WO2019103574A2 - Additif pour électrode positive, procédé de fabrication correspondant et électrode positive et batterie secondaire au lithium comprenant celle-ci - Google Patents

Additif pour électrode positive, procédé de fabrication correspondant et électrode positive et batterie secondaire au lithium comprenant celle-ci Download PDF

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WO2019103574A2
WO2019103574A2 PCT/KR2018/014723 KR2018014723W WO2019103574A2 WO 2019103574 A2 WO2019103574 A2 WO 2019103574A2 KR 2018014723 W KR2018014723 W KR 2018014723W WO 2019103574 A2 WO2019103574 A2 WO 2019103574A2
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Prior art keywords
positive electrode
oxide
lithium
nickel
additive
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PCT/KR2018/014723
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English (en)
Korean (ko)
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WO2019103574A3 (fr
Inventor
김지혜
박병천
한정민
정왕모
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020180143832A external-priority patent/KR20190062209A/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP18881948.6A priority Critical patent/EP3678240A4/fr
Priority to JP2020517272A priority patent/JP7047219B2/ja
Priority to US16/756,950 priority patent/US11404693B2/en
Priority to CN201880066167.4A priority patent/CN111226334B/zh
Publication of WO2019103574A2 publication Critical patent/WO2019103574A2/fr
Publication of WO2019103574A3 publication Critical patent/WO2019103574A3/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 lyrium secondary battery is a lithium secondary battery in which an electrode active material capable of reversibly intercalating and deintercalating lyrium ions is applied to a cathode and an anode to realize movement of lithium ions through an electrolyte, .
  • a positive electrode additive capable of canceling the irreversible capacity imbalance of the two electrodes and increasing the initial charge capacity of the anode. 2019/103574 1 »(: 1 ⁇ ⁇ 2018/014723
  • 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.
  • a positive electrode additive having an overall composition represented by the following Formula 1:
  • the positive electrode additive of one embodiment contains 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 battery.
  • the positive electrode additive of one embodiment is applied to the positive electrode together with the positive electrode active material, thereby canceling the irreversible capacity imbalance between the two electrodes during the initial charge and discharge of the battery, and contributing to increase the initial efficiency of the positive electrode.
  • the positive electrode additive of one embodiment comprises a lithium nickel oxide, a nickel oxide ( ⁇ 0), and a lithium oxide ( 20 ) represented by the following general formula (1-1) have.
  • the positive electrode additive of this embodiment can provide extra Li to the positive electrode and further increase the initial charge capacity of the positive electrode depending on the presence of the unreacted raw material, especially lithium oxide (Li 20) .
  • the positive electrode additive of one embodiment is one 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 Can be.
  • the lithium nickel oxide, the nickel oxide (NiO), and the lyrium oxide (Li 20) represented by Formula 1-1 are each crystalline, and the Fe Ka X ray X-ray diffraction (XRD).
  • 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. From this, it can be seen that the content of lithium oxide (Li 20) in the total amount (100% by weight) of the positive electrode additive in one embodiment is more than 0% by weight but not more than 15% by weight, specifically more than 0% 13% by weight or less, for example, 0% by weight or more and 12% by weight or less.
  • 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 positive electrode additive in one embodiment is more than 0 wt% and not more than 15 wt%, specifically more than 0 wt% and not more than 14 wt% By weight or less, for example, 0% by weight or more 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 content of the nickel oxide (NiO) is determined by subtracting the content of the lyrium oxide (Li 20) and the content of the nickel oxide (NiO) from the total amount (100 wt%) of the positive electrode additive of one embodiment 2019/103574 1 »(: 1/10/0/0 018/014723
  • the positive electrode additive of one embodiment includes the lyrium nickel oxide, the nickel oxide (solution 0) and the lithium oxide (1 oxide 0) represented by the formula 1-1 X, X and Z are the same as those in the formula (I), and the total composition is the same as in the above formula 1. Specifically, And the weight ratio of the lithium oxide (0 20 ).
  • 0.7 is 1.0, 0 is now ⁇ 0.15, and 0 is 0.15; 0.72 ⁇ ⁇ 1.0, 0 now £ 0.14, 0 can be ⁇ 0.14; 0.74 ⁇ ⁇ 1.0, 0 now ⁇ 0.13, 0 ⁇ 0.13; 0.74 ⁇ ⁇ 1.0, 0 now ⁇ 0.13, 0 ⁇ 0.13; 0.76 ⁇ 1.0, 0 ⁇ 0.12, and 0 ⁇ 0.12, respectively.
  • the form of the lithium nickel oxide, the nickel oxide ( ⁇ 0), and the lium oxide (0 20 ) represented by Formula 1-1 is not particularly limited.
  • the term " particles " means that the primary particles or primary particles, Can be.
  • the anode additive of this embodiment irreversibly releases lyrium ion and oxygen at a voltage at the time of initial charging of the battery, for example, 2.5 to 4.25 V 0. Ni / 0 +, and thereafter, 2 < / RTI >
  • the positive electrode additive converted into the formula 2 It may be possible to reversibly insert and desorb lithium ions similarly to a conventional positive electrode active material.
  • the positive electrode additive of one embodiment can be utilized as an additive to compensate for the initial irreversible capacity of the negative electrode, and as an active material capable of reversible insertion and desorption of lithium.
  • the positive electrode additive converted into the formula (2) Due to the content and the structural limitations thereof, it is possible to have a small reversible capacity as compared with a conventional positive electrode active material, and specifically to have a reversible capacity of 300 to 350, 111 shows. Therefore, when the initial performance of the battery is improved and long-life characteristics are secured, the cathode active material may be mixed with the cathode active material of one embodiment in a proper mixing ratio depending on the desired battery characteristics.
  • a process for preparing a nickel-based oxide comprising: preparing a nickel-based oxide represented by the following Formula 3; And heat treating the mixture of the nickel-based oxide and the lyrium oxide (1-O-O). According to this production method, 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: a step of preparing nickel hydroxide ((03 ⁇ 4 2 ) alone; Is the number of days that the heat treatment step to; or, a nickel hydroxide ( ⁇ (03 ⁇ 4 2) and M comprises a mixture of compounds.
  • the nickel hydroxide ((011 ⁇ alone; or, a nickel hydroxide ((0, P 2) and a mixture of M containing compound, heat treatment is at a temperature ranging from 500 to 700 ⁇ can be carried out in an inert atmosphere for 5 to 20 hours.
  • the step of heat treating the mixture of nickel oxide and lithium oxide (1 run 0) comprises mixing the nickel calculated product and the lithium oxide in a molar ratio of 1: 1 (0.02) 800 X: for 10 to 20 hours in an inert atmosphere.
  • the total amount mixed does not react at a molar ratio of 1: 1, and the nickel- A part thereof and a part of the lyrium oxide (? 0) react with each other to form a nickel oxide represented by the formula (1-1), and an unreacted starting material can remain.
  • the overall composition of the resulting product and the effect thereof are as described above.
  • the above-mentioned positive electrode additive In another embodiment of the present invention, 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 can be reduced and the initial efficiency of the positive electrode can be increased. In the total amount (100% by weight) of the positive electrode mixture of one embodiment, the positive electrode additive may be applied in an amount of 1 to 30% by weight. Specifically, when the positive electrode additive is compounded in the above range, (In other words, Cycle, the initial irreversible capacity of the negative electrode is sufficiently reduced with the positive electrode additive,
  • the positive electrode mixture of this embodiment can be generally implemented according to what is known in the art.
  • the positive electrode mixture of this embodiment is not limited.
  • 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.
  • cathode active material a compound represented by any one of the following formulas may be used. : ⁇ (wherein, 0.90 ⁇ 3 ⁇ 4
  • Needle 11 (3 ⁇ 40 2 (wherein 0.90 ⁇ 3 ⁇
  • Combination Combination (3 is II, 0, Mn, or a combination thereof A combination thereof; Are V, 01, 3 ⁇ 4, or a combination thereof.
  • the coating layer may comprise, as a coating element compound, an oxide, a hydroxide of a coating element, an oxyhydroxide of a coating element, an oxycarbonate of a coating element, or a hydroxycarbonate of a coating element.
  • the compound constituting these coating layers may be amorphous or crystalline.
  • As the coating element contained in the coating layer, 03, 3, show 3 ⁇ 4 or a mixture thereof.
  • 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 mixture of one embodiment may further include a conductive material, a binder, or a mixture thereof.
  • the conductive material may have conductivity Any material can be used as long as it is an electron conductive material without causing any chemical change.
  • Metal powders such as nickel, aluminum and silver, and metal fibers, and polyphenylene derivatives
  • a conductive material such as may be used by mixing one or at least one.
  • 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.
  • a lithium secondary battery including a positive electrode including the above-described positive electrode mixture, an electrolyte, and a negative electrode.
  • the above-mentioned positive electrode additive is a lyrium secondary battery which is applied to the positive electrode together with the positive electrode active material, so that the initial irreversible capacity of the negative electrode decreases, the initial efficiency of the positive electrode increases, .
  • the present invention can be generally implemented in accordance with those known in the art.
  • the positive electrode comprises: a positive electrode collector; And a positive electrode mixture layer disposed on the positive electrode collector and including the positive electrode mixture described above.
  • 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 generally has 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 have fine irregularities on the surface thereof to increase the adhesive force of 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. 2019/103574 1 »(: 1 ⁇ ⁇ 2018/014723
  • 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 ter Styrene butadiene rubber, styrene butadiene rubber, fluorine rubber, various copolymers and the like.
  • 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 carbonaceous anode active material, a lithium metal, an alloy of larium metal, 3 ⁇ 4 810 x (0 ⁇ X ⁇ 2), a composite and an alloy (the above is an alkali metal, an alkaline earth metal, A transition metal, a rare earth element, or a combination thereof, and is not), 3 ⁇ 4, 3 ⁇ 40 2 , Complex, and II is an alkali metal, an alkali 2019/103574 1 »(: 1 ⁇ ⁇ 2018/014723
  • At least one kind of negative electrode active material selected from the group consisting of a rare earth element, a rare earth element, a rare earth element, a combination thereof, and the like) may be used.
  • the negative electrode collector may generally be made to have a thickness of 3 - 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 lithium polymer battery, depending on the type of the electrolyte and / or the type of the separator.
  • the lithium secondary battery of the embodiment is a lithium ion battery using a liquid electrolyte
  • the liquid electrolyte may be impregnated into the separator.
  • the separation membrane is interposed between the anode and the cathode, and an insulating thin film having high ion permeability and mechanical strength is used.
  • the pore diameter of the membrane is generally 0.01 - 10 mm, and the thickness is generally 5 - 300 mm.
  • 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 non-aqueous electrolyte containing lithium salt is composed of a non-aqueous electrolyte and lithium.
  • Non-aqueous organic solvents, organic solid electrolytes, and inorganic solid electrolytes are used as the non-aqueous electrolyte.
  • the present invention is not limited thereto.
  • non-aqueous organic solvent examples include methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl But are not limited to, carbonates, diethyl carbonate, gamma-butylolactone, 1,2-dimethoxyethane, tetrahydroxyfuran, 2-methyltetrahydrofuran, dimethylsulfoxide, , Formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, triester phosphate, trimethoxymethane, dioxolane derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl 2-imidazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ethers, methyl pyrophosphate, ethyl propionate and the like can be used.
  • organic solid electrolyte examples include organic polymers such as a dolly ethylene derivative, a physical ethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, an agitation lysine, a polyester sulfide, a polyvinyl alcohol A polymer containing an ionic dissociation group, and the like may be used.
  • organic polymers such as a dolly ethylene derivative, a physical ethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, an agitation lysine, a polyester sulfide, a polyvinyl alcohol A polymer containing an ionic dissociation group, and the like may be used.
  • Examples of the inorganic solid electrolyte include Li 3 N, Lil, Li 5 NI 2, LisN-Lil-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3, Li 4 SiO 4 , Li 4 the Si0 4 -LiI-Li0H, Li 3 P0 4 -Li 2 S-SiS 2 and Li nitrides, halides, sulfates, etc. can be used.
  • the lithium salt is a material which is soluble in the non-aqueous electrolyte.
  • the lithium salt include LiCl, LiBr, Lil, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsFg , LiSbFe, LiAlCU, CH 3 SO 3 L1, (CF 3 S0 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic bonsanri cerium, lithium tetraphenyl borate, may be already in use include de.
  • the lithium salt-containing non-aqueous electrolyte may further contain, for the purpose of improving charge / discharge characteristics, flame retardancy, etc., for example, pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylenediamine, n-glyme, N, N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxyethanol, aluminum trichloride, 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 the like.
  • LiPF 6 LiC10 4, LiBF 4, LiN (S0 2 CF 3) the Li salt of 2, and so on, highly dielectric solvent of cyclic carbonate and chained trough or theft of EC PC DEC, DMC 2019/103574 1 »(: 1 ⁇ ⁇ 2018/014723
  • non-aqueous electrolyte containing lithium salt can be prepared by adding it to a mixed solvent of linear carbonate of the formula (I).
  • the lithium secondary battery of the 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.
  • concrete examples of the device, electric vehicles, hybrid electric vehicles, plug-in may be a hybrid electric vehicle, or a power storage system, and the like.
  • the lithium secondary battery to which the positive electrode additive of one embodiment is applied to the positive electrode has a problem 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.
  • Nickel hydroxide precursor Ni (OH) 2 was heat-treated at 600 ° C (inert atmosphere) for 10 hours to obtain Ni calculated NiO.
  • NiO nickel-based oxide NiO was mixed with lithium oxide (Li 2 O) in a molar ratio (NiO: Li 2 O) of 1: 1.1 and heat-treated at 680 ° C (inert atmosphere) for 18 hours . At this time , the temperature rise and cooling rates were set at 5 ° C per minute.
  • a positive electrode was prepared by applying the positive electrode additive of Example 1, and a lithium secondary battery containing the positive electrode thus prepared was produced.
  • the ⁇ 0 .86 (Li 2 NiO 2 ) anode additive of Example 1) ⁇ ⁇ 0. 07N1O ⁇ - ⁇ o.ovLiiO ⁇ , a conductive material (Super-P, Denka black) and a binder (PVdF) in an organic solvent (NMP) at a weight ratio of 85: 10: 5 (anode additive: conductive material:
  • NMP organic solvent
  • Li-metal Li-metal
  • EC Ethylene Carbonate
  • DMC dimethyl carbonate
  • NiO nickel-based oxide
  • Li 2 O lithium oxide
  • Example 1 Except that the positive electrode additive of Comparative Example 1 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 1.
  • Experimental Example 1 1) Analysis X-ray diffraction (XRD) analysis by Cu Ka X ray (X-ray) was performed on each of the positive electrode additives of Examples 1 to 3 and Comparative Example 1, and the results are shown in Table 1 below.
  • XRD X-ray diffraction
  • the lithium nickel oxide and the nickel oxide (NiO) are crystalline and can be detected by X-ray diffraction (XRD) by the Fe Kx X-ray (X-m).
  • Comparative Example 1 has a determination structure of Orthorhombic with a point group of Immm. From the results of the structural analysis of Table 1, Comparative Example 1 and Example 1 Have the same crystal structure. Therefore, it can be seen that Examples 1 to 3 also include a compound represented by Li ha Ni b MuO k .
  • 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 battery was prepared.
  • the anode additive of one embodiment may have a voltage at the initial charge of the cell, e.g., 2.5-4.25 V. / Ni +), it is possible to irreversibly release lyrium ions and oxygen, and thereafter convert to a composition capable of reversible insertion and desorption of lyrium ions.
  • a voltage at the initial charge of the cell e.g., 2.5-4.25 V. / Ni +
  • the positive electrode active material of one embodiment and the positive electrode active material may be mixed at an appropriate ratio.
  • the positive electrode additive of Example 1 was applied together with the positive electrode active material to prepare a positive electrode, and a lithium secondary battery including the positive electrode thus prepared was produced .
  • the weight ratio of the positive electrode active material: conductive material: binder in Example 1 was 4.825: 91.675: 1.5: 2.0 (Example 4) and 9.65: 86.85: 1.5: 2.0 Example 5).
  • the positive electrode additives comprising lithium nickel oxide, nickel oxide ( ⁇ 0), and lithium oxide (1 foot 0) It can be confirmed that the initial irreversible capacity of the cathode is compensated and the initial charging capacity of the anode is increased by irreversibly releasing lyrium ion and oxygen in preference to the cathode active material at the initial charging voltage.
  • 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 3 and 4, it can be confirmed that a capacity of 94.2% or more after 100 cycles of driving is maintained, and a capacity of 91.8% or more is maintained even after driving 200 sacks, compared with the respective initial capacities.
  • the loss of capacity is reduced by the positive electrode additive of one embodiment when the cell cycle proceeds with the initial capacity of the positive electrode increased.
  • the positive electrode additive of one embodiment irreversibly releases lithium ions and oxygen at a voltage at the initial charging of the battery, and thereafter, is switched to a composition capable of reversible insertion and desorption of lithium ions, It also means that it contributes part of the capacity implementation during the process.
  • Example 4 the initial charging capacity and lifetime characteristics of the battery were further improved in Example 4 using a positive electrode material mixture having a higher content of the positive electrode additive in one embodiment.
  • a positive electrode material mixture having a high content of the positive electrode additive in one embodiment can further improve the initial charging capacity of the battery and thereby improve the life of the battery more effectively.
  • the positive electrode additive and mixed to use the positive electrode active material in the appropriate blend ratio with It will be possible.

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  • Engineering & Computer Science (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. En particulier, selon un mode de réalisation de la présente invention, il s'agit d'un additif d'électrode positive au moyen duquel un déséquilibre de capacité irréversible entre deux électrodes peut être annulé, et la capacité de charge du 1er cycle de l'électrode positive peut être augmentée.
PCT/KR2018/014723 2017-11-27 2018-11-27 Additif pour électrode positive, procédé de fabrication correspondant et électrode positive et batterie secondaire au lithium comprenant celle-ci WO2019103574A2 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP18881948.6A EP3678240A4 (fr) 2017-11-27 2018-11-27 Additif pour électrode positive, procédé de fabrication correspondant et électrode positive et batterie secondaire au lithium comprenant celle-ci
JP2020517272A JP7047219B2 (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
US16/756,950 US11404693B2 (en) 2017-11-27 2018-11-27 Cathode additive, preparation method thereof, and cathode and lithium secondary battery comprising the same
CN201880066167.4A CN111226334B (zh) 2017-11-27 2018-11-27 正极添加剂、其制备方法以及包含其的正极和锂二次电池

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CN114788053A (zh) * 2020-02-26 2022-07-22 株式会社Lg新能源 不可逆添加剂、包含该不可逆添加剂的正极和包含该正极的锂二次电池

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JP2005187326A (ja) * 1996-01-30 2005-07-14 Showa Denko Kk ニッケル酸リチウムの製造方法
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EP2905831B1 (fr) * 2013-09-05 2017-12-20 LG Chem, Ltd. Additif de cathode pour batterie secondaire au lithium à haute capacité
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* Cited by examiner, † Cited by third party
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CN114788053A (zh) * 2020-02-26 2022-07-22 株式会社Lg新能源 不可逆添加剂、包含该不可逆添加剂的正极和包含该正极的锂二次电池
CN114788053B (zh) * 2020-02-26 2024-03-08 株式会社Lg新能源 不可逆添加剂、包含该不可逆添加剂的正极和包含该正极的锂二次电池

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