CN104064742A - Modified sulfur/carbon doped lithium cobalt oxide cathode material and preparation method thereof - Google Patents

Modified sulfur/carbon doped lithium cobalt oxide cathode material and preparation method thereof Download PDF

Info

Publication number
CN104064742A
CN104064742A CN201410269251.XA CN201410269251A CN104064742A CN 104064742 A CN104064742 A CN 104064742A CN 201410269251 A CN201410269251 A CN 201410269251A CN 104064742 A CN104064742 A CN 104064742A
Authority
CN
China
Prior art keywords
cathode material
sulphur
lithium
lithium cobaltate
cobaltate cathode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410269251.XA
Other languages
Chinese (zh)
Inventor
孙琦
李岩
孙慧英
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
QINGDAO QIANYUN HIGH-TECH NEW MATERIAL Co Ltd
Original Assignee
QINGDAO QIANYUN HIGH-TECH NEW MATERIAL Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by QINGDAO QIANYUN HIGH-TECH NEW MATERIAL Co Ltd filed Critical QINGDAO QIANYUN HIGH-TECH NEW MATERIAL Co Ltd
Priority to CN201410269251.XA priority Critical patent/CN104064742A/en
Publication of CN104064742A publication Critical patent/CN104064742A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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

Landscapes

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

Abstract

The invention relates to a modified sulfur/carbon doped lithium cobalt oxide cathode material and a preparation method thereof. The modified sulfur/carbon doped lithium cobalt oxide cathode material is prepared from the following components in parts by weight: 25 parts of sulfur/carbon composite material, 70 parts of active material, 3 parts of functional material, 10 parts of conductive material and 10 parts of binding material, wherein the functional material is 60% lithium iron nitrate solution; the cathode material is lithium cobalt oxide; the conductive agent is flake graphite. The defect of failure of lithium ion batteries caused by self-discharge of protection boards is overcome by adopting the modified sulfur/carbon doped lithium cobalt oxide cathode material, thus improving self-discharge of the whole battery pack, achieving the aim of prolonging the lithium battery storage time and ensuring that the lithium batteries can be stored for a longer time under the condition that users do not charge the electric appliances after using the electric appliances.

Description

Lithium cobaltate cathode material of a kind of modified sulphur/charcoal doping and preparation method thereof
Technical field
The present invention relates to lithium cobaltate cathode material of a kind of modified sulphur/charcoal doping and preparation method thereof.
Background technology
Lithium ion battery is since commercialization, and lithium ion battery positive electrode used is mostly cobalt acid lithium, cobalt acid lithium or ternary material etc., and its component is mainly that active material adds conductive agent adding additives again, and described active material is cobalt acid lithium, cobalt acid lithium or ternary etc.; It is active material that negative material adopts graphite mostly, then adds some conductive agents and binding agent; Its advantage is that capacity is higher, have extended cycle life, but cobalt resource is deficient, expensive and have toxicity, therefore seeks the important research direction that excellent honest and clean, the dependable performance of price, eco-friendly positive electrode become lithium ion battery.Spinel-type positive electrode and ternary material layered oxide that the cobalt acid lithium of take is representative in the past decade obtain broad research, still due to its defect existing separately, have restricted their development prospect.In addition, the system that positive and negative pole material forms has a common feature to discharge the later stage exactly, and especially, when electric discharge finishes, voltage drop is very fast, and namely, in this voltage range the inside, the capacity of lithium ion battery has not almost had.
Summary of the invention
The technical problem to be solved in the present invention is the above-mentioned defect that how to overcome prior art, and lithium cobaltate cathode material of a kind of modified sulphur/charcoal doping and preparation method thereof is provided.
For solving the problems of the technologies described above, the lithium cobaltate cathode material of this modified sulphur/charcoal doping by weight, by following component according to shown in ratio be prepared from, sulphur/carbon composite 25, active material 70, functional material 3, electric conducting material 10, binding material 10.
As optimization, the ferric nitrate lithium solution that described functional material is 60%.
As optimization, described positive electrode is cobalt acid lithium.
As optimization, described conductive agent is crystalline flake graphite.
The lithium cobaltate cathode material preparation method of this modified sulphur/charcoal doping 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, in glove box, ball grinder is injected after high purity inert gas, be placed in ball milling 5h on planetary ball mill, rotational speed of ball-mill is 500 r/min, and the mass ratio of elemental sulfur and carbon is 1:2 ~ 3: 2; Obtain sulphur/carbon composite, this sulphur/carbon composite rate of heat addition with 10 ℃/min in baking oven is warming up to 180 ℃, and is incubated 24h at this temperature;
(2) sulphur/carbon composite, active material, functional material, electric conducting material, binding material are mixed, being dispersed in volume ratio is in the water of 3:1 and the mixed solvent of acetone, water or chloroform, and ultrasonic or stirring, disperses it completely equably;
(3), under ice-water bath and inert atmosphere protection, add ammonium persulfate aqueous solution or FeCl 3chloroformic solution, stirring reaction 24h under constant temperature, then by product centrifugation, washing, the vacuum drying chamber of putting into 60 ℃ is dried, and is ground to powder.
The lithium cobaltate cathode material preparation method method of a kind of modified sulphur of the present invention/charcoal doping is simple; with low cost; overcome lithium ion battery and because of baffle self discharge, caused the defect of inefficacy; thereby improve the self discharge of whole battery pack; realize to extend the object of lithium battery resting period, guarantee that user uses electrical appliance and can store the longer time in the situation of not charging.
Embodiment
The lithium cobaltate cathode material of this modified sulphur/charcoal doping by weight, by following component according to shown in ratio be prepared from, sulphur/carbon composite 25, active material 70, functional material 3, electric conducting material 10, binding material 10.Described functional material is 60% ferric nitrate lithium solution.Described positive electrode is cobalt acid lithium.Described conductive agent is crystalline flake graphite
The lithium cobaltate cathode material preparation method of this modified sulphur/charcoal doping 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, in glove box, ball grinder is injected after high purity inert gas, be placed in ball milling 5h on planetary ball mill, rotational speed of ball-mill is 500 r/min, and the mass ratio of elemental sulfur and carbon is 1:2 ~ 3: 2; Obtain sulphur/carbon composite, this sulphur/carbon composite rate of heat addition with 10 ℃/min in baking oven is warming up to 180 ℃, and is incubated 24h at this temperature;
(2) sulphur/carbon composite, active material, functional material, electric conducting material, binding material are mixed, being dispersed in volume ratio is in the water of 3:1 and the mixed solvent of acetone, water or chloroform, and ultrasonic or stirring, disperses it completely equably;
(3), under ice-water bath and inert atmosphere protection, add ammonium persulfate aqueous solution or FeCl 3chloroformic solution, stirring reaction 24h under constant temperature, then by product centrifugation, washing, the vacuum drying chamber of putting into 60 ℃ is dried, and is ground to powder.
The present invention includes but be not limited to above-mentioned execution mode, any product that meets the description of these claims, within all falling into protection scope of the present invention.

Claims (5)

1. the lithium cobaltate cathode material of a modified sulphur/charcoal doping, it is characterized in that: by weight, the lithium cobaltate cathode material of this modified sulphur/charcoal doping by following component according to shown in ratio be prepared from, sulphur/carbon composite 25, active material 70, functional material 3, electric conducting material 10, binding material 10.
2. the lithium cobaltate cathode material of modified sulphur according to claim 1/charcoal doping, is characterized in that: the ferric nitrate lithium solution that described functional material is 60%.
3. the lithium cobaltate cathode material of modified sulphur according to claim 1/charcoal doping, is characterized in that: described positive electrode is cobalt acid lithium.
4. the lithium cobaltate cathode material of modified sulphur according to claim 1/charcoal doping, is characterized in that: described conductive agent is crystalline flake graphite.
5. the lithium cobaltate cathode material preparation method of a modified sulphur/charcoal doping, it is characterized in that: the lithium cobaltate cathode material of described modified sulphur/charcoal doping is the lithium cobaltate cathode material of claim 1 ~ 4 arbitrary described modified sulphur/charcoal doping, 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, in glove box, ball grinder is injected after high purity inert gas, be placed in ball milling 5h on planetary ball mill, rotational speed of ball-mill is 500 r/min, and the mass ratio of elemental sulfur and carbon is 1:2 ~ 3: 2; Obtain sulphur/carbon composite, this sulphur/carbon composite rate of heat addition with 10 ℃/min in baking oven is warming up to 180 ℃, and is incubated 24h at this temperature;
(2) sulphur/carbon composite, active material, functional material, electric conducting material, binding material are mixed, being dispersed in volume ratio is in the water of 3:1 and the mixed solvent of acetone, water or chloroform, and ultrasonic or stirring, disperses it completely equably;
(3), under ice-water bath and inert atmosphere protection, add ammonium persulfate aqueous solution or FeCl 3chloroformic solution, stirring reaction 24h under constant temperature, then by product centrifugation, washing, the vacuum drying chamber of putting into 60 ℃ is dried, and is ground to powder.
CN201410269251.XA 2014-06-17 2014-06-17 Modified sulfur/carbon doped lithium cobalt oxide cathode material and preparation method thereof Pending CN104064742A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410269251.XA CN104064742A (en) 2014-06-17 2014-06-17 Modified sulfur/carbon doped lithium cobalt oxide cathode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410269251.XA CN104064742A (en) 2014-06-17 2014-06-17 Modified sulfur/carbon doped lithium cobalt oxide cathode material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN104064742A true CN104064742A (en) 2014-09-24

Family

ID=51552352

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410269251.XA Pending CN104064742A (en) 2014-06-17 2014-06-17 Modified sulfur/carbon doped lithium cobalt oxide cathode material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104064742A (en)

Similar Documents

Publication Publication Date Title
CN104064737A (en) Graphene coated lithium battery cathode material and preparation method thereof
CN104064740A (en) Sulfur/carbon doped lithium nickelate cathode material and preparation method thereof
CN104064771A (en) Efficient graphene coated lithium cobalt oxide battery cathode material and preparation method thereof
CN105406059A (en) High-purity sulfur/charcoal-coated lithium cobalt oxide positive electrode material and preparation method thereof
CN104064741A (en) Efficient sulfur/carbon doped lithium cobalt oxide cathode material and preparation method thereof
CN104064758A (en) Sulfur/carbon coated lithium cobalt oxide cathode material and preparation method thereof
CN104064745A (en) Sulfur/carbon coated lithium manganate cathode material and preparation method thereof
CN105552332A (en) Efficient sulfur/carbon-coated lithium cobalt oxide cathode material and preparation method thereof
CN104064742A (en) Modified sulfur/carbon doped lithium cobalt oxide cathode material and preparation method thereof
CN104064759A (en) Novel sulfur/carbon doped lithium cobalt oxide cathode material and preparation method thereof
CN105406049A (en) High-efficiency sulfur/charcoal-coated lithium cobalt oxide positive electrode material and preparation method thereof
CN104064746A (en) Modified sulfur/carbon doped lithium manganate cathode material and preparation method thereof
CN104064760A (en) Modified sulfur/carbon coated lithium nickelate cathode material and preparation method thereof
CN104064761A (en) Novel sulfur/carbon coated lithium nickelate cathode material and preparation method thereof
CN104064762A (en) Efficient sulfur/carbon coated lithium nickelate cathode material and preparation method thereof
CN105633367A (en) High-purity S/C-coated lithium nickelate cathode material and preparation method thereof
CN105514385A (en) Modified sulfur/carbon coated lithium cobaltate cathode material and preparation method thereof
CN105514386A (en) Modified sulfur/carbon coated lithium cobaltate cathode material and preparation method thereof
CN105609724A (en) Modified graphene-doped lithium manganate battery cathode material and preparation method thereof
CN105609726A (en) High-purity sulfur/carbon coated lithium cobaltate cathode material and preparation method thereof
CN105428629A (en) Efficient sulfur/carbon coated lithium nickelate positive electrode material and preparation method thereof
CN105428630A (en) Efficient sulfur/carbon coated lithium manganate positive electrode material and preparation method thereof
CN104064757A (en) Graphene doped lithium battery cathode material and preparation method thereof
CN105609725A (en) Efficient sulfur/carbon coated lithium nickelate cathode material and preparation method thereof
CN105470458A (en) High-purity sulphur/carbon-coated lithium manganate cathode material and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20140924

WD01 Invention patent application deemed withdrawn after publication