WO2019103459A2 - Procédé de fabrication d'additif d'électrode positive destinée à une batterie secondaire au lithium - Google Patents

Procédé de fabrication d'additif d'électrode positive destinée à une batterie secondaire au lithium Download PDF

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Publication number
WO2019103459A2
WO2019103459A2 PCT/KR2018/014368 KR2018014368W WO2019103459A2 WO 2019103459 A2 WO2019103459 A2 WO 2019103459A2 KR 2018014368 W KR2018014368 W KR 2018014368W WO 2019103459 A2 WO2019103459 A2 WO 2019103459A2
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Prior art keywords
positive electrode
heat treatment
raw material
secondary battery
electrode additive
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PCT/KR2018/014368
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English (en)
Korean (ko)
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WO2019103459A3 (fr
Inventor
노은솔
전혜림
이동훈
이상욱
정왕모
강민석
백소라
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020180143870A external-priority patent/KR102646712B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to EP18881260.6A priority Critical patent/EP3608293A4/fr
Priority to JP2019559758A priority patent/JP7045557B2/ja
Priority to US16/615,519 priority patent/US11398623B2/en
Priority to CN201880028288.XA priority patent/CN110573459B/zh
Publication of WO2019103459A2 publication Critical patent/WO2019103459A2/fr
Publication of WO2019103459A3 publication Critical patent/WO2019103459A3/fr
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • 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 .
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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,
  • the heat treatment comprises a first heat treatment at 300 to 500 x; And 550 to 800 after the primary heat treatment
  • 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 :
  • M is selected from the group consisting of a transition metal, an amphoteric element, P, F, and B,
  • 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.
  • a positive electrode and a lyrium negative electrode for a lithium secondary battery comprising the positive electrode additive.
  • 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.
  • FIG. 1 is a graph showing the results of thermal analysis for a mixture for preparing a positive electrode additive in Test Example 1.
  • XRD 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.
  • the method for preparing a positive electrode additive for a lithium secondary battery 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 ≪ / RTI >
  • 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.
  • 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.
  • 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;
  • the primary heat treatment step is specifically performed at a temperature of 300 to 500 X :.
  • 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.
  • 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 3 ⁇ 4 does not occur sufficiently, resulting in a large amount of unreacted raw material, May be generated.
  • 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.
  • 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.
  • the primary heat treatment may be performed for 30 to 50% of the entire heat treatment time.
  • the reaction of the raw material of lyrium and the raw material of the element can sufficiently occur.
  • 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.
  • the first heat treatment time exceeds 50% of the total heat treatment time, the second heat treatment time is relatively reduced.
  • 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.
  • 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 ⁇ / 111. When the temperature is raised at the controlled heating rate, the reaction efficiency can be further increased.
  • the holding step may be performed for 40 to 80% of the total time of the first heat treatment step.
  • 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.
  • 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 may be performed in an inert gas atmosphere such as nitrogen, helium, or argon to suppress side reaction formation.
  • an inert gas atmosphere such as nitrogen, helium, or argon to suppress side reaction formation.
  • 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.
  • 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 03 ⁇ 4 , needle 03, 11 ⁇ 2, you 0 ⁇ Needle ( ⁇ - 3 ⁇ 40, you ⁇ you kneader, needle, needle 1, 0 ⁇ 3 ⁇ 01 [, needle 20, needle ⁇ 0 4, ⁇ 3 ⁇ 0 Needle, or Needle 3 (: 6 3 ⁇ 40 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 ).
  • Oxyhydroxides, phosphates, and the like can be used, and phosphates can be used.
  • 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.
  • the content of the reagent raw material may be such that the molar ratio of lium: (nickel + element 3 ⁇ 4) is 2: 1. If the molar ratio of nickel + element 3 ⁇ 40 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.
  • a sintering agent may be optionally added.
  • Compounds containing ammonium ions such as (i) filtration; 3 ⁇ 40 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.
  • a moisture removing agent may be optionally added.
  • 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
  • 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.
  • 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).
  • 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.
  • the second heat treatment is performed at a temperature of 550 to 8001 :.
  • 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.
  • 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.
  • 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.
  • 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
  • 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 .
  • the temperature is raised at the controlled heating rate, the reaction efficiency can be further increased.
  • the holding step may be performed for 60 to 90% of the total time of the second heat treatment step.
  • 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.
  • 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 may also be performed in an inert gas atmosphere such as nitrogen, helium, or argon to suppress side reaction formation.
  • an inert gas atmosphere such as nitrogen, helium, or argon
  • 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.
  • 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.
  • a secondary heat treatment step as described above, the primary heat treatment results included in the reaction to give you a -3 ⁇ 41-0 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:
  • 3 ⁇ 4! Is selected from the group consisting of transition metals, amphoteric elements, and 6, but not only nickel,
  • the element is 0 0,
  • And < RTI ID 0.0 > 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.
  • 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.
  • 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.
  • 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%.
  • 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.
  • 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 1'1 ⁇ 2 (81 1 stop;
  • the positive electrode additive prepared according to the above-mentioned production method is a lythum-
  • the Needle and needle 2 (3 ⁇ 4 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • carbon, nickel, titanium, , Silver or the like may be used.
  • silver or the like
  • the adhesion of the positive electrode active material in various forms such as films, sheets, foils, nets, porous bodies, foams, and nonwoven fabrics.
  • a conductive material and a binder A conductive material and a binder.
  • 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.
  • 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 ⁇ ), vinylidene fluoride-hexafluoropropylene copolymer (Acrylonitrile-butadiene copolymer).
  • 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.
  • 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.
  • Ni (: 0 0 2, Ni 0 2, 1 112 0 2 ( 3 ⁇ 3 ⁇ 4 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 13 ⁇ 43 ⁇ 40 2, needle 1 - (1 1 ⁇ 113 ⁇ 40 2 ( 0 £ 1 [ ⁇ 1), knee (on ⁇ (0 ⁇ equal ⁇ 2, 0 ⁇ 3 ⁇ 4 ⁇ 2 , 0 ⁇ (: ⁇ 2,
  • the lyotropic transition metal compound may be LiCoO 2 or LiNi 3 ⁇ 4, in consideration of the remarkable improvement effect when the combination with the lithium-based compound of the formula (1) is used.
  • 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.
  • 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.
  • the solvent examples 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.
  • DMSO dimethyl sulfoxide
  • NMP N-methylpyrrolidone
  • acetone 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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, 3 ⁇ 4,?
  • B, ⁇ 11 is, 111, Greater, 01, ⁇ alloy, alloy or 1 3 ⁇ 4 match gold or the like is alloyed with lithium can be metal compounds;
  • Or as complexes or 3 ⁇ 4 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.
  • 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
  • high-temperature sintered carbon such as petroleum and coal tar coke.
  • binder and the conductive material may be the same as those described above for the anode.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • a cyclic carbonate for example, ethylene carbonate or propylene carbonate
  • ethylene carbonate or propylene carbonate for example, ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate, etc.
  • 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.
  • 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.
  • 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, diethylene glycol, and diethylene glycol;
  • a halogenoalkylene carbonate compound such as diethyl carbonate, diethylene glycol, 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
  • 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).
  • portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles Hybrid Electric Vehicle (HEV).
  • HEV Hybrid Electric Vehicle
  • 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.
  • EV electric vehicle
  • PHEV plug-in hybrid electric vehicle
  • a power storage system a power storage system.
  • Example 3 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 / 1 ⁇ 2 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 Example 3
  • the resultant reactants were cooled to obtain positive electrode additive particles. Comparative Example 3
  • 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
  • thermogravimetric analyzer TGA
  • 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.
  • 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).
  • XRD X-ray diffraction analysis
  • 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.
  • a battery in the form of a pouch was produced using an electrolytic solution. 2019/103459 1 »(: 1 ⁇ ⁇ 2018/014368
  • the results are shown in Fig.
  • Comparative Examples 1 to 3 Ne In addition to the peak of 3 ⁇ 4 11 2 0 peak was observed with Comparative Example 4
  • 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.
  • 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un additif d'électrode positive pour une batterie secondaire au lithium, le procédé étant en mesure de réduire considérablement la quantité de gaz généré pendant le fonctionnement de l'électrode par réduction du contenu de sous-produits à base de Li générés dans un procédé de fabrication et d'oxydes de lithium n'ayant pas réagi.
PCT/KR2018/014368 2017-11-22 2018-11-21 Procédé de fabrication d'additif d'électrode positive destinée à une batterie secondaire au lithium Ceased WO2019103459A2 (fr)

Priority Applications (4)

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EP18881260.6A EP3608293A4 (fr) 2017-11-22 2018-11-21 Procédé de fabrication d'additif d'électrode positive destinée à une batterie secondaire au lithium
JP2019559758A JP7045557B2 (ja) 2017-11-22 2018-11-21 リチウム二次電池用正極添加剤の製造方法
US16/615,519 US11398623B2 (en) 2017-11-22 2018-11-21 Method for preparing positive electrode additives of lithium secondary battery
CN201880028288.XA CN110573459B (zh) 2017-11-22 2018-11-21 制备锂二次电池的正极添加剂的方法

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KR10-2018-0143870 2018-11-20

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KR0156744B1 (ko) 1990-08-24 1998-12-01 게리 리 그리스울드 분자선 에피택시 성장중에 iib-via족 반도체를 도우핑한 p형의 iib-via족 반도체층을 가진 전자 방사선 변환기

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KR100595362B1 (ko) * 2004-07-21 2006-06-30 제일모직주식회사 비수계 전해질 2차 전지 양극 활물질용 리튬-니켈 복합산화물, 그 제조방법 및 그를 포함하는 양극 활물질
KR100709833B1 (ko) * 2005-09-22 2007-04-23 삼성에스디아이 주식회사 구리 집전체의 용출을 막을 수 있는 리튬 이차 전지
KR100826074B1 (ko) * 2005-11-17 2008-04-29 주식회사 엘지화학 과방전 방지용 전극 첨가제 및 이의 제조 방법
KR101900823B1 (ko) * 2015-12-04 2018-09-20 재단법인 포항산업과학연구원 박막형 전고체 전지, 및 이의 제조 방법
KR101809720B1 (ko) * 2016-02-17 2017-12-15 한국과학기술연구원 표면 코팅된 양극 활물질, 그 제조방법 및 이를 이용한 리튬이차전지

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KR0156744B1 (ko) 1990-08-24 1998-12-01 게리 리 그리스울드 분자선 에피택시 성장중에 iib-via족 반도체를 도우핑한 p형의 iib-via족 반도체층을 가진 전자 방사선 변환기

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