CN104064745A - Sulfur/carbon coated lithium manganate cathode material and preparation method thereof - Google Patents
Sulfur/carbon coated lithium manganate cathode material and preparation method thereof Download PDFInfo
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- CN104064745A CN104064745A CN201410265895.1A CN201410265895A CN104064745A CN 104064745 A CN104064745 A CN 104064745A CN 201410265895 A CN201410265895 A CN 201410265895A CN 104064745 A CN104064745 A CN 104064745A
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- sulphur
- lithium
- cathode material
- manganate cathode
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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
- H01M4/48—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
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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
- 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
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/58—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
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- 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)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a sulfur/carbon coated lithium manganate cathode material and a preparation method thereof. The sulfur/carbon coated lithium manganate cathode material is prepared from the following components in parts by weight: 15-25 parts of sulfur/carbon composite material, 80-85 parts of active material, 5-10 parts of functional material, 4-8 parts of conductive material and 4-8 parts of binding material, wherein the functional material is 60% lithium iron nitrate solution; the cathode material is lithium manganate; 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 sulfur/carbon coated lithium manganate 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
Technical field
The present invention relates to coated manganate cathode material for lithium of a kind of 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 is mainly that active material adds conductive agent adding additives again, and described active material is LiMn2O4, LiMn2O4 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, has extended cycle life, but manganese scarcity of resources, expensive and there is toxicity, therefore seeking excellent honest and clean, the dependable performance of price, eco-friendly positive electrode becomes the important research direction of lithium ion battery.Spinel-type positive electrode and ternary material layered oxide taking LiMn2O4 as representative in the past decade obtain broad research, have still restricted their development prospect due to its defect existing separately.In addition, the system of positive and negative pole material composition has a common feature to discharge the later stage exactly, and especially, in the time that 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 coated manganate cathode material for lithium of a kind of sulphur/charcoal and preparation method thereof is provided.
For solving the problems of the technologies described above, the coated manganate cathode material for lithium of this sulphur/charcoal by weight, by following component according to shown in ratio be prepared from, sulphur/carbon composite 15 ~ 25, active material 80 ~ 85, functional material 5 ~ 10, electric conducting material 3 ~ 5, binding material 3 ~ 5.
As optimization, the ferric nitrate lithium solution that described functional material is 60%.
As optimization, described positive electrode is LiMn2O4.
As optimization, described conductive agent is crystalline flake graphite.
This sulphur/charcoal is coated manganate cathode material for lithium preparation method comprise 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 is warming up to 180 DEG C with the rate of heat addition of 10 DEG C/min in baking oven, and be incubated 24h at this temperature;
(2) sulphur/carbon composite being dispersed in to 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) by the adding in mixed solution of active material, functional material, electric conducting material, binding material, again ultrasonic or stir, add or do not add dopant acid, it is acid that whole mixed solution system is, and its pH value is between 2 ~ 4;
(4), 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 DEG C is dried, and is ground to powder.
The coated manganate cathode material for lithium preparation method method of a kind of sulphur/charcoal of the present invention is simple; with low cost; overcome lithium ion battery causes inefficacy defect because of baffle self discharge; thereby improve the self discharge of whole battery pack; realize and extend the object of lithium battery resting period, ensure that user uses electrical appliance and can store the longer time in the situation of not charging.
Embodiment
The coated manganate cathode material for lithium of this sulphur/charcoal by weight, by following component according to shown in ratio be prepared from, sulphur/carbon composite 15 ~ 25, active material 80 ~ 85, functional material 5 ~ 10, electric conducting material 3 ~ 5, binding material 3 ~ 5.Described functional material is 60% ferric nitrate lithium solution.Described positive electrode is LiMn2O4.Described conductive agent is crystalline flake graphite
This sulphur/charcoal is coated manganate cathode material for lithium preparation method comprise 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 is warming up to 180 DEG C with the rate of heat addition of 10 DEG C/min in baking oven, and be incubated 24h at this temperature;
(2) sulphur/carbon composite being dispersed in to 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) by the adding in mixed solution of active material, functional material, electric conducting material, binding material, again ultrasonic or stir, add or do not add dopant acid, it is acid that whole mixed solution system is, and its pH value is between 2 ~ 4;
(4), 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 DEG C 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 manganate cathode material for lithium that sulphur/charcoal is coated, it is characterized in that: by weight, the coated manganate cathode material for lithium of this sulphur/charcoal by following component according to shown in ratio be prepared from, sulphur/carbon composite 15 ~ 25, active material 85 ~ 95, functional material 5 ~ 10, electric conducting material 4 ~ 8, binding material 4 ~ 8.
2. the coated manganate cathode material for lithium of sulphur/charcoal according to claim 1, is characterized in that: the ferric nitrate lithium solution that described functional material is 60%.
3. the coated manganate cathode material for lithium of sulphur/charcoal according to claim 1, is characterized in that: described positive electrode is LiMn2O4.
4. the coated manganate cathode material for lithium of sulphur/charcoal according to claim 1, is characterized in that: described conductive agent is crystalline flake graphite.
5. the coated manganate cathode material for lithium preparation method of sulphur/charcoal, is characterized in that: the coated manganate cathode material for lithium of described sulphur/charcoal is the arbitrary described coated manganate cathode material for lithium of sulphur/charcoal of claim 1 ~ 4, 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 is warming up to 180 DEG C with the rate of heat addition of 10 DEG C/min in baking oven, and be incubated 24h at this temperature;
(2) sulphur/carbon composite being dispersed in to 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) by the adding in mixed solution of active material, functional material, electric conducting material, binding material, again ultrasonic or stir, add or do not add dopant acid, it is acid that whole mixed solution system is, and its pH value is between 2 ~ 4;
(4), 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 DEG C is dried, and is ground to powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410265895.1A CN104064745A (en) | 2014-06-16 | 2014-06-16 | Sulfur/carbon coated lithium manganate cathode material and preparation method thereof |
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| CN201410265895.1A CN104064745A (en) | 2014-06-16 | 2014-06-16 | Sulfur/carbon coated lithium manganate cathode material and preparation method thereof |
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| CN201410265895.1A Pending CN104064745A (en) | 2014-06-16 | 2014-06-16 | Sulfur/carbon coated lithium manganate cathode material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110729454A (en) * | 2019-10-22 | 2020-01-24 | 深圳中华自行车(集团)股份有限公司 | Battery positive pole piece and preparation method thereof |
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2014
- 2014-06-16 CN CN201410265895.1A patent/CN104064745A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110729454A (en) * | 2019-10-22 | 2020-01-24 | 深圳中华自行车(集团)股份有限公司 | Battery positive pole piece and preparation method thereof |
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Application publication date: 20140924 |
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