CN103456510B - A kind of electrode material of ultracapacitor - Google Patents
A kind of electrode material of ultracapacitor Download PDFInfo
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- CN103456510B CN103456510B CN201210179883.8A CN201210179883A CN103456510B CN 103456510 B CN103456510 B CN 103456510B CN 201210179883 A CN201210179883 A CN 201210179883A CN 103456510 B CN103456510 B CN 103456510B
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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
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- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of electrode material of ultracapacitor, wherein, this electrode material is the polymerizate obtained by aromatic nitrile compounds monomer polymerization.Electrode material provided by the invention has high-specific surface area, abundant nitrogen content and porous network structure, and the ultracapacitor that this electrode material is assembled into shows the advantages such as high specific capacitance, fast charging and discharging and good cyclical stability.In addition, electrode material provided by the invention is applicable in various types of ultracapacitors such as acid system, alkali systems and organic solution system, widely applicable.Compared with existing commercial active carbon electrode material or other electrode materials, electrode material provided by the invention has the simple high-efficiency environment friendly of preparation, with low cost, the features such as excellent performance.
Description
Technical field
The present invention relates to a kind of electrode material, particularly, relate to a kind of electrode material of ultracapacitor.
Background technology
Ultracapacitor is as a kind of energy storage device, there is relatively simple operation principle, high charge-discharge velocity (power density), good stability and useful life, thus become object (Nat.Mater., 2008.7 (11): p.845-854 of people's extensive concern and research; Chem.Soc.Rev., 2009.38 (9): p.2520-2531.).But compared with lithium battery, the energy density of ultracapacitor still relatively little (Science, 2008.321 (5889): p.651-652.), its energy density is by E=0.5CU
2calculate (C: ratio capacitance, unit F/g; U: voltage, unit V), so when voltage is identical, its energy density can be improved by improving ratio capacitance.Therefore, the research material with high specific capacitance characteristic seems extremely important as the electrode material of ultracapacitor.At present, research mainly concentrates on the specific area improving material, and adjustment aperture distributes, and add metal oxide and improve counterfeit ratio capacitance, or introducing hetero-atoms (comprising nitrogen-atoms, oxygen atom, phosphorus atoms, boron atom) changes material electronics distribution etc.Wherein the introducing of nitrogen-containing group is not only conducive to the conductivity, the wettability that change material, increases the surface area with electronically active, and can increase counterfeit ratio capacitance (EnergyEnviron.Sci., 2010.3 (9): p.1238-1251.).Therefore a kind of method that nitrogen-containing group is comparatively ideal raising material ratio capacitance characteristic is introduced.
The ultracapacitor active material of general commercialization is the active carbon material after activation modification, and the raw material that they generally adopt is coconut husk, pitch, petroleum coke etc., is generally less than 200F/g by the ratio capacitance of the ultracapacitor of its assembling.And due to the impurity content of this type of activated carbon high, therefore leakage current is large, voltage retention difference (Carbon, 2007.45 (7): p.1439-1445; JournalofPowerSources, 2008.175 (1): p.675-679.).So development structure is controlled and the material of stable performance is extremely important for the development of ultracapacitor.
Summary of the invention
The object of this invention is to provide and a kind of there is good ratio capacitance characteristic, structure-controllable and the electrode material for super capacitor of stable performance.
To achieve these goals, the invention provides a kind of electrode material of ultracapacitor, wherein, this electrode material is the polymerizate obtained by aromatic nitrile compounds monomer polymerization.
The specific area of electrode material for super capacitor provided by the invention is large, have network structure, nitrogen content is abundant and conductivity is good.In addition, electrode material provided by the invention adopts Small molecular (aromatic nitrile compounds monomer) to be polymerized, therefore, specific area, pore-size distribution, the nitrogen content of the material obtained can be controlled by controlling micromolecular type and reaction condition, and then regulate its ratio capacitance characteristic.In addition, the simple and high-efficiency environment friendly of the preparation process of electrode material provided by the invention.
Electrode material of the present invention is carried out assembling test and the application of the ultracapacitor of different system.Test result shows that this type of material has excellent ultracapacitor performance, and electrode material provided by the invention is applicable in various types of ultracapacitors such as acid system, alkali systems and organic solution system, widely applicable.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is transmission electron microscope (TEM) figure of the electrode material prepared by the method for embodiment 1 (with para-Phthalonitrile (p-DCB) for raw material, polymerization temperature is 550 DEG C);
Fig. 2 is isothermal adsorption desorption curve and the graph of pore diameter distribution of the electrode material prepared by the method for embodiment 1 (with para-Phthalonitrile (p-DCB) for raw material, polymerization temperature is 550 DEG C);
Fig. 3 is the ratio capacitance-current density plot figure of the ultracapacitor that the electrode material prepared by the method (with para-Phthalonitrile (p-DCB) for raw material, polymerization temperature is 550 DEG C) of embodiment 1 by constant current charge-discharge measurements determination is assembled;
Fig. 4 is the ratio capacitance-cycle-index curve chart of the ultracapacitor of the electrode material prepared by the method (with para-Phthalonitrile (p-DCB) for raw material, polymerization temperature is 550 DEG C) of embodiment 1 assembling recorded when current density is 10A/g.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of electrode material of ultracapacitor, wherein, this electrode material is the polymerizate obtained by aromatic nitrile compounds monomer polymerization.
The present inventor finds, so far, in the prior art, and the not open electrode material being applied to ultracapacitor as the polymerizate that polymerizable raw material obtains by aromatic nitrile compounds monomer.
In electrode material provided by the invention, selectable wider range of kind of described aromatic nitrile compounds, described aromatic nitrile compounds can comprise the aromatic compound of cyano group replacement and/or the heteroaromatic compounds of cyano group replacement.Because containing cyano group, so easily there is polymerization and rearrangement reaction in described aromatic nitrile compounds; Again because it contains aromatic rings or fragrant heterocycle, thus polymerization, reset after product structure be the large π architecture of continuous print, be conducive to the transmission of electronics.Under preferable case, the aromatic compound that described cyano group replaces is cyano group benzene and/or cyanobiphenyl, and the number of cyano substituent is at least 2, is preferably 2-4; The heteroaromatic compounds that described cyano group replaces is the hexa-atomic heteroaromatic compounds that cyano group replaces, and hetero-atom is N, and be more preferably the pyridine that cyano group replaces, the number of cyano substituent is at least 2, is preferably 2-4.Further preferably, described aromatic nitrile compounds is selected from para-Phthalonitrile (p-DCB), isophthalodinitrile (m-DCB), phthalonitrile (o-DCB), 1,3,5-tricyano benzene (TCB), 2,6-dicyanopyridines (2,6-DCP), 2,4-dicyanopyridine (2,4-DCP) and 4, one or more in 4 '-DCNBP (DCBP), but be not limited thereto.
In electrode material provided by the invention, described polymerizate preferably has porous network structure, described porous network structure can increase the specific area of polymerizate, thus improves the ratio capacitance characteristic of polymerizate, makes its electrode material as ultracapacitor have better performance.Further preferably, the specific area of described polymerizate is 300-3000m
2/ g, is preferably 1000-2800m
2/ g, pore-size distribution is 0.5-10nm.In the present invention, the specific surface of described polymerizate and pore-size distribution adopt the isothermal adsorption-desorption method of nitrogen under 77K to measure, and calculate its specific area, calculate its pore-size distribution by DFT method by BET method.
In electrode material provided by the invention, described preparation method comprises under the polymerization conditions, by the metal salt contacts of described aromatic nitrile compounds and melting.
In electrode material provided by the invention, the effect of the slaine of the described melting in described preparation method is in the reaction as solvent and catalyst, it does not decompose as long as can keep stable in the molten state, therefore the selectable range of the kind of described slaine is wider, preferably, described slaine is metal halide, further preferably, described metal halide is metal chloride, further preferably, described metal chloride is selected from one or more in zinc chloride, copper chloride, frerrous chloride and manganese chloride.The selectable range of the consumption of described slaine is wider, and preferably, the mol ratio of described slaine and described aromatic nitrile compounds monomer is 1-10:1, more preferably 2-8:1.
In the preparation method of electrode material of the present invention, the temperature that described polymeric reaction condition generally comprises contact and the time contacted, the temperature of described contact only need ensure that described slaine is in molten condition, therefore the temperature of described contact can be that the fusing point of described slaine is to the boiling point lower than slaine, preferably, described temperature is 400-700 DEG C; The selectable range of the time of described contact is wider, in order to polymerization reaction carry out more complete, the time of described contact can be more than 20 hours, and preferably, described time of contact is 20-80 hour, and further preferably, described time of contact is 40-50 hour.
Be that molten condition is temperature required general higher owing to keeping slaine, under opening system, reaction may produce some factors of instability because of the difference of place environment.Under preferable case, described contact is carried out under an inert atmosphere, thus better avoid the destabilizing factor brought because temperature is high, described inert atmosphere can be not with described aromatic nitrile compounds monomer, the gas of the slaine of melting and polymerizate reaction, preferably, described inert atmosphere is selected from nitrogen, at least one in periodic table of elements zero group gas, further preferably, described contact is carried out in closed environment, described enclosed system not only can avoid the high destabilizing factor brought of temperature, the loss because temperature is high, volatility of raw material being caused in open system can also be avoided, and can certain pressure be kept, be conducive to the carrying out reacted.
In electrode material provided by the invention, described preparation method can also comprise and carries out a series of post-processing step to described polymerizate, these steps can be purified to the further removal of impurities of polymerizate, are conducive to the application of described polymerizate as electrode material for super capacitor.Preferably, described preparation method also comprises the polymerizate cooling and obtain, then washing, the dry polymerizate through cooling.The conventional method that described cooling can adopt those skilled in the art to expect, described cooling can for being cooled to room temperature (as 20-30 DEG C).The object of described washing is the Small molecular being soluble in Conventional solvents removing rearrangement reaction and/or the decomposition reaction generation occurred in described slaine and polymerization process, and described washing can use this area conventional reagent such as water, hydrochloric acid or oxolane.Described drying purpose is the reagent of removing washing, and therefore can adopt the conventional method that those skilled in the art can expect, as natural drying, oven dry etc., baking temperature can be 20-200 DEG C.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned execution mode, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible compound mode.
In addition, also can carry out combination in any between various different execution mode of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Below will be described the present invention by embodiment.
P-DCB used, m-DCB, o-DCB, DCBP, anhydrous zinc chloride (ZnCl in embodiment
2), anhydrous cupric chloride (CuCl
2), anhydrous chlorides of rase ferrous iron (FeCl
2), anhydrous Manganese chloride (MnCl
2) all purchased from AlfaAesar company; TCB is purchased from Nanjing Kang Manlin chemical industry Industrial Co., Ltd.; 2,4-DCP, 2,6-DCP is purchased from lark prestige scientific & technical corporation.
Transmission electron microscope (TEM) is adopted to observe the structure of the electrode material of preparation in embodiment;
Under employing 77K, the isothermal adsorption desorption test of nitrogen, is then calculated the specific area of electrode material, is calculated the pore-size distribution of electrode material by DFT method by BET method;
Constant current charge-discharge method of testing is adopted to measure the ratio capacitance of the ultracapacitor of electrode material assembling.
Embodiment 1
The present embodiment is for illustration of the preparation of electrode material for super capacitor provided by the invention.
By para-Phthalonitrile (p-DCB) 1g(7.81mmol), anhydrous zinc chloride 5.32g(39.04mmol) mix, and be transferred in 10ml glass tube, the air in glass tube is fallen by argon replaces, Muffle furnace is put into after being sealed, react 40 hours at 550 DEG C, after naturally cooling to room temperature (25 DEG C), open glass tube, polymerizate is taken out, and successively with 5 % by weight hydrochloric acid, pure water, oxolane washing, then put into baking oven, at 120 DEG C, drying 10 hours, obtains electrode material.
As can be known from Fig. 1, the electrode material prepared by this embodiment has network structure that is loose, porous.
The BET specific surface area being calculated the electrode material of preparation by the data of Fig. 2 is 1724.74m
2/ g, calculates the pore-size distribution of electrode material between 0.7-10nm by DFT method.
Embodiment 2
The present embodiment is for illustration of the preparation of electrode material for super capacitor provided by the invention.
Electrode material is prepared according to the method for embodiment 1, unlike, raw material uses isophthalodinitrile (m-DCB) 1g(7.81mmol) substitute para-Phthalonitrile (p-DCB) 1g(7.81mmol).The BET specific surface area of the electrode material prepared is 1622m
2/ g, calculates the pore-size distribution of electrode material between 0.6-9nm by DFT method.
Embodiment 3
The present embodiment is for illustration of the preparation of electrode material for super capacitor provided by the invention.
Electrode material is prepared according to the method for embodiment 1, unlike, raw material uses phthalonitrile (o-DCB) 1g(7.81mmol) substitute para-Phthalonitrile (p-DCB) 1g(7.81mmol).The BET specific surface area of the electrode material prepared is 1512m
2/ g, calculates the pore-size distribution of electrode material between 0.5-8.5nm by DFT method.
Embodiment 4
The present embodiment is for illustration of the preparation of electrode material for super capacitor provided by the invention.
Electrode material is prepared according to the method for embodiment 1, unlike, raw material uses 1,3,5-tricyano benzene (TCB) 1g(6.53mmol) substitute para-Phthalonitrile (p-DCB) 1g(7.81mmol), the consumption of anhydrous zinc chloride is 4.45g(32.65mmol).The BET specific surface area of the electrode material prepared is 1223m
2/ g, calculates the pore-size distribution of electrode material between 0.5-7nm by DFT method.
Embodiment 5
The present embodiment is for illustration of the preparation of electrode material for super capacitor provided by the invention.
Electrode material is prepared according to the method for embodiment 1, unlike, raw material uses 2,6-dicyanopyridine (2,6-DCP) 1g(7.75mmol) substitute para-Phthalonitrile (p-DCB) 1g(7.81mmol), the consumption of anhydrous zinc chloride is 5.28g(38.74mmol).The BET specific surface area of the electrode material prepared is 1315m
2/ g, calculates the pore-size distribution of electrode material between 0.6-8nm by DFT method.
Embodiment 6
The present embodiment is for illustration of the preparation of electrode material for super capacitor provided by the invention.
Material is prepared according to the method for embodiment 1, unlike, raw material uses 2,4-dicyanopyridine (2,4-DCP) 1g(7.75mmol) substitute para-Phthalonitrile (p-DCB) 1g(7.81mmol), the consumption of anhydrous zinc chloride is 5.28g(38.74mmol).The BET specific surface area of the electrode material prepared is 1392m
2/ g, calculates the pore-size distribution of electrode material between 0.6-8nm by DFT method.
Embodiment 7
The present embodiment is for illustration of the preparation of electrode material for super capacitor provided by the invention.
Material is prepared according to the method for embodiment 1, unlike, raw material uses 4,4 '-DCNBP 1g(4.9mmol) substitute para-Phthalonitrile (p-DCB) 1g(7.81mmol), the consumption of anhydrous zinc chloride is 3.34g(24.5mmol).The BET specific surface area of the electrode material prepared is 1583m
2/ g, calculates the pore-size distribution of electrode material between 0.9-10nm by DFT method.
Embodiment 8
The present embodiment is for illustration of the preparation of electrode material for super capacitor provided by the invention.
Electrode material is prepared according to the method for embodiment 1, unlike, substitute anhydrous zinc chloride with anhydrous cupric chloride, the consumption of anhydrous cupric chloride is 2.10g(15.62mmol), reaction temperature is 600 DEG C, and the reaction time is 20 hours.The BET specific surface area of the electrode material prepared is 1860m
2/ g, calculates the pore-size distribution of electrode material between 0.7-10nm by DFT method.
Embodiment 9
The present embodiment is for illustration of the preparation of electrode material for super capacitor provided by the invention.
Electrode material is prepared according to the method for embodiment 1, unlike, substitute anhydrous zinc chloride with manganese chloride, consumption is 3.93g(31.24mmol), reaction temperature is 650 DEG C, and the reaction time is 60 hours.The BET specific surface area of the electrode material prepared is 2183m
2/ g, calculates the pore-size distribution of electrode material between 0.7-10nm by DFT method.
Embodiment 10
The present embodiment is for illustration of the preparation of electrode material for super capacitor provided by the invention.
Electrode material is prepared according to the method for embodiment 1, unlike, substitute anhydrous zinc chloride with frerrous chloride, consumption is 6.93g(54.67mmol), reaction temperature is 700 DEG C, and the reaction time is 80 hours.The BET specific surface area of the electrode material prepared is 2790m
2/ g, calculates the pore-size distribution of electrode material between 0.7-10nm by DFT method.
Performance test:
1, constant current charge-discharge tests the ratio capacitance of the ultracapacitor assembled by above-mentioned electrode material.
Respectively the electrode material prepared in embodiment 1-10 is mixed according to the ratio of mass ratio 8:1.5:0.5 with conductive black and binding agent (polytetrafluoroethyl-ne aqueous solution), thin slice is rolled into by roller mill, drying 10 hours at 120 DEG C, then diameter 1cm is cut into, quality is about the disk of 2.5mg, be pressed on stainless (steel) wire collector again, obtained ultracapacitor.
Test uses three-electrode system: work electrode is the electrode material that stainless (steel) wire supports, and be platinum plate electrode to electrode, reference electrode is Ag/AgCl electrode, and electrolyte is the sulfuric acid solution of 1mol/L.Carry out constant current charge-discharge test after assembling, the voltage range (relative to Ag/AgCl electrode) of test be-0.2V to 0.8V, the ratio capacitance (as shown in table 1 below) of capacitor when record current density is 0.2A/g and 10A/g.
Table 1
| Embodiment | Current density (A/g) | Ratio capacitance (F/g) | Current density (A/g) | Ratio capacitance (F/g) |
| Embodiment 1 | 0.2 | 300 | 10 | 220 |
| Embodiment 2 | 0.2 | 280 | 10 | 200 |
| Embodiment 3 | 0.2 | 295 | 10 | 215 |
| Embodiment 4 | 0.2 | 250 | 10 | 170 |
| Embodiment 5 | 0.2 | 230 | 10 | 160 |
| Embodiment 6 | 0.2 | 235 | 10 | 165 |
| Embodiment 7 | 0.2 | 260 | 10 | 185 |
| Embodiment 8 | 0.2 | 270 | 10 | 195 |
| Embodiment 9 | 0.2 | 250 | 10 | 180 |
| Embodiment 10 | 0.2 | 230 | 10 | 165 |
For embodiment 1, as can be known from Fig. 3, when current density is 0.2A/g, the ratio capacitance of the ultracapacitor of electrode material assembling is 300F/g, when current density is 10A/g, the ratio capacitance of the ultracapacitor of electrode material assembling is 220F/g, has good ratio capacitance characteristic as seen by this electrode material.
As can be known from Fig. 4, under current density is 10A/g, constant current charge-discharge circulates after 5000 times, and the ratio capacitance of the ultracapacitor of electrode material assembling is stabilized in about 220F/g and there is no obvious decay, illustrates that the cyclical stability of this ultracapacitor is good.
2, the ratio capacitance of ultracapacitor of constant current charge-discharge test electrode material assembling under alkali systems
The method of testing according to above-mentioned constant current charge-discharge tests the performance of the ultracapacitor that the electrode material prepared by embodiment 1 obtains, unlike, electrolyte is replaced by the NaOH solution of 6mol/L, collector is replaced by nickel foam, reference electrode is replaced by Hg/HgO electrode, the voltage range of test is :-0.9V is to 0V.
Test result: when current density is 0.2A/g, the ratio capacitance of the ultracapacitor of electrode material assembling is 280F/g; When current density is 10A/g, the ratio capacitance of the ultracapacitor of electrode material assembling is 200F/g.
3, the ratio capacitance of ultracapacitor of constant current charge-discharge test electrode material assembling under organic solution system
The electrode material of preparation in embodiment 1 is mixed according to mass ratio 8:1.5:0.5 ratio with conductive black and binding agent (polytetrafluoroethyl-ne aqueous solution), thin slice is rolled into by roller mill, at 120 DEG C, drying 10 hours, is then cut into the disk of diameter 1cm, then is pressed on aluminium foil.Test use two electrode system: two electrodes are the material that two panels aluminium foil identical in quality supports, and electrolyte is the solution that 1-butyl-3-methyl imidazolium tetrafluoroborate (BMIMBF4) obtains according to the volume ratio Homogeneous phase mixing of 1:1 with acetonitrile.Carry out constant current charge-discharge test after assembling, the voltage range of test is: 0V to 3.5V.
Test result: when current density is 0.2A/g, the ratio capacitance of the ultracapacitor of electrode material assembling is 140F/g; When current density is 5A/g, the ratio capacitance of the ultracapacitor of electrode material assembling is 110F/g.
By the known electrode material provided by the invention of the test result shown in embodiment 1-10 and table 1, there is high specific area, abundant porous network structure, its ultracapacitor be assembled into shows the advantages such as high specific capacitance, fast charging and discharging and good cyclical stability.The ultracapacitor being not only applicable to acid system by the known electrode material provided by the invention of constant current charge-discharge test result under alkali systems and organic solution system is also applicable in various types of ultracapacitor such as alkali systems and organic solution system, widely applicable.
Claims (11)
1. the electrode material of a ultracapacitor, it is characterized in that, this electrode material is the polymerizate obtained by aromatic nitrile compounds monomer polymerization, described aromatic nitrile compounds monomer is selected from para-Phthalonitrile, isophthalodinitrile, phthalonitrile, 1,3,5-tricyano benzene, 2,6-dicyanopyridines, 2,4-dicyanopyridine and 4, one or more in 4 '-DCNBP.
2. electrode material according to claim 1, wherein, described polymerizate has porous network structure.
3. electrode material according to claim 1 and 2, wherein, the specific area of described polymerizate is 300-3000m
2/ g, pore-size distribution is 0.5-10nm.
4. electrode material according to claim 1, wherein, the method for being polymerized the polymerizate obtained by aromatic nitrile compounds comprises: under the polymerization conditions, by the metal salt contacts of described aromatic nitrile compounds monomer and melting.
5. electrode material according to claim 4, wherein, described slaine is metal halide; The mol ratio of described slaine and described aromatic nitrile compounds monomer is 1-10:1.
6. electrode material according to claim 5, wherein, described slaine is metal chloride, described metal chloride be selected from zinc chloride, copper chloride, frerrous chloride and manganese chloride one or more, the mol ratio of described slaine and described aromatic nitrile compounds monomer is 2-8:1.
7. electrode material according to claim 4, wherein, the temperature that described polymeric reaction condition comprises contact be described slaine fusing point to the boiling point lower than slaine, time of contact is 20-80 hour.
8. electrode material according to claim 7, wherein, described time of contact is 40-50 hour.
9. electrode material according to claim 4, wherein, described contact is carried out under an inert atmosphere, and described inert atmosphere is selected from least one in nitrogen, periodic table of elements zero group gas.
10. according to the electrode material in claim 4 and 7-9 described in any one, wherein, described contact is carried out in closed environment.
11. electrode materials according to claim 4, wherein, described method also comprises the polymerizate cooling and obtain, then washing, the dry polymerizate through cooling.
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| CN103996861B (en) * | 2014-06-05 | 2018-01-09 | 国家纳米科学中心 | A kind of purposes of the polymerizate that aromatic nitrile compounds polymerize to obtain as oxygen reduction catalyst |
| CN104014367B (en) * | 2014-06-11 | 2016-08-17 | 国家纳米科学中心 | A kind of carbon back Nonmetal oxygen reduction catalyst, preparation method and its usage |
| CN105406027A (en) * | 2014-09-10 | 2016-03-16 | 国家纳米科学中心 | Complex formed from aromatic nitrile compound polymerization product and sulfur, preparation method and uses thereof |
| CN104538549A (en) * | 2014-12-30 | 2015-04-22 | 厦门大学 | Manufacturing method of SrTiO3 single-crystal resistance switch device |
| CN107240506A (en) * | 2016-03-28 | 2017-10-10 | 国家纳米科学中心 | A kind of nitrogen-doped carbon nano composite material and its production and use |
| CN110451477A (en) * | 2019-08-06 | 2019-11-15 | 大连理工大学 | A kind of one-step method prepares the method and its application of phthalonitrile base porous carbon materials |
| CN112466675B (en) * | 2019-09-09 | 2022-06-03 | 国家纳米科学中心 | Supercapacitor electrolyte additive, supercapacitor electrolyte and application of supercapacitor electrolyte additive |
| CN114725379B (en) * | 2022-05-06 | 2024-04-09 | 上海大学 | Electrode active material, lithium ion battery composite positive plate and lithium ion battery |
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