CN105390685A - Modified sulfur/carbon cladded lithium manganate anode material and preparing method thereof - Google Patents

Modified sulfur/carbon cladded lithium manganate anode material and preparing method thereof Download PDF

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Publication number
CN105390685A
CN105390685A CN201511027707.2A CN201511027707A CN105390685A CN 105390685 A CN105390685 A CN 105390685A CN 201511027707 A CN201511027707 A CN 201511027707A CN 105390685 A CN105390685 A CN 105390685A
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lithium
sulphur
charcoal
coated
carbon
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CN201511027707.2A
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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
    • H01M4/36—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
    • 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
    • H01M4/36—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a modified sulfur/carbon cladded lithium manganate anode material and a preparing method thereof. The modified sulfur/carbon cladded lithium manganate anode material is prepared from the following components in parts by weight according to the shown proportion: 40 parts of sulfur/carbon composite material, 50 parts of lithium manganate, 20 parts of 45% of ferric nitrate lithium solution, 5 parts of crystalline flake graphite and 5 parts of bonding material. The modified sulfur/carbon cladded lithium manganate anode material and the preparing method thereof overcome the defect of failure of a lithium battery caused by self discharging of a protective plate, the self discharging of the whole battery bank is improved, the aim of prolonging the storage time of the lithium battery is achieved, and longer storage time is realized under the condition that a user does not charge after using an electric appliance.

Description

Manganate cathode material for lithium that a kind of modified 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 modified 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 modified 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 modified sulphur/charcoal by weight, be prepared from according to shown ratio by following component, sulphur/carbon composite 40, the ferric nitrate lithium solution 20 of LiMn2O4 50,45%, crystalline flake graphite 5, binding material 5.
Coated manganate cathode material for lithium preparation method comprises the following steps this modified 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 modified sulphur/charcoal of the present invention 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 modified sulphur/charcoal by weight, is prepared from according to shown ratio by following component, sulphur/carbon composite 40, the ferric nitrate lithium solution 20 of LiMn2O4 50,45%, crystalline flake graphite 5, binding material 5.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 modified 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 modified sulphur/charcoal is coated, it is characterized in that: by weight, the coated manganate cathode material for lithium of this modified sulphur/charcoal is prepared from according to shown ratio by following component, sulphur/carbon composite 40, the ferric nitrate lithium solution 20 of LiMn2O4 50,45%, crystalline flake graphite 5, binding material 5.
2. the manganate cathode material for lithium preparation method that modified sulphur/charcoal is coated, is characterized in that: the coated manganate cathode material for lithium of described modified sulphur/charcoal is the coated manganate cathode material for lithium of modified sulphur/charcoal according to claim 1, 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 20h on planetary ball mill, rotational speed of ball-mill is 2000r/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.
CN201511027707.2A 2015-12-30 2015-12-30 Modified sulfur/carbon cladded lithium manganate anode material and preparing method thereof Pending CN105390685A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201511027707.2A CN105390685A (en) 2015-12-30 2015-12-30 Modified sulfur/carbon cladded lithium manganate anode material and preparing method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201511027707.2A CN105390685A (en) 2015-12-30 2015-12-30 Modified sulfur/carbon cladded lithium manganate anode material and preparing method thereof

Publications (1)

Publication Number Publication Date
CN105390685A true CN105390685A (en) 2016-03-09

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