阅读说明：本技术 一种柔性电池及其制备方法 (A kind of flexible battery and preparation method thereof ) 是由 符显珠 康晓民 司凤占 符国栋 骆静利 于 2019-07-29 设计创作，主要内容包括：本发明公开了一种柔性电池及其制备方法,其中,所述方法包括步骤：在光照条件下,将改性高分子材料、非改性高分子材料以及光催化剂进行混合,反应制得双网络凝胶电解质；将多孔碳基材料均匀掺杂到所述双网络凝胶电解质中并进行冷冻干燥处理,制得柔性多孔空气电极；将金属粉或金属线均匀掺杂到双网络凝胶电解质中并进行固化处理,制得柔性薄膜金属电极；将柔性多孔空气电极、双网络凝胶电解质以及柔性薄膜金属电极依次堆叠并进行压紧处理,制得所述柔性电池。本发明中柔性多孔空气电极以及柔性薄膜金属电极均以双网络凝胶电解质为基材制得,通过采用均一同相的材料制备双网络凝胶电解质和电极,能够有效提高柔性电池的安全稳定性以及比容量。(The invention discloses a kind of flexible batteries and preparation method thereof, wherein the method includes the steps: under illumination condition, modified polymer material, non-modified high molecular material and photochemical catalyst are mixed, reacts and dual network gel electrolyte is made；Porous carbon sill of sheet Uniform Doped into the dual network gel electrolyte and is subjected to freeze-drying process, flexible, porous air electrode is made；Metal powder or metal wire Uniform Doped into dual network gel electrolyte and are subjected to curing process, fexible film metal electrode is made；Flexible, porous air electrode, dual network gel electrolyte and fexible film metal electrode are stacked gradually and carried out compression processing, the flexible battery is made.Flexible, porous air electrode and fexible film metal electrode are made by substrate of dual network gel electrolyte in the present invention, by using the material of phase prepares dual network gel electrolyte and electrode together, the security and stability and specific capacity of flexible battery can be effectively improved.)

1. a kind of preparation method of flexible battery, which is characterized in that comprising steps of

Under illumination condition, modified polymer material, non-modified high molecular material and photochemical catalyst are mixed, reaction system Obtain dual network gel electrolyte；

Porous carbon sill of sheet Uniform Doped into the dual network gel electrolyte and is subjected to freeze-drying process, flexibility is made Porous air electrode；

Metal powder or metal wire Uniform Doped into the dual network gel electrolyte and are subjected to curing process, flexible thin is made Film metal electrode；

The flexible, porous air electrode, dual network gel electrolyte and fexible film metal electrode are stacked gradually and carried out Compression processing, is made the flexible battery.

2. the preparation method of flexible battery according to claim 1, which is characterized in that the system of the dual network gel electrolyte It is standby the following steps are included:

Under illumination condition, modified polymer material is mixed with non-modified high molecular material and photochemical catalyst, makes to change Pass through between property high molecular material and non-modified high molecular material and between modified polymer material and modified polymer material Coordination between functional group is cross-linked with each other, and dual network gel electrolyte is made.

3. the preparation method of -2 any flexible batteries according to claim 1, which is characterized in that the modified polymer material Preparation the following steps are included:

Under the action of catalyst, non-modified high molecular material is mixed with modified small molecule, is incorporated in modified small molecule coordination The non-modified polymer surface, is made the modified polymer material.

4. the preparation method of flexible battery according to claim 3, which is characterized in that the non-modified high molecular material is selected from Any one in chitin, gelatin, Sodium Polyacrylate or sodium alginate.

5. the preparation method of flexible battery according to claim 3, which is characterized in that the modified small molecule is selected from organic One of phenol, organic amine and organic carboxyl acid are a variety of.

6. the preparation method of flexible battery according to claim 1, which is characterized in that the system of the flexible, porous air electrode It is standby the following steps are included:

Under illumination condition, porous carbon sill of sheet, modified polymer material, non-modified high molecular material and photochemical catalyst are mixed Freeze-drying process is carried out after closing uniformly, the flexible, porous air electrode is made.

7. the preparation method of flexible battery according to claim 6, which is characterized in that the porous carbon sill of sheet is selected from calcining One of metal organic framework compound, carbon nanotube and graphene afterwards are a variety of.

8. the preparation method of flexible battery according to claim 1, which is characterized in that the system of the fexible film metal electrode It is standby the following steps are included:

Under illumination condition, by metal powder or metal wire and modified polymer material, non-modified high molecular material and photocatalysis Agent carries out freeze-drying process after mixing, and the fexible film metal electrode is made.

9. the preparation method of flexible battery according to claim 1, which is characterized in that described by the flexible, porous air electricity Pole, dual network gel electrolyte and fexible film metal electrode stack gradually and carry out compression processing, and the flexible electrical is made The step of pond includes:

In the interface that the flexible, porous air electrode is in contact with dual network gel electrolyte and dual network gel electricity Electrolyte is added dropwise on the interface that Xie Zhiyu fexible film metal electrode is in contact, then carries out compressing processing and constant temperature is stood, make The flexible, porous air electrode, dual network gel electrolyte and fexible film metal electrode are bonded together, and are made described Flexible battery.

10. a kind of flexible battery, which is characterized in that be made using the preparation method of claim 1-9 any one flexible battery.

Technical field

The present invention relates to field of batteries, in particular to a kind of flexible battery and preparation method thereof.

Background technique

Flexible device provides many conveniences because its is easy to carry, bent and wearable, for the modern life, and attracts The extensive concern of researcher.

The principal element of restricting current flexible battery concentrates on the safety of flexible battery, the promotion of energy density, continuation of the journey The extension of time and the promotion of long-term running stability etc..Conventional flex electrode material multiselect carbon cloth, porous metals As flexible air electrode base material or flexible electrode is directly used as etc. frivolous electronic conductor.However, due to electric in flexible battery The Xie Zhiyu electrode not equal material of phase together, these all constrain the conduction of active catalytic species useful, ion and electronics, are undergoing After long-term work, between electrode material and flexible gel electrolyte also can deformation occurs so that send out lead to poor contact between the two Even remove

Therefore, the existing technology needs to be improved and developed.

Summary of the invention

In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of flexible air battery and its preparation sides Method, it is intended to solve the problems, such as that the specific capacity of flexible air battery in the prior art is low and security and stability is poor.

Technical scheme is as follows:

A kind of preparation method of flexible battery, wherein comprising steps of

Under illumination condition, modified polymer material, non-modified high molecular material and photochemical catalyst are mixed, instead Dual network gel electrolyte should be made；

Porous carbon sill of sheet Uniform Doped into the dual network gel electrolyte and is subjected to freeze-drying process, is made Flexible, porous air electrode；

Metal powder or metal wire Uniform Doped into the dual network gel electrolyte and are subjected to curing process, are made soft Property thin-film metal electrodes；

The flexible, porous air electrode, dual network gel electrolyte and fexible film metal electrode are stacked gradually simultaneously Compression processing is carried out, the flexible battery is made.

The preparation method of the flexible battery, wherein the preparation of the dual network gel electrolyte the following steps are included:

Under illumination condition, modified polymer material is mixed with non-modified high molecular material and photochemical catalyst, Make between modified polymer material and non-modified high molecular material and between modified polymer material and modified polymer material It is cross-linked with each other by the coordination between functional group, dual network gel electrolyte is made.

The preparation method of the flexible battery, wherein the preparation of the modified polymer material the following steps are included:

Under the action of catalyst, non-modified high molecular material is mixed with modified small molecule, makes modified small molecule coordination knot It closes in the non-modified polymer surface, the modified polymer material is made.

The preparation method of the flexible battery, wherein the non-modified high molecular material is selected from chitin, gelatin, poly- third Any one in olefin(e) acid sodium or sodium alginate.

The preparation method of the flexible battery, wherein the modified small molecule is selected from organic phenol, organic amine and organic carboxyl acid One of or it is a variety of.

The preparation method of the flexible battery, wherein the preparation of the flexible, porous air electrode the following steps are included:

Under illumination condition, by porous carbon sill of sheet, modified polymer material, non-modified high molecular material and photocatalysis Agent carries out freeze-drying process after mixing, and the flexible, porous air electrode is made.

The preparation method of the flexible battery, wherein the porous carbon sill of sheet is selected from calcined metal organic frame One of compound, carbon nanotube and graphene are a variety of.

The preparation method of the flexible battery, wherein the preparation of the fexible film metal electrode the following steps are included:

Under illumination condition, by metal powder or metal wire and modified polymer material, non-modified high molecular material and light Catalyst carries out freeze-drying process after mixing, and the fexible film metal electrode is made.

The preparation method of the flexible battery, wherein described by the flexible, porous air electrode, dual network gel electrolyte The step of matter and fexible film metal electrode stack gradually and carry out compression processing, and the flexible battery is made include:

It is solidifying at the interface that the flexible, porous air electrode is in contact with dual network gel electrolyte and the dual network Electrolyte is added dropwise on the interface that glue electrolyte is in contact with fexible film metal electrode, then carries out compressing processing and constant temperature is quiet It sets, is bonded together the flexible, porous air electrode, dual network gel electrolyte and fexible film metal electrode, be made The flexible battery.

A kind of flexible battery, wherein be made using the preparation method of any one flexible battery of the invention.

The utility model has the advantages that the present invention provides a kind of preparation method of flexible battery, the flexible, porous in the flexible battery is empty Pneumoelectric pole and fexible film metal electrode adulterate porous carbon sill of sheet and gold using dual network gel electrolyte as substrate respectively Belong to (powder or line) to be made；Due to the flexible, porous air electrode and fexible film metal electrode and pair among the two Network gel electrolyte belongs to the material of phase together, electrode (flexible, porous air electrode and the fexible film metal electricity Pole) between material and dual network gel electrolyte materials will not deformation occurs, this stability that flexible battery is used is high；Into One step, since electrode material and dual network gel electrolyte materials are the equal materials of phase together, this be can be effectively reduced mutually Between interface resistance, the conduction of inside battery active catalytic species useful, ion and electronics becomes to be more easier, so that flexible battery Specific capacity be also improved.

Detailed description of the invention

Fig. 1 is a kind of flow chart of the preparation method preferred embodiment of flexible battery of the present invention.

Fig. 2 is a kind of structural schematic diagram of flexible battery preferred embodiment of the present invention.

Fig. 3 is the schematic diagram of the dual network gel electrolyte preparation of photo-initiated crosslinking in the present invention.

Fig. 4 is the ultraviolet absorption peak variation diagram of sodium alginate-modified front and back in the present invention.

Fig. 5 is the SEM for the dual network gel that sodium alginate and chitin (molar ratio 1:5) modified in the present invention are formed Figure.

Fig. 6 is the EDS member for the dual network gel that sodium alginate and chitin (molar ratio 1:5) modified in the present invention are formed Plain distribution map.

Fig. 7 is the dual network gel that sodium alginate and Sodium Polyacrylate (molar ratio 1:5) modified in the present invention are formed SEM figure.

Fig. 8 is the dual network gel that sodium alginate and Sodium Polyacrylate (molar ratio 1:5) modified in the present invention are formed EDS distribution diagram of element.

Fig. 9 is the drawing for the dual network gel that sodium alginate and polyacrylic acid (molar ratio 1:5) modified in the present invention are formed Stretch schematic diagram.

Figure 10 is the SEM figure of flexible, porous air electrode in embodiment 1.

Figure 11 is the dual network gel electrolyte that sodium alginate and chitin (molar ratio 1:5) modified in the present invention are formed Matter, the dual network gel electrolyte that is formed with polyacrylic acid (molar ratio 1:5) of sodium alginate of modification and polyacrylic acid are formed Gel electrolyte EIS test chart.

Specific embodiment

The present invention provides a kind of flexible battery and preparation method thereof, to make the object of the invention, technical solution and effect more Clear, clear, the present invention is described in more detail below.It should be appreciated that specific embodiment described herein is only used to It explains the present invention, is not intended to limit the present invention.

Referring to Fig. 1, Fig. 1 is a kind of flow chart of the preparation method preferred embodiment of flexible battery provided by the invention, As shown, comprising steps of

S10, under illumination condition, modified polymer material, non-modified high molecular material and photochemical catalyst are mixed It closes, reacts and dual network gel electrolyte is made；

S20, by porous carbon sill of sheet Uniform Doped into the dual network gel electrolyte and freeze-drying process is carried out, Flexible, porous air electrode is made；

S30, metal powder or metal wire Uniform Doped into the dual network gel electrolyte and are subjected to curing process, made Obtain fexible film metal electrode；

S40, by the flexible, porous air electrode, dual network gel electrolyte and fexible film metal electrode successively heap Compression processing is folded and carried out, the flexible battery is made.

Specifically, existing flexible zinc-air battery and lithium-air battery are all made of flexible anode, dielectric film and bear The sandwich structure of pole superposition composition.Wherein, flexible zinc-air battery mainly uses anion-exchange membrane and base gel conduct The dielectric film of battery；Flexible lithium-air battery mainly uses gel, solid and composition polymer as the dielectric film of battery； The dielectric film of above two battery and electrode material are all made of the non-material of phase together, this cause flexible battery in bending or During distortion, due to the difference of electrode material and dielectric film mechanical property, the separation of electrode and dielectric film will lead to； And due to electrolyte and the electrode not equal material of phase together in battery, the biography of active catalytic species useful, ion and electronics is constrained It leads, so that the specific capacity of existing flexible battery is low and security and stability is poor.

Based on the problems of existing flexible battery, a kind of preparation method of flexible battery is present embodiments provided, such as Shown in Fig. 2, the flexible battery is by flexible, porous air electrode 10, dual network gel electrolyte 20 and fexible film metal electricity Pole 30 stacks gradually and is made after carrying out compression processing.Flexible, porous air electrode and fexible film in the flexible battery Metal electrode is to adulterate porous carbon sill of sheet respectively using dual network gel electrolyte as substrate and metal (powder or line) is made； Due to the flexible, porous air electrode and fexible film metal electrode and the dual network gel electrolyte among the two Belong to the material of phase together, electrode (the flexible, porous air electrode and fexible film metal electrode) material and dual network Between gel electrolyte materials will not deformation occurs, this makes flexible battery security and stability high；Further, due to electrode material Material and dual network gel electrolyte materials are the equal materials of phase together, this can be effectively reduced mutual interface resistance, electric The conduction of active catalytic species useful, ion and electronics becomes to be more easier inside pond, so that the specific capacity of flexible battery is also mentioned It is high.

In some embodiments, the non-modified high molecular material is selected from chitin, gelatin, Sodium Polyacrylate or seaweed Any one in sour sodium, but not limited to this, non-modified high molecular material selected by the present embodiment is biological friendly high score Son, the biology friendly macromolecule are easy to modify functional group on its strand by modification, by taking sodium alginate as an example, contain There are a large amount of hydroxyl and carboxylic group, this provides many decorating sites to the modification of sodium alginate, is the modification of sodium alginate Advantageous condition is provided, there are also chitin, gelatin, Sodium Polyacrylates etc. for other common biological friendly macromolecules, come Source is extensive and does not pollute the environment.

The modified polymer material refers under the action of catalyst, and non-modified high molecular material is mixed with modified small molecule It closes, so that the coordinating group coordination of modified small molecule is incorporated in the non-modified polymer surface and be made, wherein the modification Small molecule is selected from one of organic phenol, organic amine and organic carboxyl acid or a variety of, but not limited to this.The present embodiment mainly passes through Chemical modification is carried out to macromolecule, modify upper such as phenolic hydroxyl group, amino, carboxyl electronegativity greatly in polymer surface and is coordinated The good functional group of property, obtains modified polymer material.

In some specific embodiments, preparing for the modified sodium alginate is as follows: in room temperature and pH is 6.5 Under conditions of, by catalyst EDC (1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride), NHS (N- hydroxyl fourth two Acid imide) and sodium alginate withModified sodium alginate is made in mixing, and reaction process is as follows:

In some embodiments, the preparation of the dual network gel electrolyte is the following steps are included: under illumination condition, Modified polymer material is mixed with non-modified high molecular material and photochemical catalyst, changes modified polymer material with non- Property high molecular material between and modified polymer material and modified polymer material between made by the coordination between functional group With being cross-linked with each other, dual network gel electrolyte is made.

In some specific embodiments, withModified polymer material and the chitin containing amino are (non-to change Property high molecular material) prepare dual network gel electrolyte for, it is described as shown in figure 3, under illumination conditionIt is modified high Molecular material and the chitin containing amino are described under the action of photochemical catalystModified polymer material and contain ammonia It can be cross-linked with each other by the coordination between group between the chitin of base, it is describedBetween modified polymer material It can be cross-linked with each other by the coordination between group, to form dual network gel electrolyte as shown in Figure 3.Double nets For network gel electrolyte as a kind of high-strength gel electrolyte, special network structure imparts its outstanding mechanical property, The mechanical property of flexible battery can be increased.

In some embodiments, the preparation of the flexible, porous air electrode is the following steps are included: under illumination condition, Porous carbon sill of sheet, modified polymer material, non-modified high molecular material and photochemical catalyst are freezed after mixing It is dried, the flexible, porous air electrode is made.

In the present embodiment, since dual network gel electrolyte only has ionic conductivity there is no electron conduction, because This can prepare flexible, porous air electricity during preparing dual network gel electrolyte by introducing porous carbon sill of sheet Pole, to improve its electron conduction and catalytic activity.In some preferred embodiments, the porous carbon sill of sheet is selected from and forges One of metal organic framework compound, carbon nanotube and graphene after burning are a variety of, but not limited to this.

In some embodiments, the preparation of the fexible film metal electrode is the following steps are included: under illumination condition, Metal powder or metal wire are carried out with modified polymer material, non-modified high molecular material and photochemical catalyst after mixing cold Freeze and be dried, the fexible film metal electrode is made.

The present embodiment is prepared equally using dual network gel electrolyte as substrate by mixing metal powder or metal wire wherein Fexible film metal electrode, to improve its electron conduction.

In some embodiments, the preparation step of the flexible battery include: the flexible, porous air electrode with The interface and the dual network gel electrolyte that dual network gel electrolyte is in contact are in contact with fexible film metal electrode Interface on electrolyte is added dropwise, then carry out compressing processing and constant temperature stood, keep the flexible, porous air electrode, dual network solidifying Glue electrolyte and fexible film metal electrode are bonded together, and the flexible battery is made.In the present embodiment, the electrolysis Liquid is the mixed solution of zinc acetate and potassium hydroxide.Preferably, in the mixed solution, acetic acid zinc concentration is 0.2M, hydrogen-oxygen The concentration for changing potassium is 6M.

In the present embodiment, due in the flexible battery flexible, porous air electrode and fexible film metal electrode it is equal It is to adulterate porous carbon sill of sheet respectively using dual network gel electrolyte as substrate and metal (powder or line) is made；The flexibility is more Hole air electrode and fexible film metal electrode and the dual network gel electrolyte being located among the two belong to phase together Material, electrode (the flexible, porous air electrode and fexible film metal electrode) material and dual network gel electrolyte materials Between will not deformation occurs, this makes flexible battery security and stability high；Further, due to electrode material and dual network gel Electrolyte is the equal material of phase together, this can be effectively reduced mutual interface resistance, inside battery active catalytic The conduction of substance, ion and electronics becomes to be more easier, so that the specific capacity of flexible battery is also improved.

In some embodiments, a kind of flexible battery is also provided, wherein using any one flexible battery of the invention Preparation method is made.

Explanation is further explained to a kind of flexible battery of the present invention and preparation method thereof below by specific embodiment: