CN102942172B - Raw material composition capable of being used for preparing mesocarbon microbeads (MCMB), preparation method thereof and preparation method of MCMB anode material - Google Patents
Raw material composition capable of being used for preparing mesocarbon microbeads (MCMB), preparation method thereof and preparation method of MCMB anode material Download PDFInfo
- Publication number
- CN102942172B CN102942172B CN201210476541.2A CN201210476541A CN102942172B CN 102942172 B CN102942172 B CN 102942172B CN 201210476541 A CN201210476541 A CN 201210476541A CN 102942172 B CN102942172 B CN 102942172B
- Authority
- CN
- China
- Prior art keywords
- coal tar
- hexane
- mcmb
- tar asphalt
- preparation
- 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.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a raw material composition capable of being used for preparing MCMB. The composition is a suspension formed by coal tar pitch extracts after dispersed on dimethicone, and the coal tar pitch extracts are insoluble substances obtained by coal tar pitch powder after dissolution and impurity removal by n-hexane or toluene. The preparation method of the raw material composition includes filling the coal tar pitch powder into a Soxhlet extractor, performing repeated extracting, dissolving and impurity removing to obtain the insoluble substances through n-hexane or toluene; and then drying and grinding, and subjecting the substances to ultrasonic dispersion on the dimethicone. The method for preparing the MCMB anode material through the raw material composition includes heating the raw material composition to subject the material to a thermal condensation reaction to form micron-sized spherulite; and then subjecting the solid-liquid mixed phase after the thermal condensation to centrifugation, n-hexane extraction, repeated scrubbing and drying sequentially to obtain the MCMB anode material. The material and the methods are simple in process steps, low in cost and capable of being used for preparing high-quality MCMB.
Description
Technical field
The invention belongs to macromolecular compound preparing technical field, particularly raw materials and the preparation technology of MCMB for cathode of lithium battery.
Background technology
MCMB (Mesocarbon Microbeads, abbreviation MCMB) structural expression is that condensed-nuclei aromatics molecule lamella is piled up the liquid crystal spheroid forming, being applicable to very much lithium ion embeds and deviates from, thereby the lithium storage content of MCMB is much larger than the theoretical capacity of graphite, is considered to a kind of extremely potential lithium secondary battery cathode material.
At present, the industrial production of MCMB adopts direct heat condensation methods mostly.Although this method technique is simple, because feed coal pitch is the multi-phase materials that comprise 5000 kinds of above aromatic compounds, each component on MCMB forming core, grow up, melt and etc. process to affect rule very complicated, directly cause thus obtained microsphere broad particle distribution.In addition, the heat treatment temperature of direct heat condensation methods is higher than 400 ℃, and light component and the thermal decomposition product volatilization meeting of following course of reaction to occur cause severe contamination to environment.
The emulsion method of development in recent years is that pitch thermal polycondensation or the crosslinked product of aromatic hydrocarbon molecule are dispersed in immiscible heat-conducting medium, utilize emulsification balling-up, pertinent literature comprises: the < < emulsion method that Li Fuhu etc. deliver is prepared the research > > of MCMB, a < < method > > (referring to CN101555008 Chinese patent literature) who prepares the controlled monodisperse carbon microsphere of form of Xu Qun etc. etc.Emulsion method can be controlled shape and the particle diameter of microballoon preferably, but complex process is loaded down with trivial details, and product separation relates to breakdown of emulsion process, has reduced to a certain extent the productive rate of microballoon.
The specification requirements such as lithium ion battery negative lithium storage content is large in order to adapt to, conductance is high, good cycling stability, are necessary existing preparation technology to be further improved.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provide that a kind of composition is simple, preparation easily, be conducive to the feedstock composition that MCMB is prepared in pyrolysis, the preparation method of this feedstock composition that also provide that a kind of technique is simple, easy to operate, product can be used for preparing high-quality MCMB, the preparation method of the MCMB negative material of provide in addition that a kind of processing step is simple, cost is low, excellent product performance, product structure are controlled.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of feedstock composition that MCMB is prepared in pyrolysis that can be used for, described feedstock composition is that coal tar asphalt extract is scattered in the suspension forming after dimethicone, and the quality of described dimethicone is 3～5 times of coal tar asphalt extract quality; Described coal tar asphalt extract is that coal tar asphalt powder dissolves through n-hexane or toluene the insoluble matter obtaining after removal of impurities.
As a total technical conceive, the present invention also provides a kind of method of preparing above-mentioned raw materials composition, comprises the following steps:
First coal tar asphalt powder is packed in apparatus,Soxhlet's, by utilizing evaporation, the backflow in apparatus,Soxhlet's of n-hexane or toluene, cyclic washing coal tar asphalt powder obtains insoluble matter after n-hexane or toluene extracting repeatedly, dissolving, removal of impurities; Insoluble matter is dried, pulverized, then in the ultrasonic dimethicone that is scattered in 3～5 times of its quality, make suspension, obtain feedstock composition.
As a total technical conceive, the present invention also provides a kind of above-mentioned feedstock composition to prepare the method for MCMB negative material, comprises the following steps:
(1) thermal polycondensation: described feedstock composition is heated to 350 ℃～400 ℃ and makes it that thermal polycondensation reaction formation micron order spherocrystal occur; Stir speed (S.S.) during thermal polycondensation reaction is preferably controlled at 500 rmin
-1～700 rmin
-1, the reaction time is preferably controlled at 2h～5h;
(2) purify: the solid-liquid mixing dependent data obtaining after thermal polycondensation is inferior after centrifugation, n-hexane extracting, cyclic washing, oven dry, obtain MCMB negative material.
In above-mentioned preparation method, preferred, described centrifugation specifically refers to that thermal polycondensation is reacted to cooled solid-liquid mixing to be moved in centrifuge tube mutually, with 2800 rmin
-1～3500 rmin
-1rotating speed centrifugation go out the solid content of solid-liquid in mixing mutually.
In above-mentioned preparation method, preferably, described n-hexane extracting specifically refers to the solid content after described centrifugation is moved in apparatus,Soxhlet's, by utilizing evaporation, the backflow of n-hexane in apparatus,Soxhlet's, cyclic washing solid content, and isolate insoluble product.
In above-mentioned preparation method, preferred, described cyclic washing refers to the insoluble product after the extracting of acetone washing n-hexane 2～3 times, then filters.
Compared with prior art, it is raw material that the present invention adopts the n-hexane insoluble matter of coal tar asphalt, by suspension pyrolysismethod, prepare MCMB negative material, the raw materials that the present invention adopts and preparation technology are keeping, on the basis of the advantages such as existing production craft step is simple, low cost of manufacture, also having the advantage of following uniqueness:
(1) by utilizing n-hexane solvent segregation to remove the part light component in coal tar asphalt, this is conducive to reduce C-C key homolysis in follow-up pyrolytic process and forms the required activation energy of free radical, and then is conducive to reduce the formation temperature of middle phase product; Because reaction temperature is little, energy consumption and process costs be corresponding reducing all;
(2) by utilizing n-hexane solvent to carry out preliminary treatment to coal tar asphalt, make the n-hexane insoluble matter after processing contain more a high proportion of condensed-nuclei aromatics compound and macromolecular substances than coal tar asphalt, this just can significantly improve the carbon content of MCMB negative material, makes that product purity is higher, carbon content is larger, conductivity is better;
Therefore (3) density due to n-hexane insoluble matter of the present invention and dimethicone is more or less the same, and can make finely dispersed suspension (being feedstock composition of the present invention) for pyrolysis, is conducive to reaction system homogenization, makes product granularity more even;
(4) the dimethicone Heat stability is good adopting in feedstock composition of the present invention, can in wider temperature range, operate, be conducive to regulate and control the growth behavior of microballoon, can need to regulate and control shape (making the spherical rule of product), microstructure and the granularity of microballoon product according to storage lithium;
(5) pollution of the light components that is conducive to avoid coal tar asphalt generation when directly carrying out pyrolysis to environment.
Above feature of the present invention, to developing low cost, polluting few MCMB manufacturing technology, improves lithium cell cathode material performance by significant.
Accompanying drawing explanation
Fig. 1 is the preparation method's of MCMB of the present invention process chart.
Fig. 2 is the microscopic appearance photo of the MCMB of preparation in the embodiment of the present invention 1.
Embodiment
Below in conjunction with Figure of description, the invention will be further described with concrete preferred embodiment, but protection range not thereby limiting the invention.
embodiment 1:
Can be used for pyrolysis and prepare a feedstock composition for MCMB, this feedstock composition is that coal tar asphalt extract is scattered in the suspension forming after dimethicone, and the quality of dimethicone is 3 times of coal tar asphalt extract quality; Coal tar asphalt extract is the insoluble matter that coal tar asphalt powder obtains after n-hexane dissolution removal of impurities.
The above-mentioned feedstock composition of the present embodiment mainly adopts following steps to prepare (process chart is referring to Fig. 1):
(1) get high temperature coal-tar pitch and grind to form coal tar asphalt powder, cross 250 mesh sieves;
(2) above-mentioned coal tar asphalt powder is packed in apparatus,Soxhlet's, then take n-hexane as organic solvent, utilize apparatus,Soxhlet's extracting n-hexane insoluble matter from coal tar pitch powder, specific operation process is as follows: get appropriate normal hexane and inject extraction flask, coal tar asphalt powder after grinding is sieved is with putting into extraction tube after fat-free filter paper parcel, then extraction tube is fixed on to extraction flask upper end, then extraction tube is connected with condenser, open cooling water; Adopt the n-hexane in electric jacket heating extraction flask, the n-hexane of gasification is risen and is entered condenser by tube connector, and the liquid that congeals into splashes in extraction tube, the soluble substance in lixiviate coal tar asphalt powder; When n-hexane liquid level reach a certain height in pipe to be extracted, through siphon pipe, flow into extraction flask; So move in circles, until extracting is complete;
(3) take out the insoluble matter in above-mentioned apparatus,Soxhlet's, dry 5h in 75 ℃ of baking ovens, fully grinds the n-hexane insoluble matter after drying, and crosses 250 mesh sieves; Then by the ultrasonic dimethicone that is scattered in 3 times of its quality of insoluble matter powder, form the feedstock composition of form of suspension.
A kind of feedstock composition with the present embodiment is prepared the method (process chart is referring to Fig. 1) of MCMB negative material, specifically comprises the following steps:
(1) thermal polycondensation: the above-mentioned feedstock composition making (being suspension) is poured in reactor; after sealing; open cooling water pipe and high pure nitrogen (protective gas), be then heated to 380 ℃ and make it that thermal polycondensation reaction occur, stir speed (S.S.) is controlled at 600 rmin
-1, isothermal reaction 3h, forms micron order spherocrystal, then naturally cools to room temperature;
(2) centrifugation: the solid-liquid obtaining after above-mentioned thermal polycondensation is mixed and moved into mutually in centrifuge tube, with 3500 rmin
-1rotating speed centrifugation go out solid content;
(3) n-hexane extracting: the solid content after centrifugation is moved in apparatus,Soxhlet's, by utilizing evaporation, the backflow of n-hexane in apparatus,Soxhlet's, cyclic washing solid content, residual soluble substances such as silicone oil in lixiviate solid content, and isolate insoluble product (method of operation of apparatus,Soxhlet's is the same);
(4) the insoluble product after the above-mentioned n-hexane extracting of use acetone cyclic washing is 2～3 times, then filters, and the solid product after filtration is dry 10h in 75 ℃ of baking ovens, obtains MCMB powder as shown in Figure 2.
embodiment 2:
Can be used for pyrolysis and prepare a feedstock composition for MCMB, this feedstock composition is that coal tar asphalt extract is scattered in the suspension forming after dimethicone, and the quality of dimethicone is 3 times of coal tar asphalt extract quality; Coal tar asphalt extract is the insoluble matter that coal tar asphalt powder obtains after toluene dissolves removal of impurities.
The above-mentioned feedstock composition of the present embodiment mainly adopts following steps to prepare (technological process and Fig. 1 are similar):
(1) get medium temperature coal tar pitch and grind to form coal tar asphalt powder, cross 300 mesh sieves;
(2) above-mentioned coal tar asphalt powder is packed in apparatus,Soxhlet's, then take toluene as organic solvent, utilize therefrom extracting toluene insolubles in warm pitch powder of apparatus,Soxhlet's, specific operation process is as follows: get appropriate toluene and inject extraction flask, coal tar asphalt powder after grinding is sieved is with putting into extraction tube after fat-free filter paper parcel, then extraction tube is fixed on to extraction flask upper end, then extraction tube is connected with condenser, open cooling water; Adopt the toluene in electric jacket heating extraction flask, the toluene of gasification is risen and is entered condenser by tube connector, and the liquid that congeals into splashes in extraction tube, the soluble substance in lixiviate coal tar asphalt powder; When toluene liquid level reach a certain height in pipe to be extracted, through siphon pipe, flow into extraction flask; So move in circles, until extracting is complete;
(3) take out the insoluble matter in above-mentioned apparatus,Soxhlet's, dry 5h in 70 ℃ of baking ovens, fully grinds the toluene insolubles after drying, and crosses 300 mesh sieves; Then by the ultrasonic dimethicone that is scattered in 3 times of its quality of insoluble matter powder, form the feedstock composition of form of suspension.
A kind of feedstock composition with the present embodiment is prepared the method (technological process and Fig. 1 are similar) of MCMB negative material, specifically comprises the following steps:
(1) thermal polycondensation: the above-mentioned feedstock composition making (being suspension) is poured in reactor; after sealing; open cooling water pipe and high pure nitrogen (protective gas), be then heated to 360 ℃ and make it that thermal polycondensation reaction occur, stir speed (S.S.) is controlled at 660 rmin
-1, isothermal reaction 3h, forms micron order spherocrystal, then naturally cools to room temperature;
(2) centrifugation: the solid-liquid obtaining after above-mentioned thermal polycondensation is mixed and moved into mutually in centrifuge tube, with 3000 rmin
-1rotating speed centrifugation go out solid content;
(3) toluene extracting: the solid content after centrifugation is moved in apparatus,Soxhlet's, by utilizing evaporation, the backflow of toluene in apparatus,Soxhlet's, cyclic washing solid content, residual soluble substances such as silicone oil in lixiviate solid content, and isolate insoluble product (method of operation of apparatus,Soxhlet's is the same);
(4) the insoluble product after the above-mentioned toluene extracting of use acetone cyclic washing is 2～3 times, then filters, and the solid product after filtration is dry 10h in 70 ℃ of baking ovens, obtains MCMB powder.
Claims (5)
1. a method of preparing MCMB negative material, comprises the following steps:
(1) thermal polycondensation: feedstock composition is heated to 350 ℃～400 ℃ and makes it that thermal polycondensation reaction formation micron order spherocrystal occur;
(2) purify: the solid-liquid mixing dependent data obtaining after thermal polycondensation is inferior after centrifugation, n-hexane extracting, cyclic washing, oven dry, obtain MCMB negative material;
Described feedstock composition is that coal tar asphalt extract is scattered in the suspension forming after dimethicone, and the quality of described dimethicone is 3～5 times of coal tar asphalt extract quality; Described coal tar asphalt extract is the insoluble matter that coal tar asphalt powder obtains after n-hexane dissolution removal of impurities;
The preparation method of described feedstock composition, comprise the following steps: first coal tar asphalt powder is packed in apparatus,Soxhlet's, by utilizing evaporation, the backflow of n-hexane in apparatus,Soxhlet's, cyclic washing coal tar asphalt powder obtains insoluble matter after n-hexane extracting repeatedly, dissolving, removal of impurities; Insoluble matter is dried, pulverized, then in the ultrasonic dimethicone that is scattered in 3～5 times of its quality, make suspension, obtain feedstock composition.
2. method according to claim 1, is characterized in that: described centrifugation specifically refers to that thermal polycondensation is reacted to cooled solid-liquid mixing to be moved in centrifuge tube mutually, with 2800 rmin
-1～3500 rmin
-1rotating speed centrifugation go out the solid content of solid-liquid in mixing mutually.
3. method according to claim 1 and 2, it is characterized in that: described n-hexane extracting specifically refers to the solid content after described centrifugation is moved in apparatus,Soxhlet's, by utilizing evaporation, the backflow of n-hexane in apparatus,Soxhlet's, cyclic washing solid content, and isolate insoluble product.
4. method according to claim 1 and 2, is characterized in that: described cyclic washing refers to the insoluble product after the extracting of acetone washing n-hexane 2～3 times, then filters.
5. method according to claim 1 and 2, is characterized in that: stir speed (S.S.) during described thermal polycondensation reaction is controlled at 500 rmin
-1～700 rmin
-1, the reaction time is controlled as 2h～5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210476541.2A CN102942172B (en) | 2012-11-22 | 2012-11-22 | Raw material composition capable of being used for preparing mesocarbon microbeads (MCMB), preparation method thereof and preparation method of MCMB anode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210476541.2A CN102942172B (en) | 2012-11-22 | 2012-11-22 | Raw material composition capable of being used for preparing mesocarbon microbeads (MCMB), preparation method thereof and preparation method of MCMB anode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102942172A CN102942172A (en) | 2013-02-27 |
| CN102942172B true CN102942172B (en) | 2014-08-20 |
Family
ID=47725196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210476541.2A Active CN102942172B (en) | 2012-11-22 | 2012-11-22 | Raw material composition capable of being used for preparing mesocarbon microbeads (MCMB), preparation method thereof and preparation method of MCMB anode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102942172B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193107B (en) * | 2014-09-16 | 2016-02-03 | 王茜茜 | A kind for the treatment of process of tar and waste water |
| CN109319758B (en) * | 2018-10-10 | 2020-09-22 | 中钢集团鞍山热能研究院有限公司 | Co-production process method of mesocarbon microbeads and negative electrode material coke |
| CN109319763A (en) * | 2018-11-26 | 2019-02-12 | 内蒙古晟源科技有限公司 | A method of mesocarbon microspheres is prepared by coal tar slurry bed hydroprocessing tailings |
| CN110931747B (en) * | 2019-12-05 | 2021-05-28 | 郑州中科新兴产业技术研究院 | Core-shell structure silicon/mesocarbon microbead composite anode material and preparation method thereof |
| CN115744868A (en) * | 2022-10-09 | 2023-03-07 | 江西浩然智能科技有限公司 | High-capacity lithium battery negative electrode material and preparation method thereof |
| CN115893372A (en) * | 2023-01-03 | 2023-04-04 | 中国石油大学(华东) | Method for preparing carbon microspheres from pitch depolymerized by supercritical methanol and application of carbon microspheres |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508903A (en) * | 2009-03-20 | 2009-08-19 | 上海宝钢化工有限公司 | Process for continuously removing quinoline insoluble substances in coal tar pitch |
| CN101811691A (en) * | 2010-04-23 | 2010-08-25 | 上海应用技术学院 | Preparation method of mesocarbon microbead |
| CN101920956A (en) * | 2010-09-15 | 2010-12-22 | 福州大学 | Method for highly-efficiently preparing asphalt-based mesocarbon microbeads |
| CN102225755A (en) * | 2011-05-26 | 2011-10-26 | 淄博矿业集团有限责任公司 | Preparation method of mesophase carbon microspheres from coal liquefaction residues |
-
2012
- 2012-11-22 CN CN201210476541.2A patent/CN102942172B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508903A (en) * | 2009-03-20 | 2009-08-19 | 上海宝钢化工有限公司 | Process for continuously removing quinoline insoluble substances in coal tar pitch |
| CN101811691A (en) * | 2010-04-23 | 2010-08-25 | 上海应用技术学院 | Preparation method of mesocarbon microbead |
| CN101920956A (en) * | 2010-09-15 | 2010-12-22 | 福州大学 | Method for highly-efficiently preparing asphalt-based mesocarbon microbeads |
| CN102225755A (en) * | 2011-05-26 | 2011-10-26 | 淄博矿业集团有限责任公司 | Preparation method of mesophase carbon microspheres from coal liquefaction residues |
Non-Patent Citations (2)
| Title |
|---|
| 硅油/煤沥青乳液制备中间相炭微球;程有亮 等;《材料工程》;20101231(第3期);57页第1栏第5行至倒数第9行,57页第1栏倒数第7行至58页第2栏第2行 * |
| 程有亮 等.硅油/煤沥青乳液制备中间相炭微球.《材料工程》.2010,(第3期), |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102942172A (en) | 2013-02-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102942172B (en) | Raw material composition capable of being used for preparing mesocarbon microbeads (MCMB), preparation method thereof and preparation method of MCMB anode material | |
| CN102225755B (en) | Preparation method of mesophase carbon microspheres from coal liquefaction residues | |
| CN103194254A (en) | Intermediate phase asphalt and preparation method thereof | |
| CN107579249B (en) | Hard carbon negative electrode material prepared from traditional Chinese medicine residues and preparation method thereof | |
| CN102399565B (en) | Method for extracting heavy liquefied oil from residue of coal direct liquefaction, extracted heavy liquefied oil, and application thereof | |
| CN104108697A (en) | Preparation method for mesocarbon microbead | |
| CN102399566B (en) | Method for extracting heavy liquefied oil and kerite substance from residue of direct coal liquefaction | |
| CN105329892B (en) | Method for producing capacitive carbon from rice husks | |
| CN101811691A (en) | Preparation method of mesocarbon microbead | |
| CN102653397A (en) | Preparation method of coal tar-based mesocarbon microbead | |
| CN103359702A (en) | Preparation method of mesophase carbon microspheres with different particle sizes | |
| CN103579624A (en) | Modified graphite crucible waste negative electrode material for lithium battery, and preparation method and application of modified graphite crucible waste negative electrode material | |
| CN107934934A (en) | A kind of method for efficiently preparing asphalt base mesocarbon microspheres | |
| CN1100093C (en) | Prepn. method of mesophase asphalt carbon microsphere | |
| CN102225756A (en) | Method for preparing asphalt mesocarbon microbeads and application in lithium battery cathode material thereof | |
| CN104485458A (en) | Method for preparing graphite spheres | |
| CN106159235A (en) | A kind of preparation method of graphite negative material of lithium ion battery | |
| CN102104141B (en) | Method for preparing graphite anode material of membrane-structural lithium ion battery by hot coating method | |
| CN106635102B (en) | Process for producing negative electrode material coke by using supercritical extraction oil slurry as raw material and application thereof | |
| CN1308113A (en) | Copolycondensation preparation of intermediate phase carbon microsphere | |
| JP2012172076A (en) | Coal upgrading system, dewatering system of carbon-containing substance, and solvent circulation system for upgrading of carbon-containing substance | |
| CN111825086A (en) | Graphene preparation method | |
| CN105645379A (en) | Asphalt hard carbon material, and preparation method and application thereof | |
| CN102633245A (en) | Control method of intermediate phase carbon microball D50 and device for producing intermediate phase carbon microball | |
| CN109179367A (en) | A kind of thermal polycondensation process prepares the method and system of carbonaceous mesophase spherules |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |