric element having three peroxyacids such as citrate; And 8, and among these, silver may be selected from the group consisting of silver, cadmium, tin, and tin. More specifically, it may be selected from the group consisting of cadmium, tin, It is possible to form a stable compound, at the time, or 8 days, and in particular, it can be either Si or I ³ .

 The lithium source material, the nickel source material and the raw material materials of the above-described lithium source material and the element may be used in an amount such that the composition ratio of the lithium source element and the nickel source element in the lithium nickel oxide represented by the formula 1 is satisfied. Specifically, the content of the reagent raw material may be such that the molar ratio of lium: (nickel + element ¾) is 2: 1. If the molar ratio of nickel + element ¾0 does not satisfy 2: 1, the composition of formula (1) is not satisfied, and as a result, it can not sufficiently function as a sacrificial anode material or irreversible additive.

In the mixing of the above raw materials, a sintering agent may be optionally added. Specifically,

Compounds containing ammonium ions such as (i) filtration; ¾0 ₃ or ₂ non-metal oxide, such as _03; Or a metal halide such as (1 ₂₎ or the like, and any one or a mixture of two or more thereof may be used. The sintering may be used in an amount of 0.01 to 0.2 mol based on 1 mol of the nickel-containing raw material. It is possible to improve the performance of the anode additive and to prevent the initial capacity reduction of the battery from progressing during charging and discharging.

In mixing the raw materials, a moisture removing agent may be optionally added. Specific examples of the moisture removing agent include citric acid, tartaric acid, glycolic acid, and maleic acid, and any one or a mixture of two or more thereof may be used. The moisture removing agent may be used in an amount of from 0.20 mol to 0.2 mol based on 1 mol of the nickel raw material. 2019/103459 1 »(: 1 ^ {2018/014368

As a result of the above-described first heat treatment, a lyrium-element containing compound is produced by the reaction of the raw material of the element with the lyrium raw material in the mixture containing the lyrium raw material, the nickel raw material and the raw material of the element. Specifically, the lyrium-element containing compound may be a compound having a ni-4-l-0 phase such as ni 0 _4, ni ₅ 0 _4, or ni _2, etc. (as described above). At this time, an unreacted lithium raw material such as Ni ₂₀ and a nickel raw material together with the lyrium-element 1 containing compound exist in the reaction product.

 Next, the second heat treatment is performed at a temperature of 550 to 8001 :. In the case where the secondary heat treatment is performed within the above-mentioned temperature range, a decrease in the discharge capacity per unit weight due to the residual of unreacted raw material, occurrence of side reaction or decomposition reaction of the reactant, It is possible to produce lithium-nickel-containing oxides of the formula (1) at an excellent efficiency without worrying, and at the same time, the content of unreacted lithium oxide can be reduced through reaction of the unreacted lyrium oxide and the nickel raw material. More specifically, considering that the effect of heating temperature control is excellent, the secondary heat treatment can be performed at a temperature of 600 to 800 ° C, more specifically, 6001: to 7001 ° C.

 The secondary heat treatment step may be performed for a time of 50 to 70% of the total heat treatment time. When the duration of the second heat treatment step is less than 50% of the total heat treatment time, a sufficient reaction between the unreacted lyrium oxide and the nickel raw material is difficult to occur due to the short reaction time, and the lithium- The effect of reducing by-products may be minimal. If the execution time of the second heat treatment step is more than 70%, there is a risk of occurrence of excessive reaction, and the heat treatment time may become excessively long, which may be ineffective in the process. More specifically, the secondary heat treatment step may be performed for a time of 50 to 65%, more specifically 50 to 60% of the total heat treatment time.

 The second heat treatment step may include a heating step of heating the mixture of the lyrium-element-1 containing compound, the nickel raw material and the unreacted lithium raw material prepared in the step 1, and a sufficient temperature And a maintenance step for allowing the user to perform the maintenance.

The temperature elevation step in the second heat treatment is specifically from 550 to 800 2019/103459 1 »(: 1 ^ {2018/014368

Specifically _, it can be carried out by heating at a temperature of from 600 to 800 (), more particularly from 600 to 7001, at a rate of from 2 to 7 7 _111111, more specifically from 2 to 5 () / ₁₁ . When the temperature is raised at the controlled heating rate, the reaction efficiency can be further increased.

 Also, the holding step may be performed for 60 to 90% of the total time of the second heat treatment step. When the holding step is performed for the above-mentioned time, the diffusion reaction between the particles can be sufficiently performed, so that the completion of the reaction between the element-containing raw material and the lithium raw material can be enhanced. Considering that the improvement effect according to the control of the holding time is excellent, the holding step may be performed for 60 to 80% of the total time of the second heat treatment step.

 Second heat treatment including the second heat treatment, specifically the temperature increase and the maintenance step, may also be performed in an inert gas atmosphere such as nitrogen, helium, or argon to suppress side reaction formation. Of these, the reaction can be carried out under a nitrogen gas atmosphere in consideration of an increase in the reaction efficiency and an excellent effect of suppressing side reaction formation. After the second heat treatment step, a cooling step may be optionally performed.

The cooling step may be performed according to a conventional method, and specifically, it may be carried out by natural cooling in a air atmosphere, hot air cooling, or the like. By a secondary heat treatment step as described above, the primary heat treatment results included in the reaction to give you a -¾1-0 phase and unreacted residual Needle ₂₀ and 0 Lyrium nickel oxide to the payload response is doped formula A positive electrode additive is prepared comprising:

 [Chemical Formula 1]

此 - 美 0 ₂

 In Formula 1,

 ¾! Is selected from the group consisting of transition metals, amphoteric elements, and 6, but not only nickel,

 0 < 5 (< 1.

Specifically, the element is 0 _0,

A transition metal element having a divalent, trivalent or pentasaccharide such as Mg1, O1, or O; An amphoteric element having an oxidation number of 3 and the like; And &lt; RTI ID = 0.0 &gt; 2019/103459 1 »(: 1 ^ {2018/014368

And may be selected from the group consisting of silver, nine, cis, and three, more specifically, may be selected from the group consisting of a poem having a good reactivity with luteum, have.

 In addition, the above elements may be included in place of the amount corresponding to the table. (<0.1, more specifically, 0.01 <) ^ <0.06 days, in consideration of the remarkable improvement effect due to the control of the substitution amount contained in the lyrium nickel oxide, have.

In addition, the unreacted residue 11, ₂₀ and, as 0, the reaction, produced positive electrode additive significantly decreases the prior art compared to the unreacted residual first amount of _[20 and 0, lithium-based by-products in particular, including the knee ₂₀ during the secondary heat treatment Is significantly reduced.

More specifically, but the positive electrode additive manufactured in the manufacturing method further comprises: the knee ₂₀ below includes ritum nickel oxide of the formula (I), and 11 wt% 0 and 1% by weight of less than about the positive electrode additive total weight The total amount of 0 wane ₂₀ may be up to 11 wt%.

More specifically, the anode additive may comprise up to 0.5 wt.% Ni ₂₀ , and more specifically no Ni ₂₀ wt. The amount of such unreacted materials and lithium byproducts can greatly reduce the amount of gas generated during battery operation.

Further, the above-mentioned positive electrode additive has a strength of 1 [ ₂₀ peaks (11, 20 = 15 to 20 [deg.]) Appearing at ₂₀ [deg.] To 30 [ the intensity of the peak appearing in the Needle ₀₂ (referred to 12, (11八12 = 0 is the number of days.

Meanwhile, in the present invention, the X-ray diffraction analysis of the positive electrode additive can be performed according to a conventional XI analysis method using an X-ray diffraction analyzer, and in the present invention,

04 - using Table 11 (16 is ^1'½ (81 1 stop;

(2 0 = 15-35 ^° , scanning speed = 4 ^° /) using XI (manufactured by XI) _. ),

 The positive electrode additive prepared according to the above-mentioned production method is a lythum-

To 5% by weight or less than, particularly by more than 4.5% by weight or less, particularly may further comprise a you of you 0 ₂ ¥ ₃ and 0.5 to 1% by weight of less than 4.2% by weight. 2019/103459 1 »(: 1 ^ {2018/014368

Further, in the Needle and needle ₂ (¾ rules include lithium-based by-products than the total of the positive electrode additive more than 0.5 to 3.5% by weight based on the weight, specifically, that may contain 0.5 to 3.1% by weight. Due to the significantly reduced nie, there is no fear of gelation during the mixing process for producing the anode. Accordingly, the positive electrode additive can exhibit a superior effect when used as a sacrificial anode material or irreversible additive for a lithium-transition metal oxide capable of absorbing and desorbing lithium ions. In addition, Ni ₂ O ₃ is located on the surface of the anode additive, which can suppress the heat generation of the anode when a short circuit occurs, and can suppress moisture adsorption in the atmosphere.

 The positive electrode additive for a lithium secondary battery produced according to the above-described production method can reduce the byproducts and unreacted matters necessarily generated in the manufacturing process, thereby significantly reducing the gas generation amount when the battery is driven. Accordingly, the positive electrode and the lithium secondary battery manufactured using the positive electrode additive can exhibit better electrochemical characteristics and life characteristics.

 In addition, the positive electrode additive may be used as a sacrificial anode material or an irreversible additive (or an overdischarge inhibitor) that can compensate for irreversible capacity loss of the negative electrode due to the presence of excess lithium.

 According to another embodiment of the present invention, there is provided a positive electrode and a lithium secondary battery for a lithium secondary battery comprising the positive electrode additive produced by the above-described production method.

 Specifically, the positive electrode includes a positive electrode collector, and a positive electrode active material layer formed on the positive electrode collector and including the positive electrode additive.

The positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in the battery. For example, carbon, nickel, titanium, , Silver or the like may be used. In addition,

It is possible to increase the adhesion of the positive electrode active material. For example, in various forms such as films, sheets, foils, nets, porous bodies, foams, and nonwoven fabrics.

In addition, the positive electrode active material layer, together with the above-described positive electrode additive, 2019/103459 1 »(: 1 ^ {2018/014368

A conductive material and a binder.

 At this time, the conductive material is used for imparting conductivity to the electrode. The conductive material can be used without particular limitation as long as it has electron conductivity without causing chemical change. Specific examples include carbon-based materials such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, summer black and carbon fiber; Graphite such as natural graphite or artificial graphite; Metal powder or metal fibers such as copper, nickel, aluminum and silver; Conductive whiskey such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; And polyphenylene derivatives. These may be used alone or in admixture of two or more. The conductive material may be included in an amount of 1% by weight to 30% by weight based on the total weight of the cathode active material layer.

In addition, the binder serves to improve the adhesion between the positive electrode active material particles and the adhesion between the positive electrode active material and the current collector. Specific examples include polyvinylidene fluoride (1 볘), vinylidene fluoride-hexafluoropropylene copolymer (Acrylonitrile-butadiene copolymer). ⁵ ), polyvinyl alcohol, polyacrylo

Starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylenetriene-diene polymer inhibitor, sulphonation-sand, styrene butadiene rubber ratio Fluorine rubber, or various copolymers thereof, and one kind or a mixture of two or more kinds of them may be used. The binder may be included in an amount of 1% by weight to 30% by weight based on the total weight of the cathode active material layer.

 When the positive electrode additive is included in the active material layer as a sacrificial positive electrode material or an irreversible additive, the positive electrode active material layer may include a lithium transition metal oxide capable of absorbing and desorbing lyrium ion as a positive electrode active material.

Specifically, as the above-mentioned transition metal compounds, Ni (: ₀ 0 _2, Ni 0 _2,

1 ₁₁₂ 0 ₂ ( _{3 {} ¾ ₅ 1 ₁₁ ( _; ) 0 ₂ (0 <size <1, 0 <1) <1, 0 <<1 + ₈ bar. = 1), needle _{1 0 (1,} 0 _2, needle) _1-line 1¾¾0 _2, needle _{1 - (1 1 \ 11¾0 2 (} 0 £ 1 [<1), knee (on穴(0 <equal <2, 0 <¾ <2 , 0 <(: <2,

₃ four七+. = 2), 1 1 1 ^ 12 ^ 16 0 4, you _{1¾ 12- 06 0 4 (0¾ <} 2), you止, or can include a slow yeodeung, over either or both of these Mixtures may be used. Of these, the lyotropic transition metal compound may be LiCoO ₂ or LiNi ¾, in consideration of the remarkable improvement effect when the combination with the lithium-based compound of the formula (1) is used.

 When the cathode active material layer includes a cathode active material, the cathode additive may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the cathode active material. The positive electrode may be produced by a conventional positive electrode manufacturing method, except that the positive electrode additive is used. Specifically, the positive electrode active material layer composition comprising the positive electrode additive and optionally the binder, conductive material, and positive electrode active material may be coated on the positive electrode collector, followed by drying and rolling. At this time, the types and contents of the cathode active material, the binder, and the conductive material are as described above.

 Examples of the solvent include dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), acetone ) Or water, and one of them or a mixture of two or more of them may be used. The amount of the solvent to be used is sufficient to dissolve or disperse the cathode active material, the conductive material and the binder in consideration of the coating thickness of the slurry and the yield of the slurry, and then to have a viscosity capable of exhibiting excellent thickness uniformity Do.

 Alternatively, the positive electrode may be produced by casting the composition for forming the positive electrode active material layer on a separate support, then peeling the support from the support, and laminating the resulting film on the positive electrode collector.

 According to another embodiment of the present invention, there is provided an electrochemical device including the anode. The electrochemical device may be specifically a battery, a capacitor, or the like, and more specifically, it may be a lithium secondary battery.

Specifically, the lithium secondary battery includes a positive electrode, a negative electrode disposed opposite to the positive electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte, as described above. The lyrium secondary battery may further include a positive electrode, a negative electrode, a battery container for storing the electrode assembly of the separator, and a sealing member for sealing the battery unit. 2019/103459 1 »(: 1 ^ {2018/014368

Meanwhile, in the lithium secondary battery according to an embodiment of the present invention, the negative electrode includes a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector.

 The negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery. For example, the negative electrode current collector may be formed on the surface of copper, stainless steel, aluminum, nickel, titanium, sintered carbon, Carbon, nickel, titanium, silver or the like, aluminum-cadmium alloy, or the like may be used. In addition, the negative electrode collector may have a thickness of Sm to 500 .mu.m, and similarly to the positive electrode collector, fine unevenness may be formed on the surface of the collector to strengthen the bonding force of the negative electrode active material. For example, it can 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 anode active material layer optionally includes a binder and a conductive material together with the anode active material. The negative electrode active material layer may be formed by applying and drying a composition for forming a negative electrode including a negative electrode active material on the negative electrode collector and, optionally, a binder and a conductive material, or by casting the composition for forming a negative electrode on a separate support , Or by laminating a film obtained by peeling from the support onto an anode current collector.

As the negative electrode active material, a compound capable of reversible intercalation and deintercalation of lithium can be used. Specific examples include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fiber and amorphous carbon; , _{Poetry, ¾,? B, å 11} , is, _111,

Greater, 01, ^ alloy, alloy or ₁ ¾ match gold or the like is alloyed with lithium can be metal compounds; A metal oxide capable of doping and dedoping lyrium, such as 510x (0 < X < 2), 2O _2, vanadium oxide, lithium vanadium oxide; Or as complexes or ¾ bokhapchegwa ₁ may be made of composites such as containing a metallic compound and a carbonaceous material, there is any one or a mixture of two or more of them may be used. Also, a metal lithium thin film may be used as the negative electrode active material. The carbon material may be both low-crystalline carbon and high-crystallinity carbon. Examples of the low-crystalline carbon include softened carbon ( ₀₃₁ 1x11 ₎ and cured carbon of 0 to ₀₃₁ width ( ₀₁₁₎ . Examples of the highly crystalline carbon include amorphous, flaky, scaly, Or fibrous natural graphite or artificial graphite, Ki sh graphite, pyrolytic carbon, mesophase-based carbon fiber, meso-carbon microbeads, ), Liquid crystal pitch

And high-temperature sintered carbon such as petroleum and coal tar coke.

 In addition, the binder and the conductive material may be the same as those described above for the anode.

 Meanwhile, in the lithium secondary battery, the separator separates the negative electrode and the positive electrode and provides a moving path of lithium ions. The separator can be used without any particular limitation as long as it is used as a separator in a lithium secondary battery. Particularly, It is preferable to have a low resistance and an excellent ability to impregnate the electrolyte. Specifically, porous polymer films such as porous polymer films made of dolly olefin-based polymers such as ethylene homopolymers, propylene homopolymers, ethylene / butene copolymers, ethylene / heptene copolymers and ethylene / methacrylate copolymers, May be used. Further, a nonwoven fabric made of a conventional porous nonwoven fabric, for example, high-melting-point eutectic fibers, polyethylene terephthalate fibers or the like may be used. Further, a coated separator containing a ceramic component or a polymer material may be used for securing heat resistance or mechanical strength, and may be optionally used as a single layer or a multilayer structure.

 Examples of the electrolyte used in the present invention include an organic-based liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel-type polymer electrolyte, a solid inorganic electrolyte, and a molten inorganic electrolyte which can be used in the production of a lithium secondary battery. It is not.

Specifically, the electrolyte may include an organic solvent and a lithium salt. The organic solvent may be used without particular limitation as long as it can act as a medium through which ions involved in an electrochemical reaction of a battery can move. Specifically, the organic solvent is methyl acetate (methyl acetate), ethyl acetate (ethyl acetate), ^_ y butyrolactone (Y -butyrolactone), £ - caprolactone (e -caprolactone) ester-based solvents, and the like; Dibutyl ether ethers such as ether or tetrahydrofuran; Ketone solvents such as cyclohexanone; Aromatic hydrocarbon solvents such as benzene and fluorobenzene; (DMC), diethylcarbonate (DEC), methylethyl carbonate (MEC), ethylmethyl carbonate (EMC), ethylene carbonate (ET) hy 1 ene carbonate (EC), propylene carbonate (PC), etc .; Alcohol solvents such as ethyl alcohol and isopropyl alcohol; R-CN (R is a straight, branched or cyclic hydrocarbon group of C2 to C20, which may contain a double bond aromatic ring or an ether bond); Amides such as dimethylformamide; Dioxolanes such as 1,3-dioxolane; Or sul folanes may be used. Among these, a carbonate-based solvent is preferable, and a cyclic carbonate (for example, ethylene carbonate or propylene carbonate) having a high ionic conductivity and a high dielectric constant, for example, such as ethylene carbonate or propylene carbonate, For example, ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate, etc.) is preferred. In this case, mixing the cyclic carbonate and the chain carbonate in a volume ratio of about 1: 1 to about 1: 9 may provide excellent performance of the electrolytic solution.

The lithium salt can be used without any particular limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery. Specifically, the lithium _{salt, LiPF 6, LiC10 4, LiAsF} 6, LiBF 4 LiSbF 6 LiA10 4, LiAlCl 4, LiCF 3 S0 3 LiC 4 F 9 S0 3, LiN (C 2 F 5 S0 3) 2, LiN ( C ₂ F ₅ SO _{2) 2,} LiN (CF ₃ SO _{2) 2} . LiCl, Li 1, or LiB (C ₂ C> _{4) 2} may be used. The concentration of the above-mentioned RICOM salt is preferably within the range of 0.1M to 2.0M. When the concentration of the lithium salt is within the above range, the electrolyte has an appropriate conductivity and viscosity, so that it can exhibit excellent electrolyte performance and the lite ion can be effectively transferred.

In addition to the above-described electrolyte components, the electrolyte may contain, for example, A halogenoalkylene carbonate compound such as diethyl carbonate, diethylene glycol, diethylene glycol, diethylene glycol, diethylene glycol, diethylene glycol, diethylene glycol, diethylene glycol, and diethylene glycol; One or more additives such as an imine dye, an N-substituted oxazolidinone, an N, N-substituted imidazolidine, an ethylene glycol dialkyl ether, an ammonium salt, pyrrole, 2-methoxyethanol or aluminum trichloride may be further included. The additive may be included in an amount of 0.1 wt% to 5 wt% based on the total weight of the electrolyte.

 As described above, since the lithium secondary battery including the positive electrode additive according to the present invention stably exhibits excellent discharge capacity, output characteristics, and capacity retention rate, it can be used in portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles Hybrid Electric Vehicle (HEV).

 According to another embodiment of the present invention, there is provided a battery module including the lithium secondary battery as a unit cell and a battery pack including the battery module.

 The battery module or the battery pack may be an electric vehicle including a power tool, an electric vehicle (EV), a hybrid electric vehicle, and a plug-in hybrid electric vehicle (PHEV) ; Or a power storage system. Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

 Example 1

_26.7 g of Li ₂₀ as a raw material of lithium, 66.5 g of NiO as a raw material of nickel and 6.8 g of ammonium phosphate as a raw material of the element M were mixed and heated under a nitrogen atmosphere at a heating rate of 400 ^The temperature was raised to about 700 ° C for about 3 hours and the temperature was raised to 700 ° C for about 2 hours and 30 minutes at a rate of 2 ° C / min under a nitrogen atmosphere. time 2019/103459 1 »(: 1 ^ {2018/014368

And then subjected to a second heat treatment. Needle _{2 0.9.} Cool the reaction to the _{result. 6} 0 ₂ a positive electrode of the additive particles was obtained. Example 2

As Lyrium raw material 1 _{2 0 26.7 _§, as the nickel raw material 0 66.5 _§, and then mixed with an aluminum phosphate 6.8 _§ as a raw material of the element, in an atmosphere of nitrogen, 21: 400 ° at a heating rate of / ₁₁₁ (: , The temperature was raised for about 3 hours, and the temperature was maintained at the same temperature for 4 hours to perform the first heat treatment. The temperature was raised to 700 ° (:) at a rate of 2 _/ ½ in a nitrogen atmosphere for about 2 hours and 30 minutes, Second heat treatment. The resultant reactants were cooled to obtain positive electrode additive particles. Example 3

As a starting material Lyrium 11 ₂ 0 26.7g, as a nickel raw material 0 _§ 66.5) and as a raw material of the elements _{03 1} and mixed with _§ 2.4, 400 ° (in a nitrogen atmosphere at a heating rate of _2/11: to about for 3 hours, temperature was raised and maintained at a w a temperature for 4 hours by heating the first, and in an atmosphere of nitrogen, 21: after w for about 2 hours and 30 minutes to a rate of / ₁₁₁ 700, and maintained for 6 hours second Heat treated. Cool the reaction to the results you _{2. 94} .. ¥ ᄋ to give a positive electrode additive particles of _{60 2.} Comparative Example 1

26.7 g of Ni ₂ O as a raw material of lithium, 0.66.5 로서 as a nickel raw material _, and 6.8 _§ of aluminum phosphate as a raw material of an element were mixed and heated at 700 ° C for about 5 hours The temperature was raised for 30 minutes and maintained for 6 hours. The resultant reactants were cooled to obtain positive electrode additive particles. Comparative Example 2

A lithium source material you ₂ 0 26.7 _§, as the nickel raw material 0 66.5 _§, and then a solution of ammonium phosphate, 6.8 and one for a raw material of the element, 5 ° under a nitrogen atmosphere (: / a heating rate of ₁₁₁ to 400 about 1 The temperature was raised for a period of time, Treated for 2 hours and then heated for 2 hours and 30 minutes to 70010 at a rate of 2 ° (: / _{11) in} a nitrogen atmosphere, and then maintained for 6 hours for secondary heat treatment. The resultant reactants were cooled to obtain positive electrode additive particles. Comparative Example 3

As Lyrium raw materials or ₂ 0 26.7 _§, as the nickel raw material 0 66.5 raised, and then a solution of ammonium phosphate, 6.8 and one for a raw material of the element, in an atmosphere of nitrogen, 11: 6 hours: 4001 at a heating rate of / ₁₁₁ And then heated for 6 hours at a temperature of 1 ° C. for 2 hours and 30 minutes at a rate of 2 ° C./1 ₁₁ under a nitrogen atmosphere. Heat treatment. The resultant reactants were cooled to obtain positive electrode additive particles. Comparative Example 4

26.7 g of Li ₂ O as a raw material of Li, 66.5 g of NiO as a raw material of nickel, and 6.8 g of aluminum phosphate as a raw material of element M were mixed and heated to 400 ° C at a heating rate of 2 ° C / min in an oxygen atmosphere The temperature was raised for about 3 hours, and the temperature was maintained at a constant temperature for 4 hours to perform a first heat treatment. The temperature was raised to 700 ° C at a rate of 2 ° C / min under a nitrogen atmosphere for about 2 hours and 30 minutes, And then subjected to a second heat treatment.

 However, as the first heat treatment is performed in an oxygen atmosphere, the cathode additive according to the present invention is not synthesized, and a lithium composite oxide layered on a layer, which is usually used as a cathode active material, is formed. Comparative Example 5

1 _[2 0 26.7g, then a solution of aluminum phosphate of 6.8 and one for a raw material for the 0 and 66.5, and the element as a nickel raw material, at a heating rate of _{2/1 11} 2001, under a nitrogen atmosphere as a lithium source material: about 1 up to time elevated temperature for half and held in a raised temperature for 4 hours to speed 4001 of the _{2/1 «under} the primary heat treatment, and a nitrogen atmosphere: after w for about an hour and 30 minutes, kept for 6 hours, the second heat treatment Respectively. However, since the crystal structure was not formed due to the low temperature during the first heat treatment, the positive electrode additive was not synthesized, and the unreacted Li ₂₀ was found to be from the X-ray diffraction analysis results (see Test Example 2). Test Example 1: Reaction temperature analysis

The mixture of u ₂ 0 NiO and ammonium phosphate as the M source used in the preparation of the positive electrode additive according to Example 1 was measured using a thermogravimetric analyzer (TGA) Were analyzed. For comparison, a Li ₂₀ single substance and a mixture of the Li ₂₀ and the M raw material were also subjected to thermal analysis, and the results are shown in FIG.

As shown in Fig. 1, via the TGA M source material is ammonium phosphate and Li ₂₀ is to first react at about 400 ^° C to form Li ₃ P0 ₄ as Li-M-0-phase, at about 700 ^° C It was confirmed that the Li-M-0 phase and the remaining Li ₂₀ and NiO reacted to form a P-doped Li ₂ NiO ₂ phase. From this, it was confirmed that the content of unreacted Li ₂₀ can be reduced through the multistage heat treatment at the temperature at which the reaction occurs. Test Example 2: Analysis of anode additives

 The positive electrode was prepared using the positive electrode additive or the positive electrode active material particles prepared in Examples 1 to 3 and Comparative Examples 1 to 5, and the positive electrode was filled at 3.8 V, and the positive electrode was subjected to X-ray diffraction analysis (XRD).

Specifically, the positive electrode additive, the carbon black conductive material and the PVdF binder prepared in Examples 1 to 3 or Comparative Examples 1 to 3 were mixed in a N-methylpyrrolidone solvent in a weight ratio of 85: 10: 5 A composition for forming an anode (viscosity: 5000 mPa.s) was prepared, applied to an aluminum current collector, and then dried and rolled to prepare a positive electrode. Li-metal was used as the negative electrode, and a mixed solvent of ethylene carbonate (EC) / dimethyl carbonate (DMC) / ethyl methyl carbonate (EMC) = 3/4/3 was added to the solution containing 1.15 M of LiPF ₆ A battery in the form of a pouch was produced using an electrolytic solution. 2019/103459 1 »(: 1 ^ {2018/014368

The manufactured battery 251: 0.1 (in up to 3: one filled with a later, separate the cathode, and 0 _1- 1 ₍₁ :(

Was performed using a ¾犯analyzed using 04- £ ₁₁ (1 ₆ O ^1¾1 (8 _1'1止Oh I reward ₍₁ ¾ status Co.) (20 = 15-35 °, scanning speed = 4 ° / min) . The results are shown in Fig.

The results, did during filling neunni ₂ 0 ₂ as converted into _02, in the embodiment including Examples 1 to 3, the anode electrode of the additive, only the Needle ₀₂ peaks were observed. Accordingly, the intensity of the peak appearing at 20 = 30 ° to 35 ° is calculated as (12 / (12 = 0), where the intensity of the peak at 29 = 15 to 20 ° is 12.

However, in the case of Comparative Examples 1 to 3 Ne. In addition to the peak of ¾ 11 ₂ 0 peak was observed with Comparative Example 4 The primary heat treatment is one that is used as a conventional positive electrode active material according to the performed under an oxygen atmosphere, ₃ la ₆ For (1 Lt; RTI ID = 0.0 &gt; of Li &lt; / RTI &gt; Further, Comparative Example 5 was due to the low temperature during the primary heat treatment has not been a positive electrode additive for the synthesis, unreacted you only ₂₀ were confirmed.

As a result, it can be confirmed that the unreacted Ni ₂ O can be reduced by the multi-step heat treatment process under controlled conditions in the production of the positive electrode additive as in the embodiments.

In addition, the ¾犯Further unreacted 11 _20, by-products from the positive electrode additives, needle ₂₀ and ₂

The content of lithium oxide was quantitatively analyzed. The results are shown in Table 1 below.

 [Table 1]

In Table 1, " - " means not measured. As shown in Table 1, the positive electrode additives of Examples 1 to 3 prepared according to the present invention exhibited significantly reduced NiO and Li ₂₀ contents as compared with Comparative Examples 1 to 3. Test Example 3: Evaluation of anode additives

 Each of the positive electrode additives prepared in Examples 1 to 3 or Comparative Examples 1 to 3 was used to prepare a positive electrode according to the following method, and the generation of gas was evaluated during charging and discharging of the battery.

Specifically, the positive electrode additive, the carbon black conductive material and the PVdF binder prepared in Examples 1 to 3 or Comparative Examples 1 to 3 were mixed in a N-methylpyrrolidone solvent at a weight ratio of 85: 10: 5 DMC / EMC mixture ratio (mixing ratio by volume: EC / DMC / EMC = 5,000 mPa) was applied to the aluminum current collector and then dried and rolled to prepare a positive electrode. A battery of pouch type was prepared by using an electrolyte containing 1.15M of LiPF ₆ in a solvent of 3/4/3.

The prepared cell was charged at 25 ^° C to 4.25 V at 0.1 C, and the gas contained in the pouch was analyzed by GC-TCD (gas chromatography-thermal conductiv- ity detector). The same experiment was repeated twice. The results are shown in FIG. 3 and Table 2. For reference, in Comparative Examples 4 and 5, the gas experiment was not performed because the desired anode additive was not formed.

[Table 2]

2019/103459 1 »(: 1 ^ {2018/014368

Experimental results show that when the positive electrode additives of Examples 1 to 3 prepared according to the production method of the present invention are contained, by-products and unreacted materials contained in the positive electrode additive are reduced, Comparative Example 1, Comparative Example 2, and Comparative Example 3, in which the first heat treatment time was too short, and Comparative Example 3 in which the first heat treatment time was too long, were significantly reduced, The gas generation amount was reduced by 50% or more.

Claims

Claims: What is claimed is: 1. A process for producing a luminescent material, comprising mixing a raw material of larium, a raw material of a nickel material and an element and then heat- Nickel oxide, said heat treatment comprising: a first heat treatment at 300-500 I; And a second heat treatment step at 550 to 800 V after the first heat treatment, wherein the first heat treatment is performed for 30 to 50% of the whole heat treatment time, and the lyrium containing the lyrium nickel oxide of the formula (1) Method for preparing positive electrode additive for secondary battery:

 [Chemical Formula 1]

1 minute 0 ₂

 In Formula 1,

 Is selected from the group consisting of a transition metal, an amphoteric element,?, And 8, provided that the terminal is not nickel,

 0 &lt;

[Claim 2]

 The method according to claim 1,

 The primary heat treatment is performed at a temperature of from 330 to 450,

Lt; RTI ID = 0.0 &gt; 45%. &Lt; / RTI &gt;

[Claim 3]

 The method according to claim 1,

Wherein the primary heat treatment is a heating step of heating at a rate of from 2 to 71: 1/1 up to 300 to 500: ₁ , and a holding step of maintaining at a heated temperature for 40 to 80% of the total time of the primary heat treatment step &Lt; / RTI &gt; by weight of the total weight of the lithium secondary battery.

[4] 2019/103459 1 »(: 1 ^ {2018/014368

The method according to claim 1,

Wherein the secondary heat treatment is carried out at a temperature of 600 to 800 占 (a process for producing a positive electrode additive for a lithium secondary battery _.

[Claim 5]

 The method according to claim 1,

The second heat treatment is a heating step of heating at a specific speed of 2 to 7 ᄃ / [ _11] up to 550 to 800 I: and a maintaining step of maintaining 60 to 90% of the total time of the second heat treatment step at the heated temperature &Lt; / RTI &gt; by weight of the total weight of the lithium secondary battery.

[Claim 6]

 The method according to claim 1,

 A method for producing a positive electrode additive for a lithium secondary battery, wherein the lithium source material is used in such an amount that the molar ratio of Li +: Ni + element becomes 2: 1 when the Li source raw material, the nickel raw material and the raw material of the element are mixed .

7.

 The method according to claim 1,

 Wherein the raw material for the ruthenium source comprises any one or a mixture of two or more selected from the group consisting of lyrium containing oxides, hydroxides, oxyhydroxides, sulfates, nitrates, acetates, carbonates, oxalates, citrates, halides, A method for manufacturing a positive electrode additive for a lithium secondary battery.

[8]

 The method according to claim 1,

The element

The containing raw material comprises any one or a mixture of two or more selected from the group consisting of elemental oxides, hydroxides, oxyhydroxides, sulfates, nitrates, acetates, carbonates, oxalates, citrates, halides, phosphates and hydrates thereof , A method for producing a positive electrode additive for a lithium secondary battery. 2019/103459 1 »(: 1 ^ {2018/014368

9]

 The method according to claim 1,

 Wherein said nickel raw material contains 0. 3. A method for producing a positive electrode additive for a lithium secondary battery,

Claim 10

 The method according to claim 1,

 Wherein the element is selected from the group consisting of I, 9, 8, and 8. 9. The method of claim 1,

Claim 11

 The method according to claim 1,

Wherein the positive electrode additive further comprises 0 and less than 1 wt% Ni ₂ O in an amount less than 11 wt% based on the total weight of the positive electrode additive, wherein the total amount of 0 and Ni ₂ O is 11 wt% Gt;

Claim 12

 A lithium nickel oxide according to claim 1,

Cathode additive, but the total weight on the knee ₂₀ further comprising less than or equal to 0 and 1% by weight of less than 11% by weight relative to the total amount of less than or equal to 0 and you ₂ 0 11% by weight, Lyrium secondary battery positive electrode additive:

 [Chemical Formula 1]

 In Formula 1,

 Is selected from the group consisting of a transition metal, an amphoteric element, and 8, provided that the group is not nickel,

0 &lt;:_{< 1} .

Claim 13 2019/103459 1 »(: 1 ^ {2018/014368

13. The method of claim 12,

 The positive electrode additive has an intensity of a peak appearing at 30 ° to 35 ° (11, 29 = 15 to 20 ° in the X-ray diffraction analysis after filling with 0.1: (12 / (12 = 0, positive electrode additive.

14.

 A positive electrode for a lithium secondary battery comprising the positive electrode additive according to claim 12.

15.

 A positive electrode comprising the positive electrode additive according to claim 12; Electrolyte; And a negative electrode.