CN107887602A - A kind of classifying porous charcoal nanometer sheet electrode material of nitrogen oxygen codope and its preparation method and application - Google Patents
A kind of classifying porous charcoal nanometer sheet electrode material of nitrogen oxygen codope and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to classifying porous charcoal nanometer sheet electrode material of a kind of nitrogen oxygen codope and its preparation method and application, Animal Bone, squama, shell are mixed with metal base or metal salt, are heat-treated under 250 ~ 650 °C of cryogenic conditions, then pickling obtains the electrode material.The material is made up of charcoal nanometer sheet, has micropore, mesoporous and macropore graded porous structure, has the characteristics that defect is more, layer of charcoal spacing is big, specific surface area is high, the doping of nitrogen oxygen atom is abundant；During as sodium ion capacitor anode, there is high reversible capacity and excellent cyclical stability and high rate performance.
Description
Technical field
The present invention relates to classifying porous charcoal nanometer sheet electrode material of a kind of nitrogen oxygen codope and preparation method thereof, and
Application in sodium-ion battery.
Background technology
As mankind's scientific and technological level develops rapidly, the energy and environmental problem gradually show, the storage and use of green energy resource
Higher requirement is proposed to the energy storage device of a new generation.As one of energy storage device, sodium-ion battery is due to sodium resource
Enrich, cost is cheap and receives significant attention.However, the larger ion size of sodium ion causes suitable for the negative of lithium ion battery
Pole material shows poor storage sodium activity.Therefore, designing and developing out has low cost, high power capacity, excellent stability and multiplying power
The new sodium ion battery electrode material of performance, the scale for sodium-ion battery use significant.
Hard carbon material has the carbon-coating spacing bigger compared with graphite, and has relatively low storage sodium potential, thus is considered as most
Has the anode material of lithium-ion battery of application prospect.In addition, can be notable to hard carbon material progress Morphological control and Heteroatom doping
Improve its reversible capacity and high rate performance as anode material of lithium-ion battery.On the one hand, hetero atom can provide extra
Storage sodium site simultaneously reduces the transport resistance of sodium ion.On the other hand, 2D or 3D open architecture is advantageous to the quick embedding of sodium ion
Enter and deviate from.Biomass castoff can be used for preparing hard carbon material as inexpensive, environment-friendly presoma.It is but general
Biomass hard carbon material there is relatively low Heteroatom doping amount, and mostly irregular block structure, as sodium-ion battery
During negative material, poor high rate performance is shown.Thus seek a kind of easy and effective, method that cost is cheap to prepare high property
The sodium-ion battery hard charcoal negative material tool of energy is of great significance.
The content of the invention
It is an aspect of the present invention to provide a kind of classifying porous charcoal nanometer sheet electrode material of nitrogen oxygen codope and its preparation side
Method, this method is easy and effective, cost is cheap.Prepared material is made up of charcoal nanometer sheet, has micropore, mesoporous and macropore point
Level loose structure, have the characteristics that defect is more, layer of charcoal spacing is big, specific surface area is high, the doping of nitrogen oxygen atom is abundant.On the other hand,
The classifying porous charcoal nanometer sheet electrode material for the nitrogen oxygen codope being prepared with this method can be used as high power capacity sodium-ion battery
Negative material, there is good cyclical stability and high rate performance.
The present invention adopts the following technical scheme that a kind of classifying porous charcoal nanometer sheet electrode material of nitrogen oxygen codope will be dynamic
Thing bone, squama, shell are mixed with metal base or metal salt, are heat-treated under 250 ~ 650 °C of cryogenic conditions, and then pickling is somebody's turn to do
Electrode material.The material is made up of charcoal nanometer sheet, has micropore, mesoporous and macropore graded porous structure, has that defect is more, charcoal
The features such as interlamellar spacing is big, specific surface area is high, the doping of nitrogen oxygen atom is abundant；, can with high during as sodium ion capacitor anode
Inverse capacity and excellent cyclical stability and high rate performance.
The present invention also protects the preparation method of the electrode material, comprises the following steps：
(1) Animal Bone, squama, shell are put into tube furnace, under an inert atmosphere with 0.5 ~ 20 °C of min-1Heating rate progressively
It is heated to 250 ~ 650 °C of temperature and is incubated 0.5 ~ 6 h；
(2) by step（1）Obtained product mixes with metal base or metal salt, mixed proportion 5:1~1:50.Mixture is put
Enter in tube furnace, under an inert atmosphere with 0.5 ~ 20 °C of min-1Heating rate be gradually heated to 250 ~ 650 °C of temperature and protect
0.5 ~ 6h of temperature；
(3) by step（2）Obtained product is dipped in 6 ~ 24 h of stirring in dilute acid soln, is then washed to neutrality, is obtained after drying
The classifying porous charcoal nanometer sheet electrode material of nitrogen oxygen codope.
In further preferred embodiment of the present invention, described Animal Bone, squama, shell are not only restricted to animal species and portion
Position, the preferably one or more in ox bone, fish scale, Carapax Eriocheir sinensis.
In further preferred embodiment of the present invention, heating rate is 2 ~ 10 °C of min in heating process-1, insulation temperature
Spend for 300 ~ 600 °C, soaking time is 1 ~ 3h；It is furthermore preferred that described heating rate is 2 ~ 5 °C of min-1, holding temperature is
350 ~ 550 °C, soaking time is 2 ~ 3 h.
In further preferred embodiment of the present invention, described metal base is in fusing point relatively low LiOH, NaOH, KOH
One or more；Affiliated metal salt is the relatively low ZnCl of fusing point2、FeCl3In one or more；Mixed proportion is 1:1~
1:20。
In further preferred embodiment of the present invention, described metal base is KOH；Affiliated metal salt is ZnCl2；It is mixed
Composition and division in a proportion example is 1:2~1:5.
In further preferred embodiment of the present invention, described dilute acid soln is in watery hydrochloric acid, dilute sulfuric acid, dust technology
One or more, concentration are 0.5 ~ 3 M；Described solution drying means is freeze-drying or heated drying.
In further preferred embodiment of the present invention, described dilute acid soln is watery hydrochloric acid, and concentration is 1 ~ 2 M.
The present invention protects a kind of anode material of lithium-ion battery, is prepared via a method which to obtain：By nitrogen obtained above
Classifying porous charcoal nanometer sheet electrode material, conductive black, the binding agent of oxygen codope are pressed（5~10）:1:1 mass ratio mixing is equal
It is even, add solvent be fully ground be modulated into homogeneous paste after even application on copper foil, then 100 ~ 120 in vacuum drying oven
DEG C dry 10 ~ 12 h.
In further preferred embodiment of the present invention, described binding agent is PVDF, PTFE, PAA, CMC, alginic acid
One or more in sodium, gelatin, described conductive black is acetylene black, the one or more in BP2000, Vulcan P, institute
Solvent is stated as the one or more in 1-METHYLPYRROLIDONE, ethanol, water.
In further preferred embodiment of the present invention, described binding agent is PVDF, and described conductive black is acetylene
Black, the solvent is 1-METHYLPYRROLIDONE.
In further preferred embodiment of the present invention, the electrode material, conductive black, the mass ratio of binding agent are
（6-8）:1:1, more preferably 7:1:1.
The present invention also application of the protection using the above-mentioned anode material of lithium-ion battery being prepared in sodium-ion battery.
Compared with prior art, the invention has the advantages that：Made with resourceful Animal Bone, squama, shell the like waste
For presoma, using the inorganic matter in presoma and metal base or the synergy of salt, obtained under relatively low heat treatment temperature
The porous carbon material of nitrogen oxygen codope with two-dimensional sheet structure, preparation method is simple, efficient energy-saving, cost are cheap.Due to
Obtaining porous charcoal nanometer sheet has micropore, mesoporous and macropore graded porous structure, while has high-ratio surface（> 500 m2 g-1）, big layer of charcoal spacing（> 0.37 nm）, the doping of nitrogen oxygen atom it is abundant（N >6 at.%, O> 10 at.%）The features such as.So that
When the material is as anode material of lithium-ion battery, in 0.7 A g-1Current density under circulate 1000 times after still have 180 mAh
g-1Reversible specific capacity above, in 7 A g-1Current density under circulate 10000 times after still have 120 mAh g-1More than can
Inverse specific capacity.In 0.7,1.75,3.5,7,10.5,17.5 A g-1Grading current density under, reversible specific capacity respectively 190,
180、150、120、110、100 mAh g-1More than, present excellent storage sodium ability, good cyclical stability and multiplying power
Performance.Simple controllable, the preparation process efficient energy-saving of preparation method of the present invention and precursor is cheap, for it is low into
Originally, the prepare with scale of the classifying porous charcoal nanometer sheet anode material of lithium-ion battery of high performance nitrogen oxygen codope and application carry
New method is supplied.
Brief description of the drawings
Fig. 1 is the scanning of the classifying porous charcoal nanometer sheet electrode material of the nitrogen oxygen codope prepared by the embodiment of the present invention 1
Electron microscope；
Fig. 2 is the transmission electron microscope of the classifying porous charcoal nanometer sheet electrode material of the nitrogen oxygen codope prepared by the embodiment of the present invention 1
Figure；
Fig. 3 is that the nitrogen suction of the classifying porous charcoal nanometer sheet electrode material of the nitrogen oxygen codope prepared by the embodiment of the present invention 1 is de-
Attached curve；
Fig. 4 is the pore-size distribution of the classifying porous charcoal nanometer sheet electrode material of the nitrogen oxygen codope prepared by the embodiment of the present invention 1
Figure；
Fig. 5 is the X ray photoelectricity of the classifying porous charcoal nanometer sheet electrode material of the nitrogen oxygen codope prepared by the embodiment of the present invention 1
Sub- energy spectrum diagram；
Fig. 6 is the classifying porous charcoal nanometer sheet electrode material of the nitrogen oxygen codope prepared by the embodiment of the present invention 1 as sodium ion
Cell negative electrode material is in 0.7,1.75,3.5,7,10.5,17.5 A g-1Circulation volume figure under current density；
Fig. 7 is the classifying porous charcoal nanometer sheet electrode material of the nitrogen oxygen codope prepared by the embodiment of the present invention 1 as sodium ion
Cell negative electrode material is in 0.7 A g-1Circulation volume figure under current density；
Fig. 8 is the classifying porous charcoal nanometer sheet electrode material of the nitrogen oxygen codope prepared by the embodiment of the present invention 1 as sodium ion
Cell negative electrode material is in 7 A g-1Circulation volume figure under current density.
Embodiment
In order that the purpose of the present invention, technical scheme and beneficial effect are clearer, present invention specific examples below
Illustrate, but the present invention is limited to absolutely not these examples.
Embodiment 1
10 g ox bones particles addition porcelain boat is placed in tube furnace, under the protection of inert atmosphere, with 2.5 °C of min-1's
Speed is warming up to 400 °C, and in this temperature 3 h.After tube furnace is down to room temperature, take out heat-treated products and KOH according to
1:1.4 ratio is mixed.Corundum porcelain boat is fed the mixture into be placed in tube furnace, under the protection of inert atmosphere, with
2.5 °C min-1Speed be warming up to 550 °C, and in this temperature 1 h.After tube furnace is down to room temperature, heat treatment is taken out
Product simultaneously soaks 12 h with 1 M watery hydrochloric acid, is then washed with deionized water to neutrality and dries, that is, obtains the classification of nitrogen oxygen codope
Porous charcoal nanometer sheet electrode material（Fig. 1 and 2）.Its specific surface area is 890 m2 g-1, pore volume be 0.48 cm3 g-1, nitrogen content
For 6.4 at.%, oxygen content is 17.1 at.%, and carbon-coating spacing is 0.41 nm.
The classifying porous charcoal nanometer sheet electrode material of nitrogen oxygen codope obtained above, acetylene black, PVDF are pressed 7:1:1
Mass ratio is well mixed, and is added 1-METHYLPYRROLIDONE and is fully ground and is modulated into after homogeneous paste coated on copper foil, then
120 °C of 12 h of drying in vacuum drying oven.Using button CR2032 type system simulated batteries, wherein being metallic sodium piece to electrode.
To investigate the high rate performance of material, the constant current charge-discharge test carried out to battery under grading current density is analyzed, and is surveyed
Strip part is：Voltage range 0.001-3 V, current density are followed successively by 0.7,1.75,3.5,7,10.5,17.5 A g-1.As sodium
During ion battery negative pole, the reversible specific capacity under grading current density is respectively 203,183,153,132,118,104
mAh g-1（Fig. 6）.
To investigate the reversible capacity of the material, cycle performance, constant current charge-discharge test analysis is carried out to battery.Test condition
For：Voltage range 0.001-3 V, the A g of current density 0.7-1With 7 A g-1.As anode material of lithium-ion battery, in 0.7 A
g-1Specific capacity remains to be maintained at 199 mAh g after circulating 1000 times-1（Fig. 7）.In 7 A g-1Circulation 10000 times after specific capacity still
151 mAh g can be maintained at-1（Fig. 8）.
Embodiment 2
For operating condition such as embodiment 1, difference is that Animal Bone used is fish scale.The classification for obtaining nitrogen oxygen codope is more
The specific surface area of hole charcoal nanometer sheet electrode material is 810 m2 g-1, pore volume be 0.42 cm3 g-1, nitrogen content be 6.9 at.%, oxygen
Content is 18.1 at.%, and carbon-coating spacing is 0.42 nm.
Electro-chemical test is carried out using method same as Example 1, the results showed that, current density is 0.7 A g-1Under,
After circulation 1000 times, specific capacity remains to be maintained at 190 mAh g-1, current density is 7 A g-1Under, after circulating 10000 times, than
Capacity remains to be maintained at 125 mAh g-1Reversible specific capacity under grading current density is respectively 195,181,150,128,
115, 105 mAh g-1。
Embodiment 3
For operating condition such as embodiment 1, difference is 2.5 °C of min of programming rate-1.Obtain the classification of nitrogen oxygen codope
The specific surface area of porous charcoal nanometer sheet electrode material is 905 m2 g-1, pore volume be 0.50 cm3 g-1, nitrogen content be 6.8 at.%,
Oxygen content is 18.5 at.%, and carbon-coating spacing is 0.40 nm.
Electro-chemical test is carried out using method same as Example 1, the results showed that, current density is 0.7 A g-1Under,
After circulation 1000 times, specific capacity remains to be maintained at 188 mAh g-1, current density is 7 A g-1Under, after circulating 10000 times, than
Capacity remains to be maintained at 123 mAh g-1Reversible specific capacity under grading current density is respectively 195,182,154,125,
113, 102 mAh g-1。
Embodiment 4
For operating condition such as embodiment 1, difference is that carbonization temperature is 600 °C.Obtain the classifying porous of nitrogen oxygen codope
The specific surface area of charcoal nanometer sheet electrode material is 920 m2 g-1, pore volume be 0.52 cm3 g-1, nitrogen content be 6.2 at.%, oxygen contains
It is 0.40 nm to measure as 19.1 at.%, carbon-coating spacing.
Electro-chemical test is carried out using method same as Example 1, the results showed that, current density is 0.7 A g-1Under,
After circulation 1000 times, specific capacity remains to be maintained at 185 mAh g-1, current density is 7 A g-1Under, after circulating 10000 times, than
Capacity remains to be maintained at 122 mAh g-1Reversible specific capacity under grading current density is respectively 192,180,152,121,
111, 100 mAh g-1。
Embodiment 5
For operating condition such as embodiment 1, difference is that it is 2h to carbonize soaking time.Obtain the classifying porous of nitrogen oxygen codope
The specific surface area of charcoal nanometer sheet electrode material is 880 m2 g-1, pore volume be 0.45 cm3 g-1, nitrogen content be 6.0 at.%, oxygen contains
It is 0.39 nm to measure as 16.1 at.%, carbon-coating spacing.
Electro-chemical test is carried out using method same as Example 1, the results showed that, current density is 0.7 A g-1Under,
After circulation 1000 times, specific capacity remains to be maintained at 184 mAh g-1, current density is 7 A g-1Under, after circulating 10000 times, than
Capacity remains to be maintained at 121 mAh g-1Reversible specific capacity under grading current density is respectively 190,181 150,121,
113, 101 mAh g-1。
Embodiment 6
For operating condition such as embodiment 1, the metal salt that difference is to choose is ZnCl2.Obtain the classification of nitrogen oxygen codope
The specific surface area of porous charcoal nanometer sheet electrode material is 580 m2 g-1, pore volume be 0.38 cm3 g-1, nitrogen content be 7.2 at.%,
Oxygen content is 15.8 at.%, and carbon-coating spacing is 0.38 nm.
Electro-chemical test is carried out using method same as Example 1, the results showed that, current density is 0.7 A g-1Under,
After circulation 1000 times, specific capacity remains to be maintained at 180 mAh g-1, current density is 7 A g-1Under, after circulating 10000 times, than
Capacity remains to be maintained at 120 mAh g-1Reversible specific capacity under grading current density is respectively 192,180 151,120,
110, 100 mAh g-1。
Embodiment 7
For operating condition such as embodiment 1, difference is that diluted acid used is 2 M nitric acid.The classification for obtaining nitrogen oxygen codope is more
The specific surface area of hole charcoal nanometer sheet electrode material is 885 m2 g-1, pore volume be 0.48 cm3 g-1, nitrogen content be 6.2 at.%, oxygen
Content is 18.8 at.%, and carbon-coating spacing is 0.41 nm.
Electro-chemical test is carried out using method same as Example 1, the results showed that, current density is 0.7 A g-1Under,
After circulation 1000 times, specific capacity remains to be maintained at 189 mAh g-1, current density is 7 A g-1Under, after circulating 10000 times, than
Capacity remains to be maintained at 128 mAh g-1Reversible specific capacity under grading current density is respectively 195,188 158,126,
115, 103 mAh g-1。
Embodiment 8
For operating condition such as embodiment 1, difference is drying means used for freeze-drying.Obtain point of nitrogen oxygen codope
The specific surface area of level porous charcoal nanometer sheet electrode material is 980 m2 g-1, pore volume be 0.55 cm3 g-1, nitrogen content 7.0
At.%, oxygen content are 18.8 at.%, and carbon-coating spacing is 0.42 nm.
Electro-chemical test is carried out using method same as Example 1, the results showed that, current density is 0.7 A g-1Under,
After circulation 1000 times, specific capacity remains to be maintained at 195 mAh g-1, current density is 7 A g-1Under, after circulating 10000 times, than
Capacity remains to be maintained at 130 mAh g-1Reversible specific capacity under grading current density is respectively 199,188 160,135,
120, 109 mAh g-1。
Presently preferred embodiments of the present invention is illustrated above, but the present invention is not limited to the embodiment,
Those skilled in the art can also make a variety of equivalent modifications or replacement on the premise of without prejudice to spirit of the invention,
These equivalent modifications or replacement are all contained in the application claim limited range.
Claims (10)
1. the classifying porous charcoal nanometer sheet electrode material of a kind of nitrogen oxygen codope, it is characterised in that by Animal Bone, squama, shell and gold
Belong to alkali or metal salt mixing, be heat-treated under 250 ~ 650 °C of cryogenic conditions, then pickling obtains the electrode material.
2. the preparation method of the classifying porous charcoal nanometer sheet electrode material of a kind of nitrogen oxygen codope, it is characterised in that including as follows
Step：
(1) Animal Bone, squama, shell are put into tube furnace, under an inert atmosphere with 0.5 ~ 20 °C of min-1Heating rate progressively
It is heated to 250 ~ 650 °C of temperature and is incubated 0.5 ~ 6 h；
(2) by step（1）Obtained product mixes with metal base or metal salt, mixed proportion 5:1~1:50；
Mixture is put into tube furnace, under an inert atmosphere with 0.5 ~ 20 °C of min-1Heating rate be gradually heated to temperature
250 ~ 650 °C and 0.5 ~ 6h of insulation；
(3) by step（2）Obtained product is dipped in 6 ~ 24 h of stirring in dilute acid soln, is then washed to neutrality, is obtained after drying
The classifying porous charcoal nanometer sheet electrode material of nitrogen oxygen codope.
3. preparation method according to claim 2, it is characterised in that described Animal Bone, squama, shell are not only restricted to animal kind
One or more in class and position, preferably ox bone, fish scale, Carapax Eriocheir sinensis.
4. preparation method according to claim 2, it is characterised in that heating rate is 2 ~ 10 °C of min in heating process-1, holding temperature is 300 ~ 600 °C, and soaking time is 1 ~ 3h；It is furthermore preferred that described heating rate is 2 ~ 5 °C of min-1,
Holding temperature is 350 ~ 550 °C, and soaking time is 2 ~ 3 h.
5. preparation method according to claim 2, it is characterised in that described metal base be the relatively low LiOH of fusing point,
One or more in NaOH, KOH, affiliated metal salt are the relatively low ZnCl of fusing point2、FeCl3In one or more, mixing
Ratio is 1:1~1:20；It is furthermore preferred that described metal base is KOH, affiliated metal salt is ZnCl2, mixed proportion 1:2~
1:5。
6. preparation method according to claim 2, it is characterised in that described dilute acid soln is watery hydrochloric acid, dilute sulfuric acid, dilute
One or more in nitric acid, concentration are 0.5 ~ 3 M；Described solution drying means is freeze-drying or heated drying；More preferably
, described dilute acid soln is watery hydrochloric acid, and concentration is 1 ~ 2 M.
7. a kind of anode material of lithium-ion battery, it is characterised in that be prepared via a method which to obtain：By in claim 2-6
The classifying porous charcoal nanometer sheet electrode material of the nitrogen oxygen codope that preparation method described in any one is prepared, conductive black,
Binding agent is pressed（5~10）:1:1 mass ratio is well mixed, and is added solvent and is fully ground and is modulated into even application after homogeneous paste
On copper foil, then 100 ~ 120 DEG C of 10 ~ 12 h of drying in vacuum drying oven.
8. anode material of lithium-ion battery according to claim 7, it is characterised in that described binding agent be PVDF,
One or more in PTFE, PAA, CMC, sodium alginate, gelatin, described conductive black are acetylene black, BP2000, Vulcan
One or more in P, the solvent are the one or more in 1-METHYLPYRROLIDONE, ethanol, water；It is it is furthermore preferred that described
Binding agent be PVDF, described conductive black is acetylene black, and the solvent is 1-METHYLPYRROLIDONE.
9. anode material of lithium-ion battery according to claim 7, it is characterised in that the electrode material, conductive black,
The mass ratio of binding agent is（6-8）:1:1, more preferably 7:1:1.
10. application of the anode material of lithium-ion battery according to any one of claim 7-9 in sodium-ion battery.
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| CN109301246A (en) * | 2018-09-28 | 2019-02-01 | 东北大学秦皇岛分校 | A kind of sulfur doping hard carbon material, preparation method and its kalium ion battery as cathode |
| CN109354004A (en) * | 2018-10-17 | 2019-02-19 | 西安理工大学 | A method of classifying porous carbon material is prepared using fish scale |
| CN109706551A (en) * | 2018-11-27 | 2019-05-03 | 陆鹏蓉 | A kind of nitrogen, the Carbon fibe beam of oxygen codope and its application as anode material of lithium-ion battery |
| CN110048099A (en) * | 2019-03-28 | 2019-07-23 | 天津大学 | Electrode material of sodium-ion battery and its preparation method and application |
| CN110148733A (en) * | 2019-05-30 | 2019-08-20 | 中南大学 | A kind of exotic atom doped porous carbon material and its preparation method and application |
| CN110197897A (en) * | 2019-05-22 | 2019-09-03 | 北京化工大学 | Biomass graded porous charcoal/sulphur anode of a kind of nano magnesia doping and its preparation method and application |
| WO2020208341A1 (en) | 2019-04-09 | 2020-10-15 | Faradion Limited | Process for preparing and use of hard-carbon containing materials |
| CN111825074A (en) * | 2019-04-15 | 2020-10-27 | 中国科学院福建物质结构研究所 | Preparation method and application of sulfur-nitrogen co-doped three-dimensional porous carbon nanosheet |
| CN113659143A (en) * | 2021-08-06 | 2021-11-16 | 东莞市创明电池技术有限公司 | Preparation method of negative electrode material of sodium ion battery, negative electrode material and sodium ion battery |
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| CN109301246B (en) * | 2018-09-28 | 2021-07-02 | 东北大学秦皇岛分校 | Sulfur-doped hard carbon material, preparation method thereof and potassium ion battery using sulfur-doped hard carbon material as negative electrode |
| CN109354004B (en) * | 2018-10-17 | 2021-06-15 | 西安理工大学 | Method for preparing hierarchical porous carbon material by using fish scales |
| CN109354004A (en) * | 2018-10-17 | 2019-02-19 | 西安理工大学 | A method of classifying porous carbon material is prepared using fish scale |
| CN109706551A (en) * | 2018-11-27 | 2019-05-03 | 陆鹏蓉 | A kind of nitrogen, the Carbon fibe beam of oxygen codope and its application as anode material of lithium-ion battery |
| CN110048099A (en) * | 2019-03-28 | 2019-07-23 | 天津大学 | Electrode material of sodium-ion battery and its preparation method and application |
| WO2020208341A1 (en) | 2019-04-09 | 2020-10-15 | Faradion Limited | Process for preparing and use of hard-carbon containing materials |
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| CN111825074A (en) * | 2019-04-15 | 2020-10-27 | 中国科学院福建物质结构研究所 | Preparation method and application of sulfur-nitrogen co-doped three-dimensional porous carbon nanosheet |
| CN110197897A (en) * | 2019-05-22 | 2019-09-03 | 北京化工大学 | Biomass graded porous charcoal/sulphur anode of a kind of nano magnesia doping and its preparation method and application |
| CN110148733A (en) * | 2019-05-30 | 2019-08-20 | 中南大学 | A kind of exotic atom doped porous carbon material and its preparation method and application |
| CN110148733B (en) * | 2019-05-30 | 2022-06-07 | 中南大学 | Hetero-atom doped porous carbon material and preparation method and application thereof |
| CN113659143A (en) * | 2021-08-06 | 2021-11-16 | 东莞市创明电池技术有限公司 | Preparation method of negative electrode material of sodium ion battery, negative electrode material and sodium ion battery |
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