CN110467173A - Amorphous carbon material and preparation method thereof, negative electrode material, lithium ion battery - Google Patents
Amorphous carbon material and preparation method thereof, negative electrode material, lithium ion battery Download PDFInfo
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- CN110467173A CN110467173A CN201910701332.5A CN201910701332A CN110467173A CN 110467173 A CN110467173 A CN 110467173A CN 201910701332 A CN201910701332 A CN 201910701332A CN 110467173 A CN110467173 A CN 110467173A
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/625—Carbon or graphite
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- 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 kind of amorphous carbon materials and preparation method thereof, negative electrode material, lithium ion battery, comprising: mixes biological material with conductive black, mixture is made；The mixture is heat-treated；The mixture after heat treatment is carbonized under an inert atmosphere, amorphous carbon material is made after carbonizing production is ground.Spherical amorphous carbon material can be not only prepared in preparation method provided in an embodiment of the present invention; thus reduce the specific surface area of amorphous carbon material, improve the mechanical performance and chemical property of amorphous carbon material, additionally it is possible to energy crisis and environmental problem be effectively relieved；And prepare that the simple process of amorphous carbon material, equipment requirement are low, preparation cost is low, therefore be convenient for industrialized production application.
Description
Technical field
The present invention relates to battery material technical field, in particular to a kind of amorphous carbon material and preparation method thereof, cathode
Material, lithium ion battery.
Background technique
Lithium ion battery is because its energy density is high, have extended cycle life, operating voltage is high, operating temperature range is wide and safety
The advantages such as good are widely applied in fields such as electronic equipment, electric car, energy-accumulating power station, aerospaces.Negative electrode material as lithium from
One of the key factor that sub- battery energy density is promoted, the extensive concern by researcher.
Currently, commercialized negative electrode material is mainly graphite, on the one hand, its theoretical capacity is only 372mAh/g, gradually
It is not able to satisfy the demand of people；On the other hand, energy crisis becomes increasingly conspicuous with environmental problem, therefore finds and a kind of novel have
The environment-friendly materials of excellent electrochemical performance replace graphite cathode material extremely urgent.
Summary of the invention
In view of this, it is an object of the invention to propose a kind of amorphous carbon material and preparation method thereof, negative electrode material, lithium
Ion battery, to solve the technical problems existing in the prior art.
In the first aspect of the invention, the embodiment of the invention provides a kind of preparation method of amorphous carbon material, packets
Include following steps:
Step (1) mixes biological material with conductive black, and mixture is made；
The mixture is heat-treated by step (2)；
Step (3) carbonizes the mixture after heat treatment under an inert atmosphere, makes after carbonizing production is ground
Obtain amorphous carbon material；
Wherein, the temperature of charing is higher than the temperature of heat treatment.
In some embodiments of the invention, in step (2), the mixture is placed in air atmosphere and carries out hot place
Reason.
In some embodiments of the invention, in step (2), the temperature of heat treatment is 200~260 DEG C, soaking time
It is 1~8 hour.
In some embodiments of the invention, in step (3), the temperature of charing is 500-1500 DEG C, and soaking time is
0.5-6 hours.
In some embodiments of the invention, it in step (2), is heated up with the heating rate of 3-12 DEG C/min, directly
To target temperature；And/or in step (3), heated up with the heating rate of 1-10 DEG C/min, until target temperature.
In some embodiments of the invention, in step (1), the quality of the biological material and the conductive black
Than for 10000:1~50:1.
In some embodiments of the invention, the biological material is sucrose, glucose, mealy potato, tapioca starch, wheat
At least one of powder, corn flour.
In the second aspect of the invention, the embodiment of the invention provides a kind of amorphous carbon material, use is any of the above-described
The preparation method of a amorphous carbon material as described in the examples is prepared, and the external morphology of the amorphous carbon material
For spherical shape.
In the third aspect of the invention, the embodiment of the invention provides a kind of negative electrode materials, comprising: binder, conduction
Amorphous carbon material described in agent and above-described embodiment.
In the fourth aspect of the invention, the embodiment of the invention provides a kind of lithium ion battery, anode and cathode are described
Cathode includes collector and any of the above-described negative electrode material as described in the examples for being coated on the collection liquid surface.
The embodiment of the present invention using natural biological material as presoma, have raw material sources extensively, no pollution to the environment,
The low advantage of cost of material；Before heat treatment, conductive black is added in biological material, so that presoma is in heat treatment process
In be heated evenly, the consistency of presoma increases, so that amorphous carbon material obtained has excellent spherical structure.By
It is spherical shape in the external morphology of amorphous carbon material, therefore it has the advantages that 1) lesser specific surface area, recycles for the first time
Lithium ion consumed by formation solid electrolyte interface film is less in the process, to improve the first effect of battery；2) lithium ion can
To enter the inside of amorphous carbon material from all directions, to improve the capacity and cycle performance of battery；3) have preferable
Mechanical performance, be not pulverized easily in charge and discharge process and destroy its structure.In addition, due to the addition of conductive black,
The excellent amorphous carbon material of preparation structure is not only contributed to, the electric conductivity of amorphous carbon material is also greatly improved, thus
Charge-transfer resistance in charge and discharge process is reduced, the cycle performance and high rate performance of amorphous carbon material are improved.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the flow chart of the preparation method of amorphous carbon material of the present invention；
Fig. 2 is the X ray diffracting spectrum of amorphous carbon material of the present invention；
Fig. 3 is the scanning electron microscope diagram of amorphous carbon material of the present invention；
Fig. 4 is the scanning electron microscope diagram of the amorphous carbon material of comparative example 1；
Fig. 5 is the scanning electron microscope diagram of the amorphous carbon material of comparative example 2.
Specific embodiment
In order to enable those skilled in the art to better understand the solution of the present invention, below in conjunction in the embodiment of the present invention
Attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is only
The embodiment of a part of the invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill people
The model that the present invention protects all should belong in member's every other embodiment obtained without making creative work
It encloses.
The graphite microcrystal of amorphous carbon material internal is disorderly arranged, is cross-linked with each other between crystallite, and crystallinity is low, graphite microcrystal
Small, during circulating battery, volume change is small, electrochemical performance, and manufacturing cost is low.But using existing preparation side
Performance of the amorphous carbon material made from method for lithium ion battery is poor.
For example, Chinese patent CN201510824176.3 discloses a kind of preparation side of the amorphous carbon material of nano tunnel
Method restores potassium permanganate by hydro-thermal method and obtains rodlike manganese dioxide, it is mixed to form hydrogel with biomass presoma, very
Carbonization treatment after sky is dry finally carries out pickling, activation processing obtains amorphous carbon material.Using the preparation side of the patent disclosure
Method preparation amorphous carbon be nano tunnel amorphous carbon, due to the invention be contemplated that based on supercapacitor carry out,
The large specific surface area of obtained nano tunnel amorphous carbon material.If the nano tunnel amorphous carbon material is used for lithium electricity
Pond can make the first effect of battery and battery capacity lower due to its high-specific surface area.In addition, the preparation method of the patent disclosure
In raw materials used (such as potassium permanganate) have corrosivity and irritation, memory requirement high, and the preparation process of this method compared with
Complexity is unfavorable for industrialized production.
In order to solve the technical problems existing in the prior art, the embodiment of the invention provides a kind of amorphous carbon materials
Preparation method, as shown in Figure 1, may comprise steps of:
Step (1) mixes biological material with conductive black, and mixture is made；
The mixture is heat-treated by step (2)；
Step (3) carbonizes the mixture after heat treatment under an inert atmosphere, makes after carbonizing production is ground
Obtain amorphous carbon material；Wherein, the temperature of charing is higher than the temperature of heat treatment.
As shown in Fig. 2, it is the X ray diffracting spectrum of amorphous carbon material of the present invention.The steamed bun peak formed from Fig. 2 can
To find out, use Carbon Materials made from preparation method provided in an embodiment of the present invention for unbodied Carbon Materials.
The embodiment of the present invention using natural biological material as presoma, have raw material sources extensively, no pollution to the environment,
The low advantage of cost of material；Before heat treatment, conductive black is added in biological material, so that presoma is in heat treatment process
In be heated evenly, the consistency of presoma increases, so that amorphous carbon material obtained has excellent spherical structure, such as
Shown in Fig. 3.Since the external morphology of amorphous carbon material is spherical shape, 1) lesser specific surface area is had the advantages that,
Lithium ion consumed by formation solid electrolyte interface film is less in cyclic process for the first time, to improve the first effect of battery；
2) lithium ion can enter the inside of amorphous carbon material from all directions, to improve the capacity and cycle performance of battery；
3) there is preferable mechanical performance, be not pulverized easily in charge and discharge process and destroy its structure.Before carbonization
It is heat-treated, is conducive to biological material and gradually forms stable spherical structure during heat treatment, prevent it subsequent
Carbonization process in melt.
In addition, not only contributing to the excellent amorphous carbon material of preparation structure due to the addition of conductive black, also mentioning significantly
The electric conductivity of amorphous carbon material has been risen, to reduce Charge-transfer resistance in charge and discharge process, has improved amorphous carbon
The cycle performance and high rate performance of material.
Therefore, spherical amorphous carbon material can be not only prepared in preparation method provided in an embodiment of the present invention, by
This reduces the specific surface area of amorphous carbon material, improves the mechanical performance and chemical property of amorphous carbon material, additionally it is possible to have
Imitate alleviating energy crisis and environmental problem；And prepare that the simple process of amorphous carbon material, equipment requirement be low, preparation cost
It is low, therefore it is convenient for industrialized production application.
Optionally, in step (1), biological material and conductive black are mixed according to the mass ratio of 10000:1~50:1
It closes.Biological material is generally powdered, is easy to appear the problem that surface temperature is high, internal temperature is low during heat treatment,
Lead to melting phenomenon occur, therefore, it is difficult to spherical amorphous carbon material is made.A small amount of conduction is mixed into biological material
Carbon black enables to presoma to be heated evenly during heat treatment, and the consistency of presoma increases, to avoid melting
Thus spherical amorphous carbon material is made in phenomenon.According to the mass ratio add conductive black, can not only guarantee presoma by
It is hot uniform, moreover it is possible to improve the electric conductivity of amorphous carbon material.Preferably, the mass ratio of biological material and conductive black is
1000:1~100:1, it is also ensured that presoma is heated evenly, moreover it is possible to improve the electric conductivity of amorphous carbon material.Wherein, raw
The mass ratio of material and conductive black is typical but preferred without limitation 10000:1,8000:1,5000:1,3300:1,
2500:1,1600:1,1000:1,750:1,500:1,300:1,120:1,100:1,50:1 etc., in these embodiments,
To guarantee that presoma is heated evenly, moreover it is possible to improve the electric conductivity of amorphous carbon material.
Optionally, in step (1), the biological material be sucrose, glucose, mealy potato, tapioca starch, wheat flour,
At least one of corn flour, the from a wealth of sources of these materials, no pollution to the environment, cost of material are low, and can be prepared
Spherical amorphous carbon material, therefore it is very suitable for the raw material as amorphous carbon material.
Optionally, in step (2), the mixture is placed in air atmosphere and is heat-treated.Mixture is placed in
It is heat-treated in air atmosphere, brings it about oxidation reaction, be conducive to the removing for accelerating moisture in biological material, to contract
Short heat treatment time.It is heat-treated it should be pointed out that the mixture can also be placed in inert atmosphere, can also reach
To technical effect of the invention, only since the removing of moisture slows, the time of heat treatment can be extended.Due to air gas
Atmosphere is easier to realize, and heat treatment time is shorter, and preferably mixture is placed in air atmosphere and is heat-treated.
Optionally, in step (2), the temperature of heat treatment is 200~260 DEG C, and soaking time is 1~8 hour, so that raw
Material gradually forms stable spherical structure during heat treatment, so that final amorphous carbon material obtained is with excellent
Good spherical structure.Preferably, the temperature of heat treatment is 210~240 DEG C in step (2), soaking time is 2~6 hours,
On the one hand so that biological material is gradually formed stable spherical structure during heat treatment, on the other hand reduce energy consumption.
Wherein, the temperature typical case of heat treatment but without limitation preferably 208 DEG C, 210 DEG C, 212 DEG C, 215 DEG C, 220 DEG C, 225 DEG C, 228
DEG C, 236 DEG C, 240 DEG C, 250 DEG C etc., soaking time it is typical but without limitation preferably 1.5 hours, 2 hours, 3 hours, it is 3.5 small
When, 4.2 hours, 5 hours, 5.5 hours, 6 hours and 7.4 hours etc., in these embodiments, biological material can be made in heat
Stable spherical structure is gradually formed in treatment process.
In step (2), heated up with the heating rate of 3-12 DEG C/min, until target temperature, so that presoma
It is heated evenly during heat treatment, avoids that melting phenomenon occurs.Preferably, being risen with the heating rate of 5-10 DEG C/min
Temperature, until target temperature, under the premise of guaranteeing that presoma is heated evenly during heat treatment, shorten heat treatment it is total when
Between.Wherein, heating rate is typical but without limitation preferably 3 DEG C/min, 4 DEG C/min, 4.5 DEG C/min, 5 DEG C/min, 7 DEG C/
Min, 8.5 DEG C/min, 9 DEG C/min, 10 DEG C/min and 11 DEG C/min etc..
Optionally, in step (3), the temperature of charing is 500-1500 DEG C, and soaking time is 0.5-6 hours, so that mixed
It closes material and is converted to amorphous carbon material.Preferably, the temperature of charing is 600-1200 DEG C.Preferably, the temperature of charing is 700-
1000℃.Under the premise of guaranteeing to obtain amorphous carbon material, energy consumption can be reduced by reducing carbonization temperature.It is optional
Ground, soaking time are also possible to 1-3 hours, and energy consumption can also be reduced by shortening soaking time.Wherein, the temperature of charing is typical
But without limitation preferably 550 DEG C, 600 DEG C, 700 DEG C, 750 DEG C, 820 DEG C, 945 DEG C, 1000 DEG C and 1100 DEG C etc., soaking time
It is typical but without limitation preferably 0.8 hour, 1 hour, 1.5 hours, 2.4 hours, 3 hours, 3.6 hours, 4 hours, 5 hours and
5.2 hours etc..
Optionally, it in step (3), is heated up with the heating rate of 1-10 DEG C/min, until target temperature.Preferably
Ground can be heated up with the heating rate of 1-3 DEG C/min, until target temperature.Wherein, heating rate is typical but non-limiting
Ground preferably 1 DEG C/min, 2 DEG C/min, 3 DEG C/min, 5 DEG C/min, 7 DEG C/min, 8.5 DEG C/min, 9 DEG C/min and 10 DEG C/min etc..
The embodiment of the invention also provides a kind of amorphous carbon materials, fixed using any of the above-described nothing as described in the examples
The preparation method of shape Carbon Materials is prepared, as shown in Fig. 2, and the amorphous carbon material external morphology be spherical shape, such as
Shown in Fig. 3.
The embodiment of the invention also provides a kind of negative electrode materials, including described in binder, conductive agent and above-described embodiment
Negative electrode material.Wherein, the mass ratio of binder, conductive agent and negative electrode material is typical but preferred without limitation 1:1:7,1:1:
8,1:1:9,1:0.5:8,2:1:8,1:1.5:8,1:1:10 etc. make it so that the negative electrode material has moderate viscosity
Even is coated on collection liquid surface.
The embodiment of the invention also provides a kind of lithium ion batteries, including anode and cathode, the cathode include collector
(such as metal foil) and any of the above-described negative electrode material as described in the examples for being coated on the collection liquid surface.
A small amount of conductive black is added using natural biological material as presoma in the embodiment of the present invention, and to biological material
The mixture of material and conductive black is heat-treated, so that presoma is heated evenly during heat treatment, so that being made
Amorphous carbon material have excellent spherical structure.Using the amorphous carbon material with spherical structure as the cathode of lithium ion
Material can be improved first effect, discharge capacity and the cycle performance of battery；And due to the addition of conductive black, not only contribute to
The excellent negative electrode material of preparation structure, also greatly improves the electric conductivity of cathode, to reduce charge in charge and discharge process
Transfger impedance improves the cycle performance and high rate performance of lithium ion battery.
Optionally, the preparation method of the lithium ion battery, comprising: negative electrode material is coated on collector (such as: copper foil),
It is dried at 115~120 DEG C, is cut into negative electrode tab, then button cell or Soft Roll is made with diaphragm, anode (such as: metal lithium sheet)
Battery, so that production obtains lithium ion battery.
In order to help to understand the solution of the present invention, the preparation process of several specific amorphous carbon materials is given below.
Embodiment 1
The preparation method for present embodiments providing a kind of amorphous carbon material, is prepared in accordance with the following steps:
Mealy potato is uniformly mixed with conductive black according to the mass ratio of 100:1 by step (1), obtains mixture；
Mixture is warming up to 230 DEG C with the heating rate of 8 DEG C/min by step (2), keeps the temperature 5 hours；
Mixture is transferred to the tube furnace for being passed through nitrogen protection atmosphere by step (3), with the heating rate liter of 2 DEG C/min
Temperature keeps the temperature 1.5 hours to 750 DEG C；By carbonizing production cooled to room temperature, amorphous carbon material is made after grinding.
Embodiment 2
The preparation method for present embodiments providing a kind of amorphous carbon material, the difference with the preparation method of embodiment 1
Place is: in step (1), the mass ratio of mealy potato and conductive black is 200:1.
Embodiment 3
The preparation method for present embodiments providing a kind of amorphous carbon material, the difference with the preparation method of embodiment 1
Place is: in step (1), the mass ratio of mealy potato and conductive black is 50:1.
Embodiment 4
The preparation method for present embodiments providing a kind of amorphous carbon material, the difference with the preparation method of embodiment 1
Place is: in step (1), the mass ratio of mealy potato and conductive black is 1000:1.
Embodiment 5
The preparation method for present embodiments providing a kind of amorphous carbon material, the difference with the preparation method of embodiment 1
Place is: in step (1), biological material is tapioca starch.
Embodiment 6
The preparation method for present embodiments providing a kind of amorphous carbon material, the difference with the preparation method of embodiment 1
Place is: in step (1), biological material is sucrose.
Embodiment 7
The preparation method for present embodiments providing a kind of amorphous carbon material, the difference with the preparation method of embodiment 1
Place is: in step (2), soaking time is 1 hour.
Embodiment 8
The preparation method for present embodiments providing a kind of amorphous carbon material, the difference with the preparation method of embodiment 1
Place is: in step (2), soaking time is 4 hours.
Embodiment 9
The preparation method for present embodiments providing a kind of amorphous carbon material, the difference with the preparation method of embodiment 1
Place is: in step (2), soaking time is 8 hours.
Embodiment 10
The preparation method for present embodiments providing a kind of amorphous carbon material, the difference with the preparation method of embodiment 1
Place is: in step (2), being warming up to 200 DEG C.
Embodiment 11
The preparation method for present embodiments providing a kind of amorphous carbon material, the difference with the preparation method of embodiment 1
Place is: in step (2), being warming up to 260 DEG C.
Embodiment 12
The preparation method for present embodiments providing a kind of amorphous carbon material, the difference with the preparation method of embodiment 1
Place is: in step (3), being warming up to 500 DEG C.
Embodiment 13
The preparation method for present embodiments providing a kind of amorphous carbon material, the difference with the preparation method of embodiment 1
Place is: in step (3), being warming up to 950 DEG C.
Embodiment 14
The preparation method for present embodiments providing a kind of amorphous carbon material, the difference with the preparation method of embodiment 1
Place is: in step (3), being warming up to 1500 DEG C.
Comparative example 1
This comparative example provides a kind of preparation method of amorphous carbon material, the difference with the preparation method of embodiment 1
Place is: in step (1), being not added with conductive black.
Comparative example 2
This comparative example provides a kind of preparation method of amorphous carbon material, the difference with the preparation method of embodiment 1
Place is: the heat treatment of step (2) is not carried out to mixture.
Comparative example 3
This comparative example provides a kind of preparation method of amorphous carbon material, the difference with the preparation method of embodiment 1
Place is: in step (1), the mass ratio of mealy potato and conductive black is 40:1.
Comparative example 4
This comparative example provides a kind of preparation method of amorphous carbon material, the difference with the preparation method of embodiment 1
Place is: in step (2), soaking time 9h.
Comparative example 5
This comparative example provides a kind of preparation method of amorphous carbon material, the difference with the preparation method of embodiment 1
Place is: in step (2), being warming up to 190 DEG C.
Comparative example 6
This comparative example provides a kind of preparation method of amorphous carbon material, the difference with the preparation method of embodiment 1
Place is: in step (2), being warming up to 270 DEG C.
Comparative example 7
This comparative example provides a kind of preparation method of amorphous carbon material, the difference with the preparation method of embodiment 1
Place is: in step (3), being warming up to 400 DEG C.
Comparative example 8
This comparative example provides a kind of preparation method of amorphous carbon material, the difference with the preparation method of embodiment 1
Place is: in step (3), being warming up to 1600 DEG C.
Performance test
Respectively by amorphous carbon material made from binder, conductive agent and embodiment 1-14 and comparative example 1-8 according to matter
Amount configures slurry than 1:1:8, obtains negative electrode slurry, negative electrode slurry is coated on copper foil, dry at 120 DEG C, be cut into diameter
The negative electrode tab of 12mm, then button cell is made with diaphragm, positive plate, so that assembling obtains lithium ion battery.
The chemical property of these lithium ion batteries is tested, test temperature is 25 DEG C, current density 50mA/g, test electricity
Pressure is 0.01-3V.For the ease of comparing, as table 1 list embodiment 1-14 and comparative example 1-8 made from lithium ion battery
Test result.
Table 1
It can be seen from Table 1 that the specific discharge capacity of embodiment 1~14 is much higher than the theoretical specific capacity 372mAh/ of graphite
g.This is primarily due to the amorphous structure of amorphous carbon provided by the invention, more embedding lithium sites is made it have, for the first time
There are more lithium ion insertion negative electrode materials in cyclic process.
By embodiment 1 and comparative example 1 as can be seen that conductive black is added in preparation method of the present invention, obtained nothing
Shape Carbon Materials, can reduce the specific capacity irreversible for the first time and Charge-transfer resistance of battery.
This is mainly due to joined conductive black in biological material, on the one hand biological material can be made in Re Chu
It is heated evenly during reason, to obtain the excellent spherical amorphous Carbon Materials of structure, therefore is easily formed on its surface stable
Solid electrolyte interface film reduces irreversible specific capacity for the first time, to mention so as to reduce the lithium ion in consumption electrolyte
The first effect of high battery；On the other hand the electric conductivity of Carbon Materials is improved, conducive to the diffusion transfer of ion, reduces electric charge transfer resistance
It is anti-.
It include the embodiment 1 of step (2) through embodiment 1 and comparative example 2 as can be seen that in preparation method of the present invention
The amorphous materials that comparative example 2 than not including step (2) obtains, can be improved the specific discharge capacity of lithium ion battery, reduce
The irreversible capacity for the first time of battery reduces Charge-transfer resistance.
This is because amorphous carbon can be made to form excellent spherical structure comprising step (2), to improve putting for battery
Electric specific capacity, reduces the irreversible capacity for the first time of battery, while reducing Charge-transfer resistance.
By comparative example 1 (be equivalent to conductive black additional amount be 0), embodiment 4 (1000:1), embodiment 2 (200:1),
Embodiment 1 (100:1), embodiment 3 (50:1) are compared with comparative example 3 (40:1), it will thus be seen that as conductive black content increases
Add, the specific discharge capacity of battery first increases to be reduced afterwards；Irreversible specific capacity gradually decreases for the first time, and Charge-transfer resistance gradually subtracts
It is small；The specific capacity difference irreversible for the first time of embodiment 3 and comparative example 3 is little, and Charge-transfer resistance difference is also little, therefore explanation
The amount for increasing conductive black again does not help the raising of battery performance not only, instead since the accounting of conductive black increases, drop
The capacity of low battery.Therefore, it can be seen that when the mass ratio of biological material and conductive black is 10000:1~50:1, it can be with
The specific capacity irreversible for the first time and Charge-transfer resistance for reducing battery, to improve the performance of battery.
Pass through comparative example 2 (0h), embodiment 7 (1h), embodiment 8 (4h), embodiment 1 (5h), embodiment 9 (8h), comparison
Example 4 (9h) is as can be seen that as soaking time increases in step (2), and the specific discharge capacity of battery increases, for the first time irreversible ratio
Capacity reduces, and Charge-transfer resistance reduces；But the indices of embodiment 9 and comparative example 4 variation it is unobvious, illustrate from 8h with
Too much influence will not be occurred to the performance of amorphous carbon material by extending the reaction time again afterwards, therefore, the heat preservation in step (2)
1-8h.
By comparative example 5 (190 DEG C), embodiment 10 (200 DEG C), embodiment 1 (230 DEG C), embodiment 11 (260 DEG C), right
It can be found that as the heat treatment temperature in step (2) increases, the specific discharge capacity of battery first increases to drop ratio 6 (270 DEG C) afterwards
Low, irreversible specific capacity first reduces for the first time increases afterwards, and Charge-transfer resistance is first to reduce to increase afterwards；And it can be seen that from data
For the temperature range at 200~260 DEG C, the performance of battery is best.When heat treatment temperature is more than 260 DEG C, biomass is former
Material molten, amorphous carbon material specific surface area obtained increase, and will increase irreversible specific capacity for the first time；Heat treatment temperature is lower than
200 DEG C, thermal effectiveness is bad.
By embodiment 12-14 with comparative example 7 it can be found that carbonization temperature is too low, charing is inadequate, leads to putting for battery
Electric specific capacity is smaller, irreversible specific capacity increases, Charge-transfer resistance increases for the first time.
By embodiment 12-14 and comparative example 8 it can be found that when carbonization temperature increases, the specific discharge capacity of negative electrode material
Reduce, irreversible specific capacity reduces for the first time, and Charge-transfer resistance reduces.This is mainly that carbonization temperature increases, amorphous carbon material
Crystallinity increase, the defect sites of material internal are reduced, and embedding lithium site is few, so specific discharge capacity declines；Journey is carbonized simultaneously
Degree is deepened, and the electric conductivity of material is promoted, and impedance reduces.But when carbonization temperature is higher than 1500 DEG C, chemical property amplitude of variation
It is smaller；Therefore the carbonization temperature in step (3) is 500-1500 DEG C.
Fig. 3 is the scanning electron microscope diagram of amorphous carbon material of the present invention, and Fig. 4 is the amorphous carbon material of comparative example 1
Scanning electron microscope diagram, Fig. 5 be comparative example 2 amorphous carbon material scanning electron microscope diagram.By comparing Fig. 3-5
As can be seen that comparative example 1 leads to uneven heating during heat treatment due to not adding conductive black in biological material
Even, the consistency of presoma is poor, is easy to happen melting, therefore the amorphous carbon material after charing is most of in the form of sheets, only
Only a few forms spherical structure.Comparative example 2 causes to mix due to not being heat-treated mixture before carbonization
The spherical structure of material is unstable, although foring spherical structure, most spherical structure is also melted, so that ball
The dimensional homogeneity of shape structure is poor.And the present invention advances due to being added to conductive black in biological material, and in charing
Heat treatment is gone, so that presoma is heated evenly during heat treatment, the consistency of presoma increases, and is conducive to biological material
Material gradually forms stable spherical structure during heat treatment, so that amorphous carbon material obtained has excellent ball
Shape structure.
It can be seen that the embodiment of the present invention is using natural biological material as presoma, have raw material sources extensively, to ring
The advantage that border is pollution-free, cost of material is low；Before heat treatment, conductive black is added in biological material, so that presoma exists
It is heated evenly in heat treatment process, the consistency of presoma increases, so that amorphous carbon material obtained is with excellent
Spherical structure.Since the external morphology of amorphous carbon material is spherical shape, 1) lesser specific surface is had the advantages that
Product, lithium ion consumed by formation solid electrolyte interface film is less in cyclic process for the first time, to improve the head of battery
Effect；2) lithium ion can enter the inside of amorphous carbon material from all directions, to improve the capacity and cyclicity of battery
Energy；3) there is preferable mechanical performance, be not pulverized easily in charge and discharge process and destroy its structure.In addition, due to leading
The addition of electric carbon black not only contributes to the excellent amorphous carbon material of preparation structure, also greatly improves amorphous carbon material
Electric conductivity, to reduce Charge-transfer resistance in charge and discharge process, improve the cycle performance of amorphous carbon material with times
Rate performance.
It should be understood by those ordinary skilled in the art that: the discussion of any of the above embodiment is exemplary only, not
It is intended to imply that the scope of the present disclosure (including claim) is limited to these examples；Under thinking of the invention, above embodiments
Or it can also be combined between the technical characteristic in different embodiments, and there are different aspects present invention as described above
Many other variations, in order to it is concise they do not provided in details.Therefore, all within the spirits and principles of the present invention,
Any omission, modification, equivalent replacement, improvement for being made etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of amorphous carbon material, which comprises the following steps:
Step (1) mixes biological material with conductive black, and mixture is made；
The mixture is heat-treated by step (2)；
Step (3) carbonizes the mixture after heat treatment under an inert atmosphere, and nothing is made after carbonizing production is ground
Shape Carbon Materials；
Wherein, the temperature of charing is higher than the temperature of heat treatment.
2. preparation method according to claim 1, which is characterized in that in step (2), the mixture is placed in air
It is heat-treated in atmosphere.
3. preparation method according to claim 1, which is characterized in that in step (2), the temperature of heat treatment is 200~
260 DEG C, soaking time is 1~8 hour.
4. preparation method according to claim 1, which is characterized in that in step (3), the temperature of charing is 500-1500
DEG C, soaking time is 0.5-6 hours.
5. preparation method according to claim 1, which is characterized in that in step (2), with the heating speed of 3-12 DEG C/min
Rate heats up, until target temperature；And/or in step (3), heated up with the heating rate of 1-10 DEG C/min, until
Target temperature.
6. preparation method according to claim 1, which is characterized in that in step (1), the biological material with it is described
The mass ratio of conductive black is 10000:1~50:1.
7. preparation method according to claim 1, which is characterized in that the biological material is sucrose, glucose, potato
At least one of powder, tapioca starch, wheat flour, corn flour.
8. a kind of amorphous carbon material, which is characterized in that using such as amorphous carbon material of any of claims 1-6
Preparation method be prepared, and the external morphology of the amorphous carbon material be spherical shape.
9. a kind of negative electrode material characterized by comprising binder, conductive agent and amorphous raw material of wood-charcoal as claimed in claim 8
Material.
10. a kind of lithium ion battery, which is characterized in that including anode and cathode, the cathode includes collector and and is coated on
The negative electrode material as claimed in claim 9 of the collection liquid surface.
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