CN113998740A - C-FeOOH lossless deformation self-supporting electrode with wolf tooth rod structure and preparation method - Google Patents
C-FeOOH lossless deformation self-supporting electrode with wolf tooth rod structure and preparation method Download PDFInfo
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- 229910002588 FeOOH Inorganic materials 0.000 title claims abstract description 39
- 241000282461 Canis lupus Species 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000000835 fiber Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- 230000001276 controlling effect Effects 0.000 claims abstract description 3
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 239000002110 nanocone Substances 0.000 claims description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000003491 array Methods 0.000 claims description 5
- 239000002134 carbon nanofiber Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000007832 Na2SO4 Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 15
- 238000004146 energy storage Methods 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 6
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- 238000003541 multi-stage reaction Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
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- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 7
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 7
- 238000009987 spinning Methods 0.000 description 7
- 238000013461 design Methods 0.000 description 6
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- 238000009656 pre-carbonization Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 235000011468 Albizia julibrissin Nutrition 0.000 description 1
- 240000001140 Mimosa pudica Species 0.000 description 1
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- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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Abstract
The invention provides a C-FeOOH lossless deformation self-supporting electrode with a wolf tooth rod structure and a preparation method thereof, belonging to the field of flexible energy storage materials. The invention obtains the layered network structure membrane material formed by stacking the hydroxyl ferric oxide nanocone @ carbon composite fiber with a wolf tooth rod-like structure by synchronously regulating and controlling the reaction temperature, the reaction time and the additive in the composite reaction process, and the network has multi-stage fully flexible structures such as free-sliding fiber, a separable layer, a compressible network and the like, thereby realizing the function of largely lossless deformation of the electrode material. The preparation process provided by the invention is simple and easy to control, high-efficiency, green and mild, is beneficial to large-scale production, and has wide application prospect in the field of flexible energy storage.
Description
Technical Field
The invention belongs to the field of flexible energy storage materials, and particularly relates to a C-FeOOH lossless deformation self-supporting electrode with a wolf tooth rod structure and a method.
Background
With the continuous development of the field of flexible electronics and wearable devices, flexible energy storage devices become the hot spot of current research as an indispensable component of electronic devices. While flexible deformable electrode materials have been extensively studied as key components in energy storage devices. These flexible electrode materials tend to have good bending deformation characteristics but are difficult to withstand true folding deformation. Even if a few electrode materials are able to withstand folding deformation, they are at the expense of structural damage and breakage and can only withstand up to several hundred times, let alone produce electrode materials that are able to undergo a large amount of folding deformation without structural damage. Such flexible electrode materials are likely to cause structural damage and breakage during random bending, excessive bending or repeated folding deformation, and cause poor contact, failure or even short circuit of the device. Therefore, it is urgent and urgently required for the development of the field to prepare an electrode which can not damage a large amount of deformation.
The flexible deformable electrode material generally takes the form of a structure in which an active functional substance is embedded in a flexible conductive substrate. Without special structural design, all flexible conductive substrate materials (mainly classified into three categories, metal, conductive polymer and inorganic nonmetal represented by graphitized carbon) are broken because they cannot withstand repeated bending deformation. The root of this is that the chemical bonds that make up them are short-range forces that cannot withstand large deformation schedules, otherwise structural damage to the material occurs, and the accumulated structural damage eventually leads to material fracture. The active functional substances generally have higher rigidity, and when the active functional substances are compounded with the conductive substrate, the flexibility of the substrate is further reduced, and the requirement of nondestructive deformation is more difficult to achieve. Therefore, it is important to find a mild and controllable synthesis method to design and prepare a composite electrode material with a special structure so as to meet the requirement of lossless deformation, both from the material itself and the preparation method thereof.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, solve the problem that the conventional flexible composite electrode cannot withstand a large number of times of nondestructive deformation, and provide a C-FeOOH nondestructively deformable self-supporting electrode with a wolf tooth rod structure and a preparation method thereof. According to the invention, the layered network structure membrane material formed by stacking the hydroxyl ferric oxide nanocone and the carbon composite fiber with the wolf tooth-like rod structure is obtained by synchronously regulating and controlling the reaction temperature, the reaction time and the additive in the composite reaction process, so that a large number of lossless deformation functions of the electrode material are realized. The preparation process provided by the invention is simple, easy to control, efficient, green and mild, is beneficial to large-scale production, and has wide application prospects in the field of flexible energy storage.
In order to achieve the above object, the present invention provides the following technical solutions:
a C-FeOOH lossless deformation self-supporting electrode of a wolf tooth rod structure is a network structure assembled by stacking hydroxyl iron oxide nanocone arrays and carbon nano composite fibers of a wolf tooth rod-like structure. The material has a multi-stage fully flexible structure of free-sliding fibers, separable layers, compressible networks and the like. The structure enables the material to form an epsilon crease structure to completely disperse stress and avoid the fracture of chemical bonds when the material is deformed in a paper folding manner, so that the material cannot generate any structural damage and fracture when being subjected to repeated folding deformation in any direction for more than 10 ten thousand times, and the nondestructive deformation function is really realized.
The invention also provides a preparation method of the C-FeOOH lossless deformation self-supporting electrode with the wolf tooth rod structure.
To produce a large number of electrode materials without damage to the deformation, it is first of all important to design their target structure, which is, however, not yet known. Biomimetic synthesis may provide a beneficial idea for the design and preparation thereof. As is known, mature silkworm cocoons are an ultra-soft material that can withstand any repetitive deformation operations; the ornamental plant Mimosa pudica Linn has the capability of opening and closing leaves repeatedly without damage. By studying the structures of the two, the inventor finds that the super flexibility of the cooked silkworm cocoon comes from the fiber network structure of the fluffy layering and the slippage and porosity of the cooked silkworm cocoon. The leaf pillow of the sensitive plant leaf is the key of the undamaged opening and closing of the sensitive plant leaf, and the leaf pillow is formed by surrounding the inner core of the vascular tissue by soft cell tissue consisting of parenchyma cells. When an external stimulation signal is generated, the soft cell tissue on one side of the vascular tissue loses water and shrinks in volume to become a cone-like structure, so that leaf occipital bending is caused to cause the leaves to open and close nondestructively, and the process is reversible and has no tissue damage. By combining the two bionic strategies, the inventor thinks that the structure of the composite electrode capable of bearing a large amount of lossless deformation should have an interface assembly structure of the nano cone @ conductive fiber, and the composite fiber is used as a layered network multi-stage structure stacked by assembly units, so that the fiber can freely slide, the layers can be separated, and the network can be compressed.
In the synthetic process of the composite material, firstly, the super-flexible conductive carbon network material composed of porous slidable carbon nanofibers is prepared by simulating an electrostatic spinning method for spinning and cocooning silkworms and a combined bionic technology of in-situ conversion and carbonization. And then, by a mild liquid phase deposition technology and by means of multi-factor accurate control of reaction kinetics, the FeOOH nanocone array imitating the mimosa leaves is embedded on the surface of the carbon nanofibers. The normal pressure low temperature reaction is adopted in the compounding process, so that the structural integrity and the structural maintenance of the carbon material in the reaction can be ensured. On the other hand, the use of hydrothermal and other high-temperature and high-pressure conditions leads to damage and fracture of the carbon material structure. And the excessive reaction concentration can promote the reaction to be quickly finished in a short time, so that the final product is not uniform and the fiber network is hardened again, and the requirements of nondestructive deformation of the final product cannot be met.
In the composite structure obtained by the invention, the compressible network, the dispersible layer, the slidable fiber, the macroporous structure, the porous structure of the fiber, the nano cone shape of the iron oxyhydroxide, the array structure, the array gap and other structures play a role in stress dispersion in the deformation process of the material, and the damage to chemical bonds is avoided, so that the composite structure is endowed with an incomparable large amount of nondestructive deformation capability. The composite structure with the multilayer stress dispersion structure coexisting is far from the synthesis method and the structural characteristics of other composite materials at present.
The invention provides a preparation method of a C-FeOOH lossless deformation self-supporting electrode with a wolf tooth rod structure, which comprises the following specific synthesis steps:
(1) preparing the super-flexible conductive carbon substrate by combining an electrostatic spinning method with an in-situ conversion carbonization technology:
(1.1) first, polyacrylonitrile was dissolved in dimethylformamide to form a 10% solution;
(1.2) carrying out electrostatic spinning on the solution obtained in the step (1.1) under the voltage of 12.5kV, the speed of 0.5mL/h, the receiving distance of 16cm and the spinning time of 4h to obtain a polymer film precursor;
(1.3) heating the polymer film precursor in the step (1.2) to 105 ℃ at a speed of 2 ℃/min in the air, preserving heat for 0.5h, continuing heating to 160 ℃ at a speed of 1 ℃/min, preserving heat for 0.5h, and then heating to 270 ℃ at a speed of 1 ℃/min, and preserving heat for 2 h. After the pre-carbonization process, continuously heating to 800 ℃ at a speed of 1 ℃/min under the nitrogen atmosphere, preserving heat for 2h, and carrying out in-situ conversion to obtain the super-flexible carbon material;
(2) preparing a nondestructive deformation C-FeOOH composite material:
and (2) performing surface hydrophilic activation on the super-flexible carbon material in the step (1) in an acid solution, then putting the activated super-flexible carbon material into a mixed solution of ferric chloride, urea and a morphology control additive, and stirring and reacting for a certain time at a low temperature to prepare the composite material capable of bearing a large amount of lossless deformation.
Preferably, the addition amount of the iron salt in the step (2) is 0.1-0.3 g, and the addition amount of the urea is 0.2-0.6 g.
Preferably, the reaction temperature in step (2) is 50 ℃.
Preferably, the reaction time in step (2) is 2-6 h.
Preferably, the additive in the step (2) is Na2SO4The amount of the additive is 0.2 to 1 g.
Compared with the prior art, the technical scheme adopted by the invention has the following beneficial effects by way of example and not limitation:
1. the invention uses the super-flexible carbon material prepared by combining electrostatic spinning and in-situ conversion carbonization as a framework and combines a low-temperature liquid phase deposition technology to realize the preparation of the composite electrode which has the characteristics of double bionic structures and can be deformed without damage for the first time. The method is simple, easy to control, high-efficiency, green and mild, and is beneficial to large-scale production and preparation.
2. The lossless deformation electrode of the wolf tooth rod structure is a composite network structure formed by FeOOH nano cone arrays and carbon nano fibers, and the network has a multi-stage fully flexible structure comprising free-sliding fibers, separable layers, a compressible network and the like. The material can form an epsilon crease structure to completely disperse stress when being folded and deformed, so that the material has no structural fracture damage when being subjected to repeated paper folding deformation in any direction for more than 10 ten thousand times, and the nondestructive deformation function is really realized.
Drawings
FIG. 1 shows SEM photograph of the C-FeOOH lossless deformable self-supporting electrode of the wolf tooth bar structure obtained in example 2.
FIG. 2 is a schematic design diagram of a C-FeOOH lossless deformable self-supporting electrode of the wolf tooth bar structure obtained in example 2.
FIG. 3 is a TEM image of the C-FeOOH lossless deformable self-supporting electrode of the mace structure obtained in example 2.
FIG. 4 is an SEM photograph of C-FeOOH lossless deformable self-supporting electrode of the wolf tooth bar structure obtained in example 2 at the crease in a folded state.
FIG. 5 shows SEM photograph of C-FeOOH lossless deformation self-supporting electrode of maceral rod structure obtained in example 2 after repeated folding 100000 times
Fig. 6 shows an SEM photograph of the composite material obtained after changing the reaction temperature and time of example 2. (example 4)
Fig. 7 shows SEM photographs of the resulting composite material after folding 1 time after changing the reaction temperature of example 2. (example 5)
Detailed Description
The technical scheme of the C-FeOOH nondestructively deformable self-supporting electrode with a wolf tooth bar structure and the preparation method thereof provided by the invention will be further explained with reference to specific embodiments and drawings thereof. The advantages and features of the present invention will become more apparent in conjunction with the following description.
It should be noted that the embodiments of the present invention have better practicability, and are not intended to limit the present invention in any form. The technical features or combinations of technical features described in the embodiments of the present invention should not be considered as being isolated, and they may be combined with each other to achieve a better technical effect. The scope of the preferred embodiments of the present invention may also include additional implementations, and this should be understood by those skilled in the art to which the embodiments of the present invention pertain.
Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
The drawings of the present invention are in simplified form and are not to scale, but rather are provided for the purpose of facilitating and clearly illustrating embodiments of the present invention and are not intended to limit the scope of the invention in which the invention may be practiced. Any modification of the structure, change of the ratio or adjustment of the size of the structure should fall within the scope of the present disclosure without affecting the effect and the purpose of the present disclosure. And the same reference numerals appearing in the drawings of the present invention denote the same features or components, which can be applied to different embodiments.
Example 1
A preparation method of a C-FeOOH lossless deformation self-supporting electrode material with a wolf tooth rod structure comprises the following specific steps:
(1) the super-flexible carbon skeleton is prepared by combining an electrostatic spinning method with an in-situ conversion carbonization technology:
(1.1) first, polyacrylonitrile was dissolved in dimethylformamide to form a 10% solution;
(1.2) carrying out electrostatic spinning on the solution obtained in the step (1.1) under the voltage of 12.5kV, the speed of 0.5mL/h, the receiving distance of 16cm and the spinning time of 4h to obtain a polymer film precursor;
(1.3) heating the polymer film precursor in the step (1.2) to 105 ℃ at a speed of 2 ℃/min in the air, preserving heat for 0.5h, continuing heating to 160 ℃ at a speed of 1 ℃/min, preserving heat for 0.5h, and then heating to 270 ℃ at a speed of 1 ℃/min, and preserving heat for 2 h. After the pre-carbonization process, continuously heating to 800 ℃ at a speed of 1 ℃/min under the nitrogen atmosphere, preserving heat for 2h, and carrying out in-situ conversion to obtain the super-flexible carbon material;
(2) preparing a super-folded carbon-based iron oxyhydroxide composite material:
soaking the super-flexible carbon material obtained in the step (1) in 50mL of aqueous solution containing 20mL of nitric acid for 12h, then washing and putting the soaked super-flexible carbon material into a mixed solution containing 0.2g of ferric chloride, 0.5g of urea and 0.5g of sodium sulfate, and stirring and reacting for 3h at the temperature of 50 ℃ under normal pressure to prepare the super-folded composite material.
Example 2
A preparation method of a C-FeOOH lossless deformation self-supporting electrode material with a wolf tooth rod structure comprises the following specific steps:
(1) the super-flexible carbon skeleton is prepared by combining an electrostatic spinning method with an in-situ conversion carbonization technology:
(1.1) first, polyacrylonitrile was dissolved in dimethylformamide to form a 10% solution;
(1.2) carrying out electrostatic spinning on the solution obtained in the step (1.1) under the voltage of 12.5kV, the speed of 0.5mL/h, the receiving distance of 16cm and the spinning time of 4h to obtain a polymer film precursor;
(1.3) heating the polymer film precursor in the step (1.2) to 105 ℃ at a speed of 2 ℃/min in the air, preserving heat for 0.5h, continuing heating to 160 ℃ at a speed of 1 ℃/min, preserving heat for 0.5h, and then heating to 270 ℃ at a speed of 1 ℃/min, and preserving heat for 2 h. After the pre-carbonization process, continuously heating to 800 ℃ at a speed of 1 ℃/min under the nitrogen atmosphere, preserving heat for 2h, and carrying out in-situ conversion to obtain the super-flexible carbon material;
(2) preparing a super-folded carbon-based iron oxyhydroxide composite material:
soaking the super-flexible carbon material obtained in the step (1) in 50mL of aqueous solution containing 20mL of nitric acid for 12h, then washing and putting the soaked super-flexible carbon material into a mixed solution containing 0.1g of ferric chloride, 0.2g of urea and 0.25g of sodium sulfate, and stirring and reacting for 6h at the temperature of 50 ℃ under normal pressure to prepare the super-folded composite material.
FIG. 1 shows SEM photograph of the C-FeOOH lossless deformable self-supporting electrode of the wolf tooth bar structure obtained in example 2. As can be seen from the figure, the composite material is a network structure formed by mutually lapping composite fibers, and FeOOH nano arrays grow on the surfaces of the composite fibers.
FIG. 2 is a schematic design diagram of a C-FeOOH lossless deformable self-supporting electrode of the wolf tooth bar structure obtained in example 2. When the leaf pillow of the sensitive plant is in a normal state, the states of the parenchyma cells at the upper part and the lower part of the leaf are the same, once the leaf pillow is collected from the outside, the cells at the lower part dehydrate, the cells at the upper part absorb water, and the pressure is unbalanced, so that the leaf pillow bends and the leaf is closed. The process brings inspiration for the lossless folding structure, namely the shape structure of the functional substance is designed by simulating the conical structure reserved space of the dehydrated cells, so that the functional substance loaded on the fiber can be ensured not to be damaged and fall off and not to cause the fracture of the fiber.
FIG. 3 is a TEM image of the C-FeOOH lossless deformable self-supporting electrode of the mace structure obtained in example 2. As can be seen from the figure, FeOOH loaded on the surface of the fiber is in a nanocone structure.
FIG. 4 is an SEM photograph of C-FeOOH lossless deformable self-supporting electrode of the wolf tooth bar structure obtained in example 2 at the crease in a folded state. As can be seen, a folded structure like epsilon is formed, thereby achieving overall stress dispersion.
FIG. 5 shows SEM photographs of the C-FeOOH lossless deformable self-supporting electrode of the wolf tooth bar structure obtained in example 2 after 100000 times of repeated folding deformation. The results show that the composite material has no fracture and damage on the microstructure, and the nondestructive deformation is realized only because the movement of the composite nano fiber forms a micro groove.
Example 3
A preparation method of a C-FeOOH lossless deformation self-supporting electrode material with a wolf tooth rod structure comprises the following specific steps:
(1) the super-flexible carbon skeleton is prepared by combining an electrostatic spinning method with an in-situ conversion carbonization technology:
(1.1) first, polyacrylonitrile was dissolved in dimethylformamide to form a 10% solution;
(1.2) carrying out electrostatic spinning on the solution obtained in the step (1.1) under the voltage of 12.5kV, the speed of 0.5mL/h, the receiving distance of 16cm and the spinning time of 4h to obtain a polymer film precursor;
(1.3) heating the polymer film precursor in the step (1.2) to 105 ℃ at a speed of 2 ℃/min in the air, preserving heat for 0.5h, continuing heating to 160 ℃ at a speed of 1 ℃/min, preserving heat for 0.5h, and then heating to 270 ℃ at a speed of 1 ℃/min, and preserving heat for 2 h. After the pre-carbonization process, continuously heating to 800 ℃ at a speed of 1 ℃/min under the nitrogen atmosphere, preserving heat for 2h, and carrying out in-situ conversion to obtain the super-flexible carbon material;
(2) preparing a super-folded carbon-based iron oxyhydroxide composite material:
soaking the super-flexible carbon material obtained in the step (1) in 50mL of aqueous solution containing 20mL of nitric acid for 12h, then washing and putting the soaked super-flexible carbon material into a mixed solution containing 0.3g of ferric chloride, 0.6g of urea and 0.8g of sodium sulfate, and stirring and reacting for 3h at the temperature of 50 ℃ under normal pressure to prepare the super-folded composite material.
Example 4 (comparative example)
The preparation method of the comparative sample which can be broken after being deformed for several times comprises the following specific steps:
(1) the super-flexible carbon skeleton is prepared by combining an electrostatic spinning method with an in-situ conversion carbonization technology:
(1.1) first, polyacrylonitrile was dissolved in dimethylformamide to form a 10% solution;
(1.2) carrying out electrostatic spinning on the solution obtained in the step (1.1) under the voltage of 12.5kV, the speed of 0.5mL/h, the receiving distance of 16cm and the spinning time of 4h to obtain a polymer film precursor;
(1.3) heating the polymer film precursor in the step (1.2) to 105 ℃ at a speed of 2 ℃/min in the air, preserving heat for 0.5h, continuing heating to 160 ℃ at a speed of 1 ℃/min, preserving heat for 0.5h, and then heating to 270 ℃ at a speed of 1 ℃/min, and preserving heat for 2 h. After the pre-carbonization process, continuously heating to 800 ℃ at a speed of 1 ℃/min under the nitrogen atmosphere, preserving heat for 2h, and carrying out in-situ conversion to obtain the super-flexible carbon material;
(2) preparing a super-folded carbon-based iron oxyhydroxide composite material:
soaking the super-flexible carbon material obtained in the step (1) in 50mL of aqueous solution containing 20mL of nitric acid for 12h, then washing and putting into a mixed solution containing 0.1g of ferric chloride, 0.2g of urea and 0.25g of sodium sulfate, stirring and reacting for 9h at 40 ℃ under normal pressure, and folding the prepared composite material for several times to break.
FIG. 4 shows an SEM image of the composite material obtained in example 4; example 4 the reaction temperature was 40 ℃ and the reaction time was 9h, and the rest of the synthesis conditions were the same as in example 2. As can be seen from fig. 4, FeOOH clusters at this temperature, and no nanocone structure can be generated and uniform loading cannot be achieved. The material breaks after undergoing several folding deformations.
Example 5 (comparative example)
The preparation method of the comparative sample which can be broken after being deformed for several times comprises the following specific steps:
(1) the super-flexible carbon skeleton is prepared by combining an electrostatic spinning method with an in-situ conversion carbonization technology:
(1.1) first, polyacrylonitrile was dissolved in dimethylformamide to form a 10% solution;
(1.2) carrying out electrostatic spinning on the solution obtained in the step (1.1) under the voltage of 12.5kV, the speed of 0.5mL/h, the receiving distance of 16cm and the spinning time of 4h to obtain a polymer film precursor;
(1.3) heating the polymer film precursor in the step (1.2) to 105 ℃ at a speed of 2 ℃/min in the air, preserving heat for 0.5h, continuing heating to 160 ℃ at a speed of 1 ℃/min, preserving heat for 0.5h, and then heating to 270 ℃ at a speed of 1 ℃/min, and preserving heat for 2 h. After the pre-carbonization process, continuously heating to 800 ℃ at a speed of 1 ℃/min under the nitrogen atmosphere, preserving heat for 2h, and carrying out in-situ conversion to obtain the super-flexible carbon material;
(2) preparing a super-folded carbon-based iron oxyhydroxide composite material:
soaking the super-flexible carbon material obtained in the step (1) in 50mL of aqueous solution containing 20mL of nitric acid for 12h, then washing and putting into a mixed solution containing 0.1g of ferric chloride, 0.2g of urea and 0.25g of sodium sulfate, stirring and reacting for 6h at 60 ℃ under normal pressure, and a large amount of structural fractures appear after the prepared composite material is folded once.
Fig. 5 shows the microstructure of the composite obtained in example 5 after 1 fold deformation, with the reaction temperature raised to 60 c and the rest of the synthesis conditions being the same as those of example 2. Under the reaction condition, the iron oxyhydroxide grows very fast and is closely stacked, and the joint of the fiber is solidified and cannot normally slide and be separated from each other, so that the stress dispersion cannot be realized. The results show that the composite material has a microscopically structural fracture after being subjected to 1 fold deformation, and after several times, the composite material will fracture into two parts.
The invention provides a C-FeOOH lossless deformation self-supporting electrode with a wolf tooth rod structure and a preparation method thereof, solves the problem that a conductive composite functional material in the field of existing flexible electronics and wearable devices cannot bear a large number of times of lossless deformation, and relates to the field of flexible energy storage materials. The electrode material is prepared by using a normal-pressure low-temperature liquid phase deposition technology, and the key point of the electrode material is that the reaction temperature, the reaction time and the additive are simultaneously adjusted so as to control the crystal growth process of the functional material on the conductive carbon substrate. The structure of the composite network is a composite network formed by FeOOH nanocone arrays and carbon nanofibers, and the network has a multi-level fully flexible structure comprising free-sliding composite fibers, separable layers, a compressible network and the like. Therefore, the self-adaptive stress dispersion function is realized, no structural fracture damage is caused in the process of undergoing folding deformation in any direction and 100000 times of repeated folding deformation, and lossless deformation is really realized. The C-FeOOH of the wolf tooth rod structure prepared by the invention realizes a large amount of nondestructive deformation functional effects for the first time, the designed novel full-flexible composite structure has wide guiding significance for preparing the nondestructive deformation conductive composite functional material, and the provided preparation process is simple, easy to control, efficient, green and mild, is beneficial to large-scale production, and has wide application prospect in the field of flexible energy storage.
The above description is only illustrative of the preferred embodiments of the present invention and should not be taken as limiting the scope of the invention in any way. Any changes or modifications made by those skilled in the art based on the above disclosure should be considered as equivalent effective embodiments, and all the changes or modifications should fall within the protection scope of the technical solution of the present invention.
Claims (6)
1. A method for preparing C-FeOOH nondestructive deformation self-supporting electrode with wolf tooth rod structure is characterized in that the preparation method comprises the step of adding conductive carbon material with surface hydrophilic treatment into the electrode containing ferric chloride, urea and Na2SO4In the aqueous solution of the additive, the crystal growth process of FeOOH on the conductive carbon substrate is regulated by simultaneously controlling the reaction temperature, the reaction time and the types of the additive.
2. The method for preparing the C-FeOOH lossless deformation self-supporting electrode with the wolf tooth bar structure according to claim 1 is characterized in that: the addition amount of the iron salt is 0.1-0.3 g, and the addition amount of the urea is 0.2-0.6 g.
3. The method for preparing the C-FeOOH lossless deformation self-supporting electrode with the wolf tooth bar structure according to claim 1 is characterized in that: the reaction temperature was 50 ℃.
4. The method for preparing the C-FeOOH lossless deformation self-supporting electrode with the wolf tooth bar structure according to claim 1 is characterized in that: the reaction time is 2-6 h.
5. The method for preparing the C-FeOOH lossless deformation self-supporting electrode with the wolf tooth bar structure according to claim 1 is characterized in that: the additive is Na2SO4The dosage is 0.1-1 g.
6. The C-FeOOH nondestructively deformable self-supporting electrode of a wolf tooth rod structure prepared by the method of any one of claims 1 to 5, characterized in that: the material is a composite network structure formed by FeOOH nano cone arrays and carbon nano fibers, and the structure has multi-stage fully flexible structures such as free-sliding fibers, separable layers and compressible networks; this structure allows the material to form an epsilon crease structure to completely distribute stresses when the material undergoes a fold-type deformation.
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