CN108862235A - A kind of hollow hard carbon material of threadiness and preparation method thereof can be used for sodium-ion battery cathode - Google Patents
A kind of hollow hard carbon material of threadiness and preparation method thereof can be used for sodium-ion battery cathode Download PDFInfo
- Publication number
- CN108862235A CN108862235A CN201810578633.9A CN201810578633A CN108862235A CN 108862235 A CN108862235 A CN 108862235A CN 201810578633 A CN201810578633 A CN 201810578633A CN 108862235 A CN108862235 A CN 108862235A
- Authority
- CN
- China
- Prior art keywords
- hard carbon
- threadiness
- carbon material
- preparation
- sodium
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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 the hollow hard carbon materials of threadiness to obtain d through Direct Pyrolysis method using fibrous biological material as raw material002Value is in 0.36 ~ 0.42nm, ID/IGThe unformed hollow hard carbon material of threadiness of amorphous state between 1.5-2.0.Preparation method includes 1）The pretreatment of raw material；2）Pintsch process.As negative electrode active material in sodium ion secondary battery, specific capacity is 150 ~ 350mAh/g, and 60% or more capacity when being able to maintain 0.1C at 2C can accomplish capacity retention ratio between 90%-100% at 100 weeks after circulation.Its advantage is：1, stable micron order fibre structure improves cycle life；2, the dynamic performance for improving the wellability of electrolyte using natural tubulose hollow structure, shortening ion transmission range, improving battery；3, preparation method is simple, and reduction prepares the processing cost of special appearance.Therefore, the present invention is the anode material of lithium-ion battery of a kind of great potential, can be applied in the large-scale energy storage systems or power battery fields such as smart grid, cleaning secondary energy sources power generation.
Description
Technical field
The present invention relates to a kind of energy-storage battery negative electrode material more particularly to a kind of fibers that can be used for sodium-ion battery cathode
Hollow hard carbon material of shape and preparation method thereof.
Background technique
In recent years, the fast development of human society and the increasingly diversification of people's demand increase, with fossil energy
It is uncontrolled to use the aggravation for leading to serious energy shortage problem and greenhouse effects.The clean energy resource of Development of Novel becomes one urgently
Problem to be solved.Currently, secondary lithium battery has become the fields such as consumption electronic product market, power battery market
Mainstream, and technology reaches its maturity.But with business large-scale use, the shortage of lithium mine, which becomes, keeps it in check applied to extensive
The key of energy storage.Sodium-ion battery and lithium ion battery possess similar electrochemical properties, and sodium is resourceful, and Regional Distribution is flat
, therefore the sodium-ion battery of low cost is with a wide range of applications in extensive energy storage.
The sodium ion battery electrode material of research and development low cost becomes the key of sodium-ion battery application.And in terms of anode,
Good progress is had been achieved for, has certain application prospect in different fields by respective advantage.Due in lithium ion
The graphite cathode material of successful commercialization does not have storage sodium performance in battery, and sodium metal negative electrode is more vivaciously led than lithium an- ode
Quick dendritic growth is caused, therefore the research of cathode is obviously more urgent.Currently, mainly having amorphous carbon material, alloy type negative
Pole material, polyanionic compound, metal oxide and organic compound.Wherein amorphous carbon material and alloy type negative material
Highest storage sodium capacity is shown, but alloy material is because serious Study of Volume Expansion leads to the broken of structure in electrochemical process
Bad, capacity is decayed rapidly.Therefore, carbon based negative electrodes material is by excellent storage sodium capacity and cyclical stability as before most having application
The negative electrode material of scape.
But carbon-based class negative electrode material is faced with the rapid relaxation phenomenon of capacity, raw material and system during fast charging and discharging
The problems such as standby at high cost, this severely limits the commercial applications of carbon based negative electrodes material.Currently, asking for capacity rapid decay
Topic, researcher generally use complicated technique and improve dynamic performance to obtain special appearance, these special appearances improve
The wellability of electrolyte and the distance for reducing ionic conduction, facilitate the improvement of material kinetics performance.
Such as artificial synthesized hollow nano wire hard carbon（Nano Lett. 2012, 12, 3783−3787）, due to hollow tubular
Structure is able to maintain under 0.2C multiplying power 60% capacity under the multiplying power of 2C, but this method increases volume on the basis of raw material again
Outer preparation cost.And from the aspect of cost, current way be select low-cost and easy-to to obtain biomass as raw material,
Such as shuck（Nano Energy 39 (2017) 489–498）, but special form is not present after the carbonization of these biological materials
Looks, under the test of the multiplying power of 0.1C ~ 2C, the capacity of 2C is less than the 1/6 of 0.1C, and the effect of optimization dynamic performance is not achieved.
Summary of the invention
The object of the present invention is to provide a kind of hollow hard carbon material of threadiness that can be used for sodium-ion battery cathode and its systems
Preparation Method.This material feedstock is inexpensive, preparation flow is simple, the hard carbon sodium ion electricity of high electrochemical performance and dynamic performance
Pond negative electrode material mentality of designing, suitable for large-scale production.
The present invention is using fibrous biological material as raw material, under the conditions of 1000 ~ 1800 DEG C of temperature, through Direct Pyrolysis method
The unformed hollow hard carbon material of threadiness of obtained amorphous state.Both special hollow tubular topography optimization kinetics had been possessed
Can, and because the raw material of low cost and simple preparation process reduce overall cost.
From the aspect of raw material and preparation cost, nowadays mainly with the system of the high cost presoma cooperation complexity such as artificial resin
Standby technique obtains high-performance hard carbon material.Prepared by hollow biomass fiber precursor that the present invention selects while saving special
The additional process and cost of material of pattern.This material successfully solves several big obstacles for keeping sodium-ion battery practical application in check,
A kind of anode material of lithium-ion battery as great some commercial potential.
Realizing the technical solution of the object of the invention is：
A kind of hollow hard carbon material of threadiness can be used for sodium-ion battery cathode, using fibrous biological material as raw material,
Under the conditions of suitable temperature, the unformed hollow hard carbon material of threadiness of the amorphous state obtained through Direct Pyrolysis method, the fiber
The d of the hollow hard carbon material of shape002Value is in 0.36 ~ 0.42nm, the integrated intensity ratio I at the peak curve D Raman and the peak GD/IGIn 1.5-2.0
Between.The threadiness biological material is in bombax cotton, poplar wadding fiber, catkin fiber, oriental plane tree wadding, ramie or jute
One kind.
The present invention provides a kind of preparation method of hollow hard carbon material of threadiness that can be used for sodium-ion battery cathode, including
Following steps：
A. the pretreatment of raw material：Fibrous biological material is cleaned, drying, is ground after being carbonized in advance under certain condition,
Obtain presoma；The condition of the pre- carbonization is under inert gas protection, 400 are raised to 2 ~ 10 DEG C/min of heating rate ~
800 DEG C and heat preservation 2 ~ 6 hours；
B. Pintsch process：After step 1 gained presoma under certain condition Pintsch process, the hollow hard carbon material of threadiness is obtained
Material；The condition of the Pintsch process is that under inert gas protection, 2 ~ 10 DEG C/min of heating rate is protected at 1000 ~ 1800 DEG C
Temperature 2 ~ 6 hours.
A kind of application of the hollow hard carbon material of threadiness, as negative electrode active material in sodium ion secondary battery, specific volume
Amount is 150 ~ 350mAh/g, and 60% or more capacity when being able to maintain 0.1C at 2C can accomplish that capacity was protected at 100 weeks after circulation
Holdup is between 90%-100%；The hollow hard carbon of the threadiness and sodium carboxymethylcellulose binding agent are with mass ratio for 95：5 prepare
Slurry is prepared at negative electrode tab, active material load capacity is in 2mg/cm2。
The hollow hard carbon material of threadiness shows that the carbon material is highly disordered through X-ray diffraction and Raman spectrum test
Amorphous carbon, d002Value is in 0.36 ~ 0.42nm, ID/IGBetween 1.5-2.0.
Although the hollow hard carbon material of threadiness shows that the carbon material is fine after Pintsch process through scanning electron microscope test
The phenomenon that dimension structure is shunk, but fibre structure can remain.
The hollow hard carbon material of threadiness is tested through constant current charge-discharge to be shown when current density is 25 mA/g, specific capacity
For 150 ~ 350mAh/g.
60% or more capacity when the hollow hard carbon material of threadiness shows that material is able to maintain 0.1C at 2C through multiplying power test,
Show there is good dynamic (dynamical) performance.
The hollow hard carbon material of threadiness is tested through long circulating constant current charge-discharge to be shown when current density is 25 mA/g,
It can accomplish capacity retention ratio between 90%-100% after circulation at 100 weeks.
The hollow hard carbon material of threadiness of the invention has the following advantages that the prior art：
1, because raw material sources are extensive and low in cost, resource utilization is effectively improved, and reduces cost in terms of raw material；
2, natural fiber hollow structure simplifies preparation process, reduces material preparation cost, is advantageously applied to industrialize
Produce the hard carbon material with special appearance；
3, the graphite flake layer spacing of 0.36 ~ 0.42nm is greater than conventional graphite piece interlamellar spacing（0.34mm）, be conducive to the embedding of sodium ion
Enter；
4, after being assembled into battery, the features such as long circulation life, high capacity, good structural stability, specific capacity are shown
Reach 150 ~ 350mAh/g, 60% when remaining very high specific capacity under the multiplying power of 0.1 ~ 2C, and being able to maintain 0.1C at 2C
Above capacity can accomplish that capacity was maintained at 90% or more after circulation at hundred weeks.
The present invention is from the limitation of the prior art, from cost of material, preparation cost and dynamic performance.With
Fibrous biological material is raw material, under the conditions of suitable temperature, the unformed fibre of the amorphous state obtained through Direct Pyrolysis method
The hollow hard carbon material of shape is tieed up, the graphite flake layer spacing of 0.36 ~ 0.42nm is obtained, is more advantageous to the insertion abjection of ion.It is assembling
After battery, the features such as long circulation life, high capacity, good structural stability are shown.Therefore, this threadiness of the present invention
Hollow hard carbon material can be applied in the large-scale energy storage systems such as smart grid, cleaning secondary energy sources power generation or power battery
Field.
Detailed description of the invention
Fig. 1 is that the embodiment of the present invention 1 provides a kind of preparation method flow chart of hard carbon material；
Fig. 2 is the XRD spectrum for the hard carbon material that the embodiment of the present invention 3 provides；
Fig. 3 is the Raman map for the hard carbon material that the embodiment of the present invention 3 provides；
Fig. 4 is all constant current charge-discharge curve comparisons of head of the sodium-ion battery for the hard carbon material preparation that the embodiment of the present invention 3 provides
Map；
Fig. 5 is the constant current charge-discharge circulation comparison map of the sodium-ion battery for the hard carbon material preparation that the embodiment of the present invention 3 provides；
Fig. 6 is the XRD spectrum for the hard carbon material that the embodiment of the present invention 4 provides；
Fig. 7 is the Raman map for the hard carbon material that the embodiment of the present invention 4 provides；
Fig. 8 is the SEM picture for the hard carbon material raw material that the embodiment of the present invention 4 provides；
Fig. 9 is the SEM picture for the hard carbon material that the embodiment of the present invention 4 provides；
Figure 10 is all constant current charge-discharge curve graphs of head of the sodium-ion battery for the hard carbon material preparation that the embodiment of the present invention 4 provides
Spectrum；
Figure 11 is that the multiplying power of the sodium-ion battery for the hard carbon material preparation that the embodiment of the present invention 4 provides tests map；
Figure 12 is the XRD spectrum for the hard carbon material that the embodiment of the present invention 5 provides；
Figure 13 is the Raman map for the hard carbon material that the embodiment of the present invention 5 provides；
Figure 14 is all constant current charge-discharge curve graphs of head of the sodium-ion battery for the hard carbon material preparation that the embodiment of the present invention 5 provides
Spectrum；
Figure 15 is that the constant current charge-discharge of the sodium-ion battery for the hard carbon material preparation that the embodiment of the present invention 5 provides recycles map；
Figure 16 is the XRD spectrum for the hard carbon material that the embodiment of the present invention 6 provides；
Figure 17 is the Raman map for the hard carbon material that the embodiment of the present invention 6 provides；
Figure 18 is all constant current charge-discharge curve graphs of head of the sodium-ion battery for the hard carbon material preparation that the embodiment of the present invention 6 provides
Spectrum；
Figure 19 is that the constant current charge-discharge of the sodium-ion battery for the hard carbon material preparation that the embodiment of the present invention 6 provides recycles map.
Specific embodiment
The present invention is described in further detail the content of present invention in conjunction with Figure of description, but be not pair by embodiment
Restriction of the invention.
Embodiment 1
A kind of preparation method of the hollow hard carbon material of threadiness, the process of preparation method is as shown in Figure 1, specifically include following several
A step：
Step 1）Cellulosic part in biomass is taken out clean, drying and is placed in graphite crucible by the pretreatment of raw material, with
The heating rate of 5 DEG C/min keeps the temperature 2 hours under 600 DEG C of protective atmospheres and grind after being carbonized in advance, prevents fiber-like hard carbon material
Material is hardened after direct Pintsch process and causes to be difficult to refine, and obtains presoma, and the biomass is bombax cotton, poplar wadding fibre
Dimension, catkin fiber, oriental plane tree wadding, ramie or jute；
Step 2）Step 1 gained presoma is placed in graphite crucible by Pintsch process, with the heating rate of 5 DEG C/min, is being protected
Under atmosphere after Pintsch process 2 hours, natural cooling is taken out and is ground, and obtains the hollow hard carbon material of threadiness.
Embodiment 2
The present embodiment provides a kind of methods that the hollow hard carbon material of threadiness of preparation is carried out electro-chemical test.Electro-chemical test
Process is that pole piece is made for anode material of lithium-ion battery and is assembled into button version battery, to test its chemical property.Firmly
Carbon material and sodium carboxymethylcellulose binding agent solution are with 95:5 ratio obtains slurry after mixing, is coated on aluminium foil,
It is placed 2 hours in 100 DEG C of vacuum drying ovens, Φ 10mm size is cut into after drying, obtain required negative electrode tab, active material load
Amount is in 2mg/cm2Left and right.Electrolyte system selects 1mol/L sodium perchlorate electrolyte, and solvent is ethylene carbonate and carbonic acid diethyl
Enester is with 1:1 volume ratio mixing and 1mol/L sodium perchlorate electrolyte, solvent are ethylene carbonate, divinyl carbonate and fluorine
For ethylene carbonate（FEC）With 47.5:47.5:5 volume ratio mixing, is assembled into button cell respectively.Using glass fibre as
Diaphragm selects pure sodium piece to electrode, and glove box under an argon atmosphere is assembled into button cell.
Embodiment 3
A kind of preparation method of the hollow hard carbon material of threadiness, in specific steps in not specified step and embodiment 1
It is identical that method prepares material, the difference is that：The raw material of the step 1 is tossa；The temperature of step 2 Pintsch process
Degree is 1200 DEG C；The step 1 and 2 atmosphere be argon gas.
The hollow hard carbon material of threadiness prepared by embodiment 3 is through X-ray diffraction（XRD）Test, as a result as shown in Fig. 2,
The diffraction maximum of the serious widthization of two of available amorphous carbon curve from figure, graphite flake layer spacing are 0.3697nm, favorably
In the storage of sodium ion.
The hollow hard carbon material of threadiness prepared by embodiment 3 is through Raman spectrum（Raman）Test, as a result as shown in figure 3,
The integrated intensity ratio I at two peaksD/IGIt is 1.6337, illustrates that material still keeps the high degree of disorder, it was demonstrated that this is a kind of hard carbon material.
The electro-chemical test process of the hollow hard carbon material of threadiness prepared by embodiment 3 is not said especially in specific steps
Bright step is identical as electro-chemical test process in embodiment 2.
Constant current charge-discharge test is carried out under the voltage range of 0-2V with the multiplying power of 0.1C and obtains its chemical property, Fig. 4,
Fig. 5 is respectively that all charging and discharging curve comparison diagrams of head of battery and circulation volume keep curve comparison figure.After adding FEC as seen from the figure
The voltage in fact of first week charging, which is increased, illustrates that producing thicker SEI film in first all discharge processes causes to fill close to 0.1V
Electric discharge polarization increases, and the battery of reversible capacity comparison and addition FEC are relatively low, and first week reversible capacity is respectively
121.3mAh/g and 159.8mAh/g can obviously observe that deintercalation process is divided into terrace part and ramp portion, platform in figure
Corresponding part is storage of the sodium ion in graphite linings edge and nanometer vacancy, and ramp portion is then that sodium ion is adsorbed on material
Capacity brought by defect and surface-active site is expected, it is seen that FEC film for additive is mainly to low-voltage terrace part
Capacity has an impact.But the cyclical stability of material is significantly improved from the addition of FEC from the point of view of cyclic curve comparison diagram, is not added with
There is 10% capacity attenuation after being circulated throughout at 200 weeks in the battery of FEC, and is added to battery capacity one after long circulating after FEC
Do not decay directly, the stabilization SEI for illustrating that FEC is formed can be effectively improved in cyclic process.
Embodiment 4
A kind of preparation method of the hollow hard carbon material of threadiness, in specific steps in not specified step and embodiment 1
It is identical that method prepares material, the difference is that：The raw material of the step 1 is bombax cotton；The temperature of step 2 Pintsch process
Degree is 1400 DEG C；The step 1 and 2 atmosphere be nitrogen.
The hollow hard carbon material of threadiness prepared by embodiment 4 is tested through X-ray diffraction, as a result as shown in fig. 6, from figure
The diffraction maximum of the serious widthization of two of available amorphous carbon curve, graphite flake layer spacing be 0.3811nm, be conducive to sodium from
The storage of son.
The hollow hard carbon material of threadiness prepared by embodiment 4 is tested through Raman spectrum, as a result as shown in fig. 7, two peaks
Integrated intensity ratio ID/IGIt is 1.7109, illustrates that material still keeps the high degree of disorder, it was demonstrated that this is a kind of hard carbon material.
The hollow hard carbon material of threadiness and kapok raw material prepared by embodiment 4 is through scanning electron microscope（SEM）Test,
Fig. 8 show raw material SEM picture, and pipe thickness is 1.5 ~ 2 μm, and caliber is at 15 ~ 25 μm or so.Although as shown in figure 9, in high temperature
The phenomenon that fibre structure is shunk after cracking, but fibre structure can remain.Its caliber is at 5-10 μm or so, micron order
Caliber and smoothness tube wall give material to provide lesser specific surface area, this is conducive to reduce surface and electrolyte contacts, improves
The coulombic efficiency in first week；Its pipe thickness is 0.2 μm or so, can effectively reduce the path of ion diffusion and improve electrolyte
Wellability, improve the dynamic performance of material.
The electro-chemical test process of the hollow hard carbon material of threadiness prepared by embodiment 4 is not said especially in specific steps
Bright step is identical as electro-chemical test process in embodiment 2, the difference is that：Electrolyte system selects 1mol/L perchloric acid
Sodium electrolyte；Solvent is ethylene carbonate and divinyl carbonate with 1:1 volume ratio mixing.
Constant current charge-discharge test and loop test are carried out under the voltage range of 0-2V with the multiplying power of 0.1C.And high rate performance
Test is then with 0.1C under the voltage range of 0-2V for initial circulation 5 weeks, and subsequent multiplying power is gradually incremented by and respectively recycles 5
It week is eventually returned to 0.1C and recycles 5 weeks, Figure 10, Figure 11 are respectively that all charging and discharging curves of head of battery and circulation volume keep curve.
The all reversible capacities of the head of material reach 292.3mAh/g as seen from the figure, and first all coulombic efficiencies are up to 79.68%, can be bright in figure
Aobvious to observe that deintercalation process is divided into terrace part and ramp portion, terrace part is corresponding to be sodium ion at graphite linings edge and receives
Storage in rice vacancy, and ramp portion is then that sodium ion is adsorbed on capacity brought by fault in material and surface-active site.
Material has also had both excellent high rate performance simultaneously, and the capacity of 167mAh/g is still maintained under 2C charge-discharge magnification.
Embodiment 5
A kind of preparation method of the hollow hard carbon material of threadiness, in specific steps in not specified step and embodiment 1
It is identical that method prepares material, the difference is that：The raw material of the step 1 is poplar wadding fiber；The temperature of step 2 Pintsch process
Degree is 1200 DEG C；The step 1 and 2 atmosphere be argon hydrogen gaseous mixture.
The hollow hard carbon material of threadiness prepared by embodiment 5 is tested through X-ray diffraction, as a result as shown in figure 12, from figure
In available amorphous carbon curve two serious widthization diffraction maximum, graphite flake layer spacing be 0 .4166nm, be conducive to sodium
The storage of ion.
The hollow hard carbon material of threadiness prepared in embodiment 5 is tested through Raman spectrum, as a result as shown in figure 13, two
The integrated intensity ratio I at peakD/IGIt is 1.8132, illustrates that material still keeps a very high degree of disorder, it was demonstrated that this is a kind of hard carbon material
Material.
The electro-chemical test process of the hollow hard carbon material of threadiness prepared by embodiment 5 is not said especially in specific steps
Bright step is identical as electro-chemical test process in embodiment 2, the difference is that：Electrolyte system selects 1mol/L perchloric acid
Sodium electrolyte, solvent are ethylene carbonate, divinyl carbonate and fluoroethylene carbonate with 47.5:47.5:5 volume ratio is mixed
It closes.
Constant current charge-discharge test is carried out under the voltage range of 0-2V with the multiplying power of 0.1C, Figure 14, Figure 15 are respectively battery
The all charging and discharging curve comparisons of head and circulation volume keep curve.The all reversible capacities of the head of material reach as seen from the figure
160.5mAh/g can obviously observe that deintercalation process is divided into terrace part and ramp portion in figure, and terrace part is corresponding to be
Storage of the sodium ion in graphite linings edge and nanometer vacancy, and ramp portion is then that sodium ion is adsorbed on fault in material and surface
Capacity brought by active site.There is good cyclical stability from material from the point of view of cyclic curve comparison diagram, battery passes through 100
Charge/discharge capacity has no decaying after Zhou Xunhuan.
Embodiment 6
A kind of preparation method of the hollow hard carbon material of threadiness, in specific steps in not specified step and embodiment 1
It is identical that method prepares material, the difference is that：The raw material of the step 1 is catkin fiber；The temperature of step 2 Pintsch process
Degree is 1600 DEG C；The step 1 and 2 atmosphere be argon gas.
The hollow hard carbon material of threadiness prepared by embodiment 6 is tested through X-ray diffraction, as a result as shown in figure 16, is
Typical amorphous carbon curve, graphite flake layer spacing are 0.4128nm, are conducive to the storage of sodium ion.
The hollow hard carbon material of threadiness prepared by embodiment 6 is tested through Raman spectrum, as a result as shown in figure 17, two peaks
Integrated intensity ratio ID/IGIt is 1.8424, illustrates that material still keeps the high degree of disorder, it was demonstrated that this is a kind of hard carbon material.
The electro-chemical test process of the hollow hard carbon material of threadiness prepared by embodiment 6 is not said especially in specific steps
Bright step is identical as electro-chemical test process in embodiment 2, the difference is that：Electrolyte system selects 1mol/L perchloric acid
Sodium electrolyte, solvent are ethylene carbonate and divinyl carbonate with 1:1 volume ratio mixing.
Constant current charge-discharge test is carried out under the voltage range of 0-2V with the multiplying power of 0.1C, Figure 18, Figure 19 are respectively battery
The all charging and discharging curves of head and circulation volume keep curve.The all reversible capacities of the head of material reach 205.5mAh/g as seen from the figure,
It can obviously observe that deintercalation process is divided into terrace part and ramp portion in figure, corresponding terrace part is sodium ion in graphite
Storage in layer edge and nanometer vacancy, and ramp portion is then that sodium ion is adsorbed on fault in material and surface-active site institute band
The capacity come.There is good cyclical stability from material from the point of view of cyclic curve comparison diagram, the charging capacity after 150 weeks circulations
Conservation rate is 91.2%.
The hard carbon material preparation provided in the above embodiment of the present invention is simple, and raw material resources are rich and easy to get, low in cost, can
It is applied in industrialized production using the active cathode material as sodium ion secondary battery, the sodium ion that acquisition is prepared is secondary
Battery, charge/discharge capacity with higher, good high rate performance, stable structure can be applied to for various purposes secondary
Sode cell, such as power battery field and the extensive energy storage device of solar power generation, wind-power electricity generation, smart grid.
Claims (1)
1. a kind of preparation method for the hollow hard carbon material of threadiness that can be used for sodium-ion battery cathode, it is characterised in that have such as
Under preparation process and step：
A. the pretreatment of raw material：Fibrous biological material is cleaned, drying, is ground after being carbonized in advance under certain condition,
Obtain presoma；The biomass is jute, ramie, bombax cotton, poplar wadding fiber, catkin fiber or cotton fiber；It is described pre-
The condition of carbonization is under inert gas protection, to be raised to 400 ~ 800 DEG C with 2 ~ 10 DEG C/min of heating rate and heat preservation 2 ~ 6 is small
When；
B. Pintsch process：After presoma obtained by above-mentioned steps a under certain condition Pintsch process, the hollow hard carbon of threadiness is obtained
Material；The condition of the Pintsch process is 2 ~ 10 DEG C/min of heating rate, at 1000 ~ 1800 DEG C under inert gas protection
Heat preservation 2 ~ 6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810578633.9A CN108862235B (en) | 2018-06-07 | 2018-06-07 | Fibrous hollow hard carbon material for sodium ion battery cathode and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810578633.9A CN108862235B (en) | 2018-06-07 | 2018-06-07 | Fibrous hollow hard carbon material for sodium ion battery cathode and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108862235A true CN108862235A (en) | 2018-11-23 |
| CN108862235B CN108862235B (en) | 2022-06-14 |
Family
ID=64337133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810578633.9A Active CN108862235B (en) | 2018-06-07 | 2018-06-07 | Fibrous hollow hard carbon material for sodium ion battery cathode and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108862235B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109560279A (en) * | 2018-11-30 | 2019-04-02 | 陕西科技大学 | A kind of method that kapok prepares multiporous biological carbon lithium-sulfur cell negative electrode material |
| CN109626370A (en) * | 2019-01-21 | 2019-04-16 | 青岛科技大学 | The preparation and its application of biomass-based porous carbon materials based on sycamore seed |
| CN109755572A (en) * | 2019-01-10 | 2019-05-14 | 电子科技大学 | A kind of electrode and preparation method thereof based on SA modification hard carbon active material |
| CN111146013A (en) * | 2020-01-10 | 2020-05-12 | 厦门理工学院 | Hollow micro-tube electrode material based on ramie, and synthesis method and application thereof |
| CN111924824A (en) * | 2020-08-14 | 2020-11-13 | 山东理工大学 | Preparation method of carbon with high specific surface area and high conductivity |
| CN112599752A (en) * | 2021-01-06 | 2021-04-02 | 天津工业大学 | Preparation method of carbon-coated hollow kapok fiber-loaded flower-shaped molybdenum disulfide composite material as sodium ion battery negative electrode material |
| CN116995231A (en) * | 2023-09-25 | 2023-11-03 | 宁德时代新能源科技股份有限公司 | Carbon material and preparation method thereof, negative electrode plate, secondary battery and power utilization device |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086034A (en) * | 2010-12-13 | 2011-06-08 | 南京邮电大学 | Carbon-nano-tube prepared from poplar catkin and willow catkin as raw materials and preparation method |
| CN102557026A (en) * | 2011-11-09 | 2012-07-11 | 南京邮电大学 | Method for preparing porous carbon micron tube from catkin, poplar seed or phoenix tree seed as raw material |
| CN103253651A (en) * | 2013-05-23 | 2013-08-21 | 广西大学 | Lignin-based porous carbon material and preparation method thereof |
| CN104386691A (en) * | 2014-10-21 | 2015-03-04 | 北京科技大学 | Method for preparing hollow tubular activated carbon electrode material for supercapacitor |
| CN104726965A (en) * | 2015-02-10 | 2015-06-24 | 中国科学院金属研究所 | Preparation method of flexible high-conductivity three-dimensional connective hollow carbon fiber |
| CN105776182A (en) * | 2016-04-29 | 2016-07-20 | 陕西科技大学 | Preparation method and application of hollow tubular biochar |
| CN107827107A (en) * | 2017-12-18 | 2018-03-23 | 中国科学院山西煤炭化学研究所 | A kind of preparation method of the hollow porous charcoal micro-pipe of kapok base or porous charcoal micro-strip |
-
2018
- 2018-06-07 CN CN201810578633.9A patent/CN108862235B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086034A (en) * | 2010-12-13 | 2011-06-08 | 南京邮电大学 | Carbon-nano-tube prepared from poplar catkin and willow catkin as raw materials and preparation method |
| CN102557026A (en) * | 2011-11-09 | 2012-07-11 | 南京邮电大学 | Method for preparing porous carbon micron tube from catkin, poplar seed or phoenix tree seed as raw material |
| CN103253651A (en) * | 2013-05-23 | 2013-08-21 | 广西大学 | Lignin-based porous carbon material and preparation method thereof |
| CN104386691A (en) * | 2014-10-21 | 2015-03-04 | 北京科技大学 | Method for preparing hollow tubular activated carbon electrode material for supercapacitor |
| CN104726965A (en) * | 2015-02-10 | 2015-06-24 | 中国科学院金属研究所 | Preparation method of flexible high-conductivity three-dimensional connective hollow carbon fiber |
| CN105776182A (en) * | 2016-04-29 | 2016-07-20 | 陕西科技大学 | Preparation method and application of hollow tubular biochar |
| CN107827107A (en) * | 2017-12-18 | 2018-03-23 | 中国科学院山西煤炭化学研究所 | A kind of preparation method of the hollow porous charcoal micro-pipe of kapok base or porous charcoal micro-strip |
Non-Patent Citations (4)
| Title |
|---|
| YANWEN MA等: "The production of carbon microtubes by the carbonization of catkins and their use in the oxygen reduction reaction", 《C A R B ON》 * |
| YUFANG CAO等: "Hollow carbon microtubes from kapok fiber:structural evolution and energy storage performance", 《SUSTAINABLE ENERGY & FUELS》 * |
| YUNMING LI等: "Hard Carbon Microtubes Made from Renewable Cotton as High-Performance Anode Material for Sodium-Ion Batteries", 《ADV. ENERGY MATER.》 * |
| 马延文等: "碳化法国梧桐絮制备碳微米管及作为超级电容器电极的研究", 《无机化学学报》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109560279A (en) * | 2018-11-30 | 2019-04-02 | 陕西科技大学 | A kind of method that kapok prepares multiporous biological carbon lithium-sulfur cell negative electrode material |
| CN109560279B (en) * | 2018-11-30 | 2021-08-10 | 陕西科技大学 | Method for preparing porous biological carbon lithium-sulfur battery positive electrode material from ceiba |
| CN109755572A (en) * | 2019-01-10 | 2019-05-14 | 电子科技大学 | A kind of electrode and preparation method thereof based on SA modification hard carbon active material |
| CN109626370A (en) * | 2019-01-21 | 2019-04-16 | 青岛科技大学 | The preparation and its application of biomass-based porous carbon materials based on sycamore seed |
| CN111146013A (en) * | 2020-01-10 | 2020-05-12 | 厦门理工学院 | Hollow micro-tube electrode material based on ramie, and synthesis method and application thereof |
| CN111924824A (en) * | 2020-08-14 | 2020-11-13 | 山东理工大学 | Preparation method of carbon with high specific surface area and high conductivity |
| CN111924824B (en) * | 2020-08-14 | 2023-02-17 | 山东理工大学 | Preparation method of carbon with high specific surface area and high conductivity |
| CN112599752A (en) * | 2021-01-06 | 2021-04-02 | 天津工业大学 | Preparation method of carbon-coated hollow kapok fiber-loaded flower-shaped molybdenum disulfide composite material as sodium ion battery negative electrode material |
| CN112599752B (en) * | 2021-01-06 | 2023-07-18 | 天津工业大学 | Preparation method of carbon-coated hollow kapok fiber-bearing flower-shaped molybdenum disulfide composite material serving as sodium ion battery anode material |
| CN116995231A (en) * | 2023-09-25 | 2023-11-03 | 宁德时代新能源科技股份有限公司 | Carbon material and preparation method thereof, negative electrode plate, secondary battery and power utilization device |
| CN116995231B (en) * | 2023-09-25 | 2024-04-09 | 宁德时代新能源科技股份有限公司 | Carbon material and preparation method thereof, negative electrode plate, secondary battery and power utilization device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108862235B (en) | 2022-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108862235A (en) | A kind of hollow hard carbon material of threadiness and preparation method thereof can be used for sodium-ion battery cathode | |
| CN109273680B (en) | Porous silicon-carbon negative electrode material, preparation method thereof and lithium ion battery | |
| CN107240680B (en) | hard carbon-metal oxide-soft carbon composite material and preparation method and application thereof | |
| CN104882607B (en) | A kind of Animal Bone base class graphene lithium ion battery negative material and preparation method thereof | |
| CN109399601B (en) | Preparation method and application of nitrogen-phosphorus co-doped biochar material | |
| CN109148847B (en) | Boron-doped modified hard carbon-coated negative electrode material with high rate performance and liquid-phase preparation method thereof | |
| CN108315028B (en) | Pyrolytic hard carbon material with longitudinal pore structure and preparation method and application thereof | |
| CN109713261B (en) | Carbonized silk fabric/transition metal oxide composite material for flexible lithium ion battery cathode and preparation method thereof | |
| CN109167025B (en) | Boron-doped modified soft carbon-coated negative electrode material with high stability in high and low temperature environments and preparation method thereof | |
| CN110155983B (en) | Preparation method of cotton-based porous biomass carbon | |
| CN108550789B (en) | Sodium ion battery cathode, preparation method thereof and sodium ion battery | |
| CN115259132B (en) | Preparation method and application of ultra-high first-effect hard carbon anode material | |
| CN111900408A (en) | MoS for lithium ion battery2@ C composite negative electrode material and preparation method thereof | |
| CN115092905B (en) | Amorphous carbon material modified by carbon dots, and preparation method and application thereof | |
| CN114291796A (en) | Potassium ion battery negative electrode material and preparation method and application thereof | |
| CN113363465A (en) | Preparation method of lithium/potassium ion battery negative electrode material | |
| CN108281627A (en) | A kind of lithium ion battery germanium carbon compound cathode materials and preparation method thereof | |
| CN107565114B (en) | Binderless sodium ion battery negative electrode material and preparation method thereof | |
| CN108766786A (en) | A kind of preparation method of high specific energy Nano carbon energy storage material | |
| CN117293303A (en) | Lithium-sulfur battery anode material and preparation method and application thereof | |
| CN113036097A (en) | Sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material and preparation method thereof | |
| CN115911284B (en) | Method for modifying hard carbon material by utilizing ion irradiation technology and application | |
| CN114551891B (en) | Tin disulfide/titanium dioxide/carbon composite material and preparation method and application thereof | |
| CN116101998A (en) | Preparation method of ultra-low temperature sodium ion battery high-surface-activity hard carbon negative electrode material | |
| CN113178562B (en) | Fabric-like carbon-coated silicon dioxide composite material and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |