CN113707840A - Manufacturing method of flexible battery, flexible battery and application - Google Patents
Manufacturing method of flexible battery, flexible battery and application Download PDFInfo
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- CN113707840A CN113707840A CN202110953927.7A CN202110953927A CN113707840A CN 113707840 A CN113707840 A CN 113707840A CN 202110953927 A CN202110953927 A CN 202110953927A CN 113707840 A CN113707840 A CN 113707840A
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/045—Cells with aqueous electrolyte characterised by aqueous electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
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Abstract
The invention discloses a manufacturing method of a flexible battery, which comprises the steps of providing a prefabricated conducting film; the conductive film is a composite structure of a carbon nano tube, MXene and polyaniline; adopting conductive silver paste to bond and fix the zinc foil and the conductive film to obtain a positive plate; cutting the conductive film to a preset size to obtain a negative plate; and adhering and fixing the positive plate and the negative plate by adopting a diaphragm, packaging the positive plate, the negative plate and the diaphragm by adopting a packaging film together, and injecting electrolyte to obtain the flexible battery. The invention ensures that the flexible battery can work normally in the bending process, has better flexibility, can be integrated with a wearable article, has good biocompatibility when contacting with the skin, and is more comfortable and safe to wear.
Description
Technical Field
The invention relates to the technical field of flexible batteries, in particular to a manufacturing method of a flexible battery, the flexible battery and application.
Background
The wearable intelligent system integrating the sensor and the energy management has great application potential in the fields of medical care, motion monitoring, personal data exchange and the like, and the development of flexible wearable energy equipment is greatly promoted. The existing battery preparation process is complex, extremely strict requirements are imposed on the temperature and humidity of the preparation environment, and short circuit is easy to occur in the bending process, so that the battery cannot be used. Under the background of new crown epidemic situation, the mask becomes an indispensable part of life of people, the health of detecting the health by integrating the sensing device on the mask is concerned by scientific research personnel, but the development of the current energy device is limited.
Biocompatibility, particularly electrolytes, of energy devices in wearable systems are of concern. The damage of organic electrolytes to human bodies, whether acidic or alkaline, has been widely verified. Although the special packaging can prevent leakage of toxic electrolytes, it can complicate the wearable device, affect its wearing comfort, and have poor fitting effects.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, a first object of the present invention is to provide a method for manufacturing a flexible battery, including:
providing a prefabricated conductive film; the conductive film is a composite structure of a carbon nano tube, MXene and polyaniline;
adopting conductive silver paste to bond and fix the zinc foil and the conductive film to obtain a positive plate; cutting the conductive film to a preset size to obtain a negative plate;
and adhering and fixing the positive plate and the negative plate by adopting a diaphragm, packaging the positive plate, the negative plate and the diaphragm by adopting a packaging film together, and injecting electrolyte to obtain the flexible battery.
Preferably, according to an embodiment of the present invention, the conducting film is prefabricated by:
ultrasonically dispersing carbon nano tubes and MXene in water to obtain a dispersion liquid, and fusing the dispersion liquid with a filter membrane to form a layer of composite film of the carbon nano tubes and the MXene on the surface of the filter membrane;
drying the obtained composite membrane, immersing the composite membrane into a solution of aniline and hydrochloric acid, and adding ammonium persulfate to soak for a preset time;
after soaking, cleaning and drying the composite film by using a solvent to obtain the conductive film; wherein the solvent is ethanol or distilled water.
Preferably, according to one embodiment of the invention, the filter membrane is a nitrocellulose water system filter membrane; the manufacturing method of the composite membrane comprises the following steps:
ultrasonically dispersing the carbon nano tube and MXene in water for 1.5-1.6 hours to obtain the dispersion liquid, and placing the filter membrane in a suction filtration device;
pouring the dispersion into the suction filtration device, and draining water;
and taking out the filter membrane, drying, and peeling the composite membrane formed on the filter membrane and the filter membrane to obtain the composite membrane.
Preferably, according to an embodiment of the present invention, the predetermined time is 30 to 50 minutes.
Preferably, according to an embodiment of the present invention, the assembling of the flexible battery includes:
respectively bonding the positive plate and the negative plate to two sides of a diaphragm, and respectively bonding copper wires to the positive plate and the negative plate by adopting the conductive silver paste to obtain dry diaphragms;
and clamping the dried membrane between the packaging films, carrying out thermoplastic sealing on the packaging films, and injecting a sodium chloride solution to obtain the flexible battery.
Preferably, according to an embodiment of the present invention, the separator is a non-woven fabric material, polyethylene or a polyethylene ceramic coating material, and the encapsulation film is an organic material.
Preferably, according to an embodiment of the present invention, the organic material is a thermoplastic elastomer (TPE), Polydimethylsiloxane (PDMS), or polyethylene terephthalate (PET).
Preferably, according to one embodiment of the present invention, the electrolyte is a sodium chloride solution and water.
The invention provides a flexible battery which is manufactured by the manufacturing method.
The invention also provides an application of the flexible battery manufactured by the manufacturing method in a wearing article.
The manufacturing method of the flexible battery provided by the invention omits a copper-aluminum foil as a current collector, avoids the problem of battery short circuit in the bending process of the flexible battery, ensures that the flexible battery can normally work in the bending process, has better flexibility, can be integrated with a wearable article, has good biocompatibility when contacting with skin, and is more comfortable and safe to wear.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for manufacturing a flexible battery according to an embodiment of the present invention;
fig. 2 is a schematic flow chart of a prefabrication step of the conductive film provided in an embodiment of the present invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
The manufacturing method of the flexible battery provided by the embodiment of the invention comprises the following steps:
s10, providing a prefabricated conducting film; the conductive film is a composite structure of a carbon nano tube, MXene and polyaniline.
In this embodiment, the carbon nanotube may be a single-walled carbon nanotube, a double-walled carbon nanotube, or a multi-walled carbon nanotube; and, MXene material is a kind of metal carbon/nitride (transition metal nitride/nitride) with two-dimensional layered structure, and its chemical formula is Mn +1XnTX, where (n ═ 1-3), M represents early transition metal, such as Ti, Zr, V, Mo, etc.; x represents a C or N element, Tx is a surface group, typically-OH, -O, -F and-Cl. Due to the similar lamellar structure of Graphene, MXene can be single-layer MXene, multi-layer MXene and small-diameter MXene; the carbon nano tube and the MXene material have good mechanical and electrical properties, and the polyaniline is a conductive polymer material, so that the interaction between the polyaniline and the conductive polymer material ensures that the battery can still normally work in the bending deformation process.
Specifically, the conducting film prefabricating step comprises the following steps:
s11, ultrasonically dispersing the carbon nano tube and the MXene in water to obtain dispersion liquid, and fusing the dispersion liquid and the filter membrane to form a layer of composite film of the carbon nano tube and the MXene on the surface of the filter membrane;
s12, drying the obtained composite membrane, immersing the composite membrane into a solution of aniline and hydrochloric acid, and adding ammonium persulfate to soak for a preset time;
s13, cleaning and drying the composite film by using a solvent after soaking to obtain a conductive film; wherein the solvent is ethanol or distilled water.
Wherein the filter membrane is a cellulose nitrate water system filter membrane; when the composite membrane is manufactured, 1.5g of multi-walled carbon nanotubes and 0.5g of single-layer MXene are added into 200ml of water, then the mixture is ultrasonically dispersed for 1.5 hours by using an ultrasonic oscillator with the power of 300W, then the cellulose nitrate membrane is placed in a suction filtration device, 20ml of dispersion liquid is poured into the suction filtration device, after the water is drained, the cellulose nitrate membrane is taken down and placed in an oven for drying at 60 ℃, and finally the upper-layer carbon nanotubes of the cellulose nitrate membrane and the MXene composite membrane are stripped to obtain the composite membrane.
Further, 15ml (with the volume concentration of 0.05M) aniline (with the volume concentration of 1M) hydrochloric acid solution is placed in a low-temperature water bath kettle (with the temperature of 5 ℃), the composite membrane is immersed in the aniline hydrochloric acid solution for 30 minutes, then 15ml ammonium persulfate (with the volume concentration of 0.05M) is dropwise added, the composite membrane is kept at the temperature of 5 ℃ for 24 hours, finally the composite membrane is washed clean by distilled water and ethanol, and dried at the temperature of 60 ℃, so that the conductive membrane is obtained, and the conductive membrane is simple in manufacturing process and better in flexibility.
S20, adopting conductive silver paste to bond and fix the zinc foil and the conductive film to obtain a positive plate; and cutting the conductive film to a preset size to obtain the negative plate.
Wherein, the binder can be prepared in advance, and 1g of PVA (polyvinyl alcohol) powder can be adopted as the binder to be added into 10ml of aqueous solution, and the mixture is fully stirred and dissolved under the condition that the aqueous solution is at 90 ℃ so as to obtain the binder; further, when the positive plate and the negative plate are manufactured, the adhesive can be coated on two sides of the diaphragm, and the positive plate and the negative plate are covered on the adhesive and are pressed and fixed. Conductive silver paste is smeared on a copper wire, the surface is stuck on a positive plate to serve as a positive pole lug, the conductive silver paste is smeared on the copper wire, the surface is stuck on a negative plate to serve as a negative pole lug and is compressed and fixed, and the negative plate is finally placed into a 60 ℃ oven to be dried for 4 hours.
And S30, adhering and fixing the positive plate and the negative plate by using the diaphragm, packaging the positive plate, the negative plate and the diaphragm by using a packaging film together, and injecting electrolyte to obtain the flexible battery.
In this embodiment, when the flexible battery is assembled, the positive plate and the negative plate are respectively bonded to two sides of the diaphragm, and the copper wires are respectively bonded to the positive plate and the negative plate by using conductive silver paste, so as to obtain a dry diaphragm; and clamping the dried membrane between packaging films, performing thermoplastic sealing on the packaging films, and injecting a sodium chloride solution to obtain the flexible battery.
The packaging film can be a TPE film, when the TPE film is prepared, 0.5g of TPE can be added into 200mL of cyclohexane, after the TPE film is fully dissolved, ultrasonic dispersion is carried out for 1.5h by an ultrasonic oscillator with the power of 300W, the prepared dispersion liquid is sprayed on a quartz glass sheet to form the TPE film, then the TPE film is soaked by ethanol and dried for later use, the dried film sheet is clamped in the TPE film, after thermoplastic sealing is carried out on three edges of the TPE film, sodium chloride solution is injected into the unsealed section, and the unsealed side can be reserved without being subjected to sealing treatment, so that the flexible battery is assembled; after the flexible battery assembly is completed, the flexible battery can be pasted on a mask, for example, a KN95 mask, one unsealed side of the flexible battery is close to a breather valve, and then water vapor breathed by a human body can be used as electrolyte, so that the battery is continuously powered, and the flexible battery is safe, non-toxic and harmless.
Optionally, the diaphragm is made of a non-woven fabric material, polyethylene or a polyethylene ceramic coating material, and the packaging film is made of an organic material; among them, the organic material may be an organic material having a low young's modulus and high elasticity, such as thermoplastic elastomer (TPE), Polydimethylsiloxane (PDMS), or polyethylene terephthalate (PET); the electrolyte is sodium chloride solution and water, and can also be sweat, for example, when the flexible battery is applied to clothes and worn, the electrolyte can be used as the electrolyte of the flexible battery through human sweat, and then the battery can be powered, so that the use is safer.
The manufacturing method of the flexible battery provided by the invention omits a copper-aluminum foil as a current collector, avoids the problem of battery short circuit in the bending process of the flexible battery, ensures that the flexible battery can normally work in the bending process, has better flexibility, can be integrated with a wearable article, has good biocompatibility when contacting with skin, and is more comfortable and safe to wear.
The flexible battery provided by the invention is prepared by the preparation method. The flexible battery can be integrated with a wearable article, and the battery has good biocompatibility when contacting with the skin, and is comfortable and safe to wear; and the organic material (TPE/PDMS) with low Young modulus and high elasticity is adopted as the outer packaging material, so that the flexibility of the flexible battery is better.
In the embodiment of the invention, the flexible battery manufactured by the manufacturing method is applied to a wearing article. Wherein, this flexible battery can be applied to wearing articles such as gauze mask on, when being applied to the gauze mask, can utilize the steam of breathing wherein as the electrolyte, and then for the battery lasts the power supply, and safe nontoxic harmless.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications and substitutions do not substantially depart from the spirit and scope of the embodiments of the present invention, and are intended to be included within the scope of the present invention.
Claims (10)
1. A method of making a flexible battery, comprising:
providing a prefabricated conductive film; the conductive film is a composite structure of a carbon nano tube, MXene and polyaniline;
adopting conductive silver paste to bond and fix the zinc foil and the conductive film to obtain a positive plate; cutting the conductive film to a preset size to obtain a negative plate;
and adhering and fixing the positive plate and the negative plate by adopting a diaphragm, packaging the positive plate, the negative plate and the diaphragm by adopting a packaging film together, and injecting electrolyte to obtain the flexible battery.
2. The method of claim 1, wherein the step of prefabricating the conductive film comprises:
ultrasonically dispersing carbon nano tubes and MXene in water to obtain a dispersion liquid, and fusing the dispersion liquid with a filter membrane to form a layer of composite film of the carbon nano tubes and the MXene on the surface of the filter membrane;
drying the obtained composite membrane, immersing the composite membrane into a solution of aniline and hydrochloric acid, and adding ammonium persulfate to soak for a preset time;
after soaking, cleaning and drying the composite film by using a solvent to obtain the conductive film; wherein the solvent is ethanol or distilled water.
3. The method of manufacturing a flexible battery according to claim 2, wherein the filter membrane is a nitrocellulose water-based filter membrane; the manufacturing method of the composite membrane comprises the following steps:
ultrasonically dispersing the carbon nano tube and MXene in water for 1.5-1.6 hours to obtain the dispersion liquid, and placing the filter membrane in a suction filtration device;
pouring the dispersion into the suction filtration device, and draining water;
and taking out the filter membrane, drying, and peeling the composite membrane formed on the filter membrane and the filter membrane to obtain the composite membrane.
4. The method of claim 2, wherein the predetermined time is 30 to 50 minutes.
5. The method of manufacturing a flexible battery according to claim 1, wherein the step of assembling the flexible battery comprises:
respectively bonding the positive plate and the negative plate to two sides of a diaphragm, and respectively bonding copper wires to the positive plate and the negative plate by adopting the conductive silver paste to obtain dry diaphragms;
and clamping the dried membrane between the packaging films, carrying out thermoplastic sealing on the packaging films, and injecting a sodium chloride solution to obtain the flexible battery.
6. The method for manufacturing the flexible battery according to claim 1, wherein the separator is made of a non-woven fabric material, polyethylene or a polyethylene ceramic coating material, and the encapsulation film is made of an organic material.
7. The method of claim 6, wherein the organic material is thermoplastic elastomer (TPE), Polydimethylsiloxane (PDMS), or polyethylene terephthalate (PET).
8. The method of claim 1, wherein the electrolyte is a sodium chloride solution and water.
9. A flexible battery, characterized in that the flexible battery is manufactured by the manufacturing method of any one of claims 1 to 8.
10. Use of a flexible battery manufactured by the manufacturing method of any one of claims 1 to 8 in an article of wear.
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