CN107978740A - A kind of laser burn preparation method of nickel-cobalt-manganternary ternary anode material - Google Patents
A kind of laser burn preparation method of nickel-cobalt-manganternary ternary anode material Download PDFInfo
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- CN107978740A CN107978740A CN201711134253.8A CN201711134253A CN107978740A CN 107978740 A CN107978740 A CN 107978740A CN 201711134253 A CN201711134253 A CN 201711134253A CN 107978740 A CN107978740 A CN 107978740A
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- cobalt
- nickel
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- ternary anode
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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
- H01M4/364—Composites as mixtures
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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
- H01M4/48—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
- 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
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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
Abstract
The present invention is suitable for technical field of lithium batteries, a kind of laser burn preparation method of nickel-cobalt-manganternary ternary anode material is provided, the nickel-cobalt-manganese ternary material that the present invention is prepared using laser burn method, pass through reasonable Ni, Co, Mn ratio, and add a certain amount of carbon nanotubes, and rationally the thickness of powder and laser reactive device is set to burn temperature, carry out burning reaction in laser reactive device, this method is more homogeneous than ternary material composition prepared by conventional method sintering, structure is more stable, so that electrical property is improved.
Description
Technical field
It is prepared by the laser burn the invention belongs to technical field of lithium batteries, more particularly to a kind of nickel-cobalt-manganternary ternary anode material
Method.
Background technology
Nickel-cobalt-manganese ternary anode material for lithium-ion batteries is due to higher energy density and relatively simple system
Standby technique is widely used in IT product and new-energy automobile field.But nickle cobalt lithium manganate prepared by conventional method sintering
(LNCM) since structural stability is not good enough, the deintercalation due to Li ions and Ni, Co, Mn ion are easy in charge and discharge process
The change of valence state causes collapsing for material structure, and the cycle life and security to material cause greatly to endanger.
The content of the invention
In view of the above problems, it is an object of the invention to provide one kind, it is intended to solves existing.
The present invention adopts the following technical scheme that：
The laser burn preparation method of nickel-cobalt-manganternary ternary anode material provided by the invention, including：
S1, configuration Ni, Co, Mn salting liquid, wherein molar ratio Ni：Co：Mn=(0.4-0.5)：0.2：(0.4-0.5)；
S2, Ni, Co, Mn salting liquid of the mixing configuration, and a certain amount of carbon nanotubes is added, stirring is after a certain period of time
Drying, obtains reaction mass；
S3, by the reaction mass and lithium source be uniformly mixed to obtain mixed powder, and it is anti-that the mixed powder is placed in laser
Answer in device, mixed powder thickness is 0.4-1.2cm；
S4, be passed through pure oxygen in laser reactive device, opens laser reactive device, controls power so that burning temperature range is
600-850℃。
Further, in step S1, Ni, Co, Mn salting liquid is nickel, cobalt, the soluble salt solutions of manganese, including carbonic acid
Salt, organic soluble salt.
Further, the carbon nanotubes is the multi-walled carbon nanotube of diameter 8-12nm.
Further, in step S2, mixing time 60min, drying temperature is 80 DEG C.
Further, the lithium source Li in molar ratio that step S3 is added：Me=(0.9-1.2):1 calculate, wherein Me for Ni,
The sum of mole of Co, Mn.
Further, the speed that step S4 is passed through pure oxygen is 18.6-65.1m3/h。
The beneficial effects of the invention are as follows：The nickel-cobalt-manganese ternary material that the present invention is prepared using laser burn method, by reasonable
Ni, Co, Mn ratio, and a certain amount of carbon nanotubes is added, and rationally set the thickness of powder and laser reactive device to burn
Temperature, carries out burning reaction, this method forms more than ternary material prepared by conventional method sintering in laser reactive device
Homogeneous, structure is more stable, so that electrical property is improved.
Brief description of the drawings
Fig. 1 is that the present invention prepares gained ternary material first circle electric discharge comparison diagram with traditional preparation methods；
Fig. 2 is that the present invention prepares gained ternary material circulation comparison diagram with traditional preparation methods.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, it is right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
In order to illustrate technical solutions according to the invention, illustrated below by specific embodiment.
The laser burn preparation method of nickel-cobalt-manganternary ternary anode material provided by the invention comprises the following steps：
S1, configuration Ni, Co, Mn salting liquid, wherein molar ratio Ni：Co：Mn=(0.4-0.5)：0.2：(0.4-0.5)；Institute
Ni, Co, Mn salting liquid are stated as nickel, cobalt, the soluble salt solutions of manganese, including carbonate, organic soluble salt.
S2, Ni, Co, Mn salting liquid of the mixing configuration, and a certain amount of carbon nanotubes is added, the carbon nanotubes is
The multi-walled carbon nanotube of diameter 8-12nm, stirring are dried after a certain period of time, obtain reaction mass, in the present embodiment, mixing time
For 60min, drying temperature is 80 DEG C.
S3, by the reaction mass and lithium source be uniformly mixed to obtain mixed powder, and it is anti-that the mixed powder is placed in laser
Answer in device, mixed powder thickness is 0.4-1.2cm.Here the lithium source added Li in molar ratio：Me=(0.9-1.2):1 meter
Calculate, wherein Me is the sum of mole of Ni, Co, Mn.
S4, be passed through pure oxygen in laser reactive device, and the speed of pure oxygen is 18.6-65.1m3/ h opens laser reactive device, control
Power processed so that burn temperature range as 600-850 DEG C.Laser reactive device width 2m, laser width 0.2m.
Illustrate effect of the present invention below by specific embodiment and comparative example.
Embodiment
It is 6 that the carbonate of Ni, Co, Mn are pressed metal molar ratio：2：2 configuration solution.It is infiltrated with the carbon nanotubes of 10nm
Solution is stated, is then dried in 80 DEG C of vacuum drying ovens.Mixed again with Li sources, Li/Me=1.05.Open laser burn reactor, control
800 degrees Celsius of temperature processed, obtains nickel-cobalt-manganese ternary material.
Comparative example
It is 6 by Ni, Co, Mn molar ratio：2：2 presoma is mixed with lithium source, wherein Li/Me=1.05.Finally by material
It is placed in roaster and sinters, finally crush, obtains nickel-cobalt-manganese ternary material.
Using above-described embodiment and comparative example material as cathode, button half-cell is assembled into, is carried out on blue electrical measurement test system
Charging and loop test.Concrete mode is：According to mass ratio it is 80 by positive electrode and acetylene black, PVDF:12:8 ratio is mixed
Close, be dissolved in a certain amount of nmp solvent, be coated on after ball milling mixing on aluminium foil as anode, born by battery of lithium piece
Pole, is assembled into button half-cell.Shown in test result attached drawing.Using the positive electrode that laser burn method obtains in 0.25C multiplying powers
Lower first discharge specific capacity reaches 185.5mAh/g, capacity retention ratio 99.1% after 50 charge-discharge cycles, and conventional method sinters
Positive electrode first discharge specific capacity is 175mAh/g, capacity retention ratio 97.8% after 50 charge-discharge cycles.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should all be included in the protection scope of the present invention.
Claims (6)
1. the laser burn preparation method of a kind of nickel-cobalt-manganternary ternary anode material, it is characterised in that the described method includes following steps
Suddenly：
S1, configuration Ni, Co, Mn salting liquid, wherein molar ratio Ni：Co：Mn=(0.4-0.5)：0.2：(0.4-0.5)；
S2, Ni, Co, Mn salting liquid of the mixing configuration, and a certain amount of carbon nanotubes is added, stirring is dried after a certain period of time
It is dry, obtain reaction mass；
S3, by the reaction mass and lithium source be uniformly mixed to obtain mixed powder, and the mixed powder is placed in laser reactive device
In, mixed powder thickness is 0.4-1.2cm；
S4, be passed through pure oxygen in laser reactive device, opens laser reactive device, controls power so that it is 600- to burn temperature range
850℃。
2. the laser burn preparation method of nickel-cobalt-manganternary ternary anode material as claimed in claim 1, it is characterised in that step S1
In, Ni, Co, Mn salting liquid is nickel, cobalt, the soluble salt solutions of manganese, including carbonate, organic soluble salt.
3. the laser burn preparation method of nickel-cobalt-manganternary ternary anode material as claimed in claim 2, it is characterised in that the carbon is received
Mitron is the multi-walled carbon nanotube of diameter 8-12nm.
4. the laser burn preparation method of nickel-cobalt-manganternary ternary anode material as claimed in claim 3, it is characterised in that step S2
In, mixing time 60min, drying temperature is 80 DEG C.
5. the laser burn preparation method of nickel-cobalt-manganternary ternary anode material as claimed in claim 4, it is characterised in that step S3 adds
The lithium source entered Li in molar ratio：Me=(0.9-1.2):1 calculates, and wherein Me is the sum of mole of Ni, Co, Mn.
6. the laser burn preparation method of nickel-cobalt-manganternary ternary anode material as claimed in claim 5, it is characterised in that step S4 leads to
The speed for entering pure oxygen is 18.6-65.1m3/h。
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| CN201711134253.8A CN107978740A (en) | 2017-11-16 | 2017-11-16 | A kind of laser burn preparation method of nickel-cobalt-manganternary ternary anode material |
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| CN201711134253.8A CN107978740A (en) | 2017-11-16 | 2017-11-16 | A kind of laser burn preparation method of nickel-cobalt-manganternary ternary anode material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915837A (en) * | 1998-11-09 | 2007-02-21 | 美商纳克公司 | Metal oxide particles |
| CN101798115A (en) * | 2010-02-26 | 2010-08-11 | 中山大学 | Preparation method of ternary oxysalt compound micro-nano material |
| CN105118986A (en) * | 2015-08-28 | 2015-12-02 | 洛阳理工学院 | Preparation method for nickel-cobalt lithium manganate serving as high-performance lithium ion battery positive electrode material |
| CN106744857A (en) * | 2016-12-30 | 2017-05-31 | 尹宗杰 | 3D printing Graphene metallic composite, preparation method and application |
-
2017
- 2017-11-16 CN CN201711134253.8A patent/CN107978740A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915837A (en) * | 1998-11-09 | 2007-02-21 | 美商纳克公司 | Metal oxide particles |
| CN101798115A (en) * | 2010-02-26 | 2010-08-11 | 中山大学 | Preparation method of ternary oxysalt compound micro-nano material |
| CN105118986A (en) * | 2015-08-28 | 2015-12-02 | 洛阳理工学院 | Preparation method for nickel-cobalt lithium manganate serving as high-performance lithium ion battery positive electrode material |
| CN106744857A (en) * | 2016-12-30 | 2017-05-31 | 尹宗杰 | 3D printing Graphene metallic composite, preparation method and application |
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