CN109231158A - Nano packaging structure enabling dynamics of active material to be controllable and preparation method - Google Patents
Nano packaging structure enabling dynamics of active material to be controllable and preparation method Download PDFInfo
- Publication number
- CN109231158A CN109231158A CN201810783976.9A CN201810783976A CN109231158A CN 109231158 A CN109231158 A CN 109231158A CN 201810783976 A CN201810783976 A CN 201810783976A CN 109231158 A CN109231158 A CN 109231158A
- Authority
- CN
- China
- Prior art keywords
- active material
- ball
- nanoencapsulation
- hydrogen
- thin layer
- 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.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
- B81C1/00126—Static structures not provided for in groups B81C1/00031 - B81C1/00119
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/16—Preventing evaporation or oxidation of non-metallic liquids by applying a floating layer, e.g. of microballoons
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a nano packaging structure and a preparation method for enabling active material dynamics to be controllable, which mainly take a nano packaging technology of graphene to active alkali metal, hydride thereof and aluminum hydride to regulate and control the hydrolysis reaction dynamics process of the graphene as an example. The method is simple and feasible, has low cost and is suitable for industrial production.
Description
Technical field
The invention belongs to new energy materials and its preparation technical field, in particular to one kind keeps active material dynamics controllable
Nanoencapsulation structure and preparation method.
Background technique
Active material such as alkali metal and its hydride and alanate etc. are due to easily aoxidizing and deliquescing, and not only storage is tired
Difficulty, while meeting water and explosive reaction occurs, and then greatly limiting its practical application.Active material (such as lithium, potassium, sodium at present
Metal and its hydride and alanate etc.) it is enclosed in light mineral oil and stores, but while using, needs in glove box activity
Material takes out from oil and wipes grease stain, uses high operation requirements.The prior art is by lithium hydride and light mineral oil, dispersing agent system
It is standby to be stored for slurry encapsulation；The prior art by calcium hydride with epoxy resin be mixed cure package after outer surface using aluminium layer into
One step is packaged.This method can effectively inhibit wherein active material and uncontrollable reaction occurs, but there are active principles
The lower problem of quality accounting.Sodium hydride also has using coating resin film or baton round encapsulation, but these balls need onboard one
An a opening, when in use to technical requirements height, this packaging method equally exists effective mass than low, and needs when use
Housing material is peeled off, oil seal type is similar to and stores.Macroscopical generally existing effective mass of packing method than low, and in use
Need to remove encapsulating material, operation needs the problems such as completing under inert ambient environment.And nanoencapsulation is due to nano material
The features such as nanometer size effect and high-specific surface area, can carry out that surface is modified or synthesis new material to material, magnetic material,
Before electronic material, optical material and high-strength, high density material sintering, catalysis, sensing etc. suffer from wide application
Scape.
The prior art utilizes Density functional theory study Zn12O12To the thermodynamics of alkali metal (Li, Na) nanoencapsulation
Matter, its Gibbs free energy is negative value after finding nanoencapsulation, can be improved the stability of alkali metal.But it is experimentally also unreal
The nanoencapsulation of existing active material.Existing nanoencapsulation has the encapsulation for being applied to opposite stabilizing material to coat, the prior art point
The nanoencapsulation of minute quantity metal is not realized by the method that similar approach synthesizes pod-like carbon nanotube, but by synthesizing
The nanoencapsulation method of cladding metal in a small amount of is obtained during carbon nanotube, the type and amount of metal are all by great
Limitation.The method that the prior art is filled by vacuum sublimation realize carbon nanotube to the nanoencapsulation of different metal and organic matter,
The type and mass ratio that the material of nanoencapsulation can be greatly improved, realize the nanoencapsulation of the poor phosphorus of stability recently.
But there is complexity to the encapsulation of different materials by carbon nanotube, poor controllability, yield is lower, is packaged material with respect to covering
The low problem of package material mass ratio, to limit its practical application.
Nanoencapsulation technology is also applied in the cladding of catalyst and then prevent the poisoning of catalyst simultaneously.The prior art is adopted
Use SiO2Mesoporous TiO2Hybrid hollow microballoon encapsulates nanogold cyclohexane oxidation catalyst；The prior art uses inverse micelle method system
For multicore nucleocapsid Au-Co@SiO2Nanosphere obtains monokaryon nanosphere to improve catalyzing manufacturing of hydrogen activity after processing.Nanometer envelope
Dress concept is also used on dendrimer skeleton in the work of growth catalyst nano particle.This method can be urged by control
The activity of agent and then the dynamic process for controlling material reaction, catalysis process are the dynamic process of raising material mostly, but
It is or the poisoning problem of catalyst can not be avoided completely.
The prior art carries out nanoencapsulation to active material using thin layer two-dimensional material, realizes that active material is steady in air
It is fixed to exist, while by the mass transport process of differential responses component in control reaction, and then control the dynamics mistake of the active material
Journey.Promote kinetic reaction process different from catalysis method, which is the mass transport process by inhibiting reactive component
And then inhibit the dynamic process of material reaction, also avoid the catalyst poisoning phenomenon that catalysis method is difficult to avoid that.Such as alkali gold
Category and its hydride and alanate carry out nanoencapsulation by thin graphene, and graphene (002) crystal face is made to be parallel to alkali gold
Belong to and its outer surface of hydride and alanate, graphene (002) crystal face closely overlap, prevents vapor and oxygen in air
Gas is entered by graphene gap to be reacted with active material alkali metal and its hydride and alanate, active material
Material is kept apart with external environment, is improved its storing and transporting security, is slowly being opened between graphene and graphene in liquid environment
Spacing realize hydrone mass transfer so that realize active material dynamics Controlling.It is well known that alkali metal and its hydride
It is that ideal solid-state hydrogen storage material, alkali metal and its hydride and alanate solid-state hydrogen storage material can overcome with alanate
The hydrogen storage and transportation problem faced now, as high-pressure gaseous hydrogen storing method bulk density is relatively small and low temperature liquid hydrogen storage liquefaction of hydrogen
The problem of condition harshness.Relative to gaseous state, the hydrogen storage method of liquid, solid-state hydrogen storage is in operational safety, energy efficiency and volume
There is significant advantage in terms of density, be acknowledged as the hydrogen storage mode of most prospect, but existing reversible hydrogen storage material is unable to satisfy
Vehicle-mounted hydrogen storage system weight/volume hydrogen-storage density, operation temperature, suction/hydrogen discharging rate, in terms of comprehensive performance
It is required that therefore hydrolyzing the solid-state hydrogen storage material such as metal hydride and alanate of releasing hydrogen as the emerging research in hydrogen storage material field
Direction.Hydrogen is released different from the high temperature of reversible hydrogen storage, the solid-state hydrogen storage material that hydrogen is released in hydrolysis can realize that the hydrogen of releasing under different temperatures is wanted
It asks or even severe winter condition (as -40 DEG C).The boron hydride for being used for general SUV for solid-state hydrogen storage material such as 2000 of hydrogen is released in hydrolysis
(sodium borohydride), high stability, hydrogen storage quality is high (21%), easily stored and can hydrolyze to obtain hydrogen in room temperature condition, but
There are reaction rates to be difficult to control for it, noble metal catalyst is needed to control its kinetics, expensive and recycling
It is difficult.
The storage of hydrogen solid-state is released in the hydrolysis for being difficult to the problem of recycling, metal and its hydride and alanate relative to boron hydride
The recycling of hydrogen material is relatively easy, and releases hydrogen process without noble metal catalyst.But hydrolysis is when releasing hydrogen, mg-based material, aluminium base
It is Mg (OH) that material hydrolysis, which can form main component on surface,2、Al(OH)3Passivation layer to preventing it from further reacting, need
It adds other metal nanoparticles or adds the material of other adjustment pH values in water and then promote the progress of reaction, at these
Reason process further decreases its hydrogen storage mass ratio；AlH3Although having very high hydrogen storage mass ratio (20%), AlH3It is synthesizing
After may at once natural and reaction need to heat and could complete, it is difficult to that realizes zubzero temperature releases hydrogen；CaH2Hydrogen storage mass ratio
It is lower, not counting only 9.6% in the case where water；LiH, NaH, KH are with the high response with water and have spontaneous wind
Danger burning；Composite alkali aluminum hydride LiAlH4And NaAlH4Various aspects hydrogen storage property is excellent, too fast but there are reaction speeds, difficult
It, when not used must moisture and oxygen in air-isolation to control and store difficulty.In conclusion alkali metal and its hydride and aluminium
Hydride can hydrolyze rapidly and release hydrogen, but often moment formed it is volatile reaction release a large amount of hydrogen, reaction is can not
Control, and to keep apart completely with moisture and oxygen in storage and transport process, certain challenge is also brought to storage and transport process.
Summary of the invention
The purpose of the present invention is to provide a kind of nanoencapsulation structure and preparation method for keeping active material dynamics controllable,
To solve the above problems.
To achieve the above object, the invention adopts the following technical scheme:
A kind of nanoencapsulation structure for keeping active material dynamics controllable, including active material, thin layer two dimension dense material,
Cure package material and active material be it is spherical, thin layer two dimension dense material is coated on the outside of active material, and it is fine and close to form two dimension
Material clad；Cure package material is coated on the outside of thin layer two dimension dense material, forms the nanoencapsulation cladding of active material
Spherical structure.
Further, the active material sphere being wrapped by is medicine ball, hollow sphere or porous ball；The active material being wrapped by
The diameter of sphere is 200 μm of -25mm.
Further, the number of plies of thin layer two dimension dense material (2) is 1-20 layers, and two-dimentional dense material coating thickness is 1-
100 atomic layer level thickness, the weight of two-dimentional dense material clad and the weight ratio of both active materials are 0.01% to 0.5%
Between.
Further, a kind of preparation method for the nanoencapsulation structure for keeping active material dynamics controllable, including following step
It is rapid:
Step 1, first that active material ball is prepared using the method for cutting, compacting or polishing under atmosphere of inert gases；
Step 2, under inert atmosphere or vacuum, thin layer two dimension dense material is coated on the surface of active material；
Step 3, it is carried out in the active material ball surface for having coated dimensional thinlayer material by the mold of cure package material
Cure package.
Further, in step 2, active material surface coat thin layer two dimension dense material the following steps are included:
A) two-dimensional material ball high-pressure graphite ball is put into the vessel for filling dilute hydrochloric acid, is cleaned by ultrasonic at room temperature, remove table
The caducous small clast in face, is then dried；
B) sphere of two-dimensional material is mixed with the microballoon being wrapped by by 1:1~1:5 volume ratio, obtains mixture A；
C) under inert atmosphere or vacuum, mixture A is placed in container and is sealed, then by mechanical mixture, makes to mix
Rolling friction occurs in a reservoir for two components closed in object A, and induction two-dimensional material thin layer is from the surface of two-dimensional material ball to micro-
The surface of ball is shifted, and mixture B is obtained；
D) two-dimensional material ball is taken out from mixture B, obtains two-dimensional material and uniformly coats microsphere particle.
Further, container is teflon seal ball grinder, stainless steel seals ball grinder, hard alloy seals ball milling
Tank, aluminium oxide/corundum seal ball grinder, zirconium oxide seals ball grinder, polyurethane ball sealing grinding jar, silicon carbide seal ball grinder,
Agate ball sealing grinding jar or nylon ball seal any one in grinding jar；Mechanical mix techniques are that ball milling mixing or roller are mixed
It closes；Ball milling mixing or roller revolving speed are between 200rpm to 700rpm；Ball-milling Time is 1h-96h.
Further, the volume ratio of integral material is 0.1-0.95 after the active material and nanoencapsulation before nanoencapsulation.
Further, the mold in step 3 is silica gel and graphite or metal alloy mold；Cure package material be resin or
Aluminum oxide film；Cure package material with a thickness of 0.02mm-4.5mm.
Compared with prior art, the present invention has following technical effect:
Active material after nanoencapsulation of the present invention in air can storage-stable, without harsh storage condition.This
The accounting of invention active material, can reach within the scope of 2-93%.
The uncontrollable reaction of active material can be regulated and controled according to practical application request after nanoencapsulation of the present invention.
Dynamics regulation of the invention is not necessarily to the participation of catalyst, avoids catalyst asking using generation catalyst poisoning
Topic.The present invention is applied to hydrolysis and releases in the high density solid-state hydrogen storage material of hydrogen, and high hydrogen storage mass ratio can be obtained in material system,
Its hydrogen storage mass ratio can reach 20wt% or more in water-free situation, aqueous to reach 10% or more, and releasing hydrogen can be in -40-
It is controllably carried out under 100 DEG C and normal pressure, while the problems such as the storage and transportation for solving hydrogen is difficult.
The nanoencapsulation method is low in cost and preparation step is simple, is easy to industrialized mass production.
Detailed description of the invention
Fig. 1 is active material package structure diagram of the invention；
Fig. 2 is active material pictorial diagram of the invention；
Fig. 3 is the pictorial diagram of the active material of dimensional thinlayer material graphene coated of the invention；
Fig. 4 is the active material pictorial diagram after nanoencapsulation of the invention, i.e., carries out cure package to the graphene of Fig. 3
(a) resin curable epoxide, (b) aluminum oxide film cure package；
Fig. 5 is that the present invention releases hydrogen datagram by taking lithium metal hydrolysis as an example；
Wherein: active material 1, thin layer two dimension dense material 2, cure package material 3.
Specific embodiment
Below in conjunction with attached drawing, the present invention is further described:
Fig. 1-Fig. 5 is please referred to,
A kind of nanoencapsulation structure for keeping active material dynamics controllable, including active material 1, thin layer two dimension dense material
2 and cure package material 3；Active material be it is spherical, thin layer two dimension dense material is coated on the outside of active material, cure package material
Material is coated on the outside of thin layer two dimension dense material, forms the nanoencapsulation cladding spherical structure of active material.
The active material sphere being wrapped by is medicine ball, hollow sphere or porous ball；The active material sphere being wrapped by it is straight
Diameter is 200 μm of -25mm.
The number of plies of thin layer two dimension dense material 2 is 1-20 layers, and two-dimentional dense material coating thickness is 1-100 atomic layers thick
Degree, the weight of two-dimentional dense material clad and the weight ratio of active material are between 0.01% to 0.5%.
A kind of preparation method for the nanoencapsulation structure for keeping active material dynamics controllable, based on described in above-mentioned any one
A kind of active material nanoencapsulation coat spherical structure, comprising the following steps:
Step 1, first that active material ball is prepared using the method for cutting, compacting or polishing under atmosphere of inert gases；
Step 2, under inert atmosphere or vacuum, thin layer two dimension dense material is coated on the surface of active material；
Step 3, it is carried out in the active material ball surface for having coated dimensional thinlayer material by the mold of cure package material
Cure package.
In step 2, active material surface coat thin layer two dimension dense material the following steps are included:
A) two-dimensional material ball high-pressure graphite ball is put into the vessel for filling dilute hydrochloric acid, is cleaned by ultrasonic at room temperature, remove table
The caducous small clast in face, is then dried；
B) by the sphere of two-dimensional material, example is mixed according to a certain volume with the microballoon that is wrapped by, obtains mixture A；
C) under inert atmosphere or vacuum, mixture A is placed in container and is covered, then by mechanical mixture, makes to mix
Rolling friction occurs in a reservoir for two components closed in object A, and induction two-dimensional material thin layer is from the surface of two-dimensional material ball to micro-
The surface of ball is shifted, and mixture B is obtained；
D) two-dimensional material ball is taken out from mixture B, obtains two-dimensional material and uniformly coats microsphere particle.
Container is teflon seal ball grinder, stainless steel seals ball grinder, hard alloy seals ball grinder, oxidation
Aluminium/corundum sealing ball grinder, zirconium oxide sealing ball grinder, polyurethane ball sealing grinding jar, silicon carbide sealing ball grinder, agate ball are close
Envelope grinding jar or nylon ball seal any one in grinding jar；Mechanical mix techniques are that ball milling mixing or roller mix；Ball milling is mixed
It closes or roller revolving speed is between 200rpm to 700rpm；Ball-milling Time is 1h-96h.
The volume ratio of material is 0.1-0.95 after the forward and backward active material of nanoencapsulation and nanoencapsulation.
Mold in step 3 is silica gel and graphite or metal alloy mold；Cure package material is resin or aluminum oxide film
Film；Cure package material with a thickness of 0.02mm-4.5mm.
Active material of the present invention is by taking alkali metal and its hydride and alanate as an example, two-dimentional dense material with graphene is
Example, shell encapsulation do into one the present invention below in conjunction with attached drawing and embodiment by taking resin or metal-oxide film as an example
Step is described in detail:
A) active material bead (see Fig. 2), ball are first prepared using the method for cutting or compacting under atmosphere of inert gases
Body diameter between 25mm, but is not limited to the range at 200 μm；
B) under an inert atmosphere in graphite of the low layer number without function dough of active material bead surface cladding thin layer densification
Alkene (see Fig. 3), wherein mass ratio≤1:40 of the graphene compared with active material；
C) it will be coated on the solid graphite alkene thin layer further progress curing process of surface of active material, prevent graphene from existing
In subsequent processes the problems such as falling off.Resin solidification is respectively adopted and two methods of aluminum oxide film carry out curing process.
1. epoxy resin cure method: the epoxy monomer and curing agent for first mixing half are added in ready-made spherical silica gel mold, about
Lithium ball is put into corresponding silica gel spherical die after two minutes, the epoxy monomer for then rapidly mixing the other half and solidification
Agent is injected into spherical silica gel mold, and the active material bead being cured and packaged is taken out stand-by (such as Fig. 4 (a)) after 30 minutes.
Wherein the cladding thickness of epoxy includes 0.3~4.5mm, can be by controlling the thickness of epoxy cured layer and the ruler of active material bead
Very little ratio regulates and controls degree come the effective mass ratio and its dynamics for controlling active material, and wherein cured layer thickness relative activity material is small
Ball dimension ratio is lower, and effective mass ratio is higher, and reaction speed is faster.2. pellumina solidification method: with the spherical shape of customization
Mold, the aluminium-foil paper that the lithium hydride aluminium ball after two-dimensional material cladding respectively puts corresponding size up and down are suppressed (such as Fig. 4 (b)),
The speed and size that graphene layer spacing is opened in subsequent reactions are controlled by pressure that upper and lower aluminium-foil paper is suppressed, and then are controlled
Its kinetics process, while active material effective mass ratio and its dynamics can be controlled by controlling the thickness of aluminium-foil paper
Regulation degree, the aluminum foil thickness of existing use includes 0.02~0.5mm, wherein cladding thickness is smaller, aluminum oxide film film thickness phase
Lower to active material bead size ratio, effective mass ratio is higher, and reaction speed is faster.
D) present invention controls the interlamellar spacing of thin layer two dimension dense material graphene by varying environment, prevents water in air
Steam and oxygen are entered by graphene gap to be reacted with active material alkali metal and its hydride and alanate,
And the spacing between graphene is slowly opened by the immersion of liquid in a liquid to control the mass transport process of different component into
And control its kinetics.1. releasing the speed of hydrogen by testing its hydrolysis for releasing the lesser active material of hydrogen total amount to test
The dynamic process of active material after nanoencapsulation.After active material after nanoencapsulation is placed 10 days in air again
It tests it and releases hydrogen amount, discovery releases hydrogen amount and has no significant change, it was demonstrated that active material can be stablized deposit in air after nanoencapsulation
?.1/3600 that hydrogen speed can be reduced to the unencapsulated lithium ball of same size is released in the hydrolysis of active material lithium ball after nanoencapsulation, and
Reaction rate can be regulated and controled according to package thickness, can at the uniform velocity be reacted within the scope of 3.6~8114ml/h/g.2. for releasing hydrogen amount
Biggish active material can detect its dynamic process by drainage.Active material lithium aluminium hydride reduction after nanoencapsulation is released
Hydrogen speed can be reduced to the 1/240 of the unencapsulated lithium hydride aluminium ball of same size, and may be implemented in even within the scope of 68~3250ml/h/g
Speed reaction.Active material lithium hydride after nanoencapsulation is reduced to water reaction speed in air compared to the lithium hydride ball with size
Originally 1/30, and reaction rate is controllable, can reach the safety in 21890ml/h/g, uniformly releases hydrogen.It can be according to actual needs
By control aluminum oxide film thickness and active material bead size than come control active material effective mass ratio and its
Dynamics regulates and controls reaction speed required for degree selects.
Embodiment 1:
A) referring to fig. 2, first lithium metal is pressed into respectively in the glove box (argon atmosphere) having a size of 3mm, 5mm, 7mm,
The lithium ball of 9mm, 11mm；
B) referring to Fig. 3, lithium ball obtained is equal by nano level active material graphene under atmosphere of inert gases or vacuum
Even to be coated on lithium ball surface, the cladding time is 36-72h, wherein mass ratio≤1:40 of the graphene compared with lithium ball；
C) choose respectively having a size of (4mm, 6mm, 8mm, 10mm, 12mm), (6mm, 8mm, 10mm, 12mm, 14mm),
(10mm,12mm,14mm,16mm,18mm)、(8mm,10mm,12mm,14mm,16mm)、(12mm,14mm,16mm,18mm,
Silica gel mould 20mm), the epoxy monomer for first mixing half and curing agent are added in ready-made spherical silica gel mold, and about two
Lithium ball is put into corresponding silica gel spherical die after minute, the epoxy monomer and curing agent for then rapidly mixing the other half
It is injected into spherical silica gel mold, takes out the active material bead being cured and packaged for use after 30 minutes.Wherein corresponding packet
It covers with a thickness of (0.5mm, 1.5mm, 2.5mm, 3.5mm, 4.5mm)
Material weight compares respectively between 1~63% after active alkali metal lithium ball coats together.The hydrogen storage quality of material system
Than up to 8.4%.
Embodiment 2:
A) referring to fig. 2, first sodium ball, sodium ball size 11mm will be pressed into after the cutting of sodium block in glove box (argon atmosphere)；
B) referring to Fig. 3, sodium ball obtained is equal by nano level active material graphene under atmosphere of inert gases or vacuum
Even to be coated on sodium ball surface, the cladding time is 36-72h, wherein mass ratio≤1:40 of the graphene compared with sodium ball；
C) silica gel mould having a size of (12mm, 14mm, 16mm, 18mm, 20mm), the epoxy for first mixing half are chosen
Monomer and curing agent are added in ready-made spherical silica gel mold, and sodium ball is put into corresponding silica gel spherical die after about two minutes
In, the epoxy monomer for then rapidly mixing the other half is injected into spherical silica gel mold with curing agent, will be consolidated after 30 minutes
Change packaged active material bead to take out for use.Corresponding cladding with a thickness of (0.5mm, 1.5mm, 2.5mm, 3.5mm,
4.5mm), active alkali metal sodium ball is with material weight ratio after cladding between 7~63%；
Embodiment 3:
A is first preparing active material lithium hydride aluminium ball in glove box (argon atmosphere), the lithium aluminium hydride for being 0.75g by quality
Powder is pressed into the lithium aluminium hydride bead that diameter is 11mm at 12MPa；
B) under an inert atmosphere, in the low layer number graphene (see Fig. 3) of active surface cladding thin layer densification, the time is coated
For 12-72h, wherein mass ratio≤1:40 of the graphene compared with lithium hydride aluminium ball；
C) aluminium-foil paper of 0.02mm is washed into the consistent disk of size with the fixation formed punch of 22mm, with the spherical die of customization
Lithium hydride aluminium ball after two-dimensional material cladding respectively puts a piece of aluminium-foil paper compacting up and down, is further encapsulated, active alkali metal
Alanate lithium hydride aluminium ball is with material weight ratio after cladding between 2~93%；
Embodiment 4:
A first is preparing active material lithium hydride bead in glove box (argon atmosphere), by lithium hydride powder at 12MPa
It is pressed into the lithium hydride bead that diameter is 11mm；
B) under an inert atmosphere, in the low layer number graphene (see Fig. 3) of active surface cladding thin layer densification, the time is coated
For 12-72h, wherein mass ratio≤1:40 of the graphene compared with lithium hydride ball；
C) aluminium-foil paper of 0.02mm is washed into the consistent disk of size with the fixation formed punch of 22mm, with the spherical die of customization
Lithium hydride ball after two-dimensional material cladding respectively puts a piece of aluminium-foil paper compacting up and down, is further encapsulated, active alkali metal hydrogen
Compound lithium hydride ball is with material weight ratio after cladding between 2~93%；
Embodiment 5:
A is first preparing active material sodium hydride bead in glove box (argon atmosphere), will in glove box (argon atmosphere)
Sodium Borohydride powder be pressed at 12MPa diameter be 11mm sodium hydride bead；
B) under an inert atmosphere, in the low layer number graphene (see Fig. 3) of active surface cladding thin layer densification, the time is coated
For 12-72h, wherein mass ratio≤1:40 of the graphene compared with sodium hydride ball；
C) aluminium-foil paper of 0.02mm is washed into the consistent disk of size with the fixation formed punch of 22mm, after two-dimensional material cladding
Sodium hydride ball respectively put the aluminium-foil paper of predetermined size up and down and further encapsulated, active alkali metal hydride sodium hydride ball is the same as wrapping
Rear material weight ratio is covered between 2~93%；
Active material active material can determine size according to actual needs, to release the standard optimal selection ruler of hydrogen high conversion rate
Very little biggish active material ball.Thickness is coated under the premise of safe preservation and transport, most thin encapsulating material is selected, to reduce
Produce the reduction of hydrogen mass ratio.
Application examples 1:
Lithium metal ball after the nanoencapsulation obtained using embodiment 1 releases hydrogen material as hydrolysis.
The ice thaw characteristics of hydrogen material are released in test, are released hydrogen material bead for 1 and are placed in 120ml aqueous solution, may remain in
Uniform speed slow releases hydrogen (releasing hydrogen datagram see the test of Fig. 6 gas-chromatography) in 10 hours；By gas Chromatographic Determination, using area outside
Mark method calculates generated amounts of hydrogen；Hydrogen material, multiple groups number are released after actual measurement 7mm lithium metal ball nanoencapsulation for the bead of 8mm
According to show this method nanoencapsulation release hydrogen material place 10 days after hydrolysis release hydrogen when free of losses；
Test condition: 6.5 DEG C/room temperature of constant temperature；
This, which releases hydrogen material hydrogen storage mass ratio, can reach 8.41%；
Release the lithium ball that hydrogen speed is compared with size without encapsulation 1/3600 of active material lithium ball after nanoencapsulation, and it is anti-
Controllable-rate is answered, it can be at the uniform velocity controllable within the scope of 3.6~8114ml/h/g.
Application examples 2:
Lithium aluminium hydride bead after the nanoencapsulation obtained using embodiment 3 releases hydrogen material as hydrolysis.
A) using the ice thaw characteristics of simple drainage device to test material, 1 is released hydrogen material bead to be placed on 15ml water-soluble
In liquid, the lithium aluminium hydride bead after surveying nanoencapsulation may remain in 1 hour or so at the uniform velocity release hydrogen and when hydrogen is released in hydrolysis without
Loss.
B) test condition: room temperature
C) high hydrogen storage mass ratio can be obtained in material system, and hydrogen storage mass ratio can reach 20wt% or more, is including water
In the case where, hydrogen storage mass ratio also can reach 10wt% or more,
D) the active material lithium aluminium hydride reduction after nanoencapsulation release hydrogen speed can drop to without encapsulation with size lithium aluminium hydride
The 1/240 of ball, and reaction rate is at the uniform velocity controllable within the scope of 68~3250ml/h/g.
Application examples 3:
It can be by lithium metal, sodium metal, lithium aluminium hydride reduction, hydrogenation using the nanoencapsulation method of embodiment 1,2,3,4,5
Lithium, sodium hydride etc. expose in air in normal temperature and pressure.It is stabilized active material, to reduce its preservation and storage and transportation
Difficult problem.
Application examples 4:
Construct the new material system of high hydrogen storage under cryogenic conditions.National grid can be made full use of to abandon electricity, be electrolysed embodiment
1,2,3,4,5 equal hydrolysates can also be made product regeneration alkali metal and its hydride and alanate and be led to by high temperature and pressure
The processing of above nanoencapsulation method is crossed, the solid-state hydrogen storage material after nanoencapsulation is transported with hydrogen area, i.e., power grid is abandoned into electricity and turned
It turns to Hydrogen Energy and transports, realize green electric power supply energy storage.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (8)
1. a kind of nanoencapsulation structure for keeping active material dynamics controllable, which is characterized in that including active material (1), thin layer
Two-dimentional dense material (2), cure package material (3) and active material be it is spherical, thin layer two dimension dense material is coated on active material
Material outside forms two-dimentional dense material clad；Cure package material is coated on the outside of thin layer two dimension dense material, forms activity
The nanoencapsulation of material coats spherical structure.
2. a kind of nanoencapsulation structure for keeping active material dynamics controllable according to claim 1, which is characterized in that quilt
The active material sphere of cladding is medicine ball, hollow sphere or porous ball；The diameter for the active material sphere being wrapped by be 200 μm-
25mm。
3. a kind of nanoencapsulation structure for keeping active material dynamics controllable according to claim 1, which is characterized in that thin
The number of plies of the two-dimentional dense material (2) of layer is 1-20 layers, and two-dimentional dense material coating thickness is 1-100 atomic layer level thickness, two dimension
The weight of dense material clad and the weight ratio of both active materials are between 0.01% to 0.5%.
4. the system for the nanoencapsulation structure for making active material dynamics controllable described in a kind of any one of Claims 1-4
Preparation Method, which comprises the following steps:
Step 1, first that active material ball is prepared using the method for cutting, compacting or polishing under atmosphere of inert gases；
Step 2, under inert atmosphere or vacuum, thin layer two dimension dense material is coated on the surface of active material；
Step 3, solidified in the active material ball surface for having coated dimensional thinlayer material by the mold of cure package material
Encapsulation.
5. a kind of preparation method of nanoencapsulation structure for keeping active material dynamics controllable according to claim 4,
Be characterized in that, in step 2, active material surface coat thin layer two dimension dense material the following steps are included:
A) two-dimensional material ball high-pressure graphite ball is put into the vessel for filling dilute hydrochloric acid, is cleaned by ultrasonic at room temperature, removal surface is easy
The small clast to fall off, is then dried；
B) sphere of two-dimensional material is mixed with the microballoon being wrapped by by 1:1~1:5 volume ratio, obtains mixture A；
C) under inert atmosphere or vacuum, mixture A is placed in container and is sealed, then by mechanical mixture, makes mixture A
In two components occur rolling friction in a reservoir, induce table of the two-dimensional material thin layer from the surface of two-dimensional material ball to microballoon
Face transfer, obtains mixture B；
D) two-dimensional material ball is taken out from mixture B, obtains two-dimensional material and uniformly coats microsphere particle.
6. a kind of preparation method of nanoencapsulation structure for keeping active material dynamics controllable according to claim 5,
It is characterized in that, container is teflon seal ball grinder, stainless steel seals ball grinder, hard alloy seals ball grinder, oxidation
Aluminium/corundum sealing ball grinder, zirconium oxide sealing ball grinder, polyurethane ball sealing grinding jar, silicon carbide sealing ball grinder, agate ball are close
Envelope grinding jar or nylon ball seal any one in grinding jar；Mechanical mix techniques are that ball milling mixing or roller mix；Ball milling is mixed
It closes or roller revolving speed is between 200rpm to 700rpm；Ball-milling Time is 1h-96h.
7. a kind of nanoencapsulation structure for keeping active material dynamics controllable according to claim 1, which is characterized in that receive
The volume ratio of integral material is 0.1-0.95 after active material and nanoencapsulation before rice encapsulation.
8. a kind of preparation method of nanoencapsulation structure for keeping active material dynamics controllable according to claim 4,
It is characterized in that, the mold in step 3 is silica gel and graphite or metal alloy mold；Cure package material is resin or aluminum oxide film
Film；Cure package material with a thickness of 0.02mm-4.5mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810783976.9A CN109231158B (en) | 2018-07-17 | 2018-07-17 | Nano packaging structure enabling dynamics of active material to be controllable and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810783976.9A CN109231158B (en) | 2018-07-17 | 2018-07-17 | Nano packaging structure enabling dynamics of active material to be controllable and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109231158A true CN109231158A (en) | 2019-01-18 |
| CN109231158B CN109231158B (en) | 2021-01-19 |
Family
ID=65071971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810783976.9A Active CN109231158B (en) | 2018-07-17 | 2018-07-17 | Nano packaging structure enabling dynamics of active material to be controllable and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109231158B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116832785A (en) * | 2023-05-24 | 2023-10-03 | 安庆市长三角未来产业研究院 | Graphene aerogel-ammonia modified ultrahigh crosslinked adsorption resin composite adsorption material, and preparation and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060078736A1 (en) * | 2004-10-13 | 2006-04-13 | Kawamura Institute Of Chemical Research | Three-dimensional periodic structure, three-dimensional periodic porous structure, and method for producing these |
| CN101733050A (en) * | 2008-11-20 | 2010-06-16 | 美国吉姆迪生物科技有限公司 | Nanometer and micropackaging, and raw material discharge |
| CN102351143A (en) * | 2010-06-02 | 2012-02-15 | 通用汽车环球科技运作有限责任公司 | Packaged reactive materials and method for making the same |
| CN105947977A (en) * | 2016-04-25 | 2016-09-21 | 东莞市联洲知识产权运营管理有限公司 | Novel nano-hydroboron hydrogen storage material and preparation method thereof |
| CN107226476A (en) * | 2016-09-28 | 2017-10-03 | 西安交通大学 | Two-dimensional thin-layer material coated on surface of microsphere and simple stripping method thereof |
| CN108193107A (en) * | 2017-12-21 | 2018-06-22 | 陕西科技大学 | A kind of novel organic coating core-shell structure copolymer nanocomposite hydrogen storage material and preparation method thereof |
-
2018
- 2018-07-17 CN CN201810783976.9A patent/CN109231158B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060078736A1 (en) * | 2004-10-13 | 2006-04-13 | Kawamura Institute Of Chemical Research | Three-dimensional periodic structure, three-dimensional periodic porous structure, and method for producing these |
| CN101733050A (en) * | 2008-11-20 | 2010-06-16 | 美国吉姆迪生物科技有限公司 | Nanometer and micropackaging, and raw material discharge |
| CN102351143A (en) * | 2010-06-02 | 2012-02-15 | 通用汽车环球科技运作有限责任公司 | Packaged reactive materials and method for making the same |
| CN105947977A (en) * | 2016-04-25 | 2016-09-21 | 东莞市联洲知识产权运营管理有限公司 | Novel nano-hydroboron hydrogen storage material and preparation method thereof |
| CN107226476A (en) * | 2016-09-28 | 2017-10-03 | 西安交通大学 | Two-dimensional thin-layer material coated on surface of microsphere and simple stripping method thereof |
| CN108193107A (en) * | 2017-12-21 | 2018-06-22 | 陕西科技大学 | A kind of novel organic coating core-shell structure copolymer nanocomposite hydrogen storage material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 蒋正武: "《水泥基自修复材料：理论与方法》", 31 January 2018, 同济大学出版社 * |
| 郝新敏等: "《功能纺织材料和防护服装》", 30 November 2010, 中国纺织出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116832785A (en) * | 2023-05-24 | 2023-10-03 | 安庆市长三角未来产业研究院 | Graphene aerogel-ammonia modified ultrahigh crosslinked adsorption resin composite adsorption material, and preparation and application thereof |
| CN116832785B (en) * | 2023-05-24 | 2024-05-17 | 安庆市长三角未来产业研究院 | Graphene aerogel-ammonia modified ultrahigh crosslinked adsorption resin composite adsorption material, and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109231158B (en) | 2021-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ren et al. | Current research trends and perspectives on materials-based hydrogen storage solutions: A critical review | |
| Ma et al. | Air-stable hydrogen generation materials and enhanced hydrolysis performance of MgH2-LiNH2 composites | |
| US7858068B2 (en) | Method of storing and generating hydrogen for fuel cell applications | |
| Duan et al. | Synthesis of core-shell α-AlH3@ Al (OH) 3 nanocomposite with improved low-temperature dehydriding properties by mechanochemical mixing and ionic liquid treatment | |
| Ianni et al. | Synthesis of NaAlH4/Al composites and their applications in hydrogen storage | |
| CN104649229A (en) | Method for preparing nanometer limited range magnesium-based hydrogen storage material | |
| Duan et al. | Novel core–shell structured MgH 2/AlH 3@ CNT nanocomposites with extremely high dehydriding–rehydriding properties derived from nanoconfinement | |
| Sazelee et al. | Enhanced dehydrogenation performance of NaAlH4 by the addition of spherical SrTiO3 | |
| CN108193107A (en) | A kind of novel organic coating core-shell structure copolymer nanocomposite hydrogen storage material and preparation method thereof | |
| CN102259837B (en) | Particle used for hydrogen production and preparation method thereof | |
| Wang et al. | Pitaya pulp structural cobalt–carbon composite for efficient hydrogen generation from borohydride hydrolysis | |
| CN103991888A (en) | Method for preparing high-activity aluminum hydroxide suspension liquid and producing hydrogen through high-activity aluminum hydroxide suspension liquid and pure aluminum powder reaction | |
| CN109231158A (en) | Nano packaging structure enabling dynamics of active material to be controllable and preparation method | |
| Zhu et al. | Synthesis and hydrogen desorption properties of nanoscale α-AlH 3 | |
| JP6977968B2 (en) | Method for producing sodium borohydride | |
| WO2021025069A1 (en) | Method for producing sodium borohydride | |
| CN103264988A (en) | Method for producing hydrogen by reaction of aluminium and water catalyzed by aluminum hydroxide or oxide | |
| CN102502488B (en) | Method for improving hydrogen storage property of lithium borohydride | |
| CN114206773A (en) | Method for producing sodium borohydride | |
| CN103274355B (en) | LiBH4 high-capacity hydrogen storage composite material preparation method | |
| CN104559070B (en) | A kind of lithium boron hydrogen four that reduces inhales reversible hydrogen storage material and the preparation method of hydrogen discharging temperature | |
| CN102296198A (en) | Method for preparing tungsten block material by dispersing and reinforcing nano tantalum carbide | |
| CN103708419A (en) | Method for preparing of high-activity LiH microspheres through wet process | |
| JP2003146604A (en) | Compression molding for hydrogen generation and method and device for generating hydrogen using the same | |
| CN103922284B (en) | A kind of preparation method of AlH3/MgCl2 nano-complex powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220509 Address after: Room 035, F2002, 20 / F, block 4-A, Xixian financial port, Fengdong new town energy gold trade zone, Xixian new area, Xi'an, Shaanxi 712000 Patentee after: Xi'an 1908 New Energy Technology Co.,Ltd. Address before: Beilin District Xianning West Road 710049, Shaanxi city of Xi'an province No. 28 Patentee before: XI'AN JIAOTONG University |