CN109768247A - The excellent high-energy density negative electrode material and preparation method thereof of a kind of high-pressure solid, high-temperature behavior - Google Patents
The excellent high-energy density negative electrode material and preparation method thereof of a kind of high-pressure solid, high-temperature behavior Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of the excellent high-energy density negative electrode material of high-pressure solid, high-temperature behavior, by by organic alkane pyrocarbon on natural spherical plumbago internal void and surface, repair natural spherical plumbago inside and surface defect, it is evenly dispersed with high-speed stirred after pitch mixing again, the negative electrode material that compacting is high, energy density is high is obtained by carbonization.The negative electrode material of the method for the present invention preparation has excellent high temperature cyclic performance, solves the problems, such as that the high temperature cyclic performance in the presence of the prior art is poor.
Description
Technical field
The present invention relates to lithium cell cathode material preparation technical fields, and in particular to a kind of high-pressure solid, high-temperature behavior are excellent
High-energy density negative electrode material and preparation method thereof.
Background technique
With the demand of production and the raising of environmental protection consciousness, new-energy automobile is grown rapidly, power battery
Demand is increasing therewith, and the lithium ion secondary battery of high-energy density receives much attention in energy storage field, this requires that electrode
Material is continuously improved and is innovated, and wherein the improvement and innovation of negative electrode material are one of first choices.
Currently, commercialized negative electrode material is mainly graphite cathode, graphite cathode includes natural graphite cathode, artificial graphite
Cathode and modified graphite cathode three classes.Natural spherical plumbago is made by material modification nodularization of high-quality natural flake graphite, squama
Piece graphite will necessarily generate more surface defect, and internal generation closed pore or through-hole during nodularization.Natural spherical plumbago by
, specific surface more in defect be big, first imitate low disadvantage and cannot individually be applied to lithium cell cathode material.Surface is generally gone through to change
Property, one layer of soft carbon or hard carbon formation core-shell structure are coated on graphite surface layer and are applied.This modified natural graphite main advantage exists
In simple production process, gram specific capacity height, processing performance is good the features such as, and in benign environment (compacting≤1.65g/cc, room temperature)
Under have preferable circulating effect.But natural spherical plumbago surface layer is compacted be declined after coating soft/hard carbon, and soft or hard carbon coating is only
Only improve natural graphite surface defect, natural graphite internal flaw can not be repaired, core-shell structure collapses under the conditions of high compacted density
It collapses, cycle performance is decayed quickly, and high-temperature behavior is very poor.
Natural spherical plumbago internal flaw can not be repaired for soft or hard carbon coating to the status of high temperature and pressure reality performance difference
Problem, people repair the internal flaw of spherical graphite using impregnation method.For example, Chinese Patent Application No. CN107814382A
A kind of natural graphite negative electrode material of the modification of long-life is disclosed, using hot isostatic press to natural spherical plumbago powder and drip
Blueness carries out impregnation, can ensure hole of the pitch at high temperature under high pressure inside filled graphite particle completely, while in graphite
Surface forms pitch carbon coating layer, but this high pressure is easy to form secondary damage to graphite, influences cycle performance.
Summary of the invention
In view of the deficiencies of the prior art, the high energy excellent the purpose of the present invention is to provide a kind of high-pressure solid, high-temperature behavior
Metric density negative electrode material.The negative electrode material is high using compacting, energy density is high, and high temperature cyclic performance is substantially improved.
In order to achieve the above object, the present invention adopts the following technical scheme:
A kind of excellent high-energy density negative electrode material of high-pressure solid, high-temperature behavior, which is characterized in that the high-energy density cathode
Material is core-shell structure, and the kernel of the high-energy density negative electrode material is made of spherical graphite, pyrolytic carbon, the pyrolytic carbon point
Cloth is pitch soft carbon material clad in spherical graphite internal interstices and surface layer, the shell of the high-energy density negative electrode material.
A kind of preparation method of the excellent high-energy density negative electrode material of high-pressure solid, high-temperature behavior, the method includes such as
Lower step:
S1, under the protection of inert gas, by alkanes carbon source pyrolytic deposition filled natural spherical graphite internal void and surface,
Obtain intermediate product；
S2, above-mentioned intermediate product and pitch are carbonized after evenly mixing, carburizing temperature be 1000 ~ 1300 DEG C, carbonization time be 5 ~
10h carries out cooling down after carbonization, sieve, except magnetic, obtains target product.
Preferably, the preparation method of the excellent high-energy density negative electrode material of a kind of high-pressure solid, high-temperature behavior, the method
Include the following steps:
S1, under the protection of inert gas, spherical natural graphite is placed in rotary furnace, heating heating, be re-filled with alkanes carbon
Source gas carries out pyrolytic deposition, so that alkanes carbon source is filled into natural spherical plumbago internal void and surface, is subsequently cooled to room
Temperature obtains the intermediate product of internal flaw reparation and surface deposition pyrolytic carbon；
S2, intermediate product prepared by step S1 uniformly being mixed with pitch, then carries out carbonization treatment, carburizing temperature is 1000 ~
1300 DEG C, carbonization time is 5 ~ 10h, carries out cooling down after carbonization treatment, sieve, except magnetic, it is excellent to obtain high-pressure solid, high-temperature behavior
High-energy density negative electrode material.
Preferably, in step S1, the average particle size range of the natural spherical plumbago raw material is 10 ~ 20 μm.
Preferably, in step S1, the alkanes carbon source is one of methane, ethane, propane, n-hexane, hexamethylene
Or at least two kinds of combinations, the inert gas are nitrogen or argon gas.
Preferably, in step S1, the mode of the alkanes carbon source pyrolytic deposition is rotary furnace pyrolytic deposition, and rotary furnace turns
Speed is 5-20r/min, and heating rate is 5-10 DEG C/min, and temperature is 900-1000 DEG C, soaking time 2-5h.
Preferably, in step S1, the total gas concentration of the alkanes carbon source Zhan is 5%-20%, the gas stream of alkanes carbon source
Amount is 2-5L/min.
Preferably, in step S2, the pitch is hard pitch of the softening point at 120 DEG C -200 DEG C, natural spherical plumbago
Ratio with the pitch is 85:15 ~ 95:5 (mass ratio), and hybrid mode is VC mixing.2-5 μm of the average grain diameter of pitch rises
5-10 DEG C of warm speed/min, the gas being filled with are nitrogen, argon gas or its mixed gas.
The present invention has following technical effect that
(1) negative electrode material of the method for the present invention preparation has the advantages that compacting is high, energy density is high, and high temperature cyclic performance is big
Width is promoted；
(2) present invention repairs natural spherical plumbago internal void using vapor deposition method, will not cause secondary damage to graphite.
The preparation method of the excellent high-energy density negative electrode material of a kind of high-pressure solid of the present invention, high-temperature behavior, by that will have
Machine alkane pyrocarbon repairs natural spherical plumbago inside and surface defect on natural spherical plumbago internal void and surface,
It is evenly dispersed with high-speed stirred after pitch mixing again, the negative electrode material that compacting is high, energy density is high is obtained by carbonization, it is described negative
The structure of pole material is as shown in Figure 1, the negative electrode material is core-shell structure, and kernel is made of spherical graphite, pyrolytic carbon, the heat
Solution carbon is distributed in spherical graphite internal interstices and surface layer, and shell is pitch soft carbon material clad.The method of the present invention preparation is born
Pole material has excellent high temperature cyclic performance, solves the problems, such as that the high temperature cyclic performance in the presence of the prior art is poor.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of high-energy density negative electrode material prepared by the present invention.
Fig. 2 is the circulation of negative electrode material prepared by negative electrode material prepared by the embodiment of the present invention 2 and comparative example 1, comparative example 2
Performance comparison figure.
Fig. 3 is the SEM figure of natural spherical plumbago surface defect pattern.
Fig. 4 is natural spherical plumbago inner cross-sectional defect shape appearance figure.
In attached drawing: 1-spherical graphite, 2-soft carbon shells, 3-internal voids, 4-deposition pyrolytic carbons.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for helping to understand the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
It (1) is that 10 μm of spherical natural graphites are placed in rotary furnace by average grain diameter, adjusting rotary furnace revolving speed is 5r/min, is filled with nitrogen
Gas shielded gas is warming up to 900 DEG C with 5.0 DEG C/min, is then charged with the mixed gas of n-hexane and nitrogen, and n-hexane volume accounts for
20%, gas flow 2L/min of total gas volume, keep the temperature 2.0h, and cooled to room temperature obtains internal flaw reparation and table
The intermediate product of face deposition pyrolytic carbon；
(2) it uses airflow milling to be crushed to average grain diameter as 2 μm or so the pitch particle that softening point is 120 DEG C, then is produced from centre
Object is mixed with pitch particle 95:5 in mass ratio, through VC high speed dispersion, is subsequently placed in batch-type furnace, is filled with nitrogen, with 5.0
DEG C/min heating rate is warming up to 1000.0 DEG C, keep the temperature 5.0h, cooled to room temperature；
(3) magnetic is sieved and removed, high temperature resistant, the high-pressure solid, high-energy density negative electrode material that average grain diameter is 10.5 μm are obtained.
Embodiment 2
It (1) is that 15 μm of spherical natural graphites are placed in rotary furnace by average grain diameter, adjusting rotary furnace revolving speed is 10r/min, is filled with
Argon gas protective gas is warming up to 950 DEG C with 8.0 DEG C/min, is then charged with the mixed gas of hexamethylene and argon gas, and hexamethylene Zhan is total
The 15% of gas volume, flow 2L/min keep the temperature 3.0h, and cooled to room temperature obtains internal flaw reparation and surface deposition
The intermediate product of pyrolytic carbon；
(2) intermediate product and airflow milling are crushed to 150 DEG C of pitch particle 90:10 in mass ratio that average grain diameter is 3 μm or so
It after mixing, through VC high speed dispersion, is subsequently placed in batch-type furnace, is filled with nitrogen, be warming up to 1200.0 with 7.0 DEG C/min heating rate
DEG C, keep the temperature 8.0h, cooled to room temperature；
(3) magnetic is sieved and removes, obtaining average grain diameter is 16 μm of high temperature resistants, high-pressure solid, high-energy density negative electrode material.
Embodiment 3
It (1) is that 20 μm of spherical natural graphites are placed in rotary furnace by average grain diameter, adjusting rotary furnace revolving speed is 20r/min, is filled with
Nitrogen protection gas is warming up to 1100 DEG C with 10.0 DEG C/min, is then charged with the mixed gas of methane and nitrogen, the total gas of methane Zhan
The 5% of body volume, flow 5L/min keep the temperature 5.0h, and cooled to room temperature obtains internal flaw reparation and surface deposition heat
Solve the intermediate product of carbon；
(2) intermediate product and airflow milling are crushed to pitch particle that softening point that average grain diameter is 5 μm or so is 200 DEG C by matter
Amount is mixed than 85:15, then through VC high speed dispersion, is subsequently placed in batch-type furnace, and nitrogen is filled with, and is heated up with 10.0 DEG C/min fast
Rate is warming up to 1300.0 DEG C, keeps the temperature 10.0h, cooled to room temperature；
(3) magnetic is sieved and removes, obtaining average grain diameter is 22 μm of high temperature resistants, high-pressure solid, high-energy density negative electrode material.
Comparative example 1
It is that 15 μm of spherical natural graphites are placed in rotary furnace by average grain diameter, adjusting rotary furnace revolving speed is 5r/min, is filled with nitrogen
Protective gas is warming up to 1000 DEG C with 10.0 DEG C/min, is then charged with the n-hexane that saturated vapor concentration is 15% and mixes with nitrogen
Gas, gas flow 2L/min keep the temperature 3.0h, and it is that 15.2 μm of internal flaws are repaired that cooled to room temperature, which obtains average particle size,
The sample of multiple and surface deposition pyrolytic carbon.
1 sample of comparative example is coated by secondary pitch soft carbon, only by pyrocarbon, although compacting it is high,
But specific surface area (SSA) is greatly, and superficial layer graphite is easy preferentially peeling-off when lithium ion deintercalation and solvent are embedding altogether, leads to high temperature
Cycle performance decaying is abnormal serious, as shown in Fig. 2, the cycle performance of 1 sample of comparative example is inferior to 2 sample of embodiment.
Comparative example 2
The natural spherical plumbago that average grain diameter is 15 μm is crushed to 150 DEG C of pitches that average grain diameter is 3 μm or so with airflow milling
Particle is pressed after 90:10 is mixed through VC high speed dispersion, is subsequently placed in batch-type furnace, is filled with nitrogen, with 10.0 DEG C/min heating rate
1200.0 DEG C are warming up to, keeps the temperature 5.0h, cooled to room temperature, obtaining average particle size is 16 μm of 2 samples of comparative example.
2 sample of comparative example is being simply mixed for natural spherical plumbago and soft carbon, and graphite internal flaw is not repaired
It is multiple, it is low compared to the compacting of 2 sample of embodiment although specific surface area is effectively reduced, and high temperature and pressure reality poor circulation.
Performance test
Sample prepared by above-described embodiment 1-3 and comparative example 1-2 carries out electrochemical property test, and result is as shown in the table:
As can be seen from the above table, the negative electrode material of the method for the present invention preparation has excellent high temperature cyclic performance.
Claims (9)
1. the excellent high-energy density negative electrode material of a kind of high-pressure solid, high-temperature behavior, which is characterized in that the high-energy density is negative
Pole material is core-shell structure, and the kernel of the high-energy density negative electrode material is made of spherical graphite, pyrolytic carbon, the pyrolytic carbon
It is distributed in spherical graphite internal interstices and surface layer, the shell of the high-energy density negative electrode material is pitch soft carbon material cladding
Layer.
2. a kind of preparation method of the excellent high-energy density negative electrode material of high-pressure solid, high-temperature behavior, which is characterized in that including such as
Lower step:
S1, under the protection of inert gas, by alkanes carbon source pyrolytic deposition filled natural spherical graphite internal void and surface,
Obtain intermediate product；
S2, above-mentioned intermediate product and pitch are carbonized after evenly mixing, carburizing temperature be 1000 ~ 1300 DEG C, carbonization time be 5 ~
10h carries out cooling down after carbonization, sieve, except magnetic, obtains target product.
3. the preparation side of the excellent high-energy density negative electrode material of a kind of high-pressure solid according to claim 1, high-temperature behavior
Method, which comprises the steps of:
S1, under the protection of inert gas, spherical natural graphite is placed in rotary furnace, heating heating, be re-filled with alkanes carbon
Source gas carries out pyrolytic deposition, so that alkanes carbon source is filled into natural spherical plumbago internal void and surface, is subsequently cooled to room
Temperature obtains the intermediate product of internal flaw reparation and surface deposition pyrolytic carbon；
S2, intermediate product prepared by step S1 uniformly being mixed with pitch, then carries out carbonization treatment, carburizing temperature is 1000 ~
1300 DEG C, carbonization time is 5 ~ 10h, carries out cooling down after carbonization treatment, sieve, except magnetic, it is excellent to obtain high-pressure solid, high-temperature behavior
High-energy density negative electrode material.
4. the preparation of the excellent high-energy density negative electrode material of a kind of high-pressure solid according to claim 2 or 3, high-temperature behavior
Method, it is characterised in that: in step S1, the average particle size range of the natural spherical plumbago raw material is 10 ~ 20 μm.
5. preferably, in step S1, the alkanes carbon source be one of methane, ethane, propane, n-hexane, hexamethylene or
At least two kinds of combinations, the inert gas are nitrogen or argon gas.
6. the preparation of the excellent high-energy density negative electrode material of a kind of high-pressure solid according to claim 2 or 3, high-temperature behavior
Method, it is characterised in that: in step S1, the mode of the alkanes carbon source pyrolytic deposition is rotary furnace pyrolytic deposition, rotary furnace
Revolving speed is 5-20r/min, and heating rate is 5-10 DEG C/min, and temperature is 900-1000 DEG C, soaking time 2-5h.
7. the preparation of the excellent high-energy density negative electrode material of a kind of high-pressure solid according to claim 2 or 3, high-temperature behavior
Method, it is characterised in that: in step S1, the total gas concentration of the alkanes carbon source Zhan is 5%-20%, the gas of alkanes carbon source
Flow is 2-5L/min.
8. the preparation of the excellent high-energy density negative electrode material of a kind of high-pressure solid according to claim 2 or 3, high-temperature behavior
Method, it is characterised in that: in step S2, the pitch is hard pitch of the softening point at 120 DEG C -200 DEG C, natural spherical plumbago
Ratio with the pitch is 85:15 ~ 95:5 (mass ratio), and hybrid mode is VC mixing.
9. 2-5 μm of the average grain diameter of pitch, 5-10 DEG C of heating rate/min, the gas being filled with are nitrogen, argon gas or its gaseous mixture
Body.
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| CN111933898A (en) * | 2020-06-12 | 2020-11-13 | 湖州凯金新能源科技有限公司 | High-performance graphite negative electrode material for lithium ion battery, and preparation method and application thereof |
| CN113113572A (en) * | 2021-03-11 | 2021-07-13 | 广东海洋大学 | High-rate natural graphite-based composite material for lithium ion battery and preparation method and application thereof |
| CN114203978A (en) * | 2020-09-17 | 2022-03-18 | 湖南中科星城石墨有限公司 | High-capacity graphite negative electrode material and preparation method and application thereof |
| CN114430040A (en) * | 2021-12-28 | 2022-05-03 | 深圳市翔丰华科技股份有限公司 | Preparation method of low-expansion long-cycle graphite negative electrode material for lithium ion battery |
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