CN107482218A - A kind of three-dimensional hollow material and preparation method thereof and the application in electrochemical energy storing device - Google Patents
A kind of three-dimensional hollow material and preparation method thereof and the application in electrochemical energy storing device Download PDFInfo
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- CN107482218A CN107482218A CN201710587626.0A CN201710587626A CN107482218A CN 107482218 A CN107482218 A CN 107482218A CN 201710587626 A CN201710587626 A CN 201710587626A CN 107482218 A CN107482218 A CN 107482218A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of three-dimensional hollow material and preparation method thereof and the application in electrochemical energy storing device.Wherein, three-dimensional hollow material carries out high temperature cabonization, obtains self-supporting three-dimensional hollow material mainly by the foam resin containing ehter bond under normal pressure and oxygen-free inert atmosphere conditions.Above-mentioned three-dimensional hollow material may be used as electrode material, you can form three-dimensional hollow carbon-based electrode；Also, three-dimensional hollow material can also be compound with height ratio capacity active electrode material, that is, forms combination electrode.Finally, three-dimensional hollow carbon-based electrode and its combination electrode are applied to electrochemical energy storing device.Constructed three-dimensional structure couples the flexible 3 D hollow material of one with hollow-core construction, can be used as electrochemical energy storing device electrode or collector.Such as it is used as that the instability problem faced during the intercalation/deintercalation of big ion (such as Na+, K+) can be overcome when sodium, kalium ion battery negative pole, while obtain higher specific capacity and longer life-span.
Description
Technical field
The present invention relates to a kind of synthesis of new material and its application in electrochemical energy storing device, more particularly to one
Plant the preparation of flexible self-supporting three-dimensional hollow carbon-based electrode and its in electrochemical energy storing device (lithium ion battery, sodium ion electricity
Pond and metal sode cell, kalium ion battery and metallic potassium battery, lithium-empty battery, aluminium ion battery, calcium ion battery, super electricity
Container) in application.
Background technology
Currently, global energy technology faces unprecedented major transformation；Develop clean energy resource, to tackle sharp climatic deterioration
With serious air pollution, it has also become the focus and difficult point of research in recent years.Electrochemical energy storage as green energy resource one kind and its
Important storage means, even more current research focus.Lithium ion battery is because possessing high-energy-density, high power, long lifespan, peace
Entirely, the advantage such as cleaning, has been widely used in every field；Including portable type electronic product, electric automobile and large-scale energy storage
Base station.But the lithium resource of nature is limited (only account for crustal elements total amount 0.0017%), and resource distribution is unbalance (main
Be distributed in South America), it is difficult to meet the needs of growing, so as to cause in recent years lithium valency rise steadily.Development resource is enriched new
Type metal ion battery, especially sodium, kalium ion battery, worldwide cause extensive interest.However, compare radius
Less lithium ionSodium ionAnd potassium ionIonic radius it is much larger, big ion exists
Deintercalation in electrode material, easily cause electrode material structure collapses, the decay of capacity and the rapid decrease of performance.
Carbon material of the hollow carbon sphere as unique structure, possess many excellent performances, including high-specific surface area, high hole
Rate, excellent electric conductivity, permeability, chemical stability and heat endurance etc..It is in electricity, optics, catalysis, separation, biology doctor
There is important application value in the field such as medicine and electrochemical energy storage.Especially in electrochemical energy storage field, such as secondary metals from
In the application of sub- battery (including lithium ion battery, sodium-ion battery, kalium ion battery, aluminium ion battery), hollow-core construction can be with
Space is provided for the storage of electrolyte so that electrode material can sufficiently soak with electrolyte, obtains preferable imbibition, protects liquid
Performance, meanwhile, hollow-core construction can also reduce ion transmission path, improve ion transmission power, mitigate interfacial electrochemistry impedance,
Promote ion quickly embedded and deviate from, obtain preferable high rate performance.Particular, it is important that the chamber portion of hollow-core construction can be with
The caused volumetric expansion during metal ion quickly embedded and deintercalation of buffer electrode material, mitigates electrode material for a long time
Structure collapses caused by cyclic process and capacity attenuation, so as to extend its life-span.Although hollow carbon sphere is as electrochemical energy storage
Material possesses many advantages, but the hollow carbon sphere preparation method of scale is extremely limited, at present, the preparation master of hollow carbon sphere
Rely on template, including hard template method and soft template method.Because shortcomings be present in template, such as seriously polluted, process
It is miscellaneous, yield is small etc..Therefore, exploitation is a kind of environment-friendly, and process is simple, the preparation method of easy scale volume production hollow carbon sphere,
Tool is of great significance.
In addition, compared with the dusty material of routine, the three-dimensional carbon electrode material of self-supporting has following advantage：Electrode can be with
Fully contact electrolyte, the effective area of electrode can be made full use of；The transmission path of various dimensions, electronics and ion can be accelerated
Quick transmission；It is preferably flexible, the stability of material can be improved；Self-supporting, without using collector and binding agent.On in view of
Plurality of advantages is stated, three-dimensional carbon electrode material has been widely used in solar cell, and fuel cell can charge and discharge secondary ion electricity
Pond, ultracapacitor.Document was once reported, using three-dimensional graphite as aluminium ion anode, it is electrical can to obtain ultrafast charge and discharge
Can be with cycle performance (Dai the et al., Nature, 520 of stabilization time length:324-328).
The content of the invention
First purpose of the present invention is to provide a kind of with the three-dimensional, preparation method of hollow structure material.
Second object of the present invention be to provide a kind of three-dimensional hollow material being prepared by above-mentioned preparation method and its
Purposes, it can be used as electrode material.Particularly as lithium ion battery, sodium-ion battery and metal sode cell, potassium ion electricity
Pond and metallic potassium battery, lithium-empty battery, aluminium ion battery, calcium ion battery, the electrode material of ultracapacitor
The object of the invention is achieved based on following technical scheme：
A kind of preparation method of three-dimensional hollow material, comprises the following steps：By the foam resin containing ehter bond normal
Under pressure and oxygen-free inert atmosphere conditions, high temperature cabonization is carried out, obtains self-supporting three-dimensional hollow material.
According to the present invention, there is no particular limitation for the content of the ehter bond, and the present invention is formed simply by the presence of ehter bond can
Described self-supporting three-dimensional hollow material.The foam resin containing ehter bond is, for example, phenol-formaldehyde resin, aminobenzene
Resinox, aniline-formaldehyde resin, melamine formaldehyde resin, the one or more in Lauxite.Preferably, exist
It is above-mentioned using formaldehyde as in the foamed resin of raw material, it is intermolecular that there is following bridged bond：-CH2-、-CH2-O-CH2-, wherein, it is described to contain
There is the bridged bond (- CH of ehter bond2-O-CH2-) ratio that accounts for above-mentioned all bridged bonds is：15-80%.
Preferably, the porosity of the foamed resin is 20-99%.
Preferably, the foam resin is melamine formaldehyde resin, Lauxite.
Preferably, the porosity of the foamed resin is 30%, 40%, 50%, 60%, 70%, 80-99%.
Preferably, the carburizing temperature be 400-1600 DEG C, for example, the temperature of the carbonization be 500 DEG C, 600 DEG C, 700
℃、800℃、900-1300℃、1400℃、1500℃、1600℃；Carbonization time is 0.5-50h, more preferably 1-5h.
Preferably, the heating rate is 0.5-20 DEG C/min, for example, 5-10 DEG C/min.
Preferably, the inert atmosphere is nitrogen, argon gas, helium, VH2/VArFor 5/95 hydrogen/argon-mixed etc..
According to the present invention, the high temperature cabonization can be carried out under conditions of adding or not adding catalyst.The catalysis
Agent is boron and its compound, iron and its compound, nickel and its compound, silicon and its compound, germanium and its compound, copper and its change
One or more in compound, calcium and its compound, magnesium and its compound, aluminium and its compound.
, according to the invention it is preferred to the foam resin is immersed in catalyst solution, the catalyst is born
It is loaded on the foam resin.
Preferably, the mass percent that the catalyst is added relative to all reactants is 0.1-30%, is, for example,
1-5%.
Preferably, the three-dimensional hollow material can further carry out activation pore-creating in the presence of pore creating material, so as to
To three-dimensional micro-porous hollow material.
According to the present invention, the pore creating material is KOH, the mass percent that the KOH is added relative to all reactants
For 5-50%.
It is described activation pore-creating method be：The three-dimensional hollow material is immersed in a period of time (example in pore-creating agent solution
Such as 5-60 minutes), taken out afterwards from solution, under an inert gas high-temperature calcination, carry out activation pore-creating.The calcining heat is excellent
Elect 400-900 DEG C, and preferably 500-800 DEG C, such as 600 DEG C as, calcination time is preferably 1-15h.Wash, dry after calcining.
Present invention also offers a kind of three-dimensional hollow material being prepared by above-mentioned preparation method.
Present invention also offers a kind of three-dimensional hollow material, the three-dimensional hollow material has self-supporting three-dimensional structure and sky
Core structure, the tie point of three-dimensional framework is hollow ball, is connected between tie point (i.e. hollow ball) by hollow pipe, is consequently formed three-dimensional
Hollow-core construction.The structure also has preferably flexible.
In the inventive method, during high temperature cabonization, the foamed resin containing ehter bond thermally decomposes, ehter bond therein
Fracture, while carbon atom is reset, inside discharges gas, and the gas of release because that can not discharge in time so that
Bubbling occurs in itself for polymer, forms three-dimensional hollow structure.And it is possible to by adding above-mentioned catalyst, pore creating material, promote to gather
Compound under cryogenic (relatively industrial 2500-2800 DEG C of graphitization temperature) obtain degree of graphitization it is high, it is porous, compare surface
The big three-dimensional material of product.
Three-dimensional hollow material of the present invention has had the advantage of three-dimensional structure and hollow-core construction concurrently, may be used as electrode material
Material.
The present invention also provides a kind of electrode, and it includes three-dimensional hollow material recited above.
According to the present invention, the electrode is made up of three-dimensional hollow material recited above.
According to the present invention, the electrode can also include height ratio capacity active electrode material, that is, form combination electrode.It is preferred that
Ground, the mass fraction that the height ratio capacity active electrode material accounts for whole combination electrode are 10-90%, it is highly preferred that being 50-
70%.
According to the present invention, the height ratio capacity active electrode material includes red phosphorus, black phosphorus, silicon, tin and tin oxide, antimony and its
Oxide, germanium and its oxide, transition metal oxide (such as the oxide of manganese, titanyl compound, the oxide of nickel, molybdenum
Oxide) in one or more.
According to the present invention, the specific preparation method of the combination electrode can be, by red phosphorus, black phosphorus, and silicon, tin, antimony, in germanium
It is one or more of to stir to form slurry with binding agent, then the three-dimensional hollow material is inserted in the slurry and impregnated, ultrasound,
Stirring, combination electrode is obtained after drying.If the height ratio capacity active electrode material uses oxide, by by described three
Dimension hollow material is placed in dipping in oxide precursor colloidal sol, ultrasound and drying, then in normal pressure and oxygen-free inert atmosphere
Carry out carbonization and form combination electrode.Wherein, the oxide precursor of tin is butter of tin or isopropanol tin, the oxide precursor of antimony
Body is antimony sulfate or nitric acid antimony, and the oxide precursor of germanium is germanium tetrachloride, and the oxide precursor of manganese is manganese nitrate, acetic acid
Manganese, manganese sulfate, the oxide precursor of nickel is nickel nitrate, nickel acetate, nickel sulfate, and the oxide precursor of molybdenum is ammonium molybdate, titanium
Oxide precursor be butyl titanate.
Present invention also offers application of the electrode in electrochemical energy storing device.The electrochemical energy storing device is for example
For lithium ion battery, sodium-ion battery and metal sode cell, kalium ion battery and metallic potassium battery, lithium-empty battery, aluminium ion are electric
Pond, calcium ion battery, ultracapacitor.
Wherein, the positive pole, negative pole or collector of the energy storage device are applied particularly to.
Preferably, it is applied particularly to the negative pole of the energy storage device.
Beneficial effects of the present invention：
The inventive method is simple to operate, and reaction is gentle, and environment-friendly, process is simple, easy scale, can construct one kind three
Dimension structure couples the three-dimensional of one, hollow material with hollow-core construction.
Three-dimensional hollow material of the present invention, three-dimensional structure and hollow-core construction are coupled into one.With traditional three-dimensional carbon materials
Material is compared, and three-dimensional hollow material of the present invention has a flexibility of height, three-dimensional structure crosslinking points by hollow-core construction carbon
Ball is formed, and the connecting line between tie point is hollow pipe, and the material is self supporting structure, and possesses excellent electric conductivity,
The electrode material of electrochemical energy storage can be directly used as, without additionally using binding agent and collector.Material of the present invention also may be used
It is compound to be carried out with other high power capacity active electrode materials, so as to prepare the high power capacity of flexibility, the three-dimensional space of high stability
Heart composite.
Electrode of the three-dimensional hollow material of the present invention as metal ion battery, metal battery and ultracapacitor
Material, many beneficial effects are embodied, it is as follows in detail：
First, as metal ion battery material (lithium ion battery, sodium-ion battery, kalium ion battery, lithium-empty battery,
Aluminium ion battery, calcium ion battery).Described flexible self-supporting three-dimensional hollow material has hollow-core construction, and it can be first
The storage of electrolyte provides space so that three-dimensional hollow electrode material can sufficiently soak with electrolyte, obtains and preferably inhales
Liquid, water retainability.Secondly, hollow-core construction can also reduce the path of ion transmission, improve ion transmission power, mitigate interface electricity
Chemical impedance, promote ion quickly embedded and deviate from, obtain preferable high rate performance.Finally and the most important, it is hollow
The chamber portion of structure can be with buffer electrode material in metal ion (the especially larger ion of radius, such as Na+, K+) quick embedded
With caused volumetric expansion during deintercalation, mitigate electrode material structure collapses and capacity caused by long-time cyclic process
Decay, extends its life-span.The three-dimensional hollow material also has three-dimensional structure, and it makes electrode material fully contact electrolyte, energy
Enough make full use of the effective area of electrode；The transmission path of various dimensions, the quick transmission of electronics and ion can be accelerated；It is preferably soft
Property, the stability of material can be improved；Self-supporting, without using collector and binding agent.So above-mentioned self-supporting three-dimensional hollow
Carbon electrode material, dexterously the advantage of the two is coupled, synergy is served, has maximally played the advantage of the two.With it is general
Logical three-dimensional material and powdery electrode material is compared, described three-dimensional hollow carbon electrode material and its composite, as electrification
Energy storage material (lithium ion battery, sodium-ion battery, kalium ion battery, and ultracapacitor) is learned, obtains height ratio capacity, high power
Rate performance, and the cycle performance of stabilization time length.And by other in charge and discharge process the larger active material of volumetric expansion
(red phosphorus and black phosphorus, silicon, tin and tin oxide, antimony, germanium) is supported on the combination electrode material formed on hollow carbon electrode material, is even more
The volumetric expansion of active material can effectively be alleviated, its height ratio capacity performance is given full play to and obtain more preferable stability.
Second, as metal battery material (metal sode cell, metallic potassium battery), the flexible self-supporting described in (1) is three-dimensional
Hollow carbon electrode material has higher percent opening and larger free space, can accommodate the lithium metal of larger face amount, sodium,
Potassium ion, the metal negative electrode of high face amount can be prepared.(2) higher percent opening and larger free space can alleviate gold
Belong to the Volume Changes in deposition/precipitation process so that whole Volume Changes of the electrode in cyclic process are smaller, so as to strengthen following
Ring stability, extend cycle life.(3) hollow structure can accommodate a part of metal, and hollow ball wall makees firm barrier, can be with
Suppress metallic dendrite growth, alleviate cyclic process in Volume Changes.(4) the flexible self-supporting three-dimensional hollow material described in is used
Make collector, there is larger electroactive surface to accumulate, so as to reduce current density, suppress the generation of metallic dendrite, improve storehouse
Human relations efficiency.(5) compared to common three-diemsnional electrode (three-dimensional copper, three-dimensional nickel, three-dimensional titanium), described flexible self-supporting three-dimensional hollow
Material is used as collector, and density is small, light weight, is advantageous to improve the energy density of whole battery.(6) flexible self-supporting described in
Three-dimensional hollow carbon electrode material has fabulous pliability and preparation method is simple and easy, is advantageously implemented the preparation of battery
Journey.
3rd, electrode material for super capacitor, described flexible self-supporting three-dimensional hollow material possesses excellent electric conductivity
Can, abundant micropore/meso-hole structure, high specific surface area, stronger imbibition ability, higher specific capacitance and overlength can be obtained
Life-span.And itself and transition metal oxide (oxide of manganese, titanyl compound, the oxide of nickel, the oxide of molybdenum) are entered
The composite that row is compound and is formed, can even more provide efficient conductive network, make the transiting metal oxidation that electric conductivity is poor
Thing can give full play to its capacity and obtain excellent stability.
Brief description of the drawings
Fig. 1 is the self-supporting three-dimensional hollow that the melamine-formaldehyde resin foam in embodiment 1 obtains after high temperature cabonization
Carbon electrode material scanning electron microscope diagram.
Fig. 2 is the self-supporting three-dimensional hollow carbon that melamine-formaldehyde resin foam obtains after high temperature cabonization in embodiment 1
The scanning electron microscope diagram that electrode material line focus ion beam technology (FIB) cuts contact hollow ball.
Fig. 3 is the flexible test figure of self-supporting three-dimensional hollow carbon electrode piece in embodiment 1.
Fig. 4 is the self-supporting three-dimensional hollow carbon that the melamine-formaldehyde resin foam of embodiment 1 obtains after high temperature cabonization
As charging and discharging curve figure of the potassium ion negative pole under 0.1C current densities.
Fig. 5 is the self-supporting three-dimensional hollow carbon electrode material that the urea formaldehyde resin foam in embodiment 2 obtains after high temperature cabonization
Expect scanning electron microscope diagram.
Fig. 6 is the self-supporting three-dimensional hollow carbon electrode material that urea formaldehyde resin foam obtains after high temperature cabonization in embodiment 2
The scanning electron microscope diagram that line focus ion beam technology (FIB) cuts contact hollow ball.
Fig. 7 is the self-supporting three-dimensional hollow carbon electrode material that the urea formaldehyde resin foam of embodiment 2 obtains after high temperature cabonization
As charging and discharging curve figure of the sodium ion negative pole under 0.1C current densities.
Fig. 8 is the scanning electron that the melamine-formaldehyde resin foam in embodiment 4 obtains through the carbonization of different heating rates
Microscope figure.(a), (b), (c) is respectively the three-dimensional hollow carbon electrode obtained under 0.5,10,20 DEG C/min ramp rate conditions
The scanning electron microscope diagram of material.
Fig. 9 is SEM of the red phosphorus with self-supporting three-dimensional hollow carbon electrode material after compound in embodiment 5
Figure.
Figure 10 is in embodiment 5, is born after red phosphorus and self-supporting three-dimensional hollow carbon electrode material are compound as sodium-ion battery
The charging and discharging curve of pole.
Figure 11 is self-supporting three-dimensional hollow carbon/MnO in embodiment 6xCombination electrode is as electrode material for super capacitor
CV figure.
Embodiment
As it was previously stated, the present invention provides a kind of three-dimensional hollow material and preparation method thereof, and above-mentioned material in electrification
Learn the application of energy storage device.The preparation method is as follows：
1. the preparation of three-dimensional hollow carbon material of the present invention, including：
1) first with resin foam (such as phenol-formaldehyde resin foam, aminobenzene resinox bubble containing ehter bond
Foam, aniline-formaldehyde resin foam, melamine formaldehyde resin foam, urea formaldehyde resin foam) cut into the specified bulk of size
Material, it is placed in the corundum or graphite crucible that can bear corresponding high temperature.Carbonisation can add catalyst (boron and its chemical combination
Thing, iron and its compound, nickel and its compound, silicon and its compound, germanium and its compound, copper and its compound, calcium and its change
Compound, magnesium and its compound, aluminium and its compound) promote its graphitization, and pore creating material can be selected, such as potassium hydroxide,
Promote its pore-forming.
2) and then by the resin foam presoma in step 1) it is heat-treated under an inert atmosphere.The present invention can make
During standby, the pattern of hollow-core construction is controlled by controlling the parameters such as carburizing temperature, carbonization time, heating rate.Reaction knot
Temperature fall is to room temperature after beam, you can obtains the three-dimensional hollow carbon material of bulk.
2. it is prepared by the self-supporting three-dimensional hollow carbon electrode material of the present invention, including：
Block three-dimensional hollow carbon material obtained above is cut into certain thickness circular or square piece, that is, obtained certainly
Support three-dimensional hollow carbon electrode material.
3. the preparation of self-supporting three-dimensional hollow carbon electrode composite of the present invention, including：
A) by block three-dimensional hollow carbon material obtained above, it is immersed in related activity material (such as silicon, tin, phosphorus, germanium)
It is ultrasonic in particle suspension liquid, allow active material to penetrate into acquisition in the free space of the inside of three-dimensional hollow carbon material block compound
Material, or the block three-dimensional hollow carbon material for the gained that is carbonized is immersed in the precursor sol of related activity material, then
It is carbonized in inert atmosphere, finally obtains block composite material.
B) by step A) in obtained block composite material cut into certain thickness circular or square piece, obtain from propping up
Support three-dimensional hollow carbon electrode composite.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.Furthermore, it is to be understood that after described content of the invention has been read, this area skill
Art personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within limited range of the present invention.
Embodiment 1
1. using melamine-formaldehyde resin as the preparation of the self-supporting three-dimensional hollow carbon of presoma
Melamine-formaldehyde resin foam containing ehter bond (ehter bond accounts for the 50% of all bridged bond ratios) is cut into bulk,
Length × width × height is 40 × 40 × 15mm, is placed in corundum crucible, is transferred in tube furnace.
Under conditions of normal pressure and the protection of the nitrogen atmosphere of anaerobic, 1000 DEG C are warming up to 15 DEG C/min speed, herein
Temperature lower calcination 6h, is cooled to room temperature afterwards, obtains the block three-dimensional hollow carbon that length × width × height is 15 × 15 × 6mm.
2. the preparation of flexible self-supporting three-dimensional hollow carbon electrode
Above-mentioned block three-dimensional hollow carbon is cut with a knife into the thin slice of 500 μ m-thicks, then with corresponding pole piece cutting tool
Thin slice is cut into a diameter of 10mm circular electric pole piece.
Fig. 1 is the self-supporting three-dimensional hollow that the melamine-formaldehyde resin foam in embodiment 1 obtains after high temperature cabonization
Carbon electrode material scanning electron microscope diagram.
Fig. 2 is the self-supporting three-dimensional hollow carbon that melamine-formaldehyde resin foam obtains after high temperature cabonization in embodiment 1
The scanning electron microscope diagram that electrode material line focus ion beam technology (FIB) cuts contact hollow ball.
Fig. 3 is the flexible test figure of self-supporting three-dimensional hollow carbon electrode piece in embodiment 1.
3. button cell assembles
Using the above-mentioned circular electric pole piece being prepared as negative pole, fibreglass diaphragm is dressed up as barrier film with metallic potassium piece
Battery, the model CR2032 of button cell, electrolyte select KPF of the concentration for 0.5M6Electrolyte, wherein, solvent is：Carbonic acid
Vinyl acetate (EC), glycol dimethyl ether (DEC).
4. battery testing
Constant current charge-discharge test is carried out to above-mentioned battery using storage battery charge/discharge tester, test voltage section is 0.01
~2V, test temperature are 25 DEG C.
Fig. 4 is the self-supporting three-dimensional hollow carbon that the melamine-formaldehyde resin foam of embodiment 1 obtains after high temperature cabonization
As charge and discharge of the kalium ion battery negative pole under 0.1C (theoretical capacity based on the embedding potassium of graphite, 1C=280mA/g) current density
Electric curve map.As a result show, the self-supporting three-dimensional hollow carbon prepared in embodiment 1 is as kalium ion battery negative pole in 0.1C electric currents
Specific capacity under density conditions is up to 342mAh/g, and coulombic efficiency is up to 74% first.
Meanwhile battery also embodies very excellent cycle performance, the battery of composition carries out discharge and recharge under 0.5C multiplying powers
Circulation, battery circulate by 150 circles, and battery capacity is substantially undamped, up to 250mAh/g, while coulombic efficiency is maintained at
More than 99.5%.
Embodiment 2
1. using Lauxite as the preparation of the self-supporting three-dimensional hollow carbon of presoma
Urea formaldehyde resin foam containing ehter bond (ehter bond accounts for the 30% of all bridged bond ratios) is cut into bulk, length × width × height
For 50 × 50 × 20mm, 0.1M FeCl is then immersed in3·6H2In O (catalyst) solution, soak time 30min, take out
Dried at 80 DEG C, be placed in corundum crucible and be transferred in tube furnace.
Under conditions of normal pressure and the protection of the nitrogen atmosphere of anaerobic, 1300 DEG C are warming up to 10 DEG C/min speed, herein
Temperature lower calcination 0.5h, room temperature is cooled to afterwards, then remnants catalyst wash is removed using 1M salpeter solutions, reuses distillation
Water washing repeatedly to neutrality, obtains the block three-dimensional hollow carbon that length × width × height is 17 × 16 × 6mm.
2. the preparation of flexible self-supporting three-dimensional hollow carbon electrode
Block three-dimensional hollow carbon is cut with a knife into the thin slice of 500 μ m-thicks, then will be thin with corresponding pole piece cutting tool
Piece is cut into a diameter of 12mm circular electric pole piece.
Fig. 5 is the self-supporting three-dimensional hollow carbon electrode material that the urea formaldehyde resin foam in embodiment 2 obtains after high temperature cabonization
Expect scanning electron microscope diagram.
Fig. 6 is the self-supporting three-dimensional hollow carbon electrode material that urea formaldehyde resin foam obtains after high temperature cabonization in embodiment 2
The scanning electron microscope diagram that line focus ion beam technology (FIB) cuts contact hollow ball.
3. button cell assembles
Using the above-mentioned circular electric pole piece being prepared as negative pole, fibreglass diaphragm assembles as barrier film with metallic sodium piece
Into battery, the model CR2032 of button cell, electrolyte selects NaClO of the concentration for 1M4Electrolyte, wherein, solvent is：Carbon
Vinyl acetate (EC) and propene carbonate (PC).
4. battery testing
Using storage battery charge/discharge tester to above-mentioned battery carry out constant current charge-discharge test, test voltage section be 0~
2V, test temperature are 25 DEG C.
Fig. 7 is the self-supporting three-dimensional hollow carbon electrode material that the urea formaldehyde resin foam of embodiment 2 obtains after high temperature cabonization
As charging and discharging curve figure of the sodium-ion battery negative pole under 0.1C (1C=300mA/g) current density.As a result show, embodiment
Specific capacity of the material prepared in 2 as sodium-ion battery negative pole under 0.1C current density conditions is up to 372mAh/g, first
Coulombic efficiency is up to 82%.
Meanwhile battery also embodies very excellent cycle performance, the battery of composition carries out discharge and recharge under 0.5C multiplying powers
Circulation, battery circulate by 100 circles, and battery capacity only decays 5%, is maintained at 280mAh/g, while coulombic efficiency is maintained at
More than 99.5%.
Embodiment 3
1st, the preparation using melamine-formaldehyde resin as the self-supporting three-dimensional hollow carbon of presoma
Melamine-formaldehyde resin foam containing ehter bond (ehter bond accounts for the 60% of all bridged bond ratios) is cut into bulk,
Length × width × height is 60 × 60 × 20mm, is placed in corundum crucible, is transferred in tube furnace.
Under conditions of normal pressure and the protection of the nitrogen atmosphere of anaerobic, 1100 DEG C are warming up to 10 DEG C/min speed, herein
Temperature lower calcination 3h, is cooled to room temperature afterwards, obtains the block three-dimensional hollow carbon that length × width × height is 21 × 21 × 12mm.
2. the preparation of flexible self-supporting three-dimensional hollow carbon electrode
Above-mentioned block three-dimensional hollow carbon is cut with a knife into the thin slice of 700 μ m-thicks, then with corresponding pole piece cutting tool
Thin slice is cut into a diameter of 12mm circular electric pole piece.
3. button cell assembles
Using the above-mentioned circular electric pole piece being prepared as negative electrode, PE membrane for polymer assembles as barrier film with metallic sodium piece
Into battery, the model CR2032 of button cell, electrolyte selects NaClO of the concentration for 1M4Electrolyte, wherein, solvent is：Carbon
Vinyl acetate (EC) and glycol dimethyl ether (DEC).
4. battery testing
Respectively in different electric current 2mA h cm-2, 4mA h cm-2, 6mA h cm-2Lower electrolytic deposition sodium, deposition current speed
For 2mA cm-2, temperature is 25 DEG C.As a result showing, sodium metal is entirely deposited on the inner space of self-supporting three-dimensional hollow carbon, and
Find no metallic dendrite growth.Deposition/precipitation efficiency of sodium metal reaches more than 90% first, reaches after 8 circulations
99% or so.The circle of circulation 100, the equal held stationary of efficiency.
Embodiment 4
1. using melamine-formaldehyde resin as the preparation of the self-supporting three-dimensional hollow carbon of presoma
Melamine-formaldehyde resin foam containing ehter bond (ehter bond accounts for the 65% of all bridged bond ratios) is cut into bulk,
Length × width × height is 50 × 50 × 20mm, is placed in corundum crucible, is transferred in tube furnace.
Under conditions of normal pressure and the protection of the nitrogen atmosphere of anaerobic, it is warming up to respectively with 0.5,10,20 DEG C/min speed
900 DEG C, 1h is calcined at this temperature, is cooled to room temperature afterwards, and taking-up obtains the different three-dimensional hollow carbon material of pattern.
Fig. 8 is the scanning electron that the melamine-formaldehyde resin foam in embodiment 4 obtains through the carbonization of different heating rates
Microscope figure.(a), (b), (c) is respectively sweeping for the three-dimensional hollow carbon that is obtained under 0.5,10,20 DEG C/min ramp rate conditions
Retouch electron microscope picture.
Embodiment 5
1. using melamine formaldehyde resin foam as the preparation of the self-supporting three-dimensional hollow carbon of presoma
Melamine formaldehyde resin foam containing ehter bond (ehter bond accounts for the 35% of all bridged bond ratios) is cut into bulk,
Length × width × height is 80 × 80 × 30mm, is placed in corundum crucible, is transferred in tube furnace.
Under conditions of normal pressure and the protection of the nitrogen atmosphere of anaerobic, 1200 DEG C are warming up to 3 DEG C/min speed, it is warm herein
The lower calcining 0.5h of degree, is cooled to room temperature, obtains the block three-dimensional hollow carbon that length × width × height is 30 × 36 × 12mm afterwards.
2. the preparation of flexible self-supporting three-dimensional hollow carbon/phosphorus combination electrode
Above-mentioned block three-dimensional hollow carbon is cut with a knife into the thin slice of 600 μ m-thicks, is then 2-30 μm by 100mg, particle diameter
Red phosphorus it is scattered in ethanol, then obtained thin slice is immersed in red phosphorus dispersion liquid, ultrasonic 1h, then takes out drying, use phase
Thin slice is cut into a diameter of 12mm circular electric pole piece by the pole piece cutting tool answered, and produces flexible self-supporting three-dimensional hollow carbon/phosphorus
Combination electrode, the mass fraction of phosphorus is 78%.
Fig. 9 is the scanning electron microscope diagram of flexible self-supporting three-dimensional hollow carbon/phosphorus combination electrode in embodiment 5.
3. button cell assembles
Using the above-mentioned circular electric pole piece being prepared as negative pole, fibreglass diaphragm assembles as barrier film with metallic sodium piece
Into battery, the model CR2032 of button cell, electrolyte selects NaClO of the concentration for 1M4Electrolyte, wherein, solvent is：Carbon
Vinyl acetate (EC) and propene carbonate (PC).
4. battery testing
Using storage battery charge/discharge tester to above-mentioned battery carry out constant current charge-discharge test, test voltage section be 0~
2V, test temperature are 25 DEG C.
Figure 10 is that flexible self-supporting three-dimensional hollow carbon/phosphorus combination electrode of embodiment 5 is electric in 0.1C as sodium ion negative pole
Charging and discharging curve figure under current density.As a result show, the material prepared in embodiment 5 is close in 0.1C electric currents as sodium ion negative pole
Specific capacity under the conditions of degree is up to 1832mAh/g.
Embodiment 6
1. using triaminobenzene resinox foam as the preparation of the self-supporting three-dimensional hollow carbon of presoma
Triaminobenzene resinox foam containing ehter bond (ehter bond accounts for the 40% of all bridged bond ratios) is cut into block
Shape, length × width × height are 70 × 80 × 30mm, are placed in corundum crucible, are transferred in tube furnace.
Under conditions of normal pressure and the protection of the nitrogen atmosphere of anaerobic, 1100 DEG C are warming up to 6 DEG C/min speed, it is warm herein
The lower calcining 5h of degree, is cooled to room temperature, obtains the block three-dimensional hollow carbon that length × width × height is 20 × 19 × 14mm afterwards.
The block three-dimensional hollow carbon of gained is immersed in 5M KOH (pore creating material) solution, soak time 30min, taken
Go out at 80 DEG C and dry, under conditions of nitrogen protection, be warming up to 600 DEG C with 2 DEG C/min speed, calcine at this temperature
5h, activation pore-creating is carried out, be cooled to room temperature afterwards, then remnants KOH is removed using 1M hydrochloric acid solutions, reuses distilled water
Washing repeatedly to neutrality, obtains block more hollow carbon of microporous three-dimensional.
2. flexible self-supporting three-dimensional hollow carbon/MnOxThe preparation of combination electrode
Block more hollow carbon of microporous three-dimensional are cut with a knife into the thin slice of 600 μ m-thicks, are then immersed in 50% nitric acid
In manganese colloidal sol, ultrasonic 0.5h, drying is taken out, then under an inert atmosphere, is warming up to 400 DEG C with 2 DEG C/min speed, is incubated 4h,
Obtain flexible self-supporting three-dimensional hollow carbon/MnOxCombination electrode, MnOx mass fraction is 28%.,
Flexible self-supporting three-dimensional hollow carbon/MnOxCombination electrode is cut into diameter 10mm electrode slice, from polyethylene film
For barrier film, after 6mol/L KOH solutions are as electrolyte, it are packaged in CR2032 button cell shells and are assembled into ultracapacitor, with
5,100mV/s carry out performance test, and operating voltage 0-1V, two specific capacities swept under speed are respectively 168,107Fg-1, Tu11Wei
Prepared capacitor sweeps the CV curve maps under speed in difference.
Comparative example 1
It is different from embodiment 1, comparative example 1 be by the hollow carbon electrode grind into powder of flexible 3 D in embodiment 1,
Then according to the hollow carbon material powder of flexible 3 D：Conductive black：Kynoar (PVDF)=80%：10%：10% (quality
Than) it is prepared into electrode slice.Remaining all battery assembling and test process are same as Example 1.Fig. 4 is comparative example 1
Material is as kalium ion battery negative pole under 0.1C (theoretical capacity based on the embedding potassium of graphite, 1C=280mA/g) current density
Charging and discharging curve figure.As a result show, the material prepared in comparative example 1 is as kalium ion battery negative pole in 0.1C current densities
Under the conditions of specific capacity be only 175mAh/g, coulombic efficiency is only 52% first.
Comparative example 2
It is different from embodiment 2, comparative example 2 be by the hollow carbon electrode grind into powder of flexible 3 D in embodiment 2,
Then according to the hollow carbon material powder of flexible 3 D：Conductive black：Kynoar (PVDF)=80%：10%：10% (quality
Than) it is prepared into electrode slice.Remaining all battery assembling and test process are same as Example 2.Fig. 7 is comparative example 2
Charging and discharging curve figure of the material as sodium-ion battery negative pole under 0.1C (1C=300mA/g) current density.As a result show, it is right
It is only than the specific capacity of the material that is prepared in embodiment 2 as sodium-ion battery negative pole under 0.1C current density conditions
225mAh/g, coulombic efficiency is only 68% first.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above-mentioned embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc., it should be included in the guarantor of the present invention
Within the scope of shield.
Claims (10)
1. a kind of preparation method of three-dimensional hollow material, it is characterised in that comprise the following steps：By the foamed resin containing ehter bond
Material carries out high temperature cabonization, obtains self-supporting three-dimensional hollow material under normal pressure and oxygen-free inert atmosphere conditions.
2. according to the method for claim 1, it is characterised in that the foam resin containing ehter bond is phenol-first
Urea formaldehyde, aminobenzene resinox, aniline-formaldehyde resin, melamine formaldehyde resin, one kind in Lauxite or several
Kind.
Preferably, it is intermolecular that there is following bridged bond above-mentioned using formaldehyde as in the foamed resin of raw material：-CH2-、-CH2-O-
CH2-, wherein, the bridged bond (- CH containing ehter bond2-O-CH2-) ratio that accounts for above-mentioned all bridged bonds is：15-80%.
Preferably, the porosity of the foamed resin is 20-99%.
Preferably, the foam resin is melamine formaldehyde resin, Lauxite.
Preferably, the porosity of the foamed resin is 30%, 40%, 50%, 60%, 70%, 80-99%.
Preferably, the carburizing temperature be 400-1600 DEG C, for example, the temperature of the carbonization be 500 DEG C, 600 DEG C, 700 DEG C,
800℃、900-1300℃、1400℃、1500℃、1600℃；Carbonization time is 0.5-50h, more preferably 1-5h.
Preferably, the heating rate is 0.5-20 DEG C/min, for example, 5-10 DEG C/min.
Preferably, the inert atmosphere is nitrogen, argon gas, helium, VH2/VArFor 5/95 hydrogen/argon-mixed.
3. method according to claim 1 or 2, it is characterised in that the high temperature cabonization can urge adding or not adding
Carried out under conditions of agent, the catalyst is boron and its compound, iron and its compound, nickel and its compound, silicon and its change
One kind in compound, germanium and its compound, copper and its compound, calcium and its compound, magnesium and its compound, aluminium and its compound
It is or several.
4. according to the method any one of claim 1-3, it is characterised in that be immersed in the foam resin and urge
In agent solution, the catalyst is supported on the foam resin.
Preferably, the mass percent that the catalyst is added relative to all reactants is 0.1-30%, for example, 1-
5%.
5. according to the method any one of claim 1-4, it is characterised in that the three-dimensional hollow material can be further
Activation pore-creating is carried out in the presence of pore creating material, so as to obtain three-dimensional micro-porous hollow material.
Preferably, the pore creating material is KOH, and the mass percent that the KOH is added relative to all reactants is 5-50%.
A kind of 6. three-dimensional hollow material, it is characterised in that three-dimensional hollow material side as any one of claim 1-5
Method is prepared.
7. a kind of three-dimensional hollow material, it is characterised in that the three-dimensional hollow material has self-supporting three-dimensional structure and hollow knot
Structure, the tie point of three-dimensional framework is hollow ball, is connected between tie point by hollow pipe, forms three-dimensional hollow structure.
8. the purposes of a kind of three-dimensional hollow material according to claim 6 or 7, it is characterised in that as electrode material.
9. a kind of electrode, it is characterised in that the electrode includes the three-dimensional hollow material according to claim 6 or 7.
Preferably, the electrode is made up of the three-dimensional hollow material.
Preferably, the electrode also includes height ratio capacity active electrode material, that is, forms combination electrode.Preferably, the high ratio
The mass fraction that capacity active electrode material accounts for whole combination electrode is 10-90%, it is highly preferred that being 50-70%.
Preferably, the height ratio capacity active electrode material includes red phosphorus, black phosphorus, silicon, tin and tin oxide, antimony and its oxide,
Germanium and its oxide, transition metal oxide (such as the oxide of manganese, titanyl compound, the oxide of nickel, the oxide of molybdenum)
In one or more.
Preferably, the specific preparation method of the combination electrode is, by red phosphorus, black phosphorus, and silicon, tin, antimony, the one or more in germanium
Stir to form slurry with binding agent, then the three-dimensional hollow material is inserted in the slurry and impregnated, ultrasound, stir, drying
After obtain combination electrode.If the height ratio capacity active electrode material uses oxide, by by the three-dimensional space heartwood
Material is placed in dipping in oxide precursor colloidal sol, ultrasound and drying, then is carbonized in normal pressure and oxygen-free inert atmosphere
Form combination electrode.Wherein, the oxide precursor of tin is butter of tin or isopropanol tin, and the oxide precursor of antimony is sulfuric acid
Antimony or nitric acid antimony, the oxide precursor of germanium are germanium tetrachloride, and the oxide precursor of manganese is manganese nitrate, manganese acetate, manganese sulfate,
The oxide precursor of nickel is nickel nitrate, nickel acetate, nickel sulfate, and the oxide precursor of molybdenum is ammonium molybdate, before titanyl compound
Drive body is butyl titanate.
10. a kind of purposes of electrode according to claim 9, it is characterised in that as electrochemical energy storing device.
Preferably, the electrochemical energy storing device is lithium ion battery, sodium-ion battery and metal sode cell, kalium ion battery and
Metallic potassium battery, lithium-empty battery, aluminium ion battery, calcium ion battery, ultracapacitor.
Preferably, the positive pole, negative pole or collector applied to the energy storage device.
Preferably, the negative pole applied to the energy storage device.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103579625A (en) * | 2012-07-24 | 2014-02-12 | 黄炳照 | Carbon-series/active-substance compound and preparation method thereof |
| CN106829914A (en) * | 2017-01-22 | 2017-06-13 | 广西大学 | A kind of three-dimensional porous carbon negative pole material of lithium ion battery |
-
2017
- 2017-07-18 CN CN201710587626.0A patent/CN107482218A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103579625A (en) * | 2012-07-24 | 2014-02-12 | 黄炳照 | Carbon-series/active-substance compound and preparation method thereof |
| CN106829914A (en) * | 2017-01-22 | 2017-06-13 | 广西大学 | A kind of three-dimensional porous carbon negative pole material of lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 王斌等: "微球型碳泡沫复合材料力学性能的研究", 《航空工程进展》 * |
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Application publication date: 20171215 |