CN1168161C - Electrode of rechargeable battery and its preparing process - Google Patents
Electrode of rechargeable battery and its preparing process Download PDFInfo
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- CN1168161C CN1168161C CNB011139404A CN01113940A CN1168161C CN 1168161 C CN1168161 C CN 1168161C CN B011139404 A CNB011139404 A CN B011139404A CN 01113940 A CN01113940 A CN 01113940A CN 1168161 C CN1168161 C CN 1168161C
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- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 8
- 230000031709 bromination Effects 0.000 claims abstract description 7
- 238000005893 bromination reaction Methods 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000012159 carrier gas Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 7
- 229930192474 thiophene Natural products 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 239000007772 electrode material Substances 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 3
- 239000007952 growth promoter Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000011282 treatment Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 27
- 239000006260 foam Substances 0.000 abstract description 8
- 239000011232 storage material Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010306 acid treatment Methods 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000007669 thermal treatment Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 18
- 229910021393 carbon nanotube Inorganic materials 0.000 description 17
- 239000002041 carbon nanotube Substances 0.000 description 17
- 239000003610 charcoal Substances 0.000 description 17
- 238000002474 experimental method Methods 0.000 description 14
- 238000000748 compression moulding Methods 0.000 description 7
- 230000005518 electrochemistry Effects 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PFUQSACCWFVIBW-UHFFFAOYSA-N [C].C1=CC=CC=C1 Chemical compound [C].C1=CC=CC=C1 PFUQSACCWFVIBW-UHFFFAOYSA-N 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 239000001996 bearing alloy Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910005438 FeTi Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
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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
- Y02E60/10—Energy storage using batteries
-
- 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
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Abstract
The present invention relates to an electrode of a rechargeable battery and a preparation method for the electrode. The present invention is characterized in that one-dimensional nanometer carbon materials which are prepared by a flowing catalyst method and have outer diameters of 3 to 500 nm are used as electrochemical hydrogen storage materials. The present invention has the preparation process that after the one-dimensional nanometer carbon materials and binder copper powder or nickel powder are mixed, the one-dimensional nanometer carbon materials mixed with the binder copper powder or nickel powder are pressed and formed on foam nickel used as framework materials, wherein before being used, the one-dimensional nanometer carbon materials are pretreated through dispersion, bromination, acid treatment, water washing, thermal treatment, etc. The present invention has high electrochemical capacity and long circulating service life.
Description
Technical field:
The present invention relates to battery technology, and a kind of novel electrode of rechargeable battery and preparation method thereof is provided especially.
Background technology:
Along with the mankind use with a large amount of the exhaustive exploitation of fossil energy, the fossil energy deposit is day by day short, environmental pollution is serious day by day, a kind of new alternative energy source of an urgent demand.Hydrogen Energy has zero to be polluted and reproducible distinct advantages, is considered to existing based on the optimal replacer of the energy industry of carbon.But the major obstacle that hinders the utilization of Hydrogen Energy scale is to lack a kind of convenience, stocking system efficiently, and hydrogen storage material produces under such background just, and is able to fast development.American Modern chemistry founder Thamas Graham discovery Metal Palladium can be inhaled hydrogen in a large number in 1886.After oneth century, on the state-run research institute of nineteen sixty-eight U.S. Brookhaven takes the lead in research at hydrogen bearing alloy, succeed, found Mg
2The Ni alloy also has hydrogen storage property.Dutch Philips research institute had found LaNi in 1970
5Hydrogen storage property.Meanwhile, the state-run research institute of the Brookhaven of the U.S. has found the FeTi hydrogen bearing alloy again, thereby has opened the new page of hydrogen bearing alloy research.Wherein study LaNi more, that technology is ripe relatively
5Be successfully applied to the Ni-MH chargeable battery, the application of other alloy material also under study for action, but the metal alloy hydrogen storage material exists hydrogen storage capability low or put problems such as hydrogen condition harshness, is difficult to be implemented in the application that Hydrogen Energy scales such as fuel cell, high power capacity chargeable battery are utilized the aspect.
Summary of the invention:
The object of the present invention is to provide a kind of novel electrode of rechargeable battery and preparation method thereof, it has very high electrochemistry capacitance and reaches the very high life-span that recycles.
The invention provides a kind of electrode of rechargeable battery, it is characterized in that the electrochemical hydrogen bearing material of described electrode is prepared by following flowing catalyst method:
With benzene, CH
4, C
2H
2Be carbon source, with ferrocene, Ni (Co)
4Being catalyst, is carrier gas with hydrogen, helium, nitrogen, with sulfur-containing compound thiophene, H
2S is a growth promoter, and the mol ratio of control carbon source and carrier gas is 0.5～0.25, and carbon and sulphur mol ratio are 600～1300: 1, and the mol ratio of catalyst and carbon source is 0.008～0.015; The sulfur-containing compound carbon source is fully mixed under gaseous state with catalyst, at the uniform velocity brought into reaction zone by carrier gas, keep 0.5～0.075S in reaction zone, the growth overall diameter is the nano carbon material in one dimension of 3～500nm under 1373～1473K.
In the electrode of rechargeable battery provided by the invention, nano carbon material in one dimension content is 4～40wt.%, and as the copper 20～80wt.% of binding agent, all the other are nickel and unavoidable impurities; Macroscopical density of electrode material is 1000～5000kg/m
3
Perhaps, in the electrode of rechargeable battery provided by the invention, nano carbon material in one dimension content is 5～50wt.%, and all the other are nickel and unavoidable impurities; Macroscopical density of electrode material is 1000～5000kg/m
3
Nano carbon material in one dimension of the present invention is that 3～100nm and the pretreated overall diameter of process are the multiple-wall carbon nanotube of 3～100nm for the overall diameter that adopts the preparation of flowing catalyst method, and its purity is 90～98wt%.
The present invention also provides the preparation method of above-mentioned electrode of rechargeable battery, after being about to the mixing of nano carbon material in one dimension and binding agent copper powder or nickel powder, compression moulding on as the nickel foam of framework material, it is characterized in that earlier the nano carbon material in one dimension by the preparation of flowing catalyst method being carried out preliminary treatment before the preparation electrode, processing procedure is as follows:
With ultrasonic dispersion 10～45 minutes, 50～100 ℃ of following poach disperseed 1～2 day with nano carbon material in one dimension;
In bromine water, under 50～95 ℃, carried out bromination 1～12 hour;
Soaked 1～24 hour with concentrated hydrochloric acid or red fuming nitric acid (RFNA), use washed with de-ionized water;
Dry back was 450～600 ℃ of heat treatments 1～2 hour.
With electrode of the present invention as work electrode, Hg/HgO is as reference electrode, 6MKOH is an electrolyte, NiOH is an auxiliary electrode, carry out the electrochemical hydrogen storage experiment then, hydrogen storage content can reach 500～3700mAh/g (press the active material nano carbon material in one dimension and calculate, down together), is equivalent to gas phase hydrogen storage 1.8wt.%～12.1wt.%.
Usually the nano carbon material in one dimension surface has the molecular level pore, there is nano level hollow tube inside, and specific area is big, in addition the graphite aspect perpendicular to fiber axis to or the nanoscale charcoal fiber of in a certain angle with the axis red herring-bone form special construction, its basal spacing is 3.37 , greater than hydrogen molecule diameter (2.89 ), therefore, a large amount of hydrogen can condense in nano carbon material in one dimension, thereby have the electrochemical hydrogen storage ability.The present invention just because of the overall diameter that adopts the preparation of flowing catalyst method be the multiple-wall carbon nanotube of 3～100nm or nanoscale charcoal fiber that diameter is 100～500nm as electrochemical hydrogen bearing material, its electrochemical hydrogen storage amount is higher than the hydrogen storage content of metal alloy hydrogen storage material far away.In addition, by the self-control nano carbon material in one dimension of patented method acquisition formerly, the purity height (＞50wt.%), draw ratio big (about 1000) have certain macroscopic orientation, thereby mechanical property is good, and is had good electrical conductivity, is particularly suitable for electrode material.The present invention is by unique nano carbon material in one dimension pretreating process, metallic catalyst, amorphous carbon and graphite particulate have been removed effectively, make the percent opening height of nano carbon material in one dimension, thereby have abundant nanometer scale pore, improved the electrochemical hydrogen storage performance of electrode greatly.Below by embodiment in detail the present invention is described in detail.
Description of drawings:
The electrochemical hydrogen storage experiment schematic diagram of accompanying drawing 1. nano carbon material in one dimension;
The photomacrograph of accompanying drawing 2. nano carbon material in one dimension;
The transmission electron microscope photo of accompanying drawing 3. nano carbon material in one dimension;
The high-resolution photo of accompanying drawing 4. nano carbon material in one dimension;
Embodiment:
Embodiment 1
The electrochemical hydrogen storage experiment is as accompanying drawing 1, and 1 is that work electrode, 2 is that reference electrode, 3 is auxiliary electrode among the figure.
Be equipped with nano carbon material in one dimension with the flowing catalyst legal system, carbon benzene flow 30ml/min, thiophene concentration 0.55%, carrier gas H
2Total flow is 620ml/min, and catalyst is a ferrocene, and weight is 0.6g.Reaction zone rises to 1200 ℃ with 15 ℃/min after rising to 1100 ℃ with 25 ℃/min earlier again, constant temperature 45min, the carbon fiber of acquisition 3～60nm.Take multiple-wall carbon nanotube that mean outside diameter is approximately 6nm through 30 minutes, 95 ℃ brominations of ultrasonic dispersion in 100 ℃ of poach 1 day, the ethanol 5 hours, concentrated hydrochloric acid was handled 20 hours, 600 ℃ heat treatments after 1 hour, pure multiple-wall carbon nanotube (50mg) is mixed by 1: 3 weight ratio with copper powder, with nickel foam (25mg) is matrix compression moulding, resultant multiple-wall carbon nanotube electrode is as work electrode, Hg/HgO is as reference electrode, 6MKOH is an electrolyte, NiOH is an auxiliary electrode, and the temperature of electrolytic cell is 25 ℃.The cycle life experiment of multiple-wall carbon nanotube electrode discharges and recharges with the current density of 500mA/g, and stopping potential is-0.4V (vs.Hg/HgO) during discharge.The high electrochemistry capacitance of multiple-wall carbon nanotube is 1483mAh/g.
Embodiment 2
The electrochemical hydrogen storage experiment is as accompanying drawing 1.
Take that embodiment 1 method makes, the multiple-wall carbon nanotube that mean outside diameter is approximately 20nm was through 15 minutes, 70 ℃ brominations of ultrasonic dispersion in 100 ℃ of poach 1 day, the ethanol 2 hours, concentrated hydrochloric acid was handled 5 hours, 500 ℃ heat treatments after 1 hour, pure multiple-wall carbon nanotube (25mg) is mixed by 1: 4 weight ratio with copper powder, with nickel foam (25mg) is matrix compression moulding, resultant multiple-wall carbon nanotube electrode is as work electrode, Hg/HgO is as reference electrode, 6MKOH is an electrolyte, NiOH is an auxiliary electrode, and the temperature of electrolytic cell is 25 ℃.The cycle life experiment of multiple-wall carbon nanotube electrode discharges and recharges with the current density of 1000mA/g, and stopping potential is-0.4V (vs.Hg/HgO) during discharge.The high electrochemistry capacitance of multiple-wall carbon nanotube is 1157mAh/g.
Embodiment 3
The electrochemical hydrogen storage experiment is as accompanying drawing 1.
Be equipped with nano carbon material in one dimension with the flowing catalyst legal system, carbon benzene flow 40ml/min, thiophene concentration 1%, carrier gas H
2Total flow is 600ml/min, and catalyst is a ferrocene, and weight is 0.7g.Reaction zone rises to 1200 ℃ with 15 ℃/min after rising to 1100 ℃ with 25 ℃/min earlier again, constant temperature 45min, the carbon fiber of acquisition 5～100nm.Take the multiple-wall carbon nanotube that mean outside diameter is approximately 80nm and handle 20 hours, 450 ℃ heat treatments after 2 hours through 2 days, 50 ℃ brominations of 15 minutes, 50 ℃ poach of ultrasonic dispersion 10 hours, concentrated hydrochloric acid, pure multiple-wall carbon nanotube (10mg) is mixed by 1: 10 weight ratio with copper powder, with nickel foam (25mg) is matrix compression moulding, thereby obtain the multiple-wall carbon nanotube electrode as work electrode, Hg/HgO is as reference electrode, 6MKOH is an electrolyte, NiOH is an auxiliary electrode, and the temperature of electrolytic cell is 25 ℃.The cycle life experiment of multiple-wall carbon nanotube electrode discharges and recharges with the current density of 400mA/g, and stopping potential is-0.4V (vs.Hg/HgO) during discharge.The high electrochemistry capacitance of multiple-wall carbon nanotube is 3700mAh/g.
Embodiment 4
The electrochemical hydrogen storage experiment is as accompanying drawing 1.
Take that embodiment 3 methods make, the nanoscale charcoal fiber of the about 100nm of diameter soaks with concentrated hydrochloric acid, clean with deionized water again.Place baking oven to dry then.Pure nanoscale charcoal fiber (50mg) is mixed by 1: 6 weight ratio with copper powder, with nickel foam (25mg) is matrix compression moulding, thereby obtain nanoscale charcoal fiber electrode as work electrode, Hg/HgO is as reference electrode, 6MKOH is an electrolyte, NiOH is an auxiliary electrode, and the temperature of electrolytic cell is 25 ℃.The cycle life experiment of nanoscale charcoal fiber electrode discharges and recharges with the current density of 1000mA/g, and stopping potential is-0.4V (vs.Hg/HgO) during discharge.The high electrochemistry capacitance of nanoscale charcoal fiber is 800mAh/g.
Embodiment 5
The electrochemical hydrogen storage experiment is as accompanying drawing 1.
Be equipped with nano carbon material in one dimension with the flowing catalyst legal system, carbon benzene flow 40ml/min, thiophene concentration 0.15%, carrier gas H
2Total flow is 600ml/min, and catalyst is a ferrocene, and weight is 0.65g.Reaction zone rises to 1200 ℃ with 15 ℃/min after rising to 1100 ℃ with 25 ℃/min earlier again, constant temperature 45min, the carbon fiber of acquisition 5～208nm.The nanoscale charcoal fiber of taking the about 200nm of diameter soaks with concentrated hydrochloric acid, cleans with deionized water again.Place baking oven to dry then.Pure nanoscale charcoal fiber (10mg) is mixed by 1: 12 weight ratio with copper powder, with nickel foam (25mg) is matrix compression moulding, thereby obtain nanoscale charcoal fiber electrode as work electrode, Hg/HgO is as reference electrode, 6MKOH is an electrolyte, NiOH is an auxiliary electrode, and the temperature of electrolytic cell is 25 ℃.The cycle life experiment of nanoscale charcoal fiber electrode discharges and recharges with the current density of 1000mA/g, and stopping potential is-0.4V (vs.Hg/HgO) during discharge.The high electrochemistry capacitance of nanoscale charcoal fiber is 500mAh/g.
Embodiment 6
The electrochemical hydrogen storage experiment is as accompanying drawing 1.
Be equipped with nano carbon material in one dimension with the flowing catalyst legal system, carbon benzene flow 30ml/min, thiophene concentration 0.55%, carrier gas H
2Total flow is 500ml/min, and catalyst is a ferrocene, and weight is 0.75g.Reaction zone rises to 1200 ℃ with 15 ℃/min after rising to 1100 ℃ with 25 ℃/min earlier again, constant temperature 45min, the carbon fiber of acquisition 5～160nm.The nanoscale charcoal fiber of taking the about 160nm of diameter soaks with concentrated hydrochloric acid, cleans with deionized water again.Place baking oven to dry then.Pure nanoscale charcoal fiber (20mg) is mixed by 1: 3 weight ratio with copper powder, with nickel foam (25mg) is matrix compression moulding, thereby obtain nanoscale charcoal fiber electrode as work electrode, Hg/HgO is as reference electrode, 6MKOH is an electrolyte, NiOH is an auxiliary electrode, and the temperature of electrolytic cell is 25 ℃.The cycle life experiment of nanoscale charcoal fiber electrode discharges and recharges with the current density of 800mA/g, and stopping potential is-0.4V (vs.Hg/HgO) during discharge.The high electrochemistry capacitance of nanoscale charcoal fiber is 610mAh/g.
Claims (4)
1, a kind of electrode of rechargeable battery is characterized in that:
The electrochemical hydrogen bearing material of described electrode is prepared by following flowing catalyst method
With benzene, CH
4, C
2H
2Be carbon source, with ferrocene, Ni (Co)
4Being catalyst, is carrier gas with hydrogen, helium, nitrogen, with sulfur-containing compound thiophene, H
2S is a growth promoter, and the mol ratio of control carbon source and carrier gas is 0.5～0.25, and carbon and sulphur mol ratio are 600～1300: 1, and the mol ratio of catalyst and carbon source is 0.008～0.015; The sulfur-containing compound carbon source is fully mixed under gaseous state with catalyst, at the uniform velocity brought into reaction zone by carrier gas, keep 0.5～0.075S in reaction zone, the growth overall diameter is the nano carbon material in one dimension of 3～500nm under 1373～1473K;
It is 4～40wt% that the material of described electrode consists of nano carbon material in one dimension content, and as the copper 20～80wt.% of binding agent, all the other are nickel;
Macroscopical density of described electrode material is 1000～5000kg/m
3
2, a kind of electrode of rechargeable battery is characterized in that:
The electrochemical hydrogen bearing material of described electrode is prepared by following method
With benzene, CH
4, C
2H
2Be carbon source, with ferrocene, Ni (Co)
4Being catalyst, is carrier gas with hydrogen, helium, nitrogen, with sulfur-containing compound thiophene, H
2S is a growth promoter, and the mol ratio of control carbon source and carrier gas is 0.5～0.25, and carbon and sulphur mol ratio are 600～1300: 1, and the mol ratio of catalyst and carbon source is 0.008～0.015; The sulfur-containing compound carbon source is fully mixed under gaseous state with catalyst, at the uniform velocity brought into reaction zone by carrier gas, keep 0.5～0.075S in reaction zone, the growth overall diameter is the nano carbon material in one dimension of 3～500nm under 1373～1473K;
It is 5～50wt.% that the material of described electrode consists of nano carbon material in one dimension content, and all the other are nickel;
Macroscopical density of described electrode material is 1000～5000kg/m
3
3, according to the described electrode of rechargeable battery of claim 1, it is characterized in that: earlier described nano carbon material in one dimension was carried out preliminary treatment before the preparation electrode, processing procedure is as follows:
With ultrasonic dispersion 10～45 minutes, 50～100 ℃ of following poach disperseed 1～2 day with nano carbon material in one dimension;
In bromine water, under 50～95 ℃, carried out bromination 1～12 hour;
Soaked 1～24 hour with concentrated hydrochloric acid or red fuming nitric acid (RFNA), use washed with de-ionized water;
Dry back was 450～600 ℃ of heat treatments 1～2 hour.
4, according to the described electrode of rechargeable battery of claim 2, it is characterized in that: earlier described nano carbon material in one dimension was carried out preliminary treatment before the preparation electrode, processing procedure is as follows:
With ultrasonic dispersion 10～45 minutes, 50～100 ℃ of following poach disperseed 1～2 day with nano carbon material in one dimension;
In bromine water, under 50～95 ℃, carried out bromination 1～12 hour;
Soaked 1～24 hour with concentrated hydrochloric acid or red fuming nitric acid (RFNA), use washed with de-ionized water;
Dry back was 450～600 ℃ of heat treatments 1～2 hour.
Priority Applications (1)
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| CNB011139404A CN1168161C (en) | 2001-05-22 | 2001-05-22 | Electrode of rechargeable battery and its preparing process |
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|---|---|---|---|
| CNB011139404A CN1168161C (en) | 2001-05-22 | 2001-05-22 | Electrode of rechargeable battery and its preparing process |
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| CN1168161C true CN1168161C (en) | 2004-09-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100389516C (en) * | 2004-12-30 | 2008-05-21 | 比亚迪股份有限公司 | Foam nickel, and method for fabricating the foam nickel, and battery of using the foam nickel |
| CN104659377A (en) * | 2013-11-21 | 2015-05-27 | 青岛润鑫伟业科贸有限公司 | Production method of electrode for battery |
| CN105244473A (en) * | 2014-07-10 | 2016-01-13 | 北京化工大学 | Post-processing method for improving electrochemical performance of lithium ion battery carbon anode material |
| CN105355463B (en) * | 2015-11-09 | 2018-10-16 | 电子科技大学 | A kind of preparation method of flexible super capacitor electrode and device |
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