CN104003452B - A kind of one dimension pattern cobalt aluminum hydrotalcite and preparation method thereof and electrochemical applications - Google Patents
A kind of one dimension pattern cobalt aluminum hydrotalcite and preparation method thereof and electrochemical applications Download PDFInfo
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Abstract
The present invention relates to one dimension pattern cobalt aluminum hydrotalcite and preparation method thereof and electrochemical applications, belong to the preparation field of inorganic non-metallic functional material.The hydrotalcite-like materials with one dimension pattern is prepared containing cobalt precursor and containing the solid-liquid ion-exchange between aluminum solutions and carbonate solution and original position crystalline phase conversion process by solid-state, improve the dispersing uniformity of material, reduce bulk density, make it be more suitable for being applied to the fields such as the energy as electric material.
Description
Technical field:
The present invention relates to a kind of one dimension pattern cobalt aluminum hydrotalcite and preparation method thereof and the electrochemical applications in super capacitor anode material, belong to inorganic functional material field.
Background technology:
Houghite is the anion intercalated material of a quasi-representative, because its main body laminate is made up of divalence and trivalent metal ion compound, therefore also known as making layered composite metal hydroxides (Layered doublehydroxides is called for short LDHs), its chemical composition is: [M
2+ 1-xm
3+ x(OH)
2]
x+a
n- x/nmH
2o.Wherein M
2+, M
3+represent divalence and trivalent metal ion respectively, x is molar fraction shared by trivalent metal ion; A
n-represent interlayer anion; M is interlayer crystallization water quantity.LDHs crystal is by positively charged class shepardite main body laminate ([M
2+ 1-xm
3+ x(OH)
2]
x+) and interlayer hydration object anion (A
n- x/nmH
2o) alternately accumulation forms.The main body laminate of LDHs is formed by connecting by covalent bond, is combined between laminate with interlayer object anion by hydrogen bond, electrostatic interaction, Van der Waals force etc., forms ordered arrangement.The character of LDHs depends on the kind of body layer sheetmetal element and ratio, the kind of interlayer object anion and quantity, and the accumulation mode of laminate, the various combination of three defines one and huge has analog structure, the LDHs material family of different physicochemical properties.The adjustable sex change of body layer sheetmetal element kind and ratio and the interchangeability of interlayer object anion are the essential characteristics of LDHs material.This architectural feature of LDHs makes the character of this material have designability, demonstrate good application prospect at numerous areas such as catalysis, absorption, Process Technology of Polymer (as additive), medicine, environmental protection, electrochemistry, photochemistry, and obtain practical application in catalysis, Process Technology of Polymer, medicine and other fields.
Electrode (Itaya K is made first from LDHs in 1987, Chang H C, Uchida I.Anion-exchanged hydrotalcite-like-clay-modified electrodes.Inorg.Chem., 1987,26:624), within 2002, LDHs is used as electrode material for super capacitor (Wohlfahrt-Mehrens M first, Schenk J, Wilde P M, etc.New materials forsupercapacitors.J.Power Sources., 2002,105 (2): 182), a series of LDHs with electro-chemical activity is successfully synthesized.Wherein, transition metal base LDHs that is nickeliferous, cobalt causes the broad interest of people.Ni-based LDHs can be used as the positive electrode of Ni-MH battery; Cobalt-based LDHs is then potential electrode material for super capacitor.
Ultracapacitor is the novel energy-storing element of a kind of performance between traditional capacitor and battery.The electric double layer that ultracapacitor utilizes electrode surface to be formed or generation two dimension/accurate two-dimentional faraday's reaction carry out power storage, have the advantages such as specific power is high, charge/discharge rates fast, have extended cycle life.Excellent pulsed discharge performance and Large Copacity energy-storage property make it have extensive use in fields such as telecommunications, electric automobile and Aero-Space.Co (OH)
2the redox characteristic good because of it and resource relative abundance, be subject to extensive research as potential high performance capacitors material always.Current research shows, with Al same order elements Co (OH)
2in part Co, formed with Co (OH)
2there is the CoAl-LDHs of phase quasi-lamellar structure, not only can improve ratio capacitance and specific area, the stability of material can also be increased, thus slow down the decay of ratio capacitance with current density, improve the power characteristic of capacitor.Cobalt-based LDHs demonstrates extraordinary application prospect as potential high-performance super capacitor material.
Although since eighties of last century nineties, the preparation method of LDHs obtains fast development, initial coprecipitation basis has successively occurred ion-exchange, roasting Reconstruction Method etc. based on " memory effect ", and the LDHs material be made up of different subjects laminate and function object is in a large number successfully synthesized by means of these methods, but, from lot of documents report, reassemble into the not heavy pattern of design and control, most LDHs synthetic product is irregular sheet or hexagon sheet-like crystallite powder.But there is different requirements in different application field to the character of LDHs material and pattern.LDHs only can conduct electricity on laminate direction, and perpendicular to non-conductive on laminate direction.Hexagon sheet LDHs crystallite haphazard packing must cause electric conductivity between crystallite and crystallite poor.The one dimension pattern LHDs (fibrous, bar-shaped, strip, whisker etc.) of laminate direction large scale is obviously the effective way addressed this problem.One dimension pattern LDHs not only keeps the continuity compared with large scale on laminate direction, can solve random overlap joint between sheet LDHs crystallite and cause the problem of poor electric conductivity, also has that bulk density is little, the advantage such as be uniformly dispersed.
The technology of preparing of existing LDHs can be divided into one-step method with Duo Walk method.Namely one-step method is directly obtained the preparation method of target LDHs by raw material one step, comprise coprecipitation (single droplet method, two methods, nucleation/crystallization isolation method and urea methods), hydro thermal method, mechanical milling method etc.Multistep processes comprises ion-exchange, roasting Reconstruction Method, sol-gal process and sacrifice template etc., and its ion exchange methods and roasting Reconstruction Method need first to produce LDHs as presoma by one-step method.The bibliographical information controlling preparation about special appearance LDHs is also little, and the technology of preparing of one dimension pattern LDHs rarely has report especially.In above-mentioned preparation method, only have and sacrifice the preparation that a few methods such as template, laser ablation can be used in special appearance LDHs, what wherein use more is sacrifice template.The method preparation process is many, and process is complicated, is mainly used for the laboratory preparation research of specific modality inorganic material.
At present, there is no and special appearance cobalt-based LDHs is reported as the research of super capacitor anode material, more without the report of one dimension pattern cobalt-based LDHs.The technology of preparing of exploitation one dimension pattern transition metal LDHs has very important realistic meaning undoubtedly.
Summary of the invention:
The object of this invention is to provide a kind of one dimension pattern cobalt aluminum hydrotalcite and preparation method thereof and electrochemical applications.The hydrotalcite-like materials with one dimension pattern is prepared containing cobalt precursor and containing the solid-liquid ion-exchange between aluminum solutions and carbonate solution and original position crystalline phase conversion process by one dimension pattern is solid-state, the dispersing uniformity of material can be improved, reduce bulk density, make it be more suitable for the applications such as electrochemistry, catalysis, absorption, ion-exchange, be particularly suitable for the electrode material as ultracapacitor.
One dimension pattern cobalt aluminum hydrotalcite of the present invention, the following general formula of its chemical formula represents:
Wherein, x is the molar fraction in laminate metal ion shared by trivalent aluminium ion, and its span is 0.2≤x≤0.5; M is the quantity of the crystallization water, and its span is 0≤m≤2.It is characterized in that: described cobalt aluminum hydrotalcite has the one dimension patterns such as threadiness, crystal whisker-shaped, bar-shaped or strip.
Present invention also offers a kind of preparation method of one dimension pattern cobalt aluminum hydrotalcite, prepare with containing solid-liquid ion-exchange between aluminum solutions and carbonate solution and original position crystalline phase conversion process containing cobalt precursor by one dimension pattern is solid-state, concrete reaction condition and step as follows:
A: preparation presoma suspension-turbid liquid: the cobalt precursor that contains with one dimension pattern is scattered in water the suspension-turbid liquid making 10 ~ 100g/L; The described any one referred to containing cobalt precursor in basic cobaltous carbonate, alkali formula cobalt chloride, alkali formula cobaltous sulfate or the cobalt hydroxide with one dimension patterns such as threadiness, crystal whisker-shaped, bar-shaped or strips with one dimension pattern, wherein preferably: one dimension pattern basic cobaltous carbonate.
B: preparation is containing aluminum solutions with containing carbonate solution: compound concentration is sodium metaaluminate or the potassium metaaluminate solution of 0.04 ~ 0.2mol/L, and concentration is sodium carbonate or the solution of potassium carbonate of 0.05 ~ 0.3mol/L;
C: under stirring at normal temperature condition, first obtains step B and is slowly added drop-wise in the obtained presoma suspension-turbid liquid of steps A containing carbonate solution, then the aluminum solutions that contains obtained by step B is slowly added drop-wise in the obtained presoma suspension-turbid liquid of steps A.Be added dropwise to complete pH=10 ~ 12 of rear adjustment suspension-turbid liquid, usually adopt NaOH or KOH solution to regulate.Then react 0 ~ 36h under agitation, reaction temperature controls at 70 ~ 120 DEG C; The preferred reaction time is 2 ~ 24h, and preferable reaction temperature is 80 ~ 100 DEG C.Containing cobalt precursor suspension-turbid liquid with containing the molar ratio of aluminum solutions be
containing aluminum solutions with containing the molar ratio of carbonate solution be
D: by reacted for step C suspension-turbid liquid through washing, filtering, be drying to obtain the cobalt aluminum hydrotalcite material with one dimension pattern.
Above-mentioned preparation process, solid-state containing the solid-liquid ion exchange process between cobalt precursor and sodium aluminate solution/sodium carbonate liquor with containing the crystalline phase conversion process of cobalt precursor to houghite compound, synchronously carry out in suspension-turbid liquid, preparation flow is short, simple, the product of preparation maintains the pattern of presoma well.In order to keep the one dimension pattern of presoma, dripping containing carbonate solution in step C, dripping containing aluminum solutions and the order regulating suspension-turbid liquid pH, and regulating the suitable pH value of suspension-turbid liquid to be crucial.
In above-mentioned steps A, one dimension pattern is commercially available or adopt and prepare with the following method containing cobalt precursor: by mol ratio be 2 ~ 4 soluble cobalt and urea be dissolved in deionized water and be mixed with mixed solution, 0.5 ~ 6h is reacted at 90 ~ 180 DEG C, product, through cooling, washing, filtration, drying, obtains the alkali formula cobalt salt presoma with one dimension pattern.Described soluble cobalt is preferably CoCl
2.
Cobalt aluminum hydrotalcite material prepared by the present invention, its major advantage is the complete pattern maintained containing cobalt precursor, by selecting suitable can prepare containing cobalt precursor threadiness, crystal whisker-shaped, bar-shaped or strip etc. to be difficult to the one dimension pattern prepared hydrotalcite-like materials with additive method, improve the dispersing uniformity of material, substantially reduce bulk density, make it be more suitable for electrochemistry, catalysis, absorption, ion-exchange, the application such as fire-retardant.
The electrochemical applications of one dimension pattern cobalt aluminum hydrotalcite prepared by the present invention: can be used as electrode material for super capacitor.
The present invention to report the electrochemical properties preparing material to carry out electrochemical applications research: by synthesis one dimension pattern cobalt aluminum hydrotalcite roasting 5h at 160 DEG C; Then mixed with mass ratio 8 ﹕ 2 with graphite by the sample after roasting, with appropriate PTFE binder mixing furnishing pasty state after grinding, compressing tablet, intercepting area is 1cm
2electrode material become 1cm with nickel foam at 12MPa pressure
2electrode slice; Made sample electrode is as work electrode, and Pt net electrode and Zn/ZnO electrode are done electrode and reference electrode respectively, and the potassium hydroxide solution of 6mol/L makes electrolyte, forms three-electrode system.Electrochemical Characterization shows, the electrode that this material obtains has good capacitance characteristic, multiplying power property, improves oxygen uptake current potential, resistance is less, and has higher ratio capacitance and cyclical stability, is the extremely potential electrode material for super capacitor of one.
Preparation method's flow process of the present invention is short, process is simple, is convenient to industry and amplifies.
Accompanying drawing illustrates:
Fig. 1: the XRD spectra of embodiment 3 presoma (a) and product (b)
Fig. 2: the FT-IR spectrogram of embodiment 3 product
Fig. 3: the SEM photo of embodiment 3 presoma
Fig. 4: the SEM photo of embodiment 3 product
Fig. 5: the TGA-DSC curve of embodiment 3 product
Fig. 6: sweep speed is 1mvs
-1time electrode material cyclic voltammetry curve
Fig. 7: the cyclic voltammetry curve of different scanning speed lower electrode material
Fig. 8: the ac impedance spectroscopy of electrode material under 0.67v current potential
Fig. 9: the charging and discharging curve of electrode material under different current density
Figure 10: the cycle life curve of electrode material under 1A/g current density
The present invention adopts the XRD-6000 type X-ray powder diffractometer of Japanese Shimadzu Corporation to carry out Crystal Structure to sample.Fig. 1 is the basic carbonate cobalt precursor of embodiment 3 preparation and the XRD spectra of hydrotalcite product, as can be seen from the curve b in Fig. 1, (003), (006), (012) of reflection LDHs architectural feature, (015), (018), (110) and (113) crystallographic plane diffraction peak is had to occur, (003) and (006) characteristic diffraction peak peak shape point alarm symmetrical, occur without assorted peak, interpret sample crystalline phase is single, generates mutually without stray crystal.
German Bruker company Vector22 type FTIS is adopted to carry out qualitative analysis to sample.Fig. 2 is Fourier trasform spectroscopy (FT-IR) spectrogram of embodiment 3 gained sample.In typical CoAl-CO
3 2-the FT-IR spectrogram of-LDHs material, free from admixture peak occurs, wherein, 1357
-1cm
-1the absworption peak at place is the C-O asymmetric stretching vibration peak of carbanion, 2800-3150cm
-1acromion position carbonate and the bridge-type vibration peak of laminate hydroxyl, show that products therefrom is carbonate intercalated houghite.
Adopt the pattern of Japanese S-4700 type scanning electron microscopy (SEM) observing samples, Fig. 3 is the SEM photo of basic carbonate cobalt precursor prepared by embodiment 3, Fig. 4 is the SEM photo of LDHs product prepared by embodiment 3, from Fig. 3,4, obtained hydrotalcite-like materials intactly maintains the one dimension pattern of presoma, is evenly distributed.
The metal element content of Japanese Shimadzu ICP S-7500 type elemental analyser to sample is adopted to analyze.LDHs product prepared by embodiment 3 carries out elementary analysis, Co and the Al mol ratio of sample approximates 1.4, and not containing Na
+deng heteroion.
Adopt METTLER Switzerland TGA/DSC STAR
ethermally-stabilised analysis is carried out to LDHs.Fig. 5 is the TGA/DSC curve of LDHs product prepared by embodiment 3.From curve, weight-loss curve is divided into three phases, and what lose respectively is adsorbed water, intermediary water molecule, interlayer carbanion, laminate hydroxyl.Each stage corresponding endothermic peak.
LDHs prepared by embodiment 3 is made work electrode, and do electrode and reference electrode respectively with Pt net electrode and Zn/ZnO electrode, the potassium hydroxide solution of 6mol/L makes electrolyte, forms three-electrode system.The Corrtest CS300 electrochemical test system adopting the Central China University of Science and Technology to produce carries out cyclic voltammetric and ac impedance measurement.Fig. 6 is sweep speed is 1mvs
-1time electrode material cyclic voltammetry curve, Fig. 7 is the cyclic voltammetry curve of different scanning speed lower electrode material, and Fig. 8 is the AC impedance spectrogram of electrode material under 0.67V current potential.This electrode material has three pairs of redox peaks as shown in Figure 6, and corresponding cobalt is by three electrode reactions of divalence to tetravalence.Pattern symmetrical illustrates that invertibity is good, and the approximate rectangular explanation of figure has good capacitive character.This electrode material has good multiplying power property as shown in Figure 7.Fig. 8 illustrates that this electrode material internal resistance is less.
Wuhan Jin Nuo Electronics Co., Ltd. Land-LCT2001A type instrument is adopted to carry out constant current charge-discharge test and cycle life test.Fig. 9 is the charging and discharging curve of electrode material under different current density.Figure 10 is the cycle life figure of electrode material.Curve approximation straight line as shown in Figure 9, illustrates that capacitive character is good.Electric discharge window is comparatively large, close to 0.7V, effectively raises oxygen uptake current potential and ratio capacitance is larger.As shown in Figure 10, after 500 circulations, ratio capacitance still can keep 86%, and this illustrates that this electrode material has outstanding cyclical stability.
Embodiment:
By way of example the present invention is further described below, but does not form limiting the scope of the invention.
Embodiment 1:
Steps A: by 4mmolCoCl
26H
2o and 12mmolCO (NH
2)
2add in 80mL deionized water, stir and form uniform solution.Solution moves in the reactor of 100mL inner liner polytetrafluoroethylene, then at 160 DEG C, reacts 1.75h, by the product washing obtained, filters, and at 70 DEG C dry 8h, obtaining molecular formula is Co (OH)
0.44(CO
3)
0.780.29H
2the rod-like basic type cobalt carbonate presoma of O (adopting the metal element content of Japanese Shimadzu ICP S-7500 type elemental analyser to sample to analyze).
Step B: get 1g basic carbonate cobalt precursors, is scattered in 100mL deionized water, first slowly drips Na under agitation
2cO
3solution (0.4545g Na
2cO
3be dissolved in 60mL deionized water), slowly drip NaAlO again
2solution (0.5860g NaAlO
2be dissolved in 100mL deionized water), then regulate pH=12 by the NaOH solution of 1mol/L, be heated to 80 DEG C of reaction 5h, by the product washing obtained, filter, dry 8h at 70 DEG C, obtains one-dimensional rod-like CoAl-LDHs product.
Embodiment 2:
Steps A: with the steps A in embodiment 1.
Step B: get 1g basic carbonate cobalt precursors, is scattered in 100mL deionized water, first slowly drips Na under agitation
2cO
3solution (0.4545g Na
2cO
3be dissolved in 60mL deionized water), more slowly drip NaAlO
2solution (0.3516g NaAlO
2be dissolved in 100mL deionized water), then regulate pH=11 by the NaOH solution of 1mol/L, be heated to 85 DEG C of reaction 8h, by the product washing obtained, filter, dry 8h at 70 DEG C, obtains one-dimensional rod-like CoAl-LDHs product.
Embodiment 3:
Steps A: with the steps A in embodiment 1.
Step B: get 1g basic carbonate cobalt precursors, is scattered in 100mL deionized water, first slowly drips Na under agitation
2cO
3solution (0.4545g Na
2cO
3be dissolved in 60mL deionized water), more slowly drip NaAlO
2solution (0.5860g NaAlO
2be dissolved in 100mL deionized water), then regulate pH=11 by the NaOH solution of 1mol/L, be heated to 90 DEG C of reaction 10h, by the product washing obtained, filter, dry 8h at 70 DEG C, obtains one-dimensional rod-like CoAl-LDHs product.
Embodiment 4:
Steps A: with the steps A in embodiment 1.
Step B: get 1g basic carbonate cobalt precursors, is scattered in 100mL deionized water, first slowly drips Na under agitation
2cO
3solution (0.2272g Na
2cO
3be dissolved in 60mL deionized water), more slowly drip NaAlO
2solution (0.176g NaAlO
2be dissolved in 100mL deionized water), then regulate pH=11 by the NaOH solution of 1mol/L, be heated to 90 DEG C of reaction 12h, by the product washing obtained, filter, dry 8h at 70 DEG C, obtains one-dimensional rod-like CoAl-LDHs product.
Embodiment 5:
Steps A: by 4mmol CoCl
26H
2o and 16mmol CO (NH
2)
2be dissolved in 100mL deionized water, move in the reactor of 100mL inner liner polytetrafluoroethylene, at 150 DEG C, react 3.0h, product is washed, filter, and at 70 DEG C dry 8h, obtain rod-like basic type cobalt carbonate presoma.
Step B: get 1g basic carbonate cobalt precursors, is scattered in 100mL deionized water, first slowly drips Na under agitation
2cO
3solution (4.545g Na
2cO
3be dissolved in 60mL deionized water), more slowly drip NaAlO
2solution (5.860g NaAlO
2be dissolved in 100mL deionized water), then regulate pH=10 by the NaOH solution of 1mol/L, be heated to 95 DEG C of reaction 9h, product washed, filter, dry 8h at 70 DEG C, obtains one-dimensional rod-like CoAl-LDHs product.
Claims (6)
1. one dimension pattern cobalt aluminum hydrotalcite, the following general formula of its chemical formula represents:
Wherein, x is the molar fraction in laminate metal ion shared by trivalent aluminium ion, and its span is 0.2≤x≤0.5; M is the quantity of the crystallization water, and its span is 0≤m≤2; It is characterized in that: described cobalt aluminum hydrotalcite has bar-shaped one dimension pattern microstructure.
2. a preparation method for one dimension pattern cobalt aluminum hydrotalcite, is prepared containing cobalt precursor and containing the solid-liquid ion-exchange between aluminum solutions and carbonate solution and original position crystalline phase conversion process by solid-state; Concrete preparation condition and step are:
A: preparation presoma suspension-turbid liquid: the cobalt precursor that contains with one dimension pattern is scattered in water the suspension-turbid liquid making 10 ~ 100g/L, has any one referred to containing cobalt precursor in basic cobaltous carbonate, alkali formula cobalt chloride, alkali formula cobaltous sulfate or the cobalt hydroxide with rod-like one-dimensional pattern of one dimension pattern;
B: preparation is containing aluminum solutions with containing carbonate solution: compound concentration is sodium metaaluminate or the potassium metaaluminate solution of 0.04 ~ 0.2mol/L, and concentration is sodium carbonate or the solution of potassium carbonate of 0.05 ~ 0.3mol/L;
C: under stirring at normal temperature condition, what first obtained by step B is slowly added drop-wise in the obtained presoma suspension-turbid liquid of steps A containing carbonate solution, more slowly drips containing aluminum solutions, then regulates the pH value of suspension-turbid liquid to be 10 ~ 12, react 0 ~ 36h under agitation, reaction temperature controls at 70 ~ 120 DEG C; Containing cobalt precursor suspension-turbid liquid with containing the molar ratio of aluminum solutions be
containing aluminum solutions with containing the molar ratio of carbonate solution be
D: step C reacted suspension-turbid liquid after filtration, washing, the dry i.e. obtained cobalt aluminum hydrotalcite material with one dimension pattern.
3. the preparation method of cobalt aluminum hydrotalcite according to claim 2, is characterized in that: in steps A, one dimension pattern is the basic cobaltous carbonate with rod-like one-dimensional pattern containing cobalt precursor.
4. the preparation method of cobalt aluminum hydrotalcite according to claim 2, is characterized in that: the reaction time of step C is 2 ~ 24h, and reaction temperature is 80 ~ 100 DEG C.
5. the preparation method of cobalt aluminum hydrotalcite according to claim 2, it is characterized in that: in steps A, one dimension pattern containing the preparation method of cobalt precursor is: by mol ratio be 2 ~ 4 soluble cobalt and urea be dissolved in deionized water and be mixed with mixed solution, under agitation, at 90-180 DEG C, reaction 0.5-6h, by product washing, filtration, drying, obtain the basic salt presoma of the cobalt of one dimension pattern.
6. the preparation method of cobalt aluminum hydrotalcite according to claim 5, is characterized in that: one dimension pattern containing cobalt precursor, to prepare soluble cobalt used be CoCl
2.
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