CN106024404B - The preparation method and applications of copper aluminium hydrotalcite-like materials - Google Patents
The preparation method and applications of copper aluminium hydrotalcite-like materials Download PDFInfo
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Abstract
The invention discloses a kind of preparation method and applications of copper aluminium hydrotalcite-like materials, preparation process are as follows：Ammonia spirit is taken first, and sodium carbonate is added and stirs to form mixed alkali liquor；Prepare the copper aluminium ion mixed solution of copper nitrate and aluminum nitrate again, be added drop-wise in the lump and prepare sodium citrate and the copper nitrate mixed ethanol aqueous solution in, ceaselessly mechanical agitation.With the pH value of acid regulation mixed solution, then crystallization, then by being centrifugally separating to obtain solid sample, then wash repeatedly, dry, obtain houghite precursor, then by calcining, obtain Cu Al CuO C houghites.The copper aluminum hydrotalcite material of the present invention has preferable electrochemical capacitance characteristic, can be used as the electrode material of electrochemical capacitance.Raw material used in the present invention is cheap and easy to get, and synthesis first make use of Na2[Cu(C6H7O5)] complex, atom high conversion rate, reduce industrialization cost.
Description
Technical field
The present invention relates to a kind of preparation technology of electrode material, more particularly to a kind of preparation method of hydrotalcite-like materials
And application, applied to electrode material for super capacitor technical field.
Background technology
Ultracapacitor is a kind of novel energy-storing, the energy saver between traditional capacitor and rechargeable battery.It is
Can be with fast charging and discharging with capacitor the characteristics of, there is the energy storage mechnism of electrochemical cell again.Compared with traditional capacitor,
Ultracapacitor has the features such as high-power density, long circulation life, pollution-free, wider operating temperature range, in power
Application in the fields such as power supply increasingly attracts attention.According to the difference of energy storage mechnism, ultracapacitor can be divided into double electricity
Layer ultracapacitor and Faradic pseudo-capacitor.The former utilizes electronics, ion or dipole in the orientation of electrode/solution surface
Electric double layer caused by arrangement stores electric charge, and the latter is then in electrode surface or the standard two of body phase by electroactive substance
Chemisorbed, desorption or pseudo capacitance caused by redox reaction occur in dimension space.In identical volume or again
In the case of amount, pseudo capacitance specific capacitance is often more than 10-100 times of electric double layer specific capacity.Therefore, electrode material
Performance directly determine the energy storage quality of capacitor.
There is document report to be applied to ultracapacitor on nickel aluminum hydrotalcite at present.Such as the patent Shen of the application such as Han Jing guest
Number it please disclose a kind of all-solid-state flexible ultracapacitor based on nickel aluminum hydrotalcite for 201310627666.5 patent application
Preparation method, on compliant conductive cloth grow nickel aluminum hydrotalcite array, be subsequently filled nano-particle in nickel aluminum hydrotalcite table
Face, obtain preferable chemical property.But the technique prepares more complicated, it is difficult to mass production is realized, and due to nickel
Magnetic and corrosivity it is stronger, be not suitable for extensive commercial application.The identified patent applications number such as Chen Zeyang are
201510180795.3 patent application disclose super capacitor using nickel aluminum hydrotalcite nano material as positive electrode
Device, a kind of positive electrode of nickel aluminum hydrotalcite material as capacitor is obtained, have higher capacity density and high power close
The characteristic of degree.Text goes out in chapter not providing the data of material circulation stability, and the stability of material is to judge that a kind of material is
The standard of no suitable large-scale production.Therefore the water a kind of environment-friendly, preparation method is simple and stability is good is developed
It is imperative that talc materials are applied to ultracapacitor.
Copper aluminum hydrotalcite is a kind of bimetallic oxide, and hydrotalcite material belongs to anionic property lamellar compound.Laminarization
Compound refer to layer structure, interlayer cation is adjustable denaturation and interlayer anion diversity, tradable a kind of compound,
The new object anion that the methods of passing through ion exchange introduces changes the structure and composition of compound.Utilize lamellar compound master
Body interchangeability of intercalation and interlayer ion possessed by under highly polar molecular action, can filling in ultracapacitor
The storage and release of electric charge are realized in discharge process, forms great energy stores.Currently, the research of copper aluminum hydrotalcite is less, only
There are the preparation method sporadicly reported on copper aluminium houghite, most commonly coprecipitation, for example, the open CuAl such as Chen Huiqin
The synthesis of hydrotalcite and its catalytic activity, synthesis chemistry, 2007,15,233-235.Used using aluminum nitrate and copper nitrate as raw material
The pillared CuAl hydrotalcites of carbanion have been prepared in coprecipitation, because copper ion result in obvious Jahn-Teller
Effect, it is difficult to obtain the good product of crystallinity.Pang Qiuyun discloses preparation and the Study on adsorption properties of copper aluminium houghite, bent
Abundant normal university's Master's thesis, 2009.4.Disclose and copper has been prepared using hydro-thermal method as raw material using copper chloride and aluminum nitrate
Aluminium houghite, but agglomeration is more serious.The patent document that identified patent applications number are 201210150905.8 discloses
A kind of preparation method of copper aluminum hydrotalcite, use aluminium chloride and Kocide SD for Material synthesis the copper aluminium neatly of better crystallinity degree
Stone, but be extremely easy in decomposition because Kocide SD is unstable as cupric oxide and water, cause to obtain hydrotalcite crystalline phase bad.So exploitation
It is a kind of that preparing novel copper-aluminium hydrotalcite-like materials turns into technical problem urgently to be resolved hurrily on a large scale.
The content of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
The preparation method and applications of copper aluminium hydrotalcite-like materials, intercalation copper aluminium houghite electrode material can be prepared on a large scale, is used for
The energy density and discharge voltage of capacitive vessel are improved, method is simple, suitable for being used on electrode of super capacitor.
Purpose is created to reach foregoing invention, using following technical proposals：
A kind of preparation method of copper aluminium hydrotalcite-like materials, comprises the following steps：
1）Quantitative soluble carbonate salt is weighed, is added in the alkaline solution containing hydroxide ion, is stirred,
With deionized water dissolving constant volume, and logical nitrogen removes the oxygen in mixed solution；Carbonate in prepared mixed solution it is dense
Degree is preferably 0.1-0.5 g/L；The alkali concn of the alkaline solution of hydroxyl-containing ion is preferably 5-20g/L；The carbonate is excellent
Elect any one in sodium salt and sylvite or two kinds of mixture as, the alkaline solution containing hydroxide ion is preferably ammoniacal liquor
Any one solution or two kinds of mixed solution in solution and sodium hydroxide solution
2）Quantitative soluble copper salt and quantitative aluminum soluble salt are weighed, according to soluble copper salt and aluminum soluble salt
Quality proportioning is（1：4）~（1：11.85）Ratio, soluble copper salt and aluminum soluble salt are mixed, use deionized water dissolving
Constant volume, and logical nitrogen removes the oxygen in mixed solution, and make wherein described step 1）In soluble carbonate salt and this step in
The mass ratio of soluble copper salt be（1：1.6）~（1：15）；In prepared mixed solution, the concentration of mantoquita is preferably
0.8-1.5 g/L, the concentration of aluminium salt is preferably 6-9.5 g/L；The mantoquita is preferably in nitrate, sulfate or chloride salt
Any one or any several mixture, the aluminium salt be preferably any one in nitrate, sulfate or chloride salt or
Any several mixture；
3）By Na2[Cu(C6H4O7)] solution is infused in three-necked flask, under nitrogen protection, by the step 1）And step
Rapid 2）Each mixed solution of middle preparation is slowly dropped to the Na in three-necked flask by partial pressure funnel2[Cu(C6H4O7)] molten
Form mixed solution system in liquid, and with 200~300 r/min speed to the mixed solution system in three-necked flask ceaselessly
Mechanical agitation is carried out, when in the step 1）With step 2）After each mixed solution of middle preparation drips, mixed with acid regulation
The pH value of solution system is 7.5~9, then at a temperature of 70~90 DEG C, crystallization 10~18 hours, is being mixed after reaction terminates
Solid product is separated out in solution system, mixed solution system is then slowly cooled to room temperature together with solid product；As preferred
Technical scheme, this step mixes 150~300 mg sodium citrate with 300~600 mg copper nitrate, adds 10~15
The ethanol of milliliter, and 30 milliliters of deionized water is added, after sodium citrate and nitric acid copper dissolution, Na is obtained by reaction2[Cu
(C6H4O7)] solution；When adjusting the pH value of mixed solution system, the acid of use is preferably any one acid in hydrochloric acid and nitric acid
Solution or two kinds of mixed acid solution, the sour concentration of use is preferably 0.2~0.8 mol/L；
4）Will be in step 3）In mixed solution system in separate out method of the solid product by centrifugation, obtain solid
Sample, then solid sample is washed repeatedly, the DDGS ion in solid sample is removed, solid sample is and then placed on drying
Beaker in be placed in 70-100 DEG C of vacuum drying chamber dry 12-24 hours, acquisition contain Cu-Al- [Cu (C6H4O7)]2-'s
Houghite compound precursor sample, there is typical houghite pattern；
5）Will be in the step 4）Middle acquisition contains Cu-Al- [Cu (C6H4O7)]2-Houghite compound precursor sample
Product under nitrogen protection, are calcined, 450-550 DEG C of calcining heat, calcination time 4-8 hours, Cu-Al- are finally prepared
CuO-C hydrotalcite-like materials.
A kind of application of the preparation method of copper aluminium hydrotalcite-like materials of the present invention, utilizes the preparation of copper aluminium hydrotalcite-like materials
Method prepares Cu-Al-CuO-C hydrotalcite-like materials, will be in the step 5）The Cu-Al-CuO-C hydrotalcite-like materials of middle synthesis
Cu-Al-CuO-C houghite powders are made in drying sample grinding, then according to Cu-Al-CuO-C houghites powder, acetylene
It is black to be with PTFE binder mixed proportion（15~18）：（1~4）：1 ratio, by Cu-Al-CuO-C houghites
Powder, acetylene black and PTFE binder are uniformly mixed and made into mixed slurry, and mixed slurry is coated in into collector foam
On nickel screen, it is placed under 70~100 DEG C of vacuum environment and drying is dried, obtains intercalation copper aluminium houghite electrode material.
It is preferred that it is according to the mixed proportion of Cu-Al-CuO-C houghites powder, acetylene black and PTFE binder
15:4:1,16:3:1 or 18:1:1 ratio, Cu-Al-CuO-C houghites powder, acetylene black and polytetrafluoroethylene (PTFE) are bonded
Agent is uniformly mixed and made into mixed slurry.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage：
1. the copper aluminum hydrotalcite of the intercalation configuration of preparation is applied to ultracapacitor as electrode material by the present invention first
Material, has given full play to the interlayer structure feature of hydrotalcite material, big specific surface area, thus the material has excellent electrochemistry
Characteristic；
2. the raw material used in preparation method of the present invention is cheap and easy to get, and atom high conversion rate, industrial chemical conversion can be reduced
This；
3. the copper source of the material prepared compared to nickel aluminum hydrotalcite electrode material, the present invention is easy to get, relative to nickel environment friend
It is good, tested by discharge and recharge and cyclical stability, the electrochemical properties of copper aluminum hydrotalcite material are better than nickel aluminum hydrotalcite.
Brief description of the drawings
Fig. 1 contains Cu-Al- [Cu (C for prepared by the embodiment of the present invention one6H4O7)]2-Houghite compound precursor sample
The X ray picture spectrogram of product and Cu-Al-CuO-C hydrotalcite-like materials.
Fig. 2 contains Cu-Al- [Cu (C for prepared by the embodiment of the present invention one6H4O7)]2-Houghite compound precursor sample
The cyclic voltammetry result curve comparison diagram of product and Cu-Al-CuO-C hydrotalcite-like materials.
Fig. 3 contains Cu-Al- [Cu (C for prepared by the embodiment of the present invention one6H4O7)]2-Houghite compound precursor sample
The cycle performance test result comparison diagram of product and Cu-Al-CuO-C hydrotalcite-like materials.
Embodiment
Details are as follows for the preferred embodiments of the present invention：
Embodiment one：
In the present embodiment, referring to Fig. 1~3, a kind of preparation method of copper aluminium hydrotalcite-like materials, comprise the following steps：
1）0.1 g sodium carbonate is weighed, adds in 10 mL ammonia spirits, stirs, with deionized water dissolving constant volume
To 100 mL, and logical nitrogen removes the oxygen in mixed solution；
2）Weigh 0.96 g copper nitrates and 7.5 g aluminum nitrates carry out mixed preparing copper nitrate and aluminum nitrate mixed solution, use
Deionized water dissolving is settled to 100 mL, and logical nitrogen removes the oxygen in mixed solution；
3）150 mg sodium citrate is mixed with 300 mg copper nitrate, adds 10 milliliters of ethanol, and add 30
The deionized water of milliliter, prepares sodium citrate and the copper nitrate mixed ethanol aqueous solution, after sodium citrate and nitric acid copper dissolution, passes through
Reaction obtains Na2[Cu(C6H4O7)] solution, by Na2[Cu(C6H4O7)] solution is infused in three-necked flask, under nitrogen protection,
By the step 1）With step 2）Each mixed solution of middle preparation is slowly dropped in three-necked flask by partial pressure funnel
Na2[Cu(C6H4O7)] mixed solution system is formed in solution, and it is molten to the mixing in three-necked flask with 300 r/min speed
Liquid system ceaselessly carries out mechanical agitation, when in the step 1）With step 2）After each mixed solution of middle preparation drips,
PH value with 0.2 mol/L nitric acid regulation mixed solution system is 8, then at a temperature of 80 DEG C, crystallization 15 hours, when reaction is tied
Solid product is separated out after beam in mixed solution system, mixed solution system is then slowly cooled to room together with solid product
Temperature；
4）Will be in step 3）In mixed solution system in separate out method of the solid product by centrifugation, obtain solid
Sample, then solid sample is washed repeatedly, the DDGS ion in solid sample is removed, solid sample is and then placed on drying
Beaker in be placed in 80 DEG C of vacuum drying chamber dry 12 hours, acquisition contain Cu-Al- [Cu (C6H4O7)]2-Houghite
Compound precursor sample, there is typical houghite pattern；
5）Will be in the step 4）Middle acquisition contains Cu-Al- [Cu (C6H4O7)]2-Houghite compound precursor sample
Product under nitrogen protection, are calcined, and 450 DEG C of calcining heat, calcination time 4 hours, Cu-Al-CuO-C are finally prepared
Hydrotalcite-like materials.
A kind of application of the preparation method of the present embodiment copper aluminium hydrotalcite-like materials, for preparing electrode material, using this
Cu-Al-CuO-C hydrotalcite-like materials prepared by the preparation method of embodiment copper aluminium hydrotalcite-like materials, will be in the step 5）
Cu-Al-CuO-C houghite powders are made in the Cu-Al-CuO-C hydrotalcite-like materials drying sample grinding of middle synthesis, then press
Mixed proportion according to Cu-Al-CuO-C houghites powder, acetylene black and PTFE binder is 15:4:1 ratio, will
Cu-Al-CuO-C houghites powder, acetylene black and PTFE binder are uniformly mixed and made into mixed slurry, by mixing slurry
Material is online coated in collector nickel foam, is placed under 80 DEG C of vacuum environment and drying is dried, obtain intercalation copper aluminium class neatly
Stone electrode material.
The experimental test and analysis of electrode material：
Using the intercalation copper aluminium houghite electrode of preparation as working electrode, reference electrode is done with saturated calomel electrode, with
Platinized platinum is cooked to electrode, and three-electrode system is formed as electrolyte using 6M KOH solution, is carried out using Shanghai Chen Hua chem workstation
Cyclic voltammetry, electrochemical property test is carried out using Arbin MSTAT4+ constant current charge-discharge tests system.
Fig. 1 XRD test results show the pattern for the typical intercalated houghite that the present embodiment has synthesized, right as shown in Figure 1
In [Cu-Al- [Cu (C6H4O7)]2-5 peaks with obvious hydrotalcite, 2θRespectively 15 °, 28 °, 38 °, 48 ° and
64 °, wherein corresponding crystal face is respectively（003）,（006）, (012), (015), (018), the spacing between XRD Zhong Feng and peak is big
About all at 10 ° or so, i.e., equidistantly illustrate to be formed is copper aluminium intercalated houghite material.And sample Cu-Al- after calcining
CuO-C crystal formation shows a very strong steamed bun peak, illustrates that carbon is contained in the material the inside after calcining, for 2θIt is worth and is
45 °, 65 ° of peaks that can be attributed to cupric oxide, illustrate that cupric oxide is contained in the material the inside after calcining.Fig. 2 is test neatly
Stone sample [Cu-Al- [Cu (C6H4O7)]2-With cyclic voltammetrics of the Cu-Al-CuO-C as electrode material in 6 M KOH solutions
Curve, sweep that speed is voltage corresponding to 5 mV/s arrow represents from -0.7 V to 0.7 V, in figure is to sweep speed electrode from small to large
The change of curve.Fig. 2 cyclic voltammetry curve shape explanation, this is faraday's capacitor.There are two pairs of peaks to occur, electrode oxygen
Change reaction（1）For：
（1）
The reduction reaction of counter electrode（2）For：
（2）
Pass through two kinds of hydrotalcites [Cu-Al- [Cu (C6H4O7)]2-It can be calculated with Cu-Al-CuO-C cyclic voltammetry curve
It is respectively 63.82 F/g to go out the corresponding specific capacitance in the case where sweeping 5 mV/s of speed, Cu-Al-CuO-C apparent 94.74 F/g electricity
Hold than [Cu-Al- [Cu (C6H4O7)]2-.Fig. 3 gives stable circulation performance test curve.That Fig. 3 shows is Cu-Al-CuO-C
In Fuan test process is circulated, the cyclical stability after 500 circles sweep speed.500 are being tested by calculating specific capacitance value
Only 17.31% loss after circle, it is a kind of super capacitor material for having potential using value to illustrate this electrode material.
The present embodiment takes ammonia spirit first, and sodium carbonate is added and stirs to form mixed alkali liquor；Copper nitrate is prepared again
With the copper aluminium ion mixed solution of aluminum nitrate, be added drop-wise in the lump and prepare sodium citrate and the copper nitrate mixed ethanol aqueous solution in,
Ceaselessly mechanical agitation.With acid regulation mixed solution pH value, then crystallization, then by being centrifugally separating to obtain solid sample, so
Wash, dry repeatedly afterwards, obtain houghite precursor, then by calcining, obtain Cu-Al-CuO-C houghites.This implementation
Copper aluminum hydrotalcite material prepared by example has preferable electrochemical capacitance characteristic, can be used as the electrode material of electrochemical capacitance.This implementation
Intercalation copper aluminum hydrotalcite electrode material prepared by example has excellent cyclical stability, can reach more than 1000 times, this implementation
Intercalation copper aluminum hydrotalcite electrode material prepared by example has preferable electrochemical capacitance characteristic, can be used as the electrode material of electrochemical capacitance
Material.Synthesis make use of Na to the present invention first2[Cu(C6H4O7)] complex, the raw material that the inventive method uses is cheap and easy to get,
Atom high conversion rate, reduce industrialization cost.
Embodiment two：
The present embodiment and embodiment one are essentially identical, are particular in that：
In the present embodiment, a kind of preparation method of copper aluminium hydrotalcite-like materials, comprises the following steps：
1）0.25 g sodium carbonate is weighed, is added in 20 mL ammonia spirits, is stirred, determined with deionized water dissolving
Hold to 100 mL, and logical nitrogen removes the oxygen in mixed solution；
2）Weigh 1.8 g copper nitrates and 14.76 g aluminum nitrates mixed, 100 mL are settled to deionized water dissolving,
And logical nitrogen removes the oxygen in mixed solution；
3）200 mg sodium citrate is mixed with 300 mg copper nitrate, adds the ethanol of 15 mL milliliters, and add 30
The deionized water of milliliter, after sodium citrate and nitric acid copper dissolution, Na is obtained by reaction2[Cu(C6H4O7)] solution, by Na2[Cu
(C6H4O7)] solution is infused in three-necked flask, under nitrogen protection, by the step 1）With step 2）Each mixing of middle preparation
Solution is slowly dropped to the Na in three-necked flask by partial pressure funnel2[Cu(C6H4O7)] mixed solution body is formed in solution
System, and mechanical agitation is ceaselessly carried out to the mixed solution system in three-necked flask with 300 r/min speed, when in the step
Rapid 1）With step 2）After each mixed solution of middle preparation drips, the pH of mixed solution system is adjusted with 0.2 mol/L nitric acid
It is worth for 8.5, then at a temperature of 85 DEG C, crystallization 15 hours, solid product is separated out in mixed solution system after reaction terminates,
Then mixed solution system is slowly cooled to room temperature together with solid product；
4）Will be in step 3）In mixed solution system in separate out method of the solid product by centrifugation, obtain solid
Sample, then solid sample is washed repeatedly, the DDGS ion in solid sample is removed, solid sample is and then placed on drying
Beaker in be placed in 80 DEG C of vacuum drying chamber dry 16 hours, acquisition contain Cu-Al- [Cu (C6H4O7)]2-Houghite
Compound precursor sample, there is typical houghite pattern；
5）Will be in the step 4）Middle acquisition contains Cu-Al- [Cu (C6H4O7)]2-Houghite compound precursor sample
Product under nitrogen protection, are calcined, and 550 DEG C of calcining heat, calcination time 5 hours, Cu-Al-CuO-C are finally prepared
Hydrotalcite-like materials.
A kind of application of the preparation method of the present embodiment copper aluminium hydrotalcite-like materials, for preparing electrode material, using this
Cu-Al-CuO-C hydrotalcite-like materials prepared by the preparation method of embodiment copper aluminium hydrotalcite-like materials, will be in the step 5）
Cu-Al-CuO-C houghite powders are made in the Cu-Al-CuO-C hydrotalcite-like materials drying sample grinding of middle synthesis, then press
Mixed proportion according to Cu-Al-CuO-C houghites powder, acetylene black and PTFE binder is 15:4:1 ratio, will
Cu-Al-CuO-C houghites powder, acetylene black and PTFE binder are uniformly mixed and made into mixed slurry, by mixing slurry
Material is online coated in collector nickel foam, is placed under 70 DEG C of vacuum environment and drying is dried, obtain intercalation copper aluminium class neatly
Stone electrode material.
Embodiment three：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, a kind of preparation method of copper aluminium hydrotalcite-like materials, comprises the following steps：
1）0.15 g sodium carbonate is weighed, is added in 15 mL ammonia spirits, is stirred, determined with deionized water dissolving
Hold to 100 mL, and logical nitrogen removes the oxygen in mixed solution；
2）Weigh 1.5 g copper nitrates and 12.3 g aluminum nitrates are mixed, 100 mL are settled to deionized water dissolving, and
Logical nitrogen removes the oxygen in mixed solution；
3）200 mg sodium citrate is mixed with 300 mg copper nitrate, adds the ethanol of 15 mL milliliters, and add 30
The deionized water of milliliter, after sodium citrate and nitric acid copper dissolution, Na is obtained by reaction2[Cu(C6H4O7)] solution, by Na2[Cu
(C6H4O7)] solution is infused in three-necked flask, under nitrogen protection, by the step 1）With step 2）Each mixing of middle preparation
Solution is slowly dropped to the Na in three-necked flask by partial pressure funnel2[Cu(C6H4O7)] mixed solution body is formed in solution
System, and mechanical agitation is ceaselessly carried out to the mixed solution system in three-necked flask with 300 r/min speed, when in the step
Rapid 1）With step 2）After each mixed solution of middle preparation drips, the pH of mixed solution system is adjusted with 0.2 mol/L nitric acid
It is worth for 7.8, then at a temperature of 85 DEG C, crystallization 15 hours, solid product is separated out in mixed solution system after reaction terminates,
Then mixed solution system is slowly cooled to room temperature together with solid product；
4）Will be in step 3）In mixed solution system in separate out method of the solid product by centrifugation, obtain solid
Sample, then solid sample is washed repeatedly, the DDGS ion in solid sample is removed, solid sample is and then placed on drying
Beaker in be placed in 80 DEG C of vacuum drying chamber dry 16 hours, acquisition contain Cu-Al- [Cu (C6H4O7)]2-Houghite
Compound precursor sample, there is typical houghite pattern；
5）Will be in the step 4）Middle acquisition contains Cu-Al- [Cu (C6H4O7)]2-Houghite compound precursor sample
Product under nitrogen protection, are calcined, and 550 DEG C of calcining heat, calcination time 5 hours, Cu-Al-CuO-C are finally prepared
Hydrotalcite-like materials.
A kind of application of the preparation method of the present embodiment copper aluminium hydrotalcite-like materials, for preparing electrode material, using this
Cu-Al-CuO-C hydrotalcite-like materials prepared by the preparation method of embodiment copper aluminium hydrotalcite-like materials, will be in the step 5）
Cu-Al-CuO-C houghite powders are made in the Cu-Al-CuO-C hydrotalcite-like materials drying sample grinding of middle synthesis, then press
Mixed proportion according to Cu-Al-CuO-C houghites powder, acetylene black and PTFE binder is 15:4:1 ratio, will
Cu-Al-CuO-C houghites powder, acetylene black and PTFE binder are uniformly mixed and made into mixed slurry, by mixing slurry
Material is online coated in collector nickel foam, is placed under 90 DEG C of vacuum environment and drying is dried, obtain intercalation copper aluminium class neatly
Stone electrode material.
The embodiment of the present invention is illustrated above in conjunction with accompanying drawing, but the invention is not restricted to above-described embodiment, can be with
A variety of changes are made according to the purpose of the innovation and creation of the present invention, under all Spirit Essence and principle according to technical solution of the present invention
Change, modification, replacement, combination or the simplification made, should be equivalent substitute mode, as long as meeting the goal of the invention of the present invention,
Technical principle and inventive concept without departing from the preparation method and applications of copper aluminium hydrotalcite-like materials of the present invention, are belonged to
Protection scope of the present invention.
Claims (9)
1. a kind of preparation method of copper aluminium hydrotalcite-like materials, it is characterised in that comprise the following steps：
1）Quantitative soluble carbonate salt is weighed, is added in the alkaline solution containing hydroxide ion, is stirred, is spent
Ionized water dissolves constant volume, and logical nitrogen removes the oxygen in mixed solution；
2）Quantitative soluble copper salt and quantitative aluminum soluble salt are weighed, according to the quality of soluble copper salt and aluminum soluble salt
Match as 1：4~1：11.85 ratio, soluble copper salt and aluminum soluble salt are mixed, with deionized water dissolving constant volume, and led to
Nitrogen removes the oxygen in mixed solution, and makes wherein described step 1）In soluble carbonate salt and this step in soluble copper
The mass ratio of salt is 1：1.6~1：15；
3）Sodium citrate is mixed with copper nitrate, addition ethanol and deionized water, after sodium citrate and nitric acid copper dissolution, by anti-
Na should be obtained2[Cu(C6H4O7)] solution, by Na2[Cu(C6H4O7)] solution is infused in three-necked flask, under nitrogen protection, will
The step 1）With step 2）Each mixed solution of middle preparation is slowly dropped in three-necked flask by partial pressure funnel
Na2[Cu(C6H4O7)] mixed solution system is formed in solution, and with 200~300 r/min speed in three-necked flask
Mixed solution system ceaselessly carries out mechanical agitation, when in the step 1）With step 2）Each mixed solution of middle preparation drips
Afterwards, the pH values that mixed solution system is adjusted with acid are 7.5~9, and then at a temperature of 70~90 DEG C, crystallization 10~18 is small
When, solid product is separated out in mixed solution system after reaction terminates, it is then that mixed solution system is slow together with solid product
Slow cool down is to room temperature；
4）Will be in step 3）In mixed solution system in separate out method of the solid product by centrifugation, obtain solid-like
Product, then solid sample is washed repeatedly, the DDGS ion in solid sample is removed, is and then placed on solid sample dry
It is placed in beaker in 70-100 DEG C of vacuum drying chamber and dries 12-24 hours, acquisition contains Cu-Al- [Cu (C6H4O7)]2-Class
Hydrotalcite compound precursor sample；
5）Will be in the step 4）Middle acquisition contains Cu-Al- [Cu (C6H4O7)]2Houghite compound precursor sample in nitrogen
Under gas shielded, calcined, 450-550 DEG C of calcining heat, calcination time 4-8 hours, Cu-Al-CuO-C is finally prepared
Hydrotalcite-like materials.
2. the preparation method of copper aluminium hydrotalcite-like materials according to claim 1, it is characterised in that：In the step 1）In,
The concentration of carbonate in prepared mixed solution is 0.1-0.5 g/L；In the step 2）In, it is molten in prepared mixing
In liquid, the concentration of mantoquita is 0.8-1.5 g/L, and the concentration of aluminium salt is 6-9.5 g/L.
3. the preparation method of copper aluminium hydrotalcite-like materials according to claim 1, it is characterised in that：In the step 1）In,
The alkali concn of the alkaline solution of hydroxyl-containing ion is 5-20 g/L.
4. the preparation method of copper aluminium hydrotalcite-like materials according to any one in claims 1 to 3, it is characterised in that：
The step 1）In, the carbonate is the mixture of any one in sodium salt and sylvite or two kinds, it is described containing hydroxyl from
The alkaline solution of son is any one solution or two kinds of mixed solution in ammonia spirit and sodium hydroxide solution.
5. the preparation method of copper aluminium hydrotalcite-like materials according to any one in claims 1 to 3, it is characterised in that：
The step 2）In, the mantoquita is any one in nitrate, sulfate or chloride salt or any several mixture, institute
Aluminium salt is stated as any one in nitrate, sulfate or chloride salt or any several mixture.
6. the preparation method of copper aluminium hydrotalcite-like materials according to any one in claims 1 to 3, it is characterised in that：
The step 3）In, 150~300 mg sodium citrate is mixed with 300~600 mg copper nitrate, adds 10~15 millis
The ethanol risen, and 30 milliliters of deionized water is added, after sodium citrate and nitric acid copper dissolution, Na is obtained by reaction2[Cu
(C6H4O7)] solution.
7. the preparation method of copper aluminium hydrotalcite-like materials according to any one in claims 1 to 3, it is characterised in that：
The step 3）In, when adjusting the pH values of mixed solution system, the acid that uses for hydrochloric acid and nitric acid in any one acid solution
Or two kinds of mixed acid solution, the sour concentration used is 0.2~0.8 mol/L.
A kind of 8. application of the preparation method of copper aluminium hydrotalcite-like materials described in claim 1, it is characterised in that：Utilize copper aluminium
The preparation method of hydrotalcite-like materials prepares Cu-Al-CuO-C hydrotalcite-like materials, will be in the step 5）The Cu- of middle synthesis
Cu-Al-CuO-C houghite powders are made in the grinding of Al-CuO-C hydrotalcite-like materials drying sample, then according to Cu-Al-
The mixed proportion of CuO-C houghites powder, acetylene black and PTFE binder is 15~18：1~4：1 ratio,
Cu-Al-CuO-C houghites powder, acetylene black and PTFE binder are uniformly mixed and made into mixed slurry, will be mixed
It is online coated in collector nickel foam to close slurry, is placed under 70~100 DEG C of vacuum environment and drying is dried, obtain intercalation copper
Aluminium houghite electrode material.
9. the application of the preparation method of copper aluminium hydrotalcite-like materials according to claim 8, it is characterised in that：According to Cu-
The mixed proportion of Al-CuO-C houghites powder, acetylene black and PTFE binder is 15:4:1,16:3:1 or 18:
1:1 ratio, Cu-Al-CuO-C houghites powder, acetylene black and PTFE binder are uniformly mixed mixed
Close slurry.
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| CN106449144A (en) * | 2016-10-25 | 2017-02-22 | 嘉善蓝欣涂料有限公司 | An intercalated ketone aluminum hydrotalcite electrode material and a preparation method thereof |
| CN108483511B (en) * | 2018-06-05 | 2020-07-24 | 北京化工大学 | Preparation method of hydrotalcite-like material |
| CN112058264A (en) * | 2020-09-17 | 2020-12-11 | 沈阳师范大学 | Preparation method of petal-shaped copper-aluminum hydrotalcite-like carrier and supported nano platinum catalyst |
| CN113804712A (en) * | 2021-08-06 | 2021-12-17 | 云南大学 | Scanning electron microscope in-situ observation sample preparation method for lamellar carbon nitride etching process |
| CN113903600B (en) * | 2021-10-11 | 2023-01-13 | 东莞理工学院 | Phosphorus and carbon co-doped molybdenum disulfide aluminum ion capacitor positive electrode material and preparation method thereof |
| CN113893679B (en) * | 2021-10-28 | 2023-07-21 | 中建材玻璃新材料研究院集团有限公司 | Purifying agent for CIGS thin film battery tail gas and preparation method thereof |
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| CN1962453A (en) * | 2006-11-22 | 2007-05-16 | 天津化工研究设计院 | Process for producing hydrotalcite-like layered hydroxide |
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| CN101181686A (en) * | 2007-12-06 | 2008-05-21 | 上海大学 | Hydrotalcite type hydrocracking catalyst and method for preparing same |
| CN102659164A (en) * | 2012-05-14 | 2012-09-12 | 浙江工业大学 | Preparation method for copper and aluminium hydrotalcite |
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| CN101181686A (en) * | 2007-12-06 | 2008-05-21 | 上海大学 | Hydrotalcite type hydrocracking catalyst and method for preparing same |
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