CN108923050A - A kind of carbon nano-structured elctro-catalyst of the nucleocapsid of high catalytic performance and preparation method thereof - Google Patents
A kind of carbon nano-structured elctro-catalyst of the nucleocapsid of high catalytic performance and preparation method thereof Download PDFInfo
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- CN108923050A CN108923050A CN201810724471.5A CN201810724471A CN108923050A CN 108923050 A CN108923050 A CN 108923050A CN 201810724471 A CN201810724471 A CN 201810724471A CN 108923050 A CN108923050 A CN 108923050A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
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- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses carbon nano-structured elctro-catalysts of the nucleocapsid of a kind of high catalytic performance and preparation method thereof.It is core using the case type poly- FePC of marginal texture as shell, conductive carbon, the Fe-N of FePC unit4Division center is its active site.Preparation method is：1) conductive carbon is added in the mixed solution of pyromellitic acid anhydride and phthalic anhydride, dry powders A；2) powders A is uniformly mixed into obtain powder B with iron compound, ammonium molybdate, urea, being heated to powder B is molten liquid, and microwave reaction brings it about home position polymerization reaction, and washing is dried to obtain the carbon nano-structured elctro-catalyst of nucleocapsid of high catalytic performance.Novel nucleocapsid C catalyst of the invention has the high oxygen reduction catalytic activity, excellent cycling stability and excellent CH for being substantially better than business Pt/C catalyst3OH/CO tolerance；It is market ripe that catalyst synthesis is raw materials used, low in cost, and preparation process is simple and easy, is suitble to commercialization large-scale production.
Description
Technical field
The invention belongs to fuel cell field, be related to a kind of carbon nano-structured elctro-catalyst of fuel battery negative pole nucleocapsid and
Preparation method.
Background technique
Energy crisis and environmental degradation are the main problem that mankind nowadays social development faces.Fuel cell has fuel hydrogen
It is resourceful, specific energy is high, discharge it is pollution-free the features such as, quilt is it is believed that be the main power source device for solving the problems, such as future source of energy
One of.For many years, the key point for restricting fuel cell scale is exactly its sky high cost.It is exciting, recent day
Originally breaking through again for fuel cell technology is realized, cost declines to a great extent, and 2014 end of the year Toyota Company release Mirai fuel cell
Automobile volume production listing plan universal has welcome a new development epoch for the business of fuel cell.
Nevertheless, the limited resources and the slow dynamic process of oxygen electrode etc. of precious metals pt, are still fuel electricity
The commercialized difficult point in pond and challenge.Therefore, low cost and high performance low Pt catalyst even completely new non-precious metal catalyst
Breakthrough to be achieved is designed and developed.A large number of studies show that Fe-NxThe catalytic performance of doping C catalyst has been shown greatly
For Pt potentiality, Fe-N4Structure is strongly active center.Based on this, we, which choose, has clear Fe-N4The phthalocyanine iron compound of structure,
The FePC@carbon black nucleocapsid C catalyst (CN201310218713.0) of high catalytic performance is designed and developed.But in subsequent work
Find that the battery performance of assembling is unable to get preferable performance in journey application study, the problem of stable circulation performance difference greatly restricts
Its industrialization process, this is also exactly the key problem in technology that such catalyst is urgently broken through.
Summary of the invention
In view of the above problems and insufficient, the present invention is by forming a stable structure, edge in conductive carbon surface aggregate
The poly- FePC shell of group closure, constructs the carbon nano-structured elctro-catalyst of c-pFePc@CB nucleocapsid, to improve C catalyst
The latent active of stable circulation performance, enhancing active site and C catalyst promotes fuel battery performance.
The present invention can be achieved through the following technical solutions：
A kind of preparation method of the carbon nano-structured elctro-catalyst of the nucleocapsid of high catalytic performance, includes the following steps：
1) pyromellitic acid anhydride and phthalic anhydride are dissolved in a solvent, conductive carbon is added, ultrasonic disperse obtains
Even mixed suspension, dry powders A；
2) powders A is uniformly mixed into obtain powder B with iron compound, ammonium molybdate, urea, heating powder B is molten liquid, will be melted
Melt liquid and be transferred in microwave reactor and bring it about home position polymerization reaction, polymerization forms a marginal texture envelope around conductive carbon
The poly- FePC shell of closed form, washing are dried to obtain the carbon nano-structured elctro-catalyst of nucleocapsid.
Preferably, in step 1), the solvent is ethyl alcohol, in acetone, dimethyl sulfoxide, dimethylformamide, water
One or more of mixtures.
Preferably, in step 1), the conductive carbon is that specific surface area is greater than 200m2The spherical, linear of/g, sheet or block
One or more of shape carbon material.
Preferably, the spherical carbon material includes one in EC600JD, EC300J, Vulcan XC72, BP2000 etc.
Kind or more, the linear carbon material includes one of carbon nanotube, carbon fiber, carbon nano rod etc. or more, institute
The sheet block shape carbon material stated includes one of such as graphene, nanobelt, active carbon or more.
Preferably, in step 2), the heating temperature is not less than 120 DEG C, to obtain molten liquid.
Preferably, in step 2), the microwave power is not less than 100W, so that it is anti-that in-situ polymerization occurs in molten liquid
It answers.
Preferably, in step 2), iron ion is+divalent and/or+trivalent in the iron compound.
Preferably, described+divalent iron compound includes ferrous sulfate, iron ammonium sulfate, frerrous chloride, ferrous nitrate, grass
One of sour iron, FePC, ferrous oxide etc. or more, described+trivalent iron compound include ferric sulfate, ferric trichloride,
One of ferric nitrate, ferric acetate, ferric acetyl acetonade, ferriporphyrin, di-iron trioxide etc. or more.
Preferably, the pyromellitic acid anhydride and conductive carbon mass ratio are 0.01~1：1；The phthalic acid
Acid anhydride and conductive carbon mass ratio are 0.2~2：1；The iron compound and conductive carbon mass ratio is 0.2~1：1；The molybdic acid
Ammonium and conductive carbon mass ratio are 0.5~5：1；The urea and conductive carbon mass ratio is 0.2~10：1.
Preferably, the carbon nano-structured elctro-catalyst of the nucleocapsid being prepared can carry out the rear place such as pickling, secondary high-temperature, pore-creating
Reason, post-processing do not change the form of catalyst itself.
The present invention also provides a kind of carbon nano-structured elctro-catalyst of the nucleocapsid of high catalytic performance, shell be poly- FePC thin layer,
Core is conductive carbon, adopts and is prepared with the aforedescribed process.
Preferably, the mass ratio of the poly- phthalocyanine iron-clad and conductive carbon core is 0.1~10:1.
In this catalyst, shell is poly- FePC thin layer, and marginal texture is enclosed type, and core is conductive carbon.
In this catalyst, the Fe-N of poly- FePC4Structure is active site.
In catalyst produced by the present invention, the atomic percentage content of Fe is 0~2at%, but is not 0；Fe is mainly with+divalent
Form exists, and is coupled to Fe-N with N4Structure.The atomic percentage content of N is 0~16at%, but is not 0；N mainly with pyridine N,
The species such as pyrroles N exist.
Compared with prior art, the invention has the characteristics that：
1) the nucleocapsid carbon nano-structured elctro-catalyst constructed has highdensity Fe-N in shell4Active site, and completely
It is exposed to catalyst coating, greatly improves the utilization rate of active site.
2) control methods for passing through " edge group closure ", substantially increase the structural stability of poly- FePC.On the one hand,
Improve the stable circulation performance of C catalyst；On the other hand, the latent active of active site and C catalyst is enhanced.
3) the carbon nano-structured elctro-catalyst of nucleocapsid of the invention has high oxygen reduction catalytic activity, with commercialization
60wt%Pt/C catalyst activity is suitable, hence it is evident that is better than the 20wt%Pt/C catalyst performance of commercialization.
4) the carbon nano-structured elctro-catalyst of nucleocapsid of the invention, catalytic activity study the carbon-supported catalysts of report more at present
With significant advantage.
5) with catalyst assembling fuel cell of the invention, performance matches in excellence or beauty in 60wt%Pt/C catalyst, better than having reported
Carbon-supported catalysts.
Detailed description of the invention
The present invention will be further described with reference to the accompanying drawings, but the embodiment in attached drawing is not constituted to any limit of the invention
System.
Fig. 1 is the synthetic route chart for the poly- FePC of border seal type (c-pFePc@CB) that embodiment 1 is prepared；
Fig. 2 is transmission electron microscope (TEM) figure for the c-pFePc@CB C catalyst that embodiment 1 is prepared；
Fig. 3 is 20wt%Pt/C and the 60wt%Pt/C catalysis for the c-pFePc@CB C catalyst comparison business being prepared
Polarization curves of oxygen reduction of the agent in 0.1M KOH electrolyte；
Fig. 4 is that the c-pFePc@CB C catalyst that embodiment 1 is prepared passes through 0.02~1.22V (vs.RHE) potential model
Enclose the polarization curves of oxygen reduction of 1000 circle front and back of scanning；
Fig. 5 is the c-pFePc@CB that embodiment 1 is prepared and business 60wt%Pt/C respectively as fuel battery negative pole
The performance test curve of catalyst assembling monocell.
Specific embodiment
In order to better understand the present invention, the present invention will be further explained with reference to the examples below.
Embodiment 1
1) preparation of the carbon nano-structured elctro-catalyst of c-pFePc@CB core-shell structure copolymer
Pyromellitic acid anhydride and phthalic anhydride solid powder are weighed respectively, and are dissolved in acetone solvent,
The EC300J conductive carbon of certain mass is added, ultrasonic disperse obtains mixed uniformly suspension, dry precursor powder.Into one
Step, precursor powder is uniformly mixed with ferrous sulfate, ammonium molybdate, urea, and is heated as molten liquid, rapidly by molten liquid
It is transferred in microwave reactor and brings it about home position polymerization reaction, polymerization forms a marginal texture enclosed type around conductive carbon
Poly- FePC shell to get the carbon nano-structured elctro-catalyst of c-pFePc@CB core-shell structure copolymer.
Wherein pyromellitic acid anhydride and conductive carbon mass ratio are 0.01~1：1；Phthalic anhydride and conductive carbon quality
Than being 0.2~2：1；Iron compound and conductive carbon mass ratio are 0.2~1：1；Ammonium molybdate and conductive carbon mass ratio are 0.5~5：1；
Urea and conductive carbon mass ratio are 0.2~10：1.
The synthetic route of the poly- FePC of marginal texture enclosed type is as shown in Figure 1, prepare the carbon nano-structured elctro-catalyst of core-shell structure copolymer
TEM it is as shown in Figure 2.
2) the structure composition analysis of elctro-catalyst
The structure composition for preparing the carbon nano-structured elctro-catalyst of c-pFePc@CB core-shell structure copolymer is carried out in conjunction with a variety of characterization techniques
It analyses in depth：Test map shows that c-pFePc CB has shown double-peak feature identical with FePc, this result
Show that c-pFePc has and the consistent Fe-N of FePc4Structure.XPS is the results show that c-pFePc@CB catalyst surface Fe, N's contains
Amount is respectively 8.08at% and 0.93at%, theoretical ratio 8 of the two ratio very close to poly- phthalocyanine iron molecule：1, and N1s essence
For thin spectrum the result shows that the existence form of N element is pyridine N and pyrroles N, the two ratio is 2.97：1 very close phthalocyanine iron molecule
3 in unit：1.In addition, further compare the infrared spectrum curve of c-pFePc and FePc, characteristic peak both as the result is shown
Position is identical, but c-pFePc peak intensity significantly improves.
3) the electrochemical property test analysis of elctro-catalyst
The c-pFePc@CB C catalyst and business Pt/C catalyst for weighing certain mass respectively are dispersed in Nafion
Aqueous isopropanol in catalyst ink, the catalyst ink of drop coating certain volume is sufficiently dry in glassy carbon electrode surface, i.e.,
It can be prepared into working electrode.At room temperature, electrochemical property test is carried out using working electrode of the three-electrode system to preparation：Platinized platinum
For to electrode, mercury/mercury oxide is reference electrode, 0.1M KOH is electrolyte.
Oxygen reduction reaction test carries out in the electrolyte that oxygen is saturated, and electrode revolving speed is 1600rpm, electrical potential scan rate
For 5mV/s.The result shows that c-pFePc@CB shows the catalytic activity better than business Pt/C, polarization curve as shown in Figure 3 can
Know：When same catalyst carrying capacity, c-pFePc@CB half wave potential shuffles about 10mV compared with business 60wt%Pt/C, compared with business 20wt%
Pt/C shuffles about 50mV.
In addition, carrying out methanol tolerance performance test to the c-pFePc@CB C catalyst of preparation, electrolyte is addition 0.1M first
The 0.1M KOH solution of alcohol is other identical as oxygen reduction reaction test condition.The results show that polarization is bent before and after addition 0.1M methanol
Line essentially coincides i.e. c-pFePc@CB catalytic activity and does not decay, and illustrates that it has very excellent methanol tolerance performance.
Further, the stable circulation performance of c-pFePc@CB C catalyst is tested.The c-pFePc@CB work that will be prepared
In the 0.1M KOH electrolyte that electrode is placed in argon gas saturation, 0.02~1.22V (vs.RHE) full potential range scans, electricity are carried out
Gesture scanning speed is 50mV/s.After scan round 1000 is enclosed, it is placed in the 0.1M KOH electrolyte of oxygen saturation and carries out hydrogen reduction
Reaction test, test results are shown in figure 4, it can be seen that polarization curve is almost the same before and after 1000 circle scan rounds, illustrates c-
PFePc@CB C catalyst has excellent stable circulation performance, is not only better than commercially available Pt/C catalyst, relative to small molecule
FePC as shell structure catalyst (CN201310218713.0) stability also more preferably.
Next, respectively using c-pFePc@CB comparison business 60wt%Pt/C as cathod catalyst, with business 60wt%Pt-
Ru/C is that anode catalyst is assembled into fuel-cell single-cell, and test result shows that c-pFePc@CB and business 60wt%Pt/C has
There is substantially identical fuel battery performance, to be substantially better than urging using small molecule FePC as shell structure in this regard
Agent (CN201310218713.0) (as shown in Figure 5).
EC300J conductive carbon used in the present embodiment can be conductive by EC600JD, Vulcan XC72, BP2000 equal sphere
One of carbon or more and the linear carbon material such as nanotube, carbon fiber, carbon nano rod and graphene, nanobelt, activity
One of sheet blocks shape carbon material such as charcoal or more substitutes, and substitution does not influence the properties of gained catalyst.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should
Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention
And range.
Claims (10)
1. a kind of preparation method of the carbon nano-structured elctro-catalyst of the nucleocapsid of high catalytic performance, which is characterized in that including walking as follows
Suddenly：
1) pyromellitic acid anhydride and phthalic anhydride are dissolved in a solvent, conductive carbon is added, ultrasonic disperse, which obtains, uniformly to be mixed
The suspension of conjunction, dry powders A；
2) powders A is uniformly mixed into obtain powder B with iron compound, ammonium molybdate, urea, heating powder B is molten liquid, by molten liquid
It is transferred in microwave reactor and brings it about home position polymerization reaction, polymerization forms a marginal texture enclosed type around conductive carbon
Poly- FePC shell, washing be dried to obtain the carbon nano-structured elctro-catalyst of nucleocapsid.
2. preparation method according to claim 1, which is characterized in that in step 1), the solvent be ethyl alcohol, acetone,
One or more of dimethyl sulfoxide, dimethylformamide, water.
3. preparation method according to claim 1, which is characterized in that in step 1), the conductive carbon is specific surface area
Greater than 200m2One or more of the spherical, linear of/g, sheet or blocky carbon material.
4. preparation method according to claim 1, which is characterized in that in step 2), the heating temperature is not less than 120
DEG C, to obtain molten liquid.
5. preparation method according to claim 1, which is characterized in that in step 2), the microwave power is not less than
100W, so as to which home position polymerization reaction occurs in molten liquid.
6. preparation method according to claim 1, which is characterized in that in step 2), in the iron compound iron ion be+
Divalent and/or+trivalent.
7. preparation method according to claim 1, which is characterized in that the pyromellitic acid anhydride and conductive carbon quality
Than being 0.01~1：1；The phthalic anhydride and conductive carbon mass ratio is 0.2~2：1；The iron compound and conduction
Carbon mass ratio is 0.2~1：1；The ammonium molybdate and conductive carbon mass ratio is 0.5~5：1；The urea and conductive carbonaceous
Amount is than being 0.2~10：1.
8. a kind of carbon nano-structured elctro-catalyst of the nucleocapsid of high catalytic performance, which is characterized in that shell is the poly- phthalocyanine of border seal type
Iron layer, core are conductive carbon.
9. the carbon nano-structured elctro-catalyst of the nucleocapsid of high catalytic performance according to claim 8, which is characterized in that described
The mass ratio of poly- phthalocyanine iron-clad and conductive carbon core is 0.1~10:1.
10. the carbon nano-structured elctro-catalyst of the nucleocapsid of high catalytic performance according to claim 8, which is characterized in that use
The described in any item methods of claim 1~7 are prepared.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109273725A (en) * | 2018-08-17 | 2019-01-25 | 上海中聚佳华电池科技有限公司 | Poly- metal phthalocyanine composition, Its Preparation Method And Use |
| CN109387508A (en) * | 2018-11-18 | 2019-02-26 | 扬州大学 | A kind of preparation method of magnetic carbon tube-molybdenum disulfide nano enzyme and its method for detecting hydrogen peroxide, glucose |
| CN113484386A (en) * | 2021-05-21 | 2021-10-08 | 郑州轻工业大学 | Preparation method and application of metal poly-phthalocyanine nano material, aptamer sensor and preparation method of aptamer sensor |
| CN113816425A (en) * | 2021-09-16 | 2021-12-21 | 陕西科技大学 | MoS2Nitrogen-doped carbon/modified activated carbon sodium ion battery negative electrode material and preparation method thereof |
| CN114068965A (en) * | 2021-11-19 | 2022-02-18 | 陕西科技大学 | Transition metal phthalocyanine coated phthalocyanine blue/asphalt coke active carbon composite material lithium-thionyl chloride battery positive electrode catalyst and preparation method thereof |
| CN114427104A (en) * | 2021-12-13 | 2022-05-03 | 深圳先进技术研究院 | Copper phthalocyanine polymer @ copper nanowire core-shell nano material as well as preparation method and application thereof |
| CN114899436A (en) * | 2022-06-06 | 2022-08-12 | 山东能源集团有限公司 | Phthalocyanine-like polymer carbonization-derived Fe/N/C oxygen reduction catalyst, preparation method thereof, air electrode and fuel cell |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103296292A (en) * | 2013-06-04 | 2013-09-11 | 武汉大学 | Alkaline fuel cell cathode carbon catalyst and preparation method thereof |
-
2018
- 2018-07-04 CN CN201810724471.5A patent/CN108923050B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103296292A (en) * | 2013-06-04 | 2013-09-11 | 武汉大学 | Alkaline fuel cell cathode carbon catalyst and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| GANESAN ANANDHABABU等: "Highly exposed Fe–N4 active sites in porous poly-iron-phthalocyanine based oxygen reduction electrocatalyst with ultrahigh performance for air cathode", 《DALTON TRANS.》 * |
| XINXIA WANG等: "Iron polyphthalocyanine sheathed multiwalled carbon nanotubes: A high-performance electrocatalyst for oxygen reduction reaction", 《NANO RESEARCH》 * |
| YAN GAO等: "A series of new Phthalocyanine derivatives with large conjugated system as catalysts for the Li/SOCl2 battery", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 * |
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| CN109273725A (en) * | 2018-08-17 | 2019-01-25 | 上海中聚佳华电池科技有限公司 | Poly- metal phthalocyanine composition, Its Preparation Method And Use |
| CN109387508A (en) * | 2018-11-18 | 2019-02-26 | 扬州大学 | A kind of preparation method of magnetic carbon tube-molybdenum disulfide nano enzyme and its method for detecting hydrogen peroxide, glucose |
| CN113484386A (en) * | 2021-05-21 | 2021-10-08 | 郑州轻工业大学 | Preparation method and application of metal poly-phthalocyanine nano material, aptamer sensor and preparation method of aptamer sensor |
| CN113484386B (en) * | 2021-05-21 | 2024-02-13 | 郑州轻工业大学 | Preparation method and application of metal phthalocyanine nano material, aptamer sensor and preparation method thereof |
| CN113816425A (en) * | 2021-09-16 | 2021-12-21 | 陕西科技大学 | MoS2Nitrogen-doped carbon/modified activated carbon sodium ion battery negative electrode material and preparation method thereof |
| CN113816425B (en) * | 2021-09-16 | 2022-08-09 | 陕西科技大学 | MoS 2 Nitrogen-doped carbon/modified activated carbon sodium ion battery negative electrode material and preparation method thereof |
| CN114068965A (en) * | 2021-11-19 | 2022-02-18 | 陕西科技大学 | Transition metal phthalocyanine coated phthalocyanine blue/asphalt coke active carbon composite material lithium-thionyl chloride battery positive electrode catalyst and preparation method thereof |
| CN114427104A (en) * | 2021-12-13 | 2022-05-03 | 深圳先进技术研究院 | Copper phthalocyanine polymer @ copper nanowire core-shell nano material as well as preparation method and application thereof |
| WO2023109596A1 (en) * | 2021-12-13 | 2023-06-22 | 深圳先进技术研究院 | Copper phthalocyanine polymer@copper nanowire core-shell nanomaterial, preparation method, and application |
| CN114899436A (en) * | 2022-06-06 | 2022-08-12 | 山东能源集团有限公司 | Phthalocyanine-like polymer carbonization-derived Fe/N/C oxygen reduction catalyst, preparation method thereof, air electrode and fuel cell |
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