WO2019103576A2 - Matière additive pour électrode positive, et électrode positive et batterie secondaire au lithium comprenant ladite matière active - Google Patents

Matière additive pour électrode positive, et électrode positive et batterie secondaire au lithium comprenant ladite matière active Download PDF

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Publication number
WO2019103576A2
WO2019103576A2 PCT/KR2018/014725 KR2018014725W WO2019103576A2 WO 2019103576 A2 WO2019103576 A2 WO 2019103576A2 KR 2018014725 W KR2018014725 W KR 2018014725W WO 2019103576 A2 WO2019103576 A2 WO 2019103576A2
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WIPO (PCT)
Prior art keywords
positive electrode
core
additive
lithium
oxide
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PCT/KR2018/014725
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English (en)
Korean (ko)
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WO2019103576A3 (fr
Inventor
김지혜
박병천
한정민
정왕모
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020180147752A external-priority patent/KR102663794B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/757,783 priority Critical patent/US11545670B2/en
Priority to CN201880066916.3A priority patent/CN111213269B/zh
Priority to JP2019566799A priority patent/JP7150380B2/ja
Priority to EP18881390.1A priority patent/EP3680970A4/fr
Publication of WO2019103576A2 publication Critical patent/WO2019103576A2/fr
Publication of WO2019103576A3 publication Critical patent/WO2019103576A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides; Hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 positive electrode additive, a process for producing the same, and a positive electrode and a lithium secondary battery comprising the same.
  • the lithium secondary battery is a lithium secondary battery in which an electrode active material capable of reversibly intercalating and deintercalating lithium ions is applied to a negative electrode and a positive electrode to realize movement of lithium ions through an electrolyte, .
  • An embodiment of the present invention provides a positive electrode additive capable of canceling the irreversible capacity imbalance of two electrodes and suppressing generation of gas in the battery while increasing an initial charging capacity of the anode.
  • a member when a member is " on " another member, it includes not only when the member is in contact with the other member, but also when there is another member between the two members.
  • " combination (s) thereof " included in the expression of the machine form means a mixture or combination of one or more elements selected from the group consisting of the constituents described in the expression of the form of a marker,
  • M represents at least one metal element forming a divalent ion or a trivalent ion, for example, And can be at least one metal element selected from the group consisting of -0.2 ⁇ 0.2, 0.5 ⁇ 1) ⁇ 1.0, -0.2 ⁇ 0.2, 0.7 ⁇ ⁇ 1.0, 0 ⁇ 0.15 , 0 ⁇ shon 0.15.
  • the core comprises an excess of lyrium relative to a conventional positive electrode active material, which is one mole of lyrium, and is capable of irreversibly releasing lithium upon initial charge and discharge of the cell.
  • the coating layer is formed by removing a lithium byproduct (one peg (0, 3 , 0), etc.) remaining on the surface of the core to generate gas in the continuous charge- It can be suppressed.
  • the positive electrode additive of one embodiment is applied to the positive electrode together with the positive electrode active material to cancel the irreversible capacity imbalance of the two electrodes during the initial charging and discharging of the battery, to increase the initial charging capacity of the positive electrode, .
  • the core is highly reactive and reacts with carbon dioxide (CO 2) , water (3 ⁇ 40), etc. in a general air atmosphere to form a mixture of carbonyllium (Li 2 CO ) (LiOH). ≪ / RTI >
  • the lithium byproduct does not participate in the electrochemical reaction in the battery, and generates a gas in the battery, thereby reducing the initial capacity and initial charge / discharge efficiency of the battery.
  • the core (Li 20) is protected by forming a coating layer on the surface of the core without simply wasting the core, while in the process of forming the coating layer Thereby converting the lithium by-product into another compound incapable of generating a gas.
  • the coating layer can be formed on the surface of the core by heat-treating a mixture of the core and ammonium phosphate (NH 4 H 2 PO 4) , as will be described later in more detail.
  • the surface of the core may be coated with the ammonium monophosphate (NH 4 H 2 PO 4) .
  • a coating layer of Li 3 PO 4 type formed by the reaction of the first ammonium phosphate (NH 4 H 2 PO 4) with the lithium by-product, for example, LiOH, may be formed.
  • the compound that can be included in the coating layer may be a compound that contains phosphorus in general and can not generate gas in the battery, but the phosphorus compound and the raw material thereof contained in the coating layer are important in the core It does not react with the factor (Li 20) , but rather prevents direct contact between the core and the electrolyte in the battery, thereby suppressing the side reaction. 2019/103576 1 »(: 1 ⁇ ⁇ 2018/014725
  • the coating layer may include 500 to 9000 1 ) 111 of the total amount of the positive electrode additive.
  • This is adjustable by controlling the content of the first ammonium phosphate to 500 to 9000 ppm based on the total amount of the core and the first ammonium phosphate.
  • the total amount of the core and the first ammonium phosphate is 500 to 9000
  • the content of the first ammonium phosphate is 500 to 9000 For example, 1000 to 8000
  • the content of the coating layer in the total amount of the positive electrode additive is controlled to 500 to 9000 For example, 1000 to 8000 ppm, 1000 to 7000 ppm, 1000 to 6000 1000 to 5000 1000 to 4000 1000 to 3000 And the like.
  • Core in the positive electrode additive of one embodiment,
  • R 5 is the same as in the formula (1).
  • the nickel-based oxide herein, it can be produced from a metal element which forms a divalent cation or a trivalent cation, 0.5 ⁇ (1 ⁇ 1.0, 1.8 ≤ 2.2) and lignite oxide (0).
  • Ni d Mul nickel-based oxide
  • Li 20 lithium oxide
  • the unreacted raw material is not removed and recovered together with a substance having the theoretical composition (that is, the lithium nickel oxide represented by the above-mentioned formula 1-1) .
  • Such cores can provide extra Li to the anode and, depending on the presence of the unreacted raw material, especially lyrium oxide (Li 20) , can further increase the initial charge capacity of the anode.
  • the core may be obtained by blending the nickel-based oxide and the lyrium oxide (Li 20) in a stoichiometric molar ratio of 1: 1.02 to 1: 0.98, followed by heat treatment, and without removing the unreacted raw material.
  • the lyrium nickel oxide, the nickel oxide (NiO), and the lyrium oxide (Li 20) represented by the formula 1-1 are each crystalline, and XRD by Fe Ka X- (X-ray Diffiaction).
  • the main peak appears in at least one range from 30 to 35 ° porcelain, from 35 to 40 ° porcelain porcelain, from 55 to 60 ° porcelain porcelain, due to the lithium oxide (Li 2 O).
  • (Li 2 O) in the total amount of the core (100 wt%) is less than or equal to 0 wt%, and more preferably, less than 10 wt% , More than 0% by weight and not more than 13% by weight, for example, more than 0% by weight and not more than 12% by weight.
  • XRD X-ray diffraction
  • the main peak intensity of the lithium nickel oxide represented by Formula 1-1 is 100 (Ref.), It is more than 0 and not more than 15, specifically more than 0 and not more than 14 and not less than 0 and not more than 13, for example, The intensity may be greater than 0 and less than or equal to 12.
  • the content of the nickel oxide (NiO) in the total amount (100 wt%) of the core is more than 0 wt% and not more than 15 wt%, more specifically 0 wt% to 14 wt% , For example, more than 0% by weight and 12% by weight or less.
  • the main peak may appear in the range.
  • the main peak may be represented by a crystal structure of orthorhombic having a point group Im mm and may be a lithium nickel oxide represented by the formula 1-1.
  • the core contains the lithium nickel oxide, the nickel oxide (0) and the lyrium oxide (0 20) represented by the formula 1-1, X and X2 in the formula (1) are the same as in the above formula 1.
  • X and 2 each represent a lithium nickel oxide, a nickel oxide, and a lithium oxide (1 pair 0) of the weight.
  • the form of the lithium nickel oxide, the nickel oxide (0), and the lium oxide (1 run 0) represented by Formula 1-1 is not particularly limited.
  • the nickel oxide (0) particle and the lithium oxide ( 20 ) particle are attached to the surface of the lithium nickel oxide particle represented by the formula (1-1)
  • lithium oxide (CrO) particles may be present in a separately existing mixture without being attached to the lyrium nickel oxide particle represented by the above formula (1-1).
  • " particle " may be the primary particle or the primary particle or the primary particle.
  • the core has a voltage at the time of initial charging of electrons, for example, 2.5 to 4.25 Lyrium ion and oxygen, and then the entire composition can be converted into the following formula (2).
  • the positive electrode additive of one embodiment can be utilized as an additive for compensating the initial irreversible capacity of the negative electrode, and as an active material capable of reversible insertion and desorption of lithium.
  • the core converted into the formula (2) may have a reversible capacity smaller than that of the conventional positive electrode active material, and may have a reversible capacity of 300 to 350 1 ⁇ 1. Therefore,
  • the cathode active material may be mixed with the cathode active material according to the desired characteristics of the battery in an appropriate mixing ratio.
  • a method for producing a positive electrode additive comprising the steps of: preparing a nickel-based oxide represented by the following formula (3); heat treating a mixture of the nickel calculated product and lithium oxide (Li 20) And heat treating the mixture of the core and ammonium phosphate (NH 4 H 2 PO 4) to form a coating layer on the surface of the core.
  • the above-mentioned positive electrode additive can be obtained.
  • the step of preparing the nickel-based oxide represented by the above-mentioned formula (3) comprises: nickel hydroxide (Ni (OH) 2) alone; Or a mixture of a nickel hydroxide (Ni (OH) 2) and an M-containing compound.
  • the heat treatment of the nickel hydroxide (Ni (OH) 2) alone or a mixture of nickel hydroxide (Ni (OH) 2) and water to be M is carried out in a temperature range of 500 to 700 C for 5 to 20 hours in an inert atmosphere Can be performed.
  • the nickel hydroxide (Ni (OH) 2) when the nickel hydroxide (Ni (OH) 2) is subjected to a heat treatment alone, dine nickel oxide (NiO x) may be formed in the above formula (3 ) .
  • a mixture of the nickel hydroxide (Ni (OH) 2) and the M-containing compound is heat-treated, an M-doped nickel-based oxide (Ni d MJO x) have.
  • the step of heat-treating the mixture of the nickel-based oxide and the lyrium oxide (1 peak 0) comprises heating the mixture of the nickel- The oxides may be mixed in a molar ratio of 1: 1 (0.02) and heat treated in an inert atmosphere for 10 to 20 hours at a temperature range of 600 to 800 ° C.
  • the nickel-containing oxide and lithium oxide to heat treatment a mixture of (Li 20), a combined total amount of 1: do not react in a molar ratio of 1, the nickel-containing oxide part and the lithium oxide ((NidM d) O x) (Li 20) reacts to form a lithium nickel oxide represented by Formula 1-1, and unreacted starting materials may remain.
  • the overall composition of the resulting product and the effect thereof are as described above. Meanwhile, in the manufacturing method of one embodiment, in the step of forming the coating layer on the surface of the core, a coating layer containing the phosphorus (P) compound may be formed.
  • the surface of the core be coated with the ammonium phosphate (NH 4 H 2 PO 4)
  • a coating layer in the form of lithium phosphate (Li 3 PO 4) formed by the reaction of the first ammonium phosphate (NH 4 H 2 PO 4) with the lyrium by-product, for example, LiOH, may be formed.
  • the amount of the first ammonium phosphate in the total amount of the blended raw materials i.e., the core and the first ammonium phosphate
  • the content of the coating layer can be adjusted to 500 to 9000 ppm.
  • the positive electrode additive of the embodiment is not limited thereto.
  • the above-mentioned positive electrode additive And a cathode active material. Since the positive electrode additive of the embodiment is applied with the positive electrode additive described above, the initial irreversible capacity of the negative electrode is reduced compared to the case where the positive electrode additive is not applied, 2019/103576 1 »(: 1 ⁇ ⁇ 2018/014725
  • the initial efficiency of the anode can be increased.
  • the positive electrode additive may be applied in an amount of 1 to 30% by weight.
  • the positive electrode additive is compounded in the above range, After the initial irreversible capacity of the cathode is sufficiently reduced with the positive electrode additive (i.e., in the cycle), reversible positive insertion and desorption of lyrium ion can be stably performed by the positive electrode active material after charge / discharge (i.e., after two cycles).
  • the positive electrode mixture of this embodiment can be generally implemented according to what is known in the art.
  • the positive electrode mixture of the embodiment is not limited thereto.
  • the cathode active material it is not particularly limited as long as it is a material capable of reversible insertion and desorption of lithium ions.
  • the cathode active material a compound represented by any one of the following formulas may be used.
  • a compound represented by any one of the following formulas may be used. In the formula, 0.90 ⁇
  • 3 ⁇ 43 ⁇ 4 (3 ⁇ 402 (wherein 0.90 ⁇ & ⁇ 1.8, 0 ⁇ 1? 0.9, 0 ⁇ 0.9, 0 ⁇ 0.5, 0 ⁇ acid ⁇ 0.5 and 0.001 ⁇ 6 <0.1); 1 ⁇ chassis (3 ⁇ 40 2 (wherein, 0.90 £ £ 1.8 and 0.001 £ I? £ 0.1); 1 ⁇ (: 0 (3 ⁇ 40 2 ( wherein, 0.90 £ £ greater 1.8 and 0.001 £ 1? £ 0.1); # 11 (3 ⁇ 40 2 (where 0.90 ⁇ 3 ⁇ 4 ⁇
  • Mn or a combination thereof
  • I is &, V, ⁇ & , 80, V, or a combination thereof
  • V (,,,, or a combination of these.
  • a compound having a coating layer on the surface of the compound may be used, or a compound having a coating layer may be mixed with the compound.
  • the coating layer may include a hydroxyl carbonate of a coating element of the oxy-carbonate, or oxyhydroxide, the coating element of the oxides, hydroxides, coating element, the coating element as a coating element compound.
  • the compound constituting these coating layers may be amorphous or crystalline. Examples of the coating element included in the coating layer include Mg, Mixtures may be used.
  • the coating layer forming step may be carried out by any of coating methods such as spray coating, dipping, and the like without adversely affecting the physical properties of the cathode active material by using these elements in the above compound.
  • the positive electrode material mixture of one embodiment may further include a conductive material, a binder, or a mixture thereof.
  • the conductive material is used for imparting conductivity to the electrode. In the battery, it is preferable that the conductive material does not cause chemical change, 2019/103576 1 »(: 1 ⁇ ⁇ 2018/014725
  • metal powder such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, copper, nickel, Phenylene derivatives, and the like can be used alone or in combination.
  • the binder serves to adhere the positive electrode active material particles to each other and to adhere the positive electrode active material to the current collector.
  • LITHOID SECONDARY BATTERY in another embodiment of the present invention, there is provided a secondary battery comprising a cathode including the above-described cathode mixture, an electrolyte, and a cathode.
  • the lithium ion secondary battery of the present invention can be generally manufactured in accordance with those known in the art.
  • the positive electrode comprises: a positive electrode collector; And a separator disposed on the positive electrode collector, 2019/103576 1 »(: 1 ⁇ ⁇ 2018/014725
  • the positive electrode may be prepared by applying an electrode mixture, which is a mixture of a positive electrode active material, a conductive material, and / or a binder, on a positive electrode collector, followed by drying. If necessary, a filler may be further added to the mixture .
  • an electrode mixture which is a mixture of a positive electrode active material, a conductive material, and / or a binder, on a positive electrode collector, followed by drying. If necessary, a filler may be further added to the mixture .
  • the cathode current collector may generally be made to have a thickness of 3 - 500.
  • a positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery.
  • the positive electrode current collector include stainless steel, aluminum, nickel, titanium, sintered carbon, aluminum or stainless steel A surface treated with carbon, nickel, titanium, silver or the like may be used.
  • the current collector may form fine irregularities on the surface of the current collector to increase the adhesion force outside the cathode active material, and various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric are possible.
  • the conductive material is usually added in an amount of 1 to 50% by weight based on the total weight of the mixture including the cathode active material.
  • a conductive material is not particularly limited as long as it has electrical conductivity without causing any chemical change in the battery, for example, graphite such as natural graphite or artificial graphite; Carbon black such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fiber and metal fiber; Metal powders such as carbon fluoride, aluminum and nickel powder, conductive whiskey such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide, Conductive materials such as polyphenylene derivatives and the like can be used.
  • the graphite-based material having elasticity may be used as a conductive material, and may be used together with the materials.
  • the binder is a component that assists in bonding of the active material and the conductive material and bonding to the current collector, and is usually added in an amount of 1 to 50 wt% based on the total weight of the mixture containing the cathode active material.
  • binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose (CM (its), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene , Polyethylene, polypropylene, ethylene-propylene-diene terpolymer, Styrene butadiene rubber, fluorine rubber, various 2019/103576 1 »(: 1 ⁇ ⁇ 2018/014725
  • the filler is not particularly limited as long as it is a fibrous material which is used selectively as a component for suppressing the expansion of the anode and does not cause chemical change in the battery.
  • the filler include olefin polymers such as polyethylene and polypropylene; Fibrous materials such as fibers and carbon fibers are used.
  • the negative electrode includes a current collector and a negative electrode active material layer formed on the current collector, and the negative electrode active material layer may include a negative electrode active material.
  • the negative electrode active material examples include a carbon-based negative electrode active material, a lithium metal, an alloy of lithium metal, a composite with 3 ⁇ 4 810x (0 ⁇ X ⁇ 2) (The above is an alkali metal, an alkaline earth metal, a Group 13 to Group 16 element, a transition metal, a rare earth element or a combination thereof, Complex, and At least one negative electrode active material selected from the group consisting of an alkali metal, an alkaline earth metal, a Group 13 to Group 16 element, a transition metal, a rare earth element, or a combination thereof, but not limited thereto.
  • the negative electrode current collector may generally be made to have a thickness of 3 to 500.
  • Such an anode current collector is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery, and examples of the anode current collector include copper, stainless steel, aluminum, nickel, titanium, sintered carbon, a surface of copper or stainless steel Aluminum, cadmium alloy, or the like may be used as the cathode collector.
  • fine unevenness may be formed on the surface to enhance the bonding force of the anode active material, A film, a sheet, a foil, a net, a porous body, a foam, a nonwoven fabric, and the like.
  • the lithium secondary battery of one embodiment may be a lithium ion battery , a lithium ion polymer battery, or a lyrium polymer battery, depending on the kind of the electrolyte and / or the type of the separator.
  • the lithium secondary battery of the embodiment is a lithium ion battery to which a liquid electrolyte is applied
  • the liquid electrolyte may be impregnated into the separator.
  • the separator is interposed between the anode and the cathode and has high ion permeability and mechanical strength
  • a thin insulating thin film is used.
  • the pore diameter of the separator is generally 0.01 - 10, and the thickness is generally 5 - 300 / zm.
  • Such separation membranes include, for example, olefinic polymers such as polypropylene, which are chemically resistant and hydrophobic; A sheet or nonwoven fabric made of glass fiber, polyethylene or the like is used.
  • a solid electrolyte such as a polymer is used as an electrolyte
  • the solid electrolyte may also serve as a separation membrane.
  • the liquid electrolyte may be a lithium salt-containing nonaqueous electrolyte.
  • the lithium salt-containing nonaqueous electrolyte is composed of a nonaqueous electrolyte and lithium.
  • a nonaqueous organic solvent, an organic solid electrolyte, an inorganic solid electrolyte and the like are used, but the present invention is not limited thereto.
  • non-aqueous organic solvent examples include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylenecarbonate, dimethyl carbonate, diethyl carbonate, gamma -Butyrolactone, 1,2-dimethoxyethane, tetrahydroxyfuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane , Acetonitrile, nitromethane, methyl formate, methyl acetate, triester phosphate, trimethoxymethane, dioxolane derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl- 2- imidazolidinone, propylene carbonate
  • Nonionic organic solvents such as tetrahydrofuran derivatives, ethers, methyl pyrophosphate and ethyl propionate may be used.
  • organic solid electrolyte examples include a polymer electrolyte such as a polyethylene derivative, a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, an agitation lysine, a polyester sulfide, a dolovinyl alcohol, a polyvinylidene fluoride, A polymer containing an ionic dissociation group, etc. may be used.
  • a polymer electrolyte such as a polyethylene derivative, a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, an agitation lysine, a polyester sulfide, a dolovinyl alcohol, a polyvinylidene fluoride, A polymer containing an ionic dissociation group, etc. may be used.
  • Examples of the inorganic solid electrolyte include Li 3 N, Lil, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , include Li 4 Si0 4 -LiI-Li0H, Li 3 P0 4 -Li 2 S-SiS 2 and Li nitrides, halides and sulfates may be used.
  • the lithium salt may be dissolved in the non-aqueous electrolyte, for example, LiCl, LiBr, Lil, LiClO 4 , LiBF 4 , LiB 10 Cl 0 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6, L1AICI4, CH3SO3L1, (CF 3 S0 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, 4 phenyl borate Lyrium, it can be already in use include de.
  • LiCl, LiBr, Lil, LiClO 4 , LiBF 4 , LiB 10 Cl 0 LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6, L1AICI4, CH3SO3L1, (CF 3 S0 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, 4 phenyl borate Lyrium
  • the lithium salt-containing nonaqueous electrolyte may contain, for example, pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylenediamine, n-glyme (gl> N, N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salts, pyrrole, 2-methoxyethanol, trichloromethane, Aluminum, etc.
  • a halogen-containing solvent such as carbon tetrachloride, ethylene trifluoride or the like may be further added in order to impart nonflammability, and a carbon dioxide gas may be further added to improve high temperature storage characteristics FEC (Fluoro-Ethylene Carbonate), PRS (Propene sultone) and so on.
  • FEC Fluoro-Ethylene Carbonate
  • PRS Pene sultone
  • LiPF 6 LiC10 4, LiBF 4, LiN (S0 2 CF 3)
  • a lithium salt of 2, and so on, highly dielectric solvent of EC or PC cyclic carbonate and a low viscosity theft bound DEC, DMC or EMC linear Carbonate is added to the mixed solvent to prepare a lithium salt-containing non-aqueous electrolyte.
  • the lithium secondary battery of one embodiment may be implemented as a battery module including a unit cell, a battery pack including the battery module, and a device including the battery pack as a power source.
  • specific examples of the device may be, but not limited to, an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, or a power storage system.
  • the lithium secondary battery to which the positive electrode additive of one embodiment is applied to the positive electrode is characterized in that the initial irreversible capacity of the negative electrode is reduced and the initial capacity and efficiency of the positive electrode are effectively increased and the energy density is lowered during driving, have.
  • Fig. 1 is a graph showing the results of measurement for each lithium secondary battery of Production Examples 1 to 3 and Comparative Example 1 2019/103576 1 »(: 1 ⁇ ⁇ 2018/014725
  • Nickel hydroxide precursor Ni (OH) 2 was heat-treated for 10 hours in an inert atmosphere of 600 X: to obtain nickel calcined product 0.
  • the nickel-based oxide green 0 was mixed with lyrium oxide (1 peak 0) in a volume ratio of 1: 1.1 (0 : 20 ) and heat-treated for 18 hours in an inert atmosphere of 680 ° (: The speed was set at 5 ° 0 per minute.
  • a positive electrode was prepared by applying the core of Preparation Example 1 as a positive electrode additive, and a lithium secondary battery including the positive electrode thus prepared was produced. Specifically, the core (anode additive) of Production Example 1
  • Lithium metal Li-metal
  • ethylene carbonate ethylene carbonate
  • DMC dimethyl carbonate
  • Carbonate in a volume ratio of 1: 2 was used to dissolve 2 wt% of VC in the solution.
  • a positive electrode and a lithium secondary battery of Production Example 2 were produced in the same manner as in Production Example 1, except that the core (preparation of positive electrode additive) of Production Example 2 was used instead of the core (positive electrode additive) of Production Example 1.
  • a positive electrode and a lithium secondary battery of Production Example 3 were produced in the same manner as in Production Example 1, except that the core of Production Example 3 (positive electrode additive) was used in place of the core (positive electrode additive) of Production Example 1.
  • X-ray diffraction (XRD) analysis by X-ray (X-m) was carried out and the results are shown in Table 1 below.
  • the lithium nickel oxide and the nickel oxide (NiO) are crystalline and can be detected by X-ray diffraction (XRD) by Fe Ka X ray (X-ra).
  • Comparative Example 1 has a determination structure of Orthorhombic with a point group of Immm. From the structural analysis results of Table 1, it was found that Comparative Example 1 and Production Examples 1 to 3 Have the same crystal structure. Therefore, it can be seen that Production Examples 1 to 3 also include a compound represented by Li 2 + a Ni b M b02 + c .
  • the cathode mixture was prepared by mixing each cathode additive in the same amount as the usual cathode active material, And Li 2 O 2.
  • the cathode active material together with the cathode additive of one embodiment including the core may be mixed at an appropriate blending ratio.
  • Example 1 The core of Example 1 was mixed with ammonium phosphate (NH 4 H 2 PO 4) and the mixture was heat-treated for 10 hours in an inert atmosphere of 700 to obtain a positive electrode additive of Example 1.
  • ammonium phosphate NH 4 H 2 PO 4
  • the amount of the first ammonium phosphate was adjusted to 2000 ppm based on the total amount of the mixture.
  • Example 1 Except that the positive electrode additive of Example 1 was used in place of the core (positive electrode additive) of Production Example 1, and the remainder was the same as Production Example 1, to prepare a positive electrode and a lithium secondary battery of Example 1.
  • Example 2 (Core: Preparation Example 1, coating amount: 500 ppm) >
  • Example 1 The mixture of the core of Example 1 and ammonium phosphate monobasic was prepared in the same manner as in Example 1 except that the amount of the ammonium phosphate was 500 ppm, ≪ / RTI >
  • Example 2 Except that the positive electrode additive of Example 2 was used in place of the positive electrode additive of Example 1, the remainder was the same as that of Example 1 to prepare a positive electrode and a lithium secondary battery of Example 2.
  • Example 3 (Core: Preparation Example 1, coating amount: 4000 ppm)
  • the amount of the first ammonium phosphate was 4000 ppm, except for one point. 2019/103576 1 »(: 1 ⁇ ⁇ 2018/014725
  • Example 3 Except that the positive electrode additive of Example 3 was used in place of the positive electrode additive of Example 1, the remainder was the same as that of Example 1, thereby preparing a positive electrode and a lithium secondary battery of Example 3.
  • Example 4 (Core: Preparation Example 1, coating amount: 8000 ppm) >
  • Example 1 When the core of Example 1 was mixed with ammonium phosphate monobasic, the amount of the ammonium phosphate monobasic was 8000 Except for one point, the remainder was the same as in Example 1 to obtain the positive electrode additive of Example 5.
  • Example 5 Except that the positive electrode additive of Example 5 was used in place of the positive electrode additive of Example 1, the remainder was the same as that of Example 1 to prepare a positive electrode and a lithium secondary battery of Example 5.
  • Example 5 (Core: Preparation Example 2, coating amount: 2000 1 > 11) >
  • Example 7 Except that the positive electrode additive of Example 7 was used in place of the positive electrode additive of Example 1, the remainder was the same as that of Example 1 to prepare a positive electrode and a lithium secondary battery of Example 7. [
  • XPS analysis was carried out on the positive electrode additive of Example 1 to determine whether the coating layer was formed on the surface of the core of Production Example 1 and, if so, what the components were.
  • the positive electrode additive of Example 1 NH 4 a H 2 P0 4 through the coating layer formation step of a coating material, to a Lyrium by-product of LiOH and NH 4 H 2 P0 4 reaction present in the core surface of Preparation 1 It can be seen that a coating layer containing Li 3 PO 4 is formed on the surface of the core.
  • Examples 2 to 8 using the same raw materials and processes as in Example 1 were also confirmed here, but only the coating layers of the same components as in Example 1 were formed on the surface of each core, It is deduced to be different.
  • each content shows the respective contents of 011 and 1 peak 0, and the total amount of these lariate by-products, based on the total amount (100 wt%) of the positive electrode additive or core.
  • the cores of Production Examples 1 to 3 show a voltage at the time of initial charging of the battery, for example,
  • each of the positive electrode additives of Examples 1 to 8 has effects of removing lithium byproducts from the coating layer and suppressing gas generation while maintaining the effect of the core (that is, decreasing the initial irreversible capacity of the negative electrode and increasing the initial efficiency of the positive electrode) Therefore, it can be seen that the initial characteristics of the battery are further improved.
  • the positive electrode mixture was prepared by mixing each positive electrode additive in the same amount as that of the usual positive electrode active material, A secondary battery was manufactured.
  • the cathode active material may be mixed with the cathode active material according to the characteristics of the desired battery at a proper mixing ratio. 2019/103576 1 »(: 1 ⁇ ⁇ 2018/014725
  • Examples 7 and 8 Mixing Application of Cathode Additive and Cathode Active Material of Example 1
  • a positive electrode was prepared by applying the positive electrode additive of Example 1 together with the positive electrode active material in the form of actually applying the positive electrode additive of Example 1, A lithium secondary battery containing the prepared positive electrode was prepared.
  • the positive electrode additive of Example 1 (Core: Production Example 1, Coating amount: 200 ( 1 ) 1 ) 1 ), LiNio . 8Coo . 1Mno . 1O2), conductive material -! » , Denka Black) and binder wire
  • Coating amount: 200 ( 1 ) 1 ) 1 ) 1 LiNio . 8Coo . 1Mno . 1O2
  • conductive material -! » conductive material -! »
  • Denka Black Denka Black
  • Example 7 the weight ratio of the positive electrode active material to the positive electrode active material: conductive material: binder in Example 1 was 4.825: 91.675: 1.5: 2 (Example 7) and 9.65: 86.85: 1.5: 2.0 Example 8).
  • Example 1 was produced in the positive electrode instead of the Example 7 and using each of the positive electrode 8 of Example 1 each of the half 2032 in the same manner as the battery 1 0 0 0 1).
  • the first embodiment of the cathode additive instead of the same amount of the positive electrode active material (1 () 0.8 (0 (). 11 ⁇ 1
  • a cathode was prepared by applying the cathode additive of Preparation Example 1 together with the cathode active material in the form of actually applying the cathode additive of Preparation Example 1, A battery made of Recom including the above prepared positive electrode was prepared.
  • a positive electrode active material (Core: Production Example 1, Bare), a positive electrode active material NCM (LiNio.sCoo.1Mno.1O2), a conductive material (Super-P, Denka Black) and a binder (PVdF)
  • NCM LiNio.sCoo.1Mno.1O2
  • Super-P Denka Black
  • PVdF binder
  • NMP solvent
  • the positive electrode mixture was coated on an aluminum current collector and dried in a vacuum oven of 120 for 30 minutes to prepare respective positive electrodes of Comparative Examples 3 and 4.
  • the difference in capacity retention rate becomes more severe as the number of cycles of the battery increases . Specifically , only 92.8% of the capacity is maintained as compared with the initial capacity after 100 cycles of the comparative example 2 , and 89.5% Is maintained. On the other hand, in the case of Examples 7 and 8, it can be confirmed that a capacity of 94.8% or more after 100 cycles of driving is maintained, and a capacity of 92.5% or more is maintained even after 200 cycles of driving, compared with the respective initial capacities.
  • the voltage at the initial charge of the cell is lower than that of the positive electrode additive of one embodiment
  • the initial characteristics and the long-term driving characteristics of the battery are different depending on the presence or absence of the surface coating of the additive under the condition that the additive has the same core composition, additive and active material. Specifically, it was confirmed that the initial characteristics and long-term driving characteristics of the cell of Example 7 were improved and the initial characteristics and the long-term driving characteristics of the cell of Example 8 were improved as compared to the Comparative Example 4,
  • Example 8 the initial charging capacity and lifetime characteristics of the battery were further improved in Example 8 using a positive electrode material mixture having a higher content of the positive electrode additive in one embodiment.
  • the positive electrode additive content using a high positive electrode material mixture improve the initial charge capacity of the battery and, means that can effectively further improve the battery life accordingly.
  • the cell It is possible to mix the positive electrode active material and the positive electrode active material according to the desired battery characteristics at a proper mixing ratio according to the desired battery characteristics.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

La présente invention concerne un additif d'électrode positive, un procédé de fabrication correspondant ainsi qu'une électrode positive et une batterie secondaire au lithium la comprenant. Plus particulièrement, un mode de réalisation de la présente invention concerne une matière additive pour électrode positive qui permet de liquider un déséquilibre de capacité irréversible entre deux électrodes, augmenter la capacité de charge de 1 ère de l'électrode positive, et freiner l'apparition de gaz dans la batterie.
PCT/KR2018/014725 2017-11-27 2018-11-27 Matière additive pour électrode positive, et électrode positive et batterie secondaire au lithium comprenant ladite matière active WO2019103576A2 (fr)

Priority Applications (4)

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US16/757,783 US11545670B2 (en) 2017-11-27 2018-11-27 Cathode additive, preparation method thereof, and cathode and lithium secondary battery comprising the same
CN201880066916.3A CN111213269B (zh) 2017-11-27 2018-11-27 正极添加剂、其制备方法和包含其的正极及锂二次电池
JP2019566799A JP7150380B2 (ja) 2017-11-27 2018-11-27 正極添加剤、その製造方法、これを含む正極およびリチウム二次電池
EP18881390.1A EP3680970A4 (fr) 2017-11-27 2018-11-27 Matière additive pour électrode positive, et électrode positive et batterie secondaire au lithium comprenant ladite matière active

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KR20170159731 2017-11-27
KR10-2017-0159731 2017-11-27
KR1020180147752A KR102663794B1 (ko) 2017-11-27 2018-11-26 양극 첨가제, 이의 제조 방법, 이를 포함하는 양극 및 리튬 이차 전지
KR10-2018-0147752 2018-11-26

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CN113764672A (zh) * 2021-11-09 2021-12-07 北京胜能能源科技有限公司 一种预锂化正极浆料及其制备方法与应用

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JP3403569B2 (ja) * 1996-03-05 2003-05-06 シャープ株式会社 リチウムニッケル複合酸化物とその製造法及びその用途
KR100889622B1 (ko) * 2007-10-29 2009-03-20 대정이엠(주) 안전성이 우수한 리튬 이차전지용 양극 활물질 및 그제조방법과 이를 포함하는 리튬 이차전지
KR20120056674A (ko) * 2010-11-25 2012-06-04 삼성에스디아이 주식회사 리튬 이차 전지용 양극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지
EP2905831B1 (fr) * 2013-09-05 2017-12-20 LG Chem, Ltd. Additif de cathode pour batterie secondaire au lithium à haute capacité
KR20170084995A (ko) * 2016-01-13 2017-07-21 삼성에스디아이 주식회사 리튬 이차 전지용 양극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113764672A (zh) * 2021-11-09 2021-12-07 北京胜能能源科技有限公司 一种预锂化正极浆料及其制备方法与应用
CN113764672B (zh) * 2021-11-09 2022-03-08 北京胜能能源科技有限公司 一种预锂化正极浆料及其制备方法与应用

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