CN108539154A - A kind of porous carbon, carbon-selenium composite material and the method for preparing anode with carbon-selenium composite material - Google Patents
A kind of porous carbon, carbon-selenium composite material and the method for preparing anode with carbon-selenium composite material Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a kind of preparation method of porous carbon, steps (1)：Discarded paper products are added to and fill H2SO4In the reactor of solution, reactor is put into autoclave, at 200 220 DEG C, after reacting 11 14h, generates material A；Step (2)：The material A filtering that will be generated in step (1), washs, dries, and grinding is spare；Step (3)：Material A after grinding in step (2) is mixed with KOH, mixture is put into crucible and is heat-treated, pH value is adjusted to 7 by obtained powder material grinding, washing, and drying obtains porous carbon.Carbon selenium composite material is prepared by using the porous carbon of preparation, and positive electrode is prepared using carbon selenium composite material；The electric conductivity of anode can be improved using porous carbon, and can also inhibit the dissolving of selenides.
Description
Technical field
The present invention relates to a kind of battery technology field, more particularly to a kind of porous carbon, carbon-selenium composite material and
The method for preparing anode with carbon-selenium composite material.
Background technology
Demand growing to energy storage device at present has promoted going deep into for high-performance secondary rechargeable battery and associated materials
Research and development.In all candidate lithium batteries, lithium-sulfur cell is big, at low cost due to its discharge capacity, it is considered to be most has
One of lithium ion battery of future.However, sulphur anode is also encountered in cyclic process in low conductivity, especially polysulfide
The high-dissolvability of mesosome causes utilization efficiency low, and cyclical stability is poor.A kind of same major element of the selenium as sulphur, also can be used as
The positive electrode of rechargeable lithium battery.Importantly, compared with S, Se can provide better electrochemical transduction rate, and intermediate more
The solubility of lithium selenide can be effectively suppressed, especially in the electrolyte based on carbonate.
However, since to be diffused in Li-Se system medium velocities not fast enough for conductivity or lithium ion, and its discharge capacity is low and follows
Ring stability is poor, prevents elemental selenium from the positive electrode directly as battery.It is the most useful in order to improve the chemical property of selenium
One of strategy is in the porous carbon for load selenium high conductivity.Therefore it provides a kind of porous carbon is preparing lithium selenium cell just with selenium
The problem of method of pole is those skilled in the art's urgent need to resolve.
Invention content
In view of this, porous carbon is prepared using discarded paper products the present invention provides a kind of, by porous carbon and the compound system of selenium
The method of standby working electrode.
To achieve the goals above, the present invention adopts the following technical scheme that：A kind of preparation method of porous carbon, feature exist
In including the following steps：
Step (1)：Discarded paper products are added to and fill H2SO4In the reactor of solution, it is anti-that reactor is put into high pressure
It answers in kettle, at 200-220 DEG C, after reacting 11-14h, generates material A；
Step (2)：The material A filtering that will be generated in step (1), washs, dries, and grinding is spare；
Step (3)：Material A after grinding in step (2) is mixed with KOH, mixture is put into crucible and is heat-treated, is obtained
PH value is adjusted to 7, dry, acquisition porous carbon by the powder material grinding arrived, washing.
The utilization rate of defective work is improved in the present invention using discarded paper products, and using the porous of above method preparation
Carbon pores diameter rationally, large specific surface area, utilization rate higher.
Preferably, in step (1) reactor by with autoclave is mating is made of material with PPL (polyparaphenylene phenol)
Hydro-thermal liner.
Preferably, H in step (1)2SO4A concentration of 0.2-4mol/L of solution, be more preferably 2mol/L discard it is made of paper
The quality and H of product2SO4The proportionate relationship of the volume of solution is (0.5-4) g：75mL is more preferably 2g：75mL.
Preferably, drying temperature is 75-85 DEG C in step (2), drying time 11-13h.It is further preferred that drying temperature
Degree is 80 DEG C, drying time 12h.
Preferably, washing process is in step (2)：First distilled water water is used to clean three times, then is cleaned to filter using ethyl alcohol
Liquid is colourless.
Preferably, the condition being heat-treated described in step (3) is in a nitrogen environment, with the heating speed of 2-10 DEG C/min
Temperature is risen to 700 DEG C by rate, and constant temperature 2-10h is heat-treated at 700 DEG C.
Preferably, the mass ratio of material B and KOH is (1:1)-(1：3).It is more preferably 1:1、1:2、1:3.
The present invention also provides a kind of preparation methods of carbon-selenium composite material, include the following steps：
Step (1)：Porous carbon is weighed, it is spare；It is spare to weigh selenium powder；
Step (2)：By porous carbon and selenium powder ground and mixed, ethyl alcohol is added and obtains mixture A, mixture A is added to water
It is heated in flat tube furnace, obtains carbon-selenium compound.
Preferably, in step (1), the grain size of selenium powder is 150-300 mesh, and the grain size of porous carbon is 150-300 mesh, porous carbon
Mass ratio with selenium powder is (1-2):(2-3).The grain size that can also be selenium powder is 200 mesh, and the grain size of porous carbon is 200 mesh, more
The mass ratio of hole carbon and selenium powder is 2:3.
Preferably, in step (2), heating temperature is 280-320 DEG C, heating time 5-7h.
Preferably, in step (2), the additive amount of ethyl alcohol is 2-6mL.
The present invention also provides the methods that a kind of carbon-selenium composite material prepares anode, include the following steps：
Step (1)：Weigh carbon-selenium compound, acetylene carbon and sodium alginate mixing；Carbon-selenium compound, acetylene carbon and seaweed
The mass ratio of sour sodium is (5-9):(0.5-2):(0.5-1)；
Step (2)：Water stirring is added in mixture in step (1), it is dry, it is cut into disk and obtains anode, the step
The dry time can be 4-6h in rapid, and drying temperature can be 60-90 DEG C.
Preferably, the mass ratio of carbon-selenium compound, acetylene carbon and sodium alginate is 7 in step (1):2:1.
It can be seen via above technical scheme that compared with prior art, discarded paper is utilized the present disclosure provides a kind of
Product prepares porous carbon, is prepared into carbon-selenium composite material using porous carbon and selenium, and prepare using carbon-selenium composite material
At the anode of lithium selenium cell, the electric conductivity of anode can be improved using porous carbon, and can also inhibit the dissolving of more selenides.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 attached drawings are X-ray diffraction (XRD) figure of porous carbon in the present invention；
Fig. 2 a, scanning electron microscope (SEM) figure that 2b, 2c, 2d, 2e, 2f attached drawing are porous carbon in the present invention；
Fig. 3 a, 3b attached drawings are the N in the present invention for porous carbon2Absorption-desorption isotherm plots figure；
Fig. 4 a, 4b attached drawings are the N in the present invention for carbon-selenium composite material2Absorption-desorption isotherm plots figure；
Fig. 5 a attached drawings are the battery charging and discharging performance chart of carbon-selenium composite material in the present invention；
Fig. 5 b attached drawings are the cycle performance of battery curve graph of carbon-selenium composite material in the present invention；
Fig. 5 c attached drawings are the battery charging and discharging performance chart of PCc-2/Se composite materials in the present invention；
Fig. 5 d attached drawings are the cyclic voltammetry curve figure of PCc-2/Se composite materials in the present invention；
Fig. 6 attached drawings are the curve graph of the high rate performance of carbon-selenium composite material in the present invention.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Such as Fig. 1, the XRD spectra that a, b, c indicate porous carbon in embodiment 1-3 respectively is sequentially consisted of；
The embodiment of the invention discloses a kind of preparation methods of porous carbon.
Embodiment 1
The preparation method of porous carbon, includes the following steps：
Step (1)：Discarded paper products are cut into pieces, takes 2g fragments to be added to and fills 75mL 2mol/L H2SO4Solution
Be liner to be put into autoclave, at 210 DEG C, instead made of material in hydro-thermal liner with PPL (polyparaphenylene phenol)
After answering 12h, generation brown ceramic powder is material A；
Step (2)：The material A filtering that will be generated in step (1), is first adopted three times wash with distilled water, then clear using ethyl alcohol
It is colourless to be washed till filtrate, 12h is dried at 80 DEG C, the material A after drying is poured into agate mortar and is pulverized, it is spare；
Step (3)：2g material As after grinding in step (2) are mixed with 2gKOH, mixture are put into crucible, in nitrogen
Under compression ring border, with the heating rate of 5 DEG C/min, temperature is risen to 700 DEG C, is heat-treated at 700 DEG C, obtained powder object
Material, powder material is poured into agate mortar and is ground, with diluted salt acid elution, is then washed with distilled water and is adjusted to pH value
7, the material that pH value is 7 is put into drying box the drying at 80 DEG C, porous carbon is obtained and is denoted as PCc-1.
Attached drawing 2a, 2b are the SEM image of porous carbon, and as can be seen from the figure Fig. 2 a are the smooth sphere in surface, and Fig. 2 b are
The smooth tablet in surface.
Embodiment 2
The preparation method of porous carbon, includes the following steps：
Step (1)：Discarded paper products are cut into pieces, takes 2g fragments to be added to and fills 75mL 2mol/L H2SO4Solution
Be liner to be put into autoclave, at 210 DEG C, instead made of material in hydro-thermal liner with PPL (polyparaphenylene phenol)
After answering 12h, generation brown ceramic powder is material A；
Step (2)：The material A filtering that will be generated in step (1), first uses distilled water water to clean three times, then use ethyl alcohol
Cleaning is colourless to filtrate, dries 12h at 80 DEG C, the material A after drying is poured into agate mortar and is pulverized, spare；
Step (3)：2g material As after grinding in step (2) are mixed with 4gKOH, mixture are put into crucible, in nitrogen
Under compression ring border, with the heating rate of 5 DEG C/min, temperature is risen to 700 DEG C, is heat-treated at 700 DEG C, obtained powder object
Material, powder material is poured into agate mortar and is ground, with diluted salt acid elution, is then washed with distilled water and is adjusted to pH value
7, the material that pH value is 7 is put into drying box the drying at 80 DEG C, porous carbon is obtained, is denoted as PCc-2.
Attached drawing 2c, 2d are the SEM image of porous carbon, as seen from the figure some macroporous structures, can promote the selenium of melting
Into in porous carbon.
Embodiment 3
The preparation method of porous carbon, includes the following steps：
Step (1)：Discarded paper products are cut into pieces, takes 2g fragments to be added to and fills 75mL 2mol/L H2SO4Solution
Be liner to be put into autoclave, at 210 DEG C, instead made of material in hydro-thermal liner with PPL (polyparaphenylene phenol)
After answering 12h, generation brown ceramic powder is material A；
Step (2)：The material A filtering that will be generated in step (1), first uses distilled water water to clean three times, then use ethyl alcohol
Cleaning is colourless to filtrate, dries 12h at 80 DEG C, the material A after drying is poured into agate mortar and is pulverized, spare；
Step (3)：2g material As after grinding in step (2) are mixed with 6g KOH, mixture is put into crucible,
Under nitrogen environment, with the heating rate of 5 DEG C/min, temperature is risen to 700 DEG C, is heat-treated at 700 DEG C, obtained powder
Powder material is poured into agate mortar and is ground by material, with diluted salt acid elution, is then washed with distilled water and is adjusted pH value
To 7, the material that pH value is 7 is put into drying box the drying at 80 DEG C, porous carbon is obtained, is denoted as PCc-3.
Attached drawing 2e, 2f, are the SEM image of porous carbon, and the porous carbon with graded porous structure can be that the selenium of melting carries
For diffusion admittance.
For embodiment 1-3, shown in attached drawing 1, each XRD lines disclose a wide diffraction maximum and are spreading out in figure
Firing angle is 24 ° or so, this is the amorphous feature because of porous carbon, also can in a weak diffraction maximum of the angle of diffraction on 44 °
It is detected, shows that carbon has seldom ordered structure.
Shown in 3a, 3b in attached drawing, specific surface area and porous knot have been calculated from nitrogen adsorption-desorption isotherm
Structure；As shown in Figure 3a, each thermoisopleth can reach higher adsorbance at low pressures, this is because nitrogen is in micropore and small
Mesoporous in occupy, illustrate porous carbon mainly in the form of micropore and small mesoporous exist.In addition, each thermoisopleth can
To find typical H1 adsorption hysteresises ring, this shows that there is also larger holes in this carbon.The hysteresis circle face of special PCc-1
Product is more than other two samples.Calculate PCc-1, PCc-2 or PCc-3 particular surface product be respectively 981.6,941.1,
790.6m2/ g, the results showed that with the increase of KOH amounts, BET specific surface area reduces.
Fig. 3 b are shown in porous distribution, it can be found that the distribution of pores of these materials be located at micro- area (<2nm) and small meso-
pore(2-8mm).In amplification factor (0-50nm), PCc-1 has larger aperture and middle boring ratio, this and the lag in Fig. 3 a
Anchor ring product is consistent.Corresponding with this to be, when volume is respectively 0.633,0.3372cm to the micropore of PCc-13/ g is less than PCc-2
(0.798,0.3890cm3/g).Due to, with the porous carbon of large surface area, high pore volume and by micropore (<It is 2nm) and small
Mesoporous (2-5nm) composition hole, be the ideal carrier material of Li-Se anodes.Therefore, with the useless of different aperture distribution
Key effect can be played in terms of the formation of carbon/selenium composite material and its chemical property by abandoning porous carbon derived from paper products.
Embodiment 4
The preparation method of carbon-selenium composite material, includes the following steps：
Step (1)：The porous carbon 0.4g obtained in embodiment 1 is weighed, it is spare；The selenium powder for weighing 200 mesh of 0.3g is spare；
Step (2)：By porous carbon and selenium powder ground and mixed, ethyl alcohol is added and obtains mixture A, mixture A is added to water
It is heated 6 hours at 300 DEG C in flat tube furnace, obtains carbon-selenium compound, be denoted as PCc-1/Se.
Embodiment 5
The preparation method of carbon-selenium composite material, includes the following steps：
Step (1)：The porous carbon 0.5g obtained in embodiment 2 is weighed, it is spare；The selenium powder for weighing 200 mesh of 0.3g is spare；
Step (2)：By porous carbon and selenium powder ground and mixed, ethyl alcohol is added and obtains mixture A, mixture A is added to water
It is heated 6 hours at 300 DEG C in flat tube furnace, obtains carbon-selenium compound, be denoted as PCc-2/Se.
Embodiment 6
The preparation method of carbon-selenium composite material, includes the following steps：
Step (1)：The porous carbon 0.6g obtained in embodiment 3 is weighed, it is spare；The selenium powder for weighing 200 mesh of 0.3g is spare；
Step (2)：By porous carbon and selenium powder ground and mixed, ethyl alcohol is added and obtains mixture A, mixture A is added to water
It is heated 6 hours at 300 DEG C in flat tube furnace, obtains carbon-selenium compound, be denoted as PCc-3/Se.
For embodiment 4-6, shown in attached drawing 4a, 4b, the carbon-adsorbance of selenium composite material at low pressures is relatively low,
Illustrate that the micropore of porous carbon disappears, be occupying due to amorphous selenium, for the carbon in embodiment 4-6-selenium composite material, absorption-
Hysteresis loop still has, especially PCc-1/Se, works as P/P0Value when being more than 0.8, adsorbance sharply increases, and shows composite material
Remain the middle macroscopic voids of part；And by attached drawing and calculate the BET of the composite material in embodiment 4-6 be respectively 29.9,
5.9、20.1m2/ g, the BET of composite material are less than the BET of porous carbon, illustrate that porous carbon and selenium material have good compound effect
Fruit.
Following table 1 be carbon, the specific surface area of carbon-selenium composite material, porous structure and selenium loading density.
Table 1
It can be preferably compound with the porous carbon that is prepared in the present invention by the way that selenium can be apparent from table 1.
Embodiment 7
The method that carbon-selenium composite material prepares anode, includes the following steps：
Step (1)：It is mixed to weigh carbon-selenium compound 0.7g, acetylene carbon 0.2g and the sodium alginate 0.1g prepared in embodiment 4
It closes；
Step (2)：Water is added in mixture in step (1) to stir evenly and to starchiness, be coated on aluminium foil, in sky
Dry 5h in gas, is cut into disk and obtains anode.
Embodiment 8
The method that carbon-selenium composite material prepares anode, includes the following steps：
Step (1)：It is mixed to weigh carbon-selenium compound 0.7g, acetylene carbon 0.2g and the sodium alginate 0.1g prepared in embodiment 5
It closes；
Step (2)：Water is added in mixture in step (1) to stir evenly and to starchiness, be coated on aluminium foil, in sky
Dry 5h in gas, is cut into disk and obtains anode.
Embodiment 9
The method that carbon-selenium composite material prepares anode, includes the following steps：
Step (1)：It is mixed to weigh carbon-selenium compound 0.7g, acetylene carbon 0.2g and the sodium alginate 0.1g prepared in embodiment 6
It closes；
Step (2)：Water is added in mixture in step (1) to stir evenly and to starchiness, be coated on aluminium foil, in sky
Dry 5h in gas, is cut into disk and obtains anode.
Electro-chemical test：
Electrochemical research is carried out by preparing CR2016 button cells.Using the working electrode conduct in embodiment 7-9
Anode, using lithium piece conduct pair and reference electrode.Polymer film (Celgarad 2400) and LiPF6Solution (LBC-301, Shenzhen
Capchem) respectively as diaphragm and electrolyte.Being assembled in a glove box full of argon gas for button cell carries out.Not
Under same current density, in 1.0-3.0V (to Li+/ Li) in voltage regime, on Neware CT-3008 battery test systems
Constant current loop test is carried out.Under the sweep speed of 0.1mV/s, with the sweep speed of 0.1mV/s, in Solartron electricity
Chemical station has carried out cyclic voltammetry (CV) test.
The initial discharge curve of PCc/Se composite materials is as shown in Figure 5 a, with the rate of current 0.2C (1C=675mA/g),
The initial discharge capacity of composite material in embodiment 4-6 is 812.9,769.5 or 667.6mAh/g, reversible charging capacity
For 413.0,499.2 or 433.7mAh/g (the theoretical weight ratio based on selenium, i.e.,:60wt%).Correspondingly, in embodiment 4-6
It is 50.8,64.9 or 64.9% that the Initial Coulombic Efficiencies of composite material, which can calculate separately,.Here, PCc-2/Se in embodiment 5
Highest Initial Coulombic Efficiencies are attributable to the encapsulation of its low surface area and effective amorphous selenium.
The cyclical stability of PCc/Se composite materials is as shown in Figure 5 b, PCc-1/Se, PCc-2/Se in embodiment 4-6,
The 2nd cycle capacity of PCc-3/Se be 425.8,517.2,454.1mAh/g, after 60 continuous cycles, capability value 349.1,
431.9,376.5mAh/g, corresponding capacity retention ratio are 81.9,83.5,82.9%.In addition, PCc-2/Se has in embodiment 5
There is good capacity to retain and high residual capacity.In fig. 5 c it can be seen that composite material PCc-2/Se's in embodiment 5 puts
Electric charge curve.It can be found that within 10 initial periods electrode capacity attenuation, can be protected in 50 subsequent periods
Keep steady fixed value.
Electrochemical process is tested using CV, as fig 5d.PCc-2/Se electrodes are only recycled in first CV in embodiment 5
The oxidizing potential near reduction potential and 2.03V near one 1.54V of middle display.Illustrate Se and Li2It is reversible between Se
It changes.In the 2nd CV is recycled, difference is reduction peak position offset, and about 1.69V is changed to from about 1.54, and illustrating can in about 1.58V
Intermediate Li can be formed2Sex。
Attached drawing 6 is the high rate performance of carbon-selenium composite material, as shown, rate capability such as Fig. 6 of carbon-selenium composite material
It is shown.It can be found that with the increase of current density, discharge capacity reduces, and the PCc-2/Se in embodiment 5 then show compared with
Good rate capacity；In 0.2,0.5,1 or 2C of current density, it can get 530.8,438.1,388.2 or 339.5mAh/g's
Discharge capacity.Under higher 4C rates, PCc-2/Se electrodes remain to provide the discharge capacity of 295.8mAh/g, work as rate recovery
When to 0.2C, the discharge capacity of 443.6mAh/g can be recycled.According to data above, it is prepared for PCc-2/Se and can be used in height
The charge and discharge of rate.
Each embodiment is described by the way of progressive in this specification, the highlights of each of the examples are with other
The difference of embodiment, just to refer each other for identical similar portion between each embodiment.For device disclosed in embodiment
For, since it is corresponded to the methods disclosed in the examples, so description is fairly simple, related place is said referring to method part
It is bright.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest range caused.
Claims (9)
1. a kind of preparation method of porous carbon, which is characterized in that include the following steps：
Step (1)：Discarded paper products are added to and fill H2SO4In the reactor of solution, reactor is put into autoclave
In, at 200-220 DEG C, after reacting 11-14h, generate material A；
Step (2)：The material A filtering that will be generated in step (1), washs, dries, and grinding is spare；
Step (3)：Material A after grinding in step (2) is mixed with KOH, mixture is put into crucible and is heat-treated, is obtained
Powder material is ground, washing, pH value is adjusted to 7, dry, acquisition porous carbon.
2. according to a kind of preparation method of porous carbon described in claim 1, which is characterized in that H described in step (1)2SO4
A concentration of 0.2-4mol/L of solution, the quality and H of the discarded paper products2SO4The proportionate relationship of the volume of solution is (0.5-
4)g：75mL.
3. according to a kind of preparation method of porous carbon described in claim 1, which is characterized in that step is dried described in (2)
Temperature is 75-85 DEG C, drying time 11-13h.
4. according to a kind of preparation method of porous carbon described in claim 1, which is characterized in that at heat described in step (3)
The condition of reason is in a nitrogen environment, with the heating rate of 2-10 DEG C/min, temperature to be risen to 700 DEG C, constant temperature 2-10h, 700
It is heat-treated at DEG C.
5. according to a kind of preparation method of porous carbon described in claim 1, which is characterized in that the matter of the material A and KOH
Amount is than being (1:1)-(1：3).
6. a kind of preparation method of carbon-selenium composite material, which is characterized in that include the following steps：
Step (1)：Weigh the porous carbon of any one of selenium powder and claim 1-5 preparation；
Step (2)：Porous carbon and selenium powder are mixed, ethyl alcohol is added and obtains mixture A, mixture A is added to horizontal pipe furnace
Middle heating obtains carbon-selenium compound.
7. according to a kind of preparation method of carbon-selenium composite material described in claim 6, which is characterized in that in step (1),
The grain size of the selenium powder is 150-300 mesh, and the grain size of the porous carbon after the grinding is 250-300 mesh, the porous carbon and selenium
The mass ratio of powder is (1-2):(2-3).
8. according to a kind of preparation method of carbon-selenium composite material described in claim 6, which is characterized in that in step (2),
The heating temperature is 280-320 DEG C, heating time 5-7h.
9. a kind of method that carbon-selenium composite material using as described in claim 6-7 prepares anode, feature exist
In including the following steps：
Step (1)：Weigh carbon-selenium compound, acetylene carbon and the sodium alginate mixing prepared in claim 5-7, wherein described
The mass ratio of carbon-selenium compound, acetylene carbon and sodium alginate is (5-9):(0.5-2):(0.5-1)；
Step (2)：Water stirring is added in mixture in step (1), it is dry, it is cut into disk and obtains anode.
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Cited By (4)
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| CN110498414A (en) * | 2019-09-09 | 2019-11-26 | 武汉轻工大学 | Preparation method, carbon-selenium composite material and the modified glassy carbon electrode of porous carbon materials |
| CN111204717A (en) * | 2020-01-14 | 2020-05-29 | 龙岩学院 | One-dimensional lithium/sodium ion battery cathode material and preparation method and application thereof |
| CN111384368A (en) * | 2018-12-28 | 2020-07-07 | 湖南农业大学 | Carbon-selenium composite material, preparation method thereof and application thereof in lithium-selenium battery |
| CN113247867A (en) * | 2020-02-07 | 2021-08-13 | Ii-Vi特拉华有限公司 | Immobilized selenium in porous carbon in the presence of oxygen, method for preparing immobilized selenium and use in rechargeable batteries |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005350292A (en) * | 2004-06-09 | 2005-12-22 | Suden:Kk | Fibrous porous carbonized product and its production method |
| CN104201349A (en) * | 2014-08-13 | 2014-12-10 | 东南大学 | Preparation method of selenium-carbon electrode material with porous structure and application of selenium-carbon electrode material |
| CN104600296A (en) * | 2014-12-31 | 2015-05-06 | 山东玉皇新能源科技有限公司 | Preparation method of Se-C positive electrode composite material of lithium-selenium battery |
| CN104733677A (en) * | 2015-03-25 | 2015-06-24 | 中国科学院化学研究所 | Lithium-selenium battery and preparation technology thereof |
| KR101664357B1 (en) * | 2015-07-14 | 2016-10-11 | 울산과학기술원 | Highly Porous Graphitic Carbon using the waste paper, METHOD FOR THE SAME, NEGATIVE ELECTRODE INCLUDING THE SAME AND ENERGY STORAGE SYSTEM INCLUDING THE SAME |
| CN106179200A (en) * | 2016-06-28 | 2016-12-07 | 河南大学 | A kind of preparation method and applications of magnetic porous carbon based on native cellulose |
| CN106711430A (en) * | 2016-12-27 | 2017-05-24 | 中南大学 | Production method of lithium/carbon fiber or porous carbon paper/copper foil composite negative electrode used for lithium-sulfur battery |
| CN106946239A (en) * | 2017-03-30 | 2017-07-14 | 张泰泓 | A kind of method and application that carbon aerogels are prepared by face tissue |
| CN107452960A (en) * | 2017-07-06 | 2017-12-08 | 陕西科技大学 | A kind of preparation method of black liquid conversion porous carbon anode material of lithium-ion battery |
| CN107785552A (en) * | 2017-10-24 | 2018-03-09 | 武汉理工大学 | A kind of flower-shaped hierarchical organization porous carbon selenium composite positive pole of N doping and preparation method and application |
-
2018
- 2018-03-29 CN CN201810269374.1A patent/CN108539154A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005350292A (en) * | 2004-06-09 | 2005-12-22 | Suden:Kk | Fibrous porous carbonized product and its production method |
| CN104201349A (en) * | 2014-08-13 | 2014-12-10 | 东南大学 | Preparation method of selenium-carbon electrode material with porous structure and application of selenium-carbon electrode material |
| CN104600296A (en) * | 2014-12-31 | 2015-05-06 | 山东玉皇新能源科技有限公司 | Preparation method of Se-C positive electrode composite material of lithium-selenium battery |
| CN104733677A (en) * | 2015-03-25 | 2015-06-24 | 中国科学院化学研究所 | Lithium-selenium battery and preparation technology thereof |
| KR101664357B1 (en) * | 2015-07-14 | 2016-10-11 | 울산과학기술원 | Highly Porous Graphitic Carbon using the waste paper, METHOD FOR THE SAME, NEGATIVE ELECTRODE INCLUDING THE SAME AND ENERGY STORAGE SYSTEM INCLUDING THE SAME |
| CN106179200A (en) * | 2016-06-28 | 2016-12-07 | 河南大学 | A kind of preparation method and applications of magnetic porous carbon based on native cellulose |
| CN106711430A (en) * | 2016-12-27 | 2017-05-24 | 中南大学 | Production method of lithium/carbon fiber or porous carbon paper/copper foil composite negative electrode used for lithium-sulfur battery |
| CN106946239A (en) * | 2017-03-30 | 2017-07-14 | 张泰泓 | A kind of method and application that carbon aerogels are prepared by face tissue |
| CN107452960A (en) * | 2017-07-06 | 2017-12-08 | 陕西科技大学 | A kind of preparation method of black liquid conversion porous carbon anode material of lithium-ion battery |
| CN107785552A (en) * | 2017-10-24 | 2018-03-09 | 武汉理工大学 | A kind of flower-shaped hierarchical organization porous carbon selenium composite positive pole of N doping and preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| ATIAN XIE ET AL: ""Hierarchical porous carbon materials derived from a waste paper towel with ultrafast and ultrahigh performance for adsorption of tetracycline"", 《ROYAL SOCIETY OF CHEMISTRY》 * |
| LI-SHENG XIE ET AL: ""Hierarchical porous carbon derived from animal bone as matric to encapsulated selenium for high performance Li-Se battery"", 《RARE METALS》 * |
| 程凤丽等: ""以蒲草绒为碳源制备多孔碳及其在电化学中的应用"", 《电池工业》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111384368A (en) * | 2018-12-28 | 2020-07-07 | 湖南农业大学 | Carbon-selenium composite material, preparation method thereof and application thereof in lithium-selenium battery |
| CN110498414A (en) * | 2019-09-09 | 2019-11-26 | 武汉轻工大学 | Preparation method, carbon-selenium composite material and the modified glassy carbon electrode of porous carbon materials |
| CN111204717A (en) * | 2020-01-14 | 2020-05-29 | 龙岩学院 | One-dimensional lithium/sodium ion battery cathode material and preparation method and application thereof |
| CN113247867A (en) * | 2020-02-07 | 2021-08-13 | Ii-Vi特拉华有限公司 | Immobilized selenium in porous carbon in the presence of oxygen, method for preparing immobilized selenium and use in rechargeable batteries |
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