CN100571933C - A kind of method with preparing onion-shaped internal coating metal nickel carbon particle with deoiling asphalt - Google Patents
A kind of method with preparing onion-shaped internal coating metal nickel carbon particle with deoiling asphalt Download PDFInfo
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- CN100571933C CN100571933C CNB200710139628XA CN200710139628A CN100571933C CN 100571933 C CN100571933 C CN 100571933C CN B200710139628X A CNB200710139628X A CN B200710139628XA CN 200710139628 A CN200710139628 A CN 200710139628A CN 100571933 C CN100571933 C CN 100571933C
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Abstract
The present invention relates to a kind of method with preparing onion-shaped internal coating metal nickel carbon particle with deoiling asphalt; it is to be raw material with de-oiled asphalt, metal nickel powder; with the metal nickel powder is catalyst, is cleaning agent with hydrochloric acid, deionized water, is protective gas with the argon gas; in tube type high-temperature furnace; under 1000 ℃ of temperature, under the argon gas whole process protection, sintering de-oiled asphalt powder; in vacuum sintering furnace, be 10 in vacuum
-3Under the Pa, in temperature is under 2000 ℃ of high temperature, constant temperature heat preservation sintering de-oiled asphalt+metallic nickel powder 60min, obtain bag metallic nickel carbon particulate product powder in the onion shape, the product powder particle is black, spheroidal, diameter is 10-30nm, surface coating layer carbon thickness of the shell is 5nm, nuclear diameter is 5-20nm in the metallic nickel, and its particle cross section has the stacked clad structure of tangible onion shape, carbon shell, metallic nickel uniform particles, have high-purity characteristics, its chemistry, stable physical property, the method technological process is short, material source is abundant, production yield rate is high, can reach 66%.
Description
Technical field
The present invention relates to a kind of method, belong to organic compound material with carbon element and the research of product and the technical field of preparation method with preparing onion-shaped internal coating metal nickel carbon particle with deoiling asphalt.
Background technology
Organic compound de-oiled asphalt Deoiled Asphalt is called for short DOA, is the accessory substance in the residual oil solvent deasphalting process, is hard and crisp solid or powder under the normal temperature, and outward appearance is black, brown, the class sapropelitic, and density is 1.1g/cm
3, there is not definite melting point, softening point＞120 ℃, phosphorus content＞80%, ash is low, and high temperature is thick semifluid down.
De-oiled asphalt often is used as coking raw material and blast furnace fuel, along with science and technology development, the application of high added value is also arisen at the historic moment, nanometer technology and nano material are the emerging fields of material science over past ten years, utilize the high characteristic of its phosphorus content, often be made into carbon fiber, carbosphere, CNT etc., be applied in fields such as electronics industry, medicine, environmental protection, chemical industry, along with the development of nanometer technology, the carbon-coated nano metallic particles has become possibility.
Metallics---nickel element has characteristics such as fusing point height, conductive and heat-conductive be good, be often used as electric energy to heat energy conversion, for example resistance-heated furnace, heating stone or metal plate for standing a stove on as a precaution against fire etc. in the value added applications of de-oiled asphalt, can be prepared into metallic nickel bag metallic nickel carbon particulate material in the onion shape.
Bag metallic nickel material with carbon element also has several different methods in the preparation onion shape, for example: chemical vapour deposition technique, arc discharge method, pyrolysismethod, liquid impregnation charring, metallic charcoal butt gel explosion method, though these methods have obtained a lot of progress, but still there are a lot of technical problems and a deficiency, be still waiting research, the production yield rate of the particle size distribution of genus covered with gold leaf, interior ratio, metal crystal formation, carbon-coating thickness, crystallization degree and the product that belongs to covered with gold leaf of control for example all is the problem that need inquire into and study.
Summary of the invention
Goal of the invention
Purpose of the present invention is exactly at disadvantages of background technology; adopt the vacuum high-temperature heat treating process; with de-oiled asphalt, metallic nickel is raw material; with the metallic nickel is catalyst; with the argon gas is protective gas, bag metallic nickel carbon particulate in the preparation onion shape, and making the carbon particulate product inner is Ni-based nuclear; external rings coiled onion shape carbon layer is to increase substantially its crystallization degree, purity and production yield rate.
Technical scheme
The raw chemical material that the present invention uses as de-oiled asphalt, metallic nickel, hydrochloric acid, deionized water, argon gas, its combination matching is: with gram, milliliter, centimetre
3Be unit
De-oiled asphalt: C
559H
690SN
7O
54g ± 0.05g
Nickel powder: Ni 2g ± 0.03g
Hydrochloric acid: HCl 600ml ± 5ml
Deionized water: H
2O 3000ml ± 20ml
Argon gas: Ar 120000cm
3± 100cm
3
Preparation method of the present invention is as follows:
(1) selected raw chemical material
The raw chemical material that preparation is used will carry out selected, and carries out purity control:
De-oiled asphalt: 98%
Nickel powder: 99.5%
Hydrochloric acid: concentration 38%
Deionized water: 96%
Argon gas: 98%
(2) the dry processing
The de-oiled asphalt that preparation is used places drying baker, carries out drying, 100 ℃ ± 10 ℃ of baking temperatures, drying time 1440min ± 60min;
(3) pulverize, grind, sieve
Will pulverize, grind, sieve the de-oiled asphalt that preparation is used, and carry out fineness control, grind repeatedly, sieve repeatedly, stay fine powder, sieve number is 200 orders, fine powder particle diameter≤0.075mm;
(4) clean the high quartz pipe
1) in the high quartz pipe, injects hydrochloric acid 100ml ± 5ml, scrub 5min with hairbrush;
2) inject deionized water 1000ml ± 5ml, wash, scrub 5min, dry then;
(5) the quartzy product boat of ultrasonic cleaning
1) hydrochloric acid cleans: quartzy product boat is placed ultrasonic cleaner, inject hydrochloric acid 200ml ± 5ml, open ultrasonic cleaner, clean 20min ± 2min, the cleaning back is removed hydrochloric acid and is dried;
2) washed with de-ionized water: in ultrasonic cleaner, add deionized water 400ml ± 5ml, open ultrasonic cleaner, clean 20min ± 2min, take out then and dry;
(6) dry, the quartzy product boat of The pre-heat treatment
Quartzy product boat is placed vacuum drying chamber, preheating under 100 ℃ ± 10 ℃ states, oven dry, the time is 60min ± 5min;
(7) inert gas cleaning quartz ampoule
Input argon gas 400cm in quartz ampoule
3± 10cm
3, input speed 100cm
3/ min drives away pernicious gas in the quartz ampoule, makes to be in the argon gas atmosphere in the quartz ampoule;
(8) put quartzy product boat and raw material
De-oiled asphalt powder 4g ± 0.05g is placed in the quartzy product boat, and quartzy product boat is placed high-temperature region, middle part in the quartz ampoule;
(9) close quartz ampoule, the input inert protective gas
Close quartz ampoule, leave the gas outlet, automatically the adjustable pipe internal gas pressure;
Open tunger tube, in quartz ampoule, import argon gas, input speed 100cm continuously
3/ min;
(10) open the quartz tube type high temperature furnace and carry out sintering
Open tube type high-temperature furnace, 4 ℃/min of programming rate when temperature rises to 1000 ℃ ± 10 ℃, stops to heat up; The de-oiled asphalt powder is at 1000 ℃ ± 10 ℃ sintering temperatures, and constant temperature, insulation 60min ± 1min;
In sintering process chemical reaction will take place, reaction equation is as follows:
In the formula:
C: carbon
H
2: hydrogen
CO
2: carbon dioxide
H
2S: hydrogen sulfide
N
2: nitrogen
H
2O: steam
(11) under argon shield, cool off with stove
Close tube type high-temperature furnace, under argon shield, be cooled to 20 ℃ ± 3 ℃ of normal temperature;
(12) collect product
Open quartz ampoule, take out quartzy product boat and product powder, i.e. de-oiled asphalt product powder behind the sintering;
(13) grind, sieve
De-oiled asphalt powder in the quartzy product boat is placed agate mortar, grind and sieve with agate pestle, sieve number is 200 orders, and powder particle diameter≤0.075mm is standby;
(14) abrasive metal nickel powder
Metal nickel powder 2g ± 0.03g is placed the agate mortar grinding and sieves sieve number 200 orders, powder particle diameter≤0.075mm;
(15) proportioning, mixing
Take by weighing de-oiled asphalt powder 1g ± 0.01g, metal nickel powder 0.2g ± 0.001g, place graphite crucible, the de-oiled asphalt powder: metal nickel powder=5: 1;
(16) cleaning vacuum sintering furnace
With compressed air cleaning vacuum sintering furnace inwall, the time is 6min ± 1min, makes its cleaning;
(17) vacuum sintering furnace sintering
1) graphite crucible that will fill de-oiled asphalt+metallic nickel powder places vacuum sintering furnace and sealing;
2) extract the sintering furnace air with vavuum pump, vacuum remains on 10 in the stove
-3Pa;
3) open vacuum sintering furnace, be warming up to 2000 ℃ ± 10 ℃, constant temperature, insulation, sintering 60min ± 1min with the programming rate of 25 ℃/min;
4) under vacuum state, cool off with stove
Close vacuum sintering furnace, cooling makes it cool to 20 ℃ ± 3 ℃ of normal temperature with the furnace under vacuum state;
In sintering, cooling procedure chemical reaction will take place, reaction equation is as follows:
In the formula:
Ni
3C: carbonization nickel
(18) collect product
Open vacuum sintering furnace, take out graphite crucible, product in the crucible is collected in the rustless steel container, its product is: bag metallic nickel carbon particulate powder in black, spheroidal, the onion shape;
(19) detect, analyze, characterize
To detect bag metallic nickel carbon particulate powder in the black, spheroidal, onion shape of preparation, detect its color and luster, composition, purity, granule-morphology, cross section architectural feature, physical and chemical performance;
With X-ray diffractometer product structure is analyzed;
Carry out onion shape morphology analysis with high resolution transmission electron microscopy;
Bag metallic nickel carbon particulate is black, spheroidal in the onion shape, and diameter is 10-30nm, and surface coating layer carbon thickness of the shell is 5nm, and nuclear diameter is 5-20nm in the metallic nickel;
(20) product stores
Bag metallic nickel carbon particulate product in the black onion shape of preparation is placed water white glass container, and airtight preservation will fire prevention, waterproof, protection against the tide, anti-soda acid corrode 20 ℃ ± 3 ℃ of storage temperatures, relative humidity≤20%.
The sintering of described de-oiled asphalt is in the quartz tube type high temperature furnace, finishes under the whole process protection of argon gas, and sintering temperature is 1000 ℃ ± 10 ℃, 4 ℃/min of programming rate, and the argon gas input speed is 100cm
3/ min, the input total amount is 100000cm
3± 100cm
3, constant temperature, insulation, sintering time are 60min ± 1min.
The sintering of bag metallic nickel carbon particulate is in vacuum sintering furnace, finish under omnidistance vacuum state in the described onion shape, its sintering temperature is 2000 ℃ ± 10 ℃, programming rate is 25 ℃/min, and constant temperature, insulation, sintering time are 60min ± 1min, and vacuum continues to remain on 10 in the sintering furnace
-3Pa.
Bag metallic nickel carbon particulate is black, spheroidal in the described onion shape, and diameter is 10-30nm, and surface coating layer carbon thickness of the shell is 5nm, and nuclear diameter is 5-20nm in the interior bag metallic nickel.
The sintering of bag metallic nickel carbon particulate in the described onion shape, its de-oiled asphalt powder is 5: 1 with the amount ratio of metallic nickel powder.
Beneficial effect
The present invention compares with background technology has tangible advance; it is to be raw material with de-oiled asphalt, metal nickel powder; with the metallic nickel is catalyst, is cleaning agent with hydrochloric acid, deionized water, is protective gas with the argon gas; in tube type high-temperature furnace; under 1000 ℃ ± 10 ℃ temperature, sintering de-oiled asphalt powder under the argon gas whole process protection is in vacuum sintering furnace; at the de-oiled asphalt powder: the amount of metallic nickel powder=5: 1 than under, be 10 in vacuum
-3Under the Pa, in temperature is under 2000 ℃ ± 10 ℃ conditions of high temperature, constant temperature, insulation, sintering 60min ± 1min, obtain bag metallic nickel carbon particulate product powder in the onion shape, product is a black, spheroidal, diameter is 10-30nm, surface coating layer carbon thickness of the shell is 5nm, nuclear diameter is 5-20nm in the interior bag metallic nickel, its cross section structure has the stacked clad structure of tangible onion shape, carbon shell, the metallic nickel uniform particles has high-purity characteristics, do not need purifying, do not have secondary product, metallic nickel is a catalyst, is again the base nuclear that belongs to covered with gold leaf in the onion shape, its chemical property, physical characteristic is stable, this preparation method's technological process is short, the preparation method is simple, material source is abundant, and it is low to produce cost, the production yield rate height can reach 66%, can use at multiple industrial circle, be the very good method with preparing onion-shaped internal coating metal nickel carbon particle with deoiling asphalt.
Description of drawings
Fig. 1 is preparation technology's flow chart
Fig. 2 is tube type high-temperature furnace sintering de-oiled asphalt powder temperature and time coordinate graph of a relation
Fig. 3 is vacuum sintering furnace sintering de-oiled asphalt+metallic nickel temperature and time coordinate graph of a relation
Fig. 4 is tube type high-temperature furnace and sintering state figure
Fig. 5 is vacuum sintering furnace and sintering state figure
Fig. 6 is bag metallic nickel carbon particulate product stacking states figure in the onion shape
Fig. 7 is bag metallic nickel carbon particulate individual particle coated state figure in the onion shape
Fig. 8 amplifies 300,000 times of appearance structure figure for bag metallic nickel carbon particulate in the onion shape
Fig. 9 amplifies 300,000 times of metallic nickel occupied state figure for bag metallic nickel carbon particulate in the onion shape
Figure 10 is a bag metallic nickel carbon particulate product diffracted intensity collection of illustrative plates in the onion shape
Shown in the figure, list of numerals is as follows:
1, body of heater, 2, quartz ampoule, 3, track, 4, quartzy product boat, 5, resistance heater, 6, quartzy tube chamber, 7, the high-temperature region, 8, tunger tube, 9, argon bottle, 10, the de-oiled asphalt powder, 11, venthole, 12, the argon gas valve, 13, resistance heater, 14, bell, 15, temp probe, 16, the vacuum furnace chamber, 17, vacuum tube, 18, vavuum pump, 19, base, 20, de-oiled asphalt powder+metallic nickel powder, 21, body of heater, 22, graphite crucible.
The specific embodiment
The present invention will be further described below in conjunction with accompanying drawing:
Shown in Figure 1, be preparation technology's flow chart, each preparation parameter is wanted strict control, and its combination matching value sets in advance in test, with gram, milliliter, centimetre
3Be measurement unit, when industrialization is produced, with kilogram, liter, rice
3Be measurement unit.
To preparing required raw chemical material: de-oiled asphalt, metallic nickel, hydrochloric acid, deionized water, argon gas want strict selected, and carry out purity, fineness control, must not have impurity to get involved, in case generate accessory substance.
Want strict weighing to preparing required chemical substance, the proportioning of de-oiled asphalt powder+metallic nickel powder wants strict value by 5: 1 to dispose, and must not plussage compare scope.
It is sufficient that the inert protective gas argon gas is wanted, and control input speed well, wants omnidistance the conveying in preparation process, must not be intermittently, and the existing protective atmosphere of argon gas has the effect of removing other pernicious gases again.
Metallic nickel is the base nuclear of bag metallic nickel carbon particulate in the onion shape; it is again the catalyst of preparation; metallic nickel is under 2000 ℃ of high temperature; but the carbon molecule of catalysis de-oiled asphalt powder is drawn close to metallic nickel powder particle base nuclear; formation is that center stack is around state with base nuclear; make basic stratum nucleare poly-more many more big more; so form the onion-like structure pattern; bag metallic nickel carbon particulate powder is black, spheroidal in the onion shape; be irregular alignment; the individual particle particle diameter is 10-30nm, and the Ni-based nuclear diameter of metal is 5-20nm, and de-oiled asphalt carbon coating layer thickness is 5nm.
The quartz tube type high temperature furnace that preparation is used, vacuum sintering furnace, quartz ampoule, product boat, grinding vessel, screen cloth, container etc. will keep clean, and pollution must not be arranged, in order to avoid generate accessory substance.
Shown in Figure 2; be tube type high-temperature furnace intensification, constant temperature, insulation, chilling temperature and time coordinate graph of a relation; when furnace temperature intersects at the A point when 20 ℃ ± 3 ℃ of normal temperature rise to 1000 ℃ ± 10 ℃; at this temperature constant temperature, insulation, sintering 60min ± 1min; both A-B sections, lowering the temperature under argon shield with stove then is cooled to 20 ℃ ± 3 ℃.
Shown in Figure 3, be vacuum sintering furnace intensification, constant temperature, insulation, chilling temperature and time coordinate graph of a relation, when furnace temperature intersects at the C point when 20 ℃ ± 3 ℃ of normal temperature rise to 2000 ℃ ± 10 ℃, at this temperature constant temperature, insulation, sintering 60min ± 1min, both C-D sections, cooling is cooled to 20 ℃ ± 3 ℃ under vacuum state then.
Shown in Figure 4, be tube type high-temperature furnace structure and sintering state figure, the bottom is a track 3 in the body of heater 1, on track 3, put quartz ampoule 2, quartz ampoule 2 left parts are provided with tunger tube 8, argon gas valve 12, argon bottle 9, and the upper right quarter of quartz ampoule 2 is provided with venthole 11, are quartzy tube chamber 6 in the quartz ampoule 2, high-temperature region, centre position 7 sections are put quartzy product boat 4 in quartzy tube chamber 6, put de-oiled asphalt powder 10 in the quartzy product boat 4.
Shown in Figure 5, be vacuum-sintering furnace structure and sintering state figure, on the top of base 19 is body of heater 21, and body of heater 21 tops are bell 14, and bell 14 is provided with temp probe 15, in the body of heater 21 is vacuum furnace chamber 16, the centre position is provided with graphite crucible 22 in furnace chamber 16, and graphite crucible 22 bottoms are resistance heater 13, puts de-oiled asphalt+metallic nickel powder 20 in the graphite crucible 22, on the furnace wall of body of heater 21, be provided with vacuum tube 17, and UNICOM's vavuum pump 18.
Shown in Figure 6, be bag metallic nickel carbon particulate product stacking states figure in the onion shape, among the figure as can be known: the product powder particle is irregular alignment, is heaped-up, and the metallic nickel particle is dispersed in the carbon matrix, and ruler units is 20nm.
Shown in Figure 7, be bag metallic nickel carbon particulate powder individual particle coated state figure in the onion shape, among the figure as can be known: the Ni-based nuclear particle of metal is spheroidal, is coated by the carbon molecule, and ruler units is 20nm.
Shown in Figure 8, for bag metallic nickel carbon particulate in the onion shape amplifies 300,000 times of appearance structure figure, among the figure as can be known: complete in crystal formation, basic cuclear density height, integument inwardly shrinks, and is well arranged, is the onion shape, ruler units is 5nm.
Shown in Figure 9, for bag metallic nickel carbon particulate in the onion shape amplifies 300,000 times of occupied state figure, among the figure as can be known: the Ni-based nuclear of metal periphery is an onion shape carbon-coating, and its slit is filled by the carbon molecule, makes the coating increase in density, and ruler units is 5nm.
Shown in Figure 10, be bag metallic nickel carbon particulate product diffracted intensity collection of illustrative plates in the onion shape, among the figure as can be known: a highest peak is arranged when the angle of diffraction 2 θ are 26 °, corresponding to carbon (002) face characteristic diffraction peak, three strong diffraction maximums near being 44.45 °, 51.75 °, 76.35 °, 2 θ are arranged, correspond respectively to Ni (111), Ni (200), Ni (220) crystal face, more sharp-pointed, contain more elemental nickel particulate in the visible product.
Claims (5)
1, a kind of method with preparing onion-shaped internal coating metal nickel carbon particle with deoiling asphalt, it is characterized in that: the raw chemical material that uses as de-oiled asphalt, metallic nickel, hydrochloric acid, deionized water, argon gas, its combination matching is: with gram, milliliter, centimetre
3Be unit
De-oiled asphalt: C
559H
690SN
7O
54g ± 0.05g
Nickel powder: Ni 2g ± 0.03g
Hydrochloric acid: HCl 600ml ± 5ml
Deionized water: H
2O 3000ml ± 20ml
Argon gas: Ar 120000cm
3± 100cm
3
The preparation method is as follows:
(1) selected raw chemical material
The raw chemical material that preparation is used will carry out selected, and carries out purity control:
De-oiled asphalt: 98%
Nickel powder: 99.5%
Hydrochloric acid: concentration 38%
Deionized water: 96%
Argon gas: 98%
(2) the dry processing
The de-oiled asphalt that preparation is used places drying baker, carries out drying, 100 ℃ ± 10 ℃ of baking temperatures, drying time 1440min ± 60min;
(3) pulverize, grind, sieve
Will pulverize, grind, sieve the de-oiled asphalt that preparation is used, and carry out fineness control, grind repeatedly, sieve repeatedly, stay fine powder, sieve number is 200 orders, fine powder particle diameter≤0.075mm;
(4) clean the high quartz pipe
1) in the high quartz pipe, injects hydrochloric acid 100ml ± 5ml, scrub 5min with hairbrush;
2) inject deionized water 1000ml ± 5ml, wash, scrub 5min, dry then;
(5) the quartzy product boat of ultrasonic cleaning
1) hydrochloric acid cleans: quartzy product boat is placed ultrasonic cleaner, inject hydrochloric acid 200ml ± 5ml, open ultrasonic cleaner, clean 20min ± 2min, the cleaning back is removed hydrochloric acid and is dried;
2) washed with de-ionized water: in ultrasonic cleaner, add deionized water 400ml ± 5ml, open ultrasonic cleaner, clean 20min ± 2min, take out then and dry;
(6) dry, the quartzy product boat of The pre-heat treatment
Quartzy product boat is placed vacuum drying chamber, preheating under 100 ℃ ± 10 ℃ states, oven dry, the time is 60min ± 5min;
(7) inert gas cleaning quartz ampoule
Input argon gas 400cm in quartz ampoule
3± 10cm
3, input speed 100cm
3/ min drives away pernicious gas in the quartz ampoule, makes to be in the argon gas atmosphere in the quartz ampoule;
(8) put quartzy product boat and raw material
De-oiled asphalt powder 4g ± 0.05g is placed in the quartzy product boat, and quartzy product boat is placed high-temperature region, middle part in the quartz ampoule;
(9) close quartz ampoule, the input inert protective gas
Close quartz ampoule, leave the gas outlet, automatically the adjustable pipe internal gas pressure;
Open tunger tube, in quartz ampoule, import argon gas, input speed 100cm continuously
3/ min;
(10) open the quartz tube type high temperature furnace and carry out sintering
Open tube type high-temperature furnace, 4 ℃/min of programming rate when temperature rises to 1000 ℃ ± 10 ℃, stops to heat up; The de-oiled asphalt powder is at 1000 ℃ ± 10 ℃ sintering temperatures, and insulation 60min ± 1min;
In sintering process chemical reaction will take place, reaction equation is as follows:
In the formula:
C: carbon
H
2: hydrogen
CO
2: carbon dioxide
H
2S: hydrogen sulfide
N
2: nitrogen
H
2O: steam
(11) under argon shield, cool off with stove
Close tube type high-temperature furnace, under argon shield, be cooled to 20 ℃ ± 3 ℃ of normal temperature;
(12) collect product
Open quartz ampoule, take out quartzy product boat and product powder, i.e. de-oiled asphalt product powder behind the sintering;
(13) grind, sieve
De-oiled asphalt powder in the quartzy product boat is placed agate mortar, grind and sieve with agate pestle, sieve number is 200 orders, and powder particle diameter≤0.075mm is standby;
(14) abrasive metal nickel powder
Metal nickel powder 2g ± 0.03g is placed the agate mortar grinding and sieves sieve number 200 orders, powder particle diameter≤0.075mm;
(15) proportioning, mixing
Take by weighing de-oiled asphalt powder 1g ± 0.01g, metal nickel powder 0.2g ± 0.001g, place graphite crucible, the de-oiled asphalt powder: metal nickel powder=5: 1;
(16) cleaning vacuum sintering furnace
With compressed air cleaning vacuum sintering furnace inwall, the time is 6min ± 1min, makes its cleaning;
(17) vacuum sintering furnace sintering
1) graphite crucible that will fill de-oiled asphalt+metallic nickel powder places vacuum sintering furnace and sealing;
2) extract the sintering furnace air with vavuum pump, vacuum remains on 10 in the stove
-3Pa;
3) open vacuum sintering furnace, be warming up to 2000 ℃ ± 10 ℃ with the programming rate of 25 ℃/min, at this temperature sintering 60min ± 1min;
4) under vacuum state, cool off with stove
Close vacuum sintering furnace, cooling makes it cool to 20 ℃ ± 3 ℃ of normal temperature with the furnace under vacuum state;
In sintering, cooling procedure chemical reaction will take place, reaction equation is as follows:
In the formula:
Ni
3C: carbonization nickel
(18) collect product
Open vacuum sintering furnace, take out graphite crucible, product in the crucible is collected in the rustless steel container, its product is: bag metallic nickel carbon particulate powder in black, spheroidal, the onion shape;
(19) detect, analyze, characterize
To detect bag metallic nickel carbon particulate powder in the black, spheroidal, onion shape of preparation, detect its color and luster, composition, purity, granule-morphology, cross section architectural feature, physical and chemical performance;
With X-ray diffractometer product structure is analyzed;
Carry out onion shape morphology analysis with high resolution transmission electron microscopy;
Bag metallic nickel carbon particulate is black, spheroidal in the onion shape, and diameter is 10-30nm, and surface coating layer carbon thickness of the shell is 5nm, and nuclear diameter is 5-20nm in the metallic nickel;
(20) product stores
Bag metallic nickel carbon particulate product in the black onion shape of preparation is placed water white glass container, and airtight preservation will fire prevention, waterproof, protection against the tide, anti-soda acid corrode 20 ℃ ± 3 ℃ of storage temperatures, relative humidity≤20%.
2, a kind of method according to claim 1 with preparing onion-shaped internal coating metal nickel carbon particle with deoiling asphalt; it is characterized in that: the sintering of described de-oiled asphalt is in the quartz tube type high temperature furnace, finishes under the whole process protection of argon gas; sintering temperature is 1000 ℃ ± 10 ℃; 4 ℃/min of programming rate, the argon gas input speed is 100cm
3/ min, sintering time are 60min ± 1min.
3, a kind of method according to claim 1 with preparing onion-shaped internal coating metal nickel carbon particle with deoiling asphalt, it is characterized in that: the sintering of bag metallic nickel carbon particulate is in vacuum sintering furnace, finish under omnidistance vacuum state in the described onion shape, its sintering temperature is 2000 ℃ ± 10 ℃, programming rate is 25 ℃/min, sintering time is 60min ± 1min, and vacuum continues to remain on 10 in the sintering furnace
-3Pa.
4, a kind of method according to claim 1 with preparing onion-shaped internal coating metal nickel carbon particle with deoiling asphalt, it is characterized in that: bag metallic nickel carbon granules powder is that black, spheroidal, diameter are 10-30nm in the described onion shape, surface coating layer carbon thickness of the shell is 5nm, and nuclear diameter is 5-20nm in the interior bag metallic nickel.
5, a kind of method according to claim 1 with preparing onion-shaped internal coating metal nickel carbon particle with deoiling asphalt, it is characterized in that: the sintering of bag metallic nickel carbon granules powder in the described onion shape, the mass ratio of its de-oiled asphalt powder and metallic nickel powder is 5: 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710139628XA CN100571933C (en) | 2007-10-24 | 2007-10-24 | A kind of method with preparing onion-shaped internal coating metal nickel carbon particle with deoiling asphalt |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710139628XA CN100571933C (en) | 2007-10-24 | 2007-10-24 | A kind of method with preparing onion-shaped internal coating metal nickel carbon particle with deoiling asphalt |
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|---|---|
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| CN100571933C true CN100571933C (en) | 2009-12-23 |
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| CN109319757B (en) * | 2018-09-21 | 2022-03-08 | 陕西榆林能源集团有限公司 | Method for preparing hollow open onion carbon lithium ion battery cathode material |
| CN110255626B (en) | 2019-07-08 | 2020-03-03 | 太原理工大学 | Method for preparing surface-active onion-shaped carbon nanospheres based on vapor deposition |
| CN112758915B (en) * | 2020-12-30 | 2022-11-22 | 温州大学 | Preparation method of highly-graphitized mesoporous-rich nano-carbon onion |
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2007
- 2007-10-24 CN CNB200710139628XA patent/CN100571933C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 热处理脱油沥青制备内包金属纳米碳洋葱. 郁军，许并社，杨永珍，张艳，刘旭光.材料热处理学报，第28卷增刊卷. 2007 |
| 热处理脱油沥青制备内包金属纳米碳洋葱. 郁军，许并社，杨永珍，张艳，刘旭光.材料热处理学报，第28卷增刊卷. 2007 * |
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