CN107497397A - A kind of bio-based oxygen, sulphur, the preparation method and applications of nitrogen co-doped porous carbon - Google Patents
A kind of bio-based oxygen, sulphur, the preparation method and applications of nitrogen co-doped porous carbon Download PDFInfo
- Publication number
- CN107497397A CN107497397A CN201710841180.XA CN201710841180A CN107497397A CN 107497397 A CN107497397 A CN 107497397A CN 201710841180 A CN201710841180 A CN 201710841180A CN 107497397 A CN107497397 A CN 107497397A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- porous carbon
- bio
- sulphur
- bone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
Abstract
The present invention relates to a kind of bio-based oxygen, sulphur, nitrogen co-doped porous carbon preparation method and applications, using aquatic skin or bone as oxygen, sulphur, nitrogen co-doped porous carbon raw material, by activate obtain afterwards bio-based oxygen, sulphur, nitrogen co-doped porous carbon specific surface area be 1144.63 ~ 1517.03 m2 g 1, itrogen content of getter with nitrogen doped can reach 5.9%, mixes sulfur content and can reach 2%.The preparation method can regulate and control the pore structure of porous carbon and realize that oxygen is sulfur and nitrogen co-doped, and craft science is reasonable, easily operated, so as to reduce the production cost of the sulfur and nitrogen co-doped material of oxygen.Bio-based oxygen, sulphur, the physical and chemical properties of nitrogen co-doped porous carbon being prepared all are significantly improved.
Description
Technical field
The invention belongs to absorbent fields, and in particular to a kind of bio-based oxygen, sulphur, the preparation method of nitrogen co-doped porous carbon
And its applied in lithium-sulfur cell.
Background technology
Porous carbon materials are widely used due to the gap structure with uniqueness, excellent physics and chemical stability
In fields such as catalysis, absorption, sensing and electrochemistry.
Porous carbon materials are carried out with Heteroatom doping can be with the composition of its surface-element, to the electronics distribution of material and crystalline substance
Lattice structure is significantly improved, and influences the hydrophily of porous carbon materials and the acid-base property of material surface, then to its chemical property
Improved.Nitrogen-atoms and carbon atom have similar atomic radius, so as to be relatively easy to replace in porous carbon materials
Carbon atom.Because nitrogen-atoms than carbon atom contains more outer-shell electrons, and its electron affinity energy is stronger, so as to change
Become the polarity of porous carbon materials.At the same time, the lone pair electrons of nitrogen-atoms form conjugation to that can obtain big pi bond with carbon material, after
And improve its electrochemistry and catalytic performance.Sulphur atom has similar electronegativity to carbon atom, while sulphur atom is compared and carbon original
The radius of son is big.Therefore spacing between carbon atomic layer can be increased by mixing sulphur atom in porous carbon materials, the defects of making porous carbon structure
Increase with stress, so that electric charge generation area.Furthermore because sulphur atom contains the d layer tracks easily to polarize, so as to
The surface-active of porous carbon materials is improved, increases its catalysis, absorption and chemical property.Therefore, nitrogen-atoms and sulphur atom are total to
It is same to be doped into the chemical and physical properties that porous carbon materials significantly increase porous carbon materials.
It is important using environmentally safe biomaterial to reduce the preparation cost of the sulfur and nitrogen co-doped porous carbon of oxygen
Developing direction.By taking tuna as an example, counted according to FAO (Food and Agriculture Organization of the United Nation), tuna year quantity of the catch surpass 6 × 1,060,000 tons and account for public affairs
More than the 70% of extra large fishery total output, it is one of important operation fingerling of world's deep-sea fishing.It can be produced in tuna process
The raw leftover bits and pieces for accounting for gross weight 50%~70%, wherein more than 30% leftover bits and pieces is skin or bone.However, aquatic skin or bone are simultaneously
It is not utilized effectively, is sold mainly as low value feed, fertilizer, or even arbitrarily abandon, had both wasted the resource of preciousness, but it is dirty
Contaminate environment.Therefore, development and environmental protection of the higher value application of aquatic skin or bone for animal industry has important meaning
Justice.The main composition of animal waste is organic matter collagen and inorganic matter hydroxyapatite crystal.The wherein group of collagen
Contain methionine into amino acid, can be as the presoma of sulphur atom containing element sulphur in methionine, and collagen can conduct
Carbon material obtains carbon and the presoma of nitrogen.At the same time, inorganic constituents hydroxyapatite, it is with form of nanoparticles point
Dissipate in mineralized collagen, therefore hydroxyapatite can regulate and control the pattern of carbon material as template.Therefore by aquatic skin or
Bone prepares the good approach that the sulfur and nitrogen co-doped porous carbon of oxygen is the reduction sulfur and nitrogen co-doped porous carbon of oxygen as raw material, while is to water
The good method that raw Animal Skin or bone rationally utilize.
The content of the invention
In order to solve the above-mentioned problems in the prior art, the present invention provides a kind of bio-based oxygen, sulphur, nitrogen co-doped more
The preparation method and applications of hole carbon, the preparation method can regulate and control the pore structure of porous carbon and realize that oxygen is sulfur and nitrogen co-doped, work
Skill is scientific and reasonable, easily operated, so as to reduce the production cost of oxygen, sulphur, nitrogen co-doped material.
In animal process, aquatic skin or bone are not utilized effectively, mainly as low value feed, fertilizer
Sell, or even arbitrarily abandon, both wasted the resource of preciousness, pollute environment again.The waste material main composition of animal is organic matter glue
Former albumen and inorganic matter hydroxyapatite crystal.Wherein there are the methionine of high level, egg in the composition amino acid of collagen
Can be as the presoma of sulphur containing element sulphur in propylhomoserin, and collagen can obtain the forerunner of carbon and nitrogen as carbon material
Body.At the same time, inorganic constituents hydroxyapatite, it is to be scattered in form of nanoparticles in mineralized collagen, therefore hydroxyl phosphorus
Lime stone can regulate and control the pattern of carbon material as template.Therefore, the present invention provides a kind of bio-based oxygen, sulphur, nitrogen co-doped porous carbon
And preparation method thereof, using aquatic skin or bone as oxygen, sulphur, nitrogen co-doped porous carbon raw material, by after activation
The bio-based oxygen that arrives, sulphur, the specific surface area of nitrogen co-doped porous carbon are 1144.63 ~ 1517.03 m2 g-1, itrogen content of getter with nitrogen doped can reach
5.9%, mix sulfur content and can reach 2%, physical and chemical properties are all significantly improved.
Further, the present invention, using potassium hydroxide as activator, passes through pre- carbon using Animal Skin and bone as presoma
Change, be carbonized, washing the step of carbon and drying.
Further, described bio-based oxygen, sulphur, the preparation method of nitrogen co-doped porous carbon comprise the following steps：
（1）The pre- carbonization treatment of low temperature：Aquatic skin or bone are cleaned, dried, and carry out low temperature and be carbonized in advance；
（2）High-temperature activation processing：Aquatic skin after pre- carbonization or bone are uniformly mixed with activator, and carry out high-temperature activation
Carbonization, obtains bio-based carbonized powder；
（3）Stripper plate step：After bio-based carbonized powder is placed in acid solution into immersion repeatedly, filtering is crossed repeatedly with deionized water
Wash, by being dried to obtain bio-based oxygen, sulphur, nitrogen co-doped porous carbon.
Further, step（1）It is middle aquatic skin or bone are fully washed drain after, be warming up to 30-100 DEG C of dry 5-
24h, aquatic skin after drying or bone meal are then broken to powder, are placed in Muffle furnace, under inert gas shielding, be heated to
200-400 DEG C is carbonized in advance, and carbonization time is 1-6 hours, preferably 2-5 hours.
Further, step（2）In aquatic skin or the part by weight 1 of bone and activator after pre- carbonization:0.1-5,
It is preferred that 1:0.5-3, adjusting furnace temperature are 500-1000 DEG C, and 600-900 DEG C of preferable temperature, carbonization time is preset as 0.5-5 hours, excellent
It is 1-3 hours to select the time；Described activator is preferably KOH.
Further, step（3）Described in acid solution be HCl, HNO3、H2SO4In one or more, sour concentration is
0.2-5mol/L, washing times are 1-10 times；It is subsequently placed at 30-100oDried in C baking ovens, drying time 5-24h.
The present invention also protects a kind of lithium-sulfur cell barrier film coating material, is made by the following method：By described bio-based
Oxygen, sulphur, nitrogen co-doped porous carbon：Acetylene black：Adhesive according to（5-10:1:1）Mass ratio be well mixed, add solvent it is abundant
Grinding is coated uniformly on PP barrier films side, the 60-100 in vacuum drying chamber after being adjusted to homogeneous pasteoC dries 10-12h.
Further, described adhesive is PVDF, PVA, PTFE one or several kinds, and the solvent is N- methyl pyrroles
Pyrrolidone.
Further, described adhesive is LA132, and the solvent is deionized water, and is made with a certain amount of isopropanol
For dispersant, the mass ratio of wherein deionized water and isopropanol is（5-10）：1.
Compared with prior art, the present invention has following beneficial technique effect：
（1）Present invention process is simple, makes full use of discarded animal（Fish）Skin or bone are initial feed, its abundance, valency
Lattice are cheap.It is mainly obtained from discarded animal processing waste material, and preparation is simple, and cost is low, safe and non-toxic, opens
Oxygen, sulphur, nitrogen co-doped porous carbon materials of the hair with potential application.
（2）The present invention is raw material from aquatic skin or bone, and three hetero atom oxygen in situ are sulfur and nitrogen co-doped, by regulating and controlling to live
Agent dosage and carburizing temperature are prepared big with high-specific surface area（More than 1100m2/g）Only exist micropore and Xiaoer Jie simultaneously
The more sulphion adsorbents of porous charcoal of pore size distribution, and realize that a variety of hetero atom co-dopeds of oxygen sulphur nitrogen, micro content are larger simultaneously
And the advantages that safe without toxic side effect.
（3）Bio-based oxygen that the present invention is prepared, sulphur, nitrogen co-doped porous carbon have good electric conductivity, can be used for
More sulphion adsorbents in lithium-sulfur cell, and show there is very strong adsorption capacity to more sulphions, substantially improve lithium sulphur
The utilization rate of cell active materials sulphur and the cycle performance of battery.
Brief description of the drawings
Fig. 1 is fish-bone base oxygen, sulphur, the pore structure study of nitrogen co-doped porous carbon prepared by the embodiment of the present invention 3；
Fig. 2 be present example 3 prepared by fish-bone base oxygen, sulphur, nitrogen co-doped porous carbon as lithium-sulfur cell barrier film coating when,
Cycle performance of the battery under 1C.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, without structure
Into limitation of the present invention.
Embodiment 1
Fish-bone is cleaned up, is subsequently placed in 60oIn C baking ovens, place 24 hours and dry.By dried fish-bone pulverizer powder
Aquatic skin or bone powder are broken into, is placed in tube furnace and is heated to 330 under atmosphere of inert gasesoC, and constant temperature enters for 3 hours
Row low temperature is carbonized in advance；By the fish-bone powder after pre- carbonization with activator according to 5:1 ratio uniform mixing, after the powder that will mix
End, which is placed in tube furnace, is warming up to 700oC, constant temperature carry out high temperature cabonization in 1 hour, obtain bio-based carbonized powder.By bio-based carbon
Change powder, which is placed in 1mol/L hydrochloric acid acid solutions, carries out 3 pickling, removes the inorganic matter template in bio-based carbonized powder and work
Property agent, after filter cleaning repeatedly with deionized water.Place products into 80oDried 24 hours in C baking ovens, obtain oxygen, sulphur, nitrogen and be co-doped with
Miscellaneous bio-based porous carbon.
Embodiment 2
Fish-bone is cleaned up, is subsequently placed in 60oIn C baking ovens, place 24 hours and dry.By dried aquatic skin or bone
Aquatic skin or bone powder are ground into pulverizer, is placed in tube furnace and is heated to 330 under atmosphere of inert gasesoC, and it is permanent
Temperature carries out low temperature for 3 hours and is carbonized in advance；By the fish-bone powder after pre- carbonization with activator according to 5:1 ratio uniform mixing, after will
The powder mixed, which is placed in tube furnace, is warming up to 800oC, constant temperature carry out high temperature cabonization in 1 hour, obtain bio-based carbonized powder.
Bio-based carbonized powder is placed in 1mol/L hydrochloric acid acid solutions and carries out 3 pickling, is removed inorganic in bio-based carbonized powder
Thing template and activating agent, after filter cleaning repeatedly with deionized water.Place products into 80oDry 24 hours, obtain in C baking ovens
Oxygen, sulphur, nitrogen co-doped bio-based porous carbon.
Embodiment 3
Fish-bone is cleaned up, is subsequently placed in 60oIn C baking ovens, place 24 hours and dry.By dried fish-bone pulverizer powder
Aquatic skin or bone powder are broken into, is placed in tube furnace and is heated to 330 under atmosphere of inert gasesoC, and constant temperature enters for 3 hours
Row low temperature is carbonized in advance；By the fish-bone powder after pre- carbonization with activator according to 5:1 ratio uniform mixing, after the powder that will mix
End, which is placed in tube furnace, is warming up to 900oC, constant temperature carry out high temperature cabonization in 1 hour, obtain bio-based carbonized powder.By bio-based carbon
Change powder, which is placed in 1mol/L hydrochloric acid acid solutions, carries out 3 pickling, removes the inorganic matter template in bio-based carbonized powder and work
Property agent, after filter cleaning repeatedly with deionized water.Place products into 80oDried 24 hours in C baking ovens, obtain oxygen, sulphur, nitrogen and be co-doped with
Miscellaneous bio-based porous carbon.
The aperture parameters of the sulfur and nitrogen co-doped porous carbon of oxygen under 1 different carburizing temperatures of table
It can be seen from table 1, the sulfur and nitrogen co-doped porous carbon of oxygen increases therewith with the rise of carburizing temperature, the specific surface area of material.
But because hydroxyapatite is 900oC temperatures above, reuniting effect easily occurs, therefore its micropore area is presented first to increase and reduced afterwards
Trend.And this effect is equally reflected on pore volume and micro pore volume, due to 800oDuring C, micropore proportion is maximum, makes
Obtaining pore volume tends to be minimum.And the activation of KOH and porous carbon is more acutely 700 under high temperatureoC and 900oC micro pore volume differences
Reason.At the same time, the effect for first reducing and increasing afterwards is presented in average pore size.
The sulfur and nitrogen co-doped porous heteroatoms incorporation of oxygen under 2 different carburizing temperatures of table
It can be seen from table 2, with the rise of carburizing temperature, the ratio of carbon content raises, and illustrates that temperature is higher, the carbonization of fish-bone material
It is more complete.From nitrogen content as the trend successively decreased occurs in the rise of carburizing temperature, and sulfur content is incremental as temperature rise has
Trend, illustrate that nitrogenous material is easier to lose with temperature rise, and the material of sulfur-bearing is smaller at any time compared to nitrogenous material.
By the porous carbon material of preparation：Acetylene black：Adhesive according to（5-10:1:1）Mass ratio be well mixed, add it is molten
Agent is fully ground be adjusted to homogeneous paste after be coated uniformly on PP barrier films side, the 60-100 in vacuum drying chamberoC is dried
10-12h.And battery pack dress is carried out, test lithium-sulfur cell high rate performance.Voltage window 1.7-2.8V, the test of discharge and recharge long circulating
Weight discharge current is 0.5C.
It can be seen from Fig. 1, the average pore size of the fish-bone base porous carbon obtained under 900 degree of high temperature cabonizations is 6.68nm, its
For the mixing of microporous carbon and mesoporous carbon, so as to effectively limit in lithium-sulfur cell, the shuttle effect of polysulfide.And its is miscellaneous
Atom N, O, S can increase carbon material and obtain electric conductivity and the suction-operated to polysulfide because its strong electronegativity, so as to
This fish-bone base porous carbon can further be improved to intermediate product-polysulfide in lithium-sulfur cell charge and discharge process
Suction-operated, and the intermediate product of absorption is recycled.Therefore as can be seen from Figure 2, using this fish-bone base porous carbon materials as
When coating membrane surface, the charging and discharging capabilities of its battery assembled are significantly improved, under 1C current density, circulation 500
Circle later stage specific discharge capacity still can maintain 700 mAh g-1, the special capacity fade amount only 0.08% often enclosed, largely
On improve the stable charge/discharge of lithium-sulfur cell, have important meaning using production to lithium-sulfur cell.
It will be recognized by those skilled in the art, can be to above-mentioned on the premise of without departing from protection scope of the present invention
Embodiment carries out various modifications, change and combination, and thinks that this modification, change and combination are the models in originality thought
Within enclosing.
Claims (9)
1. a kind of bio-based oxygen, sulphur, nitrogen co-doped porous carbon, it is characterised in that using aquatic skin or bone as oxygen, sulphur, nitrogen
The raw material of codope porous carbon, the bio-based oxygen obtained afterwards by activation, sulphur, the specific surface area of nitrogen co-doped porous carbon are
1144.63~1517.03 m2 g-1, itrogen content of getter with nitrogen doped can reach 5.9%, mixes sulfur content and can reach 2%.
2. bio-based oxygen according to claim 1, sulphur, the preparation method of nitrogen co-doped porous carbon, it is characterised in that use
Animal Skin and bone are as presoma, using potassium hydroxide as activator, by be carbonized in advance, be carbonized, wash carbon and drying the step of.
3. preparation method according to claim 2, it is characterised in that comprise the following steps：
（1）The pre- carbonization treatment of low temperature：Aquatic skin or bone are cleaned, dried, and carry out low temperature and be carbonized in advance；
（2）High-temperature activation processing：Aquatic skin after pre- carbonization or bone are uniformly mixed with activator, and carry out high-temperature activation
Carbonization, obtains bio-based carbonized powder；
（3）Stripper plate step：After bio-based carbonized powder is placed in acid solution into immersion repeatedly, filtering is crossed repeatedly with deionized water
Wash, by being dried to obtain the sulfur and nitrogen co-doped porous carbon of bio-based oxygen.
4. preparation method according to claim 3, it is characterised in that step（1）It is middle fully to wash aquatic skin or bone
Wash after draining, be warming up to 30-100 DEG C of dry 5-24h, aquatic skin after drying or bone meal are then broken to powder, are placed in horse
Not in stove, under inert gas shielding, it is heated to 200-400 DEG C and is carbonized in advance, carbonization time is 1-6 hours, and preferably 2-5 is small
When.
5. preparation method according to claim 3, it is characterised in that step（2）In aquatic skin after pre- carbonization or
The part by weight 1 of bone and activator:0.1-5, preferably 1:0.5-3, adjusting furnace temperature are 500-1000 DEG C, preferable temperature 600-900
DEG C, carbonization time is preset as 0.5-5 hours, and the preferably time is 1-3 hours；Described activator is preferably KOH.
6. preparation method according to claim 3, it is characterised in that step（3）Described in acid solution be HCl, HNO3、
H2SO4In one or more, sour concentration is 0.2-5mol/L, and washing times are 1-10 times；It is subsequently placed at 30-100oC baking ovens
Middle drying, drying time 5-24h.
7. a kind of lithium-sulfur cell barrier film coating material, it is characterised in that be made by the following method：By described in claim 2-6
Preparation method the bio-based oxygen, sulphur, the nitrogen co-doped porous carbon that are prepared：Acetylene black：Adhesive according to（5-10:1:1）'s
Mass ratio is well mixed, add solvent be fully ground be adjusted to homogeneous paste after be coated uniformly on PP barrier films side, in vacuum
60-100 in drying boxoC dries 10-12h.
8. lithium-sulfur cell barrier film coating material according to claim 7, it is characterised in that described adhesive be PVDF,
PVA, PTFE one or several kinds, the solvent are 1-METHYLPYRROLIDONE.
9. lithium-sulfur cell barrier film coating material according to claim 7, it is characterised in that described adhesive is LA132,
The solvent is deionized water, and the mass ratio by the use of a certain amount of isopropanol as dispersant, wherein deionized water and isopropanol
For（5-10）：1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710841180.XA CN107497397A (en) | 2017-09-18 | 2017-09-18 | A kind of bio-based oxygen, sulphur, the preparation method and applications of nitrogen co-doped porous carbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710841180.XA CN107497397A (en) | 2017-09-18 | 2017-09-18 | A kind of bio-based oxygen, sulphur, the preparation method and applications of nitrogen co-doped porous carbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107497397A true CN107497397A (en) | 2017-12-22 |
Family
ID=60697507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710841180.XA Pending CN107497397A (en) | 2017-09-18 | 2017-09-18 | A kind of bio-based oxygen, sulphur, the preparation method and applications of nitrogen co-doped porous carbon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107497397A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108940191A (en) * | 2018-06-05 | 2018-12-07 | 西北农林科技大学 | A kind of sulphur N doping multiporous biological charcoal, preparation method and application |
| CN109065800A (en) * | 2018-07-03 | 2018-12-21 | 华南师范大学 | A kind of preparation method of metal organic frame carbon nano tube compound material |
| 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 |
| CN110538635A (en) * | 2019-08-30 | 2019-12-06 | 江苏正业智造技术有限公司 | nitrogen-sulfur co-doped porous magnetic carbon material and adsorbent prepared from same |
| CN112647091A (en) * | 2020-12-09 | 2021-04-13 | 中国科学院广州能源研究所 | N/P/Ca in-situ doped biochar and application thereof in electrolysis of water for hydrogen evolution |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993068A (en) * | 2010-10-27 | 2011-03-30 | 北京化工大学 | Preparation method of porous structured active carbon |
| CN102107863A (en) * | 2009-12-25 | 2011-06-29 | 北京化工大学 | Porous carbon material and preparation method thereof |
| CN103420353A (en) * | 2012-05-15 | 2013-12-04 | 北京化工大学 | Porous carbon material and preparation method and application thereof |
| CN104923159A (en) * | 2015-06-15 | 2015-09-23 | 武汉理工大学 | Fish bone charcoal adsorbent and preparation method and application thereof |
| CN105261721A (en) * | 2015-08-28 | 2016-01-20 | 清华大学 | Asymmetric diaphragm and application thereof in lithium-sulfur rechargeable battery |
-
2017
- 2017-09-18 CN CN201710841180.XA patent/CN107497397A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107863A (en) * | 2009-12-25 | 2011-06-29 | 北京化工大学 | Porous carbon material and preparation method thereof |
| CN101993068A (en) * | 2010-10-27 | 2011-03-30 | 北京化工大学 | Preparation method of porous structured active carbon |
| CN103420353A (en) * | 2012-05-15 | 2013-12-04 | 北京化工大学 | Porous carbon material and preparation method and application thereof |
| CN104923159A (en) * | 2015-06-15 | 2015-09-23 | 武汉理工大学 | Fish bone charcoal adsorbent and preparation method and application thereof |
| CN105261721A (en) * | 2015-08-28 | 2016-01-20 | 清华大学 | Asymmetric diaphragm and application thereof in lithium-sulfur rechargeable battery |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108940191A (en) * | 2018-06-05 | 2018-12-07 | 西北农林科技大学 | A kind of sulphur N doping multiporous biological charcoal, preparation method and application |
| CN108940191B (en) * | 2018-06-05 | 2021-05-11 | 西北农林科技大学 | Sulfur-nitrogen doped porous biochar, and preparation method and application thereof |
| CN109065800A (en) * | 2018-07-03 | 2018-12-21 | 华南师范大学 | A kind of preparation method of metal organic frame carbon nano tube compound material |
| WO2020006788A1 (en) * | 2018-07-03 | 2020-01-09 | 华南师范大学 | Method for preparing composite material of metal-organic frameworks and carbon nanotubes |
| 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 |
| CN110538635A (en) * | 2019-08-30 | 2019-12-06 | 江苏正业智造技术有限公司 | nitrogen-sulfur co-doped porous magnetic carbon material and adsorbent prepared from same |
| CN112647091A (en) * | 2020-12-09 | 2021-04-13 | 中国科学院广州能源研究所 | N/P/Ca in-situ doped biochar and application thereof in electrolysis of water for hydrogen evolution |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107497397A (en) | A kind of bio-based oxygen, sulphur, the preparation method and applications of nitrogen co-doped porous carbon | |
| CN107887602A (en) | A kind of classifying porous charcoal nanometer sheet electrode material of nitrogen oxygen codope and its preparation method and application | |
| CN108529587A (en) | A kind of preparation method and applications of the biomass graded hole Carbon Materials of phosphorus doping | |
| CN107342405B (en) | A kind of MoS2-xOx/ carbon negative pole material and preparation method thereof | |
| CN109231204A (en) | A kind of method of biomass substep activation preparation porous charcoal | |
| CN113036099B (en) | Biomass-based graphitized carbon/Fe7S8Method for preparing composite material | |
| CN108217630A (en) | A kind of preparation method and application of the Prussian blue material of composite reduction graphene oxide | |
| CN107331525A (en) | A kind of porous charcoal nanometer sheet electrode material of polyatom codope and its preparation method and application | |
| KR20210149781A (en) | Methods and uses for the preparation of light-carbon-containing materials | |
| CN108987733B (en) | Preparation method of active porous carbon @ FeS of lithium ion battery cathode material | |
| CN108962615B (en) | A kind of preparation method of the stratification porous structure carbon material for supercapacitor | |
| CN103887488A (en) | Preparation method of peach-kernel-shaped SnO2-graphene-carbon composite material for lithium ion battery | |
| CN112563586A (en) | Method for improving performance of zinc-iodine battery based on halogen bond effect | |
| CN110620226A (en) | Preparation method of nitrogen and boron co-doped carbon fiber loaded molybdenum selenide electrode material | |
| CN112117444A (en) | Carbon-coated cobalt sulfide positive electrode material, preparation method, positive electrode and aluminum ion battery | |
| CN106848250A (en) | A kind of carbon sulfur materials of high sulfur content and preparation method thereof | |
| CN106025216A (en) | Positive electrode material for lithium-sulfur battery, preparation method of positive electrode material and lithium-sulfur battery | |
| CN114180573B (en) | Biomass-derived porous carbon electrode and preparation method and application thereof | |
| CN107681092B (en) | A kind of porous Carbon composites of nanometer hydroxyapatite and the preparation method and application thereof | |
| CN107732209B (en) | Method for preparing lithium ion carbon negative electrode material from mixed bacteria residue waste | |
| CN109704332A (en) | A kind of porous active carbon and its preparation method and application by the preparation of single carbon source one-step method | |
| CN109585181A (en) | The preparation method of storage lithium nitrating porous carbon positive electrode based on brown alga egg-box structure | |
| CN110416514A (en) | A kind of preparation method of the derivative carbide negative electrode material of humic acids | |
| CN106602065A (en) | Preparation method of self-assembled three-dimensional charcoal sodium-ion battery anode carbon material | |
| CN104600260A (en) | C/Ni/S composite material prepared from absorbent cotton and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171222 |
|
| RJ01 | Rejection of invention patent application after publication |