CN214203777U - All-solid-state graphene-based thin film lithium battery - Google Patents
All-solid-state graphene-based thin film lithium battery Download PDFInfo
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- CN214203777U CN214203777U CN202120294047.9U CN202120294047U CN214203777U CN 214203777 U CN214203777 U CN 214203777U CN 202120294047 U CN202120294047 U CN 202120294047U CN 214203777 U CN214203777 U CN 214203777U
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Abstract
The utility model provides an all solid-state graphite alkene base film lithium cell, include: a battery cell, comprising: the electrode comprises a collector substrate, and a graphene collector electrode thin film, a positive electrode thin film or a negative electrode thin film, a solid electrolyte thin film, a negative electrode thin film or a positive electrode thin film, a collector substrate thin film and a graphene collector electrode thin film which are sequentially formed on the collector substrate. The multi-layer thin film battery is formed by sequentially forming a positive electrode thin film or a negative electrode thin film, a solid electrolyte thin film, a negative electrode thin film or a positive electrode thin film between two graphene collector electrode thin films as an attaching substrate of the graphene collector electrode thin films and using the graphene collector electrode thin films as collectors of battery units, and each layer of thin film material is free of foreign matters and is tightly combined, so that the lithium battery has excellent interface associativity and harmony, the interface internal resistance is reduced, the contact surface resistance is reduced, and the energy density, specific energy, specific power, energy efficiency and energy conservation rate of the battery are improved.
Description
Technical Field
The utility model relates to an extensive energy storage, power energy field especially relate to full solid-state graphite alkene base film lithium cell.
Background
The conventional lithium ion battery has liquid electrolyte, has the problems of easy leakage, easy corrosion, short service life, poor safety, low reliability and the like, and cannot completely meet the requirement of large-scale industrial energy storage on safety. The all-solid-state lithium battery using the solid electrolyte to replace the liquid electrolyte effectively and thoroughly solves the safety problem of the battery. In the face of the requirements of new energy storage, smart grid and the like, attention is paid to all-solid-state lithium batteries with high safety in recent years.
However, since the solid materials have certain rigidity and strength, when the battery is formed, the contact surfaces of different solid materials cannot be completely attached to each other without gaps, so that the contact surface resistance of the all-solid-state lithium battery is very high, and the performance of the battery is significantly reduced, which causes the energy density, specific energy, specific power, energy efficiency and energy conservation rate of the all-solid-state battery to be limited.
Therefore, how to improve the battery structure of the all-solid-state lithium battery, reduce the contact surface resistance, and improve the energy density, specific energy, specific power, energy efficiency, and energy retention rate of the battery becomes a technical problem to be solved by those skilled in the art.
SUMMERY OF THE UTILITY MODEL
An object of the utility model is to provide an all solid-state graphite alkene base film lithium cell of solving above-mentioned problem at least partially.
The utility model relates to a further purpose improves the battery structure of all solid-state film lithium cell, provides an all solid-state graphite alkene base film lithium cell to reduce contact surface resistance, improve energy density, specific energy, specific power, energy efficiency and the energy conservation rate of battery.
The utility model discloses still another further purpose realizes stepping up and/or the dilatation of full solid-state graphite alkene base film lithium cell.
The utility model discloses another further purpose simplifies the preparation method of full solid-state graphite alkene base film lithium cell to realize the large-scale stable production of industrialization.
The utility model provides an all solid-state graphite alkene base film lithium cell, including the battery cell, it includes: the electrode comprises a collector substrate, and a graphene collector electrode thin film, a positive electrode thin film or a negative electrode thin film, a solid electrolyte thin film, a negative electrode thin film or a positive electrode thin film, a collector substrate thin film and a graphene collector electrode thin film which are sequentially formed on the collector substrate.
Optionally, the thickness of the negative electrode thin film is 1.5 to 1850 μm.
Optionally, the thickness of the solid electrolyte film is 1.5-1450 μm.
Optionally, the thickness of the positive electrode thin film is 1.5-1250 μm.
Optionally, the thickness of the graphene collector electrode thin film is 0.5-100 μm; and the sheet resistance of the graphene collector electrode thin film is 0.3-100 omega/sq.
Optionally, the all-solid-state graphene-based thin film lithium battery further includes: the packaging protection film is formed on the graphene collector electrode film on the outermost layer of the battery unit; the thickness of the packaging protection film is 9.5-1920 μm.
Optionally, there is one battery cell; the collector substrate is made of plastic, copper foil, aluminum foil or carbon nano tubes; the collector substrate film is formed by copper or aluminum through sputtering deposition; the thickness of the collector base material film is 0.355 to 3.55 nm.
Optionally, the battery unit is a plurality of battery units, and the battery units are sequentially arranged in a deposition manner, and adjacent battery units are connected in series or in parallel; the adjacent battery units are connected with the graphene collector electrode thin film through a shared collector electrode base material thin film; in the adjacent cell unit, the current collector base material film of the previously formed cell unit serves as the current collector base material of the subsequently formed cell unit.
Alternatively, in the order of formation of the plurality of battery cells, in the direction of the continuous deposition arrangement of the plurality of battery cells, a first battery cell at the head end and a last battery cell at the tail end are formed; the thickness of the common collector base material film and the thickness of the collector base material film of the last battery cell are 0.355 to 3.55nm, respectively.
Optionally, the collector substrate of the first battery cell is made of plastic, copper foil, aluminum foil or carbon nanotubes; the common collector base material film and the collector base material film of the last cell are each formed by sputtering deposition of copper or aluminum.
The utility model discloses an all solid-state graphite alkene base film lithium cell, it includes the battery unit, the battery unit includes the collecting electrode substrate and forms the graphite alkene current collecting electrode film on the collecting electrode substrate in proper order, positive pole film or negative pole film, solid-state electrolyte film, negative pole film or positive pole film, collecting electrode substrate film and graphite alkene current collecting electrode film, no foreign matter between each layer film material, combine closely, and because graphite alkene possesses high electric conductivity, good mechanical strength and mechanical properties, efficient thermal stability and superior characteristics such as chemical stability, make the utility model discloses a lithium cell has fabulous interface bonding nature and harmony, has very low interfacial internal resistance, has reduced the contact surface resistance, is favorable to improving the energy density of battery, specific energy, specific power, energy efficiency and energy conservation rate.
Further, the utility model discloses an all solid-state graphite alkene base film lithium cell, battery cell can be a plurality of, and deposit in succession in proper order and arrange, adjacent battery cell series connection or parallel connection. By adjusting the positions of the positive electrode film and the negative electrode film of each battery unit relative to the solid electrolyte, not only can a plurality of series batteries and a plurality of parallel batteries be obtained, but also a plurality of series-parallel mixed batteries can be obtained, thereby realizing the boosting and/or capacity expansion of the all-solid-state graphene-based thin film lithium battery and having the advantage of simple structure.
Furthermore, the utility model discloses an all-solid-state graphite alkene base film lithium cell, the battery material of film form can be through the direct deposit in proper order of modern vapor deposition technique, can realize the large-area industrialization batch production, can accomplish the lithium cell batch manufacturing of any specification and size very conveniently, and this is favorable to simplifying the preparation method of all-solid-state graphite alkene base film lithium cell to realize the large-scale stable production of industrialization.
The above and other objects, advantages and features of the present invention will become more apparent to those skilled in the art from the following detailed description of specific embodiments thereof, taken in conjunction with the accompanying drawings.
Drawings
Some specific embodiments of the present invention will be described in detail hereinafter, by way of illustration and not by way of limitation, with reference to the accompanying drawings. The same reference numbers in the drawings identify the same or similar elements or components. Those skilled in the art will appreciate that the drawings are not necessarily drawn to scale. In the drawings:
fig. 1 is a schematic diagram of an all-solid-state graphene-based thin film lithium battery according to an embodiment of the present invention;
fig. 2 is another schematic diagram of an all-solid-state graphene-based thin film lithium battery according to an embodiment of the present invention;
fig. 3 is yet another schematic diagram of an all-solid-state graphene-based thin film lithium battery according to an embodiment of the present invention;
fig. 4 is yet another schematic diagram of an all-solid-state graphene-based thin film lithium battery according to an embodiment of the present invention.
Detailed Description
Fig. 1 is a schematic diagram of an all-solid-state graphene-based thin film lithium battery 10 according to an embodiment of the present invention. An all-solid-state graphene-based thin film lithium battery 10 (hereinafter may be simply referred to as "lithium battery 10") may generally include a battery cell.
The battery cell includes a collector substrate 110, and a graphene collector thin film 120, a positive electrode thin film 150 or a negative electrode thin film 130, a solid electrolyte thin film 140, a negative electrode thin film 130 or a positive electrode thin film 150, a collector substrate thin film 160, and a graphene collector thin film 120, which are sequentially formed on the collector substrate 110. That is, in the lithium battery 10 of the present embodiment, the battery cells are a plurality of thin film materials stacked. The battery cell includes two graphene collector thin films 120 formed in sequence, wherein one graphene collector thin film 120 is formed on the collector substrate 110 and the other graphene collector thin film 120 is formed on the collector substrate thin film 160.
The graphene collector thin film 120 serves as a collector of the battery cell. The graphene collector electrode thin film 120 may be formed on the collector substrate 110 or the collector substrate thin film 160 by coating or growth.
Graphene as a novel all-purpose material has the characteristics of extremely high conductivity, excellent mechanical strength and mechanical properties, high-efficiency thermal stability, excellent chemical stability and the like. The collector substrate 110 or the collector substrate film 160 is used as an adhesion substrate of the graphene collector electrode film 120, the graphene collector electrode film 120 is used as a collector electrode of a battery unit, the positive electrode film 150 or the negative electrode film 130, the solid electrolyte film 140, the negative electrode film 130 or the positive electrode film 150 are sequentially formed between the two graphene collector electrode films 120 to form a multilayer film battery, and other impurities are not contained between film materials of each layer and are tightly combined, so that the lithium battery 10 of the embodiment has excellent interface combination and coordination, has very low interface internal resistance, reduces contact surface resistance, and is beneficial to improving the energy density, specific energy, specific power, energy efficiency and energy conservation rate of the battery.
Since each layer of thin film material is a solid thin film, the lithium battery 10 of this embodiment further has the advantages of high safety, non-flammability, high temperature resistance, non-corrosiveness, non-volatility, and the like.
The positive electrode film 150 or the negative electrode film 130, the solid electrolyte film 140, the negative electrode film 130 or the positive electrode film 150 are arranged between the graphene collector electrode films 120, so that perfect matching between the graphene collector electrode films 120 and other films inside the battery unit can be realized, electrochemical corrosion of the collector electrode in multiple charging and discharging processes can be reduced or avoided, the operation reliability of the battery unit can be improved, and the overall service life can be prolonged; meanwhile, the graphene collector film 120 can also be used as an excellent adhesion substrate for the solid-state positive electrode or negative electrode film 130, and can improve the bonding force between the graphene collector film and the positive electrode film 150 or the negative electrode film 130. Moreover, because the battery structure is in an all-solid-state film form, the tight combination among the collector, the anode, the solid electrolyte, the cathode and the collector is realized, the impedance among all interfaces is reduced, the generation of dendrites in the charging and discharging process of the lithium battery 10 is eliminated, the short circuit phenomenon generated in the all-solid-state graphene-based film lithium battery 10 is eliminated, and the stability, the reliability and the safety of the all-solid-state graphene-based film lithium battery 10 in long-term operation are ensured.
Since the physical property, the chemical property, and the electrochemical property of the graphene collector thin film 120 are all very stable, it is not necessary to consider whether the graphene collector thin film 120 has an adverse effect on the formation process of other thin films in a cell unit in the preparation process of the lithium battery 10, which is beneficial to simplifying the preparation process of the lithium battery 10 and improving the preparation efficiency.
In the all-solid-state graphene-based thin-film lithium battery 10 of the embodiment, the battery materials in the form of thin films can be sequentially and directly deposited by a modern vapor deposition technology, so that large-area industrial mass production can be realized, batch manufacturing of lithium batteries 10 of any specification and size can be conveniently achieved, and the method for preparing the all-solid-state graphene-based thin-film lithium battery 10 is facilitated to be simplified, so that industrial large-scale stable production can be realized.
The thickness of the graphene collector thin film 120 may be 0.5 to 100 μm, for example, 0.5 μm, 10 μm, 30 μm, 50 μm, 70 μm, 90 μm, or 100 μm. The sheet resistance of the graphene collector film 120 may be 0.3-100 Ω/sq, for example, 0.3 Ω/sq, 10 Ω/sq, 30 Ω/sq, 50 Ω/sq, 70 Ω/sq, 90 Ω/sq, and 100 Ω/sq.
Since the graphene collector thin film 120 has a small thickness and a low sheet resistance, the interface internal resistance between the graphene collector and the positive electrode thin film 150 or the negative electrode thin film 130 can be further reduced by using the graphene collector thin film 120 and the collector as a battery cell, thereby improving the electrical performance of the lithium battery 10.
In the battery cell, the positive electrode film 150 and the negative electrode film 130 respectively positioned at two sides of the solid electrolyte form a positive electrode pair and a negative electrode pair of the battery cell, and the positions of the positive electrode film 150 and the negative electrode film 130 relative to the solid electrolyte can be changed. The graphene collector film 120 of the present embodiment may be disposed on either the side of the positive electrode film 150 facing away from the solid electrolyte film 140 or the side of the negative electrode film 130 facing away from the solid electrolyte film 140, so that the serial connection and/or the parallel connection between the plurality of battery cells can be flexibly achieved.
The thickness of the negative electrode thin film 130 may be 1.5 to 1850 μm, for example, 1.5 μm, 100 μm, 400 μm, 700 μm, 1000 μm, 0 μm, 1700 μm or 1850 μm. The thickness of the solid electrolyte thin film 140 may be 1.5 to 1450 μm, for example, 1.5 μm, 100 μm, 400 μm, 700 μm, 1000 μm, 0 μm, or 1450 μm. The thickness of the positive electrode thin film 150 may be 1.5 to 1250 μm, and may be, for example, 1.5 μm, 100 μm, 400 μm, 700 μm, 1000 μm, or 1250 μm. The gram-capacity of the lithium battery 10 can be adjusted by specially designing the thicknesses of the negative electrode thin film 130, the solid electrolyte thin film 140, and the positive electrode thin film 150 of the battery cell of the lithium battery 10.
The battery unit may be one or more.
When the battery cell is one, the lithium battery 10 is a single battery, which includes only one basic cell. In fig. 1, a single battery cell is shown, the collector substrate 110 may be made of plastic, copper foil, aluminum foil, or carbon nanotubes, or may be made of other soft film materials, the collector substrate film 160 may be formed by sputtering deposition of copper or aluminum, or may be formed by sputtering deposition of other conductive materials, and the thickness of the collector substrate film 160 is 0.355 to 3.55 nm. The collector substrate 110 or the collector substrate thin film 160 is made of a material having conductivity, which is advantageous for reducing the internal resistance of the battery cell. When there is one cell, the collector substrate 110 is located at the head end of the cell, and the graphene collector thin film 120, the positive electrode thin film 150 or the negative electrode thin film 130, the solid electrolyte thin film 140, the negative electrode thin film 130 or the positive electrode thin film 150, the collector substrate thin film 160, and the graphene collector thin film 120 are stacked on the collector substrate 110 in this order.
The positive electrode thin film 150, the solid electrolyte thin film 140, the negative electrode thin film 130, and the collector substrate thin film 160 may be composed of nanoparticles, respectively. In some further embodiments the collector substrate 110 may also be comprised of nanoparticles. That is, the microstructure of each layer of the thin film material is nanoparticles for each layer of the thin film material of the battery cell. That is, each layer of thin film material is formed by arranging a plurality of nanoparticles, which can realize the transformation of the microstructure of the thin film from a common two-dimensional planar structure to a three-dimensional structure, and can improve the ratio of the capacity density to the power density of the lithium battery 10 by tens of times or even tens of times as a whole. The particle size of the nanoparticles of each layer of the film material can be 1-500 nm, for example, 1nm, 10nm, 30nm, 50nm, 70nm, 90nm, 100nm, 200nm, 300nm, 400nm or 500 nm.
In some embodiments, the battery unit is a plurality of battery units, and the plurality of battery units are sequentially arranged in a deposition manner. Herein, "continuous deposition" is to be understood in a broad sense and may include sequential deposition by vacuum magnetron sputtering, or deposition by coating or growth. Each battery unit forms a battery, and a plurality of battery units form a plurality of batteries. Adjacent cells are connected to the graphene collector film 120 through a common collector substrate film 160. Adjacent cells are connected to the graphene collector film 120 by a common collector substrate film 160. Among the adjacent cells, the collector base material film 160 of the previously formed cell serves as the collector base material 110 of the subsequently formed cell. That is, of the adjacent cells, the collector base material film 160 of the cell formed immediately before and the graphene collector film 120 formed on the collector base material film 160 serve as the collector base material 110 of the cell formed immediately after and the graphene collector film 120 formed on the collector base material 110. In the process of forming a plurality of battery cells, the battery cell formed first may be used as a basic cell of all the battery cells, and the remaining battery cells may be sequentially stacked on the side of the graphene collector electrode thin film 120 of the outermost layer of the basic cell facing away from the collector substrate thin film 160.
By adjusting the positions of the positive electrode film 150 and the negative electrode film 130 of each battery unit relative to the solid electrolyte film 140, a plurality of series-connected batteries, a plurality of parallel-connected batteries, and a plurality of series-parallel-connected hybrid batteries can be obtained, so that the boosting and/or expansion of the all-solid-state graphene-based thin film lithium battery 10 can be realized, and the all-solid-state graphene-based thin film lithium battery has the advantage of simple structure.
In the order of formation of the plurality of battery cells, a first battery cell located at the head end and a last battery cell located at the tail end are formed in the direction of the continuous deposition arrangement of the plurality of battery cells. The first formed basic cell is the first battery cell, and the last formed battery cell is the last battery cell. The collector substrate 110 of the first battery cell may be made of plastic, copper foil, aluminum foil, or carbon nanotubes, or may be made of other soft film materials. The common collector substrate film 160, and the collector substrate film 160 of the last cell unit may be deposited from copper or aluminum by sputtering, respectively.
The thickness of the common collector base material film 160 and the thickness of the collector base material film 160 of the last cell may be 0.355 to 3.55nm, for example, 0.5nm, 1nm, 2nm, 3nm, and the like.
The positive electrode thin film 150, the solid electrolyte thin film 140, the negative electrode thin film 130, the common collector base material thin film 160, and the collector base material thin film 160 of the last cell unit may be respectively composed of a plurality of nanoparticles. In some further embodiments, the current collector substrate 110 of the leading cell may also be comprised of nanoparticles. That is, the microstructures of each layer of the thin film material are nanoparticles for each layer of the thin film material of each battery cell.
The structure of an all-solid-state graphene-based thin film lithium battery 10 having a plurality of battery cells will be further described with reference to specific embodiments.
Fig. 2 is another schematic diagram of an all-solid-state graphene-based thin film lithium battery 10 according to an embodiment of the present invention, showing two series-connected battery cells, with arrows showing the stacking direction of the films. As shown in fig. 2, the lithium battery 10 is formed by sequential deposition from bottom to top. The collector substrate 110, the graphene collector thin film 120, the negative electrode thin film 130, the solid electrolyte thin film 140, the positive electrode thin film 150, the collector substrate thin film 160, and the graphene collector thin film 120, which are arranged in this order from bottom to top in fig. 2, form a basic unit, and the collector substrate thin film 160, the graphene collector thin film 120, and the negative electrode thin film 130, the solid electrolyte thin film 140, the positive electrode thin film 150, the collector substrate thin film 160, and the graphene collector thin film 120, which are located above the basic unit, form another battery cell.
Fig. 2 illustrates only two battery cells connected in series, and the number of battery cells connected in series may be any value equal to or greater than two.
Fig. 3 is yet another schematic diagram of an all-solid-state graphene-based thin film lithium battery 10 according to an embodiment of the present invention, illustrating two parallel cells, with arrows showing the stacking direction of the films of each layer. As shown in fig. 3, the lithium battery 10 is formed by sequential deposition from bottom to top. The collector substrate 110, the graphene collector electrode thin film 120, the positive electrode thin film 150, the solid electrolyte thin film 140, the negative electrode thin film 130, the collector substrate thin film 160, and the graphene collector electrode thin film 120, which are arranged in this order from bottom to top in fig. 3, form a basic unit, and the collector substrate thin film 160, the graphene collector thin film 120, and the negative electrode thin film 130, the solid electrolyte thin film 140, the positive electrode thin film 150, the collector substrate thin film 160, and the graphene collector thin film 120, which are located above the basic unit, form another battery cell.
Fig. 3 illustrates only two parallel battery cells as an example, and the number of battery cells may be any value equal to or greater than two for the parallel battery cells.
In some alternative embodiments, different battery units may be connected in series and parallel, and the number of battery units may be any value greater than or equal to four.
Fig. 4 is a further schematic diagram of an all-solid-state graphene-based thin-film lithium battery 10 according to an embodiment of the present invention, showing four battery cells in series-parallel hybrid connection, with arrows showing the stacking direction of the films. As shown in fig. 4, the lithium battery 10 is formed by deposition in order from bottom to top. The lithium battery 10 includes, in order from bottom to top: a collector substrate 110, a graphene collector thin film 120, a negative electrode thin film 130, a solid electrolyte thin film 140, a positive electrode thin film 150, a collector substrate thin film 160, a graphene collector thin film 120, a positive electrode thin film 150, a solid electrolyte thin film 140, a negative electrode thin film 130, a collector substrate thin film 160, and a graphene collector thin film 120.
Fig. 4 illustrates only four series-parallel hybrid-connected battery cells as an example, and the number of battery cells may be any value equal to or greater than four for the series-parallel hybrid battery cells.
For a single battery or a plurality of batteries, the collector substrate 110 of the basic unit may also be a copper film, an aluminum film, or a carbon nanotube film, and the copper film, the aluminum film, or the carbon nanotube film may be prepared by a vacuum magnetron sputtering method, respectively.
In some further embodiments, the lithium battery 10 may further include an encapsulation protection film formed on the graphene collector film 120 at the outermost layer of the battery cell for encapsulation and protection. The "outermost graphene collector thin film 120" refers to the graphene collector thin film 120 formed last in the process of forming a single battery or a plurality of batteries. The thickness of the packaging and protecting film can be 9.5-1920 μm. Taking a single battery as an example, according to the order of formation of each layer of thin films, the all-solid-state graphene-based thin-film lithium battery 10 sequentially includes a plastic thin film or a copper foil or an aluminum foil or a carbon nanotube (i.e., a collector substrate 110), a graphene collector thin film 120, an anode thin film 150 or a cathode thin film 130, a solid electrolyte thin film 140, a cathode thin film 130 or an anode thin film 150, a collector substrate thin film 160, a graphene collector thin film 120, and a packaging protection thin film.
The structure of the battery will be further described with reference to the method for manufacturing the all-solid-state graphene-based thin-film lithium battery 10. The preparation method can generally comprise the following steps:
step S204, a graphene film is coated or grown on the collector substrate 110 to form a graphene collector film 120, and the graphene collector film 120 serves as a collector.
Step S206, sequentially depositing the positive electrode thin film 150 or the negative electrode thin film 130, the solid electrolyte thin film 140, the negative electrode thin film 130 or the positive electrode thin film 150 on the graphene collector thin film 120. The previously deposited cathode thin film 150 or anode thin film 130 may be named as a first electrode thin film, and the subsequently deposited anode thin film 130 or cathode thin film 150 may be named as a second electrode thin film.
In step S208, a collector substrate film 160 is deposited on the second electrode film as another collector. The material of the collector substrate film 160 in this step may be copper or aluminum.
After the collector substrate film 160 is deposited on the second electrode film, a graphene film may be coated or grown on the newly formed collector substrate film 160 to form the graphene collector film 120, and thus a battery cell may be obtained. By using the above preparation method, the all-solid-state graphene-based thin film lithium battery 10 having one battery cell can be obtained. When a single cell is prepared, the collector substrate 110 in step S204 may be a plastic film, a copper foil, an aluminum foil, or a carbon nanotube, and after a graphene film is coated or grown on the newly formed collector substrate film 160, a packaging protection film may be deposited on the graphene collector film 120.
In some embodiments, after the step S208, the preparation method may further include a step S210: the collector base material film 160 of the cell deposited in step S208 is used as the collector base material 110, and steps S204 to S208 are repeatedly performed on the collector base material 110 to obtain a plurality of cells stacked one on another. In the preparation of the first battery cell, the collector substrate 110 may be a plastic film, a copper foil, an aluminum foil, or a carbon nanotube. After the second electrode thin film of the last battery cell and the collector substrate thin film 160 are deposited, a graphene thin film may be coated or grown on the newly formed collector substrate thin film 160 to form the graphene collector thin film 120, and an encapsulation protection thin film may be deposited on the newly formed graphene collector thin film 120.
The following will further illustrate the process flow of the all-solid-state graphene-based thin film lithium battery 10 with reference to more specific examples. It should be noted that the specific values, the copper foil material and the deposition sequence of each layer of the thin film in the following examples are only for illustration and should not be construed as limiting the specific values, the copper foil material and the deposition sequence.
For example, the manufacturing process for preparing the all-solid-state graphene-based thin film lithium battery 10 shown in fig. 1 includes: a graphene thin film having a thickness of 6 μm is coated on a surface of a copper foil of 1 square meter to form a graphene collector thin film 120, wherein the surface of the copper foil is clean. And a cathode sputtering target, a solid electrolyte sputtering target, an anode sputtering target, a sputtering target of the collector substrate film 160 and a sputtering target of the packaging protection film are sequentially arranged on the magnetron sputtering continuous line. Operating a magnetron sputtering continuous line, pumping the vacuum degree to a set value, introducing Ar290sccm, keeping the vacuum degree at 0.1Pa, performing sputtering deposition on the negative electrode film 130 to ensure that the thickness of the deposited negative electrode film 130 is 4.5 mu m, pumping the vacuum degree to the set value, introducing Ar 270sccm and O2 28sccm，N2Sputtering and depositing the solid electrolyte film 140 at 62sccm and keeping the vacuum degree at 0.1Pa to ensure that the thickness of the deposited solid electrolyte film 140 is 1.5 mu m, pumping Ar at 250sccm and O after the vacuum degree reaches a set value238sccm, keeping the vacuum degree at 0.1Pa, performing sputtering deposition on the anode thin film 150 to ensure that the thickness of the deposited anode thin film 150 is 15 μm, pumping the vacuum degree to a set value, introducing Ar290sccm, keeping the vacuum degree at 0.1Pa, performing sputtering deposition on the collector base thin film 160 to ensure that the thickness of the deposited collector base thin film 160 is 2nm, coating a graphene collector thin film 120 with the thickness of 6 μm on the collector base thin film 160, ensuring that the square resistance of the graphene collector thin film 120 is 0.3-100 omega/sq, pumping Ar250sccm and O after the vacuum degree is pumped to the set value238sccm, maintain vacuumAnd sputtering and depositing the packaging film at the temperature of 0.1Pa to ensure that the thickness of the deposited packaging protection film is 5 mu m. The capacity of the battery 10 obtained after chemical conversion was 12240(mA · h).
For another example, the preparation process for preparing the two serially connected all-solid-state graphene-based thin film lithium batteries 10 shown in fig. 2 includes: a graphene thin film with a thickness of 7 μm is coated on the surface of a copper foil of 1 square meter to obtain a graphene collector thin film 120, wherein the surface of the copper foil is clean. And a cathode sputtering target, a solid electrolyte sputtering target, an anode sputtering target, a sputtering target of the collector substrate film 160 and a sputtering target of the packaging protection film are sequentially arranged on the magnetron sputtering continuous line. Operating a magnetron sputtering continuous line, pumping the vacuum degree to a set value, introducing Ar 300sccm, keeping the vacuum degree at 0.1Pa, performing sputtering deposition on the negative electrode film 130 to ensure that the thickness of the deposited negative electrode film 130 of each battery 10 is 5.5 mu m, pumping the vacuum degree to the set value, introducing Ar290sccm and O2 35sccm，N269sccm, keeping the vacuum degree at 0.1Pa, performing sputtering deposition on the solid electrolyte film 140 to ensure that the thickness of the deposited solid electrolyte film 140 of each cell 10 is 2.0 μm, pumping the vacuum degree to a set value, introducing Ar 270sccm and O238sccm, keeping the vacuum degree at 0.1Pa, performing sputtering deposition on the positive electrode thin film 150 to ensure that the thickness of the deposited positive electrode thin film 150 of each battery 10 is 18.5 mu m, pumping the vacuum degree to a set value, introducing Ar290sccm, keeping the vacuum degree at 0.1Pa, performing sputtering deposition on the collector electrode base material thin film 160 to ensure that the thickness of the deposited collector electrode base material thin film 160 is 2nm, coating a graphene collector electrode thin film 120 with the thickness of 7 mu m on the collector electrode base material thin film 160, ensuring that the square resistance of the graphene collector electrode thin film 120 is 0.3-100 omega/sq, pumping Ar250sccm, O250 sccm and O after the vacuum degree is pumped to the set value2And (3) carrying out sputtering deposition on the packaging protection film by keeping the vacuum degree at 0.1Pa at 38sccm, so that the thickness of the deposited packaging protection film is 5 mu m. The capacity of the battery 10 obtained after chemical conversion was 96(mA · h).
As another example, the process flow for preparing the two parallel-connected all-solid-state graphene-based thin film lithium battery 10 shown in fig. 3 may include: the surface of the copper foil with the thickness of 1 square meter is coated withAnd 7 μm of graphene film to obtain the graphene collector film 120, wherein the surface of the copper foil is clean. And a cathode sputtering target, a solid electrolyte sputtering target, an anode sputtering target, a sputtering target of the collector substrate film 160 and a sputtering target of the packaging protection film are sequentially arranged on the magnetron sputtering continuous line. Operating a magnetron sputtering continuous line, pumping the vacuum degree to a set value, introducing Ar 310sccm, keeping the vacuum degree at 0.1Pa, performing sputtering deposition on the negative electrode film 130 to ensure that the thickness of the deposited negative electrode film 130 of each battery 10 is 6.5 mu m, pumping the vacuum degree to the set value, introducing Ar 300sccm and O2 40sccm，N273sccm, keeping the vacuum degree at 0.1Pa, performing sputtering deposition on the solid electrolyte film 140 to ensure that the thickness of the deposited solid electrolyte film 140 of each cell 10 is 2.5 μm, pumping the vacuum degree to a set value, and introducing Ar290sccm and O242sccm, keeping the vacuum degree at 0.1Pa, performing sputtering deposition on the positive electrode thin film 150 to ensure that the thickness of the deposited positive electrode thin film 150 of each battery 10 is 22 μm, pumping the vacuum degree to a set value, introducing Ar290sccm, keeping the vacuum degree at 0.1Pa, performing sputtering deposition on the collector electrode base material thin film 160 to ensure that the thickness of the deposited collector electrode base material thin film 160 is 2nm, coating a graphene collector electrode thin film 120 with the thickness of 7 μm on the collector electrode base material thin film 160, ensuring that the square resistance of the graphene collector electrode thin film 120 is 0.3-100 omega/sq, pumping the vacuum degree to a set value, introducing Ar250sccm, O2And (3) sputtering and depositing the packaging thin film by keeping the vacuum degree at 0.1Pa at 38sccm, so that the thickness of the deposited packaging protection thin film is 5 mu m. The capacity of the battery 10 obtained after chemical conversion was 35904(mA · h).
As for the preparation process of the four-section series-parallel hybrid all-solid-state graphene-based thin-film lithium battery 10 shown in fig. 4, it should be easily known by those skilled in the art based on understanding the above embodiments, and therefore, the details are not described herein.
In the above embodiments, the material of each layer of the thin film sputtering target can be selected according to actual needs. For example, the cathode sputtering target may be lithium cobaltate, the anode sputtering target may be lithium, the solid electrolyte sputtering target may be lithium phosphate, the sputtering target of the collector substrate film 160 may be copper or aluminum, and the sputtering target of the encapsulation protection film may be silicon dioxide, but is not limited thereto. It should be noted that the above is merely an example of the material of the sputtering target, and the material of the sputtering target is not limited. Those skilled in the art will be fully capable of expanding the material of the sputtering target upon understanding the above embodiments. The magnetron sputtering continuous line may be a dedicated magnetron sputtering apparatus. The sputtering parameters of the magnetron sputtering continuous line, such as vacuum degree, sputtering atmosphere and the like, can be adjusted by adjusting the operating parameters of the magnetron sputtering device.
Utilize collecting electrode substrate 110 or collecting electrode substrate film 160 to be the attached base of graphite alkene collecting electrode film 120 to set up the thin film material that the stromatolite set up on graphite alkene collecting electrode film 120 and form the battery unit, combine closely between each layer thin film material of lithium cell 10 of this embodiment, the combination mode between the key interface is closely knit succinctly, has fabulous interface associativity and harmony, has very low interface internal resistance, has reduced contact surface resistance, thereby be favorable to improving the holistic output of lithium cell 10. Meanwhile, a plurality of non-functional redundant materials and structural forms in the existing battery structure can be eliminated among the graphene collector thin film 120, the cathode thin film 150 or the anode thin film 130, the solid electrolyte thin film 140, the cathode thin film 130 or the cathode thin film 150, and the collector substrate 110 or the collector substrate thin film 160 which are directly and closely connected, so that the capacity density and the power density of the solid lithium battery 10 are improved to the greatest extent, and the energy density, the specific energy, the specific power, the energy efficiency and the energy conservation rate of the battery are improved.
Since the thin film lithium battery 10 can be manufactured by using modern industrial manufacturing techniques and equipment, the thin film type battery cell can be industrially mass-produced in a large area, and the lithium battery 10 of any specification and size can be conveniently manufactured in batch. The thin film battery material can also realize the transformation of the microstructure morphology of the thin film from a common two-dimensional plane structure to a three-dimensional structure by a novel deposition technology, thereby greatly improving the capacity density and power density ratio of the thin film lithium battery 10.
Through special design of the thickness of each layer of thin film of the lithium battery 10 and combination of a specific lamination mode, series connection and/or parallel connection are realized, and the energy density of the all-solid-state graphene-based thin film lithium battery 10 prepared by the embodiment, especially the multiple lithium batteries 10, can reach 500-1000 Wh/kg.
Thus, it should be appreciated by those skilled in the art that while a number of exemplary embodiments of the invention have been shown and described in detail herein, many other variations and modifications can be made, consistent with the principles of the invention, which are directly determined or derived from the disclosure herein, without departing from the spirit and scope of the invention. Accordingly, the scope of the present invention should be understood and interpreted to cover all such other variations or modifications.
Claims (10)
1. An all-solid-state graphene-based thin film lithium battery, characterized by comprising:
a battery cell, comprising:
the electrode comprises a collector substrate, and a graphene collector electrode thin film, a positive electrode thin film or a negative electrode thin film, a solid electrolyte thin film, a negative electrode thin film or a positive electrode thin film, a collector substrate thin film and a graphene collector electrode thin film which are sequentially formed on the collector substrate.
2. The all-solid-state graphene-based thin film lithium battery of claim 1, wherein the lithium battery comprises a lithium ion battery cell and a lithium ion battery cell
The thickness of the negative electrode film is 1.5-1850 μm.
3. The all-solid-state graphene-based thin film lithium battery of claim 1, wherein the lithium battery comprises a lithium ion battery cell and a lithium ion battery cell
The thickness of the solid electrolyte film is 1.5-1450 mu m.
4. The all-solid-state graphene-based thin film lithium battery of claim 1, wherein the lithium battery comprises a lithium ion battery cell and a lithium ion battery cell
The thickness of the positive electrode film is 1.5-1250 μm.
5. The all-solid-state graphene-based thin film lithium battery of claim 1, wherein the lithium battery comprises a lithium ion battery cell and a lithium ion battery cell
The thickness of the graphene collector electrode film is 0.5-100 mu m; and is
The sheet resistance of the graphene collector electrode film is 0.3-100 omega/sq.
6. The all-solid-state graphene-based thin film lithium battery of claim 1, further comprising:
an encapsulation protection film formed on the graphene collector electrode film at the outermost layer of the battery cell; the thickness of the packaging protection film is 9.5-1920 mu m.
7. The all-solid-state graphene-based thin film lithium battery of claim 1, wherein the lithium battery comprises a lithium ion battery cell and a lithium ion battery cell
The number of the battery units is one; and is
The collector substrate is made of plastic, copper foil, aluminum foil or carbon nano tubes; the collector base material film is formed by copper or aluminum through sputtering deposition; the thickness of the collector substrate film is 0.355-3.55 nm.
8. The all-solid-state graphene-based thin film lithium battery of claim 1, wherein the lithium battery comprises a lithium ion battery cell and a lithium ion battery cell
The battery units are sequentially and continuously arranged in a deposition manner, and adjacent battery units are connected in series or in parallel; the adjacent battery units are connected with the graphene collector film through the shared collector substrate film; and in the adjacent battery unit, the current collector substrate film of the battery unit formed in the previous step is used as the current collector substrate of the battery unit formed in the next step.
9. The all-solid-state graphene-based thin film lithium battery of claim 8, wherein the lithium battery comprises a lithium ion battery cell and a lithium ion battery cell
According to the forming sequence of the plurality of battery units, in the continuous deposition arrangement direction of the plurality of battery units, a first battery unit at the head end and a last battery unit at the tail end are formed;
the thickness of the common collector base material film and the thickness of the collector base material film of the last battery cell are 0.355 to 3.55nm, respectively.
10. The all-solid-state graphene-based thin film lithium battery of claim 9, wherein the lithium battery comprises a lithium ion battery cell and a lithium ion battery cell
The collector substrate of the first battery unit is made of plastic, copper foil, aluminum foil or carbon nanotubes; the common collector base material film and the collector base material film of the last battery cell are each formed by sputtering deposition of copper or aluminum.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114050272A (en) * | 2021-11-17 | 2022-02-15 | 鄂尔多斯市紫荆创新研究院 | Graphene substrate and thin film lithium battery with same |
| CN114069022A (en) * | 2021-11-17 | 2022-02-18 | 鄂尔多斯市紫荆创新研究院 | Single-section high-voltage thin film lithium battery |
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2021
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114050272A (en) * | 2021-11-17 | 2022-02-15 | 鄂尔多斯市紫荆创新研究院 | Graphene substrate and thin film lithium battery with same |
| CN114069022A (en) * | 2021-11-17 | 2022-02-18 | 鄂尔多斯市紫荆创新研究院 | Single-section high-voltage thin film lithium battery |
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