CN211879251U - Flexible micro energy storage device - Google Patents
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- CN211879251U CN211879251U CN202020255478.XU CN202020255478U CN211879251U CN 211879251 U CN211879251 U CN 211879251U CN 202020255478 U CN202020255478 U CN 202020255478U CN 211879251 U CN211879251 U CN 211879251U
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Abstract
The utility model discloses a flexible miniature energy storage device. The flexible micro energy storage device comprises a flexible substrate and a plurality of electrodes, wherein the electrodes are arranged on the surface of the flexible substrate, and an electrolyte layer is distributed between any two adjacent electrodes; the electrode comprises a micro-polar plate arranged on the surface of a flexible substrate, a current collector layer arranged on the surface of the micro-polar plate and an electrode material layer arranged on the surface of the current collector layer, wherein the micro-polar plate comprises a first micro-polar plate and a second micro-polar plate which are respectively provided with a first spiral structure and a second spiral structure, and the first spiral structure and the second spiral structure are matched to form a three-dimensional double-spiral micro-nano structure. The current collector layer is composed of a carbon-based material film and also serves as an in-situ growth carrier of the ternary layered double-metal hydroxide array, a stable and continuous three-dimensional integrated structure can be formed between the flexible substrate and the active substance, the mechanical stability of the electrode can be enhanced, the high-current rate performance is improved, and the stability of the cycle performance is maintained.
Description
Technical Field
The utility model relates to an energy storage device, in particular to flexible miniature energy storage device based on substrate/graphite alkene ternary layered hydroxide integrated electrode belongs to energy storage equipment technical field.
Background
In recent years, flexible electronic technology has quietly emerged as a kind of important technological change under the promotion of the development of microelectronics, material science, micromachining technology and the like, and is highly concerned and valued by academics and industry. However, although some flexible electronic devices such as flexible bionic electronic skins are approaching to people's lives, research on flexible power supplies driving these flexible electronic products is relatively lagged behind, and becomes one of the biggest challenges in developing flexible electronics, which is a research hotspot in recent years. Traditional lithium batteries, supercapacitors and the like are all rigid, and serious safety problems such as short circuit and the like are easily caused under the conditions of bending and the like. In order to meet the application requirements of flexible electronic products, the flexible energy storage device not only needs to have higher energy/power density, higher cycling stability and faster charge and discharge rate, but also needs to have good flexibility/flexibility and processability so as to meet the requirement of matching with flexible electronics.
Among many energy storage devices, a flexible micro supercapacitor, which is one of leading research directions in the field of micro-nano energy storage devices, is a new type of energy storage source that has been gradually developed in recent years. For example, the first proposed micro supercapacitor is a classic "tine" type micro supercapacitor designed based on a three-dimensional carbon tube, and compared with a common flexible supercapacitor with a sandwich structure, the inner electrolyte ions of the capacitor can be transferred in electrode materials stacked on the same horizontal plane (especially suitable for two-dimensional sheet materials), so that the transmission distance is reduced, the utilization rate of active substances is improved, the risk of layer-to-layer peeling when the stacked structure is bent is reduced, the device is more easily thinned/flexible to be two-dimensional and miniaturized while the electrochemical capacitor has the characteristics of high power density, high charge-discharge rate and the like, the requirement of flexible electrons on energy supply devices can be better met, and the development of a new branch of the supercapacitor is formed. However, the practical application of the flexible micro-supercapacitor is still limited by the lower energy density, and how to realize high energy density and stability under the light, thin and flexible conditions is one of the problems to be solved in the research of the flexible micro-supercapacitor.
SUMMERY OF THE UTILITY MODEL
The main object of the present invention is to provide a flexible micro energy storage device based on substrate/graphene/ternary layered hydroxide integrated electrode, so as to overcome the disadvantages in the prior art.
For realizing the purpose of the utility model, the utility model discloses a technical scheme include:
an embodiment of the present invention provides a flexible micro energy storage device, which includes a flexible substrate, an electrode and an electrolyte layer, wherein the electrode is disposed on a surface of the flexible substrate, and the electrolyte layer is at least distributed between two electrodes;
the electrode comprises a micro-polar plate arranged on the surface of a flexible substrate, a current collector layer arranged on the surface of the micro-polar plate and an electrode material layer arranged on the surface of the current collector layer, the micro-polar plate comprises a first micro-polar plate and a second micro-polar plate, the first micro-polar plate and the second micro-polar plate are respectively provided with a first spiral structure and a second spiral structure, and the first spiral structure and the second spiral structure are matched to form a three-dimensional double-spiral micro-nano structure.
Furthermore, the height of the first micro-polar plate and the second micro-polar plate is 10-50 μm, the width of the first micro-polar plate and the second micro-polar plate is 5-20 μm, the number of spiral turns is 10-50 turns, and the distance between the first micro-polar plate and the second micro-polar plate is larger than 30 μm and smaller than or equal to 100 μm.
Furthermore, the current collector layer is directly formed on the surface of the micro-polar plate and forms a continuous integrated interface structure with the surface of the micro-polar plate.
Further, the current collector layer comprises a carbon-based material conductive film, and the carbon-based material conductive film has a continuous interconnection structure.
Furthermore, the material of the carbon-based material conductive film comprises any one or a combination of more than two of graphene, carbon nanotubes, conductive carbon black and amorphous carbon.
Furthermore, the thickness of the carbon-based material conductive film is 2-10 μm.
Further, the electrode material layer comprises a metal element doped Ni-based layered double metal hydroxide nanosheet array.
Further, the metal element includes an element M and/or an element N, the element M includes any one of iron, copper, vanadium, zinc, molybdenum, and tin, but is not limited thereto, and the element N includes any one of cobalt, manganese, and aluminum, but is not limited thereto.
Furthermore, the molar ratio of the element M, Ni to the element N is 1: 10: 0-1: 0: 10.
Further, the electrode material layer grows on the surface of the current collector layer in situ and forms a continuous and stable interface shape with the current collector layer.
Further, the electrolyte layer includes a polymer electrolyte, and the polymer electrolyte includes an aqueous solution of any one or a combination of two or more of polyvinyl alcohol-potassium hydroxide, polyvinyl alcohol-sodium hydroxide, polyvinyl alcohol-lithium chloride, polyvinyl alcohol-potassium chloride, polyvinyl alcohol-sodium sulfate, polyvinyl alcohol-potassium sulfate, and the like.
Furthermore, an electrode wire is further arranged on the current collector layer, one end of the electrode wire is electrically combined with the current collector layer, and the other end of the electrode wire is led out from the surface of the current collector layer.
Furthermore, the flexible substrate and the micro-polar plate are of an integrated structure.
Furthermore, the flexible substrate and the micro-electrode plate are made of the same material, and the flexible substrate and the micro-electrode plate are made of any one or a combination of more than two of polyvinyl alcohol, polydimethylsiloxane, polyethylene terephthalate, polyimide and polyethylene.
Furthermore, the thickness of the flexible substrate is 20-300 mu m.
Furthermore, the flexible substrate, the micro-polar plate, the current collector layer and the electrode material layer form an integrated structure.
Furthermore, the thickness of the flexible micro energy storage device is 100-500 mu m.
Further, the flexible micro energy storage device comprises a flexible micro super capacitor.
The embodiment of the utility model provides an on the other hand still provides as the manufacturing method of flexible miniature energy memory device, it includes:
providing a template with a patterned groove on the surface, wherein the patterned groove comprises a first groove and a second groove which are respectively provided with a first spiral structure and a second spiral structure, and the first spiral structure and the second spiral structure are matched to form a three-dimensional double-spiral micro-nano structure;
applying a carbon-based material dispersion liquid on the surface of the template to form a carbon-based material conductive film, removing the carbon-based material conductive film on the surface of the template except the patterned groove, and enabling the carbon-based material conductive film remained in the first groove and the second groove to be used as a current collector layer;
coating a prepolymer for forming a flexible substrate on the surface of the template, then solidifying the prepolymer to form the flexible substrate, and separating the flexible substrate and the current collector layer which are combined with each other from the template; the prepolymers in the first groove and the second groove are solidified to form a first micro-polar plate and a second micro-polar plate respectively;
coating a mixed solution formed by mixing a metal salt aqueous solution doped with Ni and M and/or N elements and a solution containing ammonium ions and hydroxyl ions on the surface of the current collector layer, and then reacting for 3-25 h at the temperature of 25-75 ℃ to form a metal element-doped Ni-based layered double-metal hydroxide nanosheet array and further form an electrode material layer;
and forming a polymer electrolyte material at least on the surface of the electrode material layer and between the first micro-polar plate and the second micro-polar plate, and forming an electrolyte layer after solidification.
Further, the manufacturing method specifically comprises the following steps: and coating the carbon-based material dispersion liquid with the solubility of 1-10 wt% on the surface of the template, and then drying to form the carbon-based material conductive film with the continuous interconnection structure.
Further, the manufacturing method specifically comprises the following steps: and removing the carbon-based material conductive film on the surface of the template except the patterned groove by adopting a mechanical stripping mode, so that the carbon-based material conductive film in the first groove and the second groove is remained.
Further, the element M comprises any one of iron, copper, vanadium, zinc, molybdenum and tin, and the element N comprises any one of cobalt, manganese and aluminum.
Furthermore, the molar ratio of the element M, Ni to the element N is 1: 10: 0-1: 0: 10.
Further, the metal salt solution includes any one or a combination of two or more of iron nitrate, copper nitrate, vanadium nitrate, zinc nitrate, molybdenum nitrate, tin nitrate, cobalt nitrate, manganese nitrate, aluminum nitrate, nickel nitrate, ferric sulfate, copper sulfate, vanadium sulfate, zinc sulfate, molybdenum sulfate, tin sulfate, cobalt sulfate, manganese sulfate, aluminum sulfate, nickel sulfate, ferric chloride, copper chloride, vanadium chloride, zinc chloride, molybdenum chloride, tin chloride, cobalt chloride, manganese chloride, aluminum chloride, and nickel chloride, but is not limited thereto.
Further, the solution containing ammonium ions and hydroxide ions comprises NH4Cl/NaOH solution, said NH4The mol ratio of Cl to NaOH is 4: 0.5-4: 0.2.
Further, the polymer electrolyte material includes an aqueous solution of any one or a combination of two or more of polyvinyl alcohol-potassium hydroxide, polyvinyl alcohol-sodium hydroxide, polyvinyl alcohol-lithium chloride, polyvinyl alcohol-potassium chloride, polyvinyl alcohol-sodium sulfate, polyvinyl alcohol-potassium sulfate, and the like, but is not limited thereto.
Further, the manufacturing method further comprises the following steps: and electrically combining the current collector layers on the surfaces of the first and second micro-polar plates with one end of at least one electrode wire respectively, and leading the other end of the electrode wire out of the surface of the current collector layer.
Furthermore, the depth of the first groove and the second groove is 10-50 μm, the width is 5-20 μm, the number of spiral turns is 10-50 turns, and the distance between the first groove and the second groove is greater than 30 μm and less than or equal to 100 μm.
Compared with the prior art, the utility model has the advantages that:
1) the utility model discloses a flexible miniature energy storage device based on substrate/graphite alkene/ternary layered hydroxide integrated electrode that provides in a typical embodiment directly realizes the adjustable continuous micro-nano structure of appearance (namely the microelectrode plate) at flexible substrate surface, helps providing quick electron/ion transport passageway and widens the work potential window; meanwhile, the low-temperature growth of the ternary layered double-metal hydroxide array avoids damage to the flexible substrate, and the specific capacitance value is improved while the miniaturization advantage of the device is maintained;
2) the carbon-based material film is used as a current collector and a ternary layered double-metal hydroxide array in-situ growth carrier, a stable and continuous three-dimensional integrated structure can be formed between the flexible substrate and the active substance, the mechanical stability of the electrode can be enhanced, the high-current rate performance is improved, and the stability of the cycle performance is maintained; 3) the current collector layer and the ternary layered double-metal hydroxide array are both active materials, and the synergistic energy storage effect between the active materials is favorable for accelerating electrode reaction, so that the energy density is improved;
4) the utility model relates to a flexible miniature energy storage device based on substrate/graphite alkene ternary layered hydroxide integrated electrode that provides in typical embodiment has characteristics such as frivolous, soft, has wearable, can paste the advantage that applies, and integration interface structure can give the high stable characteristic of device performance under continuous bending/flexible condition, can realize energy supply application in the aspect of flexible/wearable electron.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1a is a schematic structural diagram of a micro-electrode plate on a flexible substrate of a flexible micro energy storage device based on a substrate/graphene/ternary layered hydroxide integrated electrode according to an exemplary embodiment of the present invention;
fig. 1b is a schematic cross-sectional structure diagram of a flexible micro energy storage device based on a substrate/graphene/ternary layered hydroxide integrated electrode according to an exemplary embodiment of the present invention;
fig. 2a and fig. 2b are electron microscope images of an integrated electrode based on a substrate/graphene/ternary layered hydroxide according to an exemplary embodiment of the present invention;
fig. 3 is a schematic diagram of electrochemical specific capacitance values of a flexible micro energy storage device based on a substrate/graphene/ternary layered hydroxide integrated electrode according to an exemplary embodiment of the present invention.
Detailed Description
In view of the deficiencies in the prior art, the inventor of the present invention has made extensive studies and practices to provide the technical solution of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
At present, the research on the flexible micro-supercapacitor is mainly carried out on the aspect of electrode materials, for example, the flexible micro-supercapacitor is constructed by depositing polyaniline active materials on the surface of a flexible film after etching a fork-shaped microstructure on the flexible film by utilizing photoetching, but generally speaking, the mutual compromise and coordination of the morphology of the device, the materials, the current collector and the overall structure between the substrate from the viewpoint of system integration and system optimization are lacked, the performance of the flexible micro-supercapacitor is improved by constructing an integrated electrode, electrode materials (influencing energy density core factors), a flexible micro-structure substrate (optimizing ion transfer efficiency and expanding a working voltage window) and an integral structure (influencing impedance and circulation/bending stability) related to the integrated structure are reasonably selected and designed, the high performance of the flexible micro-capacitor is realized, and related research and engineering technologies still belong to the initial stage.
The integral optimization of the structure of the energy storage device needs to consider the mutual fusion among the electrode material, the current collector and the flexible substrate, and the flexible integrated electrode is constructed by combining the three materials into one through adopting the integral structural design, so that the method is a new method for optimizing the impedance and the stability of the micro capacitor.
Compared with carbon materials and conductive polymers, the Ni-based layered composite Hydroxides (LDHs) in the pseudo-capacitor material have higher theoretical specific capacitance value (more than 3000F/g) and relatively rich resources and low price due to the fact that two energy storage mechanisms (interlayer double-layer capacitors and Faraday pseudo-capacitors of transition metal elements on the laminates) can be simultaneously utilized, and the method is an important research direction of electrode materials. However, when the powder LDHs is directly used for constructing a flexible electrode, the specific surface area is greatly reduced due to the mutual aggregation of particles, which is not favorable for ion transmission diffusion and electrode reaction kinetics, and the specific capacitance and the cycle performance are low. In order to improve the performance of Ni-based LDHs flexible capacitors, the method for constructing a nanosheet array through in-situ growth is a main research idea at present. The high specific surface area and the short ion diffusion channel characteristic of the nanosheet array accelerate the electrode reaction kinetics and improve the utilization rate of active substances; meanwhile, the nano structure can effectively relieve volume expansion and inhibit pulverization, so that the cycle performance is improved; in addition, the defect of reduction of a specific surface and a conductive network caused by addition of a non-conductive adhesive and the like can be avoided by realizing an integrated structure through in-situ growth. However, due to the fact that methods such as hydrothermal reaction and the like are commonly adopted for preparing LDHs materials with special shapes, flexible substrates such as polydimethylsiloxane/polyimide (PDMS/PI) and the like cannot bear high-temperature and high-pressure conditions, and due to the fact that LDHs arrays directly grow on inert surfaces of current collectors such as Ag/Au/Pt and the like commonly used for flexible capacitors, and the like have certain difficulty, although Ni-based LDHs materials are gradually developed in recent years, the Ni-based LDHs materials are mainly applied to the aspects of hard substrates or super capacitors with sandwich structures, so far, Ni-based LDHs nanosheet arrays are introduced into flexible micro super capacitor integrated electrodes for construction, and researches on the aspects of performance relations and influence mechanisms of the Ni-based LDHs. On the other hand, the pseudocapacitance material is mainly a semiconductor or an insulator, the performance of the pseudocapacitance material is limited to be further improved due to poor conductivity, and the electronic load capacity and the charge and discharge stability of the pseudocapacitance material can be improved by deeply improving the conventional electrode by doping elements with good conductivity in the preparation process. Therefore, the controllable preparation of the nano-sheet array of the novel ternary Ni-based LDHs electrode material on the surface of the flexible substrate is realized under mild conditions by selecting elements matched with the lattice structure of the LDHs for doping, thereby providing guarantee for obtaining the flexible micro-supercapacitor with high energy density and stability,
in addition, in order to improve the transfer efficiency of electrolyte ions among active materials, fully utilize the height space for energy storage and exert the excellent electrochemical performance of the nanosheet array, the microstructure flexible substrate grown in situ of the ternary LDHs array is optimally designed, and the method is a new idea for further improving the performance of the integrated electrode-based flexible micro-supercapacitor. The current micro capacitor structure implementation modes mainly include two types: one method is to construct a microstructure on a hard substrate and then assemble the microstructure and an electrode material into a device. Although the design can meet the harsh preparation conditions of materials and utilize the microstructure to improve the ion transfer efficiency, the application of the hard substrate in the aspect of flexible devices is limited. And secondly, the electrode material is microstructured and then assembled with the flexible substrate to form a device. Although the flexible substrate is adopted in the design, the micro-structured electrode material actually participates in electrode reaction, and the ion transfer utilization efficiency is similar to that of a common sandwich structure and is lower. The series-parallel connection is realized through the design of the internal microstructure of the device, which is a new measure for solving the problem, but the current reported capacitor microstructure mainly takes discontinuous structures such as 'fork teeth', a cuboid/cylinder array and the like as the main parts, and the direct series-parallel connection design requirements are difficult to meet. Therefore, the flexible micro-supercapacitor is constructed by the method, the problems of simple microstructure design, insufficient space utilization rate and the like of the surface of the flexible substrate exist, so that a continuous microstructure with controllable depth-to-width ratio and series-parallel connection is directly constructed on the surface of the flexible substrate, the influence rule of microstructure regulation on the active site utilization rate and ion transfer efficiency of an electrode material is analyzed, and the method is a feasible way for improving the energy density of the flexible micro-supercapacitor.
Referring to fig. 1 a-1 b, a flexible micro supercapacitor based on a substrate/graphene/ternary layered hydroxide integrated electrode according to an exemplary embodiment of the present invention includes a flexible substrate, an electrode disposed on a surface of the flexible substrate, and an electrolyte layer at least distributed between the two electrodes;
the electrode comprises a micro-polar plate 11 arranged on the surface of a flexible substrate 10, a current collector layer 20 arranged on the surface of the micro-polar plate 11 and an electrode material layer 30 arranged on the surface of the current collector layer, wherein the micro-polar plate 11 comprises a first micro-polar plate and a second micro-polar plate which are respectively provided with a first spiral structure and a second spiral structure, and the first spiral structure and the second spiral structure are matched to form a three-dimensional double-spiral micro-nano structure; the electrolyte layer 40 is disposed on the surface of the electrode material layer 30 and between at least two electrodes, and the spiral structure ensures that all active materials can be sufficiently subjected to the ion exchange reaction (i.e., electrochemical reaction) in a face-to-face manner;
specifically, the micro-polar plate 11 and the flexible substrate 10 are of an integral structure, the height of the first micro-polar plate and the height of the second micro-polar plate are 10-50 μm, the width of the first micro-polar plate is 5-20 μm, the number of spiral turns is 10-50 turns, and the distance between the first micro-polar plate and the second micro-polar plate is larger than 30 μm and smaller than or equal to 100 μm.
Specifically, the current collector layer 20 is directly formed on the surface of the micro-electrode plate 11, and forms a continuous integrated interface structure with the surface of the flexible substrate 10, and the current collector layer includes a carbon-based material conductive film having a continuous interconnection structure; the electrode material layer 30 comprises a metal element doped Ni-based layered double-metal hydroxide nanosheet array, grows on the surface of the current collector layer in situ, and forms a continuous and stable interface shape with the current collector layer; specifically, the flexible substrate, the micro-polar plate, the current collector layer and the electrode material layer form an integrated structure.
Specifically, the manufacturing method of the flexible micro supercapacitor based on the substrate/graphene/ternary layered hydroxide integrated electrode comprises the following steps:
s1, manufacturing a silicon template with a patterned groove structure by using a mask and photoetching technology, wherein the patterned groove structure comprises a first groove and a second groove which are respectively provided with a first spiral structure and a second spiral structure, the first spiral structure and the second spiral structure are matched to form a three-dimensional double-spiral micro-nano structure, the depth of the first groove and the second groove is 10-50 mu m, the width of the first groove and the second groove is 5-20 mu m, the number of spiral turns is 10-50 turns, and the distance between the first groove and the second groove is larger than 30 mu m and smaller than or equal to 100 mu m;
s2, fixing the silicon template on a hot plate, heating at the constant temperature of 55-85 ℃, and spraying ethanol dispersion liquid of a carbon-based material with the solubility of 1-10 wt% on the surface of the silicon template to form a carbon-based material continuous conductive film; then stripping the carbon-based material conductive film on the surface of the template except the patterned groove by adopting mechanical force, and taking the carbon-based material conductive film remained in the first groove and the second groove as a current collector layer; the carbon-based material comprises any one or combination of more than two of graphene, carbon nano tubes, conductive carbon black and amorphous carbon, and can be used as a current collector and an active substance as a capacitor material;
s3, spin-coating a flexible substrate material prepolymer on the surface of a silicon template with a patterned groove structure, placing the flexible substrate material prepolymer in an oven, heating the flexible substrate material prepolymer at 60-85 ℃ for 1-3 hours, and curing the flexible substrate material prepolymer to form a flexible substrate, and then stripping the cured flexible substrate and the carbon-based material conductive film from the silicon template; the flexible substrate material prepolymer distributed in the patterned groove structure is solidified to form a first micro-polar plate and a second micro-polar plate, the first micro-polar plate and the second micro-polar plate are respectively provided with a first spiral structure and a second spiral structure, the height of the first micro-polar plate and the height of the second micro-polar plate are 10-50 mu m, the width of the first micro-polar plate and the width of the second micro-polar plate are 5-20 mu m, the number of spiral turns is 10-50 circles, and the distance between the first micro-polar plate and the second micro-polar plate is larger than 30 mu m and smaller than or equal to 100 mu m; the carbon-based material conductive film is arranged on the surfaces of the first micro-polar plate and the second micro-polar plate and forms a continuous interface structure with the flexible substrate;
s4, the flexible substrate-current collector layer composite system obtained in the step S3 is immersed downwards at a certain angle into a metal salt aqueous solution doped with Ni elements, M and/or N elements and NH with certain solubility4Cl/NaOH solution (NH)4Cl and NaOH react with each other to generate weak base NH4OH, then reacting weak base with metal salt to generate double metal hydroxide precipitate; wherein the ammonium ion can also be derived from NH4)2SO4、NH4NO3(ii) a The hydroxide ions can also be from KOH, NaOH, LiOH; the NH4The Cl/NaOH solution is in very excess, for example: 25mL of NH4Adding 750 mu L of 1M metal salt aqueous solution into Cl/NaOH solution), standing at 25-75 ℃ for reaction for 3-25 h, taking out, washing and other post-treatments to obtain a metal element-doped Ni-based layered double-metal hydroxide nanosheet array as an electrode material layer, and further constructing a flexible substrate/current collector layer/metal element-doped Ni-based layered double-metal hydroxide nanosheet array flexible integrated electrode, wherein an electron microscope image of the flexible integrated electrode is shown in FIGS. 2a and 2 b; wherein, the element M includes any one of iron, copper, vanadium, zinc, molybdenum and tin, the element N includes any one of cobalt, manganese and aluminum, the molar ratio of the element M, Ni to the element N is 1: 10: 0-1: 0: 10, the metal salt solution includes any one of iron nitrate, copper nitrate, vanadium nitrate, zinc nitrate, molybdenum nitrate, tin nitrate, cobalt nitrate, manganese nitrate, aluminum nitrate, nickel nitrate, ferric sulfate, copper sulfate, vanadium sulfate, zinc sulfate, molybdenum sulfate, tin sulfate, cobalt sulfate, manganese sulfate, aluminum sulfate, nickel sulfate, iron chloride, copper chloride, vanadium chloride, zinc chloride, molybdenum chloride, tin chloride, cobalt chloride, manganese chloride, aluminum chloride and nickel chloride, or a combination of two or more thereof, but not limited thereto, the NH4The mol ratio of Cl to NaOH is 4: 0.5-4: 0.2; the Ni-based layered double-metal hydroxide has the highest theoretical specific capacitance value, the specific capacitance value of the Ni-based layered double-metal hydroxide exceeds 3000F/g, and other materials such as metal oxide 1500F/g, polymer 200F/g, carbon material 200F/g and the like cannot reach the high value, so the material can be selected for the device to obtain the highest specific capacitance value; using a nanosheet arrayActive sites of active substances can be fully exposed, so that the performance of the device is fully close to a theoretical value;
s5, spin-coating the prepared polymer electrolyte material on the surface of the flexible integrated electrode, and curing for 3-6 hours in an indoor environment to form an electrolyte layer; the polymer electrolyte layer material comprises an aqueous solution of any one or a combination of more than two of polyvinyl alcohol-potassium hydroxide, polyvinyl alcohol-sodium hydroxide, polyvinyl alcohol-lithium chloride, polyvinyl alcohol-potassium chloride, polyvinyl alcohol-sodium sulfate, polyvinyl alcohol-potassium sulfate and the like;
s6 leading out electrode wires on the surface current collector layers of the first and second micro-polar plates respectively; and the electrode wire and the current collector layer are adhered by conductive silver paste, so that the flexible micro capacitor with the complete integrated structure is obtained.
Example 1: a manufacturing method of a flexible micro supercapacitor based on a substrate/graphene/ternary layered hydroxide integrated electrode comprises the following steps:
ultrasonically cleaning a silicon template with a double-spiral groove structure (namely the patterned groove structure, the same below) prepared by a mask, photoetching and etching method for 3 times by using deionized water and ethanol/acetone respectively, and then drying, wherein the double-spiral groove structure comprises a first groove and a second groove which are respectively provided with a first spiral structure and a second spiral structure, the first spiral structure and the second spiral structure are matched to form a three-dimensional double-spiral micro-nano structure, the depth of the first groove and the second groove is 25 mu m, the width of the first groove and the second groove is 15 mu m, the number of spiral turns is 30 circles, and the distance between the first groove and the second groove is 70 mu m;
fixing the dried silicon template on a heating plate, heating at 85 ℃, spraying a prepared graphene/ethanol dispersion liquid with the solubility of 1.5 wt% on the surface of the template, forming a graphene interconnected network conductive film (which can be referred to as a graphene conductive film for short) on the surface of the silicon template after ethanol is volatilized, removing the graphene conductive film in an area outside the double-spiral groove structure in a mechanical stripping manner, and only remaining the graphene conductive film at the inner side wall and the bottom of the double-spiral groove structure, namely a current collector layer;
spin-coating a Polydimethylsiloxane (PDMS) prepolymer on the surface of the silicon template, placing the silicon template in an oven at 80 ℃ for heating and curing for 2 hours, and then stripping the cured PDMS from the surface of the silicon template to prepare the flexible substrate with the graphene current collector (namely the graphene conductive film or current collector layer) on the surface and the double-spiral-structure micro-electrode plate; the double-spiral-structure micro-polar plate is formed by solidifying polydimethylsiloxane distributed in the double-spiral groove structure, the double-spiral-structure micro-polar plate (which can be called as a micro-polar plate for short) comprises a first micro-polar plate and a second micro-polar plate which are respectively provided with a first spiral structure and a second spiral structure, the micro-polar plates are integrally formed on the surface of a flexible substrate, and a graphene current collector is formed on the surfaces of the first micro-polar plate and the second micro-polar plate;
on the basis, a low-temperature coprecipitation in-situ growth method is adopted, iron element doped ferric nitrate, nickel nitrate and cobalt nitrate metal salt aqueous solution with the molar ratio of 1: 5: 4 is prepared, then the graphene coating on the surface of the flexible substrate is downwards immersed into the solution at an angle of 45 degrees, and NH with the solubility ratio of 4: 1.5 is added into the solution4A Cl/NaOH solution is kept stand and reacts for 12 hours at the temperature of 55 ℃, and then taken out, and the flexible substrate-graphene-iron doped Ni/Co layered double hydroxide nanosheet array novel flexible integrated electrode is obtained after post-treatment such as ethanol/deionized water washing;
after two electrode wires are led out from the surface of a current collector, the novel flexible integrated electrode of the flexible substrate-graphene-iron doped Ni/Co layered double hydroxide nanosheet array is fixed on a spin coater, a polyvinyl alcohol/potassium hydroxide dispersion liquid is spin-coated on the flexible substrate, and is solidified for 3 hours at room temperature for forming, further preparing a flexible micro supercapacitor based on a substrate/graphene/ternary layered hydroxide integrated electrode, the obtained flexible miniature super capacitor based on the substrate/graphene/ternary layered hydroxide integrated electrode is subjected to performance test, the electrochemical specific capacitance value of the flexible micro supercapacitor based on the substrate/graphene/ternary layered hydroxide integrated electrode is shown in fig. 3, and the capacitance value can reach 160F/cm.2The above.
Comparative example 1
The manufacturing method of the flexible micro supercapacitor in the comparative example 1 is basically the same as that in the example 1, except that the comparative example 1 is used for manufacturing a microelectrode plate with an insertion finger structure on a flexible substrate, and manufacturing a graphene conductive film on the surface of the microelectrode plate with the insertion finger structure, so as to form a current collector layer; then, referring to the steps in the embodiment 1, the flexible micro super capacitor is manufactured, and the performance of the obtained flexible micro super capacitor is tested, wherein the specific capacitance value of the flexible micro super capacitor is 50-100F/cm-2In the meantime.
Comparative example 2
The manufacturing method of the flexible micro supercapacitor in the comparative example 2 is basically the same as that in the example 1, except that the comparative example 2 adopts common metals such as Ag/Au/Ni as current collectors, and then the flexible micro supercapacitor is obtained.
The nanosheet array cannot be directly grown on the surface of the Ag/Au, and the current collector layer can crack under the flexible condition of metal, so that the performance of the device is directly disabled under the flexible condition; and, the metal current collector itself has no activity, does not contribute to the specific capacitance value of the capacitor; in addition, the flexibility of the material such as michaene (MXene) is poor, and although the material has activity, the interfacial peeling is easy to occur in the process of bending the device, so that the device fails, and the specific capacitance value of the capacitor obtained in comparative example 2 is low.
Comparative example 3
The manufacturing method of the flexible micro supercapacitor in comparative example 3 is substantially the same as that of example 1, except that comparative example 3 employs Ni-based double hydroxide powder as an electrode material layer, thereby obtaining a flexible micro supercapacitor.
The Ni-based double hydroxide is directly used in a powder form, the theoretical performance of the Ni-based double hydroxide is difficult to exert, active sites cannot be fully contacted with electrolyte due to powder agglomeration, the quantity of active materials participating in electrochemical reaction is reduced, and the specific capacitance value of the capacitor obtained in comparative example 3 is low.
The utility model discloses a flexible miniature energy storage device based on substrate/graphite alkene/ternary layered hydroxide integrated electrode that provides in a typical embodiment directly realizes the adjustable continuous micro-nano structure of appearance (namely the microelectrode plate) at flexible substrate surface, helps providing quick electron/ion transport passageway and widens the work potential window; meanwhile, the low-temperature growth of the ternary layered double-metal hydroxide array avoids damage to the flexible substrate, and the specific capacitance value is improved while the miniaturization advantage of the device is maintained; the carbon-based material film is used as a current collector and an in-situ growth carrier of the ternary layered double-metal hydroxide array, a stable and continuous three-dimensional integrated structure can be formed between the flexible substrate and the active substance, the mechanical stability of the electrode can be enhanced, the high-current rate performance is improved, and the stability of the cycle performance is maintained; and the current collector layer and the ternary layered double-metal hydroxide array are both active materials, and the synergistic energy storage effect between the active materials is favorable for accelerating the electrode reaction, so that the energy density is improved.
The utility model relates to a flexible miniature energy storage device based on substrate/graphite alkene ternary layered hydroxide integrated electrode that provides in typical embodiment has characteristics such as frivolous, soft, has wearable, can paste the advantage that applies, and integration interface structure can give the high stable characteristic of device performance under continuous bending/flexible condition, can realize energy supply application in the aspect of flexible/wearable electron.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and to implement the present invention, and therefore, the protection scope of the present invention should not be limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered by the protection scope of the present invention.
Claims (15)
1. A flexible micro energy storage device is characterized by comprising a flexible substrate and a plurality of electrodes, wherein the electrodes are arranged on the surface of the flexible substrate, and an electrolyte layer is distributed between any two adjacent electrodes;
the electrode comprises a micro-polar plate arranged on the surface of a flexible substrate, a current collector layer arranged on the surface of the micro-polar plate and an electrode material layer arranged on the surface of the current collector layer, the micro-polar plate comprises a first micro-polar plate and a second micro-polar plate, the first micro-polar plate and the second micro-polar plate are respectively provided with a first spiral structure and a second spiral structure, and the first spiral structure and the second spiral structure are matched to form a three-dimensional double-spiral micro-nano structure.
2. The flexible micro energy storage device of claim 1, wherein: the height of the first micro-polar plate and the second micro-polar plate is 10-50 mu m, the width of the first micro-polar plate and the second micro-polar plate is 5-20 mu m, the number of spiral turns is 10-50 turns, and the distance between the first micro-polar plate and the second micro-polar plate is larger than 30 mu m and smaller than or equal to 100 mu m.
3. The flexible micro energy storage device of claim 1, wherein: the current collector layer is directly formed on the surface of the micro-polar plate and forms a continuous integrated interface structure with the surface of the micro-polar plate.
4. The flexible micro energy storage device of claim 1 or 3, wherein: the current collector layer comprises a carbon-based material conductive film which is provided with a continuous interconnection structure.
5. The flexible micro energy storage device of claim 4, wherein: the carbon-based material conductive film comprises any one or combination of more than two of a graphene film, a carbon nanotube film, a conductive carbon black film and an amorphous carbon film.
6. The flexible micro energy storage device of claim 4, wherein: the thickness of the carbon-based material conductive film is 2-10 mu m.
7. The flexible micro energy storage device of claim 1, wherein: the electrode material layer comprises a metal element doped Ni-based layered double metal hydroxide nanosheet array.
8. The flexible micro energy storage device of claim 1, wherein: the electrode material layer grows on the surface of the current collector layer in situ and forms a continuous and stable interface shape with the current collector layer.
9. The flexible micro energy storage device of claim 1, wherein: the electrolyte layer includes a polymer electrolyte.
10. The flexible micro energy storage device of claim 1, wherein: the current collector layer is also provided with an electrode wire, one end of the electrode wire is electrically combined with the current collector layer, and the other end of the electrode wire is led out from the surface of the current collector layer.
11. The flexible micro energy storage device of claim 1, wherein: the flexible substrate and the micro-polar plate are of an integrated structure.
12. The flexible micro energy storage device of claim 1, wherein: the thickness of the flexible substrate is 20-300 mu m.
13. The flexible micro energy storage device of claim 1, wherein: the flexible substrate, the micro-polar plate, the current collector layer and the electrode material layer form an integrated structure.
14. The flexible micro energy storage device of claim 1, wherein: the thickness of the flexible micro energy storage device is 100-500 mu m.
15. The flexible micro energy storage device of claim 1, wherein: the flexible micro energy storage device comprises a flexible micro super capacitor.
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| CN111261420B (en) * | 2020-03-05 | 2023-10-31 | 中国科学院苏州纳米技术与纳米仿生研究所 | Flexible miniature energy storage device and manufacturing method thereof |
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