WO2015149211A1 - Matériau actif d'électrode positive et batterie rechargeable au lithium - Google Patents

Matériau actif d'électrode positive et batterie rechargeable au lithium Download PDF

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WO2015149211A1
WO2015149211A1 PCT/CN2014/074350 CN2014074350W WO2015149211A1 WO 2015149211 A1 WO2015149211 A1 WO 2015149211A1 CN 2014074350 W CN2014074350 W CN 2014074350W WO 2015149211 A1 WO2015149211 A1 WO 2015149211A1
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positive electrode
electrode active
active material
material according
metal
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PCT/CN2014/074350
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English (en)
Inventor
Yuping Wu
Faxing WANG
Xiangwen GAO
Shiying XIAO
Akihiko Shirakawa
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Showa Denko K.K.
Fudan University
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Priority to PCT/CN2014/074350 priority Critical patent/WO2015149211A1/fr
Publication of WO2015149211A1 publication Critical patent/WO2015149211A1/fr

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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 implementation relates to a positive electrode active material and a Li secondary battery.
  • Li secondary battery has been widely used in a portable mobile device such as a cell phone, a notebook computer and a digital electronic product and in an electric car. While mobile devices, electric cars and photovoltaic industry are developing, Li secondary battery presents more broad application prospect.
  • Electrochemical performance of a Li secondary battery largely depends on positive electrode active material.
  • the positive electrode active material generally is lithium cobalt oxide (LiCo0 2 ), spinel lithium manganate (LiMn 2 0 4 ), ternary material (Li(NiCoMn)0 2 ) and olivine-type lithium iron phosphate (LiFeP0 4 ).
  • Li 2 Mn0 3 is positive electrode active material of a new type of Li secondary battery, theoretical capacity is larger than 300 mAh g "1 , which is 100% higher than LiFeP0 4 , furthermore, Mn is abundant on earth.
  • a Li secondary battery with lithium metal oxide as positive electrode active material tend to release oxygen from lattice of lithium metal oxide during initial charge and it has very low initial coulombic efficiency, furthermore, discharge capacity of the Li secondary battery with lithium metal oxide after multiple charge-discharge cycles tends to be significantly reduced.
  • Li 2 Mn0 3 For example, some researchers focus on combining Li 2 Mn0 3 with other materials such as LiCo0 2 , LiCr0 2 , LiNio .5 Mn 1 .5O4, LiNii /3 Coi 3 Mni 3 0 2 or LiMn 2 0 4 . Although such solid solution has high discharge capacity, its initial coulombic efficiency is also very low, and oxygen is also released during initial charge.
  • the present invention features, in one aspect, overcoming defects of a Li secondary battery with Lithium metal oxide as positive electrode active material in oxygen release, low initial coulombic efficiency and significant decrease in discharge capacity after multiple charge-discharge cycles.
  • One aspect of the present invention is that a composite material of Lithium metal oxide and a material through which Li ions can be passed.
  • the material is selected from a metal oxide, a metal hydroxide, a metal oxyhydroxide, a metal fluoride, a metal phosphate, a lithium insertion material, polymer or a combination thereof.
  • a positive electrode active material comprises a core portion and a coating layer on the core portion, wherein the core portion comprises a metal oxide compound and the coating layer comprises a material which can react with lithium and/or oxygen and prevent from releasing oxygen from the lattice of the metal oxide compound during charge-discharge cycles.
  • the present invention also provides the following preferable technical solutions.
  • the metal oxide compound has a general formula Li x M y O z and M is at least one selected from the group consisting of Co, Ni, Mn, Ti, V, Zr, Cr, Mg, Fe, Mo and Al.
  • the metal oxide compound has a general formula Li a M b O c (0 ⁇ a ⁇ l, 0 ⁇ b ⁇ l, 0 ⁇ c ⁇ l) and M is at least one selected from the group consisting of trivalent transition metal cation.
  • the metal oxide compound has a general formula Li 2-x M' x M"i -x 0 3-x (0 ⁇ x ⁇ l) and where M' is one or more ions having an average oxidation state of three, and where M" is one or more ions with an average oxidation state of four.
  • the metal oxide compound is Li 2 Mn0 3 .
  • the coating layer comprises at least one selected from the group consisting of a metal oxide, a metal hydroxide, a metal oxyhydroxide, a metal fluoride, a metal phosphate, a lithium insertion material and a polymer.
  • the metal oxide is at least one selected from the group consisting of Co 3 0 4 , CoO, NiO, Ru0 2 , Mo0 3 , Mn0 2 V 2 0 3 and Pb0 2 .
  • the metal hydroxide is at least one selected from the group consisting of Ni(OH) 2 and Co(OH) 2 .
  • the metal oxyhydroxide is at least one selected from the group consisting of NiOOH and FeOOH.
  • the metal fluoride is at least one selected from the group consisting of FeF 3 , FeF 2 and CuF 2 .
  • the metal phosphate is at least one selected from the group consisting of FeP0 and A1P0 4 .
  • the lithium insertion material is at least one selected from the group consisting of LiCo0 2 , LiNi0 2 , Li 0 . 44 MnO 2 , LiMn 2 0 , LiNi 0 . 5 Mni. 5 O 4 , LiMnB0 3 , LiMnP0 4 and Li 2 MnSi0 4 .
  • the polymer is a conductive polymer.
  • the polymer is a ⁇ -electron conjugated polymer.
  • the ⁇ -electron conjugated polymer is at least one selected from the group consisting of polyacetylene, polypyrrole, polyaniline, polyparaphenylenevinylene and polythiophene.
  • the coating layer accounts for 0.5 mass % ⁇ 50 mass% of the total mass of the positive electrode active material. More preferably, the coating layer accounts for 1 mass% ⁇ 40 mass% of the total mass of the positive electrode active material.
  • Another aspect of the invention provides a Li secondary battery comprising the positive electrode active material.
  • the Li secondary battery of the present implementation by using the positive electrode active material, may prevent 0 2 from releasing during initial charge, and improve initial coulombic efficiency and discharge capacity after multiple charge-discharge cycles.
  • Fig 1(a) and Fig 1(b) are examples of ex-situ X-Ray Diffraction (ex-situ XRD) spectrum and X-Ray photoelectron Spectroscopy (XPS) energy spectrum of a Li secondary battery with FeP0 4 /Li 2 Mn0 3 as positive electrode active material, respectively.
  • Fig 2 is an example of a charge-discharge graph of a Li secondary battery with Li 2 Mn0 3 as positive electrode active material of comparative example 1.
  • Fig 3 is an example of a charge-discharge graph of a Li secondary battery with FeP0 4 /Li 2 Mn0 3 as positive electrode active material of embodiment 3.
  • Fig 4 is an example of a charge-discharge graph of a Li secondary battery with Co 3 0 4 /Li 2 Mn0 3 as positive electrode active material of embodiment 1 1.
  • the Li secondary battery referred to herein may be any Li secondary battery that is capable of utilizing the following positive electrode active material.
  • the positive electrode active material comprises a core portion comprised of Lithium metal oxide and a coating layer which coats the core portion, which can make Li ions pass through, and the coating layer comprises a metal oxide, a metal hydroxide, a metal oxyhydroxide, a metal fluoride, a metal phosphate, a lithium insertion material, a polymer or a combination thereof.
  • the positive electrode active material comprises a core portion and a coating layer on the core portion, wherein the core portion comprises a metal oxide compound and the coating layer comprises a material which can react with lithium and/or oxygen and prevent from releasing oxygen from the lattice of the metal oxide compound during charge-discharge cycles.
  • the metal oxide compound can comprise at least one transition metal.
  • the transition metal can be oxidized and reduced during occluding and emitting lithium ions.
  • the metal oxide compound may be prepared by any method known to those skilled in the art without any limitation.
  • the metal oxide compound has a general formula Li x M y O z and M is at least one selected from the group consisting of Co, Ni, Mn, Ti, V, Zr, Cr, Mg, Fe, Mo and Al.
  • the metal oxide compound has a general formula Li a M b O c (0 ⁇ a ⁇ l, 0 ⁇ b ⁇ l, 0 ⁇ c ⁇ l) and M is at least one selected from the group consisting of trivalent transition metal cation.
  • the metal oxide compound has a general formula Li 2-x M' x M" 1-x 0 3-x (0 ⁇ x ⁇ l) and where M' is one or more ions having an average oxidation state of three, and where M" is one or more ions with an average oxidation state of four.
  • the metal oxide compound is Li 2 Mn0 3 .
  • the coating layer may be formed on the surface of the core portion by any method known to those skilled in the art without any limitation.
  • the coating layer can be formed by at least one method selected from the group consisting of precipitation method, solid phase method, impregnation method, hydro-thermal method, hydrolysis method and sol-gel method.
  • the coating layer can make Li ions pass through, that is, Li ions can go through the coating layer from the core portion and enter into electrolyte, or can go through the coating layer from electrolyte and arrive at the core portion, thereby realizing charge/discharge.
  • the coating layer is formed by piling up granular substances. In this case, Li-ions can go through the coating layer via gaps between the granular substances.
  • the coating layer comprises a material which can react with Li 2 0 and prevent from releasing oxygen in the lattice of the lithium metal oxide during charge-discharge cycles.
  • the coating layer comprises at least one selected from the group consisting of a metal oxide, a metal hydroxide, a metal oxyhydroxide, a metal fluoride, a metal phosphate, a lithium insertion material and a polymer.
  • Metal of the metal oxide can be a transition metal or a typical element.
  • the metal oxide is at least one selected from the group consisting of Co 3 0 4 , CoO, NiO, Ru0 2 , Mo0 3 , Mn0 2 V 2 0 3 and Pb0 2 .
  • the metal hydroxide is at least one selected from the group consisting of Ni(OH) 2 and Co(OH) 2 .
  • the metal oxyhydroxide is at least one selected from the group consisting of NiOOH and FeOOH.
  • the metal fluoride is at least one selected from the group consisting of FeF 3 , FeF 2 and CuF 2 .
  • the metal phosphate is at least one selected from the group consisting ofFeP0 4 and A1P0 4 .
  • Lithium insertion material can be a material which can occlude and include lithium ion.
  • the lithium insertion material is at least one selected from the group consisting of LiCo0 2 , LiNi0 2 , Li 044 MnO 2 , LiMn 2 0 4 , LiNi 0 5 Mn 1 . 5 O 4 , LiMnB0 3 , LiMnP0 4 and Li 2 MnSi0 4 .
  • the polymer is a conductive polymer.
  • the polymer is a ⁇ -electron conjugated polymer.
  • the ⁇ -electron conjugated polymer is at least one selected from the group consisting of polyacetylene, polypyrrole, polyaniline, polyparaphenylenevinylene and polythiophene.
  • Content of the coating layer preferably accounts for 0.5 mass% ⁇ 50 mass% of total mass of the positive electrode active material. If content of the coating layer is higher than 0.5 mass%, it can have more influence on Lithium metal oxide, and effect of improvement is more significant. If content of the coating layer is less than 50 mass%, it will increase content of the core portion material (i.e., Li 2 Mn0 3 ), thereby more increasing discharge capacity of the battery.
  • the coating layer accounts for 1 mass% ⁇ -40 mass% of total mass of the positive electrode active material.
  • a coating layer of FeP0 4 most preferable content of which is 20 mass% ⁇ 30 mass%.
  • a coating layer of Co 3 0 4 most preferable content of which is 15 mass% ⁇ -30 mass%.
  • the positive electrode active material is Li 2 Mn0 3 coated by a metal oxide, a metal hydroxide, a metal oxyhydroxide, a metal fluoride, a metal phosphate, a lithium insertion material, a polymer or a combination thereof.
  • the coating layer may prevent oxygen from releasing during initial charge, and can improve initial coulombic efficiency and discharge capacity after multiple charge-discharge cycles.
  • the positive electrode active material of the present implementation does not release 0 2 during initial charge. Meanwhile, as compared to the prior arts, Li 2 Mn0 3 without a coating layer, the positive electrode active material of the present implementation also has a charge/discharge process as shown in equation (5), thus, it can improve initial coulombic efficiency and discharge capacity after multiple charge-discharge cycles. This would be one example of the mechanisms in the present invention.
  • Charge/discharge reaction of positive electrode active material FeP0 4 /Li 2 Mn0 3 of the present implementation can be conducted as shown in the above equations (3)-(5). This mechanism can be proved by the ex-situ XRD and XPS spectra shown in Fig 1(a) and 1(b). Electrodes under test were taken out of the Li-ion batteries and rinsed with anhydrous DMC (Dimethyl carbonate), then washed by acetone and dried overnight.
  • DMC Dimethyl carbonate
  • the five spectra of Fig 1(a) from bottom to top represent ex-situ XRD spectra before charge cycle, 1 st charge to 4.8V, 1 st discharge to 2.0V, 2 nd discharge to 2.0V, 2 nd charge to 4.8V of positive electrode active material FeP0 4 /Li 2 Mn0 3 , respectively.
  • '*' represent peaks of FeP0 4
  • '#' represent peaks of Li y FeP0 4+x in Fig 1(a).
  • the five spectra of Fig 1(b) from bottom to top represent XRS spectra before charge cycle, 1 st charge to 4.8V, 1 st discharge to 2.0V, 2 nd charge to 4.8V, 2 nd discharge to 2.0V of positive electrode active material FeP0 4 /Li 2 Mn0 3 , respectively.
  • Potential difference may be 2.7-3.2 V, which may be equal to the potential difference when Li ions were extracted/inserted from/into Li y FePO x+4 and FeP0 4 t. Change in chemical valence of Fe caused by insertion/extraction of Li ions from/into Li y FePO x+ 4 was also confirmed by the XPS spectra shown in Fig 1(b).
  • the FeP0 4 in the positive electrode active material FeP0 4 /Li 2 Mn0 3 serves as a host to react with oxygen and "dead" Li ions, resulting to the existence of Li y FeP0 4+x being observed in the XRD spectra.
  • the Li ions were inserted/extracted into/from the Li y FeP0 4+x and active Mn0 2 .
  • discharge capacity of the positive electrode active material FeP0 4 /Li 2 Mn0 3 may be higher than its charge capacity.
  • equation (3) and equation (5) may be considered as the synergistic effect between Li 2 Mn0 3 and FeP0 4 .
  • Such synergistic effect successfully blocks the oxygen emission and improves capacity of the Li secondary battery.
  • Li 2 Mn0 3 prepared via solid phase method is used as a reference.
  • Li 2 Mn0 3 , acetylene black and polyvinylidene fluoride (PVDF) are accurately weighted in mass fraction of 80%: 10%: 10% and are uniformly mixed with l-Methyl-2-pyrrolidinone as solvent to form slurry.
  • the slurry is uniformly applied on an aluminum foil to form electrode plate.
  • the electrode plate is dried in vacuum below 120 ° C for more than 12 hours and is punched out by a puncher to prepare disk electrodes having diameter of 19 mm.
  • the metal lithium foil is taken as negative electrode.
  • the operating electrode is positive electrode.
  • Celgard (trademark) 2400 polypropylene micro-porous membrane, is used as membrane, lmol L "1 LiPF 6 /ethylene carbonate (EC) + diethyl carbonate (DEC) + dimethyl carbonate (DMC) (in volume ratio 1 : 1 :1) is used as electrolyte.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • DMC dimethyl carbonate
  • Those are assembled into button cells in a glove box filled with high-purity argon. The button cells are used for testing electrochemical performance.
  • Initial charge/discharge curve and cycling performance are shown in Fig 2.
  • Initial charge/discharge capacity and discharge capacity after 30 cycles are summarized in Table 1.
  • Embodiment 1 Embodiment 1
  • Preparation of Li 2 Mn0 3 is the same as that of comparative example 1. 3 mass% of FeP0 4 to total mass of the positive electrode active material is coated on surface of Li 2 Mn0 3 via both precipitation method and solid phase method. Content of FeP0 4 is calculated by the concentration of ferric nitrate (Fe(N0 3 ) 3 -9H 2 0) and the concentration of diammonium hydrogen phosphate (( H 4 ) 2 HP0 4 ).
  • Electrochemical performance test of Li secondary battery is the same as that of comparative example 1. Initial charge/discharge capacity and discharge capacity after 30 cycles are summarized in Table 1.
  • Preparation of Li 2 Mn0 3 is the same as that of comparative example 1. 8 mass% of FeP0 4 is coated on surface of Li 2 Mn0 3 via both precipitation method and solid phase method. Content of FeP0 4 is calculated by the concentration of ferric nitrate (Fe(N0 3 ) 3 -9H 2 0) and the concentration of diammonium hydrogen phosphate ((NH 4 ) 2 HP0 4 ).
  • Electrochemical performance test of Li secondary battery is the same as that of comparative example 1. Initial charge/discharge capacity and discharge capacity after 30 cycles are summarized in Table 1.
  • Preparation of Li 2 Mn0 3 is the same as that of comparative example 1. 20 mass% of FeP0 4 is coated on surface of Li 2 Mn0 3 via both precipitation method and solid phase method. Content of FeP0 4 is calculated by the concentration of ferric nitrate (Fe(N0 3 ) 3 -9H 2 0) and the concentration of diammonium hydrogen phosphate ((NH 4 ) 2 HP0 4 ).
  • Electrochemical performance test of Li secondary battery is the same as that of comparative example 1. Initial charge/discharge curve and cycling performance are shown in Fig 3, and initial charge/discharge capacity and discharge capacity after 30 cycles are summarized in Table 1.
  • Preparation of Li 2 Mn0 3 is the same as that of comparative example. 5 mass% of Mn0 2 is coated on surface of Li 2 Mn0 3 via simple both impregnation method and solid phase method. Content of Mn0 2 is calculated by the concentration of manganese nitrate solution.
  • Electrochemical performance test of Li secondary battery is the same as that of comparative example 1. Initial charge/discharge capacity and discharge capacity after 30 cycles are summarized in Table 1. Embodiment 5
  • Preparation of Li 2 Mn0 3 is the same as that of comparative example. 20 mass% of Mn0 2 is coated on surface of Li 2 Mn0 3 via both simple impregnation method and solid phase method. Content of Mn0 2 is calculated by the concentration of manganese nitrate solution.
  • Electrochemical performance test of Li secondary battery is the same as that of comparative example 1. Initial charge/discharge capacity and discharge capacity after 30 cycles are summarized in Table 1.
  • Preparation of Li 2 Mn0 3 is the same as that of comparative example. 40 mass% of Mn0 2 is coated on surface of Li 2 Mn0 3 via both simple impregnation method and solid phase method. Content of Mn0 2 is calculated by the concentration of manganese nitrate solution.
  • Electrochemical performance test of Li secondary battery is the same as that of comparative example 1. Initial charge/discharge capacity and discharge capacity after 30 cycles are summarized in Table 1.
  • Li 2 Mn0 3 Preparation of Li 2 Mn0 3 is the same as that of comparative example. 18 mass% of Mo0 3 is coated on surface of Li 2 Mn0 3 by conducting hydro-thermal treatment on peroxo molybdic acid sol (Mo0 2 (OH)(OOH)). Content of Mo0 3 is calculated by the concentration of peroxo molybdic acid sol prepared via simple substance metal molybdenum (Mo) having certain mass.
  • Electrochemical performance test of Li secondary battery is the same as that of comparative example 1. Initial charge/discharge capacity and discharge capacity after 30 cycles are summarized in Table 1.
  • Preparation of Li 2 Mn0 3 is the same as that of comparative example. 20 mass% of Pb0 2 is coated on surface of Li 2 Mn0 3 via precipitation method. Content of Pb0 2 is realized by controlling a solution of lead nitrate (Pb(N0 3 ) 2 ) with certain concentration and a solution of sodium hydroxide (NaOH) with corresponding concentration under cetyltrimethyl ammonium bromide (CTAB) environment.
  • Pb(N0 3 ) 2 a solution of lead nitrate
  • NaOH sodium hydroxide
  • CTAB cetyltrimethyl ammonium bromide
  • Electrochemical performance test of that material as positive electrode active material of Li secondary battery is the same as that of comparative example 1. Its initial charge/discharge capacity and discharge capacity after 30 cycles are summarized in Table 1.
  • Embodiment 9 Preparation of Li 2 Mn0 3 is the same as that of comparative example. 8 mass% of Co 3 0 4 is coated on surface of Li 2 Mn0 3 via hydro-thermal method and solid phase method. Content of Co 3 0 4 is realized by controlling a solution of cobalt acetate (Co(CH 3 COO) 2 -4H 2 0) with certain concentration and aqueous ammonia ( ⁇ 3 ⁇ 2 0) with corresponding concentration.
  • Co(CH 3 COO) 2 -4H 2 0 cobalt acetate
  • ⁇ 3 ⁇ 2 0 aqueous ammonia
  • Electrochemical performance test of that material as positive electrode active material of Li secondary battery is the same as that of comparative example 1. Its initial charge/discharge capacity and discharge capacity after 30 cycles are summarized in Table 1.
  • Preparation of Li 2 Mn0 3 is the same as that of comparative example. 15 mass% of Co 3 0 4 is coated on surface of Li 2 Mn0 3 via hydro-thermal method and solid phase method. Content of Co 3 0 is realized by controlling a solution of cobalt acetate (Co(CH 3 COO) 2 -4H 2 0) with certain concentration and aqueous ammonia ( ⁇ 3 ⁇ 2 0) with corresponding concentration.
  • Electrochemical performance test of that material as positive electrode active material of Li secondary battery is the same as that of comparative example. Its initial charge/discharge curve and cycling performance are shown in Fig 4, and initial charge/discharge capacity and discharge capacity after 30 cycles are summarized in Table 1.
  • Embodiment 1 1 is a diagrammatic representation of Embodiment 1 1
  • Preparation of Li 2 Mn0 3 is the same as that of comparative example. 20 mass% of Ru0 2 is coated on surface of Li 2 Mn0 3 via precipitation method and solid phase method. Content of Ru0 2 is realized by controlling a solution of ruthenium chloride (RuCl 3 ) with certain concentration and NaOH with corresponding concentration.
  • RuCl 3 ruthenium chloride
  • Electrochemical performance test of that material as positive electrode active material of Li secondary battery is the same as that of comparative example 1. Its initial charge/discharge capacity and discharge capacity after 30 cycles are summarized in Table 1.
  • Preparation of Li 2 Mn0 3 is the same as that of comparative example. 20 mass% of Ni(OH) 2 is coated on surface of Li 2 Mn0 3 via precipitation method. Content of Ni(OH) 2 is realized by controlling a solution of nickel dichloride (NiCl 2 -H 2 0) with certain concentration and aqueous ammonia ( ⁇ 3 ⁇ 2 0) with corresponding concentration.
  • NiCl 2 -H 2 0 nickel dichloride
  • ⁇ 3 ⁇ 2 0 aqueous ammonia
  • Electrochemical performance test of that material as positive electrode active material of Li secondary battery is the same as that of comparative example 1. Its initial charge/discharge capacity and discharge capacity after 30 cycles are summarized in Table 1. Embodiment 13
  • Preparation of Li 2 Mn0 3 is the same as that of comparative example. 18 mass% of FeF 3 is coated on surface of Li 2 Mn0 3 via precipitation method and drying method. Content of FeF 3 is realized by controlling a solution of ferric nitrate (Fe(N0 3 ) 3 -9H 2 0) with certain concentration and a solution of ammonium fluoride (NH 4 F) with corresponding concentration under cetyltrimethyl ammonium bromide (CTAB) environment.
  • a solution of ferric nitrate Fe(N0 3 ) 3 -9H 2 0
  • NH 4 F ammonium fluoride
  • Electrochemical performance test of that material as positive electrode active material of Li secondary battery is the same as that of comparative example 1. Its initial charge/discharge capacity and discharge capacity after 30 cycles are summarized in Table 1.
  • Li 2 Mn0 3 is the same as that of comparative example. 1 mass% of LiCo0 2 is coated on surface of Li 2 Mn0 3 via sol-gel method. Content of LiCo0 2 is realized by controlling a solution of lithium acetate (LiCH 3 C0O2H 2 0) with certain concentration, a solution of cobalt acetate (Co(CH 3 COO) 2 -4H 2 0) and a solution of citric acid (C H 8 0 7 ) under ethylene glycol environment.
  • LiCH 3 C0O2H 2 0 LiCH 3 C0O2H 2 0
  • Co(CH 3 COO) 2 -4H 2 0 a solution of cobalt acetate
  • citric acid C H 8 0 7
  • Electrochemical performance test of that material as positive electrode active material of Li secondary battery is the same as that of comparative example 1. Its initial charge/discharge capacity and discharge capacity after 30 cycles are summarized in Table 1.
  • Li 2 Mn0 3 is the same as that of comparative example. 5 mass% of LiCo0 2 is coated on surface of Li 2 Mn0 3 via sol-gel method. Content of LiCo0 2 is realized by controlling a solution of lithium acetate (LiCH 3 C0O2H 2 0) with certain concentration, a solution of cobalt acetate (Co(CH 3 COO) 2 -4H 2 0) and a solution of citric acid (C 6 H 8 0 7 ) under ethylene glycol environment.
  • LiCH 3 C0O2H 2 0 LiCH 3 C0O2H 2 0
  • Co(CH 3 COO) 2 -4H 2 0 a solution of cobalt acetate
  • citric acid C 6 H 8 0 7
  • Electrochemical performance test of that material as positive electrode active material of Li secondary battery is the same as that of comparative example 1. Its initial charge/discharge capacity and discharge capacity after 30 cycles are summarized in Table 1.
  • Li 2 Mn0 3 is the same as that of comparative example. 20 mass% of LiCo0 2 is coated on surface of Li 2 Mn0 3 via sol-gel method. Content of LiCo0 2 is realized by controlling a solution of lithium acetate (LiCH 3 C0O2H 2 0) with certain concentration, a solution of cobalt acetate (Co(CH 3 COO) 2 -4H 2 0) and a solution of citric acid (C 6 H 8 0 7 ) under ethylene glycol environment. Electrochemical performance test of that material as positive electrode active material of Li secondary battery is the same as that of comparative example 1. Its initial charge/discharge capacity and discharge capacity after 30 cycles are summarized in Table 1.
  • Li 2 Mn0 3 is the same as that of comparative example. 20 mass% of LiMn 2 0 4 is coated on surface of Li 2 Mn0 3 via hydro-thermal method and solid phase method. Content of LiMn 2 0 4 is realized by controlling a solution of manganese nitrate (Mn(N0 3 ) 2 ) with certain concentration and lithium hydroxide (LiOH H 2 0) with different masses.
  • Mn(N0 3 ) 2 manganese nitrate
  • LiOH H 2 0 lithium hydroxide
  • Electrochemical performance test of that material as positive electrode active material of Li secondary battery is the same as that of comparative example 1. Its initial charge/discharge capacity and discharge capacity after 30 cycles are summarized in Table 1.
  • Preparation of Li 2 Mn0 3 is the same as that of comparative example. 30 mass% of PPy is coated on surface of Li 2 Mn0 3 via low temperature oxidation polymerization method. Content of PPy is realized by controlling pyrrole (Py) monomer with certain mass and a solution of ferric chloride (FeCl 3 -6H 2 0) with corresponding concentration under environment of excessive sodium dodecyl benzene sulfonate solution.
  • Electrochemical performance test of that material as positive electrode active material of Li secondary battery is the same as that of comparative example 1. Its initial charge/discharge capacity and discharge capacity after 30 cycles are summarized in Table 1.
  • Preparation of Li 2 Mn0 3 is the same as that of comparative example. 30 mass% of FeOOH is coated on surface of Li 2 Mn0 3 via hydrolysis method. Content of FeOOH is realized by controlling a solution of ferric chloride (FeCl 3 -6H 2 0) with certain concentration.
  • Electrochemical performance test of that material as positive electrode active material of Li secondary battery is the same as that of comparative example 1. Its initial charge/discharge capacity and discharge capacity after 30 cycles are summarized in Table 1. Table 1
  • FeP0 4, Co 3 0 4 and Ni(OH) 2 are preferable coating materials because FeP0 4 /Li 2 Mn0 3j Co 3 0 4 /Li 2 Mn0 3 and Ni(OH) 2 /Li 2 Mn0 3 provide more than 90% of retention rate after 30% cycles.
  • FeF 3 and M0O3 are also preferable coating materials because FeF 3 /Li 2 Mn0 3 and Mo0 3 /Li 2 Mn0 3 provide relatively high discharge capacities.
  • Li secondary battery comprising the positive electrode active material of the above implementation.
  • Other components of the Li secondary battery involved in the present implementation may be any component required by a Li secondary battery that are known by those skilled in the art, and the description of which will be omitted here for brevity.
  • the Li secondary battery of the present implementation by using the above positive electrode active material, may prevent 0 2 from releasing during initial charge, and significantly improve initial coulombic efficiency and discharge capacity after multiple charge-discharge cycles.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un matériau actif d'électrode positive et une batterie rechargeable au lithium. Le matériau actif d'électrode positive selon un mode de réalisation comprend une partie centrale et une couche de revêtement sur la partie centrale, la partie centrale comprenant un composé oxyde métallique, et la couche de revêtement comprenant un matériau qui peut réagir avec le lithium et/ou l'oxygène et empêcher la libération d'oxygène à partir du réseau du composé oxyde métallique au cours de cycles de charge-décharge.
PCT/CN2014/074350 2014-03-31 2014-03-31 Matériau actif d'électrode positive et batterie rechargeable au lithium WO2015149211A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105958040A (zh) * 2016-07-13 2016-09-21 广东工业大学 一种三氟化铁复合材料及其制备方法、锂二次电池
CN106887583A (zh) * 2015-12-15 2017-06-23 中国科学院化学研究所 一种正极材料及其制备方法和应用
CN106920694A (zh) * 2015-12-24 2017-07-04 财团法人工业技术研究院 导电材料与电容器
CN109065868A (zh) * 2018-08-03 2018-12-21 上海电气集团股份有限公司 氟化钙包覆的镍锰酸锂及其制备方法
CN110235283A (zh) * 2017-01-31 2019-09-13 松下知识产权经营株式会社 电化学装置用正极和电化学装置、以及它们的制造方法
CN110931733A (zh) * 2019-11-13 2020-03-27 北京理工大学 一种表面锰掺杂及Li-Mn-PO4包覆高镍正极材料及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1985388A (zh) * 2004-05-21 2007-06-20 蒂艾克思股份有限公司 金属锂氧化物材料、合成方法及其应用
CN101436663A (zh) * 2008-12-17 2009-05-20 厦门大学 锂离子电池复合正极材料及其制备方法
CN101438436A (zh) * 2006-03-20 2009-05-20 株式会社Lg化学 化学计量的锂钴氧化物及其制备方法
CN101630729A (zh) * 2009-04-16 2010-01-20 华中科技大学 用于大功率锂二次电池的复合电极材料及其制备方法
CN102244231A (zh) * 2010-05-14 2011-11-16 中国科学院物理研究所 对正极活性材料和/或正极进行表面包覆的方法以及正极和电池的制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1985388A (zh) * 2004-05-21 2007-06-20 蒂艾克思股份有限公司 金属锂氧化物材料、合成方法及其应用
CN101438436A (zh) * 2006-03-20 2009-05-20 株式会社Lg化学 化学计量的锂钴氧化物及其制备方法
CN101436663A (zh) * 2008-12-17 2009-05-20 厦门大学 锂离子电池复合正极材料及其制备方法
CN101630729A (zh) * 2009-04-16 2010-01-20 华中科技大学 用于大功率锂二次电池的复合电极材料及其制备方法
CN102244231A (zh) * 2010-05-14 2011-11-16 中国科学院物理研究所 对正极活性材料和/或正极进行表面包覆的方法以及正极和电池的制备方法

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106887583A (zh) * 2015-12-15 2017-06-23 中国科学院化学研究所 一种正极材料及其制备方法和应用
CN106920694A (zh) * 2015-12-24 2017-07-04 财团法人工业技术研究院 导电材料与电容器
CN106920694B (zh) * 2015-12-24 2019-04-05 财团法人工业技术研究院 导电材料与电容器
US10262808B2 (en) 2015-12-24 2019-04-16 Industrial Technology Research Institute Conductive composite and capacitor utilizing the same
CN105958040A (zh) * 2016-07-13 2016-09-21 广东工业大学 一种三氟化铁复合材料及其制备方法、锂二次电池
CN110235283A (zh) * 2017-01-31 2019-09-13 松下知识产权经营株式会社 电化学装置用正极和电化学装置、以及它们的制造方法
CN110235283B (zh) * 2017-01-31 2021-12-31 松下知识产权经营株式会社 电化学装置用正极和电化学装置、以及它们的制造方法
CN109065868A (zh) * 2018-08-03 2018-12-21 上海电气集团股份有限公司 氟化钙包覆的镍锰酸锂及其制备方法
CN110931733A (zh) * 2019-11-13 2020-03-27 北京理工大学 一种表面锰掺杂及Li-Mn-PO4包覆高镍正极材料及其制备方法和应用

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