CN115171955B - Bionic multifunctional fiber composite material and multi-point flexible forming manufacturing method of component thereof - Google Patents
Bionic multifunctional fiber composite material and multi-point flexible forming manufacturing method of component thereof Download PDFInfo
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Abstract
The invention discloses a bionic multifunctional fiber composite material and a multipoint flexible forming manufacturing method of a component thereof. The manufacturing method of the component is to manufacture the composite material into the corresponding component by adopting the process of combining the bionic laying and the multi-point flexible forming of the composite material. The composite material disclosed by the invention has high energy storage capacity and strong mechanical property, so that the structural component can provide large current and large voltage, and thus, the commercial application is realized.
Description
Technical Field
The invention relates to the technical field of bionic composite materials, in particular to a bionic multifunctional fiber composite material and a multipoint flexible forming manufacturing method of a component of the bionic multifunctional fiber composite material.
Background
In recent years, in order to adapt to the development trend of light weight of transportation equipment such as automobiles or airplanes and the like and realize a series of green economic benefits such as lower oil consumption, higher transportation capacity and the like, alloy materials such as aluminum, steel and the like are replaced by light-weight and high-strength fiber reinforced resin matrix composite materials. On the basis, the energy storage element is integrated into the fiber reinforced resin matrix composite material through reasonable configuration and forming process, and multifunctional integrated composite materials including bearing, energy storage and members, namely the structural energy storage composite material, are developed, so that the method becomes an important direction for development of the technical field of composite materials.
Currently, although some conceptual documents about structural energy storage composites have been published, the following major problems still face: the energy storage density is low; the cycle life is short; potential safety hazards exist in the use of organic and flammable electrolyte; structural design strategies that can provide large currents and voltages are lacking; there is no mature method for forming and manufacturing large-sized multi-shaped structural components. In summary, there is currently no multifunctional integrated composite that combines high energy storage capacity with robust mechanical properties, is comparable to commercial carbon composites, and can be commercially applied in the fields of vehicle technology and aerospace.
Through further research and development, researchers find that structures of some organisms in the nature have special performances such as large current, large voltage discharge and the like in the process of bionics research, wherein the special performances include: as shown in figure 1a, the discharge organ of electric eel is formed by stacking thousands of lamellar muscle cells with asymmetric cell membrane structures in series, as shown in figure 1b, wrapped by connective tissues into a row, and connected in parallel at the head and tail, as shown in figure 1c, and has high voltage discharge performance; as shown in fig. 2a, the discharge organ of raja, which is a hexagonal columnar tube formed by stacking in parallel an "electric plate" composed of a piece of muscle fiber tissue separated by an insulating colloid substance, has a strong current discharge performance as shown in fig. 2 b.
The bionic method is used for simulating the biological structural characteristics of electric fishes such as the electric eels, the electric rays and the like, and provides a good idea for the structure and the laying and laminating mode of the multifunctional integrated fiber composite material.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a bionic multifunctional fiber composite material and a multipoint flexible forming manufacturing method of a component thereof, so that the composite material has high energy storage capacity and strong mechanical property, and a structural part can provide large current and large voltage, thereby realizing commercial application.
The technical scheme of the invention is as follows by combining the attached drawings of the specification:
on one hand, the invention discloses a bionic multifunctional fiber composite material, which consists of fiber reinforced resin-based coating layers respectively paved at the top and the bottom and a large-area functional core layer paved in the middle, and is characterized in that:
the large-area functional core layer is formed by connecting a plurality of structural energy storage unit cells through conducting circuits and then laying the structural energy storage unit cells on insulating fibers, wherein the structural energy storage unit cells are sequentially connected in series through the conducting circuits to form a plurality of series-connected units, and the plurality of series-connected units are connected in parallel.
Further, the structural storage unit cell comprises: a carbon fiber negative electrode, a solid electrolyte and a carbon fiber positive electrode which are sequentially stacked; wherein:
the carbon fiber negative electrode is a negative electrode pad formed by uniformly depositing high-capacity metal particles on carbon fibers;
the solid electrolyte is a three-dimensional porous structure electrolyte formed by mixing a gel organic polymer, an alkali metal ion conductive phase and epoxy resin;
the carbon fiber positive electrode is a positive electrode pad formed by uniformly coating a positive active material on carbon fibers.
Further, the high capacity metal particles are lithium, sodium, zinc, magnesium, aluminum, or iron particles;
the mass percentage of the high-capacity metal particles in the carbon fiber negative electrode is 8-16%, and the density of the high-capacity metal particles distributed on the surface of the carbon fiber is 1.2-2.4g/cm 3 ；
The thickness of the solid electrolyte is 20-300 mu m;
the gel organic polymer is one or more of polyvinyl alcohol, polyacrylamide, polyacrylic acid, polyethylene oxide and polyethylene glycol-diglycidyl ether;
the alkali metal ion conductive phase is one or more of potassium hydroxide, sulfate, chloride and trifluoromethanesulfonate;
the positive active material is mixed slurry formed by mixing at least one active material of vanadium oxide, manganese oxide and Prussian blue analogue, a conductive auxiliary agent and an adhesive in proportion;
the positive active material accounts for 12-18% of the mass of the carbon fiber positive electrode, and the density of the positive active material distributed on the surface of the carbon fiber is 1.6-3.42g/cm 3 。
Further, the fiber reinforced resin-based coating layer is formed by infiltrating one or more of ultrahigh molecular weight polyethylene fiber, basalt fiber, carbon fiber, PBO fiber and aramid fiber with a resin-based polymer;
the resin-based polymer is a uniform mixed solution of resin and a curing agent;
the resin is a thermosetting resin comprising: at least one of epoxy resin, polyester resin, phenolic resin, melamine resin and furan resin;
the volume fraction of the fiber fabrics in the fiber reinforced resin-based coating layer is 40-65%.
Further, the gaps around the structural energy storage unit cells are filled with resin-based polymers.
Further, the insulating fiber is made of one or more of glass fiber, polyester fiber and Kevlar fiber.
Further, the conductive circuit is a conductive carbon fiber filament, a metal wire or a non-conductive fiber plated with a conductive film.
Further, the large-area functional core layer is a plurality of layers;
the multiple large-area functional core layers are stacked and connected in parallel, and the adjacent large-area functional core layers are arranged in the plane of the core layers at included angles.
On the other hand, the invention also discloses a multi-point flexible manufacturing method of the component of the bionic multifunctional fiber composite material, which comprises the following steps:
the method comprises the following steps: preparing a carbon fiber negative electrode: uniformly depositing high-capacity metal particles on the surface of the carbon fiber by a film forming method of magnetron sputtering ion plating and sputtering plating to prepare a carbon fiber negative electrode;
step two: preparing a solid electrolyte: completely dissolving the gel organic polymer, the alkali metal ion conductive phase and the epoxy resin in a mixed solution of distilled water and glycol according to a proportion, injecting the solution into a mold, and cooling to prepare a solid electrolyte;
step three: preparing a carbon fiber positive electrode: mixing a conductive active material, a conductive auxiliary agent and a binder in proportion to form mixed slurry, uniformly coating the ground slurry on a carbon fiber substrate, and drying to prepare a carbon fiber positive electrode;
step four: preparing structural energy storage unit cells: mixing and stirring industrial epoxy resin and a curing agent in proportion to prepare a resin-based polymer, sequentially superposing and arranging insulating fibers, carbon fiber negative electrodes, solid electrolytes, carbon fiber positive electrodes and the resin-infiltrated insulating fibers layer by layer on a mold sprayed with a release agent, and curing at normal temperature to prepare single structural energy storage unit cells;
step five: preparing a large-area functional core layer: firstly, orderly connecting a plurality of structural energy storage unit cells in series through conducting circuits to form a multi-cell series group; then, a plurality of rows of multi-cell series-connected groups are captured and arranged in parallel in the same plane, two ends of the multi-cell series-connected groups are connected in parallel through conducting circuits, and a positive conducting circuit and a negative conducting circuit are respectively led out, so that a structural energy storage single-cell combination circuit of a sheet-shaped muscle cell structure in the electric eel-imitating discharge organ is formed; finally, coating resin-based polymers on two surfaces of the insulating fibers and the gap positions around the structural energy storage unit cells;
step six: the method adopts a process of combining bionic laying of composite materials and multi-point flexible forming to carry out member forming and manufacturing of the multifunctional integrated fiber composite material of the artificial electric fish: firstly, coating a layer of polyurethane release agent on a soft female die of a multipoint flexible forming device; then, attaching and fixing a layer of fiber reinforced resin matrix coating layer on a soft female die, sequentially laying a certain number of large-area functional core layers in a stacking manner according to actual needs, and finally placing a layer of fiber reinforced resin matrix coating layer to form a prepared component layer structure; and finally, heating, pressurizing and curing the prepared component layer structure to finally obtain the large-size multi-shape electro-fish-imitating multifunctional integrated fiber composite component.
Further, in the sixth step, the multi-point flexible forming process is completed by adopting a multi-point flexible forming device;
the multi-point flexible forming device consists of a press machine, a multi-point punch, a soft female die and a containing frame; the multipoint punch head is composed of small punch heads arranged in an array mode, and corresponding die surfaces are formed on the top of the multipoint punch head by adjusting the relative height of each small punch head, so that the required forming profile configuration is obtained, and the multipoint punch head is used for obtaining the multi-shape component with stable deformation.
Compared with the prior art, the invention has the beneficial effects that:
1. the fiber composite material disclosed by the invention simultaneously combines high energy storage capacity and strong mechanical property, and a laminated and laid structure is designed by simulating the biological characteristic structures of the electric fishes including the electric eels and the electric rays, so that the energy storage device with the structure has high energy storage density and long cycle life while having light weight, high strength, high fracture toughness, impact resistance and damage resistance. In addition, the series-parallel bionic design can be carried out according to actual needs, and large current and large voltage are provided for the load.
2. In the fiber composite material, the designed structural energy storage unit cell uses the gel polymer electrolyte to replace the organic electrolyte, so that the risk of short circuit and fire caused by electrolyte leakage and the diaphragm puncture by dendrites is avoided, and the fiber composite material is safer and more stable; the composite material has excellent designability, and different types and quantities of fiber reinforced resins can be selected as base materials according to application requirements, so that the bearing strength of the composite material can be adjusted; the modified electrolyte can be optimized by adjusting the load material and the mass of the carbon fiber positive/negative electrode, so that the energy storage function of the composite material can be adjusted.
3. The manufacturing method of the fiber composite member adopts a process combining the bionic laying and laminating technology and multi-point flexible forming, improves the deformation stability of the multi-shape member, has the advantages of convenient manufacture, low cost and contribution to large-size multi-shape industrial production, and is suitable for commercial application.
4. When the fiber composite material component is applied as a shell of an automobile or a large airplane, a solar cell can be integrated on the surface, so that the storage device can be charged by utilizing light energy in the running process of the automobile or the large airplane, and the dependence on ground refueling or charging is avoided. Therefore, the application of the multifunctional integrated fiber composite material imitating the electric fish can be expanded to the fields of a plurality of future vehicle technologies and aerospace, such as commercial jet planes, military tanks, vehicle body armor and super soldiers, and the application range is extremely wide.
Drawings
FIG. 1a is a schematic diagram of the discharge organ of an electric eel;
FIG. 1b is an enlarged view of a portion A of FIG. 1 a;
FIG. 1c is an enlarged view of a portion of FIG. 1B at B;
FIG. 2a is a schematic view of the discharge organ of ray;
FIG. 2b is an enlarged view of a portion of FIG. 2a at C;
FIG. 3 is a schematic structural view of the multifunctional integrated fiber composite material for simulating an electric fish according to the present invention;
FIG. 4 is a schematic diagram of a structure of a structural energy storage unit cell in the fiber composite material of the present invention;
FIG. 5 is a schematic diagram of a series-parallel bionic laying connection structure of an imitating electric eel discharge organ of a structural energy storage unit cell in the fiber composite material.
FIG. 6 is a schematic diagram of CV curve of structural energy storage unit cells in the fiber composite material of the present invention.
FIG. 7 is a schematic view of the charge and discharge multiplying power of a structural energy storage unit cell under different current densities in the fiber composite material.
FIG. 8 is a schematic diagram showing the comparison of the current-voltage relationship between the structural energy storage unit cell and the large-area functional core layer in the fiber composite material of the present invention.
FIG. 9 is a schematic diagram showing a comparison of tensile stress-strain relationship between a structural energy storage unit cell and a conventional structural energy storage device in the fiber composite material of the present invention.
FIG. 10 is a schematic diagram of a comparison of three-point bending experiments between a structural energy storage unit cell and a conventional structural energy storage device in the fiber composite material of the present invention.
FIG. 11 is a schematic structural diagram of a multi-angle bionic laying-out lamination of a plurality of large-area functional core layers.
Fig. 12 is a schematic structural view of a multipoint flexible molding device adopted in the process of manufacturing the fiber composite member according to the present invention.
Fig. 13 is a schematic view of the integrated connection of the fiber composite material and the solar cell according to the present invention.
In the figure:
1-fiber reinforced resin-based coating layer 2-large-area functional core layer 3-structure energy storage unit cell
4-insulating fiber 5-conductive line 6-resin based polymer
7-carbon fiber negative electrode 8-solid electrolyte 9-carbon fiber positive electrode
10-press machine 11-multipoint punch 12-soft female die
13-container 14-load 15-solar cell.
Detailed Description
For clearly and completely describing the technical scheme and the specific working process thereof, the specific implementation mode of the invention is as follows by combining the drawings in the specification:
in the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the present invention, unless expressly stated or limited otherwise, the first feature "on" or "under" the second feature may be directly contacting the second feature or the first and second features may be indirectly contacting each other through intervening media. Also, a first feature "on," "above," and "over" a second feature may be directly on or obliquely above the second feature, or simply mean that the first feature is at a higher level than the second feature. A first feature "under," "beneath," and "under" a second feature may be directly under or obliquely under the second feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
The first embodiment is as follows:
the first embodiment discloses a bionic multifunctional fiber composite material, as shown in fig. 3, the fiber composite material is of a multilayer structure, wherein the top layer and the bottom layer of the fiber composite material are two fiber reinforced resin-based coating layers 1 which are arranged in parallel up and down, and the middle inside is a multilayer overlapped large-area functional core layer 2; the large-area functional core layer 2 includes: a plurality of structural energy storage unit cells 3 are connected through conducting circuits 4 and then are laid on insulating fibers 5, and gaps around the structural energy storage unit cells 3 are filled with resin-based polymers 6.
The fiber reinforced resin matrix coating layer 1 is formed by infiltrating one or more of ultra-high molecular weight polyethylene fibers, basalt fibers, carbon fibers, PBO fibers and aramid fibers with a resin matrix polymer. The resin-based polymer is a uniform mixed solution of resin and a curing agent, and the resin is thermosetting resin and comprises at least one of epoxy resin, polyester resin, phenolic resin, melamine resin and furan resin; the volume fraction of the fiber fabric in the fiber reinforced resin base coating layer 1 is 40-65%. In the first embodiment, the fiber-reinforced resin-based coating layer 1 is preferably a high-performance fiber cloth obtained by mixing ultra-high molecular weight polyethylene fibers and basalt fibers, and the resin-based polymer is preferably a fiber cloth with a volume ratio of 3:1 epoxy resin and curing agent.
The fiber reinforced resin-based coating layer 1 plays a role in protecting the large-area functional core layer 2 arranged in the middle, and the fracture resistance toughness and the mechanical strength of a device are improved, so that the damage resistance and the shock resistance are realized.
The structure of the large-area functional core layer 2 which is stacked in multiple layers is the biological structure of imitated electric eel and imitated electric ray. As shown in fig. 1a, 1b and 1c, the discharge organ of the electric eel is formed by stacking thousands of lamellar muscle cells with asymmetric cell membrane structures in series, is wrapped by connective tissues into a column, is connected in parallel at the head and the tail, and has high-voltage discharge performance; as shown in fig. 2a and 2b, the discharge organ of raja torpedo is a hexagonal columnar tube formed by stacking in parallel an "electric plate" composed of a piece of muscle fiber tissue separated by an insulating colloid substance, and has a strong current discharge performance.
The large-area functional core layer 2 includes: a plurality of structural energy storage unit cells 3 are connected through conducting circuits 4 and then laid on insulating fibers 5, and gaps around the structural energy storage unit cells 3 are filled with resin-based polymers 6.
The insulating fiber mat 5 includes one or more of glass fiber, polyester fiber, and kevlar fiber. The insulating fiber mat 5 made of the materials is used as a carrier for the series and parallel connection of the plurality of structural energy storage chips 3, and the insulating fiber mat 5 plays a role in electrical insulation between the adjacent large-area functional core layers 2.
The conductive line 4 is preferably a high-temperature resistant and stretch-resistant conductive carbon fiber filament.
As shown in fig. 4, the structural storage unit cell 3 includes: a carbon fiber negative electrode 7, a solid electrolyte 8, and a carbon fiber positive electrode 9; wherein:
the carbon fiber negative electrode 7 is a negative electrode pad formed by uniformly depositing high-capacity metal particles on carbon fibers in a physical vapor deposition or electrochemical deposition manner; the high-capacity metal particles are lithium, sodium, zinc, magnesium, aluminum or iron and other metal particles with the characteristic of high theoretical specific capacity. The high-capacity metal particles account for 8-16% of the carbon fiber negative electrode 7 by mass; the density of the high-capacity metal particles distributed on the surface of the carbon fiber is 1.2-2.4g/cm 3 。
The solid electrolyte 8 is a three-dimensional porous structure electrolyte formed by mixing a gel organic polymer, an alkali metal ion conductive phase and epoxy resin, and the thickness of the solid electrolyte 8 is 20-300 mu m; the gel organic polymer is one or more of polyvinyl alcohol (PVA), polyacrylamide (PAM), polyacrylic acid (PAA), polyethylene oxide (PEO), polyethylene glycol-diglycidyl ether (PEGDGE) and the like; the alkali metal ion conductive phase is one or more alkali metal salts such as potassium hydroxide, sulfate, chloride, trifluoromethanesulfonate, etc. The solid electrolyte 8 made of the material can inhibit dendritic crystal growth, and has high energy density, strong cycle performance and good safety.
The carbon fiber positive electrode 9 is a positive electrode pad formed by uniformly coating a positive electrode active material on the pretreated carbon fibers; the positive active material is made of vanadium oxide, manganese oxideAt least one active material of the compound, the Prussian blue analogue and the like, a conductive additive and a binding agent are mixed according to a certain proportion to form mixed slurry. The mass fraction of the positive active material in the carbon fiber positive electrode 9 is 12-18%; the density distributed on the surface of the carbon fiber is 1.6-3.42g/cm 3 。
As shown in fig. 4 and 5, in the structural energy storage unit cell 3, the carbon fiber negative electrode 7 and the carbon fiber positive electrode 9 are arranged in an up-and-down manner, and the solid electrolyte 8 is arranged between the carbon fiber negative electrode 7 and the carbon fiber positive electrode 9; the structure energy storage single cells 3 are sequentially connected in series through the conducting circuits 4 to form a multi-cell series group, a plurality of groups of the structure energy storage single cells form the multi-cell series group in parallel, in the first embodiment, three structure energy storage single cells 3 are connected in series to form the multi-cell series group, the head and the tail of the three groups of the multi-cell series group are connected in parallel and rectified to release large voltage and large current, a 1cm gap is reserved between the adjacent structure energy storage single cells 3, resin-based polymers such as epoxy resin are filled in the gap, the flow of current in a set design direction is guaranteed while insulation and isolation are achieved, and extra mechanical strength is provided while adhesion of adjacent devices is promoted. Two ends of the parallel multi-cell series group are led out of the anode of the large-area functional core layer 2 and the cathode of the large-area functional core layer 2 through the conducting circuits 4 respectively.
The shape and size of the structural energy storage unit cell can be designed at will, and the volume density and mass fraction of the structural energy storage unit cell and the resin-based polymer in the large-area functional core layer 2 are different, so that the occupation ratio of a charge storage area and an epoxy load area in the large-area functional core layer is different, and the difference between the electrochemical energy storage capacity and the mechanical bearing capacity is caused. Due to the anisotropy of the carbon fiber electrode, the size design of the structural energy storage unit cell is not suitable to be overlarge. The area of the structural energy storage unit cell is preferably 4cm multiplied by 6cm, the voltage range is 1.5-1.8V, and the current range is 30mA-40mA. According to the current and voltage required by the load 14, a plurality of structural energy storage unit cells 3 are designed on the insulating fiber mat 5 in series to obtain the required large voltage, and the parallel design obtains the required large current.
As shown in fig. 1a, 1b, 1c, 4 and 5, a plurality of the structural energy storage unit cells 3 follow the sheet-shaped muscle cells of the asymmetric cell membrane structure in the electric eel discharge organ; each group of structural storage cells 3 with the same shape and size is similar to a discharge cell of an electric eel: depositing carbon fiber positive electrodes and carbon fiber negative electrodes of different materials to imitate cell structures with asymmetric structural functions at two sides of the electric eel discharge cells so as to generate potential difference; the aqueous gel solid electrolyte rich in the anion and cation conductive phase imitates tissue internal liquid of eel discharge cells to play a role of an ion channel; the conducting circuit 4 connected among the plurality of structural energy storage unit cells 3 imitates nerve endings on electric eel discharge cells, is used for transmitting 'electric signals' and forms a plurality of cell series connection groups; the energy storage unit cells of a plurality of groups of structures connected in series are separated by certain gaps and are used for filling epoxy resin, and the two ends of the insulating fiber pad 5 are connected in parallel and rectified to release large voltage and large current, so that the discharge organs of the artificial electric eel are insulated and protected by connective tissues and discharge is completed at the head and the tail.
Fig. 6, fig. 7 and fig. 8 show that electrochemical performance tests show that the bionic structure energy storage unit cell shown in fig. 4 has a voltage of about 1.6V and good multiplying power performance; the voltage and current of the large-area functional core layer shown in fig. 5 are about three times of those of the structural energy storage unit cell, which shows that the bionic series-parallel design can obtain the required large voltage and large current.
Fig. 9 and fig. 10 show through a tensile test and a three-point bending test that compared with a conventional structural energy storage device, the bionic structural energy storage unit cell provided by the invention has good mechanical bearing capacity.
As shown in fig. 2a, 2b and 3, the stacked arrangement of the large-area functional core layer 2 is similar to the muscular fiber tissue structure of the electric organ of raja. Furthermore, depending on the actual requirements of the load 14, a certain number and shape of the functional core layers 2 can be designed to be stacked in parallel with each other, and even the adjacent functional core layers 2 can be rotated by an angle of 15 °, 30 ° or 45 ° in the plane (xy plane) of the core layer, as shown in fig. 11, to obtain more uniform directional strength.
In addition, as shown in fig. 13, in the first embodiment, the multifunctional integrated fiber composite material for artificial electric fish can be connected with the solar cell 15 to form an integrated device in the actual use process. This embodiment one bionical multi-functional integrated fibre combined material is as energy memory, and wherein, the positive pole of large tracts of land function sandwich layer 2 links to each other with solar cell's positive pole, and the negative pole of large tracts of land function sandwich layer 2 links to each other with solar cell's negative pole. The integrated device can be used as a structural component, has the multifunctional characteristics of light weight, mechanical bearing, ion energy storage and photoelectric storage, and can be applied to the fields of vehicle technology, aerospace and the like.
The second embodiment:
the second embodiment discloses a preparation method of a component of a bionic multifunctional fiber composite material, which comprises the following specific processes:
the method comprises the following steps: preparing a carbon fiber negative electrode: adopting an FJ-S type magnetron sputtering film plating machine, using 99.99% of cylindrical metal blocks as a target material, and using high-strength carbon fibers as a matrix; uniformly depositing high-capacity metal particles such as lithium, sodium, zinc, magnesium, aluminum or iron and the like on the surface of the carbon fiber by a film forming method of magnetron sputtering ion plating and sputtering plating to prepare a carbon fiber negative electrode;
step two: preparing a solid electrolyte: dissolving gel organic polymer, alkali metal ion conductive phase and epoxy resin according to a certain proportion at the temperature of 85 ℃ and the volume ratio of 1:2, continuously stirring and completely dissolving the gel in a mixed solution of distilled water and Ethylene Glycol (EG), injecting the gel into a mold, and cooling the gel for about 20min at the temperature of below 20 ℃ to prepare a solid electrolyte;
step three: preparing a carbon fiber positive electrode: the preparation method comprises the following steps of mixing a conductive active material (comprising vanadium oxide, manganese oxide, prussian blue analogue and organic electrode material), a conductive auxiliary agent (such as carbon black and graphene) and a binder (preferably polyvinylidene fluoride (PVDF)) according to a mass ratio of 7:2:1, mixing to form mixed slurry, uniformly coating the ground slurry on a carbon fiber base material by using a four-side coater, and drying for 12 hours in a vacuum drying oven at 80 ℃ to prepare a carbon fiber positive electrode;
step four: preparing a structural energy storage unit cell: firstly, spraying a layer of polyvinyl alcohol film (PVA) on a clean mould, standing for 30min to serve as a release agent, and meanwhile, mixing industrial epoxy resin and a curing agent in a ratio of 3:1 for 20min to prepare a resin-based polymer, then sequentially stacking and laying the insulating fiber infiltrated by the resin-based polymer, the carbon fiber negative electrode, the solid electrolyte, the carbon fiber positive electrode and the insulating fiber infiltrated by the resin layer by layer on a mould, and curing at normal temperature for 24h to prepare a single structural energy storage unit cell, wherein the thickness of the single structural energy storage unit cell is about 2-3mm;
step five: preparing a large-area functional core layer: firstly, orderly connecting a plurality of structural energy storage unit cells in series through conducting circuits (such as conducting carbon fiber wires or copper foil strips) to form a multi-cell series group; then, capturing a plurality of rows of multi-cell series-connected groups in parallel in the same plane, connecting the two ends in parallel through a conducting circuit, and respectively leading out a positive conducting circuit and a negative conducting circuit to form a structural energy storage single-cell combined circuit of a sheet-shaped muscle cell structure in the imitation spot eel discharge organ; finally, coating a resin-based polymer at the position of a gap of 1cm left on the two sides of the insulating fiber mat and on the front side, the rear side, the left side and the right side of the structural energy storage unit cell, so that the current is ensured to flow according to a set design direction while insulating and isolating, and additional mechanical strength is provided while adhesion of adjacent devices is promoted;
step six: the method comprises the following steps of (1) adopting a process combining a composite material bionic laying technology and multipoint flexible forming, and forming and manufacturing a component of the electro-fish-imitated multifunctional integrated fiber composite material in a multipoint flexible forming device;
in the sixth step, as shown in fig. 12, the multi-point flexible forming device is composed of a 200t press 10, a multi-point punch 11, a soft female die 12 made of polyurethane with the hardness of 90A, and a containing frame 13; the multipoint punch 11 is composed of small punches arranged in an array manner, the ball head radius of each small punch is 8.5mm, and a corresponding die surface is formed at the top of each multipoint punch by adjusting the relative height of each small punch, so that a required forming profile configuration can be obtained to obtain a multi-shape member with stable deformation;
in the sixth step, the component molding manufacturing process is as follows:
firstly, coating a layer of polyurethane release agent on a soft female die of a multipoint flexible forming device;
then, attaching and fixing a layer of fiber reinforced resin matrix coating layer on a soft female die by using a mechanical loading or vacuum adsorption mode and the like, sequentially laying a certain number of large-area functional core layers in a laminated manner according to actual needs, and finally placing a layer of fiber reinforced resin matrix coating layer to form a prepared component layer structure;
and finally, heating, pressurizing and curing the prepared component layer structure for 24h to finally obtain the large-size and multi-shape component of the imitated electric fish multifunctional integrated fiber composite material.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A multi-point flexible forming manufacturing method of a component of a bionic multifunctional fiber composite material is characterized by comprising the following steps:
the preparation method of the component comprises the following steps:
the method comprises the following steps: preparing a carbon fiber negative electrode: uniformly depositing high-capacity metal particles on the surface of carbon fiber by a film forming method of magnetron sputtering ion plating and sputtering plating to prepare a carbon fiber negative electrode;
step two: preparing a solid electrolyte: completely dissolving the gel organic polymer, the alkali metal ion conductive phase and the epoxy resin in a mixed solution of distilled water and ethylene glycol according to a proportion, injecting the mixed solution into a mold, and cooling to prepare a solid electrolyte;
step three: preparing a carbon fiber positive electrode: mixing a conductive active material, a conductive auxiliary agent and a binder in proportion to form mixed slurry, uniformly coating the ground slurry on a carbon fiber substrate, and drying to prepare a carbon fiber positive electrode;
step four: preparing structural energy storage unit cells: mixing and stirring industrial epoxy resin and a curing agent in proportion to prepare a resin-based polymer, sequentially superposing and arranging insulating fibers, carbon fiber negative electrodes, solid electrolytes, carbon fiber positive electrodes and the resin-infiltrated insulating fibers layer by layer on a mold sprayed with a release agent, and curing at normal temperature to prepare single structural energy storage unit cells;
step five: preparing a large-area functional core layer: firstly, orderly connecting a plurality of structural energy storage unit cells in series through conducting circuits to form a multi-cell series group; then, a plurality of rows of multi-cell series-connected groups are captured and arranged in parallel in the same plane, two ends of the multi-cell series-connected groups are connected in parallel through conducting circuits, and a positive conducting circuit and a negative conducting circuit are respectively led out, so that a structural energy storage single-cell combination circuit of a sheet-shaped muscle cell structure in the electric eel-imitating discharge organ is formed; finally, coating resin-based polymer on two surfaces of the insulating fiber mat and the gap position around the structural energy storage unit cell;
step six: the method adopts a process of combining bionic laying of composite materials and multi-point flexible forming to carry out member forming and manufacturing of the multifunctional integrated fiber composite material of the artificial electric fish: firstly, coating a layer of polyurethane release agent on a soft female die of a multipoint flexible forming device; then, attaching and fixing a layer of fiber reinforced resin matrix coating layer on a soft female die, sequentially laying a certain number of large-area functional core layers in a stacking manner according to actual needs, and finally placing a layer of fiber reinforced resin matrix coating layer to form a prepared component layer structure; and finally, heating, pressurizing and curing the prepared component layer structure to finally obtain the large-size multi-shape electro-fish-imitating multifunctional integrated fiber composite component.
2. The multi-point flexible molding manufacturing method of the bionic multifunctional fiber composite material component as claimed in claim 1, characterized in that:
in the sixth step, the multi-point flexible forming process is completed by adopting a multi-point flexible forming device;
the multi-point flexible forming device consists of a press machine, a multi-point punch, a soft female die and a containing frame; the multipoint punch head is composed of small punch heads arranged in an array mode, and corresponding die surfaces are formed on the top of the multipoint punch head by adjusting the relative height of each small punch head, so that the required forming profile configuration is obtained, and the multipoint punch head is used for obtaining the multi-shape component with stable deformation.
3. The bionic multifunctional fiber composite material prepared by the method of claim 1, which consists of fiber reinforced resin-based coating layers respectively paved at the top and the bottom and a large-area functional core layer paved in the middle, and is characterized in that:
the large-area functional core layer is formed by connecting a plurality of structural energy storage unit cells through conducting circuits and then laying the structural energy storage unit cells on insulating fibers, wherein the structural energy storage unit cells are sequentially connected in series through the conducting circuits to form a plurality of series-connected units, and the plurality of series-connected units are connected in parallel.
4. The biomimetic multifunctional fiber composite according to claim 3, wherein:
the structural energy storage cell includes: a carbon fiber negative electrode, a solid electrolyte and a carbon fiber positive electrode which are sequentially stacked; wherein:
the carbon fiber negative electrode is a negative electrode pad formed by uniformly depositing high-capacity metal particles on carbon fibers;
the solid electrolyte is a three-dimensional porous structure electrolyte formed by mixing a gel organic polymer, an alkali metal ion conductive phase and epoxy resin;
the carbon fiber positive electrode is a positive electrode pad formed by uniformly coating a positive active material on carbon fibers.
5. The biomimetic multifunctional fiber composite according to claim 4, wherein:
the high-capacity metal particles are lithium, sodium, zinc, magnesium, aluminum or iron particles;
the mass percentage of the high-capacity metal particles in the carbon fiber negative electrode is 8-16%, and the density of the high-capacity metal particles distributed on the surface of the carbon fiber is 1.2-2.4g/cm 3 ；
The thickness of the solid electrolyte is 20-300 μm;
the gel organic polymer is one or more of polyvinyl alcohol, polyacrylamide, polyacrylic acid, polyethylene oxide and polyethylene glycol-diglycidyl ether;
the alkali metal ion conductive phase is one or more of potassium hydroxide, sulfate, chloride and trifluoromethanesulfonate;
the positive active material is mixed slurry formed by mixing at least one active material of vanadium oxide, manganese oxide and Prussian blue analogue, a conductive additive and an adhesive in proportion;
the positive active material accounts for 12-18% of the mass of the carbon fiber positive electrode, and the density of the positive active material distributed on the surface of the carbon fiber is 1.6-3.42g/cm 3 。
6. The biomimetic multifunctional fiber composite according to claim 3, wherein:
the fiber reinforced resin-based coating layer is formed by infiltrating one or more of ultra-high molecular weight polyethylene fibers, basalt fibers, carbon fibers, PBO fibers and aramid fibers with a resin-based polymer;
the resin-based polymer is a uniform mixed solution of resin and a curing agent;
the resin is a thermosetting resin comprising: at least one of epoxy resin, polyester resin, phenolic resin, melamine resin and furan resin;
the volume fraction of the fiber fabrics in the fiber reinforced resin-based coating layer is 40-65%.
7. The biomimetic multifunctional fiber composite according to claim 3, wherein:
and the gaps around the structural energy storage unit cells are filled with resin-based polymers.
8. The biomimetic multifunctional fiber composite according to claim 3, wherein:
the insulating fiber is made of one or more of glass fiber, polyester fiber and Kevlar fiber.
9. The biomimetic multifunctional fiber composite according to claim 3, wherein:
the conductive circuit is a conductive carbon fiber wire, a metal wire or a non-conductive fiber plated with a conductive film.
10. The biomimetic multifunctional fiber composite according to claim 3, wherein:
the large-area functional core layer is multilayer;
the multiple large-area functional core layers are stacked and connected in parallel, and the adjacent large-area functional core layers are arranged in the plane of the core layers at included angles.
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