CN111916816A - Laminated composite battery - Google Patents

Abstract

The embodiment of the invention provides a laminated composite battery, which comprises a lithium ion battery laminated unit and a super capacitor laminated unit, wherein the lithium ion battery laminated unit comprises a positive plate, a negative plate and a diaphragm which can be used for a lithium ion battery; the two outermost layers of the composite battery are selected from one of a positive plate with one side coated with a positive material and a negative plate with one side coated with a negative material; in each super capacitor lamination unit, the active material of the super capacitor positive electrode material is the same as that of the super capacitor negative electrode material. The composite battery has the advantages of both a lithium ion battery and a super capacitor, and has high power density.

Description

A laminated composite battery

technical field

The invention relates to the technical field of lithium ion batteries, in particular to a laminated composite battery.

Background technique

In recent years, with the rise and development of electric vehicles, electric bicycles, high-power start-stop equipment and other fields, there is an increasing demand for power supplies with both high energy density and high power density. Lithium-ion batteries have the advantages of large specific energy, high operating voltage, environmental friendliness, and no memory effect, but their power density is often only a fraction or even less than one-tenth of that of supercapacitor batteries, and the capacity can be exerted at lower temperatures. lower rate issues.

In contrast, supercapacitor batteries have short charge and discharge times, and can reach more than 95% of their rated capacity after charging for 1 second to 10 minutes; good ultra-low temperature characteristics, and a wide normal operating temperature range of -40°C to +70°C; high current discharge Strong capability, the power density is as high as 300-10000W/Kg, which is equivalent to several times or even dozens of times that of lithium-ion batteries. Now, supercapacitors are widely used in high current, data backup, hybrid vehicles and other fields. However, at the same time, its energy density is not high, only a fraction or even less than one-tenth of the energy density of lithium-ion batteries, which seriously limits its application in many fields with high energy density requirements.

Therefore, to develop a composite battery with the advantages of both lithium-ion batteries and supercapacitors, as well as high power and energy density, good rate characteristics, high cycle efficiency, long service life, and low unit power cost, industrial applications and development play a vital role.

SUMMARY OF THE INVENTION

The purpose of the present invention is to prepare a new type of battery that combines the advantages of lithium ion batteries and supercapacitors.

The inventors have found through research that a combination of a positive electrode sheet for a lithium ion battery and a positive electrode sheet for a supercapacitor is used in combination with a negative electrode sheet to form a composite battery that can provide a predetermined combination of different lithium ion battery properties and supercapacitor properties. This combination of cathode sheets for lithium ion batteries and cathode sheets for supercapacitors can be adjusted by simply changing the number of cathode sheets for lithium ion batteries and cathode sheets for supercapacitors to achieve different mass energy densities in hybrid batteries. (Wh/kg) and mass power density (W/kg), this composite battery can better adapt to the use of different environments, and has both the high energy density of lithium-ion batteries and the high power density of supercapacitors. When a positive electrode sheet or a negative electrode sheet coated with electrode material on one side is used as the outermost positive electrode sheet or negative electrode sheet of a composite battery, the energy density can be improved, and when a symmetric supercapacitor is used, the energy density is the same. power density.

To achieve the above object, the technical scheme adopted by the present invention is as follows:

A laminated composite battery includes a lithium ion battery laminated unit and a super capacitor laminated unit, the lithium ion battery laminated unit includes a positive electrode sheet, a negative electrode sheet and a separator that can be used for lithium ion batteries, and the super capacitor laminated unit Including a positive electrode sheet, a negative electrode sheet and a separator that can be used for supercapacitors; the two outermost layers of the composite battery are selected from a positive electrode sheet coated with a positive electrode material on one side and a negative electrode sheet coated with a negative electrode material on one side One of; in each of the supercapacitor lamination units, the active material of the positive electrode material of the supercapacitor is the same as the active material of the negative electrode material of the supercapacitor.

Further, the positive electrode sheet that can be used for supercapacitors is selected from the following positive electrode sheets:

a first positive electrode sheet, the first positive electrode sheet includes a first positive electrode current collector and a supercapacitor positive electrode material disposed on both sides of the first positive electrode current collector;

A third positive electrode sheet, the third positive electrode sheet includes a third positive electrode current collector, a lithium ion battery positive electrode material disposed on the first surface of the third positive electrode current collector, and a surface opposite to the first surface of the third positive electrode current collector A supercapacitor positive electrode material arranged on the second surface;

A fourth positive electrode sheet, the fourth positive electrode sheet includes a fourth positive electrode current collector and a supercapacitor positive electrode material disposed on one side surface of the fourth positive electrode current collector.

Further, the negative electrode sheet that can be used for supercapacitors is selected from the following negative electrode sheets:

a third negative electrode sheet, the third negative electrode sheet includes a third negative electrode current collector and a supercapacitor negative electrode material provided on both sides of the third negative electrode current collector;

a fourth negative electrode sheet, the fourth negative electrode sheet includes a fourth negative electrode current collector and a supercapacitor negative electrode material provided on one side surface of the fourth negative electrode current collector;

An eighth negative electrode sheet, the eighth negative electrode sheet includes an eighth negative electrode current collector and a first negative electrode material disposed on a first surface of the eighth negative electrode current collector, and the eighth negative electrode current collector and the first negative electrode material are The second negative electrode material on the second surface opposite the surface, the first negative electrode material is selected from a bifunctional negative electrode material and a lithium ion battery negative electrode material, the second negative electrode material is a supercapacitor negative electrode material, and the first negative electrode material and The second negative electrode material is different, and the bifunctional negative electrode material can adsorb/desorb lithium ions, and can intercalate/deintercalate lithium ions of the lithium ion battery.

Further, the positive electrode sheet coated with positive electrode material on one side is selected from the following positive electrode sheet:

a fourth positive electrode sheet, the fourth positive electrode sheet includes a fourth positive electrode current collector and a supercapacitor positive electrode material disposed on one side surface of the fourth positive electrode current collector;

A fifth positive electrode sheet, the fifth positive electrode sheet includes a fifth positive electrode current collector and a lithium ion battery positive electrode material disposed on one surface of the fifth positive electrode current collector.

Further, the negative electrode sheet coated with negative electrode material on one side is selected from the following negative electrode sheet;

a second negative electrode sheet, the second negative electrode sheet includes a second negative electrode current collector and a bifunctional negative electrode material arranged on one surface of the second negative electrode current collector, the bifunctional negative electrode material can adsorb/desorb lithium ions, And can intercalate/deintercalate lithium ions of lithium ion batteries;

a fourth negative electrode sheet, the fourth negative electrode sheet includes a fourth negative electrode current collector and a supercapacitor negative electrode material provided on one side surface of the fourth negative electrode current collector;

A sixth negative electrode sheet, the sixth negative electrode sheet includes a sixth negative electrode current collector and a lithium ion battery negative electrode material disposed on one surface of the sixth negative electrode current collector.

Further, the positive electrode sheet that can be used for lithium ion batteries is selected from the following positive electrode sheets:

a second positive electrode sheet, the second positive electrode sheet includes a second positive electrode current collector and a lithium ion battery positive electrode material disposed on both surfaces of the second positive electrode current collector;

A third positive electrode sheet, the third positive electrode sheet includes a third positive electrode current collector, a lithium ion battery positive electrode material disposed on the first surface of the third positive electrode current collector, and a surface opposite to the first surface of the third positive electrode current collector A supercapacitor positive electrode material arranged on the second surface;

A fifth positive electrode sheet, the fifth positive electrode sheet includes a fifth positive electrode current collector and a lithium ion battery positive electrode material disposed on one surface of the fifth positive electrode current collector.

Further, the negative electrode sheet that can be used for lithium ion batteries is selected from the following negative electrode sheets:

a first negative electrode sheet, the first negative electrode sheet includes a first negative electrode current collector and a bifunctional negative electrode material provided on both sides of the first negative electrode current collector, the bifunctional negative electrode material can adsorb/desorb lithium ions, And can intercalate/deintercalate lithium ions of lithium ion batteries;

a second negative electrode sheet, the second negative electrode sheet includes a second negative electrode current collector and a bifunctional negative electrode material arranged on one surface of the second negative electrode current collector, the bifunctional negative electrode material can adsorb/desorb lithium ions, And can intercalate/deintercalate lithium ions of lithium ion batteries;

a fifth negative electrode sheet, the fifth negative electrode sheet includes a fifth negative electrode current collector and a lithium ion battery negative electrode material provided on both sides of the fifth negative electrode current collector;

a sixth negative electrode sheet, the sixth negative electrode sheet includes a sixth negative electrode current collector and a lithium ion battery negative electrode material provided on one side surface of the sixth negative electrode current collector;

A seventh negative electrode sheet, the seventh negative electrode sheet includes a seventh negative electrode current collector and a first negative electrode material disposed on the first surface of the seventh negative electrode current collector, and the seventh negative electrode current collector and the first negative electrode material are The second negative electrode material on the second surface opposite the surface, the first negative electrode material and the second negative electrode material are both selected from a bifunctional negative electrode material, a supercapacitor negative electrode material and a lithium ion battery negative electrode material, the first negative electrode material Different from the second negative electrode material, the bifunctional negative electrode material is capable of adsorbing/desorbing lithium ions, and capable of intercalating/deintercalating lithium ions of a lithium ion battery.

Further, the composite battery includes a first positive electrode tab, a second positive electrode tab, and a negative electrode tab that are independent of each other; the positive electrode sheet that can be used for the supercapacitor lamination unit is connected to the first positive electrode tab; the The positive electrode sheet that can be used for the lithium ion battery stack unit is connected to the second positive electrode tab, and the negative electrode tabs of the supercapacitor stack unit and the lithium ion battery stack unit are connected to the negative electrode tab; when the composite battery includes the first electrode tab; When there are three positive electrode pieces, the third positive electrode piece is connected to the first positive electrode tab or the second positive electrode tab, the third positive electrode piece includes a third positive electrode current collector, and the lithium An ion battery positive electrode material, and a supercapacitor positive electrode material disposed on a second surface of the third positive electrode current collector opposite to the first surface.

Further, the first positive electrode tab and the second positive electrode tab are arranged on opposite sides of the composite battery, or the first positive electrode tab and the second positive electrode tab are arranged adjacent to the battery. sides.

The laminated composite battery of the embodiment of the present invention has at least the following beneficial effects:

(1) The composite battery of the embodiment of the present invention not only has the advantages of high energy density, high average output voltage, high charging efficiency, low self-discharge efficiency, good safety performance, long cycle and service life, etc. Supercapacitors have the advantages of stable performance, short charge and discharge time, long cycle life, and high power density.

(2) When the positive electrode sheet or the negative electrode sheet coated with the electrode material on one side is used as the outermost positive electrode sheet or the negative electrode sheet of the composite battery, the energy density can be improved.

(3) Further, when a symmetric supercapacitor is used, it has a higher power density when the energy density is the same.

(4) Further, when the positive electrode of the lithium ion battery and the positive electrode of the supercapacitor are respectively independently connected to two positive electrode tabs, the self-discharge effect of such a hybrid battery in the prior art can be reduced. The hybrid battery in the prior art has only one positive electrode tab. Due to the serious self-discharge defect of the supercapacitor, when the electric energy stored in the supercapacitor is consumed due to self-discharge, there is only one positive electrode tab and the positive electrode of the lithium ion battery. Directly connected, at this time, the electric energy stored in the lithium-ion battery will continue to be weakly discharged through the supercapacitor, and finally the self-discharge effect of the entire composite battery is too large and affects normal use. and substantially reduced this phenomenon. And using two independent positive electrode tabs, different charging systems and voltages can be selected for the lithium ion positive electrode of the composite battery and the positive electrode of the super capacitor, so as to ensure that the energy density and power density reach the level that is difficult to achieve with the existing ordinary technology. Compatibility, so that the battery can achieve the best performance, and can use different modes for power management of lithium-ion batteries and supercapacitors according to actual needs, so as to better play their respective advantages, which cannot be achieved by traditional single positive tabs .

Description of drawings

1 is a schematic structural diagram of a positive electrode sheet for supercapacitors according to an embodiment of the present invention, (a) is a front view of a positive electrode sheet for supercapacitors, (b) and (c) are side views, and 11 is a first positive electrode collector Fluid, 12 is a fourth positive electrode current collector, and the surface of the positive electrode current collector is coated with a supercapacitor positive electrode material (the shaded part in the figure).

2 is a schematic structural diagram of a positive electrode sheet for a lithium ion battery according to an embodiment of the present invention, (a) is a front view of the positive electrode sheet for a lithium ion battery, (b) and (c) are side views, and 21 is a second The positive electrode current collector, 22 is the fifth positive electrode current collector, and the surface of the positive electrode current collector is coated with a lithium ion battery positive electrode material (the shaded part in the figure).

3 is a schematic structural diagram of a positive electrode sheet for lithium ion batteries and supercapacitors according to an embodiment of the present invention, (a) is a front view of the positive electrode sheet in the first direction, (b) is a side view, and (c) is a positive electrode The front view of the sheet in the opposite direction to the first direction, 30 is the third positive current collector, the first surface 31 of the third positive current collector is coated with the positive electrode material of the lithium ion battery (the shaded part in the figure), the third positive current collector The two surfaces 32 are coated with supercapacitor positive electrode material (the shaded part in the figure).

4 is a schematic structural diagram of a compatible negative electrode sheet according to an embodiment of the present invention, (a) is a front view of a compatible negative electrode sheet, (b) and (c) are side views, and 41 is a first negative electrode current collector , 42 is the second negative electrode current collector, and the surface of the negative electrode current collector is coated with bifunctional negative electrode material (the shaded part in the figure).

5 is a schematic structural diagram of a negative electrode sheet for a supercapacitor according to an embodiment of the present invention, (a) is a front view of the negative electrode sheet for a supercapacitor, (b) and (c) are side views, and 51 is a third negative electrode The current collector, 52 is the fourth negative electrode current collector, and the surface of the negative electrode current collector is coated with a negative electrode material for supercapacitor (the shaded part in the figure).

6 is a schematic structural diagram of a transition negative electrode sheet according to an embodiment of the present invention, (a) is a front view of the negative electrode sheet in the first direction, (b) is a side view, and (c) is the first direction of the negative electrode sheet The front view of the opposite direction, 70 is the seventh negative current collector, the first surface 71 of the seventh negative current collector is coated with the negative electrode material of the lithium ion battery (the shaded part in the figure), and the second surface 72 of the seventh negative current collector is coated Supercapacitor anode material (shaded area in the figure).

FIG. 7 is a schematic structural diagram of a composite battery with a symmetric supercapacitor according to an embodiment of the present invention, and (a) is a front view of the battery.

FIG. 8 is a schematic structural diagram of a composite battery containing an asymmetric supercapacitor according to an embodiment of the present invention, and (a) is a front view of the battery.

9 is a schematic structural diagram of a composite battery containing both asymmetric supercapacitors and symmetric supercapacitors according to an embodiment of the present invention, (a) is a front view of the battery.

FIG. 10 is a schematic diagram of a tab structure of a hybrid battery according to an embodiment of the present invention.

Detailed ways

In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to specific embodiments and accompanying drawings. However, those skilled in the art know that the present invention is not limited to the accompanying drawings and the following embodiments. As used herein, the term "including" and its various variants can be understood as open-ended terms meaning "including but not limited to". The terms "first", "second" and similar expressions are only used to represent different technical features and have no substantial meaning.

<Composite battery>

In one solution of the present invention, a laminated composite battery according to an embodiment of the present invention includes a lithium-ion battery laminated unit and a supercapacitor laminated unit, and the lithium-ion battery laminated unit includes a A positive electrode sheet, a negative electrode sheet and a separator, the supercapacitor laminated unit includes a positive electrode sheet, a negative electrode sheet and a separator that can be used for a supercapacitor; the two outermost layers of the composite battery are both selected from one side coated with a positive electrode material. One of a positive electrode sheet and a negative electrode sheet coated with a negative electrode material on one side; in each supercapacitor lamination unit, the active material of the supercapacitor positive electrode material is the same as that of the supercapacitor negative electrode material.

In one aspect of the present invention, the positive electrode sheet that can be used for supercapacitors is selected from the following positive electrode sheets:

a first positive electrode sheet, the first positive electrode sheet includes a first positive electrode current collector and a supercapacitor positive electrode material disposed on both sides of the first positive electrode current collector;

A third positive electrode sheet, the third positive electrode sheet includes a third positive electrode current collector, a lithium ion battery positive electrode material disposed on the first surface of the third positive electrode current collector, and a surface opposite to the first surface of the third positive electrode current collector A supercapacitor positive electrode material arranged on the second surface;

A fourth positive electrode sheet, the fourth positive electrode sheet includes a fourth positive electrode current collector and a supercapacitor positive electrode material disposed on one side surface of the fourth positive electrode current collector.

In one aspect of the present invention, the negative electrode sheet that can be used for supercapacitors is selected from the following negative electrode sheets:

a third negative electrode sheet, the third negative electrode sheet includes a third negative electrode current collector and a supercapacitor negative electrode material provided on both sides of the third negative electrode current collector;

a fourth negative electrode sheet, the fourth negative electrode sheet includes a fourth negative electrode current collector and a supercapacitor negative electrode material provided on one side surface of the fourth negative electrode current collector;

An eighth negative electrode sheet, the eighth negative electrode sheet includes an eighth negative electrode current collector and a first negative electrode material disposed on a first surface of the eighth negative electrode current collector, and the eighth negative electrode current collector and the first negative electrode material are The second negative electrode material on the second surface opposite the surface, the first negative electrode material is selected from a bifunctional negative electrode material and a lithium ion battery negative electrode material, the second negative electrode material is a supercapacitor negative electrode material, and the first negative electrode material and The second negative electrode material is different, and the bifunctional negative electrode material can adsorb/desorb lithium ions, and can intercalate/deintercalate lithium ions of the lithium ion battery.

In one aspect of the present invention, the positive electrode sheet coated with positive electrode material on one side is selected from the following positive electrode sheets:

a fourth positive electrode sheet, the fourth positive electrode sheet includes a fourth positive electrode current collector and a supercapacitor positive electrode material disposed on one side surface of the fourth positive electrode current collector;

A fifth positive electrode sheet, the fifth positive electrode sheet includes a fifth positive electrode current collector and a lithium ion battery positive electrode material disposed on one surface of the fifth positive electrode current collector.

In one aspect of the present invention, the negative electrode sheet coated with the negative electrode material on one side is selected from the following negative electrode sheets;

a second negative electrode sheet, the second negative electrode sheet includes a second negative electrode current collector and a bifunctional negative electrode material arranged on one surface of the second negative electrode current collector, the bifunctional negative electrode material can adsorb/desorb lithium ions, And can intercalate/deintercalate lithium ions of lithium ion batteries;

a fourth negative electrode sheet, the fourth negative electrode sheet includes a fourth negative electrode current collector and a supercapacitor negative electrode material provided on one side surface of the fourth negative electrode current collector;

A sixth negative electrode sheet, the sixth negative electrode sheet includes a sixth negative electrode current collector and a lithium ion battery negative electrode material disposed on one surface of the sixth negative electrode current collector.

In one aspect of the present invention, the positive electrode sheet that can be used for lithium ion batteries is selected from the following positive electrode sheets:

a second positive electrode sheet, the second positive electrode sheet includes a second positive electrode current collector and a lithium ion battery positive electrode material disposed on both surfaces of the second positive electrode current collector;

A third positive electrode sheet, the third positive electrode sheet includes a third positive electrode current collector, a lithium ion battery positive electrode material disposed on the first surface of the third positive electrode current collector, and a surface opposite to the first surface of the third positive electrode current collector A supercapacitor positive electrode material arranged on the second surface;

A fifth positive electrode sheet, the fifth positive electrode sheet includes a fifth positive electrode current collector and a lithium ion battery positive electrode material disposed on one surface of the fifth positive electrode current collector.

In one aspect of the present invention, the negative electrode sheet that can be used for lithium ion batteries is selected from the following negative electrode sheets:

a first negative electrode sheet, the first negative electrode sheet includes a first negative electrode current collector and a bifunctional negative electrode material provided on both sides of the first negative electrode current collector, the bifunctional negative electrode material can adsorb/desorb lithium ions, And can intercalate/deintercalate lithium ions of lithium ion batteries;

a second negative electrode sheet, the second negative electrode sheet includes a second negative electrode current collector and a bifunctional negative electrode material arranged on one surface of the second negative electrode current collector, the bifunctional negative electrode material can adsorb/desorb lithium ions, And can intercalate/deintercalate lithium ions of lithium ion batteries;

a fifth negative electrode sheet, the fifth negative electrode sheet includes a fifth negative electrode current collector and a lithium ion battery negative electrode material provided on both sides of the fifth negative electrode current collector;

a sixth negative electrode sheet, the sixth negative electrode sheet includes a sixth negative electrode current collector and a lithium ion battery negative electrode material provided on one side surface of the sixth negative electrode current collector;

A seventh negative electrode sheet, the seventh negative electrode sheet includes a seventh negative electrode current collector and a first negative electrode material disposed on the first surface of the seventh negative electrode current collector, and the seventh negative electrode current collector and the first negative electrode material are The second negative electrode material on the second surface opposite the surface, the first negative electrode material and the second negative electrode material are both selected from a bifunctional negative electrode material, a supercapacitor negative electrode material and a lithium ion battery negative electrode material, the first negative electrode material Different from the second negative electrode material, the bifunctional negative electrode material is capable of adsorbing/desorbing lithium ions, and capable of intercalating/deintercalating lithium ions of a lithium ion battery.

In an aspect of the present invention, the composite battery includes a first positive electrode tab, a second positive electrode tab, and a negative electrode tab that are independent of each other; the positive electrode sheet that can be used in the supercapacitor laminated unit is connected to the first A positive electrode tab; the positive electrode tab that can be used for the lithium ion battery stack unit is connected to the second positive electrode tab, and the negative electrode tabs of the super capacitor stack unit and the lithium ion battery stack unit are connected to the negative electrode tab; When the composite battery includes a third positive electrode tab, the third positive electrode tab is connected to the first positive electrode tab or the second positive electrode tab, the third positive electrode tab includes a third positive electrode current collector, and the third positive electrode current collector is connected to the third positive electrode current collector. Lithium-ion battery positive electrode material arranged on the first surface, and supercapacitor positive electrode material arranged on the second surface of the third positive electrode current collector opposite to the first surface.

In one solution of the present invention, the first positive electrode tab and the second positive electrode tab are arranged on opposite sides of the composite battery, or the first positive electrode tab and the second positive electrode tab are arranged on adjacent sides of the battery.

<Positive electrode sheet for supercapacitor>

In one aspect of the present invention, the laminated composite battery of the embodiment of the present invention includes a positive electrode sheet, and the positive electrode sheet includes a first positive electrode sheet C1, and the first positive electrode sheet C1 is a positive electrode sheet for a super capacitor. The positive electrode sheet C1 includes a first positive electrode current collector for a supercapacitor and a supercapacitor positive electrode material disposed on both sides of the first positive electrode current collector.

Preferably, the positive electrode sheet in the embodiment of the present invention further includes a fourth positive electrode sheet C2, the fourth positive electrode sheet C2 is a positive electrode sheet for super capacitors, and the fourth positive electrode sheet C2 includes a fourth positive electrode current collector for super capacitors and a The supercapacitor cathode material on the surface of one side of the four cathode current collectors. Only one side of the fourth positive electrode sheet C2 is provided with a supercapacitor positive electrode material, and the fourth positive electrode sheet C2 can be used as the outermost positive electrode sheet of the composite battery.

As shown in FIG. 1 , the fourth positive electrode sheet C2 for supercapacitors coated with supercapacitor positive electrode material on the surface of the fourth positive electrode current collector is defined as C-single ((b) in FIG. 1 ); The first positive electrode sheet C1 for supercapacitors in which both surfaces of the first positive electrode current collector for supercapacitors are coated with a positive electrode material for supercapacitors is defined as C-bi ((c) in FIG. 1 ). The purpose of setting the first positive electrode sheet C1 and the fourth positive electrode sheet C2 for the supercapacitor is to form a supercapacitor positive and negative electrode pair with the matched negative electrode sheet F1, F2 or F3, so as to realize the storage of electric energy by the supercapacitor laminated unit. . In addition, C-single and C-double are mainly used in different structures to maximize the utilization of active materials, where C-single is mainly used in the lamination unit of the outermost supercapacitor, and C-double is mainly used in the non-outermost supercapacitor. in the laminated unit of the capacitor.

In one embodiment, the first positive electrode current collector and the fourth positive electrode current collector for the supercapacitor are both selected from aluminum foils.

Wherein, the supercapacitor positive electrode material includes a positive electrode active material for a supercapacitor, a positive electrode binder for a supercapacitor, and a positive electrode conductive agent for a supercapacitor.

In some embodiments, the compaction density of the first positive electrode sheet and the fourth positive electrode sheet for supercapacitors is 0.5-4.3 g/cm ³ .

In some embodiments, the positive electrode active material for supercapacitors accounts for 70-99% of the total mass of the positive electrode material of the supercapacitor, the positive electrode conductive agent for supercapacitors accounts for 0.5-15% of the total mass of the positive electrode material for the supercapacitor, and the The positive electrode binder for supercapacitor accounts for 0.5-15% of the total mass of the positive electrode material of the supercapacitor.

In some embodiments, the positive electrode active material for supercapacitors is selected from activated porous carbon materials (activated carbon powder, activated carbon fiber, carbon aerogel, carbon nanotube, carbide-derived carbon, graphite ring, graphene oxide, graphene one or more); metal oxides (such as RuO ₂ , MnO ₂ , ZnO, PbO ₂ , WO ₃ , NiO, Co ₃ O ₄ , MoO ₂ , etc.); metal sulfides (such as MnS ₂ , PbO ₂ , WS ₃ , NiS, MoS ₂ , TiS ₂ , FeS, FeS ₂ , etc.); mixed metal oxides (such as NiCo ₂ O ₄ , ZnCo ₂ O ₄ , FeCo ₂ O ₄ , MnCo ₂ O ₄ , CoNi ₂ O ₄ , ZnNi ₂ O ₄ , etc.); mixed metal sulfides (such as NiCo ₂ S ₄ , ZnCo ₂ S ₄ , FeCo ₂ S ₄ , MnCo ₂ S ₄ , CoNi ₂ S ₄ , ZnNi ₂ S ₄ , etc.); conductive polymers (such as poly (3-methyl-thiophene), polyaniline, polypyrrole, polyparaphenylene, polyacene, polythiophene and polyacetylene, etc.).

In some embodiments, the positive electrode binder for supercapacitors may be polymer materials, including but not limited to polyvinylidene fluoride and polyimide.

In some embodiments, the positive electrode conductive agent for supercapacitors may be at least one of conductive carbon black, acetylene black, Ketjen black, carbon nanotubes and graphene.

<Positive electrode sheet for lithium ion battery>

In one aspect of the present invention, the positive electrode sheet of the hybrid battery according to the embodiment of the present invention further includes a second positive electrode sheet L1, the second positive electrode sheet L1 is a positive electrode sheet for a lithium ion battery, and the second positive electrode sheet L1 includes lithium ion A second positive electrode current collector for a battery and a lithium ion battery positive electrode material disposed on both sides of the second positive electrode current collector for a lithium ion battery.

Preferably, the positive electrode sheet in the embodiment of the present invention further includes a fifth positive electrode sheet L2, the fifth positive electrode sheet L2 is a positive electrode sheet for lithium ion batteries, and the fifth positive electrode sheet L2 includes a fifth positive electrode current collector for lithium ion batteries and a A lithium ion battery positive electrode material on one side surface of the fifth positive electrode current collector. Only one side of the fifth positive electrode sheet L2 is provided with a lithium ion battery positive electrode material, and the fifth positive electrode sheet L2 can be used as the outermost positive electrode sheet of the composite battery.

As shown in FIG. 2 , the fifth positive electrode sheet L2 for lithium ion batteries coated with the positive electrode material of lithium ion batteries on one side surface of the fifth positive electrode current collector for lithium ion batteries is defined as L-single (( in FIG. 2 ). b)); The second positive electrode sheet L1 for lithium ion batteries coated with positive electrode material for lithium ion batteries on both sides of the second positive electrode current collector for lithium ion batteries is defined as L-double ((c) in FIG. 2 ) ). The purpose of setting the second positive electrode sheet L1 and the fifth positive electrode sheet L2 for the lithium ion battery is to form a positive and negative electrode pair of the lithium ion battery with the matched negative electrode sheets F1 and F2, so as to realize the lithium ion battery during charging and discharging. The intercalation and deintercalation of the lithium-ion battery form the lamination unit. In addition, L-single and L-double are mainly used in different structures to maximize the utilization of active materials, in which L-single is mainly used in the lamination unit of the outermost Li-ion battery, and L-double is mainly used in the non-outermost layer. in the laminated unit of the lithium-ion battery.

In one embodiment, the second positive electrode current collector and the fifth positive electrode current collector for the lithium ion battery are selected from aluminum foils.

Wherein, the lithium ion battery positive electrode material includes a positive electrode active material for a lithium ion battery, a positive electrode binder for a lithium ion battery, and a positive electrode conductive agent for a lithium ion battery.

In some embodiments, the compaction densities of the second positive electrode sheet and the fifth positive electrode sheet for lithium ion batteries are both 2-4.3 g/cm ³ .

In some embodiments, the positive electrode active material for lithium ion battery accounts for 75-99% of the total mass of the positive electrode material of the lithium ion battery, and the positive electrode conductive agent for lithium ion battery accounts for 0.5-15% of the total mass of the positive electrode material for the lithium ion battery %, the positive electrode binder for lithium ion battery accounts for 0.5-10% of the total mass of the positive electrode material of the lithium ion battery.

In some embodiments, the positive electrode active material for lithium ion batteries is selected from lithium iron phosphate (LiFePO ₄ ), nickel cobalt lithium manganate (L _z Ni _x Co _y Mn _1-xy O ₂ , wherein 0.95≤z≤1.05 , x>0, y>0, x+y<1), lithium nickel cobalt aluminate (Li _z Ni _x Co _y Al _1-xy O ₂ , where 0.95≤z≤1.05, x>0, y>0, 0.8≤x+y<1), lithium nickel cobalt oxide (LiNi _x Co _y O ₂ , where x>0, y>0, x+y=1), lithium nickel titanium magnesium oxide (LiNi _x Ti _y Mg _z O ₂ , where x>0, y>0, z>0, x+y+z=1), lithium nickel cobalt manganese aluminate (Li _z Ni _x Co _y Mn _w Al _1-xyw O ₂ , where 0.95≤ z≤1.05, x>0, y>0, w>0, 0.8≤x+y+w<1), lithium titanate (LiTiO ₂ ), layered lithium manganate (LiMnO ₂ ), lithium nickelate (Li ₂ NiO ₂ ), spinel lithium manganate (LiMn ₂ O ₄ ), lithium-rich manganese-based solid solution cathode material xLi ₂ MnO ₃ ·(1-x)LiMO ₂ , where M=Ni/Co/Mn.

Exemplarily, the nickel-cobalt-manganese ternary composite cathode material is LiNi _1/3 Co _1/3 Mn _1/3 , LiNi _0.5 Co _0.2 Mn _0.3 , LiNi _0.4 Co _0.2 Mn _0.4 , LiNi _0.6 Co _0.2 Mn _0.2 , LiNi 0.6 Co 0.2 Mn 0.2 , _0.8 Co _0.1 Mn _0.1 , LiNi _0.7 Co _0.2 Mn _0.1 , LiNi _0.7 Co _0.15 Mn _0.15 , LiNi _x Co _y Mn _1-xy O ₂ (wherein 0.95≤z≤1.05, 0.8≤x≤0.95, 0.03≤x≤0.2, At least one of x+y<1).

In some embodiments, the positive electrode binder for lithium ion batteries may be a polymer material, including but not limited to polyvinylidene fluoride and polyimide.

In some embodiments, the positive electrode conductive agent for lithium ion batteries may be at least one of conductive carbon black, acetylene black, Ketjen black, carbon nanotubes, graphene oxide, and graphene.

<Positive sheet for lithium ion batteries and supercapacitors>

In one aspect of the present invention, the positive electrode sheet further includes a third positive electrode sheet H, and the third positive electrode sheet H is a positive electrode sheet for lithium ion batteries and supercapacitors, including a third positive electrode collector for lithium ion batteries and supercapacitors Fluid, lithium ion battery positive electrode material disposed on the first surface of the third positive electrode current collector for lithium ion batteries and supercapacitors, and A supercapacitor cathode material on a second surface opposite one surface.

As shown in FIG. 3 , the first surface of the third positive electrode current collector for lithium ion batteries and supercapacitors is coated with positive electrode material for lithium ion batteries, and the second surface opposite to the first surface is coated with positive electrode material for supercapacitors to form a lithium ion battery. The third positive electrode sheet H for ion batteries and supercapacitors; wherein, the third positive electrode sheet H for lithium ion batteries and supercapacitors can be used as a transitional positive electrode sheet, and the third positive electrode sheet H for lithium ion batteries and supercapacitors One side can form a lithium-ion battery lamination unit, and the other side can form a supercapacitor lamination unit, realizing the transition between lithium-ion batteries and supercapacitors. The third positive electrode can be connected to the first positive electrode tab or the second positive electrode tab. When there are multiple third positive electrode tabs in the composite battery, they can be connected to the same positive electrode tab or to different ones. the positive tab.

In one embodiment, the third current collector for lithium ion batteries and supercapacitors is selected from aluminum foils.

Wherein, the definition of the positive electrode material of the lithium ion battery is the same as above.

Wherein, the definition of the supercapacitor positive electrode material is the same as above.

<Compatible negative electrode>

In one aspect of the present invention, the negative electrode sheet of the composite battery includes a first negative electrode sheet F1, and the first negative electrode sheet F1 includes a first negative electrode current collector and is disposed on both sides of the first negative electrode current collector. bifunctional anode material. The bifunctional negative electrode material can not only adsorb/desorb lithium ions, but also be capable of intercalating/deintercalating lithium ions of a lithium ion battery. The bifunctional negative electrode material has dual properties, so that the first negative electrode sheet can be used not only as a negative electrode sheet for supercapacitors, but also as a negative electrode sheet for lithium ion batteries, that is, the first negative electrode sheet is a compatible negative electrode sheet.

Preferably, the negative electrode sheet further includes a second negative electrode sheet F2, and the second negative electrode sheet F2 includes a second negative electrode current collector and a bifunctional negative electrode material disposed on one surface of the second negative electrode current collector. Only one side of the second negative electrode sheet F2 is provided with a bifunctional negative electrode material, and the second negative electrode sheet F2 can be used as the outermost negative electrode sheet of the composite battery. The second negative electrode sheet is also a compatible negative electrode sheet.

As shown in FIG. 4 , the second negative electrode sheet F2 coated with bifunctional negative electrode material on one surface of the second negative electrode current collector is defined as F2-single ((b) in FIG. 4 ) on the first negative electrode The first negative electrode sheet F1 coated with bifunctional negative electrode material on both sides of the current collector is defined as F1-bi ((c) in FIG. 4 ). The first negative electrode sheet F1 and the second negative electrode sheet F2 can be adapted to the above-mentioned positive electrode sheets L1 and L2 for lithium ion batteries, positive electrode sheets C1 and C2 for supercapacitors, or positive electrode sheets H for lithium ion batteries and supercapacitors, And form a lithium-ion battery stack unit or a supercapacitor stack unit, so that when the composite battery is charged and discharged, there are both physical energy storage of the supercapacitor and chemical energy storage of the lithium ion battery.

In one embodiment, the first negative electrode current collector and the second negative electrode current collector are both selected from copper foils, such as electrolytic copper foils or rolled copper foils.

Wherein, the bifunctional negative electrode material includes a first negative electrode active material, a first negative electrode binder and a first negative electrode conductive agent.

In some embodiments, the first negative electrode active material accounts for 70-99% of the total mass of the bifunctional negative electrode material, the first negative electrode conductive agent accounts for 0.5-15% of the total mass of the bifunctional negative electrode material, and the first negative electrode material accounts for 0.5-15% of the total mass of the bifunctional negative electrode material. The negative electrode binder accounts for 0.5-15% of the total mass of the bifunctional negative electrode material.

In some embodiments, the first negative electrode active material is any material that can deintercalate metal ions such as lithium ions, for example, the first negative electrode active material may be graphite, silicon material, silicon carbon composite material, silicon oxide material, One or more of alloy materials and lithium-containing metal composite oxide materials.

In some embodiments, the first negative electrode binder includes, but is not limited to, one or more of styrene-butadiene rubber, fluorine-based rubber, ethylene propylene diene, and hydroxymethyl cellulose.

In some embodiments, the first negative electrode conductive agent may be at least one of conductive carbon black, acetylene black, Ketjen black, carbon nanotubes and graphene.

<Negative electrode sheet for super capacitor>

In one aspect of the present invention, the negative electrode sheet includes a third negative electrode sheet F3, the third negative electrode sheet is a negative electrode sheet for supercapacitors, and the third negative electrode sheet F3 includes a third negative electrode current collector and is disposed on the Supercapacitor anode material on both sides of the third anode current collector.

Preferably, the negative electrode sheet further includes a fourth negative electrode sheet F4, the fourth negative electrode sheet is a negative electrode sheet for super capacitors, and the fourth negative electrode sheet F4 includes a fourth negative electrode current collector and a Supercapacitor anode material on the fluid side surface. Only one side of the fourth negative electrode sheet F4 is provided with a supercapacitor negative electrode material, and the fourth negative electrode sheet F4 can be used as the outermost negative electrode sheet of the composite battery.

As shown in FIG. 5 , the fourth negative electrode sheet F4 for supercapacitors coated with supercapacitor negative electrode material on the surface of the fourth negative electrode current collector is defined as F4-single ((b) in FIG. 5 ); The third negative electrode sheet F3 for supercapacitors whose surfaces on both sides of the third negative electrode current collector are coated with supercapacitor negative electrode material is defined as F3-bi ((c) in FIG. 5 ). The third negative electrode sheet F3 and the fourth negative electrode sheet F4 can be matched with the above-mentioned positive electrode sheets C1 and C2 for supercapacitors, or the positive electrode sheets H for lithium ion batteries and supercapacitors to form a supercapacitor laminated unit, in particular, when When the supercapacitor negative electrode material of the third negative electrode sheet F3 and the fourth negative electrode sheet F4 and the supercapacitor positive electrode material of the supercapacitor positive electrode sheet are the same material, a symmetrical supercapacitor laminated unit can be formed. When the supercapacitor uses the third negative electrode sheet When the supercapacitor negative electrode material of the fourth negative electrode sheet F4 and the supercapacitor positive electrode material of the supercapacitor positive electrode sheet are different materials but both are supercapacitor active materials, they can form an asymmetric supercapacitor laminated unit.

In one embodiment, the third negative electrode current collector and the fourth negative electrode current collector are selected from copper foils, such as electrolytic copper foils or rolled copper foils.

In some embodiments, the supercapacitor negative electrode material includes a negative electrode active material for a supercapacitor, a negative electrode binder for a supercapacitor, and a negative electrode conductive agent for a supercapacitor.

In some embodiments, the negative electrode active material for supercapacitors accounts for 70-99% of the total mass of the supercapacitor negative electrode material, the negative electrode conductive agent for supercapacitors accounts for 0.5-15% of the total mass of the supercapacitor negative electrode material, and the The negative electrode binder for supercapacitor accounts for 0.5-15% of the total mass of the negative electrode material of the supercapacitor.

In some embodiments, the negative active material for supercapacitors is selected from activated porous carbon materials (activated carbon powder, activated carbon fiber, carbon aerogel, carbon nanotube, carbide-derived carbon, graphite ring, graphene oxide, graphene one or more); metal oxides (such as RuO ₂ , MnO ₂ , ZnO, PbO ₂ , WO ₃ , NiO, Co ₃ O ₄ , MoO ₂ , etc.); metal sulfides (such as MnS ₂ , PbO ₂ , WS ₃ , NiS, MoS ₂ , TiS ₂ , FeS, FeS ₂ , etc.); mixed metal oxides (such as NiCo ₂ O ₄ , ZnCo ₂ O ₄ , FeCo ₂ O ₄ , MnCo ₂ O ₄ , CoNi ₂ O ₄ , ZnNi ₂ O ₄ , etc.); mixed metal sulfides (such as NiCo ₂ S ₄ , ZnCo ₂ S ₄ , FeCo ₂ S ₄ , MnCo ₂ S ₄ , CoNi ₂ S ₄ , ZnNi ₂ S ₄ , etc.); conductive polymers (such as poly (3-methyl-thiophene), polyaniline, polypyrrole, polyparaphenylene, polyacene, polythiophene and polyacetylene, etc.).

In some embodiments, the negative electrode binder for supercapacitors may be polymer materials, including but not limited to polyvinylidene fluoride and polyimide.

In some embodiments, the negative electrode conductive agent for supercapacitors may be at least one of graphite, carbon black, acetylene black, Ketjen black, carbon nanotubes and graphene.

<Negative electrode sheet for lithium ion battery>

In one aspect of the present invention, the negative electrode sheet includes a fifth negative electrode sheet, the fifth negative electrode sheet is a negative electrode sheet for lithium ion batteries, and the fifth negative electrode sheet includes a fifth negative electrode current collector and a Five lithium-ion anode materials on both sides of the anode current collector.

Preferably, the negative electrode sheet further includes a sixth negative electrode sheet, the sixth negative electrode sheet is a negative electrode sheet for lithium ion batteries, and the sixth negative electrode sheet includes a sixth negative electrode current collector and a sixth negative electrode current collector disposed on the sixth negative electrode current collector. Supercapacitor anode material on one side surface. Only one side of the sixth negative electrode sheet is provided with a lithium ion battery negative electrode material, and the sixth negative electrode sheet can be used as the outermost negative electrode sheet of the composite battery.

The structures of the fifth negative electrode sheet and the sixth negative electrode sheet are respectively the same as those of the third negative electrode sheet and the fourth negative electrode sheet, and only the negative electrode materials are different. The fifth negative electrode sheet and the sixth negative electrode sheet can be matched with the above-mentioned positive electrode sheets L1 and L2 for lithium ion batteries, or positive electrode sheets H for lithium ion batteries and supercapacitors to form a lithium ion battery structural unit. There are many kinds of negative electrode materials for lithium ion batteries, and those skilled in the art can select suitable negative electrode materials for lithium ion batteries in the prior art according to actual needs.

In one embodiment, the fifth negative electrode current collector and the sixth negative electrode current collector are both selected from copper foils, such as electrolytic copper foils or rolled copper foils.

<Negative electrode sheet for transition>

In one aspect of the present invention, the negative electrode sheet further includes a seventh negative electrode sheet F5, the seventh negative electrode sheet is a transitional negative electrode sheet, and the seventh negative electrode sheet F5 includes a seventh negative electrode current collector and a The first negative electrode material on the first surface of the negative electrode current collector, and the second negative electrode material on the second surface of the seventh negative electrode current collector opposite to the first surface, the first negative electrode material and the second negative electrode material are both One selected from the above-mentioned bifunctional negative electrode material, supercapacitor negative electrode material and lithium ion battery negative electrode material, the first negative electrode material is different from the second negative electrode material.

Exemplarily, as shown in FIG. 6 , a lithium ion battery negative electrode material is coated on the first surface of the fifth negative electrode current collector, and a second surface of the fifth negative electrode current collector opposite to the first surface is coated. Supercapacitor anode material. The first surface side of the seventh negative electrode sheet F5 can be adapted with the above-mentioned positive electrode sheets L1 and L2 for lithium ion batteries, and the positive electrode sheets H for lithium ion batteries and supercapacitors, and the second surface side can be used with supercapacitors. The positive electrode sheet C1 and C2 are adapted. Therefore, the seventh negative electrode sheet F5 can be used as a transitional negative electrode sheet, forming a lithium ion battery stack unit on one side, and a supercapacitor stack unit on the other side, so that when the composite battery is charged and discharged, both the supercapacitor and the supercapacitor are formed. There are two ways of physical energy storage and chemical energy storage of lithium-ion batteries.

Wherein, the seventh negative electrode current collector is selected from copper foil, such as electrolytic copper foil or rolled copper foil.

Wherein, the definitions of the bifunctional negative electrode material, the supercapacitor negative electrode material and the lithium ion battery negative electrode material are as described above.

In another aspect of the present invention, the negative electrode sheet further includes an eighth negative electrode sheet, the eighth negative electrode sheet is another kind of transition negative electrode sheet, and the eighth negative electrode sheet includes an eighth negative electrode current collector and a The first negative electrode material on the first surface of the eighth negative electrode current collector, and the second negative electrode material on the second surface of the eighth negative electrode current collector opposite to the first surface, the first negative electrode material is selected from One of a bifunctional negative electrode material and a lithium ion battery negative electrode material, the second negative electrode material is a supercapacitor negative electrode material, the first negative electrode material is different from the second negative electrode material, and the bifunctional negative electrode material can adsorb/desorb lithium ions, And able to intercalate/deintercalate lithium ions of lithium ion batteries.

Wherein, the seventh negative electrode current collector is selected from copper foil, such as electrolytic copper foil or rolled copper foil.

Wherein, the definitions of the bifunctional negative electrode material, the supercapacitor negative electrode material and the lithium ion battery negative electrode material are as described above.

<Lithium-ion battery stack unit>

Exemplarily, in one aspect of the present invention, the lithium ion battery positive electrode sheet L1, the separator and the compatible negative electrode sheet F1 can form a lithium ion battery laminate unit A1, and the lithium ion battery laminate unit A1 contains Lithium ion battery cell structure Y1 formed by positive electrode material for lithium ion battery, separator and negative electrode material for lithium ion battery. The compatible negative electrode sheet F1 can also be replaced with a negative electrode sheet for lithium ion batteries.

<Super capacitor lamination unit>

Exemplarily, in one solution of the present invention, the supercapacitor positive electrode sheet C1, the separator and the compatible negative electrode sheet F1 can form a supercapacitor laminated unit B1; the supercapacitor laminated unit B1 includes a supercapacitor laminated unit B1. The supercapacitor cell structure Y2 formed by the positive electrode material, the separator and the negative electrode material for supercapacitors; at the same time, when the materials of the positive electrode sheet for supercapacitors and the compatible negative electrode sheet F1 are the same material, the supercapacitor lamination unit contains a symmetrical type Supercapacitor elementary structure Y2-D; when the positive electrode sheet C and the compatible negative electrode sheet F1 are made of non-identical supercapacitor active materials, the supercapacitor lamination unit contains an asymmetric supercapacitor elementary structure Y2-F . The compatible negative plate F1 can also be replaced by a negative plate for a supercapacitor.

Exemplarily, in one aspect of the present invention, the supercapacitor positive electrode sheet, the separator, and the supercapacitor negative electrode sheet F3 can form a supercapacitor laminated unit B2; The supercapacitor elementary structure Y2 formed by the positive electrode material, the separator and the negative electrode material for the supercapacitor;

At the same time, when the materials of the positive electrode sheet for supercapacitor and the negative electrode sheet F3 for supercapacitor are the same material, the supercapacitor lamination unit contains a symmetrical supercapacitor elementary structure Y2-D; When the material of the negative electrode sheet F3 for capacitors is a non-homogeneous supercapacitor active material, the supercapacitor lamination unit contains the asymmetric supercapacitor element structure Y2-F.

Those skilled in the art can understand that the above-mentioned battery cells are only exemplary descriptions. According to the contents disclosed in this specification, those skilled in the art know how to select corresponding positive electrode sheets and negative electrode sheets to form a lithium-ion battery stack unit or a supercapacitor stack. unit.

<transition unit>

Exemplarily, in one aspect of the present invention, the positive electrode sheet L1 for lithium ion batteries, the separator and the seventh negative electrode sheet F5 can form a transition unit G1; the transition unit G1 includes a positive electrode material for lithium ion batteries, a separator Lithium-ion battery cell structure Y1 formed with negative electrode material for lithium-ion battery.

Exemplarily, in one aspect of the present invention, the positive electrode sheet H for lithium ion batteries and supercapacitors, the separator and the compatible negative electrode sheet F1 can form a transition unit G2; the transition unit G2 includes a positive electrode for lithium ion batteries Materials, separators and negative electrode materials for lithium ion batteries form a lithium ion battery elementary structure Y1, or a supercapacitor elementary structure Y2 comprising a positive electrode material for supercapacitors, a separator and a negative electrode material for supercapacitors.

Exemplarily, in one aspect of the present invention, the positive electrode sheet H for lithium ion batteries and supercapacitors, the separator and the seventh negative electrode sheet F5 can form a transition unit G3; the transition unit G3 includes a positive electrode for lithium ion batteries. Materials, separators and negative electrode materials for lithium ion batteries form a lithium ion battery elementary structure Y1, or a supercapacitor elementary structure Y2 comprising a positive electrode material for supercapacitors, a separator and a negative electrode material for supercapacitors.

Exemplarily, in one aspect of the present invention, the positive electrode sheet C1 for supercapacitors, the separator and the seventh negative electrode sheet F5 can form a transition unit G4; the transition unit G4 includes a positive electrode material for supercapacitors, a separator and a supercapacitor. The supercapacitor cell structure Y2 formed by the negative electrode material for capacitors.

Exemplarily, in one aspect of the present invention, the positive electrode sheet H for lithium ion batteries and supercapacitors, the separator and the negative electrode sheet F3 for supercapacitors can form a transition unit G5; the transition unit G5 includes a positive electrode for supercapacitors. Materials, separators, and supercapacitor elemental structures Y2 formed from anode materials for supercapacitors.

In the above solution, the positive electrode material of the lithium ion battery needs to correspond to the compatible negative electrode material; the supercapacitor positive electrode material needs to correspond to the supercapacitor negative electrode material or the compatible negative electrode material.

In one solution of the present invention, a separator is also provided between the lithium ion battery laminated unit, the supercapacitor laminated unit, and the transition unit to avoid direct contact between the positive electrode material and the negative electrode material, resulting in a short circuit.

Exemplarily, in one solution of the present invention, the separators disposed between the adjacent lithium-ion battery laminated units, supercapacitor laminated units and transition units can also form a lithium-ion battery cell structure Y1 or a supercapacitor base structure. Element structure Y2, specifically, when the two sides of the separator are respectively the positive electrode material for lithium ion battery and the negative electrode material for lithium ion battery, the primary structure Y1 of lithium ion battery can be formed; when the two sides of the separator are respectively the positive electrode material for supercapacitor and When the supercapacitor is used as a negative electrode material, the supercapacitor element structure Y2 can be formed.

In one solution of the present invention, in the composite battery according to the embodiment of the present invention, the number of the lithium ion battery elementary structures Y1 is greater than or equal to the number of the supercapacitor elementary structures Y2.

<Stacking of positive and negative electrodes in a composite battery>

In one aspect of the present invention, the composite battery includes at least one of a lithium-ion battery stack unit A1, a supercapacitor stack unit B1, a supercapacitor stack unit B2, and transition units G1, G2, G3, G4, and G5 and at the same time ensure that the composite battery includes at least one positive electrode sheet for lithium ion batteries and at least one positive electrode sheet for supercapacitors; and/or, at least one positive electrode sheet H for lithium ion batteries and supercapacitors.

In one solution of the present invention, the lithium-ion battery laminate unit A1, the supercapacitor laminate unit B1, and the supercapacitor laminate unit B2 can be transitionally connected through a separator and an optional transition unit to form a laminate type composite battery.

In the above solution, the transition connection should satisfy that the positive electrode material of the lithium ion battery corresponds to the compatible negative electrode material; the supercapacitor positive electrode material corresponds to the supercapacitor negative electrode material or the compatible negative electrode material.

In an exemplary solution, the composite battery comprises transition units-m lithium-ion battery lamination units A1-transition units; wherein, the transition units are the same or different, and are independently selected from the above transition units G1-G5, m is an integer greater than or equal to 1;

In an exemplary solution, the composite battery comprises transition units-n supercapacitor lamination units B1-transition units; wherein, the transition units are the same or different, and are independently selected from the above transition units G1-G5, and n is an integer greater than or equal to 1;

In an exemplary solution, the composite battery includes transition units-n supercapacitor lamination units B2-transition units; wherein, the transition units are the same or different, and are independently selected from the above transition units G1-G5, and n is an integer greater than or equal to 1;

In an exemplary solution, the composite battery comprises transition units-n1 supercapacitor lamination units B1-n2 supercapacitor lamination units B2-transition units; wherein the transition units are the same or different, and are independently selected from each other. For the above transition units G1-G5, n1 is an integer greater than or equal to 1, and n2 is an integer greater than or equal to 1;

In an exemplary solution, the composite battery includes transition units-m lithium-ion battery lamination units A1-transition units-n supercapacitor lamination units B1-transition units; wherein, the transition units are the same or different, and each other Independently selected from the above transition units G1-G5, n is an integer greater than or equal to 1, m is an integer greater than or equal to 1;

In an exemplary solution, the composite battery includes transition units-m lithium-ion battery lamination units A1-transition units-n supercapacitor lamination units B2-transition units; wherein, the transition units are the same or different, and each other Independently selected from the above transition units G1-G5, n is an integer greater than or equal to 1, m is an integer greater than or equal to 1;

In an exemplary solution, the composite battery includes transition units-n1 supercapacitor lamination units B1-transition unit-m lithium-ion battery lamination units A1-transition unit-n2 supercapacitor lamination units B2-transition unit ; Wherein, the transition units are the same or different, and are independently selected from the above transition units G1-G5, n1+n2 is an integer greater than or equal to 1, and m is an integer greater than or equal to 1;

In the above exemplary solution, the transition unit can select a suitable transition unit from the above transition units G1-G5 according to the difference of adjacent repeating units, so as to ensure that the positive electrode material of the lithium ion battery needs to correspond to the compatible negative electrode material; The supercapacitor positive electrode material needs to correspond to the supercapacitor negative electrode material or compatible negative electrode material.

In the above exemplary solution, if x lithium-ion battery cell structures Y1 and y supercapacitor cell structures Y2 are included at the same time, the applicable range and application of the composite battery can be adjusted by adjusting the ratio of x/y. For example, when the ratio of x/y is larger, the energy density of the composite battery is higher; the ratio of x/y is closer to 1, the power density of the composite battery is higher. The ratio of x/y can be adjusted according to the requirements of energy density and power density in a wide range of application environments, so as to meet the application requirements. In the present invention, x≧y≧1. That is, the number of the supercapacitor element structures Y2 is less than or equal to the number of the lithium ion battery element structures Y1.

<diaphragm>

In one embodiment of the present invention, the separator is selected from porous films.

Wherein, the separator is prepared from a separator material that is ionically conductive but electronically insulating, and the separator is mostly a porous film made of a polymer.

In some embodiments, the polymers include, but are not limited to: polyethylene terephthalate, polybutylene terephthalate, polyether, polyacetal, polyamide, polycarbonate, polyimide Amines, polyetheretherketone, polyethersulfone, polyphenylene oxide, polyphenylene sulfide, polyethylene naphthalene, high density polyethylene, low density polyethylene, linear low density polyethylene, ultra-high molecular weight polyethylene and polypropylene.

In some embodiments, the separator further includes an organic or inorganic coating disposed on one or both surfaces of the above-mentioned porous membrane. An organic or inorganic coating applied to the surface of a substrate, usually to enhance the resistivity of the separator, prevent direct electrical contact between opposing layers of negative electrode material and layers of positive electrode material, and remain available for immersion electrolysis Insulator material of porous structure that transports lithium ions between battery electrodes. The insulating separator can be in the form of a sheet adapted to the structure of the battery, or can be in the form of a bag adapted to the structure of the battery.

In some embodiments, the inorganic substances may specifically include but are not limited to: BaTiO ₃ , Pb(Zr, Ti)O ₃ (PZT), Pb _1-x La _x Zr _1-y Ti _y O ₃ , PB ( Mg ₃ Nb _2/3 )O ₃ -PbTiO ₃ , hafnium dioxide (HfO ₂ ), SrTiO ₃ , SnO ₂ , CeO ₂ , MgO, NiO, CaO, ZnO, ZrO ₂ , SiO ₂ , Y ₂ O ₃ , Al ₂ O ₃ , SiC, TiO ₂ and mixtures thereof.

In some embodiments, the organic substances may specifically include but are not limited to: cyanoethyl pullulan, cyanoethyl polyvinyl alcohol, cyanoethyl cellulose, cyanoethyl sucrose, polyvinylidene fluoride-co- Hexafluoropropylene, polyvinylidene fluoride-co-trichloroethylene, polymethyl methacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinyl acetate, polyethylene-co-vinyl acetate, polyimide, Polyethylene oxide, cellulose acetate, cellulose acetate butyrate and cellulose acetate propionate and mixtures thereof.

<Composite battery>

In one aspect of the present invention, the composite battery includes a positive electrode sheet for lithium ion batteries, a positive electrode sheet for supercapacitors, a positive electrode sheet for lithium ion batteries and supercapacitors, and a negative electrode sheet. The above-mentioned positive electrode sheet and negative electrode sheet are assembled with the tabs, the diaphragm, the electrolyte, and the packaging shell to form a finished battery cell.

<Electrolyte>

In one aspect of the present invention, the electrolyte solution includes a lithium salt, an organic solvent and an additive.

In some embodiments, the organic solvent is selected from carbonates (such as cyclic carbonates, chain carbonates), carboxylates (such as cyclic carboxylates, chain carboxylates), ether compounds (such as at least one of cyclic ether compounds, chain ether compounds), phosphorus-containing compounds and sulfur-containing compounds.

Wherein, the carbonate is selected from dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl-n-propyl carbonate, ethyl-n-propyl carbonate, di-n-propyl carbonate, bis(fluoromethyl) ) carbonate, bis(difluoromethyl)carbonate, bis(trifluoromethyl)carbonate, bis(2-fluoroethyl)carbonate, bis(2,2-difluoroethyl)carbonate, bis(2,2-difluoroethyl)carbonate (2,2,2-Trifluoroethyl)carbonate, 2-fluoroethylmethylcarbonate, 2,2-difluoroethylmethylcarbonate and 2,2,2-trifluoroethylmethylcarbonate at least one of carbonates.

Wherein, the carboxylate is selected from methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, sec-butyl acetate, isobutyl acetate, tert-butyl acetate, methyl propionate, Ethyl propionate, propyl propionate, isopropyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, methyl isobutyrate, ethyl isobutyrate, methyl valerate, valeric acid Ethyl, methyl and ethyl pivalate, methyl trifluoroacetate, ethyl trifluoroacetate, propyl trifluoroacetate, butyl trifluoroacetate, trifluoroacetic acid and 2,2,2-trifluoroacetate At least one of fluoroethyl esters.

Wherein, the ether compound is selected from tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 2-methyl-1,3-dioxolane, 4-methyl 1,3-dioxolane pentane, 1,3-dioxane, 1,4-dioxane, dimethoxypropane, dimethoxymethane, 1,1-dimethoxyethane, 1,2-dimethyl Oxyethane, diethoxymethane, 1,1-diethoxyethane, 1,2-diethoxyethane, ethoxymethoxymethane, 1,1-ethoxymethoxy At least one of ethyl ethane and 1,2-ethoxymethoxyethane.

Wherein, the phosphorus-containing compound is selected from trimethyl phosphate, triethyl phosphate, dimethyl ethyl phosphate, methyl diethyl phosphate, ethylene methyl phosphate, ethylene ethyl phosphate, triphenyl phosphate ester, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tris(2,2,2-trifluoroethyl) phosphate and tris(2,2,3,3,3-pentaphosphate) at least one of fluoropropyl) esters.

Wherein, the sulfur-containing compound is selected from sulfolane, 2-methyl sulfolane, 3-methyl sulfolane, dimethyl sulfone, diethyl sulfone, ethyl methyl sulfone, methyl propyl sulfone, dimethyl sulfoxide , at least one of methyl methanesulfonate, ethyl methanesulfonate, methyl ethanesulfonate, ethyl ethanesulfonate, dimethyl sulfate, diethyl sulfate and dibutyl sulfate.

In some embodiments, the organic solvent accounts for 82-88% of the total mass of the electrolyte.

In one aspect of the present invention, the lithium salt is selected from at least one of inorganic lithium salts, fluorine-containing organic lithium salts, and dicarboxylic acid complex-containing lithium salts.

Wherein, the inorganic lithium salt is selected from at least one of LiClO ₄ , LiAsF ₆ , LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiSO ₃ F, and LiN(FSO ₂ ) ₂ .

Wherein, the fluorine-containing organic lithium salt is selected from LiCF ₃ SO ₃ , LiN(FSO ₂ )(CF ₃ SO ₂ ), LiN(CF ₃ SO ₂ ) ₂ , LiN(C ₂ F ₅ SO ₂ ) ₂ , cyclic Lithium 1,3-hexafluoropropanedisulfonimide, Lithium Cyclic 1,2-tetrafluoroethanedisulfonimide, LiN(CF ₃ SO ₂ )(C ₄ F ₉ SO ₂ ), LiC(CF ₃ SO ₂ ) ₃ , LiPF ₄ (CF ₃ ) ₂ , LiPF ₄ (C ₂ F ₅ ) ₂ , LiPF ₄ (CF ₃ SO ₂ ) ₂ , LiPF ₄ (C ₂ F ₅ SO ₂ ) ₂ , LiBF ₂ (CF ₃ ) ₂ , LiBF ₂ (C ₂ F ₅ ) ₂ , LiBF ₂ (CF ₃ SO ₂ ) ₂ , LiBF ₂ (C ₂ F ₅ SO ₂ ) ₂ , and the like.

Wherein, the lithium salt containing dicarboxylic acid complex is selected from lithium bis(oxalato)borate, lithium difluorooxalatoborate, lithium tris(oxalato)phosphate, lithium difluorobis(oxalato)phosphate , at least one of tetrafluoro(oxalato) lithium phosphate.

In some embodiments, the lithium salt accounts for 13-18 wt% of the total mass of the electrolyte.

In one embodiment of the present invention, the additives are conventional additives known in the art.

<Preparation method of composite battery>

Exemplarily, the present invention also provides a method for preparing the above-mentioned composite battery, the method comprising the following steps:

(1) preparing a positive electrode sheet for lithium ion batteries and a positive electrode sheet for supercapacitors; and/or, preparing a positive electrode sheet for lithium ion batteries and supercapacitors;

(2) preparation of negative electrode sheet;

(3) Two independent positive electrode tabs are drawn from the positive electrode sheet for lithium ion batteries and the positive electrode sheet for supercapacitors, or two independent positive electrode tabs are drawn from the positive electrode sheets for lithium ion batteries and supercapacitors respectively; A negative electrode tab is drawn out of the negative electrode sheet to form a three-pole tab structure with two mutually independent positive electrode tabs and a shared negative electrode tab;

(4) Alternately stacking a negative electrode sheet, a separator, a positive electrode sheet, a separator, and a negative electrode sheet to form a composite battery.

In one aspect of the present invention, the positive electrode sheet for supercapacitors can be prepared by the following method:

The positive electrode slurry for supercapacitors is prepared and coated on one or both sides of the positive electrode current collector for supercapacitors to prepare the positive electrode sheet for supercapacitors.

In one aspect of the present invention, the positive electrode sheet for the lithium ion battery can be prepared by the following method:

The positive electrode slurry for lithium ion battery is prepared and coated on one side or both sides of the positive electrode current collector for lithium ion battery to prepare the positive electrode sheet for lithium ion battery.

In one aspect of the present invention, the positive electrode sheets for lithium ion batteries and supercapacitors can be prepared by the following methods:

The positive electrode slurry for lithium ion batteries and the positive electrode slurry for supercapacitors are prepared, and they are respectively coated on the surface of one side of the positive electrode current collector for lithium ion batteries and supercapacitors to prepare the lithium ion batteries and supercapacitors. Use positive pads.

In an embodiment of the present invention, a composite battery is formed by alternately stacking a negative electrode sheet, a separator G, a positive electrode sheet, a separator G, and a negative electrode sheet, as shown in FIG. 7 , FIG. 8 and FIG. 9 .

7 is a schematic structural diagram of a composite capacitor containing a symmetric supercapacitor according to an embodiment of the present invention, and its stacking method is F2-single, diaphragm, (L-double, diaphragm, F1-double, diaphragm), ( L-Dual, Diaphragm, F5, Diaphragm), (C-Dual, Diaphragm, F3-Dual, Diaphragm), (C-Dual, Diaphragm, F5, Diaphragm), m (L-Dual, Diaphragm, F1-Dual, Diaphragm), L-double, diaphragm, and F2-single are alternately combined. The diaphragm adopts Z-type lamination, and the positive and negative electrodes are separated and stacked to form a bare cell, which contains A1-G1-B2-G4-(A1) _m The stacked structure, wherein, F2-single, diaphragm, L-double includes lithium ion battery cell structure Y1; lithium ion battery stack unit A1 includes lithium ion battery cell structure Y1; A1-G1 forms lithium ion battery cell structure Y1 The ion battery cell structure Y1; the transition unit G1 includes the lithium ion cell cell structure Y1; the supercapacitor cell structure Y2 is formed between G1-B2; the supercapacitor lamination unit B2 includes the supercapacitor cell structure Y2; A supercapacitor cell structure Y2 is formed between B2-G4; the transition unit G4 includes a supercapacitor cell structure Y2; a lithium-ion battery cell structure Y1 is formed between G4-A1; the lithium-ion cell stack unit A1 includes Li-ion battery cell structure Y1; Li-ion cell cell structure Y1 is formed between A1-A1; L-bi, separator, and F2-single include lithium-ion cell cell structure Y1.

8 is a schematic structural diagram of a composite capacitor containing an asymmetrical supercapacitor according to an embodiment of the present invention, and its stacking method is F2-single, diaphragm, (L-double, diaphragm, F1-double, diaphragm), (C-Double, Diaphragm, F1-Double, Diaphragm), m (L-Double, Diaphragm, F1-Double, Diaphragm), L-Double, Diaphragm, F2-Single Mode Alternate Combination, Diaphragm Using Z-shaped Lamination , the positive and negative electrodes are separated and stacked to form a bare cell, forming a stacked structure containing A1-B1-(A1) _m ; wherein, F2-single, diaphragm, and L-double include lithium-ion battery cell structure Y1; lithium The ion battery lamination unit A1 includes a lithium ion battery element structure Y1; a supercapacitor element structure Y2 is formed between A1-B1; the supercapacitor lamination unit B1 includes a supercapacitor element structure Y2; B1-A1 is formed between Lithium-ion battery cell structure Y1; lithium-ion cell stack unit A1 includes lithium-ion cell cell structure Y1; lithium-ion cell cell structure Y1 is formed between A1-A1; L-double, separator, F2-single include Li-ion battery cell structure Y1.

9 is a schematic structural diagram of a composite capacitor containing asymmetric supercapacitors and symmetric supercapacitors according to an embodiment of the present invention, and the stacking method is F2-single, diaphragm, (L-double, diaphragm, F1- Double, Diaphragm), (L-Dual, Diaphragm, F5, Diaphragm), (C-Dual, Diaphragm, F1-Dual, Diaphragm), (C-Dual, Diaphragm, F5, Diaphragm), m (L-Dual, Diaphragm) Diaphragm, F1-Double, Diaphragm), L-Double, Diaphragm, and F2-Single are alternately combined. The stacked structure of G4-(A1) _m , wherein the F2-single, diaphragm, and L-double include the lithium-ion battery cell structure Y1; the lithium-ion battery stack unit A1 includes the lithium-ion cell cell structure Y1; A1 Lithium-ion battery cell structure Y1 is formed between G1; transition unit G1 includes lithium-ion cell cell structure Y1; supercapacitor cell structure Y2 is formed between G1-B1; supercapacitor lamination unit B1 includes supercapacitor cell structure Y2 Capacitor elementary structure Y2; supercapacitor elementary structure Y2 is formed between B1-G4; the transition unit G4 includes supercapacitor elementary structure Y2; lithium ion battery elementary structure Y1 is formed between G4-A1; lithium ion battery The laminated unit A1 includes a lithium-ion battery cell structure Y1; A1-A1 forms a lithium-ion cell cell structure Y1; L-double, separator, and F2-single include a lithium-ion cell cell structure Y1.

In one solution of the present invention, two independent positive electrode tabs are drawn from the positive electrode sheet for lithium ion batteries and the positive electrode sheet for supercapacitors, or two independent positive electrode tabs are drawn from the positive electrode sheets for lithium ion batteries and supercapacitors respectively. A negative electrode tab is drawn from the negative electrode sheet to form a three-pole-tab structure with two independent positive electrode tabs and a shared negative electrode tab; it can effectively solve the problem of fast self-discharge of supercapacitor batteries , and to achieve the purpose of optimal use of the hybrid electrochemical cell.

In one scheme of the present invention, the first positive electrode tab is drawn from the positive electrode sheet for supercapacitors; the second positive electrode tab is drawn from the positive electrode sheet for lithium ion batteries; the first positive electrode tab is drawn from the positive electrode sheet for lithium ion batteries and supercapacitors A positive electrode tab or a second positive electrode tab, when using multiple positive electrode tabs for lithium ion batteries and supercapacitors, some of the positive electrode tabs can also lead out the first positive tab, and some positive tabs can lead out the second positive tab.

In one solution of the present invention, the negative electrode tabs are drawn out independently or cross-connected to form negative electrode tabs.

The positions of the above-mentioned three tabs are not particularly limited. As shown in Figure 10, for example, the first positive tab connected to the positive electrode sheet of the supercapacitor and the second positive tab connected to the positive electrode sheet of the lithium ion battery are arranged in the same position of the battery. side (as shown in a in FIG. 10 ), or, the first positive electrode tab and the second positive electrode tab are arranged on opposite sides of the battery (as shown in b in FIG. 10 ), or the first positive electrode The lugs and the second positive electrode lugs are provided on adjacent sides of the battery (as shown by c and d in FIG. 10 ). When the two positive electrode tabs are arranged on adjacent two sides of the battery, the width of the positive electrode tab can be appropriately increased according to different use environments, and the positive electrode tab can be used as an excellent heat conduction medium, which can improve the heat dissipation effect of the battery.

The preparation method of the present invention will be described in further detail below with reference to specific examples. It should be understood that the following examples are only for illustrating and explaining the present invention, and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the intended protection scope of the present invention.

The experimental methods used in the following examples are conventional methods unless otherwise specified; the reagents, materials, etc. used in the following examples can be obtained from commercial sources unless otherwise specified.

Preparation Example 1 Positive electrode sheet for supercapacitor

Mix and disperse porous carbon activated carbon powder (specific surface area ≥ 1000m ² /g), binder PVDF, conductive carbon black, and carbon nanotubes in NMP (N-methylpyrrolidone), which is a positive active material for supercapacitors. The positive electrode slurry for supercapacitor is prepared by vacuum stirring to obtain a uniform dispersion. The solid content contains 93wt% of positive active material, 4wt% of binder PVDF, 2wt% of conductive carbon black and 1wt% of carbon nanotubes. The total solids content in the positive electrode slurry for supercapacitors was 40 wt%.

The positive electrode slurry for supercapacitors is evenly coated on both sides of the aluminum foil, vacuum-dried at 100-120° C. for 10-24 hours, and rolled to be compacted to 1.0-2.1 g/cm ³ to obtain a number of positive electrode sheets for supercapacitors C1. is C-double (as shown in (c) in Figure 1).

The positive electrode slurry for supercapacitors is evenly coated on one side of the aluminum foil, vacuum-dried at 100-120° C. for 10-24 hours, and rolled to be compacted to 0.9-2.1 g/cm ³ to obtain a number of positive electrode sheets for supercapacitors C2. is C-single (as shown in (b) in Figure 1).

Preparation Example 2 Positive electrode sheet for lithium ion battery

The positive electrode active material for lithium ion battery (LiNi _0.8 Co _0.1 Mn _0.1 O ₂ ), binder PVDF, conductive carbon black, and carbon nanotubes are mixed and dispersed in NMP. After mixing, vacuum stirring is performed to obtain uniform dispersion to make lithium ion battery. Use positive paste. The solid content contains 94 wt % of positive active material, 3 wt % of binder PVDF, 2 wt % of conductive carbon black and 1 wt % of carbon nanotubes. The total solid content in the positive electrode slurry for lithium ion batteries was 70 wt %.

The positive electrode slurry for lithium ion batteries is evenly coated on both sides of the aluminum foil, vacuum-dried at 100-120° C. for 10-24 hours, and rolled to be compacted to 2-4.8 g/cm ³ to obtain a positive electrode sheet L1 for lithium ion batteries Denoted as L-double (as shown in (c) in Figure 2).

The positive electrode slurry for lithium ion batteries is evenly coated on one side of the aluminum foil, vacuum-dried at 100-120° C. for 10-24 hours, and rolled to be compacted to 2-4.8 g/cm ³ to obtain a positive electrode sheet L2 for lithium ion batteries. Denoted as L-single (as shown in (b) in Figure 2).

Preparation Example 3 Cathode Sheet H for Lithium Ion Batteries and Supercapacitors

The positive electrode slurry for supercapacitors of Preparation Example 1 and the positive electrode slurry for lithium ion batteries of Preparation Example 2 were evenly coated on both sides of the aluminum foil, vacuum dried at 100-120 ° C for 10-24 hours, and compacted to 0.9 by a roller press. -3.8 g/cm ³ to obtain a positive electrode sheet H for lithium ion batteries and supercapacitors (as shown in FIG. 3 ).

Preparation Example 4 Compatible negative electrode sheet

Mix 95wt% artificial graphite, 2wt% binder SBR (polystyrene butadiene copolymer) and 3wt% conductive agent conductive carbon black in deionized water, stir and disperse uniformly to make compatible negative electrode slurry. The solid content in the compatible negative electrode slurry is 45-55 wt%.

The compatible negative electrode slurry was evenly coated on both sides of the copper foil, dried in a vacuum at 100-120°C for 10-24 hours, and compacted to 0.9-2.1 g/cm ³ by a roller press to obtain several compatible negative electrode sheets F1 and recorded as F1- Double (as shown in (c) in Figure 4).

Coat the compatible negative electrode slurry evenly on one side of the copper foil, vacuum dry at 100-120°C for 10-24 hours, and compact it to 0.9-2.1 g/cm ³ by a roller press to obtain a number of compatible negative electrode sheets F2, denoted as F2- single (as shown in (b) in Figure 4).

Preparation Example 5 Seventh negative electrode sheet

Mix and disperse porous carbon activated carbon powder (specific surface area ≥ 1000m ² /g), binder PVDF, conductive carbon black, and carbon nanotubes in NMP (N-methylpyrrolidone), which is a negative active material for supercapacitors. Vacuum stirring to obtain a uniformly dispersed negative electrode slurry for supercapacitors. The solid content contains 93wt% of negative active material, 4wt% of binder PVDF, 2wt% of conductive carbon black and 1wt% of carbon nanotubes. The total solids content in the negative electrode slurry for supercapacitors was 40 wt%.

The negative electrode slurry for supercapacitors and the compatible negative electrode slurry of Preparation Example 4 were uniformly coated on both sides of the copper foil, dried in a vacuum at 100-120 ° C for 10-24 h, and compacted to 0.9-2.1 g/cm by a roller press. ³ , to obtain several seventh negative electrode sheets F5 (as shown in Fig. 5).

Preparation Example 6 Negative electrode sheet for supercapacitor

The negative electrode slurry for supercapacitors of Preparation Example 5 was evenly coated on both sides of the copper foil, dried in a vacuum at 100-120°C for 10-24h, and compacted to 0.9-2.1g/cm ³ by a roller press to obtain several supercapacitors for The negative electrode sheet F3 is denoted as F3-bi (as shown in (c) in FIG. 6 ).

The negative electrode slurry for supercapacitors of Preparation Example 5 was evenly coated on one side of the copper foil, dried in a vacuum at 100-120° C. for 10-24 h, and compacted to 0.9-2.1 g/cm ³ by a roller press to obtain several supercapacitors for The negative electrode sheet F4 is denoted as F4-single (as shown in (b) in FIG. 6 ).

Example 1 A combination of lithium-ion batteries and symmetrical supercapacitors

The positive electrode sheet and the above-mentioned preparation examples 1-3 were punched into 60mm×45mm sheets; the negative electrode sheets of the above-mentioned preparation examples 4-6 were punched into 62mm×47mm sheets;

Place the positive and negative pole pieces according to: F2-single, diaphragm, (L-double, diaphragm, F1-double, diaphragm), (L-double, diaphragm, F5, diaphragm), 2 (C-double, diaphragm, F3) - double, diaphragm), (C-double, diaphragm, F5, diaphragm), (L-double, diaphragm, F1-double, diaphragm), L-double, diaphragm, F2-single mode alternate combination, among which, transitional One surface of the negative electrode F5 is provided with a supercapacitor negative electrode material, and the other surface is provided with a lithium ion battery negative electrode material, thereby forming a stacked structure containing A1-G1-(B2) ₂ -G4-A1, the supercapacitor positive electrode material and The active material of the supercapacitor anode material is the same. Among them, F2-single, diaphragm and L-double include lithium-ion battery cell structure Y1; lithium-ion battery stack unit A1 includes lithium-ion cell cell structure Y1; A1-G1 forms a lithium-ion cell cell structure Y1; the transition unit G1 includes a lithium-ion battery cell structure Y1; a supercapacitor cell structure Y2 is formed between G1-B2; the supercapacitor lamination unit B2 includes a supercapacitor cell structure Y2; between B2-B2 A supercapacitor cell structure Y2 is formed; the supercapacitor lamination unit B2 includes a supercapacitor cell structure Y2; a supercapacitor cell structure Y2 is formed between B2-G4; the transition unit G4 includes a supercapacitor cell structure Y2; Li-ion battery element structure Y1 is formed between G4-A1; Li-ion battery lamination unit A1 includes lithium-ion battery element structure Y1; F1-double, separator, L-double includes lithium-ion battery element structure Y1; L-Bi, Separator, F2-Single include Li-ion battery cell structure Y1.

The separator made of polypropylene (PP) or polyethylene (PE) adopts Z-type lamination, and the positive and negative electrodes are separated and stacked to form a bare cell C-1. Then, transfer the positive electrode piece L for lithium ion battery and the positive electrode piece C for supercapacitor in the bare cell C-1 out of two independent aluminum tabs, and transfer the negative electrode tab out of copper nickel-plated tabs or nickel electrodes. ear, forming a three-pole-tab bare cell C-1 with two mutually independent positive pole tabs and one common negative pole tab.

Then the bare cell is clamped with a glass clamp, the strength of the glass clamp is 100MPa/m ² , and after being baked in a high temperature vacuum at 85°C for 24 hours, it is packaged with aluminum plastic film, and the electrolyte is added. Formation and aging were carried out to obtain a flexible package battery with a length, width and thickness of 70mm×50mm×7mm. The electrolyte is a 1M lithium hexafluorophosphate electrolyte, and the solvent of the electrolyte is a mixed solvent of ethylene carbonate: dimethyl carbonate: 1,2 propylene carbonate in a volume ratio of 1:1:1.

Example 2 A combination of lithium-ion batteries and asymmetric supercapacitors

Other operations are the same as in Example 1, except that:

The positive and negative pole pieces are as follows: F2-single, diaphragm, 2 (L-double, diaphragm, F1-double, diaphragm), 3 (C-double, diaphragm, F1-double, diaphragm), 1 ( The patterns of L-Double, Diaphragm, F1-Double, Diaphragm), L-Double, Diaphragm, and F2-Single are alternately combined to form a stacked structure containing (A1) ₂ -(B1) ₃ -(A1) ₁ . Among them, F2-single, separator and L-double include lithium-ion battery cell structure Y1; lithium-ion battery stack unit A1 includes lithium-ion cell cell structure Y1; A1-A1 forms a lithium-ion cell cell structure Y1; the lithium-ion battery stack unit A1 includes a lithium-ion battery cell structure Y1; a supercapacitor cell structure Y2 is formed between A1-B1; the supercapacitor cell structure B1 includes a supercapacitor cell structure Y2; B1 A supercapacitor elementary structure Y2 is formed between B1; the supercapacitor lamination unit B1 includes a supercapacitor elementary structure Y2; a supercapacitor elementary structure Y2 is formed between B1 and B1; the supercapacitor lamination unit B1 Include supercapacitor element structure Y2; B1-A1 forms supercapacitor element structure Y2; Li-ion battery stack unit A1 includes lithium-ion battery element structure Y1; F1-double, separator, L-double include Lithium-ion battery element structure Y1; L-double, separator, and F2-single include lithium-ion battery element structure Y1.

The separator made of polypropylene (PP) or polyethylene (PE) adopts Z-type lamination, and the positive and negative electrodes are separated and stacked to form a bare cell C-2. Then, transfer the positive electrode piece L for lithium ion battery and the positive electrode piece C for supercapacitor in the bare cell C-2 out of two independent aluminum tabs, and transfer the negative electrode tab out of copper nickel-plated tabs or nickel electrodes. ear, forming a three-pole bare cell C-2 with two independent positive poles and one common negative pole.

Example 3 Combination of lithium-ion battery, symmetrical supercapacitor, and asymmetrical supercapacitor

Other operations are the same as in Example 1, except that:

Place the positive and negative pole pieces according to: F2-single, diaphragm, (L-double, diaphragm, F1-double, diaphragm), (L-double, diaphragm, F5, diaphragm), 2 (C-double, diaphragm, F1) -Double, Diaphragm), (C-Dual, Diaphragm, F5, Diaphragm), (L-Dual, Diaphragm, F1-Dual, Diaphragm), L-Double, Diaphragm, F2-Single pattern alternately combined to form a pattern containing A1- The stacked structure of G1-(B1) ₂ -G4-A1, wherein the F2-single, the diaphragm, and the L-double include the lithium ion battery cell structure Y1; the lithium ion battery stack unit A1 includes the lithium ion battery cell Structure Y1; a lithium-ion battery cell structure Y1 is formed between A1-G1; the transition unit G1 includes a lithium-ion cell cell structure Y1; a supercapacitor cell structure Y2 is formed between G1-B1; the supercapacitor lamination unit B1 includes a supercapacitor cell structure Y2; B1-B1 forms a supercapacitor cell structure Y2; the supercapacitor lamination unit B1 includes a supercapacitor cell structure Y2; B1-G4 forms a supercapacitor cell structure Structure Y2; the transition unit G4 includes a supercapacitor element structure Y2; a lithium ion battery element structure Y1 is formed between G4-A1; the lithium ion battery lamination unit A1 includes a lithium ion battery element structure Y1; F1- The double, separator, and L-double include the lithium ion battery cell structure Y1; the L-double, separator, and F2-single include the lithium ion battery cell structure Y1.

The separator made of polypropylene (PP) or polyethylene (PE) adopts Z-type lamination, and the positive and negative electrodes are separated and stacked to form a bare cell C-3. Then, transfer the positive electrode piece L for lithium ion battery and the positive electrode piece C for supercapacitor in the bare cell C-3 out of two independent aluminum tabs, and transfer the negative electrode tab out of copper nickel-plated tabs or nickel electrodes. ear, forming a three-pole-tab bare cell C-3 with two mutually independent positive pole tabs and one common negative pole tab.

Comparative Example 1 Symmetrical Supercapacitor

Other operations are the same as in Example 1, except that:

The positive and negative pole pieces are alternately combined according to the pattern of: F4-single, diaphragm, 7 (C-double, diaphragm, F3, diaphragm), C-double, diaphragm, F4-single to form a pattern containing -(B2) ₇ - The stacked structure contains 16 supercapacitor cell structures Y2.

The separator made of polypropylene (PP) or polyethylene (PE) adopts Z-type lamination, and the positive and negative electrodes are separated and stacked to form DBL-1 containing a symmetrical supercapacitor bare cell. Then, the supercapacitor in the bare cell DBL-1 is transferred out of an aluminum tab from the positive electrode sheet C, and the negative electrode sheet is transferred out of a copper nickel-plated tab or a nickel tab to form a two-pole tab bare cell DBL-1.

Comparative Example 2 Asymmetric Supercapacitor

Other operations are the same as in Example 1, except that:

The positive and negative pole pieces are alternately combined according to the pattern of: F2-single, diaphragm, 7 (C-double, diaphragm, F1-double, diaphragm), C-double, diaphragm, F2-single to form a pattern containing -(B1) _7- The stacked structure, which contains 16 supercapacitor cell structures Y2.

The separator made of polypropylene (PP) or polyethylene (PE) adopts Z-type lamination, and the positive and negative electrodes are separated and stacked to form a DBL-2 containing a symmetrical supercapacitor bare cell. Then, the supercapacitor in the bare cell DBL-2 is transferred out of an aluminum tab from the positive electrode sheet C, and the negative electrode sheet is transferred out of a copper nickel-plated tab or a nickel tab to form a two-pole bare cell DBL-2.

Comparative Example 3 Lithium-ion battery

Other operations are the same as in Example 1, except that:

The positive and negative pole pieces are alternately combined in the mode of: F2-single, diaphragm, 7 (L-double, diaphragm, F1-double, diaphragm), L-double, diaphragm, F2-single to form a pattern containing -(A1) ₇ - The stacked structure, which contains 16 lithium-ion battery cell structure Y1.

The separator made of polypropylene (PP) or polyethylene (PE) adopts Z-type lamination, and the positive and negative electrodes are separated and stacked to form a DBL-3 containing a symmetrical supercapacitor bare cell. Then, transfer the positive electrode sheet L of the lithium-ion battery in the bare cell DBL-2 out of an aluminum tab, and transfer the negative electrode sheet out of a copper nickel-plated tab or a nickel tab to form a two-pole bare cell DBL-3 .

Comparative Example 4 Hybrid lithium-ion battery, asymmetric supercapacitor bipolar lug battery

Other operations are the same as those in Example 2, except that:

The separator made of polypropylene (PP) or polyethylene (PE) adopts Z-type lamination, and the positive and negative electrodes are separated and stacked to form a bare cell DBL-4, and all lithium-ion batteries are used for positive plates L and supercapacitors. The aluminum tabs transferred from the positive electrode sheet C are welded together to form a common lead-out terminal positive electrode tab, and the negative electrode sheet is transferred out of the copper nickel-plated tabs or nickel tabs to form a two-tab bare cell DBL-4.

Table 1 Performance test results of capacitors prepared in Examples and Comparative Examples

Obviously, according to Table 1, the "capacity retention rate (%)" of the laminated composite battery of Examples 1-3 of the present invention is significantly better than that of the two-pole-tab laminated composite battery (for 60 days of 4.2V full-charge storage). ratio 4). When the supercapacitor is a symmetric supercapacitor (Example 1), its power density is significantly greater than that of an asymmetrical supercapacitor (Examples 2 and 3).

The embodiments of the present invention have been described above. However, the present invention is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (9)

1. A laminated composite battery, characterized in that it includes a lithium ion battery laminated unit and a supercapacitor laminated unit, and the lithium ion battery laminated unit includes a positive electrode sheet, a negative electrode sheet and a separator that can be used for a lithium ion battery , the supercapacitor lamination unit includes a positive electrode sheet, a negative electrode sheet and a separator that can be used for supercapacitors; the two outermost layers of the composite battery are selected from a positive electrode sheet coated with a positive electrode material on one side and a positive electrode sheet coated with a positive electrode material on one side. There is one of the negative electrode sheets of the negative electrode material; in each supercapacitor lamination unit, the active material of the positive electrode material of the supercapacitor is the same as the active material of the negative electrode material of the supercapacitor. 2. The composite battery according to claim 1, wherein the positive electrode sheet that can be used for supercapacitors is selected from the following positive electrode sheets: a first positive electrode sheet, the first positive electrode sheet includes a first positive electrode current collector and a supercapacitor positive electrode material disposed on both sides of the first positive electrode current collector; A third positive electrode sheet, the third positive electrode sheet includes a third positive electrode current collector, a lithium ion battery positive electrode material disposed on the first surface of the third positive electrode current collector, and a surface opposite to the first surface of the third positive electrode current collector A supercapacitor positive electrode material arranged on the second surface; A fourth positive electrode sheet, the fourth positive electrode sheet includes a fourth positive electrode current collector and a supercapacitor positive electrode material disposed on one side surface of the fourth positive electrode current collector. 3. The composite battery according to claim 1, wherein the negative electrode sheet that can be used for supercapacitors is selected from the following negative electrode sheets: a third negative electrode sheet, the third negative electrode sheet includes a third negative electrode current collector and a supercapacitor negative electrode material provided on both sides of the third negative electrode current collector; a fourth negative electrode sheet, the fourth negative electrode sheet includes a fourth negative electrode current collector and a supercapacitor negative electrode material provided on one side surface of the fourth negative electrode current collector; An eighth negative electrode sheet, the eighth negative electrode sheet includes an eighth negative electrode current collector and a first negative electrode material disposed on a first surface of the eighth negative electrode current collector, and the eighth negative electrode current collector and the first negative electrode material are The second negative electrode material on the second surface opposite the surface, the first negative electrode material is selected from a bifunctional negative electrode material and a lithium ion battery negative electrode material, the second negative electrode material is a supercapacitor negative electrode material, and the first negative electrode material and The second negative electrode material is different, and the bifunctional negative electrode material can adsorb/desorb lithium ions, and can intercalate/deintercalate lithium ions of the lithium ion battery. 4. The composite battery according to claim 1, wherein the positive electrode sheet coated with positive electrode material on one side is selected from the following positive electrode sheets: a fourth positive electrode sheet, the fourth positive electrode sheet includes a fourth positive electrode current collector and a supercapacitor positive electrode material disposed on one side surface of the fourth positive electrode current collector; A fifth positive electrode sheet, the fifth positive electrode sheet includes a fifth positive electrode current collector and a lithium ion battery positive electrode material disposed on one surface of the fifth positive electrode current collector. 5. The composite battery according to claim 1, wherein the negative electrode sheet coated with the negative electrode material on one side is selected from the following negative electrode sheets; a second negative electrode sheet, the second negative electrode sheet includes a second negative electrode current collector and a bifunctional negative electrode material arranged on one surface of the second negative electrode current collector, the bifunctional negative electrode material can adsorb/desorb lithium ions, And can intercalate/deintercalate lithium ions of lithium ion batteries; a fourth negative electrode sheet, the fourth negative electrode sheet includes a fourth negative electrode current collector and a supercapacitor negative electrode material provided on one side surface of the fourth negative electrode current collector; A sixth negative electrode sheet, the sixth negative electrode sheet includes a sixth negative electrode current collector and a lithium ion battery negative electrode material disposed on one surface of the sixth negative electrode current collector. 6. The composite battery according to claim 1, wherein the positive electrode sheet that can be used in a lithium ion battery is selected from the following positive electrode sheets: a second positive electrode sheet, the second positive electrode sheet includes a second positive electrode current collector and a lithium ion battery positive electrode material disposed on both surfaces of the second positive electrode current collector; A third positive electrode sheet, the third positive electrode sheet includes a third positive electrode current collector, a lithium ion battery positive electrode material disposed on the first surface of the third positive electrode current collector, and a surface opposite to the first surface of the third positive electrode current collector A supercapacitor positive electrode material arranged on the second surface; A fifth positive electrode sheet, the fifth positive electrode sheet includes a fifth positive electrode current collector and a lithium ion battery positive electrode material disposed on one surface of the fifth positive electrode current collector. 7. The composite battery according to claim 1, wherein the negative electrode sheet that can be used in a lithium ion battery is selected from the following negative electrode sheets: a first negative electrode sheet, the first negative electrode sheet includes a first negative electrode current collector and a bifunctional negative electrode material provided on both sides of the first negative electrode current collector, the bifunctional negative electrode material can adsorb/desorb lithium ions, And can intercalate/deintercalate lithium ions of lithium ion batteries; a second negative electrode sheet, the second negative electrode sheet includes a second negative electrode current collector and a bifunctional negative electrode material arranged on one surface of the second negative electrode current collector, the bifunctional negative electrode material can adsorb/desorb lithium ions, And can intercalate/deintercalate lithium ions of lithium ion batteries; a fifth negative electrode sheet, the fifth negative electrode sheet includes a fifth negative electrode current collector and a lithium ion battery negative electrode material provided on both sides of the fifth negative electrode current collector; a sixth negative electrode sheet, the sixth negative electrode sheet includes a sixth negative electrode current collector and a lithium ion battery negative electrode material provided on one side surface of the sixth negative electrode current collector; A seventh negative electrode sheet, the seventh negative electrode sheet includes a seventh negative electrode current collector and a first negative electrode material disposed on the first surface of the seventh negative electrode current collector, and the seventh negative electrode current collector and the first negative electrode material are The second negative electrode material on the second surface opposite the surface, the first negative electrode material and the second negative electrode material are both selected from a bifunctional negative electrode material, a supercapacitor negative electrode material and a lithium ion battery negative electrode material, the first negative electrode material Different from the second negative electrode material, the bifunctional negative electrode material is capable of adsorbing/desorbing lithium ions, and capable of intercalating/deintercalating lithium ions of a lithium ion battery. 8 . The composite battery according to claim 1 , wherein the composite battery comprises a first positive electrode tab and a second positive electrode tab, and a negative electrode tab that are independent of each other; The positive electrode plate used for the supercapacitor laminated unit is connected to the first positive electrode tab; the positive electrode plate that can be used for the lithium ion battery laminated unit is connected to the second positive electrode tab, and the supercapacitor laminated unit and the lithium ion battery are stacked. The negative electrodes of the sheet unit are all connected to the negative tabs; when the composite battery includes a third positive tab, the third positive tab is connected to the first positive tab or the second positive tab, and the third positive tab includes The third positive electrode current collector, the lithium ion battery positive electrode material provided on the first surface of the third positive electrode current collector, and the supercapacitor positive electrode material provided on the second surface of the third positive electrode current collector opposite to the first surface. 9 . The composite battery according to claim 8 , wherein the first positive electrode tab and the second positive electrode tab are disposed on opposite sides of the composite battery, or the first positive electrode The tabs and the second positive tab are arranged on adjacent two sides of the battery.

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