CN105470458A - High-purity sulphur/carbon-coated lithium manganate cathode material and preparation method thereof - Google Patents

High-purity sulphur/carbon-coated lithium manganate cathode material and preparation method thereof Download PDF

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Publication number
CN105470458A
CN105470458A CN201511028543.5A CN201511028543A CN105470458A CN 105470458 A CN105470458 A CN 105470458A CN 201511028543 A CN201511028543 A CN 201511028543A CN 105470458 A CN105470458 A CN 105470458A
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sulphur
lithium
cathode material
purity
manganate cathode
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姜殿凯
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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
    • H01M4/13—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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

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

Abstract

The invention relates to a high-purity sulphur/carbon-coated lithium manganate cathode material and a preparation method thereof. The high-purity sulphur/carbon-coated lithium manganate cathode material is prepared from the following components in parts by weight: 30 parts of a sulphur/carbon composite material, 60 parts of lithium manganate, 25 parts of 45% a lithium iron nitrate solution, 3 parts of flake graphite and 3 parts of a binding material. According to the high-purity sulphur/carbon-coated lithium manganate cathode material, the defect of a failure, caused by self-discharge of a protective board, of lithium-on batteries is overcome, so that self-discharge of the overall battery pack is improved; the storage time of the lithium batteries is prolonged; and the condition that an electric appliance can be stored for a relatively long period of time without being charged after being used by a user is ensured.

Description

Manganate cathode material for lithium that a kind of high-purity sulphur/charcoal is coated and preparation method thereof
Technical field
The present invention relates to coated manganate cathode material for lithium of a kind of high-purity sulphur/charcoal and preparation method thereof.
Background technology
Lithium ion battery is since commercialization, and lithium ion battery positive electrode used is mostly LiMn2O4, LiMn2O4 or ternary material etc., and its component mainly LiMn2O4 adds conductive agent adding additives again, and described LiMn2O4 is LiMn2O4, LiMn2O4 or ternary etc.; Negative material adopts graphite to be active material mostly, then adds some conductive agents and binding agent; Its advantage is that capacity is higher, has extended cycle life, but promoter manganese is deficient, expensive and have toxicity, therefore seeks excellent honest and clean, the important research direction that dependable performance, eco-friendly positive electrode become lithium ion battery of price.Be that spinel-type positive electrode and the ternary material layered oxide of representative is in the past decade extensively studied with LiMn2O4, but constrain their development prospect due to its defect existed separately.In addition, the system of positive and negative pole material composition has a common feature to discharge the later stage exactly, especially at the end of electric discharge, voltage drop quickly, namely inside this voltage range, the capacity of lithium ion battery almost without.
Summary of the invention
The technical problem to be solved in the present invention is the above-mentioned defect how overcoming prior art, manganate cathode material for lithium providing a kind of high-purity sulphur/charcoal coated and preparation method thereof.
For solving the problems of the technologies described above, the coated manganate cathode material for lithium of this high-purity sulphur/charcoal by weight, be prepared from according to shown ratio by following component, sulphur/carbon composite 30, the ferric nitrate lithium solution 25 of LiMn2O4 60,45%, crystalline flake graphite 3, binding material 3.
Coated manganate cathode material for lithium preparation method comprises the following steps this high-purity sulphur/charcoal:
(1) according to above-mentioned weight ratio, material with carbon element and sublimed sulfur or Cosan are put into zirconium dioxide or agate jar, after ball grinder being injected high purity inert gas in glove box, be placed in ball milling 5h on planetary ball mill, rotational speed of ball-mill is 500r/min, and the mass ratio of elemental sulfur and carbon is 1:2 ~ 3: 2; Obtain sulphur/carbon composite, this sulphur/carbon composite is warming up to 150 DEG C with the rate of heat addition of 10 DEG C/min in an oven, and is incubated 24h at this temperature;
(2) be dispersed in by sulphur/carbon composite in the mixed solvent of the water that volume ratio is 3:1 and acetone, water or chloroform, ultrasonic or stirring, makes it disperse completely equably;
(3) by LiMn2O4,45% ferric nitrate lithium solution, crystalline flake graphite, binding material add in mixed solution, again ultrasonic or stir, add or do not add dopant acid, whole mixed solution system is in acid, and its pH value is between 2 ~ 4;
(4) under ice-water bath and inert atmosphere protection, ammonium persulfate aqueous solution or FeCl is added 3chloroformic solution, stirring reaction 24h under constant temperature, then by product centrifugation, washing, the vacuum drying chamber putting into 60 DEG C is dried, and is ground to powder.
The coated manganate cathode material for lithium preparation method method of a kind of high-purity of the present invention sulphur/charcoal is simple; with low cost; overcome lithium ion battery causes inefficacy defect because of baffle self discharge; thus improve the self discharge of whole battery pack; realize the object extending the lithium battery resting period, when ensureing that user uses electrical appliance and do not charge, the longer time can be stored.
Embodiment
The coated manganate cathode material for lithium of this high-purity sulphur/charcoal by weight, is prepared from according to shown ratio by following component, sulphur/carbon composite 30, the ferric nitrate lithium solution 25 of LiMn2O4 60,45%, crystalline flake graphite 3, binding material 3.The ferric nitrate lithium solution of described 45% is the ferric nitrate lithium solution of 60%.Described positive electrode is LiMn2O4.Described conductive agent is crystalline flake graphite
Coated manganate cathode material for lithium preparation method comprises the following steps this high-purity sulphur/charcoal:
(1) according to above-mentioned weight ratio, material with carbon element and sublimed sulfur or Cosan are put into zirconium dioxide or agate jar, after ball grinder being injected high purity inert gas in glove box, be placed in ball milling 5h on planetary ball mill, rotational speed of ball-mill is 500r/min, and the mass ratio of elemental sulfur and carbon is 1:2 ~ 3: 2; Obtain sulphur/carbon composite, this sulphur/carbon composite is warming up to 150 DEG C with the rate of heat addition of 10 DEG C/min in an oven, and is incubated 24h at this temperature;
(2) be dispersed in by sulphur/carbon composite in the mixed solvent of the water that volume ratio is 3:1 and acetone, water or chloroform, ultrasonic or stirring, makes it disperse completely equably;
(3) by LiMn2O4,45% ferric nitrate lithium solution, crystalline flake graphite, binding material add in mixed solution, again ultrasonic or stir, add or do not add dopant acid, whole mixed solution system is in acid, and its pH value is between 2 ~ 4;
(4) under ice-water bath and inert atmosphere protection, ammonium persulfate aqueous solution or FeCl is added 3chloroformic solution, stirring reaction 24h under constant temperature, then by product centrifugation, washing, the vacuum drying chamber putting into 60 DEG C is dried, and is ground to powder.
The present invention includes but be not limited to above-mentioned execution mode, any product meeting these claims and describe, all falls within protection scope of the present invention.

Claims (2)

1. the manganate cathode material for lithium that high-purity sulphur/charcoal is coated, it is characterized in that: by weight, the coated manganate cathode material for lithium of this high-purity sulphur/charcoal is prepared from according to shown ratio by following component, sulphur/carbon composite 30, the ferric nitrate lithium solution 25 of LiMn2O4 60,45%, crystalline flake graphite 3, binding material 3.
2. the manganate cathode material for lithium preparation method that high-purity sulphur/charcoal is coated, it is characterized in that: the coated manganate cathode material for lithium of described high-purity sulphur/charcoal is the coated manganate cathode material for lithium of high-purity according to claim 1 sulphur/charcoal, and its preparation method comprises the following steps:
(1) according to above-mentioned weight ratio, material with carbon element and sublimed sulfur or Cosan are put into zirconium dioxide or agate jar, after ball grinder being injected high purity inert gas in glove box, be placed in ball milling 25h on planetary ball mill, rotational speed of ball-mill is 2500r/min, and the mass ratio of elemental sulfur and carbon is 1:2 ~ 3: 2; Obtain sulphur/carbon composite, this sulphur/carbon composite is warming up to 160 DEG C with the rate of heat addition of 10 DEG C/min in an oven, and is incubated 24h at this temperature;
(2) be dispersed in by sulphur/carbon composite in the mixed solvent of the water that volume ratio is 3:1 and acetone, water or chloroform, ultrasonic or stirring, makes it disperse completely equably;
(3) by LiMn2O4,45% ferric nitrate lithium solution, crystalline flake graphite, binding material add in mixed solution, again ultrasonic or stir, add or do not add dopant acid, whole mixed solution system is in acid, and its pH value is between 2 ~ 4;
(4) under ice-water bath and inert atmosphere protection, ammonium persulfate aqueous solution or FeCl is added 3chloroformic solution, stirring reaction 24h under constant temperature, then by product centrifugation, washing, the vacuum drying chamber putting into 60 DEG C is dried, and is ground to powder.
CN201511028543.5A 2015-12-30 2015-12-30 High-purity sulphur/carbon-coated lithium manganate cathode material and preparation method thereof Pending CN105470458A (en)

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CN201511028543.5A CN105470458A (en) 2015-12-30 2015-12-30 High-purity sulphur/carbon-coated lithium manganate cathode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201511028543.5A CN105470458A (en) 2015-12-30 2015-12-30 High-purity sulphur/carbon-coated lithium manganate cathode material and preparation method thereof

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CN105470458A true CN105470458A (en) 2016-04-06

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