CN109148838B - Anode material of lithium-ion battery and its preparation method and application - Google Patents
Anode material of lithium-ion battery and its preparation method and application Download PDFInfo
- Publication number
- CN109148838B CN109148838B CN201710904851.2A CN201710904851A CN109148838B CN 109148838 B CN109148838 B CN 109148838B CN 201710904851 A CN201710904851 A CN 201710904851A CN 109148838 B CN109148838 B CN 109148838B
- Authority
- CN
- China
- Prior art keywords
- charcoal
- pitch
- carbon
- ion battery
- bamboo
- 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
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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
-
- 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 kind of anode material of lithium-ion battery and its preparation method and application based on Carbon Materials and pitch, the anode material of lithium-ion battery are that surface coats the pattern of the orderly carbon structure of asphaltic base in the complex carbon material of irregular blocky or vertical-shaped channel shape.Using Carbon Materials and pitch as precursor material, it is heat-treated in air after mechanical mixture, it is coated on charcoal material surface after making asphalt melting, make pitch and Carbon Materials under an inert atmosphere later while carbonization, cracking reaction occurs, obtaining structure is the complex carbon material that surface is orderly, inside is unordered；Wherein, the type of the charcoal includes charcoal and bamboo charcoal, charcoal includes one of hard charcoal, black wood charcoal, active carbon and machine-made carbon or a variety of mixtures, bamboo charcoal includes one of moso bamboo, henon bamboo, bitter bamboo, Lei Zhu and bambusa textile or a variety of char-forming material mixtures, and the pitch is one of coal tar pitch, asphalt and bitumen or a variety of mixtures.
Description
Technical field
The present invention relates to field of material technology more particularly to a kind of sodium-ion battery cathode materials based on Carbon Materials and pitch
Material and its preparation method and application.
Background technique
With gradually exhausting for fossil fuel and increasingly sharpening for environmental pollution, new energy carrier is developed and used increasingly
It is valued by people.Secondary cell is played an important role as main chemical energy storage equipment in this field.It is taken with electric power
The discharge of greenhouse gases will be greatly decreased for the main energy-provision way that fossil fuel becomes the vehicles.With wind energy, solar energy,
The configuration building of the renewable energy such as thermal energy improves the service efficiency that various network systems will greatly improve renewable energy.
With its sodium, the advantages such as resourceful, widely distributed and low in cost compensate for lithium-ion electric Pooled resources to sodium-ion battery
It is rare, be unevenly distributed limitation with higher cost, in receiving the common concern of people in recent years, and obtained widely grinding
Study carefully.It is most important to the commercialization for realizing sodium-ion battery to develop high performance electrode material.So far, some positive electrodes
Research and development substantially met the requirement of application, but negative electrode material still restricts the functionization of sodium-ion battery.
In reported anode material of lithium-ion battery, amorphous carbon material with its relatively low storage sodium current potential, compared with
The high anode material of lithium-ion battery for becoming most application prospect the advantages that storing up sodium capacity and good cyclical stability.System
The presoma of standby amorphous carbon material can be divided into soft carbon and hard carbon presoma, the former is cheap, at high temperature can complete stone
Mo Hua, electric conductivity are excellent；The latter's price is higher, cannot be graphitized completely at high temperature, but the carbon material obtained after its carbonization
It stores up sodium specific capacity and first all efficiency is relatively high.In conjunction with the advantage of two kinds of presomas, the nothing that two kinds of forerunner's bluk recombinations are obtained is fixed
Type carbon material is expected to further make the most of the advantage, and promotes it as the large-scale application of sodium-ion battery cathode.
Summary of the invention
The embodiment of the invention provides a kind of anode material of lithium-ion battery based on Carbon Materials and pitch and its preparation sides
Method and application, using resourceful, cheap, reproducible charcoal and/or bamboo charcoal as raw material, and with lower-cost common stone
Oily industrial residu pitch has taken into account high capacity and excellent electric conductivity together as compound material, proposes a kind of at low cost
It is honest and clean, preparation process is simple, the degree of disorder is adjustable, it is high to produce carbon rate, suitable for the complex carbon material of large-scale production, and as cathode
Material is applied in sodium ion secondary battery.
In a first aspect, the embodiment of the invention provides a kind of anode material of lithium-ion battery based on Carbon Materials and pitch,
The anode material of lithium-ion battery is that surface coats the pattern of the orderly carbon structure of asphaltic base in irregular blocky or vertical-shaped channel
The complex carbon material of shape；It using Carbon Materials and pitch as precursor material, is heat-treated in air after mechanical mixture, keeps pitch molten
It is coated on charcoal material surface after change, makes pitch and Carbon Materials under an inert atmosphere later while carbonization occurs, cracking is prepared；
The Carbon Materials include charcoal and/or bamboo charcoal；The charcoal includes in hard charcoal, black wood charcoal, active carbon and machine-made carbon
One or more mixtures, the bamboo charcoal include one of char-forming material of moso bamboo, henon bamboo, bitter bamboo, Lei Zhu and bambusa textile or more
Kind mixture；The pitch is one of coal tar pitch, asphalt and bitumen or a variety of mixtures；
The anode material of lithium-ion battery has the structure feature that surface is orderly, inside is unordered；
It wherein, is in irregular block-like complex carbon material, size by the charcoal and the compound pattern being prepared of pitch
Between 2-10 microns, d002Value is between 0.37-0.40nm, and Lc value is between 1-4nm, and La value is between 3-5nm；By described
Charcoal and the compound pattern being prepared of pitch are in the complex carbon material of vertical-shaped channel shape, and length is 5-30 microns, pipeline aperture
It is 2-3 microns, d002Value is between 0.36-0.38nm, and Lc value is between 1-4nm, and La value is between 3-5nm；By the bamboo charcoal with
The compound pattern being prepared of pitch is in irregular block-like carbon material, and size is between 2-15 microns, d002Value is in 0.35-
Between 0.37nm, Lc value is between 1-4nm, and La value is between 3-5nm.
Preferably, the mass ratio of the Carbon Materials and the pitch is 1:(0.05-0.2).
Preferably, the charcoal is made by hophornbeam or hard weedtree through kiln process, and the bamboo charcoal is by moso bamboo through kiln process system
, the pitch is asphalt.
Second aspect, the embodiment of the invention provides anode material of lithium-ion batteries described in a kind of above-mentioned first aspect
Preparation method, comprising:
One or more charcoals or bamboo charcoal and asphalt stock are subjected to smashing mixing according to mass ratio for 1:(0.05-0.2),
Obtain coarse powder；
The coarse powder is refined, fine powder raw material of the partial size within the scope of some scale is obtained；
The fine powder raw material is put into Muffle furnace and carries out heat treatment 2-4 hours at 250-300 DEG C, is wrapped after making asphalt melting
Overlay on charcoal material surface；
Raw material after heat treatment is put into high temperature carbonization furnace, is warming up to the heating rate of 3 DEG C/min-5 DEG C/min
1200 DEG C -1600 DEG C, the raw material is heated at high temperature in an inert atmosphere, the time is 2-4 hours, so that the raw material is sent out
Raw carbonization, cracking reaction；
It is cooled to room temperature, obtaining structure is in that surface is orderly, internal unordered, and pattern is in irregular bulk or vertical-shaped channel shape
Complex carbon material is the anode material of lithium-ion battery.
Preferably, described be pulverized and mixed specifically includes: mechanical crushing, ball milling, stirring, sieving and/or ultrasonic disperse.
It preferably, is 1:(0.05-0.2 according to mass ratio by one or more charcoals or bamboo charcoal and asphalt stock described)
Before carrying out smashing mixing, the method also includes:
The charcoal and bamboo charcoal is prepared using kiln process.
Preferably, the charcoal includes hophornbeam charcoal or hard weedtree charcoal, and the bamboo charcoal includes moso bamboo charcoal, and the pitch includes
Asphalt.
The third aspect, the embodiment of the invention provides a kind of cathode pole pieces of sodium-ion battery, comprising:
Collector, coated on the collector binder and above-mentioned first aspect described in sodium-ion battery cathode
Material.
Fourth aspect, the embodiment of the invention provides a kind of sodium ions including cathode pole piece described in the above-mentioned third aspect
Secondary cell, the sodium ion secondary battery be used for mobile device, the vehicles, renewable energy power generation, smart grid peak regulation,
It is distributed power station, the energy storage device of backup power supply or communication base station.
Anode material of lithium-ion battery provided in an embodiment of the present invention based on Carbon Materials and pitch and preparation method thereof and
Using, using resourceful, cheap, reproducible charcoal and/or bamboo charcoal as raw material, and with lower-cost common petroleum work
Industry residue pitch has taken into account high capacity and excellent electric conductivity together as compound material, proposes a kind of low in cost, system
Standby simple process, the degree of disorder is adjustable, it is high to produce carbon rate, suitable for the complex carbon material of large-scale production, and as negative electrode material
Applied in sodium ion secondary battery.With the sodium ion secondary battery of negative electrode material of the present invention, operating voltage with higher and
Energy density, high rate performance is excellent, and stable cycle performance has a safety feature, and cannot be only used for mobile device and electric car
Power supply can be also used for renewable energy power generation, smart grid peak regulation, the energy storage for being distributed power station, backup power supply or communication base station
Equipment.
Detailed description of the invention
Fig. 1 is the preparation method for the complex carbon material based on Carbon Materials and pitch that the embodiment of the present invention 1 provides；
Fig. 2 be described in the embodiment of the present invention 1 formed by pitch-coating in charcoal material surface surface orderly, internal unordered knot
The schematic diagram of structure；
Fig. 3 is the thermogravimetric curve for the charcoal raw material that the embodiment of the present invention 2 provides；
Fig. 4 is the XRD spectrum for the complex carbon material that the embodiment of the present invention 3 provides；
Fig. 5 is the Raman spectrum for the complex carbon material that the embodiment of the present invention 3 provides；
Fig. 6 is the SEM figure for the complex carbon material that the embodiment of the present invention 3 provides；
Fig. 7 a is a kind of constant current charge-discharge curve graph for sodium-ion battery that the embodiment of the present invention 3 provides；
Fig. 7 b is a kind of cyclic curve figure for sodium-ion battery that the embodiment of the present invention 3 provides；
Fig. 8 is the XRD spectrum for the complex carbon material that the embodiment of the present invention 4 provides；
Fig. 9 is the Raman spectrum for the complex carbon material that the embodiment of the present invention 4 provides；
Figure 10 is the SEM figure for the complex carbon material that the embodiment of the present invention 4 provides；
Figure 11 a is a kind of constant current charge-discharge curve graph for sodium-ion battery that the embodiment of the present invention 4 provides；
Figure 11 b is a kind of cyclic curve figure for sodium-ion battery that the embodiment of the present invention 4 provides；
Figure 12 is the XRD spectrum for the complex carbon material that the embodiment of the present invention 5 provides；
Figure 13 is the SEM figure for the complex carbon material that the embodiment of the present invention 5 provides；
Figure 14 a is a kind of constant current charge-discharge curve graph for sodium-ion battery that the embodiment of the present invention 5 provides；
Figure 14 b is a kind of cyclic curve figure for sodium-ion battery that the embodiment of the present invention 5 provides；
Figure 15 is a kind of constant current charge-discharge curve graph for sodium ion full battery that the embodiment of the present invention 16 provides；
Figure 16 is a kind of constant current charge-discharge curve graph for sodium ion full battery that the embodiment of the present invention 17 provides.
Specific embodiment
Below by drawings and examples, technical scheme of the present invention will be described in further detail, but is not intended to
It limits the scope of the invention.
Embodiment 1
Fig. 1 is the preparation side of the anode material of lithium-ion battery provided in an embodiment of the present invention based on Carbon Materials and pitch
Method, step are as shown in Figure 1, comprising:
Step 110, it is 1:(0.05-0.2 according to mass ratio by one or more charcoals and/or bamboo charcoal and asphalt stock) into
Row smashes mixing, obtains coarse powder；
Specifically, the mode being pulverized and mixed is preferably mechanical mixture, including mechanical crushing, ball milling, stirring, sieving and
It is arbitrarily several in the modes such as ultrasonic disperse and above-mentioned several ways to be used cooperatively.The time of mechanical mixture can be according to institute
The size of presoma and required powder particle diameter is selected to determine.
Wherein, charcoal includes one of hard charcoal, black wood charcoal, active carbon and machine-made carbon or a variety of mixtures, and bamboo charcoal includes hair
Bamboo, henon bamboo, bitter bamboo, one of the char-forming material of Lei Zhu and bambusa textile or a variety of mixtures, pitch are coal tar pitch, asphalt
With one of bitumen or a variety of mixtures.In preferred example, charcoal selects the hophornbeam charcoal that is prepared of kiln process
Or hard weedtree charcoal, the moso bamboo charcoal that bamboo charcoal selects kiln process to be prepared, pitch is asphalt.
Step 120, coarse powder is refined, obtains fine powder raw material of the partial size within the scope of some scale；
Step 130, fine powder raw material is put into Muffle furnace and carries out heat treatment 2-4 hours at 250-300 DEG C, make asphalt melting
After be coated on charcoal material surface；
Step 140, the raw material after heat treatment is put into high temperature carbonization furnace, with the heating rate of 3 DEG C/min-5 DEG C/min
1200 DEG C -1600 DEG C are warming up to, the raw material is heated at high temperature in an inert atmosphere, the time is 2-4 hours, so that described
Carbonization, cracking reaction occur for raw material；
Wherein, the pitch that charcoal material surface is coated on when thermally treated gradually forms long-range order in carbonisation
Carbon, internal Carbon Materials, which form unordered stack of carbon-coating, has the carbon of nano aperture to get orderly to surface, internal unordered structure
(as shown in Figure 2) improves electric conductivity, and further reduces costs.
The inert gas being passed through is preferably argon gas.
Step 150, it is cooled to room temperature, obtains structure, pattern in irregular bulk or the complex carbon material of vertical-shaped channel shape
The as described anode material of lithium-ion battery.
Specifically, cooling can use natural cooling, it is cooled to room temperature and is taken out from tube furnace.
The preparation process of pyrolysis complex carbon material provided in this embodiment based on Carbon Materials and pitch is simple, raw material at
This cheap, high production efficiency is suitable for large-scale production.It is mixed by different charcoals and/or bamboo charcoal with pitch and adjusts its quality
The material of different structure and characteristic size can be obtained in ratio.By compound with pitch, the electric conductivity of carbon material can be improved,
By adjusting the disordering degree of the adjustable complex carbon material of cracking temperature, to obtain best electrification according to different needs
Learn the carbon material of performance, the negative electrode active material as sodium ion secondary battery.
Below by the structure feature for the anode material of lithium-ion battery that embodiment 2 illustrates to be prepared.
Embodiment 2
Present embodiments provide the anode material of lithium-ion battery that above-described embodiment 1 is prepared.
According to the difference of selected Carbon Materials raw material, and, the cathode material that is prepared different from the compound ratio of pitch
Expect that orderly, internal unordered and pattern is in irregular blocky or vertical-shaped channel shape to structure in surface.Through charcoal and the compound preparation of pitch
Irregular blocky carbon material, size is between 2-10 microns, d002Value between 0.37-0.40nm, Lc value between 1-4nm,
La value is between 3-5nm；Vertical-shaped channel shape carbon material through charcoal Yu the compound preparation of pitch, length is between 5-30 microns, pipe
Road aperture in the range of 2 to 3 microns, d002Value is between 0.36-0.38nm, and Lc value is between 1-4nm, and La value is between 3-5nm；Through
The irregular blocky carbon material of bamboo charcoal and the compound preparation of pitch, size is between 2-15 microns, d002Value 0.35-0.37nm it
Between, Lc value is between 1-4nm, and La value is between 3-5nm.Fig. 3 gives the cathode material of two kinds of patterns through charcoal cracking preparation
Expect the thermogravimetric curve at 900 DEG C, producing carbon rate is respectively 71.69% and 72.49%.
The sodium ion secondary battery negative electrode active material of the present embodiment is raw material based on reproducible Carbon Materials, and with one
The inexpensive soft carbon presoma pitch of certainty ratio mixes, and by the preparation process of crushing, refinement, heat treatment, carbonization cracking, retains
The distinctive appearance structures of Carbon Materials, improve the performance of negative electrode material, are conducive to improve its synthesis in sodium-ion battery
Chemical property.
The technical solution provided for a better understanding of the present invention, it is following to be illustrated respectively with multiple specific examples using the present invention
The detailed process based on the preparation of the negative electrode material of Carbon Materials and pitch that examples detailed above provides, and it is secondary as sodium ion
Cell negative electrode material is assemblied in method and its battery behavior in sodium ion secondary battery.
Embodiment 3
2g hophornbeam charcoal is weighed, 0.1g asphalt machinery is smashed, is fitted into magnetic boat after evenly mixing.It is first placed into Muffle furnace
In, 260 DEG C are warming up to the rate of 3 DEG C/min, 3 hours is kept the temperature, obtains thermally treated pitch-coating Carbon Materials.It then will be hot
Treated, and powder is put into tube furnace is passed through argon gas as protection gas, is warming up to 1400 DEG C with the rate of 3 DEG C/min, heat preservation 2
Hour；Cooled to room temperature later takes out material, obtains final complex carbon material, as sodium ion secondary battery cathode
Material.
Its XRD spectrum is referring to fig. 4.From the d of the available carbon material of XRD spectrum002=0.392nm, Lc=2.15nm.
Its Raman spectrum is referring to Fig. 5, from the L of the available carbon material of Raman spectruma=3.18nm.Fig. 6 is the present embodiment preparation
The SEM of obtained carbon material schemes, it can be seen from the figure that the carbon material pattern that the present embodiment is prepared is in irregular bulk,
Size is between 2-10 microns.
The preparation of sodium-ion battery is used for using the above-mentioned carbon material being prepared as the active material of cell negative electrode material.
The powder of the carbon material prepared is mixed with sodium alginate bonding agent according to the mass ratio of 95:5, suitable quantity of water is added
Grinding forms slurry, is then evenly applied in current collector aluminum foil uniform slurry is ground, after dry, is cut into (8 × 8) mm2
Pole piece.Pole piece under vacuum conditions, 100 DEG C drying 10 hours, it is spare to be transferred to glove box immediately.
It is carried out in the glove box for being assemblied in Ar atmosphere of simulated battery, using metallic sodium as to electrode, with 1 mole
NaPF6Being dissolved in 1L volume ratio is the ethylene carbonate and diethyl carbonate solution of 1:1 as electrolyte, is assembled into CR2032 button
Battery.Using constant current charge-discharge mode, charge-discharge test is carried out under C/10 current density.It is 0V discharging by voltage, fills
For electricity under conditions of voltage is 2.5V, test result is shown in Fig. 7 a and Fig. 7 b, reversible specific capacity 304.9mAh/g, first week coulomb
Efficiency is 90.79%, stable cycle performance.
Embodiment 4
2g hard weedtree charcoal is weighed, 0.1g asphalt machinery is smashed, is fitted into magnetic boat after evenly mixing.It is first placed into horse
Not in furnace, 270 DEG C are warming up to the rate of 3 DEG C/min, 3 hours is kept the temperature, obtains thermally treated pitch-coating Carbon Materials.Then
Powder after heat treatment is put into tube furnace and is passed through argon gas as protection gas, 1400 DEG C is warming up to the rate of 3 DEG C/min, protects
Temperature 2 hours；Cooled to room temperature later takes out material, obtains final complex carbon material, and as sodium ion secondary battery is negative
Pole material.
Its XRD spectrum is referring to Fig. 8.From the d of the available carbon material of XRD spectrum002=0.378nm, Lc=2.55nm.
Its Raman spectrum is referring to Fig. 9, from the L of the available carbon material of Raman spectruma=4.00nm.Figure 10 is the present embodiment preparation
The SEM of obtained carbon material schemes, it can be seen from the figure that the carbon material pattern that the present embodiment is prepared is in vertical-shaped channel shape,
Length is 5-30 microns, and pipeline aperture is 2-3 microns.
The preparation of sodium-ion battery is used for using the above-mentioned carbon material being prepared as the active material of cell negative electrode material,
And carry out charge discharge test.Its preparation process and test method are the same as embodiment 3.Test voltage range is 0V-2.5V, is surveyed
Test result is shown in Figure 11 a and Figure 11 b, reversible specific capacity 261.8mAh/g, and first week coulombic efficiency is 89.20%, and cycle performance is steady
It is fixed.
Embodiment 5
2g moso bamboo charcoal is weighed, 0.1g asphalt machinery is smashed, is fitted into magnetic boat after evenly mixing.It is first placed into Muffle furnace
In, 280 DEG C are warming up to the rate of 3 DEG C/min, 3 hours is kept the temperature, obtains thermally treated pitch-coating Carbon Materials.It then will be hot
Treated, and powder is put into tube furnace is passed through argon gas as protection gas, is warming up to 1400 DEG C with the rate of 3 DEG C/min, heat preservation 2
Hour；Cooled to room temperature later takes out material, obtains final complex carbon material, as sodium ion secondary battery cathode
Material.
Its XRD spectrum is referring to Figure 12.From the d of the available carbon material of XRD spectrum002=0.374nm, Lc=2.53nm,
La=3.91.Figure 13 is the SEM figure for the carbon material that the present embodiment is prepared, it can be seen from the figure that the present embodiment is prepared into
The carbon material pattern arrived is in irregular bulk, and size is between 2-15 microns.
The preparation of sodium-ion battery is used for using the above-mentioned carbon material being prepared as the active material of cell negative electrode material,
And carry out charge discharge test.Its preparation process and test method are the same as embodiment 3.Test voltage range is 0V-2.5V, is surveyed
Test result is shown in Figure 14 a and Figure 14 b, reversible specific capacity 259.7mAh/g, and first week coulombic efficiency is 89.33%, and cycle performance is steady
It is fixed.
Embodiment 6
2g hophornbeam charcoal is weighed, 0.16g asphalt machinery is smashed, is fitted into magnetic boat after evenly mixing.It is first placed into Muffle
In furnace, 270 DEG C are warming up to the rate of 3 DEG C/min, 3 hours is kept the temperature, obtains thermally treated pitch-coating Carbon Materials.Then will
Powder after heat treatment, which is put into tube furnace, is passed through argon gas as protection gas, is warming up to 1200 DEG C with the rate of 3 DEG C/min, heat preservation
2 hours；Cooled to room temperature later takes out material, obtains final complex carbon material.
The preparation of sodium-ion battery is used for using the above-mentioned carbon material being prepared as the active material of cell negative electrode material,
And carry out charge discharge test.Its preparation process and test method are the same as embodiment 3.Test voltage range is 0V-2.5V, knot
Fruit see the table below 1.
Embodiment 7
2g hard weedtree charcoal is weighed, 0.2g asphalt machinery is smashed, is fitted into magnetic boat after evenly mixing.It is first placed into horse
Not in furnace, 280 DEG C are warming up to the rate of 3 DEG C/min, 3 hours is kept the temperature, obtains thermally treated pitch-coating Carbon Materials.Then
Powder after heat treatment is put into tube furnace and is passed through argon gas as protection gas, 1400 DEG C is warming up to the rate of 3 DEG C/min, protects
Temperature 2 hours；Cooled to room temperature later takes out material, obtains final complex carbon material.
The preparation of sodium-ion battery is used for using the above-mentioned carbon material being prepared as the active material of cell negative electrode material,
And carry out charge discharge test.Its preparation process and test method are the same as embodiment 3.Test voltage range is 0V-2.5V, knot
Fruit see the table below 1.
Embodiment 8
2g moso bamboo charcoal is weighed, 0.12g asphalt machinery is smashed, is fitted into magnetic boat after evenly mixing.It is first placed into Muffle
In furnace, 290 DEG C are warming up to the rate of 3 DEG C/min, 3 hours is kept the temperature, obtains thermally treated pitch-coating Carbon Materials.Then will
Powder after heat treatment, which is put into tube furnace, is passed through argon gas as protection gas, is warming up to 1400 DEG C with the rate of 4 DEG C/min, heat preservation
2 hours；Cooled to room temperature later takes out material, obtains final complex carbon material.
The preparation of sodium-ion battery is used for using the above-mentioned carbon material being prepared as the active material of cell negative electrode material,
And carry out charge discharge test.Its preparation process and test method are the same as embodiment 3.Test voltage range is 0V-2.5V, knot
Fruit see the table below 1.
Embodiment 9
2g hophornbeam charcoal is weighed, 0.24g asphalt machinery is smashed, is fitted into magnetic boat after evenly mixing.It is first placed into Muffle
In furnace, 280 DEG C are warming up to the rate of 3 DEG C/min, 3 hours is kept the temperature, obtains thermally treated pitch-coating Carbon Materials.Then will
Powder after heat treatment, which is put into tube furnace, is passed through argon gas as protection gas, is warming up to 1600 DEG C with the rate of 4 DEG C/min, heat preservation
2 hours；Cooled to room temperature later takes out material, obtains final complex carbon material.
The preparation of sodium-ion battery is used for using the above-mentioned carbon material being prepared as the active material of cell negative electrode material,
And carry out charge discharge test.Its preparation process and test method are the same as embodiment 3.Test voltage range is 0V-2.5V, knot
Fruit see the table below 1.
Embodiment 10
2g hard weedtree charcoal is weighed, 0.3g asphalt machinery is smashed, is fitted into magnetic boat after evenly mixing.It is first placed into horse
Not in furnace, 290 DEG C are warming up to the rate of 3 DEG C/min, 3 hours is kept the temperature, obtains thermally treated pitch-coating Carbon Materials.Then
Powder after heat treatment is put into tube furnace and is passed through argon gas as protection gas, 1600 DEG C is warming up to the rate of 4 DEG C/min, protects
Temperature 2 hours；Cooled to room temperature later takes out material, obtains final complex carbon material.
The preparation of sodium-ion battery is used for using the above-mentioned carbon material being prepared as the active material of cell negative electrode material,
And carry out charge discharge test.Its preparation process and test method are the same as embodiment 3.Test voltage range is 0V-2.5V, knot
Fruit see the table below 1.
Embodiment 11
2g moso bamboo charcoal is weighed, 0.24g asphalt machinery is smashed, is fitted into magnetic boat after evenly mixing.It is first placed into Muffle
In furnace, 300 DEG C are warming up to the rate of 3 DEG C/min, 3 hours is kept the temperature, obtains thermally treated pitch-coating Carbon Materials.Then will
Powder after heat treatment, which is put into tube furnace, is passed through argon gas as protection gas, is warming up to 1400 DEG C with the rate of 4 DEG C/min, heat preservation
2 hours；Cooled to room temperature later takes out material, obtains final complex carbon material.
The preparation of sodium-ion battery is used for using the above-mentioned carbon material being prepared as the active material of cell negative electrode material,
And carry out charge discharge test.Its preparation process and test method are the same as embodiment 3.Test voltage range is 0V-2.5V, knot
Fruit see the table below 1.
Embodiment 12
2g hophornbeam charcoal is weighed, 0.32g asphalt machinery is smashed, is fitted into magnetic boat after evenly mixing.It is first placed into Muffle
In furnace, 290 DEG C are warming up to the rate of 3 DEG C/min, 3 hours is kept the temperature, obtains thermally treated pitch-coating Carbon Materials.Then will
Powder after heat treatment, which is put into tube furnace, is passed through argon gas as protection gas, is warming up to 1400 DEG C with the rate of 3 DEG C/min, heat preservation
2 hours；Cooled to room temperature later takes out material, obtains final complex carbon material.
The preparation of sodium-ion battery is used for using the above-mentioned carbon material being prepared as the active material of cell negative electrode material,
And carry out charge discharge test.Its preparation process and test method are the same as embodiment 3.Test voltage range is 0V-2.5V, knot
Fruit see the table below 1.
Embodiment 13
2g hard weedtree charcoal is weighed, 0.4g asphalt tool is smashed, is fitted into magnetic boat after evenly mixing.It is first placed into Muffle
In furnace, 280 DEG C are warming up to the rate of 3 DEG C/min, 3 hours is kept the temperature, obtains thermally treated pitch-coating Carbon Materials.Then will
Powder after heat treatment, which is put into tube furnace, is passed through argon gas as protection gas, is warming up to 1200 DEG C with the rate of 2 DEG C/min, heat preservation
2 hours；Cooled to room temperature later takes out material, obtains final complex carbon material.
The preparation of sodium-ion battery is used for using the above-mentioned carbon material being prepared as the active material of cell negative electrode material,
And carry out charge discharge test.Its preparation process and test method are the same as embodiment 3.Test voltage range is 0V-2.5V, knot
Fruit see the table below 1.
Embodiment 14
2g moso bamboo charcoal is weighed, 0.36g asphalt machinery is smashed, is fitted into magnetic boat after evenly mixing.It is first placed into Muffle
In furnace, 270 DEG C are warming up to the rate of 3 DEG C/min, 3 hours is kept the temperature, obtains thermally treated pitch-coating Carbon Materials.Then will
Powder after heat treatment, which is put into tube furnace, is passed through argon gas as protection gas, is warming up to 1400 DEG C with the rate of 4 DEG C/min, heat preservation
2 hours；Cooled to room temperature later takes out material, obtains final complex carbon material.
The preparation of sodium-ion battery is used for using the above-mentioned carbon material being prepared as the active material of cell negative electrode material,
And carry out charge discharge test.Its preparation process and test method are the same as embodiment 3.Test voltage range is 0V-2.5V, knot
Fruit see the table below 1.
Embodiment 15
2g hophornbeam charcoal is weighed, 0.4g asphalt machinery is smashed, is fitted into magnetic boat after evenly mixing.It is first placed into Muffle furnace
In, 300 DEG C are warming up to the rate of 3 DEG C/min, 3 hours is kept the temperature, obtains thermally treated pitch-coating Carbon Materials.It then will be hot
Treated, and powder is put into tube furnace is passed through argon gas as protection gas, is warming up to 1400 DEG C with the rate of 3 DEG C/min, heat preservation 2
Hour；Cooled to room temperature later takes out material, obtains final complex carbon material.
The preparation of sodium-ion battery is used for using the above-mentioned carbon material being prepared as the active material of cell negative electrode material,
And carry out charge discharge test.Its preparation process and test method are the same as embodiment 3.Test voltage range is 0V-2.5V, knot
Fruit see the table below 1.
Embodiment 16
Using the carbon material that embodiment 3 provides as the active material of sodium ion secondary battery negative electrode material, using O3-
NaCu1/9Ni2/9Fe1/3Mn1/3O2As positive electrode active materials, for the preparation of sodium ion full battery, preparation process and test
Method is same as Example 3, and carries out charge discharge test.Test voltage range 1.5-4.0V, charge-discharge test result
See Figure 15.
Embodiment 17
Using the carbon material that embodiment 4 provides as the active material of sodium ion secondary battery negative electrode material, using O3-
NaCu1/9Ni2/9Fe1/3Mn1/3O2As positive electrode active materials, for the preparation of sodium ion full battery, preparation process and test
Method is same as Example 3, and carries out charge discharge test.Test voltage range 1.5-4.0V, charge-discharge test result
See Figure 16.
The dependency structure parameter and specific capacity of the negative electrode material prepared in the different embodiments of table 1
The sodium ion secondary battery negative electrode material provided in the above embodiment of the present invention, raw material resources are abundant, cost
Cheap, preparation process is simple, high production efficiency, is suitable for large-scale production.It is obtained using preparation method provided in an embodiment of the present invention
Negative electrode active material of the complex carbon material obtained as sodium-ion battery, the sodium-ion battery measured operating voltage with higher
And energy density, high rate performance is excellent, and stable cycle performance has a safety feature, and cannot be only used for mobile device and electric car
Power supply, can be also used for the storages such as renewable energy power generation, smart grid peak regulation, distribution power station, backup power supply or communication base station
It can equipment.
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail, it should be understood that being not intended to limit the present invention the foregoing is merely a specific embodiment of the invention
Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Claims (9)
1. a kind of anode material of lithium-ion battery based on Carbon Materials and pitch, which is characterized in that the sodium-ion battery cathode
Material is that surface coats the pattern of the orderly carbon structure of asphaltic base in the complex carbon material of irregular blocky or vertical-shaped channel shape；With charcoal
Material and pitch are precursor material, are heat-treated in air after mechanical mixture, are coated on Carbon Materials table after making asphalt melting
Face makes pitch and Carbon Materials under an inert atmosphere later while carbonization occurs, cracking is prepared；
The Carbon Materials include charcoal and/or bamboo charcoal；The charcoal includes one of hard charcoal, black wood charcoal, active carbon and machine-made carbon
Or a variety of mixtures, the bamboo charcoal include one of char-forming material of moso bamboo, henon bamboo, bitter bamboo, Lei Zhu and bambusa textile or a variety of mixed
Close object；The pitch is one of coal tar pitch, asphalt and bitumen or a variety of mixtures；
The anode material of lithium-ion battery has the structure feature that surface is orderly, inside is unordered；
It wherein, is in irregular block-like complex carbon material by the charcoal and the compound pattern being prepared of pitch, size is in 2-
Between 10 microns, d002Value is between 0.37-0.40nm, and Lc value is between 1-4nm, and La value is between 3-5nm；By the charcoal
It is in the complex carbon material of vertical-shaped channel shape with the compound pattern being prepared of pitch, length is 5-30 microns, and pipeline aperture is 2-3
Micron, d002Value is between 0.36-0.38nm, and Lc value is between 1-4nm, and La value is between 3-5nm；By the bamboo charcoal and pitch
The compound pattern being prepared is in irregular block-like carbon material, and size is between 2-15 microns, d002Value is in 0.35-0.37nm
Between, Lc value is between 1-4nm, and La value is between 3-5nm.
2. anode material of lithium-ion battery according to claim 1, which is characterized in that the Carbon Materials and the pitch
Mass ratio is 1:(0.05-0.2).
3. anode material of lithium-ion battery according to claim 1, which is characterized in that the charcoal is miscellaneous by hophornbeam or hard
Wood is made through kiln process, and the bamboo charcoal is made by moso bamboo through kiln process.
4. a kind of preparation method of any anode material of lithium-ion battery of the claims 1-3, which is characterized in that institute
The method of stating includes:
One or more Carbon Materials and asphalt stock are subjected to smashing mixing according to mass ratio for 1:(0.05-0.2), are obtained thick
Powder；
The coarse powder is refined, fine powder raw material of the partial size within the scope of some scale is obtained；
Fine powder raw material is put into Muffle furnace and carries out heat treatment 2-4 hours at 250-300 DEG C, is coated on raw material of wood-charcoal after making asphalt melting
Expect surface；
Raw material after heat treatment is put into high temperature carbonization furnace, with the heating rate of 3 DEG C/min-5 DEG C/min be warming up to 1200 DEG C-
1600 DEG C, the raw material being heated at high temperature in an inert atmosphere, the time is 2-4 hours, so that raw material generation carbonization,
Cracking reaction；
Be cooled to room temperature, obtain structure in surface orderly, it is internal unordered, pattern is compound in irregular blocky or vertical-shaped channel shape
Carbon material is the anode material of lithium-ion battery.
5. the preparation method according to claim 4, which is characterized in that described that one or more Carbon Materials and pitch are former
Before material carries out smashing mixing according to mass ratio for 1:(0.05-0.2), the method also includes:
The charcoal and bamboo charcoal is prepared using kiln process.
6. the preparation method according to claim 4, which is characterized in that the charcoal includes hophornbeam charcoal or hard weedtree charcoal,
The bamboo charcoal includes moso bamboo charcoal.
7. the preparation method according to claim 4, which is characterized in that at Carbon Materials and pitch in air low-temperature heat
Reason, is coated on charcoal material surface after making asphalt melting, is formed after high temperature cabonization in an inert atmosphere external orderly, internal unordered
Complex carbon material.
8. a kind of cathode pole piece of sodium-ion battery, which is characterized in that the cathode pole piece includes:
Collector, coated on the binder and any sodium-ion battery of the claims 1-3 on the collector
Negative electrode material.
9. a kind of sodium ion secondary battery including cathode pole piece described in the claims 8, which is characterized in that the sodium from
Sub- secondary cell is for mobile device, the vehicles and renewable energy power generation, smart grid peak regulation, distribution power station, standby
The extensive energy storage device of power supply or communication base station.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710904851.2A CN109148838B (en) | 2017-09-29 | 2017-09-29 | Anode material of lithium-ion battery and its preparation method and application |
| PCT/CN2018/104035 WO2019062495A1 (en) | 2017-09-29 | 2018-09-04 | Carbon material and asphalt-based negative electrode material for sodium-ion battery, and preparation method therefor and applications thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710904851.2A CN109148838B (en) | 2017-09-29 | 2017-09-29 | Anode material of lithium-ion battery and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109148838A CN109148838A (en) | 2019-01-04 |
| CN109148838B true CN109148838B (en) | 2019-07-23 |
Family
ID=64803663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710904851.2A Active CN109148838B (en) | 2017-09-29 | 2017-09-29 | Anode material of lithium-ion battery and its preparation method and application |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109148838B (en) |
| WO (1) | WO2019062495A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110451475B (en) * | 2019-07-05 | 2021-03-26 | 北京化工大学 | Preparation method of asphalt-based carbon microspheres and application of asphalt-based carbon microspheres as sodium ion battery electrode material |
| CN111293309B (en) * | 2020-03-04 | 2023-01-17 | 溧阳中科海钠科技有限责任公司 | Performance improvement method and application of coal-based sodium ion battery negative electrode material |
| CN113493193A (en) * | 2020-03-20 | 2021-10-12 | 国家能源投资集团有限责任公司 | Amorphous carbon material and preparation method thereof, sodium ion battery cathode and sodium ion battery |
| CN113526489B (en) * | 2021-07-15 | 2022-06-24 | 上海大学 | Performance improvement method and application of sodium ion battery carbon-based negative electrode material |
| CN114275764A (en) * | 2021-12-28 | 2022-04-05 | 哈尔滨工业大学 | Preparation method and application of carbon material based on co-carbonization of porous carbon and thermoplastic carbon source |
| CN114512646A (en) * | 2022-01-24 | 2022-05-17 | 西南大学 | Amorphous carbon material with multilayer gradient microstructure and preparation method and application thereof |
| CN114709393A (en) * | 2022-04-11 | 2022-07-05 | 深圳市翔丰华科技股份有限公司 | Preparation method of negative electrode material for sodium ion battery |
| US11728486B1 (en) | 2022-07-27 | 2023-08-15 | Jing Wang | Electrode materials prepared by nanoporous carbon composite technology |
| CN115159503A (en) * | 2022-08-19 | 2022-10-11 | 中国科学技术大学 | Preparation method and application of carbon material with adjustable degree of order |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014519135A (en) * | 2012-05-02 | 2014-08-07 | 昭和電工株式会社 | Negative electrode material for lithium ion battery and its use |
| CN104620428A (en) * | 2012-08-30 | 2015-05-13 | 株式会社吴羽 | Carbon material for nonaqueous electrolyte secondary battery and method for manufacturing same, and negative electrode using carbon material and nonaqueous electrolyte secondary battery |
| CN105098186A (en) * | 2014-11-11 | 2015-11-25 | 中国科学院物理研究所 | Pyrolysis amorphous carbon material and preparation method and application thereof |
-
2017
- 2017-09-29 CN CN201710904851.2A patent/CN109148838B/en active Active
-
2018
- 2018-09-04 WO PCT/CN2018/104035 patent/WO2019062495A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014519135A (en) * | 2012-05-02 | 2014-08-07 | 昭和電工株式会社 | Negative electrode material for lithium ion battery and its use |
| CN104620428A (en) * | 2012-08-30 | 2015-05-13 | 株式会社吴羽 | Carbon material for nonaqueous electrolyte secondary battery and method for manufacturing same, and negative electrode using carbon material and nonaqueous electrolyte secondary battery |
| CN105098186A (en) * | 2014-11-11 | 2015-11-25 | 中国科学院物理研究所 | Pyrolysis amorphous carbon material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019062495A1 (en) | 2019-04-04 |
| CN109148838A (en) | 2019-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109148838B (en) | Anode material of lithium-ion battery and its preparation method and application | |
| CN105261734B (en) | A kind of composite negative electrode material of lithium ion battery, preparation method and applications | |
| CN109148883A (en) | Anode material of lithium-ion battery and its preparation method and application based on pitch | |
| CN103214245B (en) | Carbon/carbon composite microsphere material, production method and lithium ion battery | |
| CN101572305B (en) | Preparation method of LiFePO*/C cathode material with high rate performance | |
| WO2016074479A1 (en) | Pyrolytic amorphous carbon material, preparation method and use thereof | |
| CN101587948B (en) | Preparation method for LiTiO/C compound electrode material | |
| CN109921018A (en) | The preparation method of sodium-ion battery high capacity biomass hard charcoal negative electrode material | |
| CN104218214B (en) | A kind of lithium ion battery negative material and preparation method thereof | |
| CN103107319B (en) | Lithium ion battery carbon microsphere negative electrode material and preparation method thereof | |
| CN105185997A (en) | Sodion secondary battery negative electrode material and preparing method and application thereof | |
| CN108315028B (en) | Pyrolytic hard carbon material with longitudinal pore structure and preparation method and application thereof | |
| CN105576223B (en) | A kind of tin oxide base negative electrode material and preparation method thereof with high reversible capacity | |
| CN103346317B (en) | Composite mixed and cladded type anode material for lithium-ion batteries LiFePO 4and preparation method thereof | |
| CN107946568B (en) | High-performance silicon oxide/hard carbon/graphite composite material and preparation method and application thereof | |
| CN101728517A (en) | Method for preparing surface self-grown titanium nitride conducting film modified lithium titanate | |
| CN105895873A (en) | Silicon/carbon compound anode material for lithium ion battery as well as preparation method and application thereof | |
| CN109148847A (en) | A kind of the hard carbon cladding negative electrode material and its liquid phase preparation process of the boron doping modification with high rate capability | |
| CN114956037A (en) | Carbon material for sodium ion battery negative electrode, preparation method of carbon material, sodium ion battery negative electrode piece and sodium ion battery | |
| CN108281627B (en) | Germanium-carbon composite negative electrode material for lithium ion battery and preparation method thereof | |
| CN108199023A (en) | The preparation method of biological silicon carbon material, biological silicon carbon material and application | |
| CN107706383A (en) | A kind of titanium doped carbon coating in situ aoxidizes sub- silicon/graphite material and preparation method thereof | |
| CN103545492A (en) | Preparation method of multiple composite anode material of lithium ion battery | |
| CN106299301B (en) | A kind of Li with excellent storage lithium performance3VO4The pattern of nano wire mutually regulates and controls method with object | |
| CN104505502A (en) | Lithium titanate composite negative material for lithium ion battery and preparation method of lithium titanate composite negative material |
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 |