CN102912344B - Nickel-based nickel titanium hydrotalcite film material, preparation method and application thereof - Google Patents

Nickel-based nickel titanium hydrotalcite film material, preparation method and application thereof Download PDF

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CN102912344B
CN102912344B CN201210350544.1A CN201210350544A CN102912344B CN 102912344 B CN102912344 B CN 102912344B CN 201210350544 A CN201210350544 A CN 201210350544A CN 102912344 B CN102912344 B CN 102912344B
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hydrotalcite film
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deionized water
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CN102912344A (en
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雷晓东
谷耀行
孙晓明
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Beijing University of Chemical Technology
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Abstract

The invention provides a nickel-based nickel titanium hydrotalcite film material, a preparation method and application of the nickel-based nickel titanium hydrotalcite film material. The material can be used as a super capacitance material and an electric adsorption material; the nickel-based nickel titanium hydrotalcite film material takes foam nickel as a base material, and a nickel-titanium hydrotalcite film grows in situ on the surface. The film has the advantages of complete crystal shape, uniform density, and high adhesive force, and does not easily fall off. The preparation method comprises the steps of: placing a foam nickel sheet into mixed solution of nickel nitrate and titanous sulfate, and planting the nickel-titanium hydrotalcite film in situ on the foam nickel sheet by controlling the reaction conditions such as pH, a reaction temperature and time. A nickel source disclosed by the nickel-based nickel titanium hydrotalcite film material is from the foam nickel surface and nickel salt dissolved into a solution. Compared with a pure hydrotalcite film deposited on a substrate, the prepared film is stronger in adhesive force on a base body, and the material has a better super capacitive property and an electric adsorption performance, and can be used as a super capacitance electrode material and an electric adsorption electrode material.

Description

Ni-based NiTi hydrotalcite film material and its preparation method and application
Technical field
The present invention relates to a kind of neatly thin-film material and preparation method thereof, be specifically related to NiTi hydrotalcite film material and its preparation method and application.
Background technology
Under the trend developing rapidly in current science and technology, electronic component diminishes increasingly and electromobile is popularized gradually, and the ultracapacitor of power supply and memory candidate device causes people's extensive concern in support.The super capacitor material of main flow is formed by ruthenium oxide membrane system and the exploitation of carbon electrostatic double layer at present.At Electrochem.Solid State Lett, 2000,3 (5): the ruthenium chromium composite oxides specific storage that in 205-208, the people such as Manthiram makes is up to 840F/g.But the ruthenium material required for the large value capacitor in battery-electrical condenser mixing system of electric vehicle power source is very expensive, this is also a universal very important factor of restriction ultracapacitor.At document Adv.Mater, in 2006,18,2807-2824, Bavykin has reported TiO 2nano-tube array can reach 338mA h/g as the electrical capacity of the anode of lithium ion battery.And Ni is owing to having high-capacitance in NiH battery, Zhang etc. are at Nano.Res, propose β-Ni (OH) in 2010,3,643 2calcinate porous NiO can reach the ratio electric capacity of 390F/g at 5A/g.Composite oxide material is excellent property and cheap not only, therefore caused broad research and concern in electrochemical field.At document Energy Fuels, in 2010,24:6463 – 6467, the people such as Wang utilize Wyler's process that nickel aluminum hydrotalcite powder is deposited in the middle of nickel foam, at 10mA/cm 2current density is issued to 701F/g.
Electro-adsorption material, as the deciding factor of electro adsorption capacity, is subject to extensive concern always.Due to electro-adsorption ultimate principle be ion in when energising water by respectively to the migration of opposite charges electrode and by this electrode adsorption at the electrostatic double layer that electrode surface formed, therefore electrostatic double layer theory is its basic theory.The domestic and international main first-selection using Carbon Materials as electro-adsorption material at present.According to the difference of material, main research both at home and abroad comprises the electro-adsorption technology of doing electro-adsorption material with materials such as graphite, gac, active carbon fibre peacekeeping charcoal-aero gels.At document Desalination, in 2011,270:285 – 290, the people such as Li with the gac of titania modified mistake as sorbent material adsorbing chloride ions, this method advantage is that absorbent charcoal material has larger specific surface area and loading capacity, has the effect of good heavy-metal ion removal.Shortcoming be high resistance own and resistance to mass transfer drawbacks limit its application in practice.At document Ind.Eng.Chem.Res, in 2011,50:5334-5345, the people such as Gao prepare NiTi hydrotalcite, and successfully Sodium dodecylbenzene sulfonate are inserted into hydrotalcite layers, and the poisonous organic reagents such as pentachlorophenol have been realized to good absorption property.
Summary of the invention
The object of this invention is to provide a kind of NiTi hydrotalcite film material and preparation method thereof, this material can be used as the electrode materials of electrochemical capacitance and electro-adsorption.
Ni-based NiTi hydrotalcite film provided by the invention is taking nickel foam as matrix, and at its surface in situ growth NiTi hydrotalcite film, the chemical formula of this film is:
[Ni 1-xTi x(OH) 2] 2x+(CO 3 2-) x·mH 2O
Wherein Ni 2+with Ti 4+be positioned at main stor(e)y plate; CO 3 2-for interlayer anion; Ni 2+/ Ti 4+molar ratio be 1.5～4.6; Preferably ratio is 2～4:1; M represents middle water.This Ni-based NiTi hydrotalcite film has complete in crystal formation, size distribution homogeneous, the characteristics such as sticking power is high, difficult drop-off.
The concrete preparation process of Ni-based NiTi hydrotalcite film is as follows:
A. adopting purity to be greater than 90% nickel foam sheet is matrix, is cut on demand different size and shapes, with mass concentration be 36% concentrated hydrochloric acid ultrasonic cleaning, then clean up with deionized water and dehydrated alcohol respectively, put into 60 DEG C of baking oven dry for standby;
B. with Ti (SO 4) 2for Ti source, with Ni (NO 3) 2as Ni source, with deionized water Ni in molar ratio 2+: Ti 4+the ratio preparation nickel of=2～4:1, titanium mixing salt solution a, wherein Ti (SO 4) 2be 0.05～0.20mol/L; Again with deionized water by NaOH and Na 2cO 3according to mol ratio NaOH:Na 2cO 3=5～9:2.2 preparation basic solution b, wherein Na 2cO 3be 0.7～1.0mol/L; Basic solution b is dropwise added in nickel, titanium mixing salt solution a, regulate pH value between 8～10, then nickel foam sheet after treatment in steps A is inserted wherein, at 50～90 DEG C, react 6～14h; Take out nickel sheet, use deionized water ultrasonic cleaning, dry 12h at 60 DEG C;
C. use Ti (SO 4) 2, Ni (NO 3) 2with deionized water preparation nickel, titanium mixing salt solution c, wherein Ni 2+: Ti 4+mol ratio is 2～4:1, Ti (SO 4) 2volumetric molar concentration is 0.05～0.20mol/L; Use again Na 2cO 3, ammoniacal liquor and deionized water preparation basic solution d, wherein NH 3: Na 2cO 3mol ratio is 7～11:2.2, Na 2cO 3volumetric molar concentration is 0.7～1.0mol/L; Basic solution d is dropwise added in nickel, titanium mixing salt solution c, regulate between pH value to 8.5～10; Put into again the nickel sheet after step B is dried, at 60～70 DEG C, react 10～14h, the NiTi hydrotalcite film that obtains growing on nickel foam substrate.
The wherein volumetric molar concentration of the nickel in the nickel in step B, titanium mixing solutions a and step C, titanium mixing solutions c and can be the same or different.In step B, mixing salt solution mixes with basic solution, forms NiTi hydrotalcite powder and is deposited on nickel foam surface, for step C growth nickel foam film provides nucleus.And step C utilizes the complexing action of ammonium ion, at nickel foam substrate growth NiTi hydrotalcite film, the nickel adding, titanium mixing solutions provide Yu Tai source, nickel source for growth hydrotalcite.
In above-mentioned preparation process, the NiTi hydrotalcite powder that is deposited on nickel foam surface by step B coprecipitation method provides nucleus, and for next step reaction provides presoma, the ammoniacal liquor in step C can provide OH for solution by hydrolysis -and NH 4 +.And this mixing solutions pH value is between 8.5～10, and then provide suitable pH value condition for hydrotalcite is synthetic.Nickel foam sheet is in weakly alkaline solution, at NH 4 +effect under, first form complex compound with ammonium ion, then slowly release Ni +, for the growth of hydrotalcite provides Ni source, after reaching supersaturation, the ionic concn on nickel sheet surface can form hydrotalcite nucleus, then grow up gradually, form the NiTi hydrotalcite film material of even compact on Ni substrate surface.
Nickel foam x-ray powder diffraction instrument used embodiment 1-5 (XRD) is analyzed, and result as shown in Figure 1, has the absorption peak of two stronger nickel at 44.9 and 52.4 places.
Fig. 2 is the XRD figure spectrum of the NiTi hydrotalcite film powder that scrapes from nickel foam substrate in embodiment 1.In figure, occur characteristic diffraction peak in (003), (006), (009), (110), the active ingredient in the thin-film material that this explanation is prepared is NiTi hydrotalcite material.
Fig. 3 is the XRD characteristic diffraction peak of the NiTi hydrotalcite film with nickel foam substrate of embodiment 1.As seen from the figure, except occurring nickel foam characteristic peak 44.9 and 52.4, also there is characteristic peak in (003), (006), (009), (110), illustrate in nickel foam surface growth and gone out NiTi hydrotalcite film.
Fig. 5 is that the scanning electronic microscope of the NiTi hydrotalcite film material that obtains of embodiment 1 characterizes.There is as seen from the figure a kind of very fine and close sheet hydrotalcite film on the surface of nickel foam, the about 20nm of the thickness left and right of this hydrotalcite nano piece.
Fig. 6 is NiTi hydrotalcite film that embodiment 1 the is obtained cyclic voltammetry curve in the KOH of 1mol/L electrolytic solution, and scanning speed is respectively 1mVs -1, 5mVs -1, 10mVs -1and 50mVs -1.A pair of redox peak in figure, has reacted the transformation of the different oxidation state of nickel, and volt-ampere cyclic curve has reacted faraday's redox reaction that fake capacitance mainly comes from NiTi hydrotalcite.The potential difference at negative electrode and anode peak is relevant with the electrochemical capacitance of the NiTi hydrotalcite film material specific conductivity low with electro-adsorption membrane electrode.Along with the increase of scanning speed, redox electric current increase, oxidation peak is offset to positive pole, reduction peak is offset to negative pole, this bearing reaction redox reversibility.
Fig. 7 is the Ni-based NiTi hydrotalcite film that obtains in embodiment 1 charging and discharging curve under different current density in the KOH of 1mol/L electrolytic solution, and charge and discharge process is to carry out between 0-0.45V, and capacitance is calculated by following formula:
Cm=IΔt/ΔV
C mrepresent electric capacity (Fg -1), I is charging and discharging currents (mA), and Δ t is the time (s) discharging and recharging, and Δ V is voltage (V).Be respectively 10,20 by can be calculated in current density, 30mAcm -2time, 7.93,6.00,5.34F/cm the capacitance of Ni-based hydrotalcite film is respectively: 2.Capacitance reduces along with the rising of current density, may be to cause due to the resistance of Ni-based NiTi hydrotalcite film material in Dicharged at High Current Desity situation and the deficiency of Faraday's active substance redox reaction, but still can keep good electrochemical capacitance performance.
Fig. 8 is the stable circulation linearity curve of the Ni-based NiTi hydrotalcite film of embodiment 1, is 20mA/cm as can be seen from Figure in current density 2time, 1000 circulations still keep 84% capacity afterwards, illustrate that this material has permanent stability.
Fig. 9 is Ni-based NiTi hydrotalcite film electro-adsorption/desorption circulation chlorine ion concentration curve over time.Do negative electrode with graphite, Ni-based NiTi hydrotalcite film, as anode, is put in the middle of the NaCl solution of 0.001mol/L, carries out 5 inhale/attached desorptions circulations of electricity under constant voltage 1.2V condition.As seen from the figure, adsorption rate 13.3% for the first time, desorption rate approaches 100%, the time 40min of electro-adsorption and desorption.The features such as compare with similar electro-adsorption material, the electro-adsorption material impact-resistant that has solved preparation is in the past poor, is combined the problem such as not tight with matrix, and has adsorption rate fast, and electro-adsorption rate and electric desorption rate are relatively stable.
Fig. 1-5 have illustrated in the length of the surface of nickel foam the NiTi hydrotalcite film of one deck densification, the about 20nm of thickness.Ni-based NiTi hydrotalcite film material prepared by Fig. 6-8 explanation the present invention has very large ratio electric capacity, and under high charge-discharge speed, has higher capacity.Illustrate that in situ synthesis is conducive to ionogen and conducts fast by electrode, reduced the electric transmission distance of electrode materials inside, make NiTi hydrotalcite film material there is very high ratio electric capacity and charge-discharge performance.Therefore this NiTi hydrotalcite film material is a kind of well electrochemical capacitance electrode materials.
Beneficial effect of the present invention: with in situ synthesis in the surface growth of nickel foam one deck NiTi hydrotalcite film, this film provides nickel source by nickel foam substrate, be combined with substrate closely, difficult drop-off.The Ni-based NiTi hydrotalcite film of growth in situ is because the pattern on nickel foam substrate surface has larger contact area, the anodizing reduction reaction occurring by substrate and active substance, electronics transmits faster than traditional method, under high discharging current, Ni-based NiTi hydrotalcite film electrode has showed very large ratio electric capacity, likely becomes the electrical condenser of a kind of heavy body and two-forty.Find that by the test of electro-adsorption and electric desorption this Ni-based NiTi hydrotalcite film can be used as electro-adsorbent, and can reuse, and electro-adsorption and desorption performance good.
Brief description of the drawings
Fig. 1 is the XRD figure spectrum of nickel foam used in embodiment 1-5.
Fig. 2 is that the nickel foam surface that embodiment 1 is prepared from step C scrapes NiTi hydrotalcite powder XRD diffraction peak.
Fig. 3 is the NiTi hydrotalcite film XRD diffraction peak that embodiment 1 grows in nickel foam substrate.
Fig. 4 is that the SEM of embodiment 1 nickel foam used characterizes.
Fig. 5 is that the SEM of the NiTi hydrotalcite film prepared of embodiment 1 characterizes.
Fig. 6 is that the Ni-based NiTi hydrotalcite film material of preparing taking embodiment 1 is electrode cyclic voltammetry curve under different scanning rates in the KOH of 1mol/L electrolytic solution.
Fig. 7 is the Ni-based NiTi hydrotalcite film material prepared taking embodiment 1 is electrode discharge curve under different current density in the KOH of 1mol/L electrolytic solution.
Fig. 8 is the stable circulation linearity curve of the Ni-based NiTi hydrotalcite film material for preparing of embodiment 1.
Fig. 9 be in embodiment 1 preparation-obtained NiTi hydrotalcite film material in the NaCl of 0.001mol/L through the curve of Cl-concentration changes with time in 5 electro-adsorption and electric desorption process.
Embodiment
Embodiment 1
A. being greater than 90% nickel foam by purity is base material, cuts into the sheet of 10*15cm size, and the concentrated hydrochloric acid with 30% cleans 50s, then uses deionized water ultrasonic cleaning 3 times, and dehydrated alcohol cleans one time, puts into 60 DEG C of baking oven dry for standby.
B. with deionized water by 26.4g Ti (SO 4) 2and 58.15gNi (NO 3) 2be mixed with 1000ml solution a, then with deionized water by 17.5g Na 2cO 3be mixed with 200ml solution b with 18.65gNaOH.By inserting in solution a through the nickel foam of processing of step A, then under violent stirring, solution b is dropwise joined in solution a, reach 9.5 to pH value of solution, transfer to together in tetrafluoroethylene reactor, put into baking oven in 90 DEG C of reaction 6h.Reaction finishes rear taking-up nickel foam, washes the unnecessary throw out in surface with deionized water, dries 12h at 60 DEG C.
C. the preparation 1000ml solution c identical with solution a in step B; Again to 19ml ammoniacal liquor and 15.7g Na 2cO 3drip deionized water and be mixed with 100ml solution d, put into step B and dry the nickel foam sheet obtaining; Solution d is splashed in solution c, reach 9.5 to pH value of solution, transfer to tetrafluoroethylene reactor, at 70 DEG C, react 14h.Reaction finishes rear taking-up nickel foam, puts into baking oven, at 60 DEG C, dries 12h, is Ni-based NiTi hydrotalcite film material.Chemical formula is Ni 3ti (OH) 8cO 3.
Embodiment 2
A. being greater than 90% nickel foam by purity is base material, cuts into the sheet of 10*15cm size, and the concentrated hydrochloric acid with 30% cleans 50s, uses subsequently deionized water ultrasonic cleaning 3 times, and dehydrated alcohol cleans one time, puts into 60 DEG C of baking oven dry for standby.
B. with deionized water by 39.6g Ti (SO 4) 2and 87.24gNi (NO 3) 2be mixed with 800ml solution a, then with deionized water preparation 28gNOH and 23.3gNa 2cO 3225ml mixing solutions b.By inserting in solution a through the nickel foam of processing of step A, then under violent stirring, solution b is dropwise joined in solution a, reach 9 to pH value of solution, transfer to together subsequently in 1000ml beaker, seal beaker mouth with preservative film.Vigorous stirring in 60 DEG C of water-baths, reaction 5h, reaction finishes rear taking-up nickel foam deionized water and cleans up, and puts into baking oven, at 60 DEG C, dries 12h.
C. with deionized water by 26.4g Ti (SO 4) 2and 58.15g Ni (NO 3) 2be mixed with 1000ml solution c, re-use deionized water by 70ml ammoniacal liquor and 16.5g Na 2cO 3be mixed with 200ml solution d, solution d is dropwise added in solution c, put into step B simultaneously and dry the nickel foam obtaining, reach 9.5 to pH value of solution, put into together in tetrafluoroethylene and react 12h at 80 DEG C.Reaction finishes rear taking-up nickel foam, at 60 DEG C, dries 12h, is Ni-based NiTi hydrotalcite film material.
Embodiment 3
A. being greater than 90% nickel foam by purity is base material, cuts into the sheet of 10*15cm size, and the concentrated hydrochloric acid with 30% cleans 50s, uses subsequently deionized water ultrasonic cleaning 3 times, and dehydrated alcohol cleans one time, puts into 60 DEG C of baking oven dry for standby.
B. with deionized water by 19.8g Ti (SO 4) 2and 43.6g Ni (NO 3) 2be mixed with 750ml solution a, with deionized water by 14gNOH and 11.85gNa 2cO 3be mixed with 250ml solution b, by inserting in solution a through the nickel foam of processing of step A, then under violent stirring, solution b dropwise joined in solution a, reach 8.5 to pH value of solution, join together in the middle of tetrafluoroethylene reactor, react 10h at 80 DEG C.After reaction finishes, nickel foam is cleaned up, put into baking oven, at 60 DEG C, dry 12h for subsequent use.
C. with deionized water by 19.8g Ti (SO 4) 2and 43.6g Ni (NO 3) 2be mixed with 750ml solution c, then with deionized water by 60ml ammoniacal liquor and 12gNa 2cO 3be mixed with 250ml solution d, solution d is dropwise joined in the middle of solution c, put into step B simultaneously and dry the nickel foam obtaining.After reaching 9 to pH value of solution, join together in the middle of tetrafluoroethylene and react 8h at 60 DEG C.Reaction finishes rear taking-up nickel foam, at 60 DEG C, dries 12h, is Ni-based NiTi hydrotalcite film material.
Embodiment 4
A. being greater than 90% nickel foam by purity is base material, cuts into the sheet of 10*15cm size, and the concentrated hydrochloric acid with 30% cleans 50s, uses subsequently deionized water ultrasonic cleaning 3 times, and dehydrated alcohol cleans one time, puts into 60 DEG C of baking oven dry for standby.
B. by 17.6g Ti (SO 4) 2and 38.77g Ni (NO 3) 2be mixed with 750ml solution a with deionized water, then with deionized water by 11.2gNOH and 10.8gNa 2cO 3be mixed with 250ml solution b.By inserting in solution a through the nickel foam of processing of step A, then under violent stirring, solution b is dropwise joined in solution a, reach at 9 o'clock to pH value of solution, be poured into together with nickel foam in the middle of tetrafluoroethylene and react 5h at 80 DEG C.After reaction finishes, put into baking oven, at 60 DEG C, dry 12h.
C. by 17.6g Ti (SO 4) 2and 38.77g Ni (NO 3) 2be mixed with 750ml solution c, then with deionized water by 51ml ammoniacal liquor and 11.7gNa 2cO 3be mixed with 250ml solution d, solution d is dropwise joined in the middle of solution c, put into step B simultaneously and dry the nickel foam obtaining.After stirring, reach 10 to pH value of solution, be transferred in the middle of tetrafluoroethylene and react 14h at 60 DEG C.Reaction finishes rear taking-up nickel foam and puts into baking oven, at 60 DEG C, dries 12h, is Ni-based NiTi hydrotalcite film material.
Embodiment 5
A. being greater than 90% nickel foam by purity is base material, cuts into the sheet of 10*15cm size, and the concentrated hydrochloric acid with 30% cleans 50s, uses subsequently deionized water ultrasonic cleaning 3 times, and dehydrated alcohol cleans one time, puts into 60 DEG C of baking oven dry for standby.
B. with deionized water by 39.6g Ti (SO 4) 2and 87.24gNi (NO 3) 2, be mixed with 800ml solution a, then with deionized water by 23.4gNOH and 23.3gNa 2cO 3be mixed with 225ml solution b.By inserting in solution a through the nickel foam of processing of step A, then under violent stirring, solution b is dropwise splashed in the middle of solution a, regulate pH to 8.5, transfer to together in 1000nl beaker, seal beaker mouth with preservative film.60 DEG C of condensing refluxes under vigorous stirring, reaction 5h, reaction finishes rear taking-up nickel foam deionized water and cleans up, and puts into baking oven, at 60 DEG C, dries 12h.
C. with deionized water by 19.8g Ti (SO 4) 2and 43.6g Ni (NO 3) 2be mixed with 750ml solution c, with again with deionized water by 60ml ammoniacal liquor and 12gNa 2cO 3be mixed with 250ml solution d, solution d is dropwise joined in the middle of solution c, put into step B simultaneously and dry the nickel foam obtaining.After reaching 8.5 to pH value of solution, join together in the middle of tetrafluoroethylene, react 8h at 60 DEG C.Reaction finishes rear taking-up nickel foam and puts into baking oven, and at 60 DEG C, dry 12h, is Ni-based NiTi hydrotalcite film material.

Claims (3)

1. a preparation method for Ni-based NiTi hydrotalcite film, concrete preparation process is as follows:
A. adopting purity to be greater than 90% nickel foam sheet is matrix, is cut on demand different size and shapes, with mass concentration be 36% concentrated hydrochloric acid ultrasonic cleaning, then clean up with deionized water and dehydrated alcohol respectively, put into 60 DEG C of baking oven dry for standby;
B. with Ti (SO 4) 2for Ti source, with Ni (NO 3) 2as Ni source, with deionized water Ni in molar ratio 2+: Ti 4+the ratio preparation nickel of=2～4:1, titanium mixing salt solution a, wherein Ti (SO 4) 2be 0.05～0.20mol/L; Again with deionized water by NaOH and Na 2cO 3according to mol ratio NaOH:Na 2cO 3=5～9:2.2 preparation basic solution b, wherein Na 2cO 3be 0.7～1.0mol/L; Basic solution b is dropwise added in nickel, titanium mixing salt solution a, regulate pH value between 8～10, then nickel foam sheet after treatment in steps A is inserted wherein, at 50～90 DEG C, react 6～14h; Take out nickel sheet, use deionized water ultrasonic cleaning, dry 12h at 60 DEG C;
C. use Ti (SO 4) 2, Ni (NO 3) 2with deionized water preparation nickel, titanium mixing salt solution c, wherein Ni 2+: Ti 4+mol ratio is 2～4:1, Ti (SO 4) 2volumetric molar concentration is 0.05～0.20mol/L; Use again Na 2cO 3, ammoniacal liquor and deionized water preparation basic solution d, wherein NH 3: Na 2cO 3mol ratio is 7～11:2.2, Na 2cO 3volumetric molar concentration is 0.7～1.0mol/L; Basic solution d is dropwise added in nickel, titanium mixing salt solution c, regulate between pH value to 8.5～10; Put into again the nickel sheet after step B is dried, at 60～70 DEG C, react 10～14h, obtain the NiTi hydrotalcite film of growing on nickel foam sheet matrix.
2. the Ni-based NiTi hydrotalcite film that prepared by method according to claim 1, be taking nickel foam sheet as matrix at its surface in situ growth NiTi hydrotalcite film, the chemical formula of this film is:
[Ni 1-xTi x(OH) 2] 2x+(CO 3 2-) x·mH 2O
Wherein Ni 2+with Ti 4+be positioned at main stor(e)y plate; CO 3 2-for interlayer anion; Ni 2+/ Ti 4+molar ratio be 2～4:1; M represents middle water molecule number.
3. an application for Ni-based NiTi hydrotalcite film claimed in claim 2, this film is as the electrode materials of electrochemical capacitance and electro-adsorption.
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CN103233268B (en) * 2013-04-28 2015-10-28 北京化工大学 A kind of Nickel-base basic nickel carbonate thin-film material and its preparation method and application
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101140257A (en) * 2007-10-18 2008-03-12 北京化工大学 Biologic sensor enzyme functional susceptivity film containing nickel and aluminum hydrotalcite nano piece and method of producing the same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8227046B2 (en) * 2002-11-29 2012-07-24 Council Of Scientific And Industrial Research Process for preparing self-assembling nanobinary and ternary oxy/hydroxides

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101140257A (en) * 2007-10-18 2008-03-12 北京化工大学 Biologic sensor enzyme functional susceptivity film containing nickel and aluminum hydrotalcite nano piece and method of producing the same

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Engineering Chemistry Research》.2011,第50卷(第9期), *
Xin Shu,et al..Fromation of Ni-Ti-layered double hydroxides using homogeneous precipitation method.《Solid State Sciences》.2006,第8卷(第6期), *
Zhiyue Gao，et al..Adsorption of Pentachlorophenol from Aqueous Solution on Dodecylbenzenesulfonate Modified Nickel-Titanium Layered Double Hydroxide Nanocomposites.《Industrial & Engineering Chemistry Research》.2011,第50卷(第9期),
Zhiyue Gao,et al..Adsorption of Pentachlorophenol from Aqueous Solution on Dodecylbenzenesulfonate Modified Nickel-Titanium Layered Double Hydroxide Nanocomposites.《Industrial &amp *

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