CN116864795A - High-efficiency self-charging battery device and manufacturing method thereof - Google Patents
High-efficiency self-charging battery device and manufacturing method thereof Download PDFInfo
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- CN116864795A CN116864795A CN202310794629.7A CN202310794629A CN116864795A CN 116864795 A CN116864795 A CN 116864795A CN 202310794629 A CN202310794629 A CN 202310794629A CN 116864795 A CN116864795 A CN 116864795A
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- piezoelectric film
- negative electrode
- positive electrode
- battery device
- battery
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Classifications
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- H—ELECTRICITY
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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- H—ELECTRICITY
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- 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
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Abstract
The invention provides a high-efficiency self-charging battery device and a manufacturing method thereof, and relates to the technical field of batteries. The battery device comprises a shell and a single-layer battery, wherein the shell is provided with a cavity, and the single-layer battery is arranged in the cavity. According to the battery device, when external force is applied to the battery device, the first piezoelectric film generates a piezoelectric electric field under the action of the external force, so that lithium ions move from the positive electrode component to the negative electrode component, and the single-layer battery is charged. Because a plurality of individual layer batteries pile up in proper order, perhaps individual layer battery is around locating the outer peripheral face of supporter, when applying external force to battery device, first piezoelectric film can produce a plurality of piezoelectric fields, and a plurality of piezoelectric fields promote lithium ion by anodal subassembly to negative pole subassembly removal simultaneously, have improved battery device self-charging's charging efficiency, have expanded battery device's service scenario.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a high-efficiency self-charging battery device and a manufacturing method thereof.
Background
The lithium ion battery is a rechargeable battery, and is widely applied in daily life due to the advantages of convenient application, portability and the like. The lithium ion battery consists of a positive electrode, an electrolyte, a negative electrode and a polymer diaphragm. The positive electrode material generally employs a lithium ion-containing compound. The polymer membrane is generally provided with a microporous structure, which can allow lithium ions to pass freely, but electrons cannot pass. The working principle of the lithium ion battery is as follows: when the battery is charged, li+ is deintercalated from the positive electrode, and is inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; during discharge, li+ is deintercalated from the negative electrode and returned to the positive electrode through the electrolyte. Traditional lithium ion batteries rely on external power sources to charge themselves, and batteries are only charge storage devices.
A material in which a voltage difference occurs between two opposite surfaces of the material under the action of an external force is called a piezoelectric material, and this phenomenon is called a piezoelectric effect. The piezoelectric effect is a force-electricity coupling phenomenon, the crystal symmetry of the piezoelectric material is low, and the piezoelectric material can deform under the action of mechanical force. The principle of positive piezoelectric effect is: when the upper and lower surfaces of the crystal are extruded by external force, polarization can occur in the material, charges are outwards diffused, charges with opposite positive and negative polarities are generated on the two surfaces, and after the external force is removed, the crystal is restored to the original state. The positive piezoelectric effect reflects the ability of a piezoelectric material to convert mechanical energy into electrical energy, and piezoelectric materials can only be applied to the field of energy collection due to the positive piezoelectric effect.
In recent years, with exhaustion of conventional petrochemical resources and increasing deterioration of ecological environment, development of clean green energy has become a global hot spot. In green energy utilization, energy conversion and storage are very important technologies, and usually they are implemented by different devices and different methods, such as a common piezoelectric nano generator and a lithium ion battery. Combining such two separate steps typically requires additional technical unit support, which increases both the complexity and economic cost of the device and also results in time and energy losses in the process. Therefore, if the two processes can be combined into one in a single device, the energy utilization and conversion efficiency can be greatly improved, and the economic and time costs can be saved.
The Self-charging battery (namely Self-Charging Power Cell, abbreviated as SCPC) adopts smart device structural design, and the nano generator and the lithium ion battery are fused into a device unit, so that a new thought is provided for solving the problems. The self-charging battery is realized by using a polyvinylidene fluoride (PVDF) film with a piezoelectric effect to replace a Polyethylene (PE) film in a conventional lithium ion battery on the basis of the basic structural design of the lithium ion battery. The PVDF film after polarization has good piezoelectric effect. When it is subjected to pressure, the PVDF film is compressively deformed in the vertical direction, and a piezoelectric field is generated in the thickness direction thereof from the positive electrode to the negative electrode due to the piezoelectric effect of PVDF. Lithium ions in the electrolyte move from the anode to the cathode of the battery under the action of the electric field to shield the piezoelectric field, so that oxidation-reduction reaction occurs at the anode and the cathode of the battery, thereby realizing real-time energy storage, and the piezoelectric-electrochemical reaction finally shows self-charging behavior of the battery. The self-charging battery can independently complete two processes of self-power generation and self-charging by collecting mechanical vibration or deformation generated in the surrounding environment, and the mechanical energy is directly converted into electric energy on a single device and stored.
Principle of self-charging battery (LiCoO) 2 Positive electrode and negative electrode as graphite):
at the beginning, the self-charging battery is in a discharge state, at which time LiCoO 2 And aluminum foil as positive graphite and copper foil as negative electrode of battery, liPF 6 The solution is uniformly distributed throughout the battery as an electrolyte of the battery. The PVDF piezoelectric film is used as a diaphragm of the self-charging battery and is in intimate contact with the anode and the cathode of the battery, when the battery is subjected to external compressive force, the polarized PVDF-based piezoelectric diaphragm can generate compression deformation, and a piezoelectric field pointing from the anode of the battery to the cathode of the battery is generated in the thickness direction of the PVDF-based piezoelectric film. In order to shield the piezoelectric field generated by the PVDF piezoelectric diaphragm, lithium ions distributed in the electrolyte move from the positive electrode to the negative electrode of the battery through the PVDF diaphragm. Due to the directional movement of lithium ions, the lithium ions in the electrolyte are redistributed, the lithium ion concentration at the positive end of the battery decreases, the lithium ion concentration at the negative end increases, so that the electrochemical balance at the two poles of the battery is broken, and the electrochemical balance reaction (in LiCo0 2 For example, liCo0 2 ～Li 1- x Co0 2 +xLi + +xe - ) Moving to the right, liCoO 2 Li in (B) is extracted and Li is generated 1-x Co0 2 The positive electrode is negatively charged, while the electrochemical equilibrium reaction at the negative electrode (6c+xli, in the case of graphite + +xe - ～Li x C 6 ) Moving to the right, li is intercalated into C to form Li x C 6 . In the process, ions can continuously move from the positive electrode of the battery to the negative electrode of the battery until the lithium ions move to end and a new electric field is generated when the concentration gradient generated by the movement of the lithium ions just can shield the piezoelectric fieldThe chemical equilibrium is re-established and the self-charging reaction is completed. At this point, a small portion of the lithium ions have been intercalated into the graphite and a portion of the charge is stored in the battery. In the above process, mechanical energy is successfully converted into electrical energy and stored in the form of chemical energy by PVDF piezoelectric diaphragms, a process also known as a piezoelectrochemical process.
When the external compressive force is removed, the compression set of PVDF is removed and the piezoelectric field created by it is also removed. Because of the concentration difference of lithium ions at the two poles of the battery, a small amount of lithium ions can diffuse from the negative pole of the battery back to the positive pole of the battery through the PVDF piezoelectric diaphragm. The ions continue to diffuse in the electrolyte until uniformly distributed throughout the cell. At this point, a complete charging process of the self-charging battery is completed. With a small amount of LiCo0 at the positive electrode of the cell 2 Because Li is converted into Li 1-x Co0 2 While a small amount of Li is intercalated into the negative electrode of the battery to form LixC6, and the battery is charged with a small amount of electricity. When the self-charging battery is subjected to external compressive stress again, the above process occurs again and the battery is charged again by a small amount. By applying periodic compressive stress to the self-charging battery, the self-charging process is repeated, the voltage of the battery is continuously increased, and the battery power is continuously increased.
In the self-charging process of the self-charging battery, the PVDF-based piezoelectric diaphragm is not only a diaphragm for preventing the battery from being short-circuited in the battery, but also is equivalent to a direct current power supply used in a common lithium ion battery, and the directional movement of lithium ions in the battery is driven to charge the battery. When the direct current power supply is used for charging, electrons are driven by the direct current power supply to move from an external circuit to the negative electrode of the battery, meanwhile, lithium ions in the battery move from the positive electrode of the battery to the negative electrode of the battery, and the two poles of the battery undergo corresponding chemical reactions due to the concentration change of the lithium ions. In the self-charging process, a piezoelectric electric field is generated when the PVDF-based piezoelectric diaphragm is subjected to external pressure, mechanical energy is converted into electric energy, lithium ions can move from the anode of the battery to the cathode of the battery through the PVDF-based piezoelectric diaphragm under the action of the piezoelectric electric field, and corresponding chemical reactions occur at the two poles of the battery, so that self-charging is completed, and energy conversion and energy storage in a single device are realized. Under the action of pressure or ultrasonic waves, the self-charging battery can provide enough potential for lithium ions to move from the positive electrode to the negative electrode and to be embedded, so that self-charging driving is completed. The lithium battery can reach a full state by repeating the above process for a plurality of times.
The current self-charging battery has a single structure, which is a sandwich structure of a single-layer positive electrode, a single-layer diaphragm and a single-layer negative electrode, so that only mechanical energy from the vertical direction of a contact surface can be collected. On the one hand, the single-layer structure leads to that the piezoelectric diaphragm can generate induced charges once only by releasing the primary pressure, and the charging efficiency is low. On the other hand, the single-layer structure causes that a plurality of self-charging batteries are difficult to be connected in parallel, and the current generated by the self-charging batteries is small, so that the use scene of the self-charging batteries is greatly limited.
Disclosure of Invention
The invention provides a high-efficiency self-charging battery device, which is used for solving the defects of low charging efficiency, small generated current and few use scenes of a self-charging battery in the prior art, improving the self-charging efficiency of the battery device and expanding the use scenes of the battery device.
The invention provides a high-efficiency self-charging battery device, comprising:
a housing provided with a cavity;
the single-layer battery is arranged in the cavity and comprises an anode component, a cathode component, a first piezoelectric film and a second piezoelectric film, wherein the anode component, the first piezoelectric film, the cathode component and the second piezoelectric film are sequentially stacked; the first piezoelectric film and the second piezoelectric film are gel polymer piezoelectric films;
the single-layer batteries are stacked in sequence, or the single-layer batteries are wound on the outer peripheral surface of the support body.
According to the high-efficiency self-charging battery device provided by the embodiment of the invention, when a plurality of single-layer batteries are stacked in sequence, the first end of the first piezoelectric film and the first end of the second piezoelectric film are integrally formed, and the second end of the second piezoelectric film and the second end of the first piezoelectric film of the adjacent single-layer battery are integrally formed.
According to an embodiment of the present invention, there is provided a high-efficiency self-charging battery device, the positive electrode assembly including:
a positive electrode tab;
the positive electrode current collector is connected with the positive electrode lug at one side;
the positive electrode current collector is attached to the positive electrode;
the negative electrode assembly includes:
a negative electrode tab;
a negative electrode current collector; one side of the negative electrode current collector is connected with the negative electrode tab;
and the negative electrode current collector is attached to the negative electrode.
According to the high-efficiency self-charging battery device provided by the embodiment of the invention, the positive electrode tab and the negative electrode tab are positioned on the same side of the single-layer battery.
The invention also provides a manufacturing method of the high-efficiency self-charging battery device, which is based on any one of the high-efficiency self-charging battery devices, and comprises the following steps:
sequentially stacking the positive electrode component, the first piezoelectric film, the negative electrode component and the second piezoelectric film to form a single-layer battery;
stacking a plurality of single-layer batteries in sequence; or winding the single-layer battery around the outer peripheral surface of the support body;
heat-sealing the single-layer battery in an oxygen-free environment to form a case outside the single-layer battery;
extracting the positive electrode component and the negative electrode component from an opening of the shell;
and heat-sealing the opening of the shell.
According to the method for manufacturing the efficient self-charging battery device provided by the embodiment of the invention, after the step of heat-sealing the opening of the shell, the method further comprises the following steps:
the opening of the housing is sealed by an epoxy resin.
According to the method for manufacturing the efficient self-charging battery device provided by the embodiment of the invention, before the step of sequentially stacking the positive electrode component, the first piezoelectric film, the negative electrode component and the second piezoelectric film to form a single-layer battery, the method further comprises the following steps:
grinding and mixing a positive electrode material, a binder and a conductive agent uniformly according to a preset mass ratio, adding an organic solvent, stirring to form first slurry, and coating the first slurry on the positive electrode current collector through a film coater to form a positive electrode with a first preset thickness;
and drying the positive electrode, and connecting one side of the positive electrode current collector with the positive electrode lug.
According to the method for manufacturing the efficient self-charging battery device provided by the embodiment of the invention, before the step of sequentially stacking the positive electrode component, the first piezoelectric film, the negative electrode component and the second piezoelectric film to form a single-layer battery, the method further comprises the following steps:
grinding and mixing a negative electrode material, a binder and a conductive agent uniformly according to a preset mass ratio, adding an organic solvent, stirring to form second slurry, and coating the second slurry on a negative electrode current collector through a film coater to form a negative electrode with a second preset thickness;
and drying the negative electrode, and connecting one side of the negative electrode current collector with the negative electrode tab.
According to the method for manufacturing the efficient self-charging battery device provided by the embodiment of the invention, before the step of sequentially stacking the positive electrode component, the first piezoelectric film, the negative electrode component and the second piezoelectric film to form a single-layer battery, the method further comprises the following steps:
dispersing a high-molecular piezoelectric material, an inorganic nano piezoelectric material and a pore-forming agent in an organic solvent to form a third slurry;
preparing the third slurry into the first piezoelectric film and the second piezoelectric film with predetermined thicknesses by coating or electrospinning;
drying the first piezoelectric film and the second piezoelectric film in a vacuum environment;
soaking the first piezoelectric film and the second piezoelectric film in etching liquid for a first preset time and then drying;
the first piezoelectric film and the second piezoelectric film are polarized at a predetermined voltage.
According to the method for manufacturing the high-efficiency self-charging battery device provided by the embodiment of the invention, after the step of polarizing the first piezoelectric film and the second piezoelectric film under the preset voltage, the method further comprises the following steps:
the first piezoelectric film and the second piezoelectric film are immersed in an electrolyte for a second predetermined time in an oxygen-free environment.
According to the high-efficiency self-charging battery device provided by the embodiment of the invention, when external force is applied to the battery device, the first piezoelectric film generates a piezoelectric electric field under the action of the external force, so that lithium ions move from the positive electrode component to the negative electrode component, and the single-layer battery is charged. Short circuit between single-layer batteries is avoided by arranging the second piezoelectric film. Because a plurality of individual layer batteries pile up in proper order, perhaps individual layer battery is around locating the outer peripheral face of supporter, when applying external force to battery device, first piezoelectric film can produce a plurality of piezoelectric fields, and a plurality of piezoelectric fields promote lithium ion by anodal subassembly to negative pole subassembly removal simultaneously, have improved battery device self-charging's charging efficiency, have expanded battery device's service scenario. When the battery device is filled with the liquid electrolyte, although the battery device has good ion mobility, the battery device is at risk of leakage and explosion, and the battery device cannot be bent and pressed greatly, so that the performance of the battery device is greatly limited, and the flexibility of the battery device is also not facilitated. Through setting the first piezoelectric film and the second piezoelectric film as gel polymer piezoelectric films, liquid electrolyte is prevented from being filled, production safety problems such as electrode corrosion and oxidation combustion caused by liquid leakage are reduced, the battery device has better mechanical properties, the battery device is more beneficial to the flexibility of the battery device, the battery device can bear large-amplitude bending and multiple pressing, and the energy utilization rate of the battery device is greatly improved.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic cross-sectional front view of a battery device for efficient self-charging according to an embodiment of the present invention;
fig. 2 is a schematic perspective view of a single-layer battery according to an embodiment of the present invention;
FIG. 3 is a schematic diagram showing a second perspective structure of a single-layer battery according to an embodiment of the present invention;
fig. 4 is a schematic perspective view of a high-efficiency self-charging battery device according to an embodiment of the present invention;
FIG. 5 is a third schematic perspective view of a single-layer battery according to an embodiment of the present invention;
fig. 6 is a schematic side view of a single-layer battery according to an embodiment of the present invention;
fig. 7 is a schematic top sectional view of a high-efficiency self-charging battery device according to an embodiment of the present invention;
FIG. 8 is a schematic diagram showing a second perspective structure of a high-efficiency self-charging battery device according to an embodiment of the present invention;
fig. 9 is a flowchart of a method for manufacturing a high-efficiency self-charging battery device according to an embodiment of the present invention.
Reference numerals:
10. a housing; 110. a support body; 20. a single layer battery; 210. a positive electrode assembly; 211. a positive electrode tab; 212. a positive electrode current collector; 213. a positive electrode; 220. a negative electrode assembly; 221. a negative electrode tab; 222. a negative electrode current collector; 223. a negative electrode; 230. a first piezoelectric film; 240. and a second piezoelectric film.
Detailed Description
Embodiments of the present invention are described in further detail below with reference to the accompanying drawings and examples. The following examples are illustrative of the invention but are not intended to limit the scope of the invention.
In the description of the embodiments of the present invention, it should be noted that the terms "center", "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the embodiments of the present invention and simplifying the description, and do not indicate or imply that the apparatus or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the embodiments of the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In describing embodiments of the present invention, it should be noted that, unless explicitly stated and limited otherwise, the terms "coupled," "coupled," and "connected" should be construed broadly, and may be either a fixed connection, a removable connection, or an integral connection, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium. The specific meaning of the above terms in embodiments of the present invention will be understood in detail by those of ordinary skill in the art.
In embodiments of the invention, unless expressly specified and limited otherwise, a first feature "up" or "down" on a second feature may be that the first and second features are in direct contact, or that the first and second features are in indirect contact via an intervening medium. Moreover, a first feature being "above," "over" and "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is less level than the second feature.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means 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 embodiments of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
The following describes a highly efficient self-charging battery device and a method for manufacturing the same according to an embodiment of the present invention with reference to fig. 1 to 9.
Fig. 1 illustrates a schematic front sectional structure of a high-efficiency self-charging battery device according to an embodiment of the present invention, fig. 2 illustrates one of schematic perspective views of a single-layer battery according to an embodiment of the present invention, fig. 3 illustrates two of schematic perspective views of a single-layer battery according to an embodiment of the present invention, fig. 4 illustrates one of schematic perspective views of a high-efficiency self-charging battery device according to an embodiment of the present invention, fig. 5 illustrates three of schematic perspective views of a single-layer battery according to an embodiment of the present invention, fig. 6 illustrates a side view of a single-layer battery according to an embodiment of the present invention, and as shown in fig. 1 to 6, the high-efficiency self-charging battery device includes a case 10 and a single-layer battery 20, the case 10 is provided with a cavity, and the single-layer battery 20 is provided in the cavity. The single-layer battery 20 includes a positive electrode assembly 210, a negative electrode assembly 220, a first piezoelectric film 230, and a second piezoelectric film 240, and the positive electrode assembly 210, the first piezoelectric film 230, the negative electrode assembly 220, and the second piezoelectric film 240 are sequentially stacked. The first piezoelectric film and the second piezoelectric film are both gel polymer piezoelectric films. The plurality of single-layer batteries 20 are stacked in sequence, or the single-layer batteries 20 are wound around the outer circumferential surface of the support 110.
In the efficient self-charging battery device provided by the embodiment of the invention, when an external force is applied to the battery device, the first piezoelectric film 230 generates a piezoelectric field under the action of the external force, so that lithium ions move from the positive electrode assembly 210 to the negative electrode assembly 220, and the single-layer battery 20 is charged. Short-circuiting between the single-layer batteries 20 is prevented by providing the second piezoelectric film 240. Since the plurality of single-layer batteries 20 are stacked in sequence, or the single-layer batteries 20 are wound around the outer circumferential surface of the support body 110, when an external force is applied to the battery device, the first piezoelectric film 230 can generate a plurality of piezoelectric fields, and the plurality of piezoelectric fields simultaneously promote lithium ions to move from the positive electrode assembly 210 to the negative electrode assembly 220, so that the self-charging efficiency of the battery device is improved, and the service scenario of the battery device is expanded. When the battery device is filled with the liquid electrolyte, although the battery device has good ion mobility, the battery device is at risk of leakage and explosion, and the battery device cannot be bent and pressed greatly, so that the performance of the battery device is greatly limited, and the flexibility of the battery device is also not facilitated. Through setting the first piezoelectric film 230 and the second piezoelectric film 240 as gel polymer piezoelectric films, liquid electrolyte is prevented from being filled, production safety problems such as electrode corrosion and oxidation combustion caused by liquid leakage are reduced, the battery device has better mechanical properties, the battery device is more beneficial to the flexibility of the battery device, the battery device can bear large-amplitude bending and multiple pressing, and the energy utilization rate of the battery device is greatly improved.
Fig. 7 illustrates a schematic top sectional structure of a high-efficiency self-charging battery device according to an embodiment of the present invention, and fig. 8 illustrates a second perspective structure of a high-efficiency self-charging battery device according to an embodiment of the present invention, as shown in fig. 7 and 8, in which the supporting body 110 is made of a material having a certain rigidity, such as a metal, a polymer material, etc., so that the supporting body 110 can resist external pressure.
In the embodiment of the present invention, when a plurality of single-layer batteries 20 are stacked in sequence, the first end of the first piezoelectric film 230 is integrally formed with the first end of the second piezoelectric film 240, and the second end of the second piezoelectric film 240 is integrally formed with the second end of the first piezoelectric film 230 of the adjacent single-layer battery 20And (5) forming the body. The first piezoelectric film 230 and the second piezoelectric film 240 are made of high molecular piezoelectric materials, such as polyvinylidene fluoride and its copolymer, and polyethylene-tetrafluoroethylene copolymer. The first piezoelectric film 230 and the second piezoelectric film 240 may be polymer piezoelectric material based piezoelectric composite films such as PVDF-PZT piezoelectric film, PVDF-BaTiO 3 Piezoelectric films, and the like. When the first and second piezoelectric films 230 and 240 are integrally formed, a spacing gap is formed between the first and second piezoelectric films 230 and 240 of the single-layered battery 20 by folding, and the positive electrode assembly 210 and the negative electrode assembly 220 are alternately disposed in the spacing gap so that the plurality of single-layered batteries 20 are sequentially stacked. The thickness of the first piezoelectric film 230 and the second piezoelectric film 240 ranges from 30 to 100 μm.
In an embodiment of the present invention, the positive electrode assembly 210 includes a positive electrode tab 211, a positive electrode current collector 212, and a positive electrode 213. One side of the positive electrode current collector 212 is connected to the positive electrode tab 211, and the positive electrode current collector 212 is bonded to the positive electrode 213. The negative electrode assembly 220 includes a negative electrode tab 221, a negative electrode current collector 222, and a negative electrode 223. One side of the negative electrode current collector 222 is connected to the negative electrode tab 221, and the negative electrode current collector 222 is bonded to the negative electrode 223.
The positive electrode 213 is used to release lithium ions when charged and store lithium ions when discharged; the negative electrode 223 serves to release lithium ions upon discharge and store lithium ions upon charge. Because the positive current collector 212 is attached to the positive electrode 213, the negative current collector 222 is attached to the negative electrode 223, and the current generated by the battery device can be collected through the positive current collector 212 and the negative current collector 222, so that a larger current can be formed, and the efficiency of the battery device for externally outputting electric energy can be improved. Since one side of the positive electrode current collector 212 is connected to the positive electrode tab 211, one side of the negative electrode current collector 222 is connected to the negative electrode tab 221, and is simultaneously connected to the power consumption device through the positive electrode tab 211 and the negative electrode tab 221, so that the electric energy of the battery device is output to the power consumption device.
In an embodiment of the present invention, the material of the positive electrode 213 may be a lithium ion intercalation compound, such as lithium manganate, lithium iron phosphate, lithium cobaltate or Li-Ni-Co-Mn-O ternary positive electrode material. The material of the negative electrode 223 may be a carbon material or a composite thereof, for example, a carbon material such as graphite, amorphous carbon, carbon fiber, coke, or activated carbon, a composite of a carbon material and a metal such as silicon, tin, or silver, or an oxide of these metals. The materials of the positive electrode current collector 212 and the negative electrode current collector 222 may be conductive materials such as aluminum, copper, nickel, polyaniline, polyacetylene, polypyrrole, polythiophene, polyparaphenylene, and polyphenylacetylene. The material of the positive electrode tab 211 may be aluminum. The negative electrode tab 221 may be made of nickel or copper nickel (ni—cu) plating material.
In the embodiment of the present invention, the positive electrode tab 211 and the negative electrode tab 221 are located on the same side of the single-layer battery 20. Because the positive electrode tab 211 and the negative electrode tab 221 are positioned on the same side of the single-layer battery 20, the space occupied by the battery device is reduced, and the battery device is convenient to be connected with an electric device for outputting electric energy.
Fig. 9 illustrates a flowchart of a method for manufacturing a high-efficiency self-charging battery device according to an embodiment of the present invention, and as shown in fig. 9, the embodiment of the present invention further provides a method for manufacturing a high-efficiency self-charging battery device, where the method for manufacturing a high-efficiency self-charging battery device is based on the high-efficiency self-charging battery device of any one of the above, and includes:
step S100, stacking the positive electrode assembly 210, the first piezoelectric film 230, the negative electrode assembly 220, and the second piezoelectric film 240 in order to form a single-layer battery 20;
step S200, stacking a plurality of single-layer batteries 20 in sequence; or the single-layer battery 20 is wound around the outer circumferential surface of the support 110;
step S300 of heat-sealing the single-layer battery 20 in an oxygen-free environment to form the case 10 outside the single-layer battery 20;
step S400, leading the positive electrode assembly 210 and the negative electrode assembly 220 out of the opening of the case 10;
for example, the single-layer battery 20 is heat-sealed by a laminator using a PET or PI film in a glove box having an oxygen-free atmosphere to form the case 10 outside the single-layer battery 20. The positive electrode tab 211 and the negative electrode tab 221 extend out of the housing 10 to be connected to an electric device for conducting electricity. The plurality of positive electrode tabs 211 may be connected as one unit and the plurality of negative electrode tabs 221 may be connected as another unit, so that the structure of the battery device is simplified and electric power is output to the outside.
Step S500, heat-sealing the opening of the case 10.
In the embodiment of the present invention, after the step of heat-sealing the opening of the case 10, it further includes:
the opening of the case 10 is sealed by epoxy resin so as to strengthen the isolation of oxygen, and prevent oxygen from entering the inside of the battery device, thereby damaging the performance of the battery device.
In an embodiment of the present invention, before the step of sequentially stacking the positive electrode assembly 210, the first piezoelectric film 230, the negative electrode assembly 220, and the second piezoelectric film 240 to form the single-layer battery 20, the method further includes:
grinding and mixing the anode material, the binder and the conductive agent uniformly according to a preset mass ratio, adding an organic solvent, stirring to form first slurry, and coating the first slurry on the anode current collector 212 through a film coater to form an anode 213 with a first preset thickness;
for example, the positive electrode material, the binder and the conductive agent are ground and mixed uniformly according to a mass ratio of 8:1:1. The concentration of the first slurry determines the first predetermined thickness, and the concentration of the first slurry ranges from 0.5mg/cm to 1.0mg/cm.
The positive electrode 213 is dried, and one side of the positive electrode current collector 212 is connected to the positive electrode tab 211.
The positive electrode 213 was dried at 60℃for 2h. When the battery device is assembled, the positive electrode 213, the positive electrode current collector 212 and the positive electrode tab 211 can be dried in a vacuum drying oven at 120 ℃ for 12 hours, so that the organic solvent is completely volatilized, and oxygen and moisture are prevented from being brought into the battery device, and the performance of the battery device is affected.
In an embodiment of the present invention, before the step of sequentially stacking the positive electrode assembly 210, the first piezoelectric film 230, the negative electrode assembly 220, and the second piezoelectric film 240 to form the single-layer battery 20, the method further includes:
grinding and mixing the anode material, the binder and the conductive agent uniformly according to a preset mass ratio, adding an organic solvent, stirring to form second slurry, and coating the second slurry on the anode current collector 222 through a film coater to form an anode 223 with a second preset thickness;
and grinding and uniformly mixing the anode material, the binder and the conductive agent according to the mass ratio of 8:1:1. The concentration of the second slurry determines a second predetermined thickness, and the concentration of the second slurry ranges from 0.5mg/cm to 1.0mg/cm.
The negative electrode 223 is dried, and one side of the negative electrode current collector 222 is connected to the negative electrode tab 221.
Negative electrode 223 was also dried at 60 ℃ for 2h. When the battery device is assembled, the negative electrode 223, the negative electrode current collector 222 and the negative electrode tab 221 are dried in a vacuum drying oven at 120 ℃ for 12 hours, so that the organic solvent is completely volatilized and oxygen and moisture are prevented from being brought into the battery device, and the performance of the battery device is affected.
The conductive agent is conductive carbon nanomaterial, such as fullerene, carbon black, carbon nanotube, carbon fiber, graphene oxide, graphene, and other conductive carbon nanomaterial. The binder can be polyvinylidene fluoride, binary copolymer of polyvinylidene fluoride and hexafluoropropylene, sodium carboxymethylcellulose sodium alginate, polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polymethyl methacrylate, polyhydroxyethyl methacrylate polypropylene oxide, polyesteramine, polyacrylamide, etc.
In the examples of the present invention, 800mg of lithium cobaltate, 100mg of conductive carbon and 100mg of polyvinylidene fluoride (PVDF) were uniformly ground, followed by dissolution in 5ml of N-methylpyrrolidone (NMP) solution, followed by ultrasonic dispersion for 1 hour, to obtain a black uniform first slurry. The first slurry was applied to the aluminum foil by a doctor blade having a gauge of 75 μm, and then the aluminum foil coated with the first slurry was dried in a blast drying oven at 60 ℃ for 12 hours. Finally, one side of the aluminum foil is connected to the positive electrode tab 211.
In the examples of the present invention, 800mg of graphite, 100mg of conductive carbon and 100mg of polyvinylidene fluoride (PVDF) were uniformly ground, then dissolved in 5ml of an n-methylpyrrolidone (NMP) solution, and stirred uniformly to obtain a black pasty second slurry, the second slurry was coated on a copper foil by a doctor blade having a specification of 75 μm, and then the copper foil coated with the second slurry was dried in a blast drying oven at 60 ℃ for 12 hours. Finally, one side of the copper foil is connected to the negative electrode tab 221.
In an embodiment of the present invention, before the step of sequentially stacking the positive electrode assembly 210, the first piezoelectric film 230, the negative electrode assembly 220, and the second piezoelectric film 240 to form the single-layer battery 20, the method further includes:
dispersing a high-molecular piezoelectric material, an inorganic nano piezoelectric material and a pore-forming agent in an organic solvent to form a third slurry;
preparing the third slurry into a first piezoelectric film 230 and a second piezoelectric film 240 having a predetermined thickness by coating or electrospinning;
the organic solvent can be N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), dimethylacetamide (DMAC); the pore-forming agent can be ZnO nano particles or SiO 2 Microspheres, PS microspheres, DBP and the like are soluble in acid or organic solvent and have a size of 200-500 nm.
Drying the first and second piezoelectric films 230 and 240 in a vacuum environment;
in the drying, the first piezoelectric film 230 and the second piezoelectric film 240 may be placed in a vacuum drying oven and dried at 60-100 deg.c for 6-12 hours to remove the excessive organic solvent.
The first piezoelectric film 230 and the second piezoelectric film 240 are immersed in the etching solution for a first predetermined time and then dried. The etching liquid may be acids such as hydrochloric acid and hydrofluoric acid, or organic solvents such as acetone and ethanol, and the first predetermined time may be in the range of 12-24 hours.
Polarizing the first piezoelectric film 230 and the second piezoelectric film 240 at a predetermined voltage;
when polarization is performed, the first piezoelectric film 230 and the second piezoelectric film 240 may be placed in a 400-2000V voltage environment for polarization for 6-12h, so as to promote the generation of PVDF β phase.
In the embodiment of the invention, 1.5g of PVDF powder is weighed and dissolved in DMF solvent to prepare a uniform solution with 15wt%, then PVDF/ZnO suspension obtained by adding zinc oxide particles with the same mass as PVDF is added, and the PVDF/ZnO suspension is subjected to magnetic stirring for 2 hours and ultrasonic treatment for 1 hour to uniformly disperse the solute. The PVDF/ZnO suspension was coated on a glass substrate repeatedly cleaned with acetone and deionized water in advance to prepare a first piezoelectric film 230 and a second piezoelectric film 240 having a thickness of 30 μm.
The glass substrate coated with the first and second piezoelectric films 230 and 240 was placed in a vacuum drying oven and dried at 60 ℃. After the solvent is sufficiently volatilized, the first piezoelectric film 230 and the second piezoelectric film 240 can be peeled off. The stripped first piezoelectric film and the stripped second piezoelectric film are placed in 37wt% HCI solution for ultrasonic treatment for 1h, so that ZnO particles in the films are completely etched. Repeatedly cleaning with deionized water and drying to obtain the required porous PVDF film which can be used as a self-charging battery diaphragm.
The upper and lower sides of the first piezoelectric film and the second piezoelectric film are respectively connected with the two poles of a high-voltage direct-current power supply through copper foils, and beta-type dipoles originally distributed randomly in the first piezoelectric film and the second piezoelectric film are orderly arranged through a polarization process. The polarization voltage was 500V, the temperature was 90℃and the polarization time was 3h.
In an embodiment of the present invention, after the step of polarizing the first piezoelectric film 230 and the second piezoelectric film 240 at a predetermined voltage, it further includes:
the first piezoelectric film and the second piezoelectric film are immersed in the electrolyte for a second predetermined time in an oxygen-free environment so that the first piezoelectric film and the second piezoelectric film are prepared as gel polymer piezoelectric films. The second predetermined time may be 12-24 hours.
The electrolyte used in the invention consists of an organic solvent and electrolyte salt. For example, a mixture of ethylene carbonate, diethyl carbonate and dimethyl carbonate was prepared at a mass ratio of 1:1:1, and 1MLiPF was used 6 And dissolving in the mixed solution to form an electrolyte. The electrolyte salt may be LiClO 4 、LiBF 4 、LiI、LiPF 6 、LiCF 3 SO 3 、LiCF 3 CO 2 、LiAsF 6 、LiSbF 6 、LiAlCl 4 、LiCl、LiBr、LiB(C 2 H 5 ) 4 、LiCH 3 SO 3 、LiC 4 F 9 SO 3 、Li(CF 3 SO 2 ) 2 N, etc. The organic solvent can beExamples of the organic solvent include esters and ethers of organic solvents, such as carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate, lactones such as γ -butyrolactone, ethers such as dimethoxymethane, trimethoxymethane, 1, 2-dimethoxyethane, tetrahydrofuran and 2-methyltetrahydrofuran, sulfoxides such as dimethyl sulfoxide, oxorings such as 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, nitrogen-containing compounds such as acetonitrile nitromethane, esters such as methyl formate, methyl acetate, butyl acetate and methyl propionate, glymes such as diglyme, triglyme and tetraglyme, ketones such as acetone, diethyl ketone, methyl ethyl ketone and methyl isobutyl ketone, sulfones such as sulfolane, and sultones such as 1, 3-propane sultone and 4-butane sultone.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A high efficiency self-charging battery device, comprising:
a housing provided with a cavity;
the single-layer battery is arranged in the cavity and comprises an anode component, a cathode component, a first piezoelectric film and a second piezoelectric film, wherein the anode component, the first piezoelectric film, the cathode component and the second piezoelectric film are sequentially stacked; the first piezoelectric film and the second piezoelectric film are gel polymer piezoelectric films;
the single-layer batteries are stacked in sequence, or the single-layer batteries are wound on the outer peripheral surface of the support body.
2. The efficient self-charging battery device of claim 1, wherein when a plurality of the single-layer batteries are stacked in sequence, a first end of the first piezoelectric film is integrally formed with a first end of the second piezoelectric film, and a second end of the second piezoelectric film is integrally formed with a second end of the first piezoelectric film adjacent to the single-layer battery.
3. The efficient self-charging battery device of claim 2, wherein the positive electrode assembly comprises:
a positive electrode tab;
the positive electrode current collector is connected with the positive electrode lug at one side;
the positive electrode current collector is attached to the positive electrode;
the negative electrode assembly includes:
a negative electrode tab;
the negative electrode current collector is connected with the negative electrode tab at one side;
and the negative electrode current collector is attached to the negative electrode.
4. The efficient self-charging battery device of claim 3, wherein the positive tab and the negative tab are on the same side of the single-layer battery.
5. A method of manufacturing a highly efficient self-charging battery device, the method being based on the highly efficient self-charging battery device according to any one of claims 1 to 4, comprising:
sequentially stacking the positive electrode component, the first piezoelectric film, the negative electrode component and the second piezoelectric film to form a single-layer battery;
stacking a plurality of single-layer batteries in sequence; or winding the single-layer battery around the outer peripheral surface of the support body;
heat-sealing the single-layer battery in an oxygen-free environment to form a case outside the single-layer battery;
extracting the positive electrode component and the negative electrode component from an opening of the shell;
and heat-sealing the opening of the shell.
6. The method of manufacturing a highly efficient self-charging battery device according to claim 5, further comprising, after the step of heat-sealing the opening of the case:
the opening of the housing is sealed by an epoxy resin.
7. The method of manufacturing a highly efficient self-charging battery device according to claim 5 or 6, further comprising, before the step of sequentially stacking the positive electrode assembly, the first piezoelectric film, the negative electrode assembly, and the second piezoelectric film to form a single-layer battery:
grinding and mixing a positive electrode material, a binder and a conductive agent uniformly according to a preset mass ratio, adding an organic solvent, stirring to form first slurry, and coating the first slurry on the positive electrode current collector through a film coater to form a positive electrode with a first preset thickness;
and drying the positive electrode, and connecting one side of the positive electrode current collector with the positive electrode lug.
8. The method of manufacturing a highly efficient self-charging battery device according to claim 5 or 6, further comprising, before the step of sequentially stacking the positive electrode assembly, the first piezoelectric film, the negative electrode assembly, and the second piezoelectric film to form a single-layer battery:
grinding and mixing a negative electrode material, a binder and a conductive agent uniformly according to a preset mass ratio, adding an organic solvent, stirring to form second slurry, and coating the second slurry on a negative electrode current collector through a film coater to form a negative electrode with a second preset thickness;
and drying the negative electrode, and connecting one side of the negative electrode current collector with the negative electrode tab.
9. The method of manufacturing a highly efficient self-charging battery device according to claim 5 or 6, further comprising, before the step of sequentially stacking the positive electrode assembly, the first piezoelectric film, the negative electrode assembly, and the second piezoelectric film to form a single-layer battery:
dispersing a high-molecular piezoelectric material, an inorganic nano piezoelectric material and a pore-forming agent in an organic solvent to form a third slurry;
preparing the third slurry into the first piezoelectric film and the second piezoelectric film with predetermined thicknesses by coating or electrospinning;
drying the first piezoelectric film and the second piezoelectric film in a vacuum environment;
soaking the first piezoelectric film and the second piezoelectric film in etching liquid for a first preset time and then drying;
the first piezoelectric film and the second piezoelectric film are polarized at a predetermined voltage.
10. The method of manufacturing a highly efficient self-charging battery device according to claim 9, further comprising, after the step of polarizing the first piezoelectric film and the second piezoelectric film at a predetermined voltage:
the first piezoelectric film and the second piezoelectric film are immersed in an electrolyte for a second predetermined time in an oxygen-free environment.
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| CN202310794629.7A CN116864795A (en) | 2023-06-30 | 2023-06-30 | High-efficiency self-charging battery device and manufacturing method thereof |
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