CN105226251A - A kind of pure carbon compound cathode materials and preparation method thereof - Google Patents
A kind of pure carbon compound cathode materials and preparation method thereof Download PDFInfo
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- CN105226251A CN105226251A CN201510590301.9A CN201510590301A CN105226251A CN 105226251 A CN105226251 A CN 105226251A CN 201510590301 A CN201510590301 A CN 201510590301A CN 105226251 A CN105226251 A CN 105226251A
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- cathode materials
- carbon compound
- compound cathode
- graphite
- pure carbon
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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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- 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
- H01M4/58—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 invention provides a kind of pure carbon compound cathode materials, this composite negative pole material take spherical natural graphite as core, and the coating layer being 10-15nm through Jacket thickness forms, and described coating layer is that amorphous carbon and outermost micro crystal graphite form by secondary skin.Present invention also offers a kind of preparation method simultaneously, specifically amorphous carbon is dissolved in decentralized medium, adds spherical natural graphite, add defoamer; Be placed in mixing hollander again and stir, the slurry obtained carries out being atomized in spray dryer, dry and granulation obtains powder material; Finally the powder material obtained is placed in stove and carries out nitrogen atmosphere heat treatment, treated powder is pure carbon compound cathode materials after being cooled to room temperature.Specific capacity superelevation, the good cycling stability of the pure material with carbon element of pure carbon compound cathode materials of the present invention; Micro crystal graphite and amorphous carbon exist simultaneously, effectively can disperse the stress of the embedding lithium accumulation of the degree of depth, thus suppress to peel off because of graphite synusia the capacity attenuation phenomenon caused.
Description
Technical field
The present invention relates to pure carbon compound cathode materials of a kind of high-energy-density and preparation method thereof, belong to electrochemical power source technical field.
Background technology
Energy density is large, open circuit voltage is high because having for lithium ion battery, have extended cycle life, self discharge is little, memory-less effect and the advantage such as pollution-free, becomes the secondary cell the most extensively adopted in portable type electronic product.But along with portable type electronic product miniaturization and lithium ion battery, the demand in aviation, military affairs and automobile industry is day by day vigorous, and capacity and the energy density of battery all urgently increase substantially.At present, commercial lithium-ion batteries mainly adopts the modified natural graphite and Delanium with excellent cycling performance as negative material.But such material also also exist cycle performance difference, with compatibility of electrolyte is poor, high rate performance is bad etc. shortcoming.With regard to artificial graphite material, its reversible specific capacity maintains 330mAhg
-1(theoretical capacity of graphite is 372mAhg
-1), its cycle performance is undesirable, and raw material (pitch class aromatic compound) price fluctuation is large.
In recent years, research for reversible embedding/de-lithium titanate cathode material is very active, except modified graphite and Delanium, much research aims at Novel high-specific capacity flexible negative material: storage lithium metal and oxide thereof are (as Sn, and lithium transition-metal phosphide Si), these materials embedding/de-lithium time there is huge bulk effect, easily break and efflorescence, thus lose the contact with collector, cause cycle performance sharply to decline; These Novel anode materials is embedding simultaneously/de-lithium voltage platform higher (being greater than 0.5V), and it is unfavorable that the energy density for material improves.
At present, modified natural graphite negative material due to good cycling stability, operating potential low (being about 0.2V), higher (the > 350mAhg of reversible capacity
-1), the advantage such as the low and preparation technology of preparation cost is simple, captured most of commercial Li-ion battery negative material market.Material specific capacity is brought up to 360mAhg by modification work for graphite cathode
-1left and right, current material architecture basics continues little (the pure graphite theoretical capacity limits 372mAhg in space of hoist capacity
-1).Therefore, the present invention, by the pure carbon compound cathode materials of high-energy-density of a kind of novel structure of preparation, is significantly promoting material specific capacity (420mAhg
-1) basis on, keep embedding/de-lithium characteristic (embedding/de-lithium voltage platform is less than 0.2V) of graphite cathode material excellence, finally significantly promote the energy density of material.
Summary of the invention
The object of the present invention is to provide a kind of pure carbon compound cathode materials and preparation method thereof, wherein pure carbon compound cathode materials has high-energy high density, this composite negative pole material take spherical natural graphite as core, the coating layer being 10-15nm through Jacket thickness forms, described coating layer is that amorphous carbon and outermost micro crystal graphite form by secondary skin, by weight, amorphous carbon is 5%-15%, and spherical natural graphite is 85%-95%." ordering " of micro crystal graphite is conducive to the transmission of electric charge in charge and discharge process, improves its cycle performance; Micro crystal graphite not only efficiently avoid native graphite with the existence of amorphous carbon and contacts with the direct of electrolyte, and has effectively disperseed the stress of the embedding lithium accumulation of the degree of depth, thus inhibits because graphite synusia peels off the capacity attenuation phenomenon caused; The defect that micro crystal graphite and amorphous carbon exist can provide extra storage lithium space, and this makes material while low embedding/de-lithium voltage platform of maintenance graphite cathode, the specific capacity far above existing graphite cathode material that also can discharge.
The negative material of gained of the present invention, while significantly improving reversible capacity, can keep the voltage curve feature of graphite cathode, and discharge and recharge reaction generation less than 0.2 volt.
Described amorphous carbon comprises any one in citric acid, glucose, sucrose, and its purity is all greater than 99%.
The particle diameter of described spherical natural graphite is 10 ~ 25 μm, and its purity is all greater than 99%.
Described secondary skin is at least one deck, is preferably layer 2-3.
Described outermost layer is at least one deck, is preferably 3-5 layer.
The preparation method of the pure carbon compound cathode materials of high-energy-density of the present invention: first amorphous carbon, spherical natural graphite and decentralized medium are mixed, add after defoamer and stir, gained slurry carries out being atomized in spray dryer, dry and granulation obtains powder material; The high temperature graphitization stove powder material obtained being placed in nitrogen protection is heat-treated, and after powder is cooled to room temperature, grinds, sieves, and namely obtains the pure carbon compound cathode materials of high-energy-density.The negative material obtained and acetylene black, Kynoar (PVdF) are stirred into slurry by certain mass than in 1-METHYLPYRROLIDONE (NMP) medium, coats on Copper Foil, make the pure carbon compound cathode electrode of high-energy-density through super-dry, press mold.
Described decentralized medium is water or alcohol.
Described heat treatment is carried out in two steps: after 600 ~ 800 ° of C are incubated 2 ~ 4h, and 900 ~ 2900 ° of C are incubated 3 ~ 7h.
The pure carbon compound cathode materials of high-energy-density of the present invention has following advantage compared with existing graphite cathode material: specific capacity superelevation, the good cycling stability of (1) pure material with carbon element; (2) micro crystal graphite and amorphous carbon exist simultaneously, effectively can disperse the stress of the embedding lithium accumulation of the degree of depth, thus suppress to peel off because of graphite synusia the capacity attenuation phenomenon caused; (3) there is a large amount of defects in micro crystal graphite and amorphous carbon, can provide extra storage lithium space; (4) doff lithium voltage platform low (lower than 0.2V); (5) synthesis technique is simple, is easy to industrialization; (6) material preparation cost is cheap, pollutes little; (7) preparation process is without noxious gas emission.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph of embodiment 4 sample.
Fig. 2 is the high resolution transmission electron microscope photo of embodiment 4 sample.
Fig. 3 is the chemical property curve of embodiment 4 sample.
Embodiment
Below by the description of embodiment and comparative example, set forth substantive distinguishing features of the present invention and advantage further.For convenience of description, first comparative example is described, and then described embodiment, compared with it, demonstrated effect of the present invention.
comparative example 1
By natural spherical plumbago micro mist and Kynoar (PVdF) by mass ratio furnishing slurry in 1-METHYLPYRROLIDONE (NMP) medium of 9:1, coat on Copper Foil, make work electrode through super-dry, press mold.Be to electrode with metallic lithium foil, Celgard2400 is barrier film, 1MLiPF
6/ (EC+DMC) (1:1) carries out constant current charge-discharge test for electrolyte is assembled into battery, and current density is 0.15mA/cm
2, voltage range is between 0 ~ 1.5V.Embedding lithium capacity is 395.6mAhg first
-1, de-lithium capacity is 317.8mAhg
-1, coulombic efficiency is 80.35%; The embedding lithium capacity that circulates for 100th time is 192.6mAhg
-1, de-lithium capacity is 192.4mAhg
-1.The bad explanation of cyclical stability directly with natural spherical plumbago micro mist for directly contacting with electrolyte because of graphite when active material prepares electrode, make solvation Lithium-ion embeding graphite flake layer, cause graphite occur when degree of depth discharge and recharge peel off lost efficacy.
embodiment 1
Citric acid, spherical natural graphite and decentralized medium are mixed, adds defoamer and stir, the slurry obtained carries out being atomized in spray dryer, dry and granulation obtains powder material.The powder material obtained is placed in nitrogen protection high temperature graphitization stove, be first incubated 2h at 800 ° of C, then sinter 3h under 900 ° of C, after being cooled to room temperature, grind, sieve, the material marking obtained is G/C-900.By G/C-900 and Kynoar (PVdF) by mass ratio furnishing slurry in 1-METHYLPYRROLIDONE (NMP) medium of 9:1, coat on Copper Foil, make work electrode through super-dry, press mold.Be to electrode with metallic lithium foil, Celgard2400 is barrier film, 1MLiPF
6/ (EC+DMC) (1:1) carries out constant current charge-discharge test for electrolyte is assembled into battery, and current density is 0.15mA/cm
2, voltage range is between 0 ~ 1.5V.Embedding lithium capacity is 432.5mAhg first
-1, de-lithium capacity is 356.5mAhg
-1, coulombic efficiency is 82.43%; The embedding lithium capacity that circulates for 100th time is 288.9mAhg
-1, de-lithium capacity is 288.7mAhg
-1, the cyclical stability of material improves.
embodiment 2
Citric acid, spherical natural graphite and decentralized medium are mixed, adds defoamer and stir, the slurry obtained carries out being atomized in spray dryer, dry and granulation obtains powder material.The powder material obtained is placed in nitrogen protection high temperature graphitization stove, be first incubated 2h at 800 ° of C, then sinter 3h under 1200 ° of C, after being cooled to room temperature, grind, sieve, the material marking obtained is G/C-1200.By G/C-1200 and Kynoar (PVdF) by mass ratio furnishing slurry in 1-METHYLPYRROLIDONE (NMP) medium of 9:1, coat on Copper Foil, make work electrode through super-dry, press mold.Be to electrode with metallic lithium foil, Celgard2400 is barrier film, 1MLiPF
6/ (EC+DMC) (1:1) carries out constant current charge-discharge test for electrolyte is assembled into battery, and current density is 0.15mA/cm
2, voltage range is between 0 ~ 1.5V.Embedding lithium capacity is 453.9mAhg first
-1, de-lithium capacity is 398.2mAhg
-1, coulombic efficiency is 87.73%; The embedding lithium capacity that circulates for 100th time is 364.4mAhg
-1, de-lithium capacity is 363.8mAhg
-1, material circulation stability be improved significantly, and reversible capacity is close to the theoretical capacity (372mAhg of graphite
-1).
embodiment 3
Citric acid, spherical natural graphite and decentralized medium are mixed, adds defoamer and stir, the slurry obtained carries out being atomized in spray dryer, dry and granulation obtains powder material.The powder material obtained is placed in nitrogen protection high temperature graphitization stove, be first incubated 2h at 800 ° of C, then sinter 3h under 1500 ° of C, after being cooled to room temperature, grind, sieve, the material marking obtained is G/C-1500.By G/C-1500 and Kynoar (PVdF) by mass ratio furnishing slurry in 1-METHYLPYRROLIDONE (NMP) medium of 9:1, coat on Copper Foil, make work electrode through super-dry, press mold.Be to electrode with metallic lithium foil, Celgard2400 is barrier film, 1MLiPF
6/ (EC+DMC) (1:1) carries out constant current charge-discharge test for electrolyte is assembled into battery, and current density is 0.15mA/cm
2, voltage range is between 0 ~ 1.5V.Embedding lithium capacity is 482.4mAhg first
-1, de-lithium capacity is 410.8mAhg
-1, coulombic efficiency is 85.16%; The embedding lithium capacity that circulates for 100th time is 385.4mAhg
-1, de-lithium capacity is 385.4mAhg
-1, the cyclical stability of material is further improved, and reversible capacity is greater than the theoretical capacity of graphite.
embodiment 4
Citric acid, spherical natural graphite and decentralized medium are mixed, adds defoamer and stir, the slurry obtained carries out being atomized in spray dryer, dry and granulation obtains powder material.The powder material obtained is placed in nitrogen protection high temperature graphitization stove, be first incubated 2h at 800 ° of C, then sinter 3h under 2900 ° of C, after being cooled to room temperature, grind, sieve, the material marking obtained is G/C-2900.By G/C-2900 and Kynoar (PVdF) by mass ratio furnishing slurry in 1-METHYLPYRROLIDONE (NMP) medium of 9:1, coat on Copper Foil, make work electrode through super-dry, press mold.Be to electrode with metallic lithium foil, Celgard2400 is barrier film, 1MLiPF
6/ (EC+DMC) (1:1) carries out constant current charge-discharge test for electrolyte is assembled into battery, and current density is 0.15mA/cm
2, voltage range is between 0 ~ 1.5V.Embedding lithium capacity is 470.8mAhg first
-1, de-lithium capacity is 403.1mAhg
-1, coulombic efficiency is 85.63%; The embedding lithium capacity that circulates for 100th time is 421.8mAhg
-1, de-lithium capacity is 421.3mAhg
-1.Cyclical stability significantly improves, and reversible capacity is far above the theoretical capacity of graphite.
Claims (7)
1. a pure carbon compound cathode materials, this negative material is while significantly improving reversible capacity, the voltage curve feature of graphite cathode can be kept, and discharge and recharge reaction generation less than 0.2 volt, it is characterized in that: this composite negative pole material take spherical natural graphite as core, and the coating layer being 10-15nm through Jacket thickness forms, described coating layer is that amorphous carbon and outermost micro crystal graphite form by secondary skin, by weight, amorphous carbon is 5%-15%, and spherical natural graphite is 85%-95%.
2. pure carbon compound cathode materials according to claim 1, it is characterized in that: described amorphous carbon comprises any one in citric acid, glucose, sucrose, its purity is all greater than 99%.
3. pure carbon compound cathode materials according to claim 1, is characterized in that: the particle diameter of described spherical natural graphite is 10 ~ 25 μm, and its purity is all greater than 99%.
4. pure carbon compound cathode materials according to claim 1, is characterized in that: described secondary skin is at least one deck, is preferably layer 2-3.
5. pure carbon compound cathode materials according to claim 1, is characterized in that: described outermost layer is at least one deck, is preferably 3-5 layer.
6. the preparation method of the pure carbon compound cathode materials described in any one of claim 1-5, is characterized in that: comprise the steps: that amorphous carbon is dissolved in decentralized medium by (1), add spherical natural graphite, adds defoamer; (2) be placed in mixing hollander and stir, the slurry obtained carries out being atomized in spray dryer, dry and granulation obtains powder material; (3) powder material obtained is placed in stove and carries out nitrogen atmosphere heat treatment, treated powder is pure carbon compound cathode materials after being cooled to room temperature.
7. the method preparing the pure carbon compound cathode materials of high-energy-density according to claim 6, is characterized in that: the decentralized medium in step (1) is water or alcohol; After 600 ~ 800 ° of C insulation 2 ~ 3h in a nitrogen atmosphere in step (3), then sinter 3 ~ 7h at 900 ~ 2900 ° of C.
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Cited By (3)
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| CN107673347A (en) * | 2017-10-31 | 2018-02-09 | 湖南国盛石墨科技有限公司 | A kind of preparation method of spherical micro crystal graphite |
| TWI631077B (en) * | 2016-09-06 | 2018-08-01 | 財團法人工業技術研究院 | Graphite composite structure, method of fabricating the same and composite electrode of the same |
| CN111613785A (en) * | 2020-05-28 | 2020-09-01 | 贝特瑞新材料集团股份有限公司 | Composite coated negative electrode material, preparation method thereof and lithium ion battery |
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Application publication date: 20160106 |