CN115275308A

CN115275308A - Integrated forming device of flexible surface type solid-state battery and working method thereof

Info

Publication number: CN115275308A
Application number: CN202210963319.9A
Authority: CN
Inventors: 李绿洲; 丁建宁; 王茜; 董旭; 江瑶瑶; 曹晓婷
Original assignee: Yangzhou University
Current assignee: Yangzhou University
Priority date: 2022-08-11
Filing date: 2022-08-11
Publication date: 2022-11-01
Anticipated expiration: 2042-08-11
Also published as: CN115275308B

Abstract

The invention relates to the field of solid-state batteries, in particular to an integrated forming device of a flexible surface type solid-state battery, which comprises a first seat body, a second seat body and an adjusting device, wherein the first seat body is provided with a first groove; the first seat body is provided with a first groove, the second seat body is provided with a second groove, the bottom planes of the first groove and the second groove are arranged in parallel, and the distance between the bottom planes of the grooves is adjusted by the adjusting device; the first seat body and the second seat body are both of light-transmitting glass structures, the first seat body is provided with a liquid injection channel, and the outlet end of the liquid injection channel deviates from the position of the first groove and is positioned between the two seat bodies. The invention provides a device capable of integrally forming a flexible surface type solid-state battery, which solves the problem of insufficient interface contact caused by respectively solidifying and forming a counter electrode and a solid electrolyte and then assembling at present, thereby effectively reducing the interface impedance and improving the capacity, the multiplying power and the cycle life of the solid-state battery to a certain extent. The invention also claims a working method of the forming device.

Description

Integrated forming device of flexible surface type solid-state battery and working method thereof

Technical Field

The invention relates to the field of solid-state batteries, in particular to an integrated forming device of a flexible surface type solid-state battery and a working method thereof.

Background

With the progress of science and technology, high-flexibility, convenient, light and thin flexible wearable electronic equipment is the mainstream direction of the development of electronic products. In order to realize the wearability of the whole equipment, an energy storage device with high flexibility, light weight and small volume needs to be developed, and the surface type solid-state battery has great application potential and value in the fields of flexible intelligence, wearability and integrated electronic migration.

The flexible all-solid-state battery is prepared by mainly adopting the technology of making each component in the battery into flexibility, wherein each component comprises solid electrolyte, a current collector, an electrode and packaging materials. In most schemes, flexible conductive objects in a fabric-like shape and the like are selected as current collectors to construct flexible electrodes, and a sheet-shaped solid electrolyte is placed between the two electrodes to assemble the flexible surface type solid battery.

In the battery structure, the two flexible electrodes and the electrolyte are assembled after being in a solid state, so that the prepared flexible battery has the problems of insufficient contact between the electrodes and the solid electrolyte, large interface resistance and the like.

Disclosure of Invention

The invention mainly aims to provide an integrated forming device of a flexible surface type solid-state battery and a working method thereof, thereby effectively solving the problems in the background art.

In order to achieve the technical purpose, the invention adopts the following technical scheme:

the integrated forming device of the flexible surface type solid-state battery comprises a first seat body, a second seat body and an adjusting device;

the first seat body is provided with a first groove, the second seat body is provided with a second groove, the groove bottom planes of the first groove and the second groove are arranged in parallel, and the adjusting device is used for adjusting the distance between the first seat body and the second seat body;

the first seat body and the second seat body are both of light-transmitting glass structures, a liquid injection channel is arranged on the first seat body, and the outlet end of the liquid injection channel deviates from the position of the first groove and is located between the two seat bodies.

Furthermore, the first groove and the second groove are at least provided with a light-transmitting hydrophobic surface layer at the bottom plane position of the groove.

Further, the adjusting device comprises a first leading-out end, a second leading-out end and a distance adjusting component;

the first leading-out end is respectively connected with the first base body and the distance adjusting component;

the second leading-out end is respectively connected with the second seat body and the distance adjusting component;

the distance adjusting component drives the first seat body and the second seat body to perform relative linear motion through two leading-out ends.

Further, the distance adjusting assembly comprises an inner pipe body, an outer pipe body and a locking piece;

the inner pipe body and the outer pipe body are respectively connected with one of the leading-out ends, the outer pipe body is provided with a cavity, and the inner pipe body is inserted into the cavity and is attached to the inner wall of the cavity; the retaining member penetrates through the side wall of the cavity, and the inner pipe body is fixed relative to the insertion depth of the outer pipe body through extrusion of the inner pipe body.

Further, the distance adjusting assembly comprises a first adjusting seat, a second adjusting seat, a screw rod and a guide rod;

the first adjusting seat and the second adjusting seat are respectively connected with one of the leading-out ends;

at least one of the first adjusting seat and the second adjusting seat is provided with a threaded hole, the first adjusting seat and the second adjusting seat are in threaded connection with the screw rod through the threaded hole and move linearly in the rotating process of the screw rod, and the guide rod is arranged in parallel with the screw rod and guides the adjusting seat moving relative to the screw rod.

Further, the second seat body comprises a main body, a blocking block and a power end;

the main body is provided with a through area, and the plugging block is inserted into the through area and is in sealing fit with the side wall of the through area;

the blockout piece terminal surface with link up regional lateral wall and form jointly the second recess, the blockout piece is in link up the regional interior free motion of orientation of following through, the power end does the blockout piece provides motion power and/or for the blockout piece provides the orientation the extrusion force of second recess internal electrode.

Further, the second seat body inclines from the edge to the inside of the second groove towards the second end face of the first seat body;

the first base faces the first end face of the second base and is parallel to the second end face.

Furthermore, at least one row of the first grooves is arranged on the first seat body, and the second grooves are arranged on the second seat body in one-to-one correspondence with the first grooves;

each group of corresponding first groove and second groove is correspondingly provided with a liquid injection channel on the first seat body;

the liquid filling device further comprises a distribution device, wherein the distribution device is provided with an inlet and outlets which correspond to the liquid filling channels one to one, and the outlets are communicated with the liquid filling channels.

An operating method of the integrated forming device of the flexible surface type solid-state battery comprises the following steps:

placing the first base on the top, and placing a layer of electrode in the first groove;

at least one layer of electrode is placed in the second groove;

the electrodes of all layers are separated and arranged at intervals by an external structure, and at least partial areas in the grooves enable a separation space to be obtained between two adjacent layers of the electrodes;

adjusting the interval between the first seat body and the second seat body until the extrusion force on each electrode reaches a set value, and establishing a sealing area between the first seat body and the second seat body, wherein the sealing area surrounds the positions of the groove and the liquid injection channel;

injecting liquid electrolyte into a region surrounded by the first groove, the second groove and the sealing region through the liquid injection channel, wherein the liquid electrolyte enters between the electrodes of each layer through the space between the first seat body and the second seat body and the space between the electrodes of adjacent layers;

and irradiating the first base body and the second base body by ultraviolet light to solidify the liquid electrolyte.

An operation method of the integrated forming device of the flexible surface type solid-state battery comprises the following steps:

by moving the block, the second groove obtains a greater depth than actually required;

at least one layer of electrode is placed in the second groove;

the electrodes of all levels are separated and arranged at intervals by two opposite edges through external structures, the external structures are arranged in the area between the planes of the opposite groove bottoms, and an interval space is obtained between the external structures at two sides between two adjacent layers of the electrodes;

adjusting the interval between the first seat body and the second seat body to a set distance, and establishing a sealing area between the first seat body and the second seat body, wherein the sealing area surrounds the position of the groove and the position of the liquid injection channel;

the depth of the second groove is adjusted by moving the blocking block until the extrusion force on each electrode reaches a set value;

Through the technical scheme, the invention has the beneficial effects that:

the invention provides a device capable of integrally forming a flexible surface type solid-state battery, which solves the problem of insufficient interface contact caused by respectively solidifying and forming a counter electrode and a solid electrolyte and then assembling at present, thereby effectively reducing the interface impedance and improving the capacity, the multiplying power and the cycle life of the solid-state battery to a certain degree. The invention also claims a working method of the forming device.

The forming device can effectively regulate and control the thickness of the solid-state battery, and different numbers of base plates are superposed between the first seat body and the second seat body, so that the integrated forming of the laminated flexible surface type solid-state battery can be realized.

The invention makes the inner surface hydrophobic and easy to demould, the obtained integrated solid battery is complete, the forming device can be repeatedly used, and the invention has the characteristics of strong operability, amplification and mass production.

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 embodiments or the description of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and it is also possible for those skilled in the art to obtain other drawings based on the drawings without creative efforts.

Fig. 1 is a schematic view of an embodiment of an integrated molding apparatus for a flexible surface type solid-state battery;

fig. 2 is a schematic diagram illustrating a corresponding position relationship of the electrode with respect to the second base;

FIG. 3 is a comparative schematic illustration of the adjustment device after separation and assembly;

fig. 4 is a schematic view of another embodiment of an integrated molding apparatus for a flexible surface type solid-state battery;

FIG. 5 is a schematic view of the location of a paraffin coating;

FIG. 6 is a schematic illustration of a multilayer electrode stack arrangement;

fig. 7 is a schematic view of the working state of the second seat body in a split arrangement;

fig. 8 is a schematic structural view of the second seat body which is arranged in a split manner;

fig. 9 is a schematic view of the integrated forming device of the flexible surface type solid-state battery in a partially cut-away state of the first seat when the second seat is separately arranged;

fig. 10 is a partially enlarged view at a in fig. 9 (including the flow direction of the liquid electrolyte);

fig. 11 is a schematic structural view of an integrated molding apparatus for a flexible surface type solid-state battery when a first groove and a second groove are provided in a row;

FIG. 12 is an impedance plot of a flexible solid-state battery of different construction;

reference numerals: 1. a first seat body; 11. a liquid injection channel; 2. a second seat body; 21. a second groove; 21a, a groove bottom plane; 21b, a groove side wall; 22. a main body; 23. blocking; 24. a power end; 25. a second end face; 3. an adjustment device; 31. a first leading-out terminal; 32. a second leading-out terminal; 33. a distance adjustment assembly; 33a, an inner tube; 33b, an outer tube; 33c, a locking member; 33d, a first adjusting seat; 33e, a second adjusting seat; 33f, a screw rod; 33g, a guide rod; 33h, a motor; 4. an electrode; 41. a polar ear region; 42. a paraffin coating layer; 5. a base plate; 6. a gap; 7. a dispensing device.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

Example one

The integrated forming device of the flexible surface type solid-state battery comprises a first seat body 1, a second seat body 2 and an adjusting device 3; the first seat body 1 is provided with a first groove, the second seat body 2 is provided with a second groove 21, the groove bottom planes 21a of the first groove and the second groove 21 are arranged in parallel, and the adjusting device 3 is used for adjusting the distance between the two seat bodies; the first seat body 1 and the second seat body 2 are both of a light-transmitting glass structure, the first seat body 1 is provided with a liquid injection channel 11, and the outlet end of the liquid injection channel 11 deviates from the position of the first groove and is positioned between the two seat bodies.

As shown in fig. 1 and 2, the present invention provides a device for integrally forming a flexible surface type solid-state battery, which solves the problem of insufficient interface contact caused by the respective solidification and forming of the counter electrode 4 and the solid-state electrolyte, and then assembling, thereby effectively reducing the interface impedance, and improving the capacity, rate and cycle life of the solid-state battery to a certain extent.

In the use process, first recess and second recess 21 are used for placing the flexible positive pole and the flexible negative pole that preliminary manufacture has been accomplished respectively, wherein, the final distance after adjusting between two tank bottom planes 21a has decided the distance between the electrode 4, it needs to guarantee to have the space that supplies liquid electrolyte to get into between each layer electrode 4, then pour into liquid electrolyte into through annotating liquid passageway 11, liquid electrolyte is through the circulation in the recess, can effectual and flexible positive pole and flexible negative pole surface contact, then accessible ultraviolet ray runs through the mode of printing opacity glass structure and makes liquid electrolyte solidify according to certain speed range, obtain the structure with flexible positive pole and the integration of flexible negative pole.

In practice, the flexible negative electrode and the flexible positive electrode may be constructed in any feasible manner, such as: the flexible negative electrode is constructed by placing a planar flexible conductive matrix in the MXene single-layer solution to enable MXene to be uniformly self-assembled on the surface of the planar flexible conductive matrix; and the flexible positive electrode is further placed in an N-methylpyrrolidone solution of polyaniline, stands for a proper time, and is subjected to vacuum drying to construct the flexible MXene/polyaniline positive electrode.

The liquid electrolyte can also be configured in various ways, such as: firstly preparing a sulfuric acid aqueous solution, then adding PVP into the sulfuric acid solution for dissolving, sequentially adding an initiator hydrogen peroxide and a cross-linking agent ethylene glycol dimethacrylate, stirring and pre-crosslinking to obtain the polyethylene glycol dimethacrylate.

Of course, the above-mentioned method is only an example of obtaining flexible positive and negative electrodes and electrolyte solution, and is not a limitation to the scope of the present invention, wherein the flexible conductive substrate of planar type may be any one of carbon cloth, flexible metal substrate electrode, self-supporting flexible electrode, graphite paper, electrospun fiber membrane, and the like.

In the present invention, both the base bodies are made of transparent glass, so as to allow the curing process to be controlled by the irradiation of ultraviolet light after the liquid electrolyte is injected, for example, when the liquid electrolyte in the above embodiment is used, the curing process of the solid electrolyte can be accelerated by using ultraviolet light, specifically, the outer electrolyte can be irradiated by high-power ultraviolet light for a short time and focused for a short time, so that the outer electrolyte is cured quickly, and then the inner electrolyte is cured uniformly by irradiating with relative low-power ultraviolet light for a short time.

The outlet of the liquid injection channel 11 deviates from the position of the first groove, so that the influence on the electrode 4 arranged in the first groove can be avoided, wherein the influence on at least one aspect comprises impact and falling off from the first groove.

As a preference of the above embodiment, the first and second grooves 21 are provided with a light-transmitting hydrophobic surface layer at least at the position of the groove bottom plane 21 a. Therefore, the demolding process after curing and molding is easier, and as an optimal mode, the light-transmitting hydrophobic surface layer can be obtained by adopting lithium fluoride for treatment, so that a better ultraviolet light transmission effect can be obtained. Certainly, the side wall 21b of the groove body can also be provided with a hydrophobic surface layer, but the height of the hydrophobic surface layer is relatively low, so that the influence degree on the demolding difficulty is small; through the arrangement of the hydrophobic surface layer, the obtained integrated solid-state battery is complete, and the forming device can be repeatedly used, so that the method has the characteristics of strong operability, amplification and mass production.

In the using process, the first seat body 1 and the second seat body 2 are arranged up and down, and the inlet of the liquid injection channel 11 is positioned on the upper surface of the first seat body 1, so that the liquid electrolyte can enter between the two placed electrodes 4 by means of gravity, and better interface contact with the two electrodes 4 is realized after solidification.

In the implementation, since there may be a requirement to obtain flexible surface type solid-state batteries of different thicknesses, as a specific way of the adjustment means 3, the adjustment means 3 includes a first lead-out terminal 31, a second lead-out terminal 32, and a distance adjustment member 33; the first leading-out terminal 31 is respectively connected with the first seat body 1 and the distance adjusting component 33; the second leading-out terminal 32 is respectively connected with the second seat 2 and the distance adjusting component 33; the distance adjusting assembly 33 drives the first seat 1 and the second seat 2 to move linearly through the two leading-out ends.

In the device, the first seat body 1 and the second seat body 2 are both of light-transmitting glass structures, so that the distance is preferably adjusted by taking an external leading-out end as a connecting position, and the reliability of the structure is ensured; the structural form of the first leading-out terminal 31 is not specifically required, and rod bodies with various sections, seat bodies or multi-structure combination forms and the like can be used as leading-out terminals; in the adjusting process, the maximum range of the distance between the two seat bodies can be expanded to 10cm, so that the electrode 4 can be conveniently arranged under the distance, and the minimum range can be reduced to approximate fit of the two seat bodies; the distance adjusting assembly 33 is connected with the first seat body 1 and the second seat body 2 through two leading-out ends respectively, so that more convenience is achieved, more structural possibilities can be obtained, and as one of manual adjusting structures, the distance adjusting assembly 33 comprises an inner tube body 33a, an outer tube body 33b and a locking piece 33c; the inner pipe body 33a and the outer pipe body 33b are respectively connected with one leading-out end, the outer pipe body 33b is provided with a cavity, and the inner pipe body 33a is inserted into the cavity and is attached to the inner wall of the cavity; the locking member 33c penetrates through the sidewall of the cavity, and the inner tube 33a is fixed with respect to the outer tube 33b by pressing the inner tube 33 a.

As shown in fig. 3, a schematic view of the inner tube 33a and the outer tube 33b after being separated and combined is shown, wherein the retaining member 33c is preferably screwed through the sidewall of the cavity, and the inner tube 33a can be fixed by tightening the retaining member 33 c.

In the above embodiment, the upper and lower relationship between the inner tube 33a and the outer tube 33b are interchangeable, and fig. 3 shows that the inner tube 33a is on the upper side, and the outer tube 33b is on the lower side, which is a preferable way, so as to make the structure more stable, and the manual adjustment way can not realize fine adjustment once the distance between the first seat body 1 and the second seat body 2 is determined, because the precision realized by manual control is necessarily limited, but is the best way in terms of cost.

Of course, as an optimized way to realize automatic control, in addition to the manual way, the distance adjusting assembly 33 includes a first adjusting seat 33d, a second adjusting seat 33e, a screw rod 33f and a guide rod 33g; the first adjusting seat 33d and the second adjusting seat 33e are respectively connected with one of the leading-out ends; at least one of the first adjusting seat 33d and the second adjusting seat 33e is provided with a threaded hole, the threaded hole is in threaded connection with the screw rod 33f and moves linearly in the rotating process of the screw rod 33f, and the guide rod 33g and the screw rod 33f are arranged in parallel to guide the adjusting seat moving relative to the screw rod 33 f.

As shown in fig. 4, a schematic view of an application of the distance adjustment assembly 33 in the above-mentioned structure is shown, in which a first adjustment seat 33d is connected with the first lead-out terminal 31, and a second adjustment seat 33e is connected with the second lead-out terminal 32, and wherein only the first adjustment seat 33d is provided with a threaded hole, and is in threaded connection with a screw rod 33f, and the screw rod 33f penetrates through the first adjustment seat 33d; when the screw rod 33f is driven by a power device such as a motor 33h to rotate, an assembly of the screw rod 33f is formed among the screw rod 33f, the first adjusting seat 33d and the guide rod 33g, so that the linear motion of the first adjusting seat 33d relative to the length direction of the screw rod 33f is realized.

In this form, the second base 2 can be set to be a fixed structure, the second leading-out end 32 and the second adjusting base 33e are also fixed therewith, it is necessary that the end portions of the second adjusting base 33e and the lead screw 33f are directly or rotationally connected through a bearing, and of course, the other end of the lead screw 33f also needs to be rotationally connected with the fixed structure, so as to realize stable fixation.

As another mode of relative movement between the first seat body 1 and the second seat body 2 in the above-mentioned mode, the first adjusting seat 33d and the second adjusting seat 33e are both provided with threaded holes, and in this way, the screw rod 33f is provided with upper and lower sections of reverse threads, so that the two seat bodies can move relative to each other or be away from each other, and only an additional fixing structure is needed to realize the rotation fixing of the two ends of the screw rod 33f and the fixing of the two ends of the guide rod 33 g.

By adopting the structural form of the screw 33f component, the distance between the two seat bodies can be accurately adjusted by using the servo motor, so that more possibilities of adjusting the position, such as reciprocating and different-distance movement, variable-speed movement process, dynamic control process and the like, can be realized.

In the implementation process, one mode of the sealing between the two seat bodies in the invention is as follows: when the distance between the two bases is adjusted and the two electrodes 4 are mounted, in order to achieve the sealing between the two bases, paraffin may be coated around the grooves to form a paraffin coating layer 42 as shown in fig. 5, which only shows the manner of disposing the layer on the inverted first base 1; similarly, the second seat body 2 can be correspondingly arranged; wherein, it should be noted that the paraffin coating layer 42 needs to avoid the position of the outlet of the liquid injection channel 11 and surround to the periphery thereof; when the two bases are close to each other to a sufficient distance, an annular sealing area is formed between the two bases through the sealing of the paraffin coating 42, so that the electrolyte solution is prevented from leaking.

Specifically, in order to achieve the tab installation, when the electrode 4 is installed relative to the groove, the electrode 4 may be extended outward by a proper distance on two opposite sides of the groove to form the tab area 41 as shown in fig. 2, and the coverage of the paraffin coating 42 also includes the coverage of the tab area 41, which may result in better fixation of the electrode 4.

The molding device of the present invention is also applicable to a method in which the multilayer electrodes 4 are stacked: as shown in fig. 6, a schematic diagram of the stacking approach is shown; in the stacking process, the backing plate 5 is used as an external structure, that is, the integrated forming device of the flexible surface type solid-state battery in the invention may further include the backing plate 5, so as to realize the separation between the two stacked electrodes 4 in the tab region 41, and obtain a space for liquid electrolyte to enter between the two adjacent electrodes 4, in this way, the stacking of the electrodes 4 is very convenient, and the electrodes 4 with different polarities can be selected according to requirements; meanwhile, the adjustment of the interval between two adjacent layers of electrodes 4 can be realized by adjusting the thickness of the backing plate 5. Wherein, the backing plate 5 can adopt polytetrafluoroethylene plates with different thicknesses, the thickness can be adjusted to 10 mu m-1cm according to different requirements, and the electrode 4 pole ear area 41 is covered by the backing plate 5 when in use, so that the groove inner electrode 4 is exposed.

Example two

In the above manner, since the depth of the groove is fixedly set in a non-adjustable manner, when the number of layers of the electrode 4 increases, due to the setting of the backing plate 5, the distance between the first seat 1 and the second seat 2 will inevitably be increased, so that the thickness of the paraffin coating layer 42 for sealing will also increase, which will cause a certain influence on the sealing effect, and the sealing stability will also be appropriately reduced by a smaller thickness, therefore, as an embodiment of the present invention, another sealing form between the two seats can be realized, in this embodiment, there is a second seat 2 different from the above embodiment, specifically, the second seat 2 includes a main body 22, a blocking block 23 and a power end 24; the main body 22 is provided with a through area, and the blocking block 23 is inserted into the through area and is in sealing fit with the side wall of the through area; the end surface of the block 23 and the side wall of the through area together form a second groove 21, the block 23 is free to move in the through area in the through direction, and the power end 24 provides the block 23 with movement power and/or provides the block 23 with a pressing force towards the electrode 4 in the second groove 21.

As shown in fig. 7 and 8, a second holder body 2 capable of realizing the depth adjustment of the second groove 21 is provided, and this holder body structure is particularly suitable for use in the molding of a flexible surface-type solid-state battery having a multilayer electrode 4; in particular, the depth of the channel of the second groove 21 can be varied during use by varying the depth of insertion of the block 23 relative to the through-going zone, in such a way as to vary the form of superposition of the multilayer electrode 4, in which the electrode 4 can be placed completely in the groove, without any need to consider the problem of fixing the electrode 4 by covering the tab zone 41 with a paraffin coating.

Of course, after the first seat 1 and the second seat 2 approach each other, it is necessary to ensure that a gap 6 with a certain distance is left between the two, so as to ensure that the liquid electrolyte can smoothly flow into between two adjacent layers of electrodes 4 from the gap between the two, and similarly, the gap 6 needs to be sealed by the paraffin coating layer 42, and the specific sealing manner is the same as that in the above embodiment.

In the implementation process, the electrodes 4 may be laid in the second recess 21 layer by layer, and only one layer of electrodes 4 is disposed in the first recess, and the electrodes 4 of each layer may not extend out of the recess. In the above embodiment, it should be noted that the pads 5 only support the ear regions 41 and are disposed on opposite sides of the electrodes 4, and preferably, the topmost pad 5 is at least partially disposed in the gap 6, so as to allow the liquid electrolyte to better enter between the top two electrodes 4, as shown in fig. 7; similarly, in order to achieve better circulation of the liquid electrolyte, the edges of the electrodes 4 at the top layer and the bottom layer can be attached to the side wall 21b of the cell body, and the electrodes 4 at the middle layer can form a proper interval at least at the side where the liquid electrolyte enters and between the side wall 21b of the cell body, so that the liquid electrolyte can better circulate from the interval, and the purpose of better reaching the electrodes 4 at each layer from top to bottom can be achieved; fig. 10 shows a schematic view of a flow path of the liquid electrolyte, and the space formed between the electrode 4 of the intermediate stage and the tank side wall 21b is also shown in the figure, so that it is clear from the figure that the liquid electrolyte enters from the liquid injection channel 11 and flows between the electrodes 4 of the respective stages.

In the above embodiment, a cylinder structure is preferably adopted for the power end 24, the giving of the pushing force and/or the extrusion force is realized by means of upward pushing, and the control of the fixed pressure value can be realized for the extrusion force, so that different requirements are effectively ensured.

As a preference of the above embodiment, the second seat 2 is inclined from the edge toward the second end face 25 of the first seat 1 into the second groove 21; the first end face of the first seat 1 facing the second seat 2 is parallel to the second end face 25.

As shown in fig. 7 to 10, the above-mentioned conditions are all demonstrated, and the liquid electrolyte can better reach the second groove 21 in the entering process by the above-mentioned optimization method.

In the above drawings, embodiments are shown in which the first seat body 1 and the second seat body 2 are both provided with one groove, and in order to improve the molding efficiency, as shown in fig. 11, as a preference of the above embodiments, at least one row of first grooves is provided on the first seat body 1, and the second grooves 21 are provided on the second seat body 2 in one-to-one correspondence with the first grooves; each group of corresponding first groove and second groove 21 is correspondingly provided with a liquid injection channel 11 on the first seat body 1; the device also comprises a distribution device 7 which is provided with an inlet and an outlet corresponding to the liquid injection channel 11 one by one, and the outlet is communicated with the liquid injection channel 11.

By the forming device in the form, synchronous forming of a plurality of flexible surface type solid-state batteries can be realized by one-time operation, which is obviously beneficial to improving efficiency; in the molding apparatus of the above form, the optimization schemes in the above embodiments can be embodied in the present embodiment, and are not described herein again. Wherein the distribution device 7 is arranged to ensure that each recess is supplied with a synchronized supply of liquid electrolyte.

EXAMPLE III

A working method of an integrated device of a flexible surface type solid-state battery according to the first embodiment, comprising the following steps:

s1: placing the first base body 1 on the top, and placing a layer of electrode 4 in the first groove; the size of the electrode 4 can be selected according to actual needs, and since the first seat body 1 is positioned at the top, the flat laying of the electrode 4 at one layer is a better mode in order to avoid the falling of the layer;

s2: at least one layer of electrode 4 is placed in the second groove 21; the level of the electrode 4 can be selected according to the actual requirement, and certainly, the selection of polarity is also included, in the forming process of the forming device of the invention for the solid-state battery, the electrode 4 is an indispensable level, but when other level structures are also included in the actual product structure design, the technical scheme of the invention can also be adopted; of course, in order to ensure a stable mounting of the various levels, it is preferred to arrange more levels in the second recess 21;

wherein, the two opposite edges of the electrodes 4 of all levels are separated by an external structure and arranged at intervals, and at least partial areas in the grooves ensure that an interval space is obtained between the two adjacent layers of electrodes 4; the outer structure may be a layered structure formed by the paraffin coating layer 42 as described in the above embodiments, or may be the backing plate 5, or both; the two structures can be adopted in the following modes: when only one layer of electrode 4 is arranged in each of the two grooves, the edge of the electrode 4 preferably extends to the outside of the groove and is fixed through the paraffin coating 42, the paraffin coating 42 can participate in the sealing between the two seat bodies and can also realize the interval between the two electrodes 4, the fixation of the electrodes 4 is relatively stable in this way, and when the number of layers of the electrodes 4 is increased in this way, the backing plate 5 is preferably additionally arranged to realize the separation between the rest of each layer and the top and bottom electrodes 4; alternatively, the electrodes 4 may be placed entirely in the grooves, in which case the separation between the electrodes 4 is preferably achieved by the backing plate 5, and the pressing of the backing plate 5 also ensures that the edges of the electrodes 4 obtain the ear regions 41;

wherein the backing plate 5 and the electrode 4 can be directly attached, and other layers can be clamped in the middle; in the above embodiment, the electrode 4 can be placed entirely in the recess, while the lug region 41 is formed by the arrangement of the backing plate 5, or can extend partially outside the recess, only to ensure that there is sufficient spacing area for the liquid electrolyte to enter inside the recess;

s3: adjusting the interval between the first seat body 1 and the second seat body 2 until the extrusion force on each electrode 4 reaches a set value, and establishing a sealing area between the first seat body 1 and the second seat body 2, wherein the sealing area surrounds the position of the groove and the position of the liquid injection channel 11; at the above-mentioned set distance, it is sufficient to have a distance sufficient for the liquid electrolyte to enter, and to ensure sufficient pressing force to the internal electrode 4 and the backing plate 5;

s4: injecting liquid electrolyte into a region surrounded by the first groove, the second groove 21 and the sealing region through the liquid injection channel 11, wherein the liquid electrolyte enters between the electrodes 4 of each layer through the space between the first seat body 1 and the second seat body 2 and the space between the electrodes 4 of the adjacent layers; in order to realize better circulation of the liquid electrolyte, the preferred embodiments in the above embodiments can be applied to the present embodiment;

s5: irradiating the first seat body 1 and the second seat body 2 by ultraviolet light to solidify the liquid electrolyte; in this step, how to cure the liquid electrolyte is critical, and specifically, the curing may be performed by using an ultraviolet light variable power mode, wherein the rapid curing of the outer ring electrolyte may be first achieved by using high power ultraviolet light, and then the uniform curing of the inner electrolyte may be achieved by using low power for a longer time. After the steps are completed, the two seat bodies are separated, and the formed product is taken out.

Example four

In the above embodiment, when the first seat 1 and the second seat 2 are both of an integral structure, the interval between the two seat will inevitably change due to the change of the number of layers of the electrode 4, and therefore the establishment of the sealing area cannot always be in accordance with the same standard, which inevitably causes difficulty in establishing the sealing area, when the sealing area is established by the butting of paraffin, the operation time is long, and the operation time is reduced to obtain a uniform sealing standard, and the operation method as another forming device suitable for the split arrangement of the second seat 2 is specifically as follows:

a working method of the integrated forming device of the flexible surface type solid-state battery according to the second embodiment includes the following steps:

a1: by moving the blocking piece 23 the second groove 21 obtains a greater depth than actually required; this is the most important difference of the present embodiment with respect to the above-described embodiments;

a2: placing the first base body 1 on the top, and placing a layer of electrode 4 in the first groove;

a3: at least one layer of electrode 4 is placed in the second groove 21;

in this embodiment, it should be noted that, in order to adapt the number of layers of the electrodes 4 to the same sealing area, all the electrodes 4 need to be placed in the corresponding areas of the grooves, and there can be no part extending to the outside;

the two opposite edges of the electrodes 4 of all levels are separated by external structures and arranged at intervals, the external structures are arranged in the area between the two opposite groove bottom planes 21a, and an interval space is obtained between the external structures at two sides between the two adjacent layers of electrodes 4;

a4: the distance between the first seat body 1 and the second seat body 2 is adjusted to a set distance, a sealing area is established between the first seat body 1 and the second seat body 2, the sealing area surrounds the position of the groove and the liquid injection channel 11, and the difference here is also from the above embodiment, and the determination of the distance is the basic condition suitable for the same sealing area, so that the structure for establishing the sealing area is more flexible, the traditional sealing ring can be adopted, the distance between the first seat body 1 and the second seat body 2 can be properly reduced, and the forming effect is improved;

a5: the depth of the second groove 21 is adjusted by moving the blocking piece 23 until the extrusion force on each electrode 4 reaches a set value;

a6: injecting liquid electrolyte into a region surrounded by the first groove, the second groove 21 and the sealing region through the liquid injection channel 11, wherein the liquid electrolyte enters between the electrodes 4 of each layer through the space between the first seat body 1 and the second seat body 2 and the space between the electrodes 4 of the adjacent layers;

a7: the liquid electrolyte is cured by irradiating the first holder body 1 and the second holder body 2 with ultraviolet light.

In the invention, the manufacturing processes of the flexible negative electrode, the flexible positive electrode and the liquid electrolyte of the solid-state battery and the whole forming method of the solid-state battery are compared by specific data examples, so that the forming device can play a better using effect when the flexible surface-type solid-state battery is manufactured by a specific working method:

the method I comprises the following steps:

manufacturing an electrode: taking carbon cloth as a surface type flexible conductive substrate, respectively placing the two carbon cloths in 5 mg/ml MXene single-layer solution, standing for 1 hour to ensure that MXene is uniformly self-assembled on the surface of the flexible substrate, and vacuum drying to obtain a flexible MXene cathode, wherein the surface type flexible conductive substrate can be cut into a required size, the method takes cutting into two rectangular strips with the size of 3cm multiplied by 5cm as an example, and the size is also adopted in the following method, so that the comparison significance is realized; placing a piece of the flexible MXene negative electrode in 5 mg/ml polyaniline/N-methylpyrrolidone solution, standing for 1h, and performing vacuum drying to obtain a flexible MXene/polyaniline positive electrode;

preparing a solid electrolyte: and (2) preparing 20ml of 3M sulfuric acid aqueous solution for the flexible electrode with the size, adding 2 g of PVP into the sulfuric acid solution for dissolving, sequentially adding 1 wt.% of initiator hydrogen peroxide and 1 wt.% of cross-linking agent ethylene glycol dimethacrylate, stirring for 1 hour, and pre-crosslinking.

When in use, the electrolyte still in liquid state is slowly poured from the inlet of the liquid injection channel 11 and stands for 1 hour; aiming at the ultraviolet light accelerated solid electrolyte curing process, firstly, focusing and irradiating the outer ring electrolyte for 2s by using high-power ultraviolet light of 600 mW/cm for a short time to quickly cure the outer ring electrolyte, and then irradiating the inner ring electrolyte for 10 s by using low-power ultraviolet light of 100 mW/cm to uniformly cure the inner electrolyte; and after the solidification is finished, sequentially disassembling the forming devices to obtain the integrally formed flexible surface type solid-state battery.

Mode two

Manufacturing an electrode: and the carbon cloth is also used as a surface type flexible conductive substrate and is cut into 6 rectangular strips with the size of 3cm multiplied by 5 cm. Respectively placing 2 carbon cloths in the MXene single-layer solution of 5 mg/ml, standing for 1 hour to enable MXene to be uniformly self-assembled on the surface of the flexible matrix, and performing vacuum drying to obtain a flexible MXene negative electrode; taking 3 pieces of the flexible MXene negative electrode, placing the flexible MXene negative electrode in 5 mg/ml polyaniline/N-methylpyrrolidone solution, standing for 1h, and performing vacuum drying to obtain a flexible MXene/polyaniline positive electrode;

When in use, 6 layers of electrodes are arranged in an integrated forming device in a stacking way, the electrolyte still in liquid state is slowly poured into the integrated forming device from the liquid injection channel 11, and the integrated forming device is kept stand for 2 hours; aiming at the ultraviolet light accelerated solid electrolyte curing process, firstly, focusing and irradiating the outer ring electrolyte for 5s by using high-power ultraviolet light of 600 mW/cm for a short time to quickly cure the outer ring electrolyte, and then irradiating the inner ring electrolyte for 20 s by using low-power ultraviolet light of 400 mW/cm to uniformly cure the inner electrolyte; and after the solidification is finished, sequentially disassembling the forming devices to obtain the three-layer laminated integrally-formed flexible surface type solid-state battery.

Mode III

Manufacturing an electrode: cutting carbon cloth serving as a surface type flexible conductive matrix into 2 rectangular strips with the size of 3cm multiplied by 5cm, respectively placing the two carbon cloths in 5 mg/ml MXene single-layer solution, standing for 1 hour to enable MXene to be uniformly self-assembled on the surface of the flexible matrix, and performing vacuum drying to obtain a flexible MXene negative electrode; taking 1 block of the flexible MXene negative electrode, placing the flexible MXene negative electrode in 5 mg/ml polyaniline/N-methylpyrrolidone solution, standing for 1 hour, and performing vacuum drying to obtain a flexible MXene/polyaniline positive electrode;

preparing a solid electrolyte: preparing 20ml of 3M sulfuric acid aqueous solution, adding 2 g of PVP into the sulfuric acid solution for dissolving, sequentially adding 1 wt.% of initiator hydrogen peroxide and 1 wt.% of cross-linking agent ethylene glycol dimethacrylate, stirring for 1 hour, and pre-crosslinking;

the difference between the two modes is that the forming device is not adopted, the pre-crosslinked electrolyte is poured into a polytetrafluoroethylene template, a square groove with the depth of 1mm is formed in the template, and the template is kept stand for 1.5 hours; accelerating the solid electrolyte curing process by using ultraviolet light, and firstly irradiating the electrolyte for 15 s by using the ultraviolet light of 200 mW/cm, so that the electrolyte is uniformly cured; and after the solidification is finished, taking out the solid electrolyte, and assembling the solid electrolyte, the flexible MXene anode and the flexible MXene cathode into a flexible surface type solid-state battery with a sandwich structure.

The performance test of the flexible surface type solid-state battery prepared in the first to third modes was performed, and the results are shown in table 1:

as can be seen from the performance test results in the table, the material prepared by the working method of the invention has more excellent electrochemical performance. In the third mode, the flexible solid-state battery is constructed by using a traditional sandwich structure, and the obtained battery electrode material is easy to fall off, short in service life, large in interface resistance and poor in multiplying power performance; the impedance ratio of the flexible solid-state battery with different structures of the sandwich structure and the integrated structure obtained in the invention is shown in fig. 12.

In the first mode and the second mode, a novel integrated forming method of the flexible surface type solid-state battery, which can adopt the forming device of the invention, is provided, and the pre-crosslinked liquid electrolyte is poured into the integrated forming device, so that the electrolyte completely infiltrates the surface of the flexible fabric-shaped electrode and is crosslinked in situ on the surface of the electrode, and the problem of the interface between the solid electrolyte and the electrode is effectively solved; meanwhile, the solid electrolyte completely wraps the fibers in the woven fabric electrode, so that the falling of the self-assembled electrode material is prevented, and the stability of the flexible solid battery is further improved.

The solid electrolyte used in the mode is PVP solid electrolyte of high-concentration sulfuric acid, has good low-temperature resistance, and the prepared flexible solid battery has good low-temperature resistance by combining an ultrathin integrated structure; by using a solid electrolyte forming means combining chemical crosslinking and photocuring, the network-shaped multi-channel solid electrolyte can be formed, and the solid electrolyte forming time can be greatly shortened.

The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims

1. The integrated forming device of the flexible surface type solid-state battery is characterized by comprising a first seat body, a second seat body and an adjusting device;

the first seat body is provided with a first groove, the second seat body is provided with a second groove, the bottom planes of the first groove and the second groove are arranged in parallel, and the adjusting device is used for adjusting the distance between the first seat body and the second seat body;

2. The integrated molding apparatus for a flexible flat-type solid-state battery according to claim 1, wherein the first and second grooves are provided with a light-transmitting hydrophobic surface layer at least at the bottom plane of the groove.

3. The integrated molding apparatus of a flexible surface type solid-state battery according to claim 1, wherein the adjusting means comprises a first lead-out terminal, a second lead-out terminal, and a distance adjusting member;

the first leading-out end is respectively connected with the first seat body and the distance adjusting component;

4. The integrated molding apparatus of a flexible surface type solid-state battery according to claim 3, wherein the distance adjusting member comprises an inner tube, an outer tube and a locker;

5. The integrated molding apparatus of a flexible surface type solid-state battery according to claim 3, wherein the distance adjusting assembly comprises a first adjusting seat, a second adjusting seat, a lead screw and a guide rod;

6. The integrated molding apparatus of a flexible surface type solid-state battery according to claim 1, wherein the second housing comprises a main body, a block, and a power end;

7. The integrated molding apparatus for a flexible surface type solid-state battery according to any one of claims 1 to 6, wherein the second seat body is inclined from an edge into the second groove toward the second end face of the first seat body;

8. The integrated molding device for the flexible surface type solid-state battery according to any one of claims 1 to 6, wherein at least one row of the first grooves is arranged on the first seat body, and the second grooves are arranged on the second seat body in one-to-one correspondence with the first grooves;

the liquid injection device is characterized by also comprising a distribution device, wherein the distribution device is provided with an inlet and outlets which correspond to the liquid injection channels one to one, and the outlets are communicated with the liquid injection channels.

9. A working method of the integrated molding device of the flexible surface type solid-state battery according to any one of claims 1 to 5, characterized by comprising the following steps:

placing the first base body on the top, and placing a layer of electrode in the first groove;

at least one layer of electrode is placed in the second groove;

the electrodes of all layers are separated and arranged at intervals by an external structure at two opposite edges, and at least partial areas in the grooves enable an interval space to be obtained between two adjacent layers of the electrodes;

adjusting the interval between the first seat body and the second seat body until the extrusion force on each electrode reaches a set value, and establishing a sealing area between the first seat body and the second seat body, wherein the sealing area surrounds the position of the groove and the position of the liquid injection channel;

injecting liquid electrolyte into a region surrounded by the first groove, the second groove and the sealing region through the liquid injection channel, wherein the liquid electrolyte enters between the electrodes of each layer through the space between the first seat body and the second seat body and the space between the electrodes of the adjacent layers;

10. An operation method of an integrated apparatus of a flexible surface type solid-state battery according to claim 6, comprising the steps of:

placing at least one layer of electrode in the second groove;

the electrodes of all levels are separated and arranged at intervals by external structures at two opposite edges, the external structures are arranged in the area between the planes of the opposite groove bottoms, and a spacing space is obtained between the external structures at two sides between two adjacent layers of the electrodes;

and irradiating the first holder body and the second holder body by ultraviolet light to solidify the liquid electrolyte.