CN106082129A - There is the MgH of high hydrogen discharging rate2m G mixture system material and raising MgH2the method of hydrogen discharging rate - Google Patents
There is the MgH of high hydrogen discharging rate2m G mixture system material and raising MgH2the method of hydrogen discharging rate Download PDFInfo
- Publication number
- CN106082129A CN106082129A CN201610420034.5A CN201610420034A CN106082129A CN 106082129 A CN106082129 A CN 106082129A CN 201610420034 A CN201610420034 A CN 201610420034A CN 106082129 A CN106082129 A CN 106082129A
- Authority
- CN
- China
- Prior art keywords
- mgh
- hydrogen
- powder
- oxide
- discharging rate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/04—Hydrides of alkali metals, alkaline earth metals, beryllium or magnesium; Addition complexes thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of MgH with high hydrogen discharging rate2M G mixture system material and raising MgH2The method of hydrogen discharging rate, adds to have under microwave irradiation effect and inhales the oxide-based medium of ripple and catalysis dual function to improve MgH2The method of hydrogen discharging rate.The invention have the characteristics that and use oxide M simultaneously as wave absorbing agent and catalyst, its molar content is 3 9mol%；G(graphite) as the auxiliary thermit powder of microwave, its molar content is 1 5mol%；Use the method for ball milling by MgH2, oxide M and G under the protection of noble gas after ball mill mixing, the MgH of high 2 ~ 10 times under the conditions of having than common heating under microwave heating condition2Hydrogen discharging rate.It is an advantage of the current invention that microwave absorption and the catalysis dual function utilizing oxide M to have so that it is there is under microwave field more preferable catalytic action, thus significantly improve MgH2Hydrogen discharging rate under microwave irradiation effect.
Description
Technical field
The present invention relates to a kind of hydrogen storage material and hydrogen method for releasing thereof, particularly relate to a kind of Mg based hydrogen storage material and hydrogen thereof
Method for releasing, is applied to hydrogen storage material preparation technology and applied technical field.
Background technology
Hydrogen Energy, owing to having the advantages such as combustion heat value height, the product cleaning of burning and aboundresources, receives increasingly
Many attention.During hydrogen utilization, the storing hydrogen technology of highly effective and safe becomes restriction Hydrogen Energy application to a great extent
Bottleneck with development.Current hydrogen storage technology is broadly divided into solid-state hydrogen storage, liquid hydrogen storage and three kinds of methods of gaseous state hydrogen storage.Wherein,
Solid-state hydrogen storage material has that hydrogen storage content is big, safety advantages of higher, receives and studies widely.Researchers have probed into multiple solid
State hydrogen storage media, Mg based hydrogen storage material becomes the most promising due to many advantages such as light weight, big, the wide material sources of capacity
Hydrogen storage material.But the problems such as its hydrogen discharging temperature is high, hydrogen desorption kinetics difference limit actually used.Researcher use nanorize,
The methods such as compound, catalysis make the performance of Mg based hydrogen storage material be greatly improved.But its hydrogen discharging temperature is far above combustion
The operating temperature of material battery.How to improve MgH2Hydrogen discharging rate at low temperatures, becomes the weight of current Mg based hydrogen storage material research
Point.
Microwave refers to frequency electromagnetic wave about in wavelength is 300 MHz to 300 GHz range.Microwave can change ion
Migrate and dipole rotation situation, but do not cause the change of molecular structure, belong to non-ionic radiation energy.Microwave has uniqueness
Mode of heating, electromagnetic energy is radiated media interior with the form of ripple, utilizes and add inside and outside the dielectric loss of medium simultaneously by it
Heat, makes medium molecule reach polarized state, the motion of aggravation molecule and collision within the extremely short time.Microwave heating has selection
Property heating, firing rate be fast, homogeneous heating, thermal losses is little, the thermal efficiency is high, the feature such as easily controllable and pollution-free, even more important
, microwave heating has the effect reducing chemical reaction temperature, and microwave energy can make atom and molecule generation vibration at high speed, for
Chemical reaction creates more favorable condition.
Leng et al. is at MgH2Middle addition LiBH4, find along with LiBH4Adding, the microwave heating performance of sample is improved
(Journal of Alloys and Compounds, 597,136-141,2014).MgH in the method2-LiBH4System is micro-
Hydrogen discharging rate under wave radiation is significantly higher than the speed under conventional heating.But, along with LiBH4Increasing of addition, system
Hydrogen discharging rate declines on the contrary, and this is mainly due to MgH2With LiBH4Between there occurs that H-H exchanges, and LiBH4Do not play and urge
The effect changed.Zhang et al. loads hydrogen storage material by using the honeycomb ceramics block (Ni-HCM) of a kind of Ni of scribbling thin layer
Material, Ni-HCM, as a microwave absorption carrier, is heat energy microwave energy, so that hydrogen storage material puts hydrogen rapidly
(International Journal of Hydrogen Energy, 36,7580-7586,2011).But the method is the most abundant
Utilize the catalytic performance inhaling ripple material.MgH2Hydrogen storage capability big, reversible hydrogen sucking function is good, but its microwave absorbing property is poor.
Summary of the invention
In order to solve prior art problem, it is an object of the invention to the deficiency overcoming prior art to exist, it is provided that a kind of
There is the MgH of high hydrogen discharging rate2-M-G mixture system material and raising MgH2The method of hydrogen discharging rate, by MgH2In add
Enter oxide M as the auxiliary thermit powder of microwave as wave absorbing agent and catalyst, addition G, to use microwave heating, give full play to microwave heating
Advantage and TiO2Catalysis and microwave absorbing property, thus significantly improve MgH2Hydrogen discharging rate.The inventive method is simple, both
Overcome MgH2The problem of heat conductivility difference, improves the efficiency of heating surface, promotes again MgH2Hydrogen desorption kinetics performance.
Creating purpose for reaching foregoing invention, the present invention uses following technical proposals:
A kind of MgH with high hydrogen discharging rate2-M-G mixture system material, using oxide M as wave absorbing agent and catalyst, with
Graphite is as the auxiliary thermit powder of microwave, to MgH2A certain amount of oxide M of middle addition and graphite, formed and put hydrogen for microwave irradiation
MgH2-M-G mixture system material, at MgH2In-M-G mixture system material, the content of oxide M and graphite all by mole
Percentages, wherein the content of oxide M is 3-9mol%, and the content of graphite is 1-5mol%, described MgH2-M-G mixes object
Based material is the mixture material of powder shaped, MgH2The powder size of-M-G mixture system material is 100-200 mesh.
As currently preferred technical scheme, described oxide M uses TiO2、Fe3O4And V2O5In any one oxygen
Compound or any several hopcalite.
A kind of raising MgH2The method of hydrogen discharging rate, has a below step:
a. MgH2The preparation of-M-G mixture system material: using oxide M as wave absorbing agent and catalyst, using graphite as micro-
The auxiliary thermit powder of ripple, weighs MgH by certain proportioning2Powder, oxide M powder and powdered graphite, as raw material components, are joined at raw material
During material, the content of oxide M and graphite all presses raw material components molar percent, each during wherein the content of oxide M is raw material
Planting the 3-9mol% of dispensing component total mole number, the content of graphite is the 1-5mol% of various dispensing total mole numbers in raw material, will be each
Raw material components material is collectively disposed in ball mill and is sufficiently mixed, and ball mill ball material weight ratio is 30:1, and the driving shaft of ball mill turns
Speed is 200r/min, and countershaft rotating speed is 400r/min, and major-minor axle steer is contrary, uses each ball milling 10min to stop the interruption of 10min
Ball milling method, ball milling total time is 3h, obtains even-grained MgH2-M-G mixture system material powder, due to part material
Component material is oxidizable, and the weighing of raw material components and ball milling dress sample are all carried out under nonoxidizing atmosphere is protected；The title of raw material components
Amount and ball milling dress sample are the most preferably carried out under inert gas atmosphere is protected, and further preferably carry out under Ar atmosphere protection；Institute
State oxide M and preferably employ TiO2、Fe3O4And V2O5In any one oxide or any several hopcalite；Ball
MgH after mill is uniform2The powder size of-M-G mixture system material is 100-200 mesh；
B. microwave irradiation puts hydrogen: by the MgH after ball milling in described step a is uniform2-M-G mixture system material powder
Load and airtight put hydrogen production device, 400~Heat under the conditions of 1500W microwave power, make MgH2-M-G mixture system material powder is fast
Speed is warming up to 550~600K, the hydrogen release carrying out hydrogen storage material puts, MgH2Hydrogen discharging rate than significantly improving under traditional heating mode
2.0-10.7 times.When the hydrogen release carrying out hydrogen storage material is put, it is preferred to use microwave frequency be 2.45GHz, it is preferred to use
The field pattern of microwave is multimode field pattern.
Feature and the mechanism of the inventive method are as follows:
The present invention adds appropriate graphite to MgH2In sample so that sample can be heated uniformly to rapidly put hydrogen temperature under microwave
Degree, has given full play to the advantage uniform, quick of microwave heating；Ripple and the metal oxygen of catalytic action is inhaled by adding appropriate having
Compound, has given full play to catalyst catalysis activity under microwave heating, thus has significantly improved MgH2Hydrogen discharging rate.
The present invention compared with prior art, has and the most obviously highlights substantive distinguishing features and remarkable advantage:
MgH the most of the present invention2Heating rate is fast, and the efficiency of heating surface is high, MgH2Hydrogen discharging rate significantly improves, with traditional mode of heating
Comparing, hydrogen discharging rate improves 2.2-10.7 times, wherein with the addition of 5mol%TiO2Exist with the hydrogen material sample of putting of 4.2mol% G
Traditional heating stove only has in 5min under 573K the MgH of 46%2Decompose, and at mutually synthermal microwave heating of the present invention
Lower MgH2Decompose the most completely；
2. to make the metal-oxide with wave absorbtion and catalytic performance play under microwave heating important for the inventive method
Catalytic action, thus significantly improve MgH2Hydrogen discharging rate.
Accompanying drawing explanation
Fig. 1 is the MgH of the embodiment of the present invention one preparation2-M-G mixture system material is made at microwave radiation and conventional heating
At the hydrogen desorption kinetics curve comparison figure of 573K under with.
Detailed description of the invention
Details are as follows for the preferred embodiments of the present invention:
Embodiment one:
In the present embodiment, Fig. 1, a kind of raising MgH are seen2The method of hydrogen discharging rate, has a below step:
a. MgH2-TiO2The feed proportioning of-G mixture system material: using titanium dioxide as wave absorbing agent and catalyst, with stone
Ink, as the auxiliary thermit powder of microwave, weighs, by proportioning, the MgH that purity is 80wt.%2Powder 1g, purity is the titanium dioxide of 98 wt.%
(TiO2) powder 0.1 g, purity be graphite (G) powder 0.02 g of 95 wt.% as raw material components, i.e. when feed proportioning,
The content of titanium dioxide and graphite all presses raw material components molar percent, and wherein the content of titanium dioxide is various in being raw material joins
The 5.0mol% of material component total mole number, the content of graphite is the 4.2mol% of various dispensing total mole numbers in raw material, former for preventing
Material component material is oxidized, and the weighing of raw material components is carried out in Ar gas glove box；
b. MgH2-TiO2The preparation of-G mixture system material powder: by same for each raw material components material of weighing in step a
Time be collectively disposed at and go at express speed Pulverisette 4 planetary high-energy ball mill is sufficiently mixed, for preventing raw material components material by oxygen
Changing, carry out the canned sample of ball milling in Ar gas glove box, the ball grinder volume used is 80cm3, ball mill ball material weight ratio is
30:1, the driving shaft rotating speed of ball mill is 200r/min, and countershaft rotating speed is 400r/min, and major-minor axle steer is contrary, uses every time
Ball milling 10min stops the interruption ball milling method of 10min, and ball milling total time is 3h, obtains even-grained MgH2-TiO2-G mixture
System material powder body；
C. microwave irradiation puts hydrogen: in glove box, weighs 0.3g MgH after described step b ball milling is uniform2-TiO2-G
Mixture system material powder is placed in corundum crucible, is then transferred in microwave tube type oven, is passed through purity >=99. after evacuation
The argon of 999% is protected, and opens microwave power supply, and setting power is 800W, by MgH2-TiO2-G mixture system material powder
Being heated to 300 DEG C, the hydrogen release carrying out hydrogen storage material is put.
The present embodiment experimental test and analysis:
Drainage is used to record MgH2Hydrogen discharging rate curve as shown in Figure 1.As a comparison, Fig. 1 gives the present embodiment system
Standby MgH2-TiO2-G mixture system material powder is heated to the hydrogen discharging rate curve after 573K in common heating furnace, it is seen that
Under microwave heating, in 5 minutes, sample puts hydrogen completely, and the hydrogen desorption capacity under the conditions of common heating only has 46%, i.e. microwave heating
Lower hydrogen discharging rate is 2.2 times under conventional heating, sees table 1.
Embodiment two:
The present embodiment is essentially identical with embodiment one, is particular in that:
In the present embodiment, a kind of raising MgH2The method of hydrogen discharging rate, has a below step:
a. MgH2-TiO2The feed proportioning of-G mixture system material: using titanium dioxide as wave absorbing agent and catalyst, with stone
Ink, as the auxiliary thermit powder of microwave, weighs, by proportioning, the MgH that purity is 80wt.%2Powder, purity are the titanium dioxide of 98 wt.%
(TiO2) powder and graphite (G) powder that purity is 95 wt.% are as raw material components, i.e. when feed proportioning, titanium dioxide with
The content of graphite all presses raw material components molar percent, wherein the content of titanium dioxide in being raw material various dispensing components always rub
The 5.0mol% of your number, the content of graphite is the 2.0mol% of various dispensing total mole numbers in raw material, for preventing raw material components material
Oxidized, the weighing of raw material components is carried out in Ar gas glove box；
B. this step is identical with embodiment one；
C. microwave irradiation puts hydrogen: in glove box, weighs 0.3g MgH after described step b ball milling is uniform2-TiO2-G
Mixture system material powder is placed in corundum crucible, is then transferred in microwave tube type oven, is passed through purity >=99. after evacuation
The argon of 999% is protected, and opens microwave power supply, and setting power is 800W, by MgH2-TiO2-G mixture system material powder
Being heated to 320 DEG C, the hydrogen release carrying out hydrogen storage material is put.
The present embodiment experimental test and analysis:
Drainage is used to record MgH2Hydrogen discharging rate curve as shown in Figure 1.As a comparison, Fig. 1 gives the present embodiment system
Standby MgH2-TiO2-G mixture system material powder is heated to the hydrogen discharging rate curve after 573K in common heating furnace, it is seen that
Under microwave heating, in 5 minutes, sample puts hydrogen completely, and the hydrogen desorption capacity under the conditions of common heating only has 46%, i.e. microwave heating
Lower hydrogen discharging rate is 2.2 times under conventional heating, sees table 1.
Embodiment three:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of raising MgH2The method of hydrogen discharging rate, has a below step:
a. MgH2-TiO2The feed proportioning of-G mixture system material: using titanium dioxide as wave absorbing agent and catalyst, with stone
Ink, as the auxiliary thermit powder of microwave, weighs, by proportioning, the MgH that purity is 80wt.%2Powder, purity are the titanium dioxide of 98 wt.%
(TiO2) powder and graphite (G) powder that purity is 95 wt.% are as raw material components, i.e. when feed proportioning, titanium dioxide with
The content of graphite all presses raw material components molar percent, wherein the content of titanium dioxide in being raw material various dispensing components always rub
The 9.0mol% of your number, the content of graphite is the 2.0mol% of various dispensing total mole numbers in raw material, for preventing raw material components material
Oxidized, the weighing of raw material components is carried out in Ar gas glove box；
B. this step is identical with embodiment one；
C. microwave irradiation puts hydrogen: in glove box, weighs 0.3g MgH after described step b ball milling is uniform2-TiO2-G
Mixture system material powder is placed in corundum crucible, is then transferred in microwave tube type oven, is passed through purity >=99. after evacuation
The argon of 999% is protected, and opens microwave power supply, and setting power is 800W, by MgH2-TiO2-G mixture system material powder
Being heated to 320 DEG C, the hydrogen release carrying out hydrogen storage material is put.
The present embodiment experimental test and analysis:
Drainage is used to record MgH2Hydrogen discharging rate curve as shown in Figure 1.As a comparison, Fig. 1 gives the present embodiment system
Standby MgH2-TiO2-G mixture system material powder is heated to the hydrogen discharging rate curve after 573K in common heating furnace, it is seen that
Under microwave heating, in 5 minutes, sample puts hydrogen completely, and the hydrogen desorption capacity under the conditions of common heating only has 46%, i.e. microwave heating
Lower hydrogen discharging rate is 5.6 times under conventional heating, sees table 1.
Embodiment four:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of raising MgH2The method of hydrogen discharging rate, has a below step:
a. MgH2-TiO2The feed proportioning of-G mixture system material: using titanium dioxide as wave absorbing agent and catalyst, with stone
Ink, as the auxiliary thermit powder of microwave, weighs, by proportioning, the MgH that purity is 80wt.%2Powder, purity are the titanium dioxide of 98 wt.%
(TiO2) powder and graphite (G) powder that purity is 95 wt.% are as raw material components, i.e. when feed proportioning, titanium dioxide with
The content of graphite all presses raw material components molar percent, wherein the content of titanium dioxide in being raw material various dispensing components always rub
The 5.0mol% of your number, the content of graphite is the 5.0mol% of various dispensing total mole numbers in raw material, for preventing raw material components material
Oxidized, the weighing of raw material components is carried out in Ar gas glove box；
B. this step is identical with embodiment one；
C. microwave irradiation puts hydrogen: in glove box, weighs 0.3g MgH after described step b ball milling is uniform2-TiO2-G
Mixture system material powder is placed in corundum crucible, is then transferred in microwave tube type oven, is passed through purity >=99. after evacuation
The argon of 999% is protected, and opens microwave power supply, and setting power is 800W, by MgH2-TiO2-G mixture system material powder
Being heated to 280 DEG C, the hydrogen release carrying out hydrogen storage material is put.
The present embodiment experimental test and analysis:
Drainage is used to record MgH2Hydrogen discharging rate curve as shown in Figure 1.As a comparison, Fig. 1 gives the present embodiment system
Standby MgH2-TiO2-G mixture system material powder is heated to the hydrogen discharging rate curve after 573K in common heating furnace, it is seen that
Under microwave heating, in 5 minutes, sample puts hydrogen completely, and the hydrogen desorption capacity under the conditions of common heating only has 46%, i.e. microwave heating
Lower hydrogen discharging rate is 3.5 times under conventional heating, sees table 1.
Embodiment five:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of raising MgH2The method of hydrogen discharging rate, has a below step:
a. MgH2-TiO2The feed proportioning of-G mixture system material: using titanium dioxide as wave absorbing agent and catalyst, with stone
Ink, as the auxiliary thermit powder of microwave, weighs, by proportioning, the MgH that purity is 80wt.%2Powder, purity are the titanium dioxide of 98 wt.%
(TiO2) powder and graphite (G) powder that purity is 95 wt.% are as raw material components, i.e. when feed proportioning, titanium dioxide with
The content of graphite all presses raw material components molar percent, wherein the content of titanium dioxide in being raw material various dispensing components always rub
The 3.0mol% of your number, the content of graphite is the 2.0mol% of various dispensing total mole numbers in raw material, for preventing raw material components material
Oxidized, the weighing of raw material components is carried out in Ar gas glove box；
B. this step is identical with embodiment one；
C. microwave irradiation puts hydrogen: in glove box, weighs 0.3g MgH after described step b ball milling is uniform2-TiO2-G
Mixture system material powder is placed in corundum crucible, is then transferred in microwave tube type oven, is passed through purity >=99. after evacuation
The argon of 999% is protected, and opens microwave power supply, and setting power is 800W, by MgH2-TiO2-G mixture system material powder
Being heated to 320 DEG C, the hydrogen release carrying out hydrogen storage material is put.
The present embodiment experimental test and analysis:
Drainage is used to record MgH2Hydrogen discharging rate curve as shown in Figure 1.As a comparison, Fig. 1 gives the present embodiment system
Standby MgH2-TiO2-G mixture system material powder is heated to the hydrogen discharging rate curve after 573K in common heating furnace, it is seen that
Under microwave heating, in 5 minutes, sample puts hydrogen completely, and the hydrogen desorption capacity under the conditions of common heating only has 46%, i.e. microwave heating
Lower hydrogen discharging rate is 2.2 times under conventional heating, sees table 1.
Embodiment six:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of raising MgH2The method of hydrogen discharging rate, has a below step:
a. MgH2-Fe3O4The feed proportioning of-G mixture system material: with Fe3O4As wave absorbing agent and catalyst, make with graphite
For the auxiliary thermit powder of microwave, weigh, by proportioning, the MgH that purity is 80wt.%2Powder 1g, purity is the Fe of 98 wt.%3O4Powder 0.1 g,
Purity be graphite (G) powder 0.02 g of 95 wt.% as raw material components, i.e. when feed proportioning, Fe3O4Content with graphite
All press raw material components molar percent, wherein Fe3O4Content be the 5.0mol% of various dispensing component total mole numbers in raw material,
The content of graphite is the 3.0mol% of various dispensing total mole numbers in raw material, for preventing raw material components material oxidized, raw material components
Weighing carry out in Ar gas glove box；
b. MgH2-Fe3O4The preparation of-G mixture system material powder: by same for each raw material components material of weighing in step a
Time be collectively disposed at and go at express speed Pulverisette 4 planetary high-energy ball mill is sufficiently mixed, for preventing raw material components material by oxygen
Changing, carry out the canned sample of ball milling in Ar gas glove box, the ball grinder volume used is 80cm3, ball mill ball material weight ratio is
30:1, the driving shaft rotating speed of ball mill is 200r/min, and countershaft rotating speed is 400r/min, and major-minor axle steer is contrary, uses every time
Ball milling 10min stops the interruption ball milling method of 10min, and ball milling total time is 3h, obtains even-grained MgH2-Fe3O4-G mixture
System material powder body；
C. microwave irradiation puts hydrogen: in glove box, weighs 0.3g MgH after described step b ball milling is uniform2-Fe3O4-G
Mixture system material powder is placed in corundum crucible, is then transferred in microwave tube type oven, is passed through purity >=99. after evacuation
The argon of 999% is protected, and opens microwave power supply, and setting power is 800W, by MgH2-Fe3O4-G mixture system material powder
Body is heated to 280 DEG C, and the hydrogen release carrying out hydrogen storage material is put.
The present embodiment experimental test and analysis:
Drainage is used to record MgH2Hydrogen discharging rate curve as shown in Figure 1.As a comparison, Fig. 1 gives the present embodiment system
Standby MgH2-Fe3O4-G mixture system material powder is heated to the hydrogen discharging rate curve after 573K in common heating furnace, can
See that in 5 minutes, sample puts hydrogen completely under microwave heating, and the hydrogen desorption capacity under the conditions of common heating only has 46%, i.e. microwave adds
The lower hydrogen discharging rate of heat is 7.9 times under conventional heating, sees table 1.
Embodiment seven:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of raising MgH2The method of hydrogen discharging rate, has a below step:
a. MgH2-Fe3O4The feed proportioning of-G mixture system material: with Fe3O4As wave absorbing agent and catalyst, make with graphite
For the auxiliary thermit powder of microwave, weigh, by proportioning, the MgH that purity is 80wt.%2Powder 1g, purity is the Fe of 98 wt.%3O4Powder 0.1 g,
Purity be graphite (G) powder 0.02 g of 95 wt.% as raw material components, i.e. when feed proportioning, Fe3O4Content with graphite
All press raw material components molar percent, wherein Fe3O4Content be the 5.0mol% of various dispensing component total mole numbers in raw material,
The content of graphite is the 3.0mol% of various dispensing total mole numbers in raw material, for preventing raw material components material oxidized, raw material components
Weighing carry out in Ar gas glove box；
b. MgH2-Fe3O4The preparation of-G mixture system material powder: by same for each raw material components material of weighing in step a
Time be collectively disposed at and go at express speed Pulverisette 4 planetary high-energy ball mill is sufficiently mixed, for preventing raw material components material by oxygen
Changing, carry out the canned sample of ball milling in Ar gas glove box, the ball grinder volume used is 80cm3, ball mill ball material weight ratio is
30:1, the driving shaft rotating speed of ball mill is 200r/min, and countershaft rotating speed is 400r/min, and major-minor axle steer is contrary, uses every time
Ball milling 10min stops the interruption ball milling method of 10min, and ball milling total time is 3h, obtains even-grained MgH2-Fe3O4-G mixture
System material powder body；
C. microwave irradiation puts hydrogen: in glove box, weighs 0.3g MgH after described step b ball milling is uniform2-Fe3O4-G
Mixture system material powder is placed in corundum crucible, is then transferred in microwave tube type oven, is passed through purity >=99. after evacuation
The argon of 999% is protected, and opens microwave power supply, and setting power is 800W, by MgH2-Fe3O4-G mixture system material powder
Body is heated to 300 DEG C, and the hydrogen release carrying out hydrogen storage material is put.
The present embodiment experimental test and analysis:
Drainage is used to record MgH2Hydrogen discharging rate curve as shown in Figure 1.As a comparison, Fig. 1 gives the present embodiment system
Standby MgH2-Fe3O4-G mixture system material powder is heated to the hydrogen discharging rate curve after 573K in common heating furnace, can
See that in 5 minutes, sample puts hydrogen completely under microwave heating, and the hydrogen desorption capacity under the conditions of common heating only has 46%, i.e. microwave adds
The lower hydrogen discharging rate of heat is 10.3 times under conventional heating, sees table 1.
Embodiment eight:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of raising MgH2The method of hydrogen discharging rate, has a below step:
a. MgH2-Fe3O4The feed proportioning of-G mixture system material: with Fe3O4As wave absorbing agent and catalyst, make with graphite
For the auxiliary thermit powder of microwave, weigh, by proportioning, the MgH that purity is 80wt.%2Powder 1g, purity is the Fe of 98 wt.%3O4Powder 0.1 g,
Purity be graphite (G) powder 0.02 g of 95 wt.% as raw material components, i.e. when feed proportioning, Fe3O4Content with graphite
All press raw material components molar percent, wherein Fe3O4Content be the 5.0mol% of various dispensing component total mole numbers in raw material,
The content of graphite is the 3.0mol% of various dispensing total mole numbers in raw material, for preventing raw material components material oxidized, raw material components
Weighing carry out in Ar gas glove box；
b. MgH2-Fe3O4The preparation of-G mixture system material powder: by same for each raw material components material of weighing in step a
Time be collectively disposed at and go at express speed Pulverisette 4 planetary high-energy ball mill is sufficiently mixed, for preventing raw material components material by oxygen
Changing, carry out the canned sample of ball milling in Ar gas glove box, the ball grinder volume used is 80cm3, ball mill ball material weight ratio is
30:1, the driving shaft rotating speed of ball mill is 200r/min, and countershaft rotating speed is 400r/min, and major-minor axle steer is contrary, uses every time
Ball milling 10min stops the interruption ball milling method of 10min, and ball milling total time is 3h, obtains even-grained MgH2-Fe3O4-G mixture
System material powder body；
C. microwave irradiation puts hydrogen: in glove box, weighs 0.3g MgH after described step b ball milling is uniform2-Fe3O4-G
Mixture system material powder is placed in corundum crucible, is then transferred in microwave tube type oven, is passed through purity >=99. after evacuation
The argon of 999% is protected, and opens microwave power supply, and setting power is 800W, by MgH2-Fe3O4-G mixture system material powder
Body is heated to 320 DEG C, and the hydrogen release carrying out hydrogen storage material is put.
The present embodiment experimental test and analysis:
Drainage is used to record MgH2Hydrogen discharging rate curve as shown in Figure 1.As a comparison, Fig. 1 gives the present embodiment system
Standby MgH2-Fe3O4-G mixture system material powder is heated to the hydrogen discharging rate curve after 573K in common heating furnace, can
See that in 5 minutes, sample puts hydrogen completely under microwave heating, and the hydrogen desorption capacity under the conditions of common heating only has 46%, i.e. microwave adds
The lower hydrogen discharging rate of heat is 10.7 times under conventional heating, sees table 1.
Embodiment nine:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of raising MgH2The method of hydrogen discharging rate, has a below step:
a. MgH2-Fe3O4The feed proportioning of-G mixture system material: with Fe3O4As wave absorbing agent and catalyst, make with graphite
For the auxiliary thermit powder of microwave, weigh, by proportioning, the MgH that purity is 80wt.%2Powder 1g, purity is the Fe of 98 wt.%3O4Powder 0.1 g,
Purity be graphite (G) powder 0.02 g of 95 wt.% as raw material components, i.e. when feed proportioning, Fe3O4Content with graphite
All press raw material components molar percent, wherein Fe3O4Content be the 5.0mol% of various dispensing component total mole numbers in raw material,
The content of graphite is the 4.0mol% of various dispensing total mole numbers in raw material, for preventing raw material components material oxidized, raw material components
Weighing carry out in Ar gas glove box；
b. MgH2-Fe3O4The preparation of-G mixture system material powder: by same for each raw material components material of weighing in step a
Time be collectively disposed at and go at express speed Pulverisette 4 planetary high-energy ball mill is sufficiently mixed, for preventing raw material components material by oxygen
Changing, carry out the canned sample of ball milling in Ar gas glove box, the ball grinder volume used is 80cm3, ball mill ball material weight ratio is
30:1, the driving shaft rotating speed of ball mill is 200r/min, and countershaft rotating speed is 400r/min, and major-minor axle steer is contrary, uses every time
Ball milling 10min stops the interruption ball milling method of 10min, and ball milling total time is 3h, obtains even-grained MgH2-Fe3O4-G mixture
System material powder body；
C. microwave irradiation puts hydrogen: in glove box, weighs 0.3g MgH after described step b ball milling is uniform2-Fe3O4-G
Mixture system material powder is placed in corundum crucible, is then transferred in microwave tube type oven, is passed through purity >=99. after evacuation
The argon of 999% is protected, and opens microwave power supply, and setting power is 800W, by MgH2-Fe3O4-G mixture system material powder
Body is heated to 320 DEG C, and the hydrogen release carrying out hydrogen storage material is put.
The present embodiment experimental test and analysis:
Drainage is used to record MgH2Hydrogen discharging rate curve as shown in Figure 1.As a comparison, Fig. 1 gives the present embodiment system
Standby MgH2-Fe3O4-G mixture system material powder is heated to the hydrogen discharging rate curve after 573K in common heating furnace, can
See that in 5 minutes, sample puts hydrogen completely under microwave heating, and the hydrogen desorption capacity under the conditions of common heating only has 46%, i.e. microwave adds
The lower hydrogen discharging rate of heat is 9.8 times under conventional heating, sees table 1.
Table 1. the above embodiment of the present invention experimental test and analysis situation contrast table
The above embodiment of the present invention adds the oxide-based medium having suction ripple with catalysis dual function under microwave irradiation effect
Improve MgH2Hydrogen discharging rate, the above embodiment of the present invention is respectively adopted oxide TiO2Or Fe3O4Simultaneously as wave absorbing agent and urging
Agent, and use G(graphite) as the auxiliary thermit powder of microwave, use the method for ball milling by MgH2, oxide and G be the guarantor of noble gas
After protecting lower ball mill mixing, the MgH of high 2.2 ~ 10.7 times under the conditions of having than common heating under microwave heating condition2Put hydrogen speed
Rate.The advantage of the above embodiment of the present invention method is microwave absorption and the catalysis dual function utilizing oxide to have so that it is
There is under microwave field more preferable catalytic action, thus significantly improve MgH2Hydrogen discharging rate under microwave irradiation effect.
Above in conjunction with accompanying drawing, the embodiment of the present invention is illustrated, but the invention is not restricted to above-described embodiment, it is also possible to
The purpose of the innovation and creation according to the present invention makes multiple change, under all spirit according to technical solution of the present invention and principle
The change made, modify, substitute, combine or simplify, all should be the substitute mode of equivalence, as long as meeting the goal of the invention of the present invention,
There is the MgH of high hydrogen discharging rate without departing from the present invention2-M-G mixture system material and raising MgH2The method of hydrogen discharging rate
Know-why and inventive concept, broadly fall into protection scope of the present invention.
Claims (8)
1. a MgH with high hydrogen discharging rate2-M-G mixture system material, it is characterised in that: using oxide M as inhaling ripple
Agent and catalyst, using graphite as the auxiliary thermit powder of microwave, to MgH2A certain amount of oxide M of middle addition and graphite, formed for micro-
Wave radiation method puts the MgH of hydrogen2-M-G mixture system material, at MgH2In-M-G mixture system material, oxide M and graphite
Content all by mole meter, wherein the content of oxide M is 3-9mol%, and the content of graphite is 1-5mol%, described
MgH2-M-G mixture system material is the mixture material of powder shaped, described MgH2The powder grain of-M-G mixture system material
Degree is 100-200 mesh.
The most according to claim 1, there is the MgH of high hydrogen discharging rate2-M-G mixture system material, it is characterised in that: described
Oxide M uses TiO2、Fe3O4And V2O5In any one oxide or any several hopcalite.
3. one kind is improved MgH2The method of hydrogen discharging rate, it is characterised in that there is below step:
a. MgH2The preparation of-M-G mixture system material: using oxide M as wave absorbing agent and catalyst, using graphite as microwave
Auxiliary thermit powder, weighs MgH by certain proportioning2Powder, oxide M powder and powdered graphite are as raw material components, at feed proportioning
Time, the content of oxide M and graphite all presses raw material components molar percent, and wherein the content of oxide M is various in being raw material
The 3-9mol% of dispensing component total mole number, the content of graphite is the 1-5mol%, Jiang Geyuan of various dispensing total mole numbers in raw material
Material component material is collectively disposed in ball mill and is sufficiently mixed, and ball mill ball material weight ratio is 30:1, the driving shaft rotating speed of ball mill
For 200r/min, countershaft rotating speed is 400r/min, and major-minor axle steer is contrary, uses each ball milling 10min to stop between 10min and intercepts
Mill mode, ball milling total time is 3h, obtains even-grained MgH2-M-G mixture system material powder, the weighing of raw material components
All carry out under nonoxidizing atmosphere is protected with ball milling dress sample；
B. microwave irradiation puts hydrogen: by the MgH after ball milling in described step a is uniform2-M-G mixture system material powder
Load and airtight put hydrogen production device, 400~Heat under the conditions of 1500W microwave power, make MgH2-M-G mixture system material powder is fast
Speed is warming up to 550~600K, the hydrogen release carrying out hydrogen storage material is put.
Improve MgH the most according to claim 32The method of hydrogen discharging rate, it is characterised in that: in described step a, raw material group
The weighing divided and ball milling dress sample are all carried out under inert gas atmosphere is protected.
Improve MgH the most according to claim 32The method of hydrogen discharging rate, it is characterised in that: in described step a, raw material group
The weighing divided and ball milling dress sample are all carried out under Ar atmosphere protection.
6. according to improving MgH described in any one in claim 3～52The method of hydrogen discharging rate, it is characterised in that: in described step
MgH in rapid a, after ball milling is uniform2The powder size of-M-G mixture system material powder is 100-200 mesh.
7. according to improving MgH described in any one in claim 3～52The method of hydrogen discharging rate, it is characterised in that: in described step
In rapid b, when the hydrogen release carrying out hydrogen storage material is put, the microwave frequency of employing is 2.45GHz, and the field pattern of the microwave of employing is multimode
Field pattern.
8. according to improving MgH described in any one in claim 3～52The method of hydrogen discharging rate, it is characterised in that: in described step
In rapid a, described oxide M uses TiO2、Fe3O4And V2O5In any one oxide or the mixing of any several oxide
Thing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610420034.5A CN106082129A (en) | 2016-06-13 | 2016-06-13 | There is the MgH of high hydrogen discharging rate2m G mixture system material and raising MgH2the method of hydrogen discharging rate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610420034.5A CN106082129A (en) | 2016-06-13 | 2016-06-13 | There is the MgH of high hydrogen discharging rate2m G mixture system material and raising MgH2the method of hydrogen discharging rate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106082129A true CN106082129A (en) | 2016-11-09 |
Family
ID=57846032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610420034.5A Pending CN106082129A (en) | 2016-06-13 | 2016-06-13 | There is the MgH of high hydrogen discharging rate2m G mixture system material and raising MgH2the method of hydrogen discharging rate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106082129A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021142742A1 (en) * | 2020-01-17 | 2021-07-22 | 湖南三重理想储能科技有限公司 | Energy storage medium and adsorption medium microwave heating apparatus |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102021354A (en) * | 2010-11-09 | 2011-04-20 | 上海大学 | Magnesium-nickel-cerium/graphite composite hydrogen storage material and preparation method thereof |
| CN103264159A (en) * | 2013-05-29 | 2013-08-28 | 上海大学 | Method for achieving rapid hydrogen desorption of MgH2 under microwave |
-
2016
- 2016-06-13 CN CN201610420034.5A patent/CN106082129A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102021354A (en) * | 2010-11-09 | 2011-04-20 | 上海大学 | Magnesium-nickel-cerium/graphite composite hydrogen storage material and preparation method thereof |
| CN103264159A (en) * | 2013-05-29 | 2013-08-28 | 上海大学 | Method for achieving rapid hydrogen desorption of MgH2 under microwave |
Non-Patent Citations (2)
| Title |
|---|
| D.MIRABILE GATTIA ET AL.: "Microstructure and kinetics evolution in MgH2-TiO2 pellets after hydrogen cycling", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| 孙宝龙 等: "MgH2-graphene复合储氢材料吸放氢性能", 《安徽工业大学学报（自然科学版）》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021142742A1 (en) * | 2020-01-17 | 2021-07-22 | 湖南三重理想储能科技有限公司 | Energy storage medium and adsorption medium microwave heating apparatus |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103736515A (en) | High-property absorption and wave absorption type catalyst for VOCs (Volatile Organic Chemicals) catalytic oxidation and preparation of catalyst | |
| Mirochnik et al. | Crystal structure and luminescence of the [Eu (Phen) 2 (NO3) 3] complex. The role of the ion-coactivator | |
| Parkkima et al. | The YBaCo4O7+ δ‐Based Functional Oxide Material Family: A Review | |
| CN105329876A (en) | Preparation method of boron-nitrogen-co-doped carbon dots | |
| CN103264159B (en) | Method for achieving rapid hydrogen desorption of MgH2 under microwave | |
| CN103236545A (en) | Natural graphite with coating modification and preparation method thereof | |
| CN108054381A (en) | A kind of rear-earth-doped type lithium manganese silicate anode material and its microwave radiation technology preparation method | |
| CN108993563A (en) | A kind of preparation method of the three-dimensional network frame of montmorillonite and graphite phase carbon nitride | |
| Cai et al. | High-entropy layered oxide cathode enabling high-rate for solid-state sodium-ion batteries | |
| CN104587471A (en) | Functional hollow mesoporous SiO2 nanometer composite material and preparation method thereof | |
| CN101944594A (en) | Lithium ferrous silicate anode material for high-performance lithium ion battery and preparation method thereof | |
| CN102731110A (en) | Method for fast preparing boron carbide ceramic powder | |
| CN103252240A (en) | A solvothermal method for solid solution catalyst NixM1-x-yMgyO (M is Ce, co, sn, mn) used for dry gas reforming of CH4-CO2 | |
| CN104987057A (en) | High-emissivity infrared energy-saving material and applications thereof | |
| CN102924083B (en) | Method for preparing zirconium carbide ceramic powder | |
| CN110152701B (en) | Bi2O2CO3/Bi2WO6:Yb3+、Er3+Photocatalyst and preparation method and application thereof | |
| CN106082129A (en) | There is the MgH of high hydrogen discharging rate2m G mixture system material and raising MgH2the method of hydrogen discharging rate | |
| Li et al. | Enhancement of green upconversion luminescence of Yb3+/Tb3+ co-doped BiOBr nanosheets and its potential applications in photocatalysis | |
| CN101891193B (en) | Sol-gel Method for preparing nano vanadium carbide | |
| CN106362677A (en) | Method for preparing doping type carbon dioxide adsorbent ceramic | |
| CN101886202B (en) | Method for synthesizing La-Mg hydrogen storage alloy by microwave aid heating | |
| CN101186300A (en) | Method for preparing titanium-silicon compound and doping material thereof by microwave irradiation | |
| Lu et al. | A visible‐light‐driven photocatalyst of NASICON Li2Ni2 (MoO4) 3 nanoparticles | |
| US20220306543A1 (en) | Method for preparing boron carbide material | |
| CN103588171B (en) | Circulate under a kind of Li-N-H of realization system microwave and put the method for hydrogen fast |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161109 |