CN106185862A - A kind of pyrolyzed hard carbon material and application thereof - Google Patents
A kind of pyrolyzed hard carbon material and application thereof Download PDFInfo
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- CN106185862A CN106185862A CN201610505671.2A CN201610505671A CN106185862A CN 106185862 A CN106185862 A CN 106185862A CN 201610505671 A CN201610505671 A CN 201610505671A CN 106185862 A CN106185862 A CN 106185862A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention discloses a kind of pyrolyzed hard carbon material, in one embodiment, this material prepares by the following method: by abandoned biomass dried；It is warming up to 300 DEG C 600 DEG C under an inert atmosphere, pre-carbonization 1 5h；It is warming up to 1000 DEG C 1600 DEG C under an inert atmosphere, carbonization, cracks 1 10h；Described pyrolytic carbon material is i.e. obtained after cooling；Wherein, it is thus achieved that described pyrolyzed hard carbon material be irregular blocky-shaped particle, particle size is 1 20 μm, and mean diameter is 5 10 μm；d002It is worth between 0.38 0.41nm, LcIt is worth between 1.3 1.5nm, LaValue is between 3.7 4.7nm.The pyrolyzed hard carbon material preparation that the present invention provides is simple, raw material resources is abundant, with low cost, it it is free of contamination green material, use above-mentioned material as the sodium ion secondary battery of negative active core-shell material, there is higher running voltage and energy density, stable circulation, security performance good, can apply to solar electrical energy generation, wind-power electricity generation, intelligent grid peak regulation, distribution power station, back-up source or the extensive energy storage device of communication base station.
Description
Technical field
The present invention relates to field of material technology, particularly relate to a kind of pyrolyzed hard carbon material and application thereof.
Background technology
Lithium ion battery is with its high voltage, the advantage such as high-energy-density and high security so that it is lead at mancarried electronic aid
Territory occupies the status that can not be substituted, and shows up prominently the most rapidly in electrokinetic cell field.Compared with lithium ion battery, sodium ion electricity
Pond, due to sodium aboundresources, has potential price advantage, and has broad application prospects in large-scale energy storage system.
The main negative material of the lithium ion battery of business application at present is graphite material, for sodium-ion battery, by
In thermodynamic one, sodium ion cannot realize stable reversible deintercalation in graphite layers, and therefore sodium-ion battery to find other
New material as negative material.
Amorphous carbon presses graphited complexity, is generally divided into soft carbon (easy graphitized carbon) and hard carbon (difficult graphitization
Carbon).Wherein belong to soft carbon after the carbonization such as oil, coal, Colophonium, polrvinyl chloride and anthracene, and the costs such as these predecessors such as Colophonium
Cheap, produce carbon rate higher；Hard carbon is belonged to after the carbonizations such as cellulose, saccharide, furane resins, phenolic resin and polyvinylidene chloride.
Hard carbon material has most the negative pole material of application prospect owing to the advantages such as its specific capacity is high, storage sodium voltage is low become sodium ion secondary battery
Material.
Although hard carbon material has significant advantage as sodium-ion battery, but produces forerunner used by hard carbon material at present
In body, carbon content is low, and its mass loss during high temperature cabonization is big, and product carbon rate is low, causes hard carbon relatively costly, constrains it
Widespread adoption.
The present invention uses discarded biomass to be raw material, prepares a kind of hard carbon material by technique simple to operation,
Not only achieve the recycling of abandoned biomass, and reduce the production cost of hard carbon, this material be particularly suitable as sodium from
The negative material of sub-secondary cell.
Summary of the invention
It is an object of the invention to overcome that to produce carbon content in presoma used by hard carbon material in prior art low, and at height
In temperature carbonisation, mass loss is big, and product carbon rate is low, causes the problem that hard carbon material is relatively costly, performance is the highest, on solving
State problem, embodiments provide a kind of pyrolyzed hard carbon material and purposes.The biomass that the employing of this hard carbon material is discarded are
Raw material, is prepared from by technique simple to operation, and preparation method is simple, raw material is easy to get, with low cost, and resulting materials
Phosphorus content battery performance that is high and that utilize this material to prepare is good, is suitable for large-scale production.
First aspect, embodiments provides a kind of pyrolyzed hard carbon material, prepares by the following method: will be discarded
Biomass dried；It is warming up to 300 DEG C-600 DEG C under an inert atmosphere, pre-carbonization 1-5h；It is warming up under an inert atmosphere
1000 DEG C-1600 DEG C, carbonization, cracking 1-10h；Described pyrolytic carbon material is i.e. obtained after cooling；Wherein,
The described pyrolyzed hard carbon material obtained is irregular blocky-shaped particle, and particle size is 1-20 μm, and mean diameter is
5-10μm；d002It is worth between 0.38-0.41nm, LcIt is worth between 1.3-1.5nm, LaValue is between 3.7-4.7nm.
Preferably, the one or many during described abandoned biomass includes Semen Maydis flesh, Semen Maydis residue, corn stalk and skin of Semen Maydis
Kind.
Preferably, the phosphorus content of described pyrolyzed hard carbon material is not less than 95%.
Preferably, the surface of described material has soft carbon coating layer.
Second aspect, the invention provides a kind of negative material, and described negative active core-shell material includes above-mentioned first aspect institute
The pyrolyzed hard carbon material stated.
The third aspect, the invention provides the cathode pole piece of a kind of sodium ion secondary battery, it is characterised in that described negative pole
Pole piece includes: collector, is coated on the binding agent on described collector and the sodium ion secondary as described in above-mentioned second aspect
Cell negative electrode material.
Fourth aspect, the invention provides the secondary cell of a kind of cathode pole piece included described in the above-mentioned third aspect.
It is an object of the invention to, seek and a kind of use abandoned biomass to the method preparing hard carbon.The method meets to be worked as
The front society demand to the clean energy resource of environmental protection.Semen Maydis flesh and corn stalk after a large amount of disengagings are often directly burned, no
Only it is not carried out the value of recycling, also environment is caused pollution.The present invention is by by discarded Semen Maydis flesh, corn stalk and jade
Rice residue recycling, it is provided that a kind of technique is simple, with low cost and in being applicable to the method for large-scale production with provide one
Kind be widely used, particularly in sodium ion secondary battery as the pyrolyzed hard carbon material of negative material, in circulating battery process
In, stable cycle performance.
Accompanying drawing explanation
The preparation method of the material that Fig. 1 provides for the embodiment of the present invention 1；
The XRD figure spectrum of the hard carbon material that Fig. 2 provides for the embodiment of the present invention 2；
The Raman spectrum of the hard carbon material that Fig. 3 provides for the embodiment of the present invention 2；
The SEM figure of the hard carbon material that Fig. 4 provides for the embodiment of the present invention 2；
The charging and discharging curve figure of a kind of sodium-ion battery that Fig. 5 provides for the embodiment of the present invention 2；
The XRD figure spectrum of the hard carbon material that Fig. 6 provides for the embodiment of the present invention 3；
The Raman spectrum of the hard carbon material that Fig. 7 provides for the embodiment of the present invention 3；
The SEM figure of the hard carbon material that Fig. 8 provides for the embodiment of the present invention 3；
The charging and discharging curve figure of a kind of sodium-ion battery that Fig. 9 provides for the embodiment of the present invention 3；
The XRD figure spectrum of the hard carbon material that Figure 10 provides for the embodiment of the present invention 4；
The Raman spectrum of the hard carbon material that Figure 11 provides for the embodiment of the present invention 4；
The SEM figure of the hard carbon material that Figure 12 provides for the embodiment of the present invention 4；
The charging and discharging curve figure of a kind of sodium-ion battery that Figure 13 provides for the embodiment of the present invention 4；
The charging and discharging curve figure of a kind of sodium-ion battery that Figure 14 provides for the embodiment of the present invention 5；
The XRD figure spectrum of the hard carbon material that Figure 15 provides for the embodiment of the present invention 6；
The Raman spectrum of the hard carbon material that Figure 16 provides for the embodiment of the present invention 6；
The SEM figure of the hard carbon material that Figure 17 provides for the embodiment of the present invention 6；
The charging and discharging curve figure of a kind of sodium-ion battery that Figure 18 provides for the embodiment of the present invention 6；
The charging and discharging curve figure of a kind of sodium-ion battery that Figure 19 provides for comparative example of the present invention.
Detailed description of the invention
Below by drawings and Examples, the present invention is described in further detail, but is not intended to limit this
Bright protection domain.
Embodiment 1
The embodiment of the present invention 1 provides a kind of pyrolyzed hard carbon material, and its preparation method is as it is shown in figure 1, comprise the following steps:
(1) abandoned biomass is dried process.
Specifically, using abandoned biomass as hard carbon presoma, i.e. it is prepared pyrolytic carbon with abandoned biomass for raw material
Material.Preferably, the one or many during described abandoned biomass can select Semen Maydis flesh, Semen Maydis residue, corn stalk and skin of Semen Maydis
Kind.For removing the moisture content in hard carbon presoma, hard carbon presoma is put into row dried, e.g., hard carbon presoma is placed on
Baking 20-30h in the baking oven of 50-120 DEG C, removes the moisture content in hard carbon presoma.It is pointed out that for ease of be dried and after
Continuous heat treatment, before hard carbon precursor is dried process, can carry out precomminution by hard carbon presoma.
(2) it is warming up to 300 DEG C-600 DEG C under an inert atmosphere, reacts 1-5h.
Specifically, the material after drying loads in magnetic boat puts tube furnace into, passes first into noble gas, preferably nitrogen
Gas, is then slowly ramped to 300 DEG C-600 DEG C, preheats under this condition, it is therefore an objective to material is carried out pre-carbonization.Preferably
Ground, with the ramp of 0.5-10 DEG C/min in temperature-rise period.
(3) it is warming up to 1000 DEG C-1600 DEG C under an inert atmosphere, reacts 1-10h.
Specifically, after pre-carbonization completes, in tube furnace, it is slowly ramped to 1000 DEG C-1600 DEG C, is persistently incubated 1-
10h, carries out carbonization treatment, it may be assumed that make hard carbon presoma generation cracking reaction.Preferably, in temperature-rise period with 0.5-10 DEG C/
The ramp of min.
Optionally, for reducing the surface area of material, it is also possible to the gas added containing Hydrocarbon in course of reaction enters
Row Surface coating so that it is surface has in soft carbon coating layer, preferably methane, ethane, toluene, ethylene, acetylene and propine
Plant or multiple.
Hard carbon presoma generation cracking reaction in the process, generates hard carbon material.
(4), after cooling crush, described pyrolyzed hard carbon material is obtained.
Concrete, cooling can use natural cooling, is taken out by tube furnace after being down to room temperature, i.e. obtains required after pulverizing
Hard carbon material.
Optionally, in order to remove the impurity in hard carbon material, after being pulverized, follow-up acid pickling step can also be increased.Preferably
Ground, the liquid for pickling includes dilute hydrochloric acid, Fluohydric acid. or its mixture, and in acid cleaning process, soak time is 1-5h.
Above-mentioned acquisition hard carbon material phosphorus content is not less than 95%, has nano-pore, and is irregular blocky-shaped particle, granule
A size of 1-20 μm, mean diameter is 5-10 μm；d002It is worth between 0.38-0.41nm, LcIt is worth between 1.3-1.5nm, LaValue
Between 3.7-4.7nm..
The preparation of the pyrolyzed hard carbon material that the present embodiment provides is simple, and raw material is easy to get, with low cost, and resulting materials contains
Carbon amounts is high (being not less than 95%), is suitable for large-scale production.The biomass that preparation employing is discarded, can as hard carbon precursor material
To improve the phosphorus content of gained hard carbon material.By changing hard carbon presoma kind, and adjust cracking temperature, difference can be obtained
The granular materials of characteristic size, has different electrochemical properties, thus can obtain the hard of optimum performance according to different demands
Material with carbon element, for the negative material of sodium ion secondary battery.
The technical scheme provided for a better understanding of the present invention, following is described separately the application present invention with multiple instantiations
The preparation method that above-described embodiment 1 provides carries out detailed process prepared by pyrolyzed hard carbon material, and is applied to sodium ion
Secondary battery cathode material and the method for sodium ion secondary battery and battery behavior thereof.
Embodiment 2
The preparation of pyrolyzed hard carbon material: the Semen Maydis flesh removing niblet is cut into the segment of wide about 1cm, is placed in beaker,
It is placed in 80 DEG C of constant temperature ovens baking 26h.It is placed on after drying in the porcelain boat of about 5cm*2cm*2cm, prepares for high temperature cabonization.
With porcelain boat, Semen Maydis flesh is placed on tube furnace, and (pipe range about 100cm, diameter 6cm, following example use identical
Tube furnace) in, under argon shield, with the ramp of 1 DEG C/min to 500 DEG C, argon flow amount is 25mL/min, at 500 DEG C
Pre-carbonization 2h, then the ramp to 1300 DEG C with 5 DEG C/min, be incubated 2h, naturally cool to room temperature afterwards.Jade by carbonization
Rice section is taken out, and grind into powder in mortar i.e. obtains pyrolyzed hard carbon product.Its X-ray diffraction (XRD) collection of illustrative plates sees Fig. 2.From
XRD figure spectrum can obtain the d of this hard carbon material002=0.398nm, Lc=1.39nm.Its Raman spectrum sees Fig. 3, passes through Raman
Collection of illustrative plates can obtain the La=4.32nm of this hard carbon material.Fig. 4 is the powder microgram shot by scanning electron microscope (SEM)
Sheet, it can be seen that particle size is between 5-20 μm.
The pyrolyzed hard carbon material of above-mentioned preparation is used for as battery cathode active material the preparation of sodium ion secondary battery.
The powder of the above-mentioned pyrolyzed hard carbon material prepared is mixed into the mass ratio of 95:5 with sodium alginate binding agent
Uniform powder, adds appropriate amount of deionized water, then grinds a period of time and form uniform slurry, is coated on the aluminum as collector
On paper tinsel.After the pole piece obtained stands about 3h at normal temperatures, moisture evaporation is clean, and dry pole piece is cut into 0.8cm*0.8cm's
Square sheet, places in vacuum drying oven, dries 8h, obtain hard carbon cathode pole piece, transfer to glove box immediately at a temperature of 120 DEG C
Interior standby.
Being assembled into CR2032 experimental button cell in argon filling glove box, in glove box, water, partial pressure of oxygen are not higher than 1ppm.With
The metallic sodium sheet of thickness about 0.3mm, a diameter of 1cm is as to electrode, with the NaPF of 1mol6It is dissolved in the carbonic acid that 1L volume ratio is 1:1
Vinyl acetate and diethyl carbonate solution, as electrolyte, are assembled into CR2032 button cell.This battery is carried out electrochemistry charge and discharge
Electrical testing, the multiplying power tested is 0.1C, and discharge cut-off voltage is 0.0V, and charge cutoff voltage is 2.0V.Its charging and discharging curve
Seeing that Fig. 5, first all discharge capacities are about 340mAh/g, first all coulombic efficiencies are 86.3%, and its reversible capacity is about 300mAh/g,
The cyclic process of 50 weeks does not has obvious capacity attenuation.Its cyclic curve has the stable charge and discharge platform of below 0.2V,
In reversible capacity, the terrace part capacity of below 0.2V accounts for the 72.0% of total capacity, and higher platform capacity is to designing with this
Material is that the battery of electrode active material has great importance.
Embodiment 3
The preparation of pyrolyzed hard carbon material: the Semen Maydis flesh removing niblet is cut into the segment of wide about 1cm, is placed in beaker,
It is placed in 50 DEG C of constant temperature ovens drying 30h.It is placed on after drying in the porcelain boat of about 5cm*2cm*2cm, prepares for high temperature cabonization.
Semen Maydis flesh is placed in tube furnace with porcelain boat, under argon shield, with the ramp of 1 DEG C/min to 500
DEG C, argon flow amount is 25mL/min, preheats 2h, then the ramp to 1000 DEG C with 5 DEG C/min at 500 DEG C, is incubated 2h, afterwards
Naturally cool to room temperature.The Semen Maydis flesh of carbonization is taken out, grind into powder in mortar, i.e. obtain pyrolyzed hard carbon product.Its X
X ray diffraction (XRD) collection of illustrative plates sees Fig. 6.The d of this hard carbon material can be obtained from XRD figure spectrum002=0.408nm, Lc=
1.34nm.Its Raman spectrum sees Fig. 7, can be obtained the L of this hard carbon material by Raman collection of illustrative platesa=4.61nm.Fig. 8 is for sweeping
Retouch the powder microcosmic picture that ultramicroscope (SEM) shoots, it can be seen that particle size is between 10-20 μm.
The above-mentioned pyrolyzed hard carbon material prepared is used for sodium-ion battery as the active substance of cell negative electrode material
Preparation, and carry out charge discharge test.Its preparation process and method of testing are with embodiment 3.The multiplying power tested is
0.1C, discharge cut-off voltage is 0.0V, and charge cutoff voltage is 2.0V.Its charging and discharging curve is shown in Fig. 9, and first all discharge capacities are about
340mAg/g, first all coulombic efficiencies 76.5%, its reversible capacity is about 230mAh/g, in the cyclic process of 50 weeks the most substantially
Capacity attenuation.Its cyclic curve has first charge and discharge platform smoothly, in reversible capacity, terrace part capacity at below 0.2V
Ratio is 57.9%.
Embodiment 4
The preparation of pyrolyzed hard carbon material: the Semen Maydis flesh removing niblet is cut into the segment of wide about 1cm, is placed in beaker,
It is placed in 80 DEG C of constant temperature ovens drying 26h.It is placed on after drying in the porcelain boat of about 5cm*2cm*2cm, prepares for high temperature cabonization.
Semen Maydis flesh is placed in tube furnace with porcelain boat, under argon shield, with the ramp of 1 DEG C/min to 500
DEG C, argon flow amount is 25mL/min, preheats 2h, then the ramp to 1600 DEG C with 5 DEG C/min at 500 DEG C, is incubated 2h, afterwards
Naturally cool to room temperature.The Semen Maydis flesh of carbonization is taken out, grind into powder in mortar, i.e. obtain pyrolyzed hard carbon product.Its X
X ray diffraction (XRD) collection of illustrative plates sees Figure 10.The d of this hard carbon material can be obtained from XRD figure spectrum002=0.389nm, Lc=
1.47nm.Its Raman spectrum sees Figure 11, can be obtained the L of this hard carbon material by Raman collection of illustrative platesa=3.75nm.Figure 12 is for using
The powder microcosmic picture that scanning electron microscope (SEM) shoots, it can be seen that particle size is between 10-20 μm.
The above-mentioned pyrolyzed hard carbon material prepared is used for sodium-ion battery as the active substance of cell negative electrode material
Preparation, and carry out charge discharge test.Its preparation process and method of testing are with embodiment 3.The multiplying power tested is
0.1C, discharge cut-off voltage is 0.0V, and charge cutoff voltage is 2.0V.Its charging and discharging curve is shown in Figure 13, and first all discharge capacities are about
320mAg/g, first all coulombic efficiencies 87.0%, its reversible capacity is about 270mAh/g, in the cyclic process of 50 weeks the most substantially
Capacity attenuation.Its cyclic curve has first charge and discharge platform smoothly, in reversible capacity, terrace part capacity at below 0.2V
Ratio is 81.1%.
Embodiment 5
The preparation process of pyrolyzed hard carbon material is with embodiment 2.
The above-mentioned pyrolyzed hard carbon material prepared is used for sodium-ion battery as the active substance of cell negative electrode material
Preparation, and carry out charge discharge test.Its preparation process and method of testing are with embodiment 1.The multiplying power tested is
0.2C, discharge cut-off voltage is 0.0V, and charge cutoff voltage is 2.0V.Its charging and discharging curve is shown in Figure 14, and its reversible capacity is about
280mAh/g, under the circulating ratio of 2 times of original batteries, although the battery capacity of assembling decreases, but still keeps higher
Cyclical stability.
Embodiment 6
The preparation of pyrolyzed hard carbon material: remaining Semen Maydis grit after squeezing the juice is placed in beaker, is placed in 100 DEG C of constant temperature ovens
Dry 24h.After taking-up, weigh about 1g Semen Maydis grit, be placed in the porcelain boat of about 5cm*2cm*2cm, prepare for high temperature cabonization.
This product is placed in tube furnace with porcelain boat, under argon shield, with the ramp of 1 DEG C/min to 500
DEG C, argon flow amount is 25mL/min, preheats 2h, then the ramp to 1300 DEG C with 5 DEG C/min at 500 DEG C, is incubated 2h, afterwards
Naturally cool to room temperature.The Semen Maydis grit of carbonization is taken out, grind into powder in mortar, i.e. obtain pyrolyzed hard carbon product.Its X
X ray diffraction (XRD) collection of illustrative plates sees Figure 15.Its Raman spectrum sees Figure 16.Figure 17 is for shooting by scanning electron microscope (SEM)
Powder microcosmic picture, it can be seen that particle size is about 10 μm.
The above-mentioned pyrolyzed hard carbon material prepared is used for sodium-ion battery as the active substance of cell negative electrode material
Preparation, and carry out charge discharge test.Its preparation process and method of testing are with embodiment 2.The multiplying power tested is
0.1C, discharge cut-off voltage is 0.0V, and charge cutoff voltage is 2.0V.Its charging and discharging curve is shown in Figure 18, and its reversible capacity is about
270mAh/g, cycle performance is preferable.
Embodiment 7
The preparation of pyrolyzed hard carbon material: remaining Semen Maydis grit after squeezing the juice is placed in beaker, is placed in 120 DEG C of constant temperature ovens
Dry 20h.After taking-up, weigh about 1g Semen Maydis grit, be placed in the porcelain boat of about 5cm*2cm*2cm, prepare for high temperature cabonization.
This product is placed in tube furnace with porcelain boat, under argon shield, with the ramp of 1 DEG C/min to 500
DEG C, argon flow amount is 25mL/min, preheats 2h, then the ramp to 1000 DEG C with 5 DEG C/min at 500 DEG C, is incubated 2h, afterwards
Naturally cool to room temperature.The Semen Maydis grit of carbonization is taken out, grind into powder in mortar, i.e. obtain pyrolyzed hard carbon product.
The above-mentioned pyrolyzed hard carbon material prepared is used for sodium-ion battery as the active substance of cell negative electrode material
Preparation, and carry out charge discharge test.Its preparation process and method of testing are with embodiment 2.The multiplying power tested is
0.1C, discharge cut-off voltage is 0.0V, and charge cutoff voltage is 2.0V.Result see table 1 and (contrasts for convenience, by embodiment
The test result of 3-7 is put in Table 1 the most in the lump).
Embodiment 8
The preparation of pyrolyzed hard carbon material: remaining Semen Maydis grit after squeezing the juice is placed in beaker, is placed in 80 DEG C of constant temperature ovens
Dry 26h.After taking-up, weigh about 1g Semen Maydis grit, be placed in the porcelain boat of about 5cm*2cm*2cm, prepare for high temperature cabonization.
This product is placed in tube furnace with porcelain boat, under argon shield, with the ramp of 1 DEG C/min to 500
DEG C, argon flow amount is 25mL/min, preheats 2h, then the ramp to 1600 DEG C with 5 DEG C/min at 500 DEG C, is incubated 2h, afterwards
Naturally cool to room temperature.The Semen Maydis grit of carbonization is taken out, grind into powder in mortar, i.e. obtain pyrolyzed hard carbon product.
The above-mentioned pyrolyzed hard carbon material prepared is used for sodium-ion battery as the active substance of cell negative electrode material
Preparation, and carry out charge discharge test.Its preparation process and method of testing are with embodiment 2.The multiplying power tested is
0.1C, discharge cut-off voltage is 0.0V, and charge cutoff voltage is 2.0V.Result see table 1.
Embodiment 9
The preparation of pyrolyzed hard carbon material: corn stalk wash clean, go the removal of impurity, after being cut into the thick segment of about 1cm, is placed on burning
Drying 26h it is placed in 80 DEG C of constant temperature ovens in Bei.It is placed on after drying in the porcelain boat of about 5cm*2cm*2cm, prepares for pyrocarbon
Change.
This product is placed in tube furnace with porcelain boat, under argon shield, with the ramp of 1 DEG C/min to 500
DEG C, argon flow amount is 25mL/min, preheats 2h, then the ramp to 1300 DEG C with 5 DEG C/min at 500 DEG C, is incubated 2h, afterwards
Naturally cool to room temperature.The corn stalk of carbonization is taken out, grind into powder in mortar, i.e. obtain pyrolyzed hard carbon product.
The above-mentioned pyrolyzed hard carbon material prepared is used for sodium-ion battery as the active substance of cell negative electrode material
Preparation, and carry out charge discharge test.Its preparation process and method of testing are with embodiment 2.The multiplying power tested is
0.1C, discharge cut-off voltage is 0.0V, and charge cutoff voltage is 2.0V.Result see table 1.
Embodiment 10
The preparation of pyrolyzed hard carbon material: corn stalk wash clean, go the removal of impurity, after being cut into the thick segment of about 1cm, is placed on burning
Drying 26h it is placed in 80 DEG C of constant temperature ovens in Bei.It is placed on after drying in the porcelain boat of about 5cm*2cm*2cm, prepares for pyrocarbon
Change.
This product is placed in tube furnace with porcelain boat, under argon shield, with the ramp of 1 DEG C/min to 500
DEG C, argon flow amount is 25mL/min, preheats 2h, then the ramp to 1000 DEG C with 5 DEG C/min at 500 DEG C, is incubated 2h, afterwards
Naturally cool to room temperature.The corn stalk of carbonization is taken out, grind into powder in mortar, i.e. obtain pyrolyzed hard carbon product.
The above-mentioned pyrolyzed hard carbon material prepared is used for sodium-ion battery as the active substance of cell negative electrode material
Preparation, and carry out charge discharge test.Its preparation process and method of testing are with embodiment 2.The multiplying power tested is
0.1C, discharge cut-off voltage is 0.0V, and charge cutoff voltage is 2.0V.Result see table 1.
Embodiment 11
The preparation of pyrolyzed hard carbon material: corn stalk wash clean, go the removal of impurity, after being cut into the thick segment of about 1cm, is placed on burning
Drying 28h it is placed in 60 DEG C of constant temperature ovens in Bei.It is placed on after drying in the porcelain boat of about 5cm*2cm*2cm, prepares for pyrocarbon
Change.
This product is placed in tube furnace with porcelain boat, under argon shield, with the ramp of 1 DEG C/min to 500
DEG C, argon flow amount is 25mL/min, preheats 2h, then the ramp to 1600 DEG C with 5 DEG C/min at 500 DEG C, is incubated 2h, afterwards
Naturally cool to room temperature.The corn stalk of carbonization is taken out, grind into powder in mortar, i.e. obtain pyrolyzed hard carbon product.
The above-mentioned pyrolyzed hard carbon material prepared is used for sodium-ion battery as the active substance of cell negative electrode material
Preparation, and carry out charge discharge test.Its preparation process and method of testing are with embodiment 2.The multiplying power tested is
0.1C, discharge cut-off voltage is 0.0V, and charge cutoff voltage is 2.0V.Result see table 1.
Embodiment 12
The preparation of pyrolyzed hard carbon material: skin of Semen Maydis wash clean, go the removal of impurity, after being cut into less than the fragment of 1cm*1cm, puts
Drying 22h it is placed in 90 DEG C of constant temperature ovens in beaker.It is placed on after drying in the porcelain boat of about 5cm*2cm*2cm, prepares for height
Temperature carbonization.
This product is placed in tube furnace with porcelain boat, under argon shield, with the ramp of 1 DEG C/min to 500
DEG C, argon flow amount is 25mL/min, preheats 2h, then the ramp to 1300 DEG C with 5 DEG C/min at 500 DEG C, is incubated 2h, afterwards
Naturally cool to room temperature.The skin of Semen Maydis of carbonization is taken out, grind into powder in mortar, i.e. obtain pyrolyzed hard carbon product.
The above-mentioned pyrolyzed hard carbon material prepared is used for sodium-ion battery as the active substance of cell negative electrode material
Preparation, and carry out charge discharge test.Its preparation process and method of testing are with embodiment 2.The multiplying power tested is
0.1C, discharge cut-off voltage is 0.0V, and charge cutoff voltage is 2.0V.Result see table 1.
Embodiment 13
The preparation of pyrolyzed hard carbon material: skin of Semen Maydis wash clean, go the removal of impurity, after being cut into less than the fragment of 1cm*1cm, puts
Drying 26h it is placed in 80 DEG C of constant temperature ovens in beaker.It is placed on after drying in the porcelain boat of about 5cm*2cm*2cm, prepares for height
Temperature carbonization.
This product is placed in tube furnace with porcelain boat, under argon shield, with the ramp of 1 DEG C/min to 500
DEG C, argon flow amount is 25mL/min, preheats 2h, then the ramp to 1000 DEG C with 5 DEG C/min at 500 DEG C, is incubated 2h, afterwards
Naturally cool to room temperature.The skin of Semen Maydis of carbonization is taken out, grind into powder in mortar, i.e. obtain pyrolyzed hard carbon product.
The above-mentioned pyrolyzed hard carbon material prepared is used for sodium-ion battery as the active substance of cell negative electrode material
Preparation, and carry out charge discharge test.Its preparation process and method of testing are with embodiment 2.The multiplying power tested is
0.1C, discharge cut-off voltage is 0.0V, and charge cutoff voltage is 2.0V.Result see table 1.
Embodiment 14
The preparation of pyrolyzed hard carbon material: skin of Semen Maydis wash clean, go the removal of impurity, after being cut into less than the fragment of 1cm*1cm, puts
Drying 27h it is placed in 70 DEG C of constant temperature ovens in beaker.It is placed on after drying in the porcelain boat of about 5cm*2cm*2cm, prepares for height
Temperature carbonization.
This product is placed in tube furnace with porcelain boat, under argon shield, with the ramp of 1 DEG C/min to 500
DEG C, argon flow amount is 25mL/min, preheats 2h, then the ramp to 1600 DEG C with 5 DEG C/min at 500 DEG C, is incubated 2h, afterwards
Naturally cool to room temperature.The skin of Semen Maydis of carbonization is taken out, grind into powder in mortar, i.e. obtain pyrolyzed hard carbon product.
The above-mentioned pyrolyzed hard carbon material prepared is used for sodium-ion battery as the active substance of cell negative electrode material
Preparation, and carry out charge discharge test.Its preparation process and method of testing are with embodiment 2.The multiplying power tested is
0.1C, discharge cut-off voltage is 0.0V, and charge cutoff voltage is 2.0V.Result see table 1.
The dependency structure parameter of the material prepared in the different embodiment of table 1 and specific capacity
Comparative example
The preparation of hard carbon material: the Semen Maydis flesh removing niblet is cut into the segment of wide about 1cm, is placed in beaker, is placed in
24h is toasted in 80 DEG C of constant temperature ovens.It is placed on after drying in the porcelain boat of about 5cm*2cm*2cm, prepares for high temperature cabonization.
With porcelain boat, Semen Maydis flesh is placed on tube furnace, and (pipe range about 100cm, diameter 6cm, following example use identical
Tube furnace) in, under argon shield, with the ramp of 1 DEG C/min to 500 DEG C, argon flow amount is 25mL/min, at 500 DEG C
Pre-carbonization 2h, then the ramp to 800 DEG C with 5 DEG C/min, be incubated 2h, naturally cool to room temperature afterwards.Jade by carbonization
Rice section is taken out, and grind into powder in mortar i.e. obtains pyrolyzed hard carbon product.
The above-mentioned hard carbon material prepared is used for as the active substance of cell negative electrode material the system of sodium-ion battery
Standby, and carry out charge discharge test.Its preparation process and method of testing are with embodiment 2.The multiplying power tested is 0.1C, puts
Electricity blanking voltage is 0.0V, and charge cutoff voltage is 2.0V.Its charging and discharging curve is shown in Figure 19, first week discharge capacity about 280mAg/
G, first all coulombic efficiencies 70.7%, its reversible capacity is about 200mAh/g.Compared with embodiment 3-5, first all coulombs of this material
Efficiency is lower, and reversible capacity is the lowest.It is different from the cycle performance of other 1000 DEG C of high temperature above pyrolytic materials, following of this material
Ring curve does not show platform in the part of below 0.2V, but in ramped shaped, in reversible capacity, 0.2V holds with lower part
Amount ratio is 45.2%.Data above shows, being pyrolyzed its chemical property of material obtained under relatively low carburizing temperature cannot expire
The performance requirement of foot actual battery.
The hard carbon material preparation provided in the above embodiment of the present invention is simple, raw material resources is abundant, with low cost, is nothing
The green material polluted, can be applied in secondary cell as the negative active core-shell material of sodium ion secondary battery.By with right
Ratio compares, it can be seen that use pyrolyzed hard carbon material and the sodium ion secondary battery that obtains that the embodiment of the present invention provides,
There is higher running voltage and energy density, stable circulation, security performance good, hence it is evident that be pyrolyzed higher than under relatively low carburizing temperature
Its chemical property of the material obtained, can apply to solar electrical energy generation, wind-power electricity generation, intelligent grid peak regulation, distribution power station, after
Stand-by power source or the extensive energy storage device of communication base station.
Above-described detailed description of the invention, has been carried out the purpose of the present invention, technical scheme and beneficial effect further
Describe in detail, be it should be understood that the detailed description of the invention that the foregoing is only the present invention, be not intended to limit the present invention
Protection domain, all within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. done, all should comprise
Within protection scope of the present invention.
Claims (7)
1. a pyrolyzed hard carbon material, it is characterised in that prepare by the following method: by abandoned biomass dried；?
300 DEG C-600 DEG C it are warming up to, pre-carbonization 1-5h under inert atmosphere；It is warming up to 1000 DEG C-1600 DEG C under an inert atmosphere, carbonization,
Cracking 1-10h；Described pyrolytic carbon material is i.e. obtained after cooling；Wherein,
The described pyrolyzed hard carbon material obtained is irregular blocky-shaped particle, and particle size is 1-20 μm, and mean diameter is 5-10 μ
m；d002It is worth between 0.38-0.41nm, LcIt is worth between 1.3-1.5nm, LaValue is between 3.7-4.7nm.
Pyrolyzed hard carbon material the most according to claim 1, it is characterised in that described abandoned biomass includes Semen Maydis flesh, jade
One or more in rice residue, corn stalk and skin of Semen Maydis.
Pyrolyzed hard carbon material the most according to claim 1, it is characterised in that the phosphorus content of described pyrolyzed hard carbon material is the lowest
In 95%.
Pyrolyzed hard carbon material the most according to claim 1, it is characterised in that the surface of described material has soft carbon cladding
Layer.
5. the negative material of a sodium ion secondary battery, it is characterised in that described negative active core-shell material includes such as claim
Pyrolyzed hard carbon material described in any one of 1-4.
6. the cathode pole piece of a sodium ion secondary battery, it is characterised in that described cathode pole piece includes:
Collector, is coated on the binding agent on described collector and the sodium ion secondary battery as described in the claims 5
Negative material.
7. the secondary cell of the cathode pole piece included described in the claims 6.
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