CN112713277B - Hard carbon material, preparation method and application thereof, and lithium ion battery - Google Patents
Hard carbon material, preparation method and application thereof, and lithium ion battery Download PDFInfo
- Publication number
- CN112713277B CN112713277B CN202011612702.7A CN202011612702A CN112713277B CN 112713277 B CN112713277 B CN 112713277B CN 202011612702 A CN202011612702 A CN 202011612702A CN 112713277 B CN112713277 B CN 112713277B
- Authority
- CN
- China
- Prior art keywords
- hard carbon
- conductive agent
- carbon material
- material according
- hard
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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 a hard carbon material, a preparation method and application thereof, and a lithium ion battery. The hard carbon material comprises hard carbon and a conductive agent; the conductive agent is dispersed in the hard carbon; the content of the conductive agent is 0.1-20%; the percentage is the mass percentage of the conductive agent in the hard carbon material. The hard carbon material has low resistivity and uniform overall resistivity, and has high reversible capacity, good heavy current performance and excellent cycle performance when used as a lithium ion battery cathode material; and the preparation method is simple.
Description
Technical Field
The invention relates to a hard carbon material, a preparation method and application thereof, and a lithium ion battery.
Background
The graphite cathode material has the advantages of stable capacity, high efficiency and low voltage platform, so that the graphite cathode material is generally adopted in the traditional lithium ion battery. However, because the graphite cathode material has small graphite flake spacing and large grain size, the lithium ion diffusion in the graphite cathode material can only proceed along a specific direction and path; and the lithium ion has large migration resistance among graphite lattices, so that the dynamic performance of the lithium ion battery is insufficient and the lithium ion battery is difficult to apply to a large-current continuous charging and discharging environment.
The microstructure of the hard carbon material is different from that of a graphite material, and the hard carbon material mainly comprises a short-range ordered graphite microcrystal region, an orientation ordered region, an orientation disordered region and micropores formed by disordered stacking. Therefore, the diffusion of lithium ions in the hard carbon material is approximately isotropic, the diffusion resistance is small, and the diffusion rate is high. And the interlayer spacing of the short-range ordered graphite microcrystals in the hard carbon material is far greater than 0.3354nm of graphite, so that the migration resistance of lithium ions in the hard carbon is low, and the lithium ions can be rapidly migrated and diffused in the hard carbon material. In addition, when the hard carbon material is used as the negative electrode material of the lithium ion battery, the lithium ion battery has higher electrochemical potential and negative lithium precipitation potential, so that the lithium ion battery using the hard carbon material as the negative electrode has higher safety. Therefore, when the hard carbon material is used for the lithium ion battery, the hard carbon material not only has excellent rate characteristic and higher safety performance, but also has excellent performances of stable electrochemical cycle, long service life, good low-temperature performance and the like.
However, since the graphite crystallite region and the orientation disorder region of the hard carbon material have an imperfect graphite lattice structure, the conductivity of the hard carbon material is low due to the weak electron conductivity of the region. The lower conductivity of the hard carbon material is a main factor for restricting the poor dynamic performance of the hard carbon material when the hard carbon material is applied to the cathode of a lithium ion battery, and is also one of the reasons for causing the voltage hysteresis of the hard carbon material.
At present, in the prior art, a conductive agent is coated on the surface of a hard carbon material, or the conductive agent is added when the hard carbon material is prepared into an electrode, so that the resistivity of the hard carbon material is improved. However, the surface coating cannot effectively improve the internal conductivity of the hard carbon material, so that the problems of increased electrochemical polarization, potential lag, easy generation of battery heating and the like are caused; and when the hard carbon material is prepared into the electrode, the process of adding the conductive agent is complex, and the improvement degree is limited. Therefore, it is desirable to provide a hard carbon material with low resistivity and excellent electrochemical performance and a preparation method thereof.
Disclosure of Invention
The invention aims to overcome the defects of high resistivity or uneven resistivity distribution of a hard carbon material in the prior art, and provides the hard carbon material, a preparation method and application thereof and a lithium ion battery. The hard carbon material has low resistivity and uniform overall resistivity, and has high reversible capacity, good heavy current performance and excellent cycle performance when used as a lithium ion battery cathode material; and the preparation method is simple.
In order to achieve the purpose, the invention provides the following technical scheme:
one of the technical schemes provided by the invention is as follows: a hard carbon material comprising hard carbon and a conductive agent;
the conductive agent is dispersed inside the hard carbon;
the content of the conductive agent is 0.1-20%; the percentage is the mass percentage of the conductive agent in the hard carbon material.
In the invention, the conductive agent can be one or more of carbon nano tube, graphene, conductive graphite, ultrathin flake graphite, graphite micropowder, ruthenium oxide and acetylene black; preferably one or more of carbon nano tube, graphite micropowder and ultrathin flake graphite; more preferably carbon nanotubes and ultra-thin flake graphite.
Preferably, the conductive agent is a carbon nanotube and ultrathin flake graphite, and the mass ratio of the carbon nanotube to the ultrathin flake graphite is preferably 1: (1-100).
Preferably, the conductive agent is a carbon nanotube and a graphite micropowder, and the mass ratio of the carbon nanotube to the graphite micropowder is preferably 1: (1-100).
The particle diameter D50 of the graphite fine powder may be 5 μm or less.
The particle size D50 of the ultrathin flake graphite can be less than 10 mu m.
In the invention, the content of the conductive agent is preferably 0.1-10%; for example, 0.1 to 2%, or, 2 to 10%; the percentage is the mass percentage of the conductive agent in the hard carbon material.
Preferably, the conductive agent is carbon nanotubes and/or graphene, and the content of the conductive agent is preferably 0.1 to 2 percent, and the percentage is the mass percentage of the conductive agent in the hard carbon material.
Preferably, the conductive agent is conductive graphite, and the content of the conductive agent is preferably 2-10%, and the percentage is the mass percentage of the conductive agent in the hard carbon material.
The second technical scheme provided by the invention is as follows: a preparation method of a hard carbon material comprises the following steps: mixing and melting hard carbon raw materials to prepare a hard carbon precursor, and sequentially carrying out oxidation curing treatment and carbonization treatment on the hard carbon precursor;
wherein the hard carbon raw material comprises asphalt and a conductive agent;
the content of the conductive agent is 0.1-20%; the percentage is the mass percentage of the conductive agent in the hard carbon raw material according to the carbon residue value of the hard carbon raw material.
In the present invention, the pitch may be conventional in the art, such as petroleum pitch or coal tar pitch. The softening point of the bitumen may be in the range 200 to 320 ℃, for example 220 ℃ or 250 ℃.
In the present invention, the conductive agent is as described above.
In the present invention, preferably, the mixing includes mixing the conductive agent with a dispersant to obtain a conductive agent dispersion, and mixing the conductive agent dispersion with the asphalt.
The dispersant may be tetrahydrofuran or N, N Dimethylformamide (DMF).
Preferably, the conductive agent is a carbon nanotube, and the dispersant is tetrahydrofuran. Wherein, the mass ratio of the carbon nano tube can be 0.1-3%, preferably 1%; the percentage is the mass percentage of the carbon nano tube in the conductive agent dispersion liquid.
The conductive agent dispersion is generally commercially available according to conventional practices in the art.
In a preferred embodiment of the present invention, the asphalt is petroleum asphalt, and the conductive agent is carbon nanotubes and ultrathin flake graphite. Wherein the softening point of the petroleum asphalt is 250 ℃. The dispersant of the carbon nano tube is tetrahydrofuran preferably, and the mass percentage of the carbon nano tube in the carbon nano tube-tetrahydrofuran dispersion liquid is 1%.
In a preferred embodiment of the present invention, the pitch is coal tar pitch, and the conductive agent is carbon nanotubes and ultrathin flake graphite. Wherein the softening point of the coal tar pitch is 220 ℃. The dispersant of the carbon nano tube is tetrahydrofuran preferably, and the mass percentage of the carbon nano tube in the carbon nano tube-tetrahydrofuran dispersion liquid is 1%.
In a preferred embodiment of the present invention, the asphalt is petroleum asphalt, and the conductive agent is carbon nanotubes and ultrathin flake graphite. Wherein the softening point of the petroleum asphalt is 220 ℃. The dispersing agent of the carbon nano tube is preferably N, N Dimethylformamide (DMF), and the mass percent of the carbon nano tube in the carbon nano tube-N, N Dimethylformamide (DMF) dispersion liquid is 1%.
In the present invention, the melting temperature may be 50 to 160 ℃ above the softening point of the asphalt.
The melting can be carried out under any atmosphere.
The melting may be followed by a cooling step to room temperature, as is conventional in the art.
In the present invention, the particle diameter D50 of the hard carbon precursor may be 20 μm or less. The particle size D50 of the hard carbon precursor may be achieved by a pulverization treatment according to a conventional method in the art.
In the present invention, the oxidative curing treatment may be performed in an oxygen-containing atmosphere. The oxygen-containing atmosphere refers to an atmosphere containing oxygen and/or ozone. The oxygen-containing atmosphere can have an oxygen content of 15-100%, wherein the oxygen content refers to the volume percentage of oxygen and/or ozone in the oxygen-containing atmosphere.
The oxygen-containing atmosphere may comprise one or more of air, oxygen and ozone. Optionally, an inert gas may also be included. The oxygen-containing atmosphere is preferably a mixed gas of: air and oxygen, air and ozone, air and inert gas, oxygen and inert gas, or ozone and inert gas.
The ventilation amount of the oxygen-containing atmosphere can be 0.1-2L/(Kg min).
The temperature of the oxidative curing treatment may be conventional in the art, for example, 200 to 380 ℃, preferably 250 to 360 ℃, more preferably 280 ℃.
The temperature of the oxidative curing treatment may be raised by a temperature programming method, and the temperature raising rate of the temperature programming may be conventional in the art, and is preferably 0.1 to 3 ℃/min.
The time of the oxidative curing treatment may be conventional in the art, and is preferably 2 to 8 hours, and more preferably 4 hours.
The equipment for the oxidative curing treatment may be conventional in the art, and is preferably a rotary kiln, heating jacket or box furnace.
In the present invention, after the oxidative curing treatment is finished, a step of cooling to room temperature may be included according to the conventional practice in the art; and cooling to obtain the pitch hard carbon powder after oxidation curing treatment.
After the oxidation curing treatment is finished, the method also comprises the step of crushing the pitch hard carbon powder after the oxidation curing treatment. After the pulverization, the particle diameter D50 of the pitch hard carbon powder after the oxidation curing treatment is preferably 4 to 15 μm.
In the present invention, the carbonization treatment may be conventional in the art.
The temperature of the carbonization treatment can be 800-1300 ℃; preferably 1000 ℃ or 1100 ℃. The temperature rise mode can be temperature programming, and the temperature rise rate of the temperature programming can be 1-5 ℃/min.
The carbonization treatment time can be 1-5 hours.
The carbonization treatment may be carried out under a protective gas. Wherein, the protective gas can be inert gas, nitrogen or reducing gas. The inert gas is preferably argon. The flow rate of the protective gas is preferably 0.001-0.05L/(Kg & min).
The equipment for the carbonization treatment may be conventional in the art, and is preferably kiln equipment such as a rotary kiln, a tube furnace, a box furnace, a pusher kiln, a tunnel kiln or a roller kiln.
In the invention, the carbonization treatment also comprises a step of grading or screening the carbonized products.
The third technical scheme provided by the invention is as follows: a hard carbon material is prepared by the preparation method of the hard carbon material.
The fourth technical scheme provided by the invention is as follows: an application of the hard carbon material in a lithium ion battery or a super capacitor.
Wherein the supercapacitor may be an asymmetric supercapacitor.
The fifth technical scheme provided by the invention is as follows: a lithium ion battery whose electrode material comprises a hard carbon material as described above.
Wherein the electrode material is preferably a negative electrode material. The preparation method of the lithium ion battery may be a conventional method in the art.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the hard carbon material has low resistivity (less than 0.26 omega cm), and the overall resistivity of the material is uniformly distributed; when the material is used as a lithium ion battery cathode material, the reversible capacity is high (the first charge capacity can reach over 304mAh/g, the first efficiency can reach over 81 percent), the heavy current performance is good, the quick charge performance is excellent (the 5C quick discharge constant current ratio can reach over 61 percent), and the cycle performance is excellent; the preparation method of the hard carbon material is simple.
Drawings
Fig. 1 is an SEM image of the hard carbon material prepared in example 2.
FIG. 2 is an X-ray diffraction pattern of the hard carbon material prepared in example 2.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. Experimental procedures without specifying specific conditions in the following examples were selected in accordance with conventional procedures and conditions, or in accordance with commercial instructions.
In the following examples and comparative examples: the particle size D50 of the ultrathin flake graphite is 5 mu m, and the thickness is less than 0.1nm.
EXAMPLE 1 preparation of hard carbon Material
(1) Preparing a hard carbon precursor: taking 130g of petroleum asphalt with the softening point of 250 ℃ and the particle size of less than 0.1mm, adding 20g of carbon nanotube-tetrahydrofuran dispersion (the mass percentage of the carbon nanotubes in the carbon nanotube-tetrahydrofuran dispersion is 1%), adding 5g of ultrathin flake graphite with the particle size, uniformly mixing at room temperature, heating to 300 ℃ by using a stainless steel reaction kettle for full melting, heating to 360 ℃ after 2 hours, and naturally cooling to the room temperature to obtain the hard carbon precursor.
Wherein, the content of the conductive agent is (20 g × 1% +5 g)/(130 g × 75% +20g × 1% +5 g) =5.1%;75% is the carbon residue value of the petroleum asphalt with the softening point of 250 ℃.
(2) Oxidation curing treatment: crushing the hard carbon precursor prepared in the step (1) by using airflow crushing equipment, wherein the particle size D50 after crushing is 8 microns; 50g of crushed hard carbon precursor powder is loaded into a rotary furnace, the rotary furnace is rotated at 10 revolutions per minute, air is introduced at 0.1L per minute, the temperature is increased to 200 ℃ at the rate of 3 ℃/minute, then the temperature is increased to 280 ℃ at the rate of 0.5 ℃/minute, and the temperature is kept for 4 hours; and cooling to room temperature to obtain the hard carbon precursor powder subjected to oxidation curing.
(3) Carbonizing treatment: and (3) putting the oxidation-cured hard carbon precursor powder prepared in the step (2) into a tubular furnace, heating to 1000 ℃ at the speed of 3 ℃/min for carbonization, keeping the temperature for 3 hours, cooling to room temperature, and discharging to obtain the hard carbon material.
EXAMPLE 2 preparation of hard carbon Material
Example 2 the pitch in step (1) was a coal tar pitch having a softening point of 220 ℃;
wherein, the content of the conductive agent is (20 g × 1% +5 g)/(130 g × 70% +20g × 1% +5 g) =5.4%;70% is the carbon residue value of the coal tar pitch with a softening point of 220 ℃.
The rest of the procedure was the same as in example 1.
EXAMPLE 3 preparation of hard carbon Material
Example 3 the asphalt in step (1) was petroleum asphalt with a softening point of 220 ℃, and the conductive agent was 10g of carbon nanotube-N, N Dimethylformamide (DMF) dispersion (mass percentage of carbon nanotubes in carbon nanotube-N, N Dimethylformamide (DMF) dispersion was 1%) and 5g of ultrathin flake graphite with a particle size;
wherein, the content of the conductive agent is (10 g × 1% +5 g)/(130 g × 70% +10g × 1% +5 g) =5.3%;70% is the carbon residue value of the petroleum asphalt with a softening point of 220 ℃.
The rest of the procedure was the same as in example 1.
EXAMPLE 4 preparation of hard carbon Material
Example 4 the temperature of the carbonization treatment in the step (3) was 1100 ℃; the rest was the same as in example 1.
EXAMPLE 5 preparation of hard carbon Material
Example 5 the conductive agent in step (1) was 5g of acetylene black;
wherein, the content of the conductive agent is 5 g/(130 g × 75% +5 g) =4.8%;75% is the carbon residue value of the petroleum asphalt with the softening point of 250 ℃.
The rest of the procedure was the same as in example 1.
EXAMPLE 6 preparation of hard carbon Material
Example 6 in the step (2), the temperature was raised to 400 ℃ at a rate of 3 ℃/min and then raised to 500 ℃ at a rate of 0.5 ℃/min; the rest of the procedure was the same as in example 1.
Comparative example 1 preparation of hard carbon Material
Comparative example 1 no conductive agent was added in step (1), and the rest was the same as in example 1.
Comparative example 2 preparation of hard carbon Material
Comparative example 2 in the step (1), the conductive agent is acetylene black, and the content is 0.09%; the rest of the procedure was the same as in example 1.
Comparative example 3 preparation of hard carbon Material
Comparative example 1 in the step (1), the conductive agent is ultrathin flake graphite with the content of 22%; the rest of the procedure was the same as in example 1.
Comparative example 4 preparation of hard carbon Material
Comparative example 4 does not include the oxidative curing treatment, and the rest is the same as example 1.
Effect example 1 testing of morphology and Structure of hard carbon Material
(1) The appearance of the hard carbon material prepared by the above embodiment is tested by a ZEISS 500 field emission scanning electron microscope. Fig. 1 is an SEM image of the hard carbon material prepared in example 2.
(2) The hard carbon material prepared in the above example was tested for its X-ray diffraction pattern using a brook D8X-ray diffractometer. FIG. 2 is an X-ray diffraction pattern of the hard carbon material prepared in example 2.
(3) The resistivity of the hard carbon material prepared in the above example or comparative example was measured using an RTS-4 type four-probe tester. The results are shown in table 1 below.
(4) The hard char materials from the above examples or comparative examples were tested for particle size D50 using Mastersize 2000 (malvern 2000). The results are shown in table 1 below.
Effect example 2 testing of electrochemical properties of hard carbon material
The hard carbon material prepared in the above example or comparative example was mixed with an acetylene black conductive agent and a PVDF binder at a mass ratio of 8 2 Then the copper foil is put into a vacuum drying oven to be dried for 12 hours at the temperature of 80 ℃. Cutting the dried copper foil into 2cm in area 2 The wafer of (2) is made into a working electrode.
Using metal lithium sheet as negative electrode and counter electrode, celgard2400 polypropylene porous membrane as diaphragm, 1mol/L LiPF 6 DEC (volume ratio of 1: 1) solution as electrolyte, assembling into CR-2032 type button cell in vacuum glove box, and sealing mechanically. Electrochemical testing was started after the assembled cell was allowed to stand at room temperature for 24 h.
On a Land CT2001A battery test system, according to the design capacity of 360mAh/g, the current of 0.1C is adopted in the first test week, and the charging and discharging voltage interval is 5 mV-1.5V. The mixture was left for 5 minutes after the completion of the charge or discharge. The button cell 5C rapid discharge constant current ratio test adopts the button cell after 3 weeks of 0.1C circulation, firstly carries out 0.1C charge to 2V, then firstly discharges to 5mV by using 5C to obtain the capacity a, and then discharges to 5mV by using 0.1C to obtain the capacity b. The 5C rapid discharge constant current ratio is a/(a + b) × 100%. The results are given in table 1 below.
TABLE 1
As can be seen from Table 1, the hard carbon material prepared in the above example has a significant advantage in 5C fast discharge constant current ratio. In particular, in the embodiments 1 to 4, the carbon nanotube is added as a conductive agent in the preparation of the hard carbon precursor, so that the carbon nanotube forms a conductive network in the hard carbon material, thereby increasing the conductive capability of the hard carbon material and having a high 5C rapid discharge constant current ratio; the problem that the lithium ion fast desorption and insertion capability of 5C of the hard carbon material is influenced due to high resistivity of the hard carbon material is solved. The oxidation temperature in example 6 was higher than the other examples, resulting in less formation of hard carbon structure and thus lower first charge capacity.
Comparative example 1 although the first charge capacity and the first efficiency are not much different from those of examples 1 to 6, the resistivity is high and the 5C fast discharge constant current ratio is also low because a conductive network is not constructed inside the hard carbon material. The ultra-thin crystalline flake graphite in comparative example 3 has better conductivity and can provide partial capacity, but the 5C constant current of the graphite is lower, so that the 5C constant current of the prepared hard carbon material is also lower. Comparative example 4 has a low capacity and a low 5C constant current ratio because it does not include an oxidative curing process step and forms a soft carbon structure.
Claims (35)
1. A hard carbon material comprising hard carbon and a conductive agent;
the conductive agent is dispersed inside the hard carbon;
the content of the conductive agent is 0.1 to 10 percent; the percentage is the mass percentage of the conductive agent in the hard carbon material;
the preparation method of the hard carbon material comprises the following steps: mixing and melting hard carbon raw materials to prepare a hard carbon precursor, and sequentially carrying out oxidation curing treatment and carbonization treatment on the hard carbon precursor;
wherein the hard carbon raw material comprises asphalt and a conductive agent; the content of the conductive agent is 0.1 to 10 percent; the percentage is the mass percentage of the conductive agent in the hard carbon raw material according to the carbon residue value of the hard carbon raw material;
the softening point of the asphalt is 200 to 320 ℃;
the temperature of the oxidation curing treatment is 200 to 280 ℃;
the conductive agent includes carbon nanotubes.
2. The hard carbon material according to claim 1, wherein the conductive agent is carbon nanotubes and one or more of graphene, conductive graphite, ultra-thin flake graphite, graphite micropowder, ruthenium oxide, and acetylene black;
and/or the content of the conductive agent is 0.1 to 2 percent; the percentage is the mass percentage of the conductive agent in the hard carbon material.
3. The hard carbon material according to claim 2, wherein the conductive agent is one or more of carbon nanotubes and graphite micropowder and ultrathin flake graphite.
4. The hard carbon material of claim 3, wherein the conductive agent is carbon nanotubes and ultrathin flake graphite.
5. The hard carbon material according to claim 2, wherein the conductive agent is a carbon nanotube and ultrathin flake graphite, and the mass ratio of the carbon nanotube to the ultrathin flake graphite is 1: (1 to 100).
6. The hard carbon material according to claim 2, wherein the conductive agent is a carbon nanotube and a graphite micropowder, and the mass ratio of the carbon nanotube to the graphite micropowder is 1: (1 to 100).
7. The hard carbon material according to claim 2, wherein the particle diameter D50 of the fine graphite powder is 5 μm or less.
8. The hard carbon material according to claim 2, wherein the particle diameter D50 of the ultrathin flake graphite is 10 μm or less.
9. The hard carbon material according to claim 1, wherein the content of the conductive agent is 2 to 10%; the percentage is the mass percentage of the conductive agent in the hard carbon material.
10. The hard carbon material as claimed in claim 2, wherein the conductive agent is carbon nanotubes and graphene, and the content of the conductive agent is 0.1 to 2 percent, and the percentage is the mass percentage of the conductive agent in the hard carbon material.
11. The preparation method of the hard carbon material is characterized by comprising the following steps: mixing and melting hard carbon raw materials to prepare a hard carbon precursor, and sequentially carrying out oxidation curing treatment and carbonization treatment on the hard carbon precursor; wherein the hard carbon raw material comprises asphalt and a conductive agent; the content of the conductive agent is 0.1 to 10 percent; the percentage is the mass percentage of the conductive agent in the hard carbon raw material according to the carbon residue value of the hard carbon raw material;
the softening point of the asphalt is 200 to 320 ℃;
the conductive agent comprises carbon nanotubes;
the temperature of the oxidation curing treatment is 200 to 280 ℃;
in the prepared hard carbon material, the conductive agent is dispersed in the hard carbon.
12. The method for producing a hard carbon material according to claim 11, wherein the pitch is petroleum pitch or coal tar pitch;
and/or the asphalt has a softening point of 220 ℃ or 250 ℃;
and/or, the mixing comprises mixing the conductive agent and a dispersant to obtain a conductive agent dispersion liquid, and then mixing the conductive agent dispersion liquid and the asphalt;
and/or, after the melting, further comprising the step of cooling to room temperature;
and/or the particle size D50 of the hard carbon precursor is less than 20 microns, and the particle size D50 of the hard carbon precursor is realized by crushing treatment.
13. The method for producing a hard carbon material according to claim 12, wherein the dispersant is tetrahydrofuran or N, N dimethylformamide.
14. The method for preparing a hard carbon material according to claim 12, wherein the conductive agent is carbon nanotubes, and the dispersant is tetrahydrofuran; wherein the mass ratio of the carbon nano tube is 0.1 to 3 percent, and the percentage is the mass percentage of the carbon nano tube in the conductive agent dispersion liquid.
15. The method for preparing a hard carbon material according to claim 14, wherein the mass ratio of the carbon nanotubes is 1%; the percentage is the mass percentage of the carbon nano tube in the conductive agent dispersion liquid.
16. The method for producing a hard carbon material according to claim 11, wherein the oxidative curing treatment is performed in an oxygen-containing atmosphere;
and/or the temperature of the oxidative curing treatment is 250 to 280 ℃;
and/or the temperature of the oxidation curing treatment is raised in a programmed temperature manner;
and/or the time of the oxidative curing treatment is 2 to 8 hours.
17. The method for producing a hard carbon material according to claim 16, wherein the oxygen content of the oxygen-containing atmosphere is 15 to 100%.
18. The method of preparing a hard char material of claim 16, wherein the oxygen-containing atmosphere comprises one or more of air, oxygen, and ozone.
19. The method of preparing a hard carbon material of claim 18, wherein the oxygen-containing atmosphere further comprises an inert gas.
20. The method for preparing a hard carbon material according to claim 16, wherein the oxygen-containing atmosphere is a mixed gas of: air and oxygen, air and ozone, air and inert gas, oxygen and inert gas, or ozone and inert gas.
21. The method for preparing a hard carbon material according to claim 16, wherein the ventilation volume of the oxygen-containing atmosphere is 0.1 to 2L/(Kgmin).
22. The method for preparing a hard carbon material according to claim 16, wherein the temperature rise rate of the temperature programming is 0.1 to 3 ℃/min;
and/or the time of the oxidative curing treatment is 4 hours.
23. The method for producing a hard char material according to claim 11, wherein the equipment for the oxidative curing treatment is a rotary kiln, a heating mantle or a box furnace;
and/or after the oxidative curing treatment is finished, cooling to room temperature; cooling to obtain asphalt hard carbon powder after oxidation curing treatment;
and/or after the oxidation curing treatment is finished, the method also comprises the step of crushing the pitch hard carbon powder after the oxidation curing treatment.
24. The method for producing a hard carbon material according to claim 23, wherein the asphalt hard carbon powder after the oxidative curing has a particle diameter D50 of 4 to 15 μm after the pulverization.
25. The method for preparing a hard carbon material according to claim 11, wherein the temperature of the carbonization treatment is 800 to 1300 ℃;
and/or the carbonization treatment time is 1 to 5 hours;
and/or the carbonization treatment is carried out under protective gas;
the protective gas is inert gas, nitrogen or reducing gas;
the flow rate of the protective gas is 0.001 to 0.05L/(Kg & min);
and/or the carbonization treatment equipment is kiln equipment;
and/or after the carbonization treatment, the method also comprises the step of grading or screening the carbonized products.
26. The method for preparing a hard carbon material according to claim 25, wherein the temperature of the carbonization treatment is 1000 ℃ or 1100 ℃.
27. The method of claim 25, wherein the temperature is raised by a programmed temperature.
28. The method for preparing a hard carbon material according to claim 27, wherein the temperature rise rate of the temperature programming is 1 to 5 ℃/min.
29. The method of preparing a hard char material of claim 25, wherein the inert gas is argon.
30. The method for producing a hard carbon material according to claim 25, wherein the carbonizing apparatus is a rotary kiln, a tube kiln, a box kiln, a pusher kiln, a tunnel kiln or a roller kiln.
31. A hard carbon material prepared by the method for preparing the hard carbon material as claimed in any one of claims 11 to 30.
32. Use of a hard carbon material as claimed in claim 1 or 31 in a lithium ion battery or supercapacitor.
33. Use of the hard carbon material of claim 32 in a lithium ion battery or a supercapacitor; the super capacitor is an asymmetric super capacitor.
34. A lithium ion battery, characterized in that the electrode material of the lithium ion battery comprises the hard carbon material of claim 1 or 31.
35. The lithium ion battery of claim 34, wherein the electrode material is a negative electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011612702.7A CN112713277B (en) | 2020-12-30 | 2020-12-30 | Hard carbon material, preparation method and application thereof, and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011612702.7A CN112713277B (en) | 2020-12-30 | 2020-12-30 | Hard carbon material, preparation method and application thereof, and lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112713277A CN112713277A (en) | 2021-04-27 |
| CN112713277B true CN112713277B (en) | 2022-12-23 |
Family
ID=75547339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011612702.7A Active CN112713277B (en) | 2020-12-30 | 2020-12-30 | Hard carbon material, preparation method and application thereof, and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112713277B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117466278A (en) * | 2023-11-01 | 2024-01-30 | 东北大学 | Method for ball milling modification of hard carbon material and application of ball milling modification of hard carbon material in negative electrode of sodium ion battery |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102364727A (en) * | 2011-11-15 | 2012-02-29 | 中国东方电气集团有限公司 | Hard carbon micro-spherical composite anode material of lithium battery and preparation method for hard carbon micro-spherical composite anode material |
| CN104064365A (en) * | 2013-03-18 | 2014-09-24 | 海洋王照明科技股份有限公司 | Graphene hard carbon composite material, preparation method thereof and application thereof |
| CN103500815B (en) * | 2013-09-26 | 2016-09-28 | 深圳市贝特瑞新能源材料股份有限公司 | Soft-carbon composite cathode material of lithium ion battery and preparation method thereof |
| CN105645379B (en) * | 2016-01-11 | 2018-03-02 | 神华集团有限责任公司 | Asphalt hard carbon material, its preparation method and its application |
| WO2018032322A1 (en) * | 2016-08-16 | 2018-02-22 | 肖丽芳 | Method for manufacturing positive electrode of lithium-ion capacitor |
| CN107528049B (en) * | 2017-07-31 | 2019-09-10 | 山西三元炭素有限责任公司 | A kind of production technology of lithium cell cathode material |
| CN109037601B (en) * | 2018-03-05 | 2022-07-29 | 贝特瑞新材料集团股份有限公司 | Amorphous carbon composite material and preparation method and application thereof |
| CN110797513B (en) * | 2018-08-03 | 2022-04-05 | 天津大学 | Graphite-hard carbon coated material and preparation method thereof |
| CN111244401B (en) * | 2018-11-28 | 2022-09-23 | 上海杉杉科技有限公司 | Hard carbon coated graphite negative electrode material, lithium ion battery and preparation method and application thereof |
| CN109888200A (en) * | 2018-12-29 | 2019-06-14 | 深圳市卓能新能源股份有限公司 | Battery cathode coating, battery cathode sheet and its manufacturing method, lithium ion battery |
| CN111153392B (en) * | 2019-12-26 | 2022-11-04 | 合肥国轩高科动力能源有限公司 | High-rate lithium ion battery negative electrode material and preparation method thereof |
-
2020
- 2020-12-30 CN CN202011612702.7A patent/CN112713277B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112713277A (en) | 2021-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2022121136A1 (en) | Artificial graphite negative electrode material for high-rate lithium ion battery and preparation method therefor | |
| CN107946576B (en) | High-rate graphite negative electrode material, preparation method thereof and lithium ion battery | |
| CN112758911B (en) | Hard carbon material, preparation method and application thereof, and lithium ion battery | |
| KR20140120861A (en) | Graphite negative electrode material for lithium ion batteries and preparing method thereof | |
| KR20140030319A (en) | Lithium-ion battery negative electrode material, preparation method therefor, and lithium-ion battery | |
| CN112803001B (en) | Coating agent, quick-charge graphite, preparation method and application of coating agent and quick-charge graphite, and battery | |
| CN112768691B (en) | Coating agent, coating modified graphite negative electrode material, preparation method and application thereof, and lithium ion battery | |
| CN107946553B (en) | High-graphitization three-dimensional carbon nanotube graphene composite material and preparation and application thereof | |
| CN113113572B (en) | High-rate natural graphite-based composite material for lithium ion battery and preparation method and application thereof | |
| Lu et al. | Yolk-shell Si/SiO x@ Void@ C composites as anode materials for lithium-ion batteries | |
| CN109360962B (en) | High-stability silicon-carbon negative electrode material for lithium battery and preparation method thereof | |
| CN114188511B (en) | Nitrogen-doped carbon-coated graphite composite material and preparation method and application thereof | |
| CN115417397A (en) | Preparation method of waste biomass hard carbon negative electrode material for sodium ion battery | |
| CN116314773A (en) | Pre-oxidized asphalt-based sodium ion battery anode material, preparation method thereof and obtained product | |
| CN111799098A (en) | Porous carbon/metal oxide composite material and preparation method and application thereof | |
| CN112713277B (en) | Hard carbon material, preparation method and application thereof, and lithium ion battery | |
| CN108682828B (en) | Preparation method of nitrogen-doped carbon-coated positive electrode material | |
| CN113851614A (en) | Low-temperature quick-charging artificial graphite cathode material, preparation method thereof and low-temperature quick-charging battery | |
| CN113991077B (en) | Graphite composite material for lithium battery and preparation method thereof | |
| CN115719801A (en) | Silicon-carbon composite material, preparation method thereof, negative plate and lithium secondary battery | |
| CN111725507B (en) | High-compaction silicon-carbon negative electrode material for lithium ion battery and preparation method thereof | |
| CN109786722B (en) | Method for producing electrochemically active material | |
| CN110600738B (en) | Method for preparing low-temperature lithium ion battery hard carbon negative electrode material | |
| CN112701288A (en) | Coated modified graphite material, preparation method and application thereof, and lithium ion battery | |
| CN115472827A (en) | Coal-based graphite negative electrode material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |