CN106784618A - A kind of layered cathode material of lithium ion battery of surface coating decoration and preparation method thereof - Google Patents
A kind of layered cathode material of lithium ion battery of surface coating decoration and preparation method thereof Download PDFInfo
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- CN106784618A CN106784618A CN201611173939.3A CN201611173939A CN106784618A CN 106784618 A CN106784618 A CN 106784618A CN 201611173939 A CN201611173939 A CN 201611173939A CN 106784618 A CN106784618 A CN 106784618A
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- ion battery
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- lithium ion
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- layered 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
- H01M4/13—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
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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
- H01M4/139—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
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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
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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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Abstract
The invention discloses a kind of layered cathode material of lithium ion battery of surface coating decoration and preparation method thereof, comprise the following steps：(1) synthetic graphite type carbonitride, melamine powder is prepared the graphite type carbon nitride of yellow block shape, is then stripped into laminar graphite type carbon nitride, forms uniform graphite type carbon nitride dispersion liquid；(2) synthesis of anode material of lithium-ion battery dispersion liquid, layered cathode material of lithium ion battery dispersion liquid is dissolved into by layered cathode material of lithium ion battery；(3) layered cathode material of lithium ion battery dispersion liquid is added to graphite type carbon nitride dispersion liquid and mixed by the anode material for lithium-ion batteries of synthetic surface cladding, then suction filtration, drying, and grinding obtains final product surface coated anode material for lithium-ion batteries.Preparation method of the invention has that security is good, specific capacity is high, with low cost and excellent cycle performance the characteristics of.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries technical field, specially a kind of lithium-ion electric of surface coating decoration
Pond layered cathode material and preparation method thereof.
Background technology
Lithium ion battery is a kind of a kind of novel battery grown up on the basis of lithium battery, relies primarily on lithium ion and exists
Movement carrys out work between positive pole and negative pole.Its chemical property depends primarily on electrode material, the selection of electrode material and quality
Directly decide the characteristic and price of lithium ion battery.But for a long time, anode material for lithium-ion batteries is limiting lithium ion
The key factor of battery development, and directly affect the energy density and specific power characteristic of battery.Current commercialized lithium ion
Cell positive material is typically all using cobalt acid lithium, LiMn2O4, LiFePO 4 and ternary material etc., but they are in environment friend
There are many shortcomings in the aspects such as good, cyclical stability, this also constrains their commercial application.Layer structure containing lithium metal
The oxide such as positive electrode such as nickel cobalt manganese eyes material, cobalt acid lithium is because electrical conductivity is higher, high rate performance is preferable, theoretical specific capacity is high
And be widely used, but they only have 140 ~ 160mAh/ in the specific capacity that the charging voltage of conventional 4.2V can actually be released
G, will such as obtain more height ratio capacity, then need to charge to more than 4.35V.Traditional stratiform oxide anode material in high voltage for example
Capacitance loss is more in cyclic process under the charge condition of more than 4.35V, and cyclical stability is poor, it is impossible to meet commercial applications,
And there is larger potential safety hazard..
The content of the invention
Layered cathode material of lithium ion battery and its preparation side it is an object of the invention to provide a kind of surface coating decoration
Method, with security it is good, specific capacity is high, with low cost and excellent cycle performance the characteristics of.
The present invention can be achieved through the following technical solutions：
The invention discloses a kind of preparation method of the layered cathode material of lithium ion battery of surface coating decoration, including following step
Suddenly：
(1) synthetic graphite type carbonitride
Melamine powder is heated to 550 DEG C of thermal polymerization 4h, 20 DEG C/min of programming rate, the graphite mould of yellow block shape is obtained
, then be put into graphite type carbon nitride in beaker by carbonitride, adds 200ml methanol solution ultrasonic disperse 5h, the graphite of block shape
Type carbonitride carbon is stripped into laminar graphite type carbon nitride, forms uniform graphite type carbon nitride dispersion liquid；
(2) synthesis of anode material of lithium-ion battery dispersion liquid
Layered cathode material of lithium ion battery is added to 25 DEG C of dispersed with stirring 1h in 100ml methanol solutions first, rotating speed is
500r/min, obtains layered cathode material of lithium ion battery dispersion liquid；
(3) anode material for lithium-ion batteries of synthetic surface cladding
Layered cathode material of lithium ion battery dispersion liquid is added to 25 DEG C of stirring 24h, rotating speed in graphite type carbon nitride dispersion liquid
It is 700r/min, then suction filtration, drying, grinding, obtain final product surface coated anode material for lithium-ion batteries.
Further, the quality of the block graphite type carbon nitride is the 0.5%~5% of electrode material.
Further, the anode material for lithium-ion batteries is cobalt acid lithium, LiMn2O4 and/or nickel-cobalt-manganese ternary material.
A kind of layered cathode material of lithium ion battery of surface coating decoration, is prepared using the preparation method of the above.
A kind of preparation method of the layered cathode material of lithium ion battery of surface coating decoration of the present invention, has with following
Beneficial effect：
Firstth, security is good, the layered cathode material of lithium ion battery of surface coating decoration of the invention, the graphite mould of its cladding
Carbonitride is in chemical inertness, at high temperature under high pressure good stability, can effectively prevent the part point of positive electrode metal oxide
Solution（These decompose the product for producing can cause the unsafe problems such as battery flatulence, blast to the catalytic decomposition of electrolyte) so that
Improve the cyclical stability and security performance under battery high pressure；
Secondth, specific capacity is high, and appropriate graphite type carbon nitride has embedding lithium function, is conducive to the fortune of lithium ion in charge and discharge process
It is defeated, so as to improve the specific capacity of lithium ion battery；
3rd, it is with low cost, the layered cathode material of lithium ion battery of surface coating decoration of the invention, due to its preparation process
In raw material used be cheap carbonitride, and wide material sources, therefore it is the characteristics of have preparation cost low；
4th, cycle performance is excellent, and the layered cathode material of lithium ion battery of surface coating decoration of the invention is fabricated to lithium ion
When battery is used, compared with traditional anode material for lithium-ion batteries, in the survey of Application Example and application comparative examples
Can intuitively be found very much in examination, specific capacity and cyclical stability all improve a lot, therefore, the lithium of the surface coating decoration
Ion battery positive electrode make anode slice of lithium ion battery using having that specific capacity is high, good cycling stability and have a safety feature
The advantages of.
Brief description of the drawings
Fig. 1 is embodiment 1~4, the cycle performance curve map of comparative example 1.
Fig. 2 for embodiment 5 first, the charging/discharging voltage curve map of 50 times and 100 times.
Fig. 3 is the scanning electron microscope (SEM) photograph of embodiment 6.
Fig. 4 is the transmission electron microscope comparison diagram of comparative example 2 and embodiment 6.
Specific embodiment
In order that those skilled in the art will better understand the technical solution of the present invention, with reference to embodiment and to this
Invention product is described in further detail.
It is by following preparation side the invention discloses a kind of layered cathode material of lithium ion battery of surface coating decoration
Prepared by method：
(1) synthetic graphite type carbonitride
Melamine powder is heated to 550 DEG C of thermal polymerization 4h, 20 DEG C/min of programming rate, the graphite mould of yellow block shape is obtained
, then be put into graphite type carbon nitride in beaker by carbonitride, adds 200ml methanol solution ultrasonic disperse 5h, the graphite of block shape
Type carbonitride carbon is stripped into laminar graphite type carbon nitride, forms uniform graphite type carbon nitride dispersion liquid；
(2) synthesis of anode material of lithium-ion battery dispersion liquid
Layered cathode material of lithium ion battery is added to 25 DEG C of dispersed with stirring 1h in 100ml methanol solutions first, rotating speed is
500r/min, obtains layered cathode material of lithium ion battery dispersion liquid；
(3) anode material for lithium-ion batteries of synthetic surface cladding
Layered cathode material of lithium ion battery dispersion liquid is added to 25 DEG C of stirring 24h, rotating speed in graphite type carbon nitride dispersion liquid
It is 700r/min, then suction filtration, drying, grinding, obtain final product surface coated anode material for lithium-ion batteries.
In the present invention, the quality of the block graphite type carbon nitride is the 0.5%~5% of electrode material.
In the present invention, the anode material for lithium-ion batteries is cobalt acid lithium, LiMn2O4 and/or nickel-cobalt-manganese ternary material.
In order to assess the performance of resulting materials of the present invention, the positive electrode of gained is prepared into anode pole piece carries out performance survey
Try, specific preparation method is：Take 0.8g anode material for lithium-ion batteries obtained above, 0.1gSuper P, 0.1gPVDF bondings
Agent, grinds to form color uniformity, adds 1-METHYLPYRROLIDONE（NMP）Mechanical agitation 5h, is uniformly applied on aluminium foil, is first placed in
80 DEG C commonly dry 1h in vacuum drying chamber, and then 120 DEG C of vacuum drying 12h are to be obtained anode slice of lithium ion battery.
In the present invention, solvent for use 1-METHYLPYRROLIDONE（NMP）, analyze pure, the limited public affairs of Chinese medicines group chemical reagent
Department's production；Melamine used, Chemical Reagent Co., Ltd., Sinopharm Group's production；PVDF used（Kynoar）Gluing
Agent, Super P are purchased from brilliant limited production company of Shenzhen section.One is entered to technical scheme below in conjunction with specific embodiment
Step is illustrated：
Meanwhile, only to include the positive plate of 523 nickel-cobalt-manganese ternary materials as a comparison case 1, only to contain cobalt acid lithium material
Anode pole piece contrasts comparative example 2, and comparative example 1 is identical with the pole piece preparation method and embodiment 1~8 of comparative example 2.
In order to further assess performance of the invention, with the lithium ion battery obtained by embodiment 1~8, comparative example 1~2
Anode pole piece is working electrode, using lithium metal as reference electrode, with 1mol/L LiPF6/ EC/DMC (volume ratios 1：1) it is electricity
Solution liquid, barrier film is UBE3025, is combined into button cell, in high accuracy battery Performance Test System（The new Weir electronics in Shenzhen is limited
Company, model CT-3008-5V1mA）On carry out electro-chemical test, test multiplying power is 0.5C, test voltage scope is 2.5 ~
4.4V, the data for measuring are as shown in table 1：
The different embodiment the performance test results of table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative example 1 | Comparative example 2 | |
| Initial reversible specific capacity (mAh/g) | 182 | 194 | 181 | 177 | 189 | 197 | 181 | 178 | 142 | 144 |
| First discharge and recharge coulombic efficiency (%) | 89 | 93 | 87 | 88 | 86 | 92 | 87 | 89 | 79 | 76 |
| Specific capacity (mAh/g) after 100 circulations | 163 | 180 | 162 | 155 | 171 | 183 | 164 | 160 | 96 | 95 |
| 100 circulation volume conservation rates (%) | 89.6 | 92.8 | 89.5 | 87.6 | 90.5 | 92.9 | 90.6 | 89.9 | 67.6 | 66.0 |
From table 1 this it appears that through the layered cathode material of lithium ion battery of surface coating decoration, compared to traditional commercialization
Layered cathode material of lithium ion battery, either specific capacity or cyclical stability be all significantly improved, be indicated above use
Not only specific capacity is improved the layered cathode material of lithium ion battery of surface coating decoration of the invention, while there is good circulation steady
Qualitative and security performance.
The above, only presently preferred embodiments of the present invention not makees any formal limitation to the present invention；It is all
The those of ordinary skill of the industry can described in by specification and the above and swimmingly implement the present invention；But, it is all to be familiar with
Professional and technical personnel without departing from the scope of the present invention, makes using disclosed above technology contents
A little variation, modification and evolution equivalent variations, be Equivalent embodiments of the invention；Meanwhile, it is all according to reality of the invention
Variation, modification and evolution of any equivalent variations that matter technology is made to above example etc., still fall within technology of the invention
Within the protection domain of scheme.
Claims (4)
1. a kind of preparation method of the layered cathode material of lithium ion battery of surface coating decoration, it is characterised in that including following step
Suddenly：
(1) synthetic graphite type carbonitride
Melamine powder is heated to 550 DEG C of thermal polymerization 4h, 20 DEG C/min of programming rate, the graphite mould of yellow block shape is obtained
, then be put into graphite type carbon nitride in beaker by carbonitride, adds 200ml methanol solution ultrasonic disperse 5h, the graphite of block shape
Type carbonitride carbon is stripped into laminar graphite type carbon nitride, forms uniform graphite type carbon nitride dispersion liquid；
(2) synthesis of anode material of lithium-ion battery dispersion liquid
Layered cathode material of lithium ion battery is added to 25 DEG C of dispersed with stirring 1h in 100ml methanol solutions first, rotating speed is
500r/min, obtains layered cathode material of lithium ion battery dispersion liquid；
(3) anode material for lithium-ion batteries of synthetic surface cladding
Layered cathode material of lithium ion battery dispersion liquid is added to 25 DEG C of stirring 24h, rotating speed in graphite type carbon nitride dispersion liquid
It is 700r/min, then suction filtration, drying, grinding, obtain final product surface coated anode material for lithium-ion batteries.
2. the preparation method of the layered cathode material of lithium ion battery of surface coating decoration according to claim 1, it is special
Levy and be：The quality of the block graphite type carbon nitride is the 0.5%~5% of electrode material.
3. the preparation method of the layered cathode material of lithium ion battery of surface coating decoration according to claim 1, it is special
Levy and be：The anode material for lithium-ion batteries is cobalt acid lithium, LiMn2O4 and/or nickel-cobalt-manganese ternary material.
4. a kind of layered cathode material of lithium ion battery of surface coating decoration, it is characterised in that any using claims 1 to 3
Preparation method described in item claim is prepared.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107689272A (en) * | 2017-08-25 | 2018-02-13 | 南昌航空大学 | One species graphene carbonitride Modification on Al adulterates the preparation method of ZnO transparent conductive thin film |
| CN108011097A (en) * | 2017-11-28 | 2018-05-08 | 中国科学院大学 | A kind of preparation method for the anode material for lithium-ion batteries for improving chemical property |
| CN108232153A (en) * | 2017-12-30 | 2018-06-29 | 国联汽车动力电池研究院有限责任公司 | A kind of lithium ion battery nickeliferous layered cathode material/carbon composite and preparation method thereof |
| CN109065889A (en) * | 2018-08-20 | 2018-12-21 | 中南大学 | All-solid-state lithium battery and preparation method thereof |
| CN109686963A (en) * | 2019-01-31 | 2019-04-26 | 新奥石墨烯技术有限公司 | A kind of LiFePO4 class graphene composite material synthetic method |
| CN112615074A (en) * | 2021-01-27 | 2021-04-06 | 湖南清锋新材料科技有限公司 | Secondary battery electrolyte and preparation method thereof |
| CN113937264A (en) * | 2021-09-28 | 2022-01-14 | 桂林理工大学 | Preparation method of nitrogen compound modified manganese vanadate at normal temperature and application of nitrogen compound modified manganese vanadate in water-based zinc ion battery |
| CN114843486A (en) * | 2022-05-27 | 2022-08-02 | 江苏理工学院 | Lithium ion battery |
| CN114914420A (en) * | 2022-05-17 | 2022-08-16 | 长沙理工大学 | Dual-modified lithium ion battery negative electrode material and preparation method thereof |
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| CN103232458A (en) * | 2013-04-25 | 2013-08-07 | 大连理工大学 | Method for preparing graphite phase carbon nitride material with monatomic layer structure |
| CN105206809A (en) * | 2015-09-11 | 2015-12-30 | 合肥国轩高科动力能源有限公司 | C3N4-carbon-coated lithium iron phosphate composite anode material and preparation method thereof |
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| CN103232458A (en) * | 2013-04-25 | 2013-08-07 | 大连理工大学 | Method for preparing graphite phase carbon nitride material with monatomic layer structure |
| CN105206809A (en) * | 2015-09-11 | 2015-12-30 | 合肥国轩高科动力能源有限公司 | C3N4-carbon-coated lithium iron phosphate composite anode material and preparation method thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107689272A (en) * | 2017-08-25 | 2018-02-13 | 南昌航空大学 | One species graphene carbonitride Modification on Al adulterates the preparation method of ZnO transparent conductive thin film |
| CN107689272B (en) * | 2017-08-25 | 2019-02-05 | 南昌航空大学 | The preparation method of one type graphene carbonitride Modification on Al doping ZnO transparent conductive thin film |
| CN108011097A (en) * | 2017-11-28 | 2018-05-08 | 中国科学院大学 | A kind of preparation method for the anode material for lithium-ion batteries for improving chemical property |
| CN108232153B (en) * | 2017-12-30 | 2020-11-27 | 国联汽车动力电池研究院有限责任公司 | Nickel-containing layered positive electrode material/carbon composite material for lithium ion battery and preparation method thereof |
| CN108232153A (en) * | 2017-12-30 | 2018-06-29 | 国联汽车动力电池研究院有限责任公司 | A kind of lithium ion battery nickeliferous layered cathode material/carbon composite and preparation method thereof |
| CN109065889A (en) * | 2018-08-20 | 2018-12-21 | 中南大学 | All-solid-state lithium battery and preparation method thereof |
| CN109686963A (en) * | 2019-01-31 | 2019-04-26 | 新奥石墨烯技术有限公司 | A kind of LiFePO4 class graphene composite material synthetic method |
| CN112615074A (en) * | 2021-01-27 | 2021-04-06 | 湖南清锋新材料科技有限公司 | Secondary battery electrolyte and preparation method thereof |
| CN113937264A (en) * | 2021-09-28 | 2022-01-14 | 桂林理工大学 | Preparation method of nitrogen compound modified manganese vanadate at normal temperature and application of nitrogen compound modified manganese vanadate in water-based zinc ion battery |
| CN113937264B (en) * | 2021-09-28 | 2023-12-19 | 桂林理工大学 | Preparation method of carbon-nitrogen compound modified manganese vanadate at normal temperature and application of carbon-nitrogen compound modified manganese vanadate in water-based zinc ion battery |
| CN114914420A (en) * | 2022-05-17 | 2022-08-16 | 长沙理工大学 | Dual-modified lithium ion battery negative electrode material and preparation method thereof |
| CN114914420B (en) * | 2022-05-17 | 2023-12-05 | 长沙理工大学 | Double-modified lithium ion battery anode material and preparation method thereof |
| CN114843486A (en) * | 2022-05-27 | 2022-08-02 | 江苏理工学院 | Lithium ion battery |
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