CN111118908B - Layered double-metal hydroxide-polyaniline modified porous conductive composite material and preparation method and application thereof - Google Patents
Layered double-metal hydroxide-polyaniline modified porous conductive composite material and preparation method and application thereof Download PDFInfo
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- CN111118908B CN111118908B CN201911411534.2A CN201911411534A CN111118908B CN 111118908 B CN111118908 B CN 111118908B CN 201911411534 A CN201911411534 A CN 201911411534A CN 111118908 B CN111118908 B CN 111118908B
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 106
- 239000002184 metal Substances 0.000 title claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 239000004020 conductor Substances 0.000 claims abstract description 19
- 238000004146 energy storage Methods 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000002848 electrochemical method Methods 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- 239000004744 fabric Substances 0.000 claims description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 66
- 229910052799 carbon Inorganic materials 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 10
- 238000002484 cyclic voltammetry Methods 0.000 claims description 9
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 6
- 238000004070 electrodeposition Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 28
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- 239000000243 solution Substances 0.000 description 24
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- 239000013078 crystal Substances 0.000 description 7
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 238000010277 constant-current charging Methods 0.000 description 6
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
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- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 3
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- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229920002749 Bacterial cellulose Polymers 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 2
- 229910003266 NiCo Inorganic materials 0.000 description 2
- JLCHNBRGUPQWKF-UHFFFAOYSA-J [OH-].[C+4].[OH-].[OH-].[OH-] Chemical compound [OH-].[C+4].[OH-].[OH-].[OH-] JLCHNBRGUPQWKF-UHFFFAOYSA-J 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
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- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical group [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
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Abstract
The invention discloses a layered double metal hydroxide-polyaniline modified porous conductive composite material, which takes a porous conductive material as a substrate; a polyaniline layer grows on the surface of a substrate, and an LDH nano coil with the thickness of 1-2 mu m grows on the surface of polyaniline in situ. The invention also discloses a preparation method of the porous conductive composite material, which comprises the following steps: (1) adding aniline into a sulfuric acid aqueous solution to serve as an electrolyte solution; preparing a polyaniline-deposited porous conductive material by an electrochemical method by taking the porous conductive material as a working electrode; (2) immersing the porous conducting material deposited by polyaniline into alkaline water containing two soluble metal salts for hydrothermal reaction. The preparation method provided by the invention has the advantages of simple steps, easiness in operation, time saving and low cost, and the obtained porous conductive composite material has high specific capacitance and excellent rate performance and cycle performance. The porous conductive composite material can be used for preparing energy storage devices, and has high specific capacitance and large energy storage capacity.
Description
Technical Field
The invention relates to the technical field of novel energy storage materials, in particular to a layered double metal hydroxide-polyaniline modified porous conductive composite material and a preparation method and application thereof.
Background
At present, human beings are facing the examination of gradual environmental deterioration and continuous resource consumption, and the research on novel environment-friendly energy storage devices is always concerned widely. The super capacitor is used as an energy storage device and has the characteristics of high power density, high charge and discharge rate, long service life and the like. The performance of the capacitor can be improved by increasing the specific surface area of the material and increasing the active sites in contact with the electrolyte. Therefore, researchers often adopt methods of designing a multi-level structure, an array structure, synthesizing a material with a special morphology such as one-dimensional morphology, and the like.
Layered Double Hydroxides (LDH) are hydrotalcite compounds having exchangeable anions between layers, and the composition can be represented by the following general formula: [ M ] A2+ 1-xM3+ x(OH)2](An-)x/n·mH2O, wherein M2+、M3+Respectively divalent and trivalent metal cations, A, located in the octahedral voids of the host laminan-Is an anion which is stably present in an alkaline solution and is positioned between layers. The LDH has high specific surface area, and cations in the host laminate can perform reversible redox reaction, so the LDH is a good super capacitor anode material. But the conductivity of the LDH is poor, and the crystal form and morphology are easy to change in the cyclic process, which limits its further application. The research work reported at present adopts a method of compounding with polyaniline and other conductive polymers to improve the performance of materials. But such studies are less concerned with the morphological dependence of LDH performance. Therefore, it is challenging and necessary to design and apply composite materials of LDH and polyaniline of novel structures to the frontier field.
For the preparation of polyaniline and layered double hydroxide composite materials, Liu et al (Hierarchical NiCo) reported in the prior research2S4@ PANI core/shell nanowire growth on carbon fiber with enhanced electrochemical performance for hybrid surfactants Chemical Engineering Journal,2017,323, 330-2S4A nano-rod, and finally, a layer of polyaniline is electrochemically deposited on the surface to prepare NiCo with a one-dimensional array structure2S4the/PANI composite electrode. However, the method covers polyaniline on the surface of the active material, and reduces LDH and electrolyte solutionThe contact area.
The documents high ply flexible, foldable and curable Ni-Co layered double hydroxide/polyaniline/bacterial cell electrolytes for high-performance all-solid-state superparameters, journal of Materials Chemistry A2018,6(34),16617-16626 report that polyaniline is prepared on a bacterial cellulose membrane by an oxidation-reduction method, and then petal-shaped LDH nanosheets are synthesized by a hydrothermal method. Bacterial cellulose films are not electrically conductive and to render them electrically conductive, a large and thick layer of polyaniline must be deposited on their surface by redox. The method is long in time consumption, the substrate preparation process is complicated, and the problems of poor multiplying power performance and deformation and agglomeration after multiple cycles cannot be solved by the structure of the disordered LDH arrangement.
Disclosure of Invention
The invention provides a layered double-metal hydroxide-polyaniline modified porous conductive composite material which has high specific capacitance and excellent rate capability and cycle performance.
The technical scheme provided by the invention for solving the technical problems is as follows:
the invention provides a layered double metal hydroxide-polyaniline modified porous conductive composite material, which takes a porous conductive material as a substrate; a polyaniline layer is deposited on the surface of the porous conductive material; and LDH nano rolls with the thickness of 1-3 mu m grow on the surface of the polyaniline layer in situ.
The layered double metal hydroxides (LDH) are arranged on the surface of the polyaniline-deposited porous conducting material in a vertical coil shape. Only the extremely thin micron sheet or nano sheet can form a roll-shaped structure at the later stage of the hydrothermal reaction, and the structure shows that the LDH sheet is very thin and has extremely high specific surface area, so that more electrochemical reaction sites can be provided, and the electrochemical performance of the material is enhanced.
The porous conductive composite material provided by the invention has a higher specific surface area, and the electrochemical performance of the material is enhanced. The polyaniline not only plays a role in promoting and inducing the orderly growth of the LDH nanocoils, but also strengthens the interaction between the LDH and the substrate and improves the cycling stability of the material.
The porous conductive material is carbon cloth, metal mesh or foam metal.
The invention also provides application of the layered double hydroxide-polyaniline modified porous conductive composite material in preparation of an energy storage device.
The nano-roll structure can provide larger surface area, more electrochemical reaction sites, higher specific capacitance and larger energy storage capacity.
The energy storage device is a super capacitor. The super capacitor is assembled by taking the porous conductive composite material as a main component, and the LDH nano coil structure can provide more electrochemical reaction sites, so that the energy storage capacity of the capacitor is larger.
The invention also provides a preparation method of the layered double metal hydroxide-polyaniline modified porous conductive composite material, which comprises the following steps:
(1) adding aniline into a sulfuric acid aqueous solution to serve as an electrolyte solution; preparing a polyaniline-deposited porous conductive material by an electrochemical method by taking the porous conductive material as a working electrode;
(2) immersing the porous conducting material deposited by polyaniline into alkaline water containing two soluble metal salts for hydrothermal reaction.
Compared with the method of synthesizing a metal compound and then depositing polyaniline on the surface, the layered double hydroxide-polyaniline modified porous conductive composite material prepared by the invention firstly deposits polyaniline to induce the orderly growth of LDH on the surface of a matrix, can better control the morphology and avoid the loss and the heterogeneity of LDH in the deposition process; meanwhile, the strong interaction between the LDH and the surface of the matrix is ensured, and the cycling stability of the material is improved.
The substrate adopted by the invention is a porous conductive material (carbon cloth, metal mesh, foam metal and the like), has better conductivity, and is plated with a thin and uniform polyaniline layer on the surface by adopting an electrochemical method.
The polyaniline prepared by the electrochemical method has rich functional groups, including nitrogen-containing groups such as imino, cationic amino and the like. On one hand, the catalyst can generate coordination with LDH growth elements, promote the nucleation of LDH and improve the loading capacity of active substances; on the other hand, the method can also induce the orderly growth of the LDH on the surface of the matrix, and realizes the arrangement of the vertical coil-shaped appearance of the LDH on the surface of the substrate.
The electrochemical method is a constant voltage electrodeposition method and a cyclic voltammetry method.
The constant voltage electrodeposition method adopts the following process parameters: the voltage is 0.3-1V, and the deposition time is 0.5-15 min.
The cyclic voltammetry adopts the following process parameters: the scanning speed is 10-200 mV/s, the voltage window is-0.5-1V, and the scanning time is 0.5-30 min.
In the step (1), the concentration of the sulfuric acid aqueous solution is 0.1-5 mol/L, and after aniline is added, the concentration of aniline in the electrolyte solution is 0.01-1.5 mol/L.
In the step (2), the soluble metal salt is a soluble divalent metal salt or a soluble trivalent metal salt or a mixture thereof.
Further, in the soluble divalent metal salt, the divalent metal ion is Co2+、Ni2+、Mg2+、Fe2+、Zn2+Or Cu2+。
Further, the soluble divalent metal salt is CoSO4、NiSO4、Co(NO3)2、Ni(NO3)2、MgSO4、CoCl2Or NiCl2。
Further, in the trivalent metal salt, the trivalent metal ion is Al3+、Cr3+Or Fe3+。
Further, the soluble trivalent metal salt is Al (NO)3)3Or Cr2(SO4)3。
Further, the two soluble metal salts are CoSO4/NiSO4、Co(NO3)2/Ni(NO3)2、Co(NO3)2/Al(NO3)3、MgSO4/NiSO4、Cr2(SO4)3/NiSO4Or CoCl2/NiCl2。
Co and Ni have higher electrochemical activity and better electrochemical performance.
The total concentration of the soluble metal salt is 0.024-1.2 mol/L.
The concentration of soluble metal salts and the alkali species and their concentration will affect the growth of LDH, with too high a concentration of metal ions, LDH growing too densely, and the rate performance becoming worse.
Further, the total concentration of the soluble metal salt is 0.1-1.0 mol/L.
In the step (2), the alkali is urea, sodium carbonate or ammonia water. The type and concentration of the base mainly affects the LDH nucleation rate. Further, the alkali is urea.
In the step (2), the molar ratio of the soluble metal salt to the alkaline substance is 1: 1-10.
The molar ratio mainly influences the nucleation and growth speed of LDH, the concentration of alkali is too low, the nucleation and growth speed is low, and the nano-coil structure cannot be obtained.
Furthermore, the molar ratio of the soluble metal salt to the alkaline substance is 1: 1-8.
In the step (2), the temperature of the hydrothermal reaction is 90-125 ℃; the hydrothermal reaction time is 6-24 h.
The hydrothermal reaction temperature is too low, the nucleation and growth speed of LDH is slow, and the loading capacity of LDH is low; the hydrothermal reaction temperature is too high, and in the later period of the reaction, urea decomposes to generate carbonate ions, so that carbonate ions are formed among LDH layers, a roll-shaped structure cannot be formed, and the LDH loading capacity is low.
Further, the temperature of the hydrothermal reaction is 95-120 ℃, and the time of the hydrothermal reaction is 8-20 hours.
The invention has the following beneficial effects:
1. according to the invention, the porous conductive material deposited by polyaniline is prepared by an electrochemical method, polyaniline not only plays a role in promoting and inducing the orderly growth of LDH nanocoils, but also strengthens the interaction between LDH and a substrate, improves the cycling stability of the material, and enables the finally obtained porous conductive composite material to have higher specific surface area and good electrochemical performance.
2. The layered double hydroxide-polyaniline modified porous conductive composite material has high specific capacitance, excellent rate performance and good cycle performance.
3. The preparation method disclosed by the invention is mild in reaction conditions, simple in steps, easy to operate, strong in controllability and low in cost.
4. The LDH nano-coil structure can provide larger surface area and more electrochemical reaction sites, and the energy storage device prepared by the layered double-metal hydroxide-polyaniline modified porous conductive composite material has higher specific capacitance and larger energy storage capacity.
Drawings
Fig. 1 is a constant current charge and discharge curve diagram of the polyaniline carbon cloth with the layered double hydroxide grown on the surface, prepared in example 1, under different current densities.
Fig. 2 is an SEM image of the polyaniline carbon cloth with layered double hydroxide grown on the surface prepared in example 1.
FIG. 3 is a TEM image of the surface-grown layered double hydroxide nanocolumn obtained in example 1.
Fig. 4 is an SEM image of the polyaniline carbon cloth with layered double hydroxide grown on the surface prepared in example 1 after 5000 cycles.
Fig. 5 is an SEM image of the layered double hydroxide carbon cloth prepared in comparative example 1.
Fig. 6 is an SEM image of the layered double hydroxide carbon cloth prepared in comparative example 1 after 1000 cycles.
Detailed Description
The present invention will now be described in detail by way of examples, which are given for the purpose of illustration only and are not intended to limit the scope of the invention. The compounds of the present invention may be prepared by a variety of synthetic methods well known to those skilled in the art, including the specific embodiments listed below, embodiments formed by combinations thereof with other methods of compound synthesis, and equivalents thereof known to those skilled in the art, and may also be commercially available. Preferred embodiments include, but are not limited to, examples of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made in the specific embodiments of the invention without departing from the spirit and scope of the invention.
Example 1:
to 100mL of a 1mol/L sulfuric acid aqueous solution, 0.934mL of aniline was added, and the mixture was stirred until the solution became clear. And (3) performing cyclic sweep voltammetry by taking the solution as an electrolyte solution and the carbon cloth as a working electrode to obtain the carbon cloth deposited by the polyaniline. The sweep rate of cyclic voltammetry was 100mV/s, the voltage window was-0.2 to 0.8V, and the sweep time was 2 min. And washing the obtained carbon cloth deposited with the polyaniline with deionized water for multiple times, and then drying in vacuum.
To 50mL of deionized water, 0.45g of CoSO was added4、0.21g NiSO4And 1.153g of urea were dissolved with stirring. And adding the carbon cloth with the polyaniline deposited on the surface into the solution, and fully immersing.
And (3) moving the system into a hydrothermal kettle, and putting the hydrothermal kettle into a vacuum oven to crystallize for 12 hours at 110 ℃. And after the reaction is finished, taking out the polyaniline carbon cloth after the temperature is reduced to the room temperature, washing the polyaniline carbon cloth for a plurality of times by using deionized water, and finally drying the polyaniline carbon cloth in vacuum to obtain the polyaniline carbon cloth with the layered double hydroxide growing on the surface.
The constant current charge and discharge curves of the polyaniline carbon cloth with the layered double hydroxide grown on the surface prepared in example 1 at different current densities are shown in fig. 1. The observation of the curve shows that the material has obvious platforms in both charge and discharge curves, which shows the energy storage mechanism of LDH pseudo-capacitance, namely Co2+、Ni2+Reversible redox reaction of (2). Calculating the electrode of the composite material at 1Ag by using the graph 1-1The specific time capacitance is as high as 1835F g-1And in 10Ag-1The specific time capacitance is still as high as 1235F g-1And has excellent rate performance.
The SEM photograph of the polyaniline carbon cloth with layered double hydroxide grown on the surface prepared in example 1 is shown in fig. 2, and it can be seen from the figure that one-dimensional LDH nanocolloids are uniformly and densely vertically arranged on the surface of the substrate to form a shape similar to a test tube brush. The LDH nanocolloid structure is shown in FIG. 3, and has a diameter of about 30-50 nm and a length of about 1-2 μm.
SEM photographs of the polyaniline carbon cloth with layered double hydroxide grown on the surface prepared in example 1 after 5000 cycles are shown in fig. 4. From the figure, it can be found that the LDH morphology does not change much before and after the cycle. The retention of the specific capacitance of the electrode after 3000 cycles can still reach 78% by calculating from the charging and discharging curve.
Example 2:
to 100mL of a 1mol/L sulfuric acid aqueous solution, 1.5mL of aniline was added and the mixture was stirred until the solution became clear. And (3) performing constant-voltage electrodeposition by using the solution as an electrolyte solution and using foamed nickel as a working electrode. The deposition voltage was 0.8V and the deposition time was 4 min. And washing the obtained polyaniline deposited foam nickel with deionized water for multiple times, and then drying in vacuum.
To 50mL of deionized water, 1.5g of CoSO was added4、0.75g NiSO4And 2.153g of urea were dissolved with stirring. And adding the foamed nickel with the polyaniline deposited on the surface into the solution, and fully immersing.
And (3) moving the system into a hydrothermal kettle, and putting the hydrothermal kettle into a vacuum oven to crystallize for 8 hours at 110 ℃. And after the reaction is finished, taking out the polyaniline foam nickel after the temperature is reduced to the room temperature, washing the polyaniline foam nickel for a plurality of times by using deionized water, and finally drying the polyaniline foam nickel in vacuum to obtain the polyaniline foam nickel with the surface growing layered double hydroxides.
The constant-current charge-discharge curve of the polyaniline nickel foam with the layered double hydroxide growing on the surface prepared in example 2 under different current densities is similar to that in FIG. 1, and the constant-current charge-discharge curve is similar to that in 1Ag-1Specific time capacitance is as high as 1948F g-1And in 10Ag-1The specific time capacitance is still as high as 1320F g-1。
The SEM photograph of the nickel polyaniline foam prepared in example 2 with layered double hydroxide grown on the surface is similar to that of fig. 2. The one-dimensional LDH nano-coil is uniformly and densely vertically arranged on the surface of the substrate to form a shape similar to a test tube brush. The LDH nanocolloid structure is similar to that of FIG. 3, with a diameter of 30-50 nm and a length of 1-2 μm.
Example 3:
to 100mL of a 5mol/L aqueous sulfuric acid solution, 9.34mL of aniline was added and the mixture was stirred until the solution became clear. And (3) performing cyclic sweep voltammetry by taking the solution as an electrolyte solution and the stainless steel mesh as a working electrode to obtain the polyaniline-deposited stainless steel mesh. The sweep rate of cyclic voltammetry was 10mV/s, the voltage window was-0.6 to 1V, and the sweep time was 25 min. And cleaning the obtained polyaniline-deposited stainless steel mesh with deionized water for multiple times, and then drying in vacuum.
To 50mL of deionized water, 0.9g of Co (NO) was added3)2、0.42g Ni(NO3)2And 2.30g of urea were dissolved with stirring. And adding the stainless steel mesh with the polyaniline deposited on the surface into the solution, and fully immersing.
And (3) moving the system into a hydrothermal kettle, and putting the hydrothermal kettle into a vacuum oven to crystallize for 12 hours at 110 ℃. And after the reaction is finished, taking out the polyaniline stainless steel mesh after the temperature is reduced to the room temperature, washing the polyaniline stainless steel mesh for a plurality of times by using deionized water, and finally drying the polyaniline stainless steel mesh in vacuum to obtain the polyaniline stainless steel mesh with the surface growing layered double hydroxides.
The constant-current charging and discharging curves of the polyaniline stainless steel mesh with the layered double hydroxide growing on the surface prepared in the example 3 under different current densities are similar to those in fig. 1, and all represent energy storage mechanisms of LDH pseudocapacitance. This example was calculated at 1A g-1The specific capacitance time is as high as 1732F g-1And at 10A g-1The specific capacitance can still reach 1256F g-1。
The SEM photograph of the polyaniline stainless steel mesh with layered double hydroxide grown on the surface prepared in example 3 is similar to that of fig. 2. The one-dimensional LDH nano-coil is uniformly and densely vertically arranged on the surface of the substrate to form a shape similar to a test tube brush. The LDH nanocolloid structure is similar to that of FIG. 3, with a diameter of 30-50 nm and a length of 1-2 μm.
Example 4:
to 100mL of a 1mol/L sulfuric acid aqueous solution, 0.5mL of aniline was added and the mixture was stirred until the solution became clear. And (3) performing cyclic sweep voltammetry by taking the solution as an electrolyte solution and the carbon cloth as a working electrode to obtain the carbon cloth deposited by the polyaniline. The sweep rate of cyclic voltammetry was 400mV/s, the voltage window was 0 to 0.8V, and the sweep time was 0.5 min. And washing the obtained carbon cloth deposited with the polyaniline with deionized water for multiple times, and then drying in vacuum.
To 50mL of deionized water, 1.5g of Co (NO) was added3)2、0.8g Al(NO3)3And 2.5g of urea were dissolved with stirring. And adding the carbon cloth with the polyaniline deposited on the surface into the solution, and fully immersing.
And (3) moving the system into a hydrothermal kettle, and putting the hydrothermal kettle into a vacuum oven to crystallize for 6 hours at 120 ℃. And after the reaction is finished, taking out the polyaniline carbon cloth after the temperature is reduced to the room temperature, washing the polyaniline carbon cloth for a plurality of times by using deionized water, and finally drying the polyaniline carbon cloth in vacuum to obtain the polyaniline carbon cloth with the layered double hydroxide growing on the surface.
The SEM photograph of the polyaniline carbon cloth with layered double hydroxide grown on the surface prepared in example 4 is similar to that of fig. 2, but the crystal is denser and the length of the nanoconjugate is longer than that of example 1. The one-dimensional LDH nano-coil is uniformly and densely vertically arranged on the surface of the substrate to form a shape similar to a test tube brush. The structure of the LDH nano-coil is similar to that of FIG. 3, the diameter is 30-50 nm, and the length is about 2 μm.
The constant current charging and discharging curves of the polyaniline carbon cloth with the layered double hydroxide growing on the surface prepared in the example 4 under different current densities are similar to those in fig. 1, and all represent the energy storage mechanism of the LDH pseudocapacitance. This example was calculated at 1A g-1Specific capacitance of time is up to 1132F g-1And at 10A g-1The specific capacitance can still reach 956F g-1。
Example 5:
to 100mL of an aqueous solution of sulfuric acid having a concentration of 0.5mol/L, 0.93mL of aniline was added, and the mixture was stirred until the solution became clear. And (3) performing cyclic sweep voltammetry by taking the solution as an electrolyte solution and the carbon cloth as a working electrode to obtain the carbon cloth deposited by the polyaniline. The sweep rate of cyclic voltammetry was 10mV/s, the voltage window was-0.2 to 1V, and the sweep time was 60 min. And washing the obtained carbon cloth deposited with the polyaniline with deionized water for multiple times, and then drying in vacuum.
To 50mL of deionized water, 0.90g MgSO was added4、0.42g NiSO4And 2.3g sodium carbonate were stirred. Carbon with polyaniline deposited on surfaceCloth was added to the above solution and immersed sufficiently.
And (3) moving the system into a hydrothermal kettle, and putting the hydrothermal kettle into a vacuum oven to crystallize for 15 hours at 110 ℃. And after the reaction is finished, taking out the polyaniline carbon cloth after the temperature is reduced to the room temperature, washing the polyaniline carbon cloth for a plurality of times by using deionized water, and finally drying the polyaniline carbon cloth in vacuum to obtain the polyaniline carbon cloth with the layered double hydroxide growing on the surface.
In example 5, the constant current charging and discharging curves of the polyaniline carbon cloth with the layered double hydroxide grown on the surface are similar to those in fig. 1 under different current densities, and both represent the energy storage mechanism of the LDH pseudocapacitance. This example was calculated at 1A g-1The specific time capacitance is as high as 1232F g-1And in 10Ag-1The specific capacitance can still reach 876F g-1。
Example 5 SEM photograph of polyaniline carbon cloth with layered double hydroxide grown on the surface is similar to fig. 2, but the crystal is denser and the length of the nanoconjugate is longer than example 1. The one-dimensional LDH nano-coil is uniformly and densely vertically arranged on the surface of the substrate to form a shape similar to a test tube brush. The structure of the LDH nanocolloid is similar to that of FIG. 3, the diameter is 30-50 nm, and the length is 2-3 μm.
Example 6:
to 100mL of a 0.2mol/L sulfuric acid aqueous solution, 0.934mL of aniline was added, and the mixture was stirred until the solution became clear. And (3) performing cyclic sweep voltammetry by taking the solution as an electrolyte solution and the carbon cloth as a working electrode to obtain the carbon cloth deposited by the polyaniline. The cyclic voltammetry scanning rate is 100mV/s, the voltage window is-0.5 to 0.8V, and the scanning time is 5 min. And washing the obtained carbon cloth deposited with the polyaniline with deionized water for multiple times, and then drying in vacuum.
To 45mL of deionized water, 0.76g of Cr was added2(SO4)3、0.33g NiSO4And 5mL of 20% ammonia water. And adding the carbon cloth with the polyaniline deposited on the surface into the solution, and fully immersing.
And (3) moving the system into a hydrothermal kettle, and putting the hydrothermal kettle into a vacuum oven to crystallize for 24 hours at the temperature of 95 ℃. And after the reaction is finished, taking out the polyaniline carbon cloth after the temperature is reduced to the room temperature, washing the polyaniline carbon cloth for a plurality of times by using deionized water, and finally drying the polyaniline carbon cloth in vacuum to obtain the polyaniline carbon cloth with the layered double hydroxide growing on the surface.
The constant current charging and discharging curves of the polyaniline carbon cloth with the layered double hydroxide grown on the surface prepared in the example 6 under different current densities are similar to those in fig. 1, and all represent the energy storage mechanism of the LDH pseudocapacitance. This example was calculated at 1A g-1The specific time capacitance is as high as 1373F g-1And at 10A g-1The specific capacitance can still reach 896F g-1。
The SEM photograph of the polyaniline carbon cloth with layered double hydroxide grown on the surface prepared in example 6 is similar to that of fig. 2, but after reducing the concentration of urea, the crystal arrangement is looser and the length of the nanoconjugate is shorter than that of example 1. The one-dimensional LDH nano-coil is uniformly and densely vertically arranged on the surface of the substrate to form a shape similar to a test tube brush. The structure of the LDH nano-coil is similar to that of FIG. 3, the diameter is 30-50 nm, and the length is about 1 μm.
Example 7:
to 100mL of a 1mol/L sulfuric acid aqueous solution, 0.934mL of aniline was added, and the mixture was stirred until the solution became clear. And (3) performing cyclic sweep voltammetry by taking the solution as an electrolyte solution and foamy copper as a working electrode to obtain the carbon cloth deposited by the polyaniline. The sweep rate of cyclic voltammetry was 100mV/s, the voltage window was-0.2 to 0.8V, and the sweep time was 2 min. And washing the obtained polyaniline deposited foamy copper with deionized water for many times, and then drying in vacuum.
To 50mL of deionized water, 0.65g of CoCl was added2、0.34g NiCl2And 1.72g of urea were dissolved with stirring. And adding the copper foam with the polyaniline deposited on the surface into the solution, and fully immersing.
And (3) moving the system into a hydrothermal kettle, and putting the hydrothermal kettle into a vacuum oven to crystallize for 10 hours at 108 ℃. And after the reaction is finished, taking out the polyaniline copper foam after the temperature is reduced to room temperature, washing the polyaniline copper foam for a plurality of times by using deionized water, and finally drying the polyaniline copper foam in vacuum to obtain the polyaniline copper foam with the surface growing layered double hydroxides.
The constant-current charge and discharge curves of the polyaniline copper foam with the layered double hydroxide growing on the surface prepared in example 7 under different current densities are similar to those in fig. 1, and all represent the energy storage mechanism of the LDH pseudocapacitance. This example was calculated at 1A g-1Specific time capacitance up to 1512F g-1And at 10A g-1The specific capacitance is still as high as 1138F g-1。
The SEM photograph of the polyaniline copper foam with layered double hydroxide grown on the surface prepared in example 7 is similar to that of fig. 2, but the morphology of the crystal is closer to the nanoneedle array than that of the crystal in example 1. The one-dimensional LDH nanometer needles are uniformly and densely vertically arranged on the surface of the substrate, and the length of the LDH nanometer needles is about 2 mu m.
Comparative example 1:
to 50mL of deionized water, 0.45g of CoSO was added4、0.21g NiSO4And 1.153g of urea were dissolved with stirring. A commercial carbon cloth without any treatment was added to the above solution, and sufficiently immersed.
And (3) moving the system into a hydrothermal kettle, and putting the hydrothermal kettle into a vacuum oven to crystallize for 12 hours at 110 ℃. And after the reaction is finished, taking out the carbon cloth after the temperature is reduced to the room temperature, washing the carbon cloth for a plurality of times by using deionized water, and finally drying the carbon cloth in vacuum to obtain the carbon cloth with the surface growing layered double-metal hydroxide nanosheets.
The SEM photograph of the layered double hydroxide coated carbon cloth prepared in this comparative example is shown in fig. 5, from which it can be seen that the morphology of LDH appears as twisted nano-platelets with a longitudinal length of less than 1 micron.
The constant current charging and discharging curve of the layered double-metal hydroxide coated carbon cloth prepared in the comparative example 1 under different current densities is similar to that of the carbon cloth in the figure 1, and still shows a standard pseudo-capacitance behavior. But the specific capacitance is greatly reduced compared with the sample deposited with polyaniline, and is 1A g-1Specific time capacitance of only 1130F g-1At 10A g-1Specific time capacitance of only 820F g-1。
SEM photographs of the layered double hydroxide-coated carbon cloth prepared in comparative example 1 after 1000 charge and discharge cycles are shown in fig. 6. From the figure, it can be found that after 1000 charge-discharge cycles, a large amount of LDH was peeled off from the surface of the carbon cloth. This phenomenon indicates that the interaction between the carbon cloth surface not subjected to polyaniline deposition and LDH is weak, and ordered growth of LDH cannot be achieved. The specific capacity retention decreased to 51% after 1000 cycles.
Comparative example 2
In 50mL of deionized water0.90g of CoSO was added4、0.42g NiSO4And 2.3g of urea were dissolved with stirring. And adding the carbon cloth without the polyaniline deposition into the solution, and fully immersing.
And (3) moving the system into a hydrothermal kettle, and putting the hydrothermal kettle into a vacuum oven to crystallize for 15 hours at 110 ℃. And after the reaction is finished, taking out the carbon cloth after the temperature is reduced to the room temperature, washing the carbon cloth for a plurality of times by using deionized water, and finally drying the carbon cloth in vacuum to obtain the carbon cloth with the surface growing layered double-metal hydroxide nanosheets.
The SEM photograph of the layered double hydroxide coated carbon cloth prepared in comparative example 2 is similar to that of fig. 4, but the LDH grows more densely and some bulky clusters appear on the surface.
The constant current charging and discharging curve of the layered double metal hydroxide coated carbon cloth prepared in the comparative example 2 under different current densities is similar to that of the graph shown in the figure 1, but the specific capacitance is reduced compared with that of the comparative example 1 due to more serious agglomeration among LDH crystals and is 1A g-1Specific time capacitance of only 811F g-1At 10A g-1Specific time capacitance of only 508F g-1。
Claims (10)
1. A layered double metal hydroxide-polyaniline modified porous conductive composite material is characterized in that the porous conductive composite material takes a porous conductive material as a substrate; a polyaniline layer is deposited on the surface of the porous conductive material; and (3) growing a 1-3 mu m layered double-metal hydroxide nano coil on the surface of the polyaniline layer in situ.
2. The porous conductive composite of claim 1, wherein the porous conductive material is a carbon cloth, a metal mesh or a metal foam.
3. Use of the layered double hydroxide-polyaniline modified porous conductive composite material according to claim 1 or 2 in the preparation of an energy storage device.
4. The method for preparing the layered double hydroxide-polyaniline-modified porous conductive composite material as claimed in claim 1 or 2, which comprises the steps of:
(1) adding aniline into a sulfuric acid aqueous solution to serve as an electrolyte solution, taking a porous conductive material as a working electrode, and preparing the polyaniline-deposited porous conductive material by an electrochemical method;
(2) immersing the porous conducting material deposited by polyaniline into alkaline water containing two soluble metal salts for hydrothermal reaction.
5. The method according to claim 4, wherein in the step (1), the electrochemical method is a constant voltage electrodeposition method or cyclic voltammetry.
6. The preparation method according to claim 4, wherein in the step (1), the concentration of aniline in the electrolyte solution is 0.01-1 mol/L.
7. The method according to claim 4, wherein in the step (2), the soluble metal salt is a soluble divalent metal salt or a soluble trivalent metal salt or a mixture thereof.
8. The preparation method according to claim 4, wherein the total concentration of the soluble metal salt in the step (2) is 0.024-1.2 mol/L.
9. The method according to claim 4, wherein in the step (2), the molar ratio of the soluble metal salt to the base is 1: 1-10.
10. The preparation method according to claim 4, wherein in the step (2), the temperature of the hydrothermal reaction is 90-125 ℃; the hydrothermal reaction time is 6-24 h.
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