CN114709365A - High-safety lithium ion battery positive plate, preparation method thereof and lithium ion battery - Google Patents
High-safety lithium ion battery positive plate, preparation method thereof and lithium ion battery Download PDFInfo
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Abstract
The invention provides a high-safety lithium ion battery positive plate and a preparation method thereof. And then sequentially coating the expansion adhesive tape in a subsequent manner according to the sequence of the positive plate, the first diaphragm, the negative plate and the second diaphragm, fixing the expansion adhesive tape outside the winding core by adopting the expansion adhesive tape, and then placing the expansion adhesive tape in the shell to obtain the qualified lithium ion battery.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a high-safety lithium ion battery positive plate and a preparation method thereof, and a lithium ion battery.
Background
With the development of nearly 30 years, lithium ion batteries have been widely used, such as: new energy automobile, electric tool and 3C digital domain battery etc.. In the development of lithium ion batteries in lithium battery anode and cathode materials in industries involving energy storage, the mass production of the anode materials can be divided into five types: lithium manganate, lithium cobaltate, lithium iron phosphate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate; the negative electrode material can be classified into two major types, namely a carbon material and a non-carbon material, wherein the former comprises graphite carbon materials such as artificial graphite and natural graphite and amorphous carbon materials such as soft carbon and hard carbon; the latter includes tin-based, silicon-based, titanium-based, and like alloy materials. In addition, silicon has very high specific capacity of lithium deintercalation and lower potential of lithium deintercalation, so that the silicon is the next generation of lithium ion battery negative electrode material with the highest potential to replace graphite for large-scale use.
The existing lithium battery mainly comprises a cylindrical, square, button and special-shaped oblate structure, and a lithium ion battery anode main material system mainly comprises lithium manganate, lithium cobaltate, lithium iron phosphate or lithium nickel cobalt manganese oxide and the like; in the aspect of safety performance, the existing lithium battery with a nickel and lithium cobaltate system has the advantages of high energy density, resource shortage and the like, and the safety performance is poor at a high temperature state, so that danger is easily caused. For nickel cobalt lithium manganate and lithium cobaltate, a large amount of oxygen generation is difficult to avoid under a high-temperature full-charge state, and treatment methods such as coating, specific surface area reduction and the like probably improve the result a little, but cannot improve the safety performance of the material fundamentally. The safety problem inevitable exists when the lithium ion battery is applied in practice, for example, the lithium ion battery is easy to generate thermal runaway and fire and explode when the battery meets some extreme conditions.
Disclosure of Invention
Aiming at the safety performance problem of the lithium ion battery, the invention provides a high-safety lithium ion battery positive plate and a preparation method thereof, the lithium ion battery adopts graphene-coated lithium iron phosphate and zinc oxide-coated lithium cobaltate or lithium nickel cobalt manganese oxide as positive materials, and the graphene-coated lithium iron phosphate positive material, a conductive agent, a binder and N-methylpyrrolidone are mixed into slurry to be coated on a first layer of a current collector to prepare a positive plate A; mixing a zinc oxide-coated lithium cobaltate or nickel cobalt lithium manganate positive electrode material, a conductive agent, a binder and an N-methyl pyrrolidone solvent into slurry, and coating the slurry on a positive electrode sheet A to obtain a qualified positive electrode sheet; graphite or silicon base is used as a negative electrode material, then the negative electrode material, a binder, a conductive agent and deionized water are mixed into slurry to be coated on a current collector to prepare a negative electrode plate, and the diaphragm is a high-strength high-elongation coated aluminum oxide isolating membrane; the qualified lithium ion battery is assembled by injecting an organic electrolyte and the like into the positive plate, the aluminum oxide isolating membrane, the negative plate and the expansion adhesive tape.
Specifically, the invention provides a high-safety lithium ion battery positive plate, which comprises: an intermediate substrate layer, a first dressing region and a second dressing region; wherein the content of the first and second substances,
the first dressing area is distributed on the upper surface and the lower surface of the middle base material layer, and a first anode material is coated by a first coating layer to obtain first mixed slurry; coating the first mixed slurry on the first dressing area to obtain an initial positive plate;
and the second dressing area is distributed on the upper surface and the lower surface of the initial positive plate, a second coating layer is adopted to coat a second positive material to obtain a second mixed slurry, and the second mixed slurry is coated in the second dressing area to obtain a qualified positive plate.
The first positive electrode material is formed by mixing a lithium iron phosphate positive electrode material, a conductive agent, a binder and N-methylpyrrolidone.
Furthermore, the second positive electrode material is formed by mixing a lithium cobaltate or nickel cobalt lithium manganate positive electrode material, a conductive agent, a binder and an N-methylpyrrolidone solvent.
Further, the first coating layer adopts a graphene material as a coating layer; the second coating layer adopts a zinc oxide material as a coating layer.
As another preferred mode, the invention further provides a preparation method of the high-safety lithium ion battery positive plate, which comprises the following steps:
s1: coating the first positive electrode material by using a first coating layer to obtain first mixed slurry;
s2: coating the first mixed slurry on the first dressing areas on the surfaces of the upper layer and the lower layer of the middle base material layer to prepare an initial positive plate;
s3: coating the second positive electrode material by using a second coating layer to obtain second mixed slurry;
s4: and coating the second mixed slurry on the second dressing areas on the upper and lower surfaces of the initial positive plate to obtain the qualified positive plate.
The first positive electrode material is formed by mixing a lithium iron phosphate positive electrode material, a conductive agent, a binder and N-methylpyrrolidone.
The second positive electrode material is formed by mixing a lithium cobaltate or nickel cobalt lithium manganate positive electrode material, a conductive agent, a binder and an N-methyl pyrrolidone solvent.
The first coating layer adopts a graphene material as a coating layer.
The second coating layer adopts a zinc oxide material as a coating layer.
As another preferred aspect, the present invention further provides a lithium ion battery, which includes a winding core, a positive plate, a negative plate and a casing.
The lithium ion battery of the invention also comprises: and fixing the roll core by adopting an expansion adhesive tape outside the roll core, sequentially wrapping the expansion adhesive tape by a positive plate, a first diaphragm, a negative plate and a second diaphragm, and then placing the expansion adhesive tape in the shell.
The positive plate further comprises an intermediate substrate layer, a first dressing area and a second dressing area; wherein the content of the first and second substances,
the first dressing area is distributed on the upper and lower surfaces of the middle base material layer and used for coating a first positive electrode material to obtain an initial positive electrode plate.
And the second dressing areas are distributed on the upper and lower surfaces of the initial positive plate and used for coating a second positive material.
The first positive electrode material is formed by mixing a lithium iron phosphate positive electrode material, a conductive agent, a binder and N-methylpyrrolidone; and coating the first positive electrode material by adopting a first coating layer to obtain first mixed slurry, wherein the first mixed slurry is coated in the first dressing area.
The second positive electrode material is formed by mixing a lithium cobaltate or nickel cobalt lithium manganate positive electrode material, a conductive agent, a binder and an N-methylpyrrolidone solvent; and coating a second anode material by using a second coating layer to obtain second mixed slurry, and coating the second mixed slurry on the first dressing area respectively.
The first coating layer adopts a graphene material as a coating layer; the second coating layer adopts a zinc oxide material as a coating layer.
The negative electrode material comprises graphite or a silicon-based material, and then the negative electrode material, a binder, a conductive agent and deionized water are mixed into slurry to be coated on a current collector to prepare the negative electrode plate.
Further, the first diaphragm and the second diaphragm adopt double-sided coated ceramic isolating films, and the double-sided coated ceramic isolating films are composed of a polyethylene microporous film at the innermost layer, polyvinylidene fluoride at the middle layer and an aluminum oxide dressing coating at the outermost layer;
the positive plate and the negative plate are respectively connected to the upper end and the lower end, or the left end and the right end, of the winding core.
The positive plate is connected with the winding core through an aluminum-to-nickel tab.
The negative plate is connected with the winding core through a nickel or copper-nickel composite tab.
The invention has the beneficial effects that:
(1) adopting graphene-coated lithium iron phosphate and zinc oxide-coated lithium cobaltate or lithium nickel cobalt manganese oxide as positive electrode materials; graphite or silicon base is used as a negative electrode material, and then the negative electrode material, a binder, a conductive agent and deionized water are mixed to form slurry to be coated on a current collector to prepare a negative electrode plate.
(2) The method adopts a double-sided coated ceramic isolation film, wherein the tensile strength of the diaphragm 2 is 1850-2250kgf/cm2, the puncture strength of the diaphragm 2 is 550-700gf, the longitudinal and transverse breaking elongation of the diaphragm 2 is 125-185%, the transverse shrinkage rate of the diaphragm 2 is less than or equal to 0.5% in a 110-degree environment, and the longitudinal shrinkage rate is less than or equal to 1.0%. The electrolyte has the advantages of organic solvent resistance, high thermal stability and chemical inertness, can well isolate the positive electrode and the negative electrode of the battery, prevents the two electrodes from contacting and short-circuiting, and is beneficial to the passing of electrolyte ions.
(3) After the expansion adhesive tape is adopted and meets the organic solvent of the electrolyte, the expansion adhesive tape can swell, the swelling multiple is more than 2.5 times, the hardness of the battery is increased, and the compression resistance and the impact resistance are achieved.
(4) The invention not only realizes the effective improvement of the safety performance and the cycle performance, but also improves the structural design of the lithium ion battery, has simple operation in production, is easy to realize batch production, properly reduces the use amount of lithium cobaltate and nickel resources, ensures the energy density and reduces the dependence on noble metals.
Drawings
Fig. 1 is a schematic diagram of a high-safety lithium ion battery positive plate in an embodiment of the invention.
Fig. 2 is a flow chart of a method for preparing a high-safety lithium ion battery positive plate in one embodiment of the invention.
Fig. 3 is a schematic diagram of a lithium ion battery according to an embodiment of the invention.
The adhesive tape comprises a 1-expanded adhesive tape, a 2-diaphragm, a 2-1-first diaphragm, a 2-2-second diaphragm, a 3-positive plate, a 4-negative plate, a 5-positive tab, a 6-negative tab, a 7-first dressing area, a 8-second dressing area and a 9-middle base material layer.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1, the present invention provides a high-safety lithium ion battery positive electrode sheet, including: an intermediate substrate layer, a first dressing region and a second dressing region; wherein the content of the first and second substances,
the first dressing area is distributed on the upper surface and the lower surface of the middle base material layer, and a first anode material is coated by a first coating layer to obtain first mixed slurry; coating the first mixed slurry on the first dressing area to obtain an initial positive plate; the first dressing area is used as a coating of the lithium iron phosphate dressing area, and preferably, the coating thickness of the first dressing area, namely the lithium iron phosphate dressing area, is 0.1-3 um. Because the P-O bond in the lithium iron phosphate crystal is stable and hard to decompose, and a strong oxidizing substance cannot be formed due to structural collapse and heating even if the battery is abnormally short-circuited at high temperature, the safety of the battery can be greatly improved.
The first mixed slurry is formed by mixing a lithium iron phosphate positive electrode material, a conductive agent, a binder and N-methyl pyrrolidone.
And the second dressing area is distributed on the upper surface and the lower surface of the initial positive plate, a second coating layer is adopted to coat a second positive material to obtain a second mixed slurry, and the second mixed slurry is coated in the second dressing area to obtain a qualified positive plate.
The second positive electrode material is formed by mixing a lithium cobaltate or nickel cobalt lithium manganate positive electrode material, a conductive agent, a binder and an N-methylpyrrolidone solvent.
Further, the first coating layer adopts a graphene material as a coating layer; the second coating layer adopts a zinc oxide material as a coating layer.
The middle base material layer comprises a current collector, a current collector coating is arranged on the outer side of the current collector, and a positive coating material is used on the outer side of the current collector coating.
As another preferred aspect, the present invention further provides a method for preparing a high-safety lithium ion battery positive plate, as shown in fig. 2, including the following steps:
s1: coating the first positive electrode material by using a first coating layer to obtain first mixed slurry;
s2: coating the first mixed slurry on the first dressing areas on the surfaces of the upper layer and the lower layer of the middle base material layer to prepare an initial positive plate;
s3: coating the second positive electrode material by using a second coating layer to obtain second mixed slurry;
s4: and coating the second mixed slurry on the second dressing areas on the upper and lower surfaces of the initial positive plate to obtain the qualified positive plate.
The first positive electrode material is formed by mixing a lithium iron phosphate positive electrode material, a conductive agent, a binder and N-methylpyrrolidone.
The second positive electrode material is formed by mixing a lithium cobaltate or nickel cobalt lithium manganate positive electrode material, a conductive agent, a binder and an N-methylpyrrolidone solvent.
The first coating layer adopts a graphene material as a coating layer.
The second coating layer adopts a zinc oxide material as a coating layer.
As another preferred mode, as shown in fig. 3, the present invention further provides a lithium ion battery, which includes a winding core, a positive electrode tab, a negative electrode tab and a casing.
The lithium ion battery of the invention also comprises: and fixing the roll core by adopting an expansion adhesive tape outside the roll core, sequentially wrapping the expansion adhesive tape by using a positive plate, a first diaphragm, a negative plate and a second diaphragm, and then placing the expansion adhesive tape in the shell.
The thickness of the expansion adhesive tape adopted by the invention is 50 +/-1 um, the expansion adhesive tape is wound on the outer side of the winding core for 1-3 circles, and the expansion adhesive tape can swell when meeting organic solvents of electrolyte, the swelling multiple is more than 2.5 times, the hardness of the battery is increased, and the compression resistance and the impact resistance are realized.
The positive plate further comprises an intermediate substrate layer, a first dressing area and a second dressing area;
the first dressing area is distributed on the upper and lower surfaces of the middle base material layer and used for coating a first positive electrode material to obtain an initial positive electrode plate.
The first dressing area is used for coating a first positive electrode material by adopting a first coating layer to obtain first mixed slurry; applying the first mixed slurry to the first dressing region.
The first mixed slurry is formed by mixing a lithium iron phosphate positive electrode material, a conductive agent, a binder and N-methyl pyrrolidone.
And the second dressing areas are distributed on the upper and lower surfaces of the initial positive plate and used for coating a second positive material.
And coating a second anode material by adopting a second coating layer to obtain second mixed slurry, and coating the second mixed slurry on the second dressing area to obtain the qualified anode plate.
The second mixed slurry is formed by mixing a lithium cobaltate or nickel cobalt lithium manganate positive electrode material, a conductive agent, a binder and an N-methyl pyrrolidone solvent;
the first coating layer adopts a graphene material as a coating layer; the second coating layer adopts a zinc oxide material as a coating layer.
The negative electrode material mainly adopts graphite or silicon base as the negative electrode material, and then the negative electrode material, the binder, the conductive agent and the deionized water are mixed into slurry to be coated on the current collector to prepare the negative electrode plate. Preferably, the graphite or silicon-based material coating thickness is 0.1-300 um.
Furthermore, the first diaphragm and the second diaphragm adopt double-sided coated ceramic isolating films, and the double-sided coated ceramic isolating films are composed of polyethylene microporous films at the innermost layer, polyvinylidene fluoride at the middle layer and aluminum oxide dressing coatings at the outermost layer. The double-sided coated ceramic isolating membrane has organic solvent resistance, high thermal stability and chemical inertness, can well isolate the positive electrode and the negative electrode of a battery, prevents the two electrodes from contacting and short-circuiting, and is beneficial to the passing of electrolyte ions.
Preferably, the double-sided coating ceramic isolating membrane adopted by the invention has the thickness of 16-25 μm; tensile strength of 1850-; puncture resistance strength 550-; the longitudinal and transverse breaking elongation of the double-sided coated ceramic isolating film is 125-185%, the transverse shrinkage rate of the double-sided coated ceramic isolating film is less than or equal to 0.5% in an environment of 110 ℃, and the longitudinal shrinkage rate of the double-sided coated ceramic isolating film is less than or equal to 1.0%.
Preferably, the double-side coated ceramic isolating membrane comprises a polyethylene microporous membrane with the thickness of 16-25um, a polyvinylidene fluoride with the thickness of a second coating layer of 0.2-2.5 mu m and an aluminum oxide dressing coating with the thickness of a third coating layer of 0.2-2.5 mu m.
The positive plate and the negative plate are respectively connected to the upper end and the lower end, or the left end and the right end, of the winding core; the positive plate and the negative plate are respectively connected with the winding core through an aluminum-to-nickel tab and a nickel or copper-nickel composite tab. For example, the positive electrode tab is connected to the upper end of the winding core in the axial direction, and the negative electrode tab is connected to the lower end of the winding core in the axial direction. Preferably, the square winding core positive plate is connected to the left end of the axial direction of the winding core, and the negative plate is connected to the right end of the axial direction of the winding core and is arranged in the shell.
Although the illustrative embodiments have been described herein with reference to the accompanying drawings, it is to be understood that the foregoing illustrative embodiments are merely exemplary and are not intended to limit the scope of the invention thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the scope or spirit of the present invention. All such changes and modifications are intended to be included within the scope of the present invention as set forth in the appended claims.
In the several embodiments provided in the present application, it should be understood that the disclosed apparatus and method may be implemented in other ways. For example, the above-described device embodiments are merely illustrative, and for example, the division of the units is only one logical functional division, and other divisions may be realized in practice, for example, a plurality of units or components may be combined or integrated into another device, or some features may be omitted, or not executed.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A high-safety lithium ion battery positive plate is characterized by comprising: an intermediate substrate layer, a first dressing region and a second dressing region; wherein the content of the first and second substances,
the first dressing area is distributed on the upper surface and the lower surface of the middle base material layer, and a first anode material is coated by a first coating layer to obtain first mixed slurry; coating the first mixed slurry on the first dressing area to obtain an initial positive plate;
and the second dressing area is distributed on the upper surface and the lower surface of the initial positive plate, a second coating layer is adopted to coat a second positive material to obtain a second mixed slurry, and the second mixed slurry is coated in the second dressing area to obtain a qualified positive plate.
2. The positive plate of the high-safety lithium ion battery according to claim 1, further comprising: the first positive electrode material is formed by mixing a lithium iron phosphate positive electrode material, a conductive agent, a binder and N-methyl pyrrolidone.
3. The positive plate of the high-safety lithium ion battery according to claim 2, further comprising: the second positive electrode material is formed by mixing a lithium cobaltate or nickel cobalt lithium manganate positive electrode material, a conductive agent, a binder and an N-methyl pyrrolidone solvent.
4. The positive plate of the high-safety lithium ion battery according to claim 3, further comprising: the first coating layer adopts a graphene material as a coating layer; the second coating layer adopts a zinc oxide material as a coating layer.
5. A preparation method of a high-safety lithium ion battery positive plate is characterized by comprising the following steps:
s1: coating the first positive electrode material by using a first coating layer to obtain first mixed slurry;
s2: coating the first mixed slurry on the first dressing areas on the surfaces of the upper layer and the lower layer of the middle base material layer to prepare an initial positive plate;
s3: coating the second positive electrode material by using a second coating layer to obtain second mixed slurry;
s4: and coating the second mixed slurry on the second dressing areas on the upper and lower surfaces of the initial positive plate to obtain the qualified positive plate.
6. The method for preparing the positive plate of the high-safety lithium ion battery according to claim 5, further comprising the following steps:
the first positive electrode material is formed by mixing a lithium iron phosphate positive electrode material, a conductive agent, a binder and N-methyl pyrrolidone;
the second positive electrode material is formed by mixing a lithium cobaltate or lithium nickel cobalt manganese oxide positive electrode material, a conductive agent, a binder and an N-methylpyrrolidone solvent;
the first coating layer adopts a graphene material as a coating layer;
the second coating layer is made of zinc oxide material and serves as a coating layer.
7. A lithium ion battery comprises a winding core, a positive plate, a negative plate and a shell; it is characterized by also comprising: fixing the roll core by adopting an expansion adhesive tape outside the roll core, sequentially wrapping the expansion adhesive tape by using a positive plate, a first diaphragm, a negative plate and a second diaphragm, and then placing the roll core in the shell;
the positive plate further comprises an intermediate substrate layer, a first dressing area and a second dressing area; wherein, the first and the second end of the pipe are connected with each other,
the first dressing areas are distributed on the surfaces of the upper layer and the lower layer of the middle base material layer and used for coating a first positive electrode material to prepare an initial positive electrode plate;
and the second dressing areas are distributed on the upper and lower surfaces of the initial positive plate and used for coating a second positive material.
8. The lithium ion battery of claim 7, further comprising:
the first positive electrode material is formed by mixing a lithium iron phosphate positive electrode material, a conductive agent, a binder and N-methyl pyrrolidone; coating the first positive electrode material by using a first coating layer to obtain first mixed slurry, wherein the first mixed slurry is coated in the first dressing area;
the second positive electrode material is formed by mixing a lithium cobaltate or nickel cobalt lithium manganate positive electrode material, a conductive agent, a binder and an N-methylpyrrolidone solvent; coating a second anode material by using a second coating layer to obtain second mixed slurry, and coating the second mixed slurry on the first dressing area respectively;
the first coating layer adopts a graphene material as a coating layer; the second coating layer adopts a zinc oxide material as a coating layer.
9. The lithium ion battery of claim 8, wherein the negative electrode sheet further comprises:
the negative electrode material comprises graphite or silicon material, and the negative electrode material, the binder, the conductive agent and the deionized water are mixed into slurry to be coated on the current collector to prepare the negative electrode plate.
10. The lithium ion battery of claim 9, further comprising:
the first diaphragm and the second diaphragm adopt double-sided coated ceramic isolating films, and the double-sided coated ceramic isolating films are composed of polyethylene microporous films at the innermost layer, polyvinylidene fluoride at the middle layer and aluminum oxide dressing coatings at the outermost layer;
the positive plate and the negative plate are respectively connected to the upper end and the lower end, or the left end and the right end, of the winding core;
the positive plate is connected with the winding core through an aluminum-to-nickel tab;
the negative plate is connected with the winding core through a nickel or copper-nickel composite tab.
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