CN106450230A - Lithium removal method by sulfur-doped modulation carbon materials on voltage platform - Google Patents
Lithium removal method by sulfur-doped modulation carbon materials on voltage platform Download PDFInfo
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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
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
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- 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 relates to a lithium removal method by sulfur-doped modulation carbon materials on a voltage platform. The method includes the steps: introducing sulfur elements into carbon-containing precursors in a sulfonated manner; carbonizing to prepare sulfur-doped carbon materials; controlling the atomic percentage of sulfur in the sulfur-doped carbon materials to be 0.5-2%; increasing specific capacity of carbon negative electrode materials of a lithium ion battery on a 1V lithium removal voltage platform. According to the lithium removal method, by the aid of low-cost raw materials, the carbon negative electrode materials of the lithium ion battery removed lithium on about 1V voltage platform are obtained and have the advantages of low voltage platform and high specific capacity.
Description
Technical field
The invention belongs to technical field of lithium ion battery negative, in particular relate to a kind of using mixing sulphur modulation material with carbon element
The method of de- lithium voltage platform.
Background technology
Material with carbon element is widely used as cell negative electrode material.For example, the petroleum coke that petrochemical industry obtains in producing can be used for adding
Work Delanium, and Delanium can be used as the carbon negative electrode material of lithium ion cell having good stability after modification.
Graphite material good conductivity, degree of crystallinity is higher, and has good layer structure, the embedded-deintercalation of suitable lithium, forms lithium-stone
Black intercalation compound, charge/discharge capacity is up to 300mAh.g-1More than, more than 90%, irreversible capacity is less than efficiency for charge-discharge
50mAh.g-1.Lithium deintercalation reaction in graphite, in 0～0.25V, has a good charge and discharge platform, can with lithium source is provided
Positive pole material of lithium cobalt acid, LiMn2O4, lithium nickelate etc. mate, and the battery average output voltage of composition is high, is current lithium ion battery
Apply most negative materials.But, the lithium ion memory capacity of graphite material is relatively low, and the carbon negative pole material obtaining high power capacity becomes
A focus for current research.In recent years, with material with carbon element research work deepen continuously it has been found that by graphite and
All kinds of material with carbon elements carry out surface modification and structural adjustment, or make graphite part disordering, or form nanometer in all kinds of material with carbon elements
The structure such as the hole of level, hole and passage, lithium embedded deintercalation wherein not only can stoichiometrically LiC6Carry out, but also
Non-stoichiometry can be had to embed-deintercalation, its specific capacity greatly increases, by LiC6Theoretical value 372mAh/g bring up to 700～
1000mAh/g, so that the specific capacity of lithium ion battery greatly increases.Yun et al. (Journal of Power
Sources2014；262(0):79-85) with Yan et al. (Chemical Communications 2012；48(86):10663-
10665) report all shows that the material with carbon element of sulfur doping has higher lithium ion memory capacity than unadulterated material with carbon element.But
It is that, along with the raising of capacity, the de- lithium voltage platform of the material with carbon element that adulterates often significantly raises, and this can lead to the output of battery
Voltage declines, thus reducing the energy density of battery, existing doping material with carbon element (such as ACS App.Mater.＆Interfaces
2014,6 (18), 15950-15958) generally take off lithium voltage wider distribution in the interval of 0～3V, the voltage not exhibiting 1V is put down
Platform, this is because sulfur content is too high and the distributing inhomogeneity of sulphur, has sulphur simple substance particle in charge and discharge process and separates out,
Thus show 2V about voltage platform, this is unfavorable for the raising of battery energy density.Therefore, how to put down in relatively low voltage
The specific capacity increase realizing material with carbon element on platform is very important.
Content of the invention
Present invention is primarily targeted at providing a kind of method mixing the de- lithium voltage platform of sulphur modulation material with carbon element, the method can
The specific capacity being significantly higher than graphite cathode material is obtained on about 1V voltage platform.
For reaching above-mentioned purpose, the present invention provides a kind of method using mixing the de- lithium voltage platform of sulphur modulation material with carbon element, wherein,
Element sulphur is introduced in containing carbon matrix precursor by sulfonation, is obtained after carbonization and mixes sulphur material with carbon element, described in control, mix sulphur in sulphur material with carbon element
Atom percentage content be 0.5～2%, thus 1V take off lithium voltage platform on increased carbon negative electrode material of lithium ion cell
Specific capacity.
The present invention, by carrying out sulfonation process to containing carbon matrix precursor, realizes being uniformly added into of element sulphur, obtains sulphur after carbonization
Element is finely dispersed to mix sulphur material with carbon element, controls the suitable concentration of element sulphur, thus realize obtaining on about 1V voltage platform showing
Write the specific capacity higher than graphite cathode material；Present invention preparation mixes that sulphur material with carbon element method running cost is low and process is simple, can
Realize industrialized production.
The present invention contains carbon matrix precursor using earlier sulfonation and then carbonization prepares and mixes sulphur material with carbon element.Sulfur-bearing in sulfonation process
Group with define stable combination containing carbon matrix precursor, during carbonization, element sulphur can equably be retained in material with carbon element, thus obtaining
Element sulphur is equally distributed mixes sulphur material with carbon element.Theoretical calculation shows：The structure that sulphur atom is combined with carbon hexatomic ring is in de- lithium
The Gibbs free producing is significantly smaller than the Gibbs free in de- lithium for the sulphur simple substance, because potential is existed with Gibbs free
Proportional relationship, this also implies that the de- lithium voltage of the carbon six-membered ring structure of sulfur doping will be less than the de- lithium voltage of sulphur simple substance
(～2V).Proposed by the present invention mix sulphur carbon materials preparation method for material, it is possible to achieve homogeneous point of low concentration in material with carbon element for the element sulphur
Cloth, thus be prevented effectively from the precipitation of sulphur simple substance；In actual measurement, present invention discover that controlling this of the suitable concentration of element sulphur
The mixing sulphur material with carbon element and can show on the voltage platform of about 1V and be significantly higher than the lithium ion storage of graphite and hold of bright method preparation
Amount.Therefore, the invention provides a kind of method that material with carbon element specific capacity can be significantly improved on about 1V voltage platform.
The conventional persursor material that material with carbon element can be prepared containing carbon matrix precursor for this area of the present invention, the present invention is preferred
It is higher than one of slurry oil, pitch and decompression residuum of 500 DEG C of cuts or many in cellulose, starch, catalytic cracking product
The mixing planted.
According to method of the present invention, the wherein said preparation mixing sulphur material with carbon element comprises the steps：
(1) carry out sulfonation process to containing carbon matrix precursor first, the concentrated sulfuric acid is mixed with containing carbon matrix precursor, be uniformly mixing to obtain
Suspension, suction filtration, dry；
(2) the product calcination process obtaining step (1), after being cooled to room temperature, product is washed to after neutrality and dries
Dry obtain described mixing sulphur material with carbon element.
According to preparation method of the present invention, wherein the present invention further preferably described containing carbon matrix precursor and the concentrated sulfuric acid
Mass ratio is 2:1～1:56.
The concentrated sulfuric acid of the present invention is the conventional commercial concentrated sulfuric acid, and it is more than or equal to 70% H for mass fraction2SO4Water-soluble
Liquid.
Decompression residuum of the present invention is known in the art, the residue oil that such as Vacuum Tower In Refinery bottom is extracted out.
According to method of the present invention, the wherein described drying of step (1) can be the conventional drying operation of prior art,
Such as dry 2～24h at 100 DEG C.
According to method of the present invention, the described calcination process of preferred steps (2) of the present invention is roasting at 300～900 DEG C
Burning is processed；Calcination process further preferably at 550～850 DEG C.
According to preparation method of the present invention, the described calcination process of preferred steps (2) of the present invention is that exist in shielding gas
Under carry out calcination process；Wherein said shielding gas can be further preferably described for the conventional inert gas in this area, the present invention
Shielding gas is selected from the combination of one or more of nitrogen, argon gas and helium.
According to method of the present invention, the described calcination process of preferred steps (2) of the present invention is roasting in the presence of shielding gas
Burn 0.5～10h；More preferably 1～3h.
According to method of the present invention, the described calcination process of preferred steps (2) of the present invention is with the speed of 15 DEG C/min
Heated up, then carried out calcination process.
Calcination process of the present invention can adopt prior art conventional equipment, and currently preferred is in horizontal tube
Carry out calcination process in stove.
According to method of the present invention, the present invention is further preferably in the preparation process mix sulphur material with carbon element, in step (1)
Drying terminate after, the product after also including drying adds template, grinds, the step mixing, then will mix
The product calcination process obtaining afterwards.
According to method of the present invention, template of the present invention is selected from magnesia, MgAlO lamellar compound, oxygen
Change the mixing of one or more of calcium, cupric oxide, manganese oxide and zinc oxide.
Preferably, described magnesia be divided into non-calcination processing and calcination processing, calcination process be at 550 DEG C insulation
1h.
It is further preferred that described template and the described mass ratio containing carbon matrix precursor are 2:1～15:1.
The method that sulphur material with carbon element is mixed in the preparation that the present invention provides has that running cost is low and process is simple, is capable of industry
The advantage that metaplasia is produced, the method is using being higher than the slurry oil of 500 DEG C of cuts, pitch in cellulose, starch, catalytic cracking product, subtract
Pressure residual oil one of or mixture be presoma, using magnesia, aluminum oxide, MgAlO lamellar compound, calcium oxide,
Cupric oxide, manganese oxide and zinc oxide one or more of as template, first carry out sulfonation process, the excessive concentrated sulfuric acid adds
Enter to a certain amount of containing in carbon matrix precursor so as to abundant sulfonation；Product after sulfonation is fully mixed with template according to a certain percentage
Close, be subsequently placed in horizontal pipe furnace, the mixture of the one or more than one among nitrogen, argon gas, helium is as guarantor
It is warmed up to 300 DEG C～900 DEG C under the atmosphere of shield gas and carry out carbonisation；Question response device naturally cools to room temperature, takes out carbon respectively
Product after change, through washing, is dried, obtains the material with carbon element mixing sulphur.
According to the method for the invention, wherein, described sulphur material with carbon element of mixing shows higher than graphite in 0～2V discharge and recharge interval
The lithium ion memory capacity of negative material theoretical capacity (372mAh/g).
In the present invention mix sulphur material with carbon element refer in the skeleton structure of C atomic building in material with carbon element by C atom replace or
The additional other elements of person, such as mix S element.
In sum, the invention provides a kind of using mix sulphur modulation material with carbon element take off lithium voltage platform method.The present invention
Method have the advantage that：Using cheap raw material, permissible using preparing sulfur-bearing material with carbon element containing carbon matrix precursor after sulfonation
Ensure being uniformly distributed of element sulphur；As lithium ion battery negative material, control the inventive method of the suitable concentration of element sulphur
The S material with carbon element of mixing of preparation shows higher reversible capacity, excellent high rate performance, particularly has on about 1V voltage platform
It is significantly higher than the specific capacity of graphite cathode material, this does not have on sulphur material with carbon element in conventional mixing, and is expected to as high-performance lithium
Ion battery cathode material substitutes existing commercialization graphite cathode material.
Brief description
Fig. 1 is respectively low power, high power transmission electron microscope (TEM) picture of mixing sulphur material with carbon element of preparation in embodiment 1.
Fig. 2 is the X-ray photoelectron spectroscopic analysis mixing sulphur material with carbon element of preparation in embodiment 1.
Fig. 3 is respectively charging and discharging curve and the high rate performance curve of mixing sulphur material with carbon element of preparation in embodiment 1.
Fig. 4 is the transmission electron microscope photo mixing sulphur material with carbon element of preparation in embodiment 2.
Fig. 5 is the X-ray photoelectron spectroscopic analysis mixing sulphur material with carbon element of preparation in embodiment 2.
Fig. 6 is specific surface area and the pore size distribution test result of mixing sulphur material with carbon element of preparation in embodiment 2.
Fig. 7 is the charging and discharging curve comparison diagram (0～2V area mixing sulphur material with carbon element of preparation in embodiment 1,2,3 and comparative example 1
Interior discharge and recharge).
Fig. 8 is transmission electron microscope (TEM) picture mixing sulphur porous charcoal of preparation in comparative example 1.
Fig. 9 is specific surface area and the pore size distribution test result of mixing sulphur porous charcoal of preparation in comparative example 1.
Figure 10 is the sulphur porous charcoal of mixing of preparation in comparative example 1 is 50mA g in current density-1When front discharge and recharge twice bent
Line (discharge and recharge in 0～3V interval).
Specific embodiment
Describe the implementation process of the present invention and the beneficial effect of generation below by way of specific embodiment in detail it is intended to help read
Reader more fully understands essence and the feature of the present invention, not as to this case can practical range restriction.
Embodiment 1
This gives a kind of have the method for high specific capacity on 1V voltage platform using mixing sulphur material with carbon element and obtain, bag
The preparation process mixing sulphur carbon material negative pole and electrochemical property test result are included.
Weigh 4g slurry oil, be heated to liquid (60～90 degree), add the 2ml concentrated sulfuric acid (mass fraction is 98%), stirring
60min, suction filtration, drying, grinding, the material of powdered form is placed in porcelain boat, is passed through Ar, simultaneously after putting into horizontal pipe furnace in stove
Horizontal stove rises to 700 DEG C with 15 DEG C/min heating rate, and keeps 60min, naturally cools to taking-up product after room temperature after furnace temperature,
Obtain mixing sulphur material with carbon element.
In Fig. 1, (a), (b) are respectively low power, the high power TEM figure of mixing sulphur material with carbon element being obtained.As seen from the figure when being not added with
Obtain when template is block material with carbon element.According to X-ray photoelectron spectroscopic analysis (XPS is shown in Fig. 2), this kind of technique bar
What part was obtained mixes sulfur-bearing 0.9% (atomic percent) in sulphur material with carbon element.
Sulphur material with carbon element is mixed as negative pole using prepared above, using lithium piece as to electrode, glove box assembles button
Formula half-cell, carries out negative pole performance test, and charging/discharging voltage is interval to be 0.01～2V.As shown in (a) in Fig. 3, this negative material
Have near 1V and significantly take off lithium voltage platform, in the test interval of 0～2V, de- lithium process is (close in the electric current of 50mA/g
Under degree) specific capacity reach～600mAh/g, be significantly higher than the theoretical capacity of graphite.In Fig. 3 (b) give mix sulphur material with carbon element bear
Pole is contrasted it can be seen that under different current densities, mixing the specific volume of sulphur material with carbon element from the high rate performance of commercial graphite cathode material
Amount is all remarkably higher than commercial graphite, and in (a) in Fig. 3, (b), SC represents that the present embodiment gained mixes sulphur material with carbon element.
Embodiment 2
This gives a kind of by mixing the method that sulphur modulation material with carbon element takes off lithium voltage platform, including mixing sulphur porous charcoal
Preparation process and electrochemical property test result, with embodiment 1 preparation mix sulphur material with carbon element compared with, this mix sulphur porous charcoal
Higher specific capacity is shown in the voltage range of 1～2V.
Weigh 4g slurry oil, be heated to liquid (60～90 degree), add the 8ml concentrated sulfuric acid (mass fraction is 98%), stirring
60min, rinses post-drying, grinding with water, adds the MgO after 8g calcining, is ground, the material of powdered form is placed in porcelain boat,
Put in horizontal pipe furnace, be passed through Ar in stove, horizontal stove rises to 700 DEG C with 15 DEG C/min heating rate, and keeps simultaneously
60min, naturally cools to taking-up product after room temperature after furnace temperature, obtains mixing sulphur material with carbon element.
In Fig. 4, (a), (b) are respectively low power, the high power TEM figure of mixing sulphur material with carbon element being obtained.Work as addition as seen from the figure
Obtain when template is the porous carbon materials of sheet.According to X-ray photoelectron spectroscopic analysis (XPS, Fig. 5), this kind of technique
Sulfur-bearing 1.08% (atomic percent) in the material with carbon element that condition is obtained.According to specific surface and pore analysis (A and B in Fig. 6), should
Planting the prepared sulfur-bearing material with carbon element specific surface of process conditions is 266.3m2/ g, aperture is 4-6nm.
The typical charging and discharging curve that this mixes sulphur porous charcoal is as shown in Figure 7.Compared with the sample in embodiment 1, the present embodiment
Preparation mix sulphur porous charcoal have similar in～1V about voltage platform, and the specific capacity in the range of 1～2V also has
Increase further, the specific capacity increase near 1.5V is attributable to storage in nano pore structure for the lithium ion.
Embodiment 3
Using with implement 2 identical operating procedures, simply in sulfonation process increase sulfuric acid usage amount be 20mL.XPS
Test shows that the prepared sulfur content mixing sulphur porous charcoal is 1.8%, than the sulfur content mixing sulphur material with carbon element in embodiment 1 and 2
Higher.As shown in fig. 7, after sulfur content improves further, the specific capacity near 1V does not increase, but 1.5～2V's
The increase of specific capacity is occurred in that, the increase of the lithium memory capacity of this part is attributable to be formed in charge and discharge process in voltage range
Sulphur simple substance nano particle lithium storage.The present embodiment realizes having the scheme of de- lithium capacity on about 1V voltage platform, its
De- lithium capacity is had on 1V and 1.5～2V voltage platform.
As can be seen here, the method by being given in embodiment 1～3, it is possible to achieve the tune of the de- lithium voltage platform of material with carbon element
Control.
Comparative example 1
Weigh pitch 1g with beaker, pour the dissolving of 10ml toluene into, small beaker is positioned over ultrasonic vibration in ultrasonic cleaning machine
30min.Add the 20ml concentrated sulfuric acid to the toluene solution of pitch, stir 60min, abundant sulfonation, dry, be subsequently adding 5g alkali formula sulphur
Sour magnesium (being crossed with calcination processing), then add 10ml toluene, ultrasonic vibration 60min in beaker, dry, standby.By powdered form
Material be placed in porcelain boat, be passed through Ar after putting into horizontal pipe furnace in stove, horizontal stove is with 15 DEG C/min heating rate liter simultaneously
To 750 DEG C, and keep 60min, naturally cool to taking-up gray product after room temperature after furnace temperature.This product is placed in excessive watery hydrochloric acid
In, water boils backflow pickling 1h, and last deionized water is washed till under the conditions of neutrality is placed in 80 DEG C and is dried to obtain sheet material with carbon element.
Fig. 8 is that the TEM of the material with carbon element being obtained through sulfonation carbonisation schemes it can be seen that this material has loose structure,
Specific surface area and pore size distribution test result (Fig. 9) also show this point.According to X-ray photoelectron spectroscopic analysis, this kind of technique
Sulfur-bearing 13.16% (atomic percent) in the material with carbon element that condition is obtained.
In electro-chemical test, the present invention has carried out prelithiation to mixing sulphur porous carbon electrode, that is, will be many containing mixing sulphur
The pole piece of hole carbon coating and lithium piece directly contact (operating in the glove box full of argon gas), and impregnate 30 points in the electrolytic solution
Clock.What Figure 10 gave prelithiation mixes sulphur porous charcoal in 50mA g-1When front charging and discharging curve twice it can be seen that 2～
There is the platform that significant specific capacity increases, this is that typical sulphur simple substance reacts, with lithium, the specific volume being formed in the voltage range of 2.5V
Amount platform.During due to using as negative material, the voltage platform of material with carbon element is lower, is more conducive to carrying of battery energy density
Height, therefore compared with Example 1, the de- lithium voltage platform of the material of this comparative example is too high, is not suitable for making as negative material
With.Fig. 7 give the discharge and recharge in 0～2V voltage range of this different materials comparison diagram it can be seen that 0～2V interval in,
The de- lithium capacity of comparative example 1 is minimum.The present invention has carried out transmission electron microscope observation to the material after discharge and recharge, sends out
Sulphur porous charcoal surface after discharge and recharge of mixing of existing comparative example 1 can be observed obvious sulphur simple substance nano particle, and in embodiment 1
Material do not find there is sulphur simple substance particle after charge and discharge cycles.Here it is the two chemical property occur significance difference away from former
Cause.
Comparative example 2
Using sulfur oil slurry as carbon source, directly it is heated to 700 DEG C of carbonizations in a nitrogen atmosphere, prepares and mix sulphur carbon materials
Material.Sulphur material with carbon element is mixed to this and carries out XPS analysis, find that in this material, content is 0.37% (atomic percent).Further, to this
The negative pole performance mixing sulphur material with carbon element is investigated, and assembles half-cell using method in the same manner as in Example 1 and carries out discharge and recharge
Test.Test result shows：This material in 1V about do not exist significantly take off lithium voltage platform, entirely take off lithium during, electricity
Pressure scope wider distribution.This explanation, although the material with carbon element that this comparative example obtains contains a small amount of S element, S constituent content is slightly
Chemical property that is low, can not promoting material with carbon element occurs effectively to change, not it is observed that significantly therefore in charge and discharge process
About 1V voltage platform；The sulfonation of this explanation exactly this case appropriateness ensure that extensive, homogeneous, the appropriate distribution of S element.
Finally illustrate is：Above example is merely to illustrate implementation process and the feature of the present invention, and unrestricted is sent out
Bright technical scheme, although being described in detail to the present invention with reference to above-described embodiment, those of ordinary skill in the art should
Work as understanding：Still the present invention can be modified or equivalent, without departing from the spirit and scope of the present invention any
Modification or local are replaced, and all should cover in the middle of protection scope of the present invention.
Claims (10)
1. a kind of using mix sulphur modulation material with carbon element take off lithium voltage platform method it is characterised in that by sulfonation containing carbon matrix precursor
Middle introducing element sulphur, is obtained after carbonization and mixes sulphur material with carbon element, and the atom percentage content mixing sulphur in sulphur material with carbon element described in control is 0.5
～2%, thus take off the specific capacity that carbon negative electrode material of lithium ion cell be increased on lithium voltage platform in 1V.
2. method according to claim 1 is it is characterised in that the described preparation mixing sulphur material with carbon element comprises the steps：
(1) carry out sulfonation process to containing carbon matrix precursor first, the concentrated sulfuric acid is mixed with containing carbon matrix precursor, be uniformly mixing to obtain suspended
Liquid, suction filtration, dry；Preferably, the described mass ratio containing carbon matrix precursor and the concentrated sulfuric acid is 2:1～1:56；
(2) the product calcination process obtaining step (1), after being cooled to room temperature, product is washed to neutral post-drying and obtains
Mix sulphur material with carbon element to described.
3. method according to claim 2 is it is characterised in that described split selected from cellulose, starch, catalysis containing carbon matrix precursor
It is higher than the mixing of one or more of slurry oil, pitch and the decompression residuum of 500 DEG C of cuts in change product.
4. method according to claim 2 is it is characterised in that the described calcination process of step (2) is roasting at 300～900 DEG C
Burning is processed；Calcination process preferably at 550～850 DEG C.
5. method according to claim 2 is it is characterised in that the described calcination process of step (2) is roasting in the presence of shielding gas
Burn 0.5～10h；It is preferably 1～3h.
6. method according to claim 5 is it is characterised in that described shielding gas is selected from one of nitrogen, argon gas and helium
Or multiple combinations.
7. method according to claim 4 is it is characterised in that the described calcination process of step (2) is with the speed of 15 DEG C/min
Heated up, then carried out calcination process.
8. during the method according to any one of claim 2～7 is it is characterised in that mix the preparation process of sulphur material with carbon element, in step
Suddenly, after the drying of (1) terminates, also include for the product after drying adding template, grind, the step mixing, then will mix
The product calcination process obtaining after uniformly.
9. method according to claim 8 it is characterised in that described template be magnesia, MgAlO lamellar compound,
The mixing of one or more of calcium oxide, cupric oxide, manganese oxide and zinc oxide；Wherein preferably described template and described carbon containing
The mass ratio of presoma is 2:1～15:1.
10. method according to claim 1 is it is characterised in that described sulphur material with carbon element of mixing is in the interval performance of 0～2V discharge and recharge
Go out the lithium ion memory capacity higher than graphite cathode material theoretical capacity.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108502869A (en) * | 2018-04-19 | 2018-09-07 | 中国石油大学(北京) | A kind of preparation method for mixing sulphur carbon material |
| CN108539137A (en) * | 2017-03-03 | 2018-09-14 | Tdk株式会社 | Negative electrode active material, cathode and lithium rechargeable battery |
| CN110723735A (en) * | 2018-07-16 | 2020-01-24 | 深圳市环球绿地新材料有限公司 | Spherical super-capacity carbon, preparation method and application thereof |
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| CN103213968A (en) * | 2013-04-22 | 2013-07-24 | 北京化工大学 | Heteroatom doped carbon material, and preparation method and application thereof |
| CN103395767A (en) * | 2013-07-25 | 2013-11-20 | 中国石油大学(北京) | Preparation method of sulfur-containing carbon material as well as sulfur-containing carbon material prepared by using same |
| CN104528685A (en) * | 2014-12-24 | 2015-04-22 | 中国石油大学(北京) | Sulfur-carbon-doped material and preparation method thereof |
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| CN103213968A (en) * | 2013-04-22 | 2013-07-24 | 北京化工大学 | Heteroatom doped carbon material, and preparation method and application thereof |
| CN103395767A (en) * | 2013-07-25 | 2013-11-20 | 中国石油大学(北京) | Preparation method of sulfur-containing carbon material as well as sulfur-containing carbon material prepared by using same |
| CN104528685A (en) * | 2014-12-24 | 2015-04-22 | 中国石油大学(北京) | Sulfur-carbon-doped material and preparation method thereof |
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| CN108539137A (en) * | 2017-03-03 | 2018-09-14 | Tdk株式会社 | Negative electrode active material, cathode and lithium rechargeable battery |
| CN108502869A (en) * | 2018-04-19 | 2018-09-07 | 中国石油大学(北京) | A kind of preparation method for mixing sulphur carbon material |
| CN110723735A (en) * | 2018-07-16 | 2020-01-24 | 深圳市环球绿地新材料有限公司 | Spherical super-capacity carbon, preparation method and application thereof |
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