CN109461934A - Electrode material and secondary battery - Google Patents
Electrode material and secondary battery Download PDFInfo
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- CN109461934A CN109461934A CN201710796211.4A CN201710796211A CN109461934A CN 109461934 A CN109461934 A CN 109461934A CN 201710796211 A CN201710796211 A CN 201710796211A CN 109461934 A CN109461934 A CN 109461934A
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- electrode material
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- average grain
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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
-
- 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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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 discloses an electrode material and a secondary battery. The electrode material is a graphitized carbon material, the graphitization degree of the graphitized carbon material is 92-97%, and the average particle size Dv50 is 8-15 mu m. A lithium ion secondary battery using the electrode material can have both high capacity and good cycle stability.
Description
Technical field
The invention belongs to battery technology field, it is more particularly related to a kind of electrode material and use the material
Secondary cell.
Background technique
With becoming increasingly popular for electric car, the requirement to battery is also increasingly stringenter.It is good again high capacity should to be possessed
Good cyclical stability.Important component of the electrode material as lithium ion battery plays key to the promotion of battery performance
Property effect.Wherein, graphite material has good charging/discharging voltage platform, the battery of composition preferable with positive electrode matching
Average output voltage is high.In addition, graphite material also has the advantages that preferable stability and lower cost, it is that a kind of performance is excellent
Different electrode material, the large-scale application on lithium ion battery.
The capacity of usual electrode material and first effect are affected to the performance of battery.The electrode material of low capacity will lead to electricity
The energy density in pond is low, and the course continuation mileage of corresponding battery is insufficient；Low its surface-active site of electrode material of low first effect is more, charge and discharge
Side reaction in electric process increases.It is secondary since the generation of side reaction will generate a series of by-products in the use process of battery
Product will deteriorate to certain degree the cycle performance of battery in the accumulation of electrode material.
Therefore in the secondary battery, how to guarantee that battery under the premise of with high capacity, combines cyclical stability
It is a problem to be solved.
Summary of the invention
In view of above-mentioned secondary cell there are the problem of, it is necessory to provide a kind of electrode material for being able to solve the above problem
Material.
In order to achieve the above object, it is graphitized carbon material this application provides a kind of electrode material, while meets stone
Mo Huadu is 92%-97%, and average grain diameter Dv50 is 8-15 μm.
Inventors have found that degree of graphitization and material particle size of graphitized carbon material etc. can unexpectedly change by optimization
Kind battery performance, especially energy density and cyclical stability.Specifically, when inventor has found that degree of graphitization is lower than 92%, material
The gram volume and actual use compacted density of material do not reach requirement；When degree of graphitization is higher than 97%, its duct is tied under high densification
Structure influences electrolyte distribution, to influence the long-term cycle performance of battery vulnerable to destruction；When Dv50 is less than 8 μm, material surface
There are more active sites, side reaction is more during first charge-discharge, and coulombic efficiency is relatively low for the first time；When Dv50 is greater than 15 μm,
The dynamic performance of material is poor, and the long-term cycle performance of battery is affected.
In the present invention, the degree of graphitization of the electrode material is 92-97%, preferred scope 93-95%.
In the present invention, the Dv50 of the electrode material is 8-15 μm, 9-12 μm of preferred scope.
In order to further increase dynamic performance (the especially high rate performance of battery), the material surface can also have packet
Coating.Clad is usually amorphous carbon, such as selected from least one of carbon black, coke, soft carbon, hard carbon.The amorphous carbon
Content relative to the electrode material total weight is usually 3-10%, preferably 5-9%.In some embodiments, the nothing
Setting carbon is by selected from least one of polyvinyl butyral, pitch, furfural resin, epoxy resin or phenolic resin material
Through obtained from (high temperature) charing.
Compared with prior art, electrode material provided by the invention, by controlling degree of graphitization and material particle size one
Determine in range, can effectively maintain stability and cellular structure of the material in cyclic process so that the active material of anode it
Between contact interface keep complete, promote material circulation performance.By this material in the secondary battery, battery can be made to have
Under the premise of high capacity, cyclical stability is combined.It is that can not pass through based on existing theoretical and experience, the improvement of these performances
What the parameters such as degree of graphitization, partial size were simply calculated or were predicted, but must be just detectable by a large amount of arduous experiments.
In the present invention, " graphitized carbon material " has the normally understood meaning of those skilled in the art institute, that is, is suitable for
Inside for battery electrode material is mainly in the carbon material of graphite laminated structure.Graphitized carbon material can be natural graphite, people
Make the mixture of graphite, or both.It is raw material through high temperature that artificial graphite, which is usually with pitch coke, petroleum coke, metallurgical coke, coal tar etc.,
Graphitization processing and the material obtained.
In a preferred embodiment of the invention, the graphitized carbon material is artificial graphite or artificial graphite and natural
The mixture of graphite.In present invention further optimization embodiment, the artificial graphite be petroleum forging after needle coke or
The artificial graphite that needle coke is obtained through high temperature graphitization processing after coal measures forging.
In the present invention, the size of the degree of graphitization of the graphitized carbon material can carry out with method known in this field
Measurement, such as be measured with X-ray diffractometer (such as may refer to: Qian Chongliang etc. the, " graphitization of XRD determining carbon material
Degree ", " Zhongnan Polytechnic Univ's journal " the 3rd phase of volume 32, in June, 2001).The degree of graphitization of artificial graphite used in the present invention can
It is controlled with preparing by control the reaction conditions such as temperature, time of the graphitization reaction of artificial graphite.Natural graphite
Degree of graphitization then may be different with its place of production, purity etc..
In the present invention, the average grain diameter of the graphitized carbon material is suitable for being characterized with Dv50, i.e. the body of material granule
Granularity (particle size) corresponding to integrating 50% in cloth.The bulky grain partial size of the graphitized carbon material is suitable for Dv90 come table
Sign, i.e., granularity corresponding to 90% is less than the partial size (particle size) in the volume distribution of material granule.The graphitization carbon materials
The little particle partial size of material is suitable for being characterized with Dv10, i.e., granularity corresponding to 10% is less than the grain in the volume distribution of material granule
Diameter (particle size).Dv50, Dv90, Dv10 etc. can use laser particle size analyzer (such as Malvern Master Size
2000) it easily measures.
In the present invention, the graphitized carbon material Dv90 is 18-30 μm, and preferred scope is 19-25 μm, and benefit is material
Expect that processing performance is good, stability is preferable in cyclic process.
On the other hand, the present invention also provides a kind of secondary cells comprising above-mentioned electrode material.In addition to having used this
Outside the electrode material of invention, the construction of these secondary cells and preparation method itself are well known.
On the other hand, the invention further relates to a kind of methods for preparing the electrode material, comprising the following steps: will drip
The raw materials such as green coke, needle coke are crushed, and the raw material that average grain diameter is 10-18 μm is obtained；And the raw material is put into graphite
Change and carries out high temperature graphitization processing in furnace.
Needle coke after needle coke or coal measures are forged after the raw material is forged it is preferable to use petroleum.
In order to improve yield, the raw material that can be preferably 10-18 μm to average grain diameter carries out Shape correction.Shape correction
It is the common processing method in artificial graphite preparation process, is well known to those skilled in the art.Shape correction passes through trimmer
Graphite raw material grain corner is polished, its pattern is made to become regular consequently facilitating subsequent graphitization processing；But Shape correction
It will lead to and more fine powder occur, thus usually require cooperation classification processing.Shape correction can be used commonly used in the art any
Trimmer or other shaping devices, also can be used Chinese patent application CN201520275340.5, CN201410139952.1,
Shaping device disclosed in CN201320354100.5 etc..Classification processing can be used classifying screen commonly used in the art (sieve method),
Gravity selector, centrifugal separator etc. are realized.The purpose of classification processing is to remove excessive and too small particle, adjusts particle
Diameter distribution, therefore usually pass through classification processing and remove the little particle of bulky grain of the partial size greater than Dv90 and partial size less than Dv10.
High temperature graphitization can carry out in such as acheson furnace.Graphited temperature for example can be in 2800-
3250 DEG C, preferably 2850-3200 DEG C.
Conventional screening can be carried out after high temperature graphitization, except the post-processing such as magnetic, thus collect meet the present invention claims
Graphitized carbon material.
Therefore, electrode material of the invention preferred preparation method the following steps are included:
(1) needle coke is crushed after needle coke or coal measures are forged after forging petroleum, and obtaining average grain diameter is 10-18 μm
Raw material；
(2) Shape correction is carried out to raw material in (1), carries out classification processing again then to adjust raw material particle size distribution (preferably
Ground, removes bulky grain of the partial size greater than Dv90 and partial size is less than the little particle of Dv10)；
(3) raw material after shaping classification in (2) is put into 2800-3250 DEG C of (preferably 2850-3200 of progress in graphitizing furnace
DEG C) high temperature graphitization processing；
(4) material obtained in (3) is sieved, except magnetic is to get the electrode material.
Optionally, cladding carbonization can be carried out after step (3), before step (4):
(3 ') by the product of (3) acquisition and selected from polyvinyl butyral, pitch, furfural resin, epoxy resin or phenolic aldehyde
The mixing of at least one of resin material, carries out high temperature carbonization processing.
The temperature of charing process is for example at 900-1500 DEG C, such as 1000-1400 DEG C or 1100-1300 DEG C.
In the following with reference to the drawings and specific embodiments, to electrode material of the present invention, secondary cell and its advantages carry out into
One step is described in detail.
Detailed description of the invention
Fig. 1 shows the battery charging and discharging curve of cell embodiments 2.
Fig. 2 shows the cycle performance of battery of cell embodiments 2.
Specific embodiment
In order to be more clear goal of the invention of the invention, technical solution and advantageous effects, with reference to embodiments
The present invention is described in further detail with attached drawing.However, it should be understood that the embodiment of the present invention is just for the sake of this hair of explanation
It is bright, it is not intended to the limitation present invention, and the embodiment of the present invention is not limited to the embodiment provided in specification.In embodiment
The routinely condition production of experiment condition is not specified, or is made by the condition that material supplier is recommended.
Illustrate beneficial effects of the present invention with reference to embodiments.
Embodiment 1
In the present embodiment electrode material the preparation method is as follows:
(1) be crushed: needle coke is crushed using airflow milling or roll mill after petroleum is forged, and removal raw material is broken thin
Powder obtains Dv50:15-16 μm of average grain diameter of raw material；
(2) shaping: carrying out shaping for raw material in (1), carries out classification processing by screening, removal partial size is big greater than Dv90's
The little particle of particle and partial size less than Dv10 is so as to adjust raw material particle size distribution；
(3) it is graphitized: the raw material after shaping in (2) is put into 2850 DEG C of high temperature graphitizations of progress in acheson furnace
Processing；
(4) it sieves, remove magnetic: material obtained in (3) is sieved, remove magnetic, packaging.
The electrode obtained material and raw material 2000 laser particle size analyzer of Malvern Master Size in the present embodiment
It is tested.Raw material average grain diameter Dv50 is 15.6 μm, and electrode material average grain diameter Dv50 is 14.5 μm.Gained in the present embodiment
Electrode material tests material degree of graphitization with X-ray diffractometer, degree of graphitization 92.3%.
Embodiment 2
Identical as 1 preparation method of embodiment, difference is: Dv50:13-14 μm of average grain diameter of the present embodiment raw material, stone
Inkization treatment temperature is 3000 DEG C.The electrode obtained material and raw material are swashed with Malvern Master Size 2000 in the present embodiment
Light Particle Size Analyzer is tested.Raw material average grain diameter Dv50 is 13.9 μm, and electrode material average grain diameter Dv50 is 12.3 μm.This
The electrode obtained material tests material degree of graphitization with X-ray diffractometer in embodiment, degree of graphitization 94.2%.
Embodiment 3
Identical as 1 preparation method of embodiment, difference is: Dv50:10-11 μm of average grain diameter of the present embodiment raw material, stone
Inkization treatment temperature is 3200 DEG C.The electrode obtained material and raw material are swashed with Malvern Master Size 2000 in the present embodiment
Light Particle Size Analyzer is tested.Raw material average grain diameter Dv50 is 10.2 μm, and electrode material average grain diameter Dv50 is 8.1 μm.This
The electrode obtained material tests material degree of graphitization with X-ray diffractometer in embodiment, degree of graphitization 95.5%.
Embodiment 4
In the present embodiment electrode material the preparation method is as follows:
(1) be crushed: needle coke is crushed using airflow milling or roll mill after petroleum is forged, and removal raw material is broken thin
Powder obtains Dv50:13-14 μm of average grain diameter of raw material；
(2) shaping: carrying out shaping for raw material in (1), carries out classification processing by screening, removal partial size is big greater than Dv90's
The little particle of particle and partial size less than Dv10 is so as to adjust raw material particle size distribution；
(3) it is graphitized: the raw material after shaping in (2) is put into 3000 DEG C of high temperature graphitizations of progress in acheson furnace
Processing；
(4) cladding charing: by sample in (3) and polyvinyl butyral, pitch, furfural resin, epoxy resin or phenolic aldehyde
At least one of resin is mixed by 3wt%, and charing process is carried out at 1200 DEG C；
(5) it sieves, remove magnetic: material obtained in (4) is sieved, remove magnetic, packaging.
The electrode obtained material and raw material 2000 laser particle size analyzer of Malvern Master Size in the present embodiment
It is tested.Raw material average grain diameter Dv50 is 13.9 μm, and electrode material average grain diameter Dv50 is 12.8 μm.Gained in the present embodiment
Electrode material tests material degree of graphitization with X-ray diffractometer, degree of graphitization 93.9%.
Embodiment 5
Identical as 4 preparation method of embodiment, difference is: cladding mixed proportion is 6wt% in step (4).This implementation
The electrode obtained material and raw material are tested with 2000 laser particle size analyzer of Malvern Master Size in example.Raw material is flat
Equal partial size Dv50 is 13.9 μm, and electrode material average grain diameter Dv50 is 13.7 μm.The electrode obtained material X-ray in the present embodiment
Diffractometer tests material degree of graphitization, degree of graphitization 93.5%.
Embodiment 6
Identical as 4 preparation method of embodiment, difference is: cladding mixed proportion is 9wt% in step (4).This implementation
The electrode obtained material and raw material are tested with 2000 laser particle size analyzer of Malvern Master Size in example.Raw material is flat
Equal partial size Dv50 is 13.9 μm, and electrode material average grain diameter Dv50 is 15.0 μm.The electrode obtained material X-ray in the present embodiment
Diffractometer tests material degree of graphitization, degree of graphitization 93.0%.
Cell embodiments 1
It prepares battery according to hereafter " CR2430 type battery performance test method " is described and battery is tested for the property.
That is, by the electrode material prepared in embodiment 1, Super P (conductive carbon black), CMC (carboxymethyl cellulose), SBR (butylbenzene rubber
Glue) slurry is made in 94.5:1.5:1.5:2.5 in mass ratio, and the slurry prepared is coated on copper foil, vacuum drying is placed on
It is used as anode spare after toasting 12h in case.It is to electrode with metal lithium sheet, Celgard film is diaphragm, is dissolved with LiPF6
(1mol/L) EC+DMC+DEC (i.e. volume ratio be 1:1:1 ethylene carbonate, dimethyl carbonate, diethyl carbonate mixture)
Solution be electrolyte, argon gas protection glove box in be assembled into CR2430 type button cell.
Battery pack stands 12h after installing, then in 0.05C and 1C current density, 0.005-2.0V charge and discharge blanking voltage item
Charge-discharge performance test is carried out under part；It was found that its 0.05C reversible capacity is 354.7mAh/g, coulombic efficiency is 92.4% for the first time；
Capacity retention ratio is 92.0% after 200 circulations under 1C current density；Capacity retention ratio is 85.2% under 2C multiplying power.
Cell embodiments 2
Identical as 1 preparation method of cell embodiments, difference is: the electrode material that anode is prepared using embodiment 2.This
Its 0.05C reversible capacity of the made battery of embodiment is 356.1mAh/g, and coulombic efficiency is 94.6% for the first time.Under 1C current density
Capacity retention ratio is 93.2% after 200 circulations；Capacity retention ratio is 87.5% under 2C multiplying power.
Cell embodiments 3
Identical as 1 preparation method of cell embodiments, difference is: anode adopts electrode material prepared with embodiment 3.This
Its 0.05C reversible capacity of the made battery of embodiment is 358.2mAh/g, and coulombic efficiency is 93.7% for the first time.Under 1C current density
Capacity retention ratio is 92.3% after 200 circulations；Capacity retention ratio is 87.0% under 2C multiplying power.
Cell embodiments 4
Identical as 1 preparation method of cell embodiments, difference is: the electrode material that anode is prepared using embodiment 4.This
Its 0.05C reversible capacity of the made battery of embodiment is 355.6mAh/g, and coulombic efficiency is 94.1% for the first time.Under 1C current density
Capacity retention ratio is 93.0% after 200 circulations；Capacity retention ratio is 89.5% under 2C multiplying power.
Cell embodiments 5
Identical as 1 preparation method of cell embodiments, difference is: the electrode material that anode is prepared using embodiment 5.This
Its 0.05C reversible capacity of the made battery of embodiment is 354.8mAh/g, and coulombic efficiency is 93.2% for the first time.Under 1C current density
Capacity retention ratio is 93.4% after 200 circulations；Capacity retention ratio is 90.3% under 2C multiplying power.
Cell embodiments 6
Identical as 1 preparation method of cell embodiments, difference is: the electrode material that anode is prepared using embodiment 6.This
Its 0.05C reversible capacity of the made battery of embodiment is 353.7mAh/g, and coulombic efficiency is 92.1% for the first time.Under 1C current density
Capacity retention ratio is 93.8% after 200 circulations；Capacity retention ratio is 91.6% under 2C multiplying power.
Comparative example 1
In this comparative example electrode material the preparation method is as follows:
(1) be crushed: needle coke is crushed to obtain Dv50:15-16 μm of average grain diameter of raw material after petroleum is forged；
(2) it is graphitized: broken raw material in (1) is put into 2600 DEG C of high temperature graphitizations of progress in acheson furnace
Processing；
(3) it sieves, remove magnetic: material obtained in (2) is sieved, remove magnetic, packaging；
The electrode obtained material and raw material 2000 laser particle size analyzer of Malvern Master Size in this comparative example
It is tested.Raw material average grain diameter Dv50 is 15.6 μm, and electrode material average grain diameter Dv50 is 14.7 μm.Gained in this comparative example
Electrode material tests material degree of graphitization with X-ray diffractometer, degree of graphitization 90.1%.
Comparative example 2
Identical as 1 method of comparative example, difference is: DV50:10-11 μm of average grain diameter of this comparative example raw material, graphitization
Treatment temperature is 3300 DEG C.The electrode obtained material and raw material 2000 laser grain of Malvern Master Size in this comparative example
Degree analyzer is tested.Raw material average grain diameter Dv50 is 10.2 μm, and electrode material average grain diameter Dv50 is 8.5 μm.This comparison
The electrode obtained material tests material degree of graphitization with X-ray diffractometer in example, degree of graphitization 97.2%.
Comparative example 3
Identical as 1 method of comparative example, difference is: Dv50:8-9 μm of average grain diameter of this comparative example raw material, at graphitization
Managing temperature is 3000 DEG C.The electrode obtained material and raw material 2000 laser particle size of Malvern Master Size in this comparative example
Analyzer is tested.Raw material average grain diameter Dv50 is 8.1 μm, and electrode material average grain diameter Dv50 is 6.8 μm.In this comparative example
The electrode obtained material tests material degree of graphitization with X-ray diffractometer, degree of graphitization 92.1%.
Comparative example 4
Identical as 1 method of comparative example, difference is: Dv50:17-18 μm of average grain diameter of this comparative example raw material, graphitization
Treatment temperature is 3000 DEG C.The electrode obtained material and raw material 2000 laser grain of Malvern Master Size in this comparative example
Degree analyzer is tested.Raw material average grain diameter Dv50 is 17.4 μm, and electrode material average grain diameter Dv50 is 16.3 μm.This comparison
The electrode obtained material tests material degree of graphitization with X-ray diffractometer in example, degree of graphitization 95.6%.
Comparative example 5
In the present embodiment electrode material the preparation method is as follows:
(1) be crushed: needle coke is crushed using airflow milling or roll mill after petroleum is forged, and removal raw material is broken thin
Powder obtains Dv50:13-14 μm of average grain diameter of raw material；
(2) shaping: carrying out shaping for raw material in (1), carries out classification processing by screening, removal partial size is big greater than Dv90's
The little particle of particle and partial size less than Dv10 is so as to adjust raw material particle size distribution；
(3) it is graphitized: the raw material after shaping in (2) is put into 3000 DEG C of high temperature graphitizations of progress in acheson furnace
Processing；
(4) cladding charing: by sample in (3) and polyvinyl butyral, pitch, furfural resin, epoxy resin or phenolic aldehyde
At least one of resin is mixed by 1wt%, and charing process is carried out at 1200 DEG C；
(5) it sieves, remove magnetic: material obtained in (4) is sieved, remove magnetic, packaging.
The electrode obtained material and raw material 2000 laser particle size analyzer of Malvern Master Size in the present embodiment
It is tested.Raw material average grain diameter Dv50 is 13.9 μm, and electrode material average grain diameter Dv50 is 12.4 μm.Gained in the present embodiment
Electrode material tests material degree of graphitization with X-ray diffractometer, degree of graphitization 94.0%.
Comparative example 6
Identical as 5 preparation method of comparative example, difference is: cladding mixed proportion is 12wt% in step (4).This implementation
The electrode obtained material and raw material are tested with 2000 laser particle size analyzer of Malvern Master Size in example.Raw material is flat
Equal partial size Dv50 is 13.9 μm, and electrode material average grain diameter Dv50 is 16.2 μm.The electrode obtained material X-ray in the present embodiment
Diffractometer tests material degree of graphitization, degree of graphitization 92.0%.
Battery comparative example 1
Identical as 1 preparation method of cell embodiments, difference is: the electrode material prepared using comparative example 1.This comparison
Made its 0.05C reversible capacity of battery of example is 349.3mAh/g, and coulombic efficiency is 91.0% for the first time.200 under 1C current density
Capacity retention ratio is 91.5% after secondary circulation；Capacity retention ratio is 84.0% under 2C multiplying power.
Battery comparative example 2
Identical as 1 preparation method of cell embodiments, difference is: the electrode material prepared using comparative example 2.This comparison
Made its 0.05C reversible capacity of battery of example is 359.1mAh/g, and coulombic efficiency is 91.9% for the first time.200 under 1C current density
Capacity retention ratio is 85.6% after secondary circulation；Capacity retention ratio is 83.6% under 2C multiplying power.
Battery comparative example 3
Identical as 1 preparation method of cell embodiments, difference is: the electrode material prepared using comparative example 3.This comparison
Made its 0.05C reversible capacity of battery of example is 353.4mAh/g, and coulombic efficiency is 90.2% for the first time.200 under 1C current density
Capacity retention ratio is 89.4% after secondary circulation；Capacity retention ratio is 85.6% under 2C multiplying power.
Battery comparative example 4
Identical as 1 preparation method of cell embodiments, difference is: the electrode material prepared using comparative example 4.This comparison
Made its 0.05C reversible capacity of battery of example is 356.3mAh/g, and coulombic efficiency is 92.1% for the first time.200 under 1C current density
Capacity retention ratio is 90.8% after secondary circulation；Capacity retention ratio is 83.2% under 2C multiplying power.
Battery comparative example 5
Identical as 1 preparation method of cell embodiments, difference is: the electrode material prepared using comparative example 5.This comparison
Made its 0.05C reversible capacity of battery of example is 355.8mAh/g, and coulombic efficiency is 94.0% for the first time.200 under 1C current density
Capacity retention ratio is 92.5% after secondary circulation；Capacity retention ratio is 88.0% under 2C multiplying power.
Battery comparative example 6
Identical as 1 preparation method of cell embodiments, difference is: the electrode material prepared using comparative example 6.This comparison
Made its 0.05C reversible capacity of battery of example is 352.2mAh/g, and coulombic efficiency is 82.0% for the first time.200 under 1C current density
Capacity retention ratio is 91.1% after secondary circulation；Capacity retention ratio is 90.2% under 2C multiplying power.
CR2430 type battery performance test method
1, gram volume is tested:
Slurry is made in electrode material, Super P, CMC, SBR 94.5:1.5:1.5:2.5 in mass ratio of preparation, will prepare
Good slurry is coated on copper foil, is placed spare as anode after toasting 12h in a vacuum drying oven.It is to electricity with metal lithium sheet
Pole, Celgard film are diaphragm, are dissolved with LiPF6The solution of the EC+DMC+DEC (volume ratio 1:1:1) of (1mol/L) is electrolysis
Liquid is assembled into CR2430 type button cell in the glove box of argon gas protection.Battery pack stands 12h after installing, then in 0.05C and
1C current density carries out charge-discharge performance test under the conditions of 0.005-2.0V charge and discharge blanking voltage.
2, cycle performance is tested:
In 25 DEG C of environment, charge-discharge test is carried out, 1C's (i.e. bleeding off the current value of theoretical capacity in 1h completely)
Constant-current discharge is carried out under charging current, until voltage be 50mV, constant-current charge is then carried out under the charging current of 1C, until most
Whole voltage is 2V, records the charging capacity recycled for the first time；It then carries out continuing charge and discharge cycles.
Circulation volume conservation rate=(charging capacity of n-th circulation/charging capacity recycled for the first time) × 100%.
3, high rate performance is tested:
In 25 DEG C of environment, charge-discharge test is carried out, 0.05C (i.e. bleeding off the current value of theoretical capacity in 1h completely)
Electric discharge electricity electric current under carry out constant-current discharge, until voltage be 50mV, then under the charging current of 0.05C carry out constant current fill
Electricity, until final voltage is 2V；
50mV is then discharged under 0.05C multiplying power, record discharge capacity is 0.05C discharge capacity.It is charged again with 0.05C
Electric current constant-current charge is to 2V.
50mV is then discharged under 2.0C multiplying power, record discharge capacity is 2.0C discharge capacity.It is charged again with 0.05C electric
Constant-current charge is flowed to 2V.
Rate capability conservation rate=(discharge capacity/0.05C discharge capacity of 2C) × 100%.
The battery performance of cell embodiments 1-6 and battery comparative example 1-6 are summarized in table 1.
The performance test results of table 1, each embodiment and comparative example
Found out by the data of table 1, can be obtained by the comparison of cell embodiments 1-3 and battery comparative example 1-4, degree of graphitization and
When Dv50 control is in given range, material can combine high capacity, Gao Shouxiao and high circulation stability.
Found out by the data of table 1, can be obtained by the comparison of cell embodiments 1-3 and battery comparative example 3-4, when the stone of material
Mo Huadu is in given range, and when given range is not achieved in Dv50, head effect or cyclical stability are poor.
Found out by the data of table 1, can be obtained by the comparison of cell embodiments 1-3 and battery comparative example 1-2, when material
For Dv50 in given range, but when given range is not achieved in degree of graphitization, capacity or cyclical stability are poor.
Found out by the data of table 1, can be obtained by the comparison of cell embodiments 2,4-6 and battery comparative example 5-6, when material
Covering amount can significantly mention (when such as from about 5-9%) under the premise of taking into account capacity, first effect and cycle performance in a certain range
Rise the high rate performance of battery.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula carries out change and modification appropriate.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to this
Some modifications and changes of invention should also be as falling into the scope of the claims of the present invention.In addition, although this specification
In use some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.
Claims (9)
1. a kind of electrode material for secondary cell, it is characterised in that: the material is graphitized carbon material, degree of graphitization
It is 8-15 μm, preferably 9-12 μm for 92%-97%, preferably 93-95%, average grain diameter Dv50.
2. electrode material according to claim 1, the material is selected from least one of artificial graphite, natural graphite.
3. electrode material according to claim 1 or 2, the material average grain diameter Dv90 is 18-30 μm, preferably 19-25 μ
m。
4. electrode material according to claim 1, the material surface has clad, and the clad is amorphous carbon.
5. electrode material according to claim 4, the amorphous carbon in carbon black, coke, soft carbon, hard carbon at least
It is a kind of.
6. electrode material according to claim 4, content of the amorphous carbon relative to the electrode material total weight
For 3-10%, preferably 5-9%.
7. a kind of method for preparing the described in any item electrode materials of claim 1-3, comprising the following steps:
(1) needle coke is crushed after needle coke or coal measures are forged after forging petroleum, obtains the original that average grain diameter is 10-18 μm
Material；
(2) Shape correction is carried out to raw material in (1), carries out classification processing again then to adjust raw material particle size distribution；
(3) raw material after shaping classification in (2) is put into 2800-3250 DEG C (preferably 2850-3200 DEG C) of progress in graphitizing furnace
High temperature graphitization processing；
(4) material obtained in (3) is sieved, except magnetic treatment.
8. according to the method described in claim 7, it is characterized by: being carried out after being also included in step (3), before step (4)
Cladding, charing process by the product of (3) acquisition and are selected from polyvinyl butyral, pitch, furfural resin, epoxy resin or phenol
The mixing of at least one of urea formaldehyde material, carries out high temperature carbonization processing.
9. a kind of secondary cell, including electrode material described in any one of claims 1 to 6.
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| WO2021196141A1 (en) * | 2020-04-02 | 2021-10-07 | 宁德时代新能源科技股份有限公司 | Secondary battery and device comprising secondary battery |
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