The present disclosure relates to a high-orientation collector for a lithium-ion battery, a manufacturing method therefor and an application thereof.
In the past two decades, lithium-ion batteries become the most important power source for new energy vehicles. In order to make it widely available, it is necessary to further reduce the cost of the lithium-ion batteries while its performance is improved. In addition, in order to improve the driving mileage of electric vehicles, the industry still pursues the lithium-ion batteries with the higher energy density continuously. For the design of the electric vehicles, compared to the improvement of the energy density of a single cell, the improvement of the energy density of the entire Pack may meet the requirements of the electric vehicles for a Pack design in the case of guaranteeing the safety. In addition, an existing battery pack design is composed of Cell→Module→Pack, and the complexity and space utilization rate of the design are further increased.
A purpose of the present disclosure is to provide a method for preparing a high-orientation collector with simple operation and large area.
Another purpose of the present disclosure is to provide a high-orientation collector prepared by the above method.
Another purpose of the present disclosure is to provide an application of the above collector.
The present disclosure is achieved by the following technical schemes.
In one aspect, the present disclosure provides a collector, and it is made of a resin material added with conductive particles.
In the collector of the present disclosure, the conductive particles and the resin material are distributed at intervals, herein the conductive particles form a conductive path; in an X-Y direction, the number of the conductive particles forming the conductive path does not exceed 20% of the total number (number) of the conductive particles; and in a Z direction, the number of the conductive particles forming the conductive path is not less than 60% of the total number (number) of the conductive particles.
According to a specific scheme of the present disclosure, in the collector of the present disclosure, the material of the conductive particles may be carbon material nanoparticles, for example, one or a combination of two or more of a carbon black, a ketjen black, a carbon nanotube, a graphene, a carbon fiber, a vapor growth carbon fiber (VGCF) and the like. Herein the particle size of the graphene is 5 nm-100 nm; the particle size of the carbon black and the ketjen black is 1 nm-100 nm; the carbon nanotube may be selected from a single-wall carbon nanotube or a multi-wall carbon nanotube, the diameter is 1 nm-5 nm, and the length is 10 nm-500 nm; the diameter of the carbon fiber and VGCF is 80 nm-200 nm, Brunauer-Emmett-Teller (BET) is 5 m2/g-30 m2/g, and the length is 200 nm-5 µm. While two or more combined carbon materials are used, the solid content of the carbon material is 10 wt%-70 wt%, for example, it may be a mixture of graphene + carbon nanotube, or a mixture of carbon black + ketjen black, or a mixture of carbon black + ketjen black + carbon nanotube.
In the collector of the present disclosure, a polyolefin-based material may be used as the resin material (organic matrix). For example, a copolymer or a mixture formed by one or a combination of two or more of a high-density polyethylene, a low-density polyethylene, a polypropylene, a polybutene, a polymethylpentene and the like. According to the relative density, it is divided into the low-density polyethylene (LDPE) and the high-density polyethylene (HDPE), the density of LDPE is 0.91-0.925 g/cm3 and the density of HDPE is >0.94 g/cm3.
The above resin material is more stable in potential relative to a positive electrode and a negative electrode, and has the lower density than the metal, so it is beneficial to improve the weight energy density of the battery. For example, charge-discharge voltage range: 2.5-3.8V (LiFePO4 (LFP)); 2.5-4.2V (Nickel-Cobalt-Manganese (NCM)); positive compaction density: 2.3-2.6 g/cc (LFP); 3.5-3.8 g/cc (NCM); and negative compaction density: 1.3-1.7 g/cc (graphite).
In the collector of the present disclosure, the volume percentage of the spherical metal particles accounting for the collector is 30 wt%-70 wt%.
The thickness of the high-orientation resin collector of the present disclosure is preferably 5-30 µm. More preferably, the thickness of the collector is less than 20 µm, preferably less than 15 µm, and more preferably less than 10 µm.
In the collector of the present disclosure, the conductive particles form the conductive path of which the width is 500 nm-5 µm; adjacent conductive paths are filled with the resin material, the resin material is non-conductive, and the distance between the adjacent conductive paths is 500 nm-5 µm.
According to a specific implementation scheme of the present disclosure, the surface impedance of the collector of the present disclosure is lower than 15 mohm/sq, or lower than 10 mohm/sq.
The collector of the present disclosure adopts the resin filled with the conductive particles as the collector, and has the lower conductivity in the X-Y direction and the higher conductivity in the Z direction. While a short circuit occurs, only a few active materials may be activated in the X-Y direction, and thermal runaway may not eventually occur. In the present disclosure, the X-Y direction is a horizontal direction of the collector, and the Z direction is a thickness direction of the collector.
The density of the collector of the present disclosure is lower than that of the metal, and a higher weight energy density may be achieved. The density of the collector is <0.7 g/cc, the energy density of LFP (lithium iron phosphate battery) may be >190 Wh/kg, and the energy density of NCM (nickel-cobalt-manganate lithium battery) may be >300Wh/kg.
On the other hand, the present disclosure further provides a preparation method for the high-orientation collector, the method is mainly to prepare a high-orientation resin collector by a melt stretching method, including:
Both the thickness and the orientation degree of the collector of the present disclosure depend on the ratio of the resin to the conductive particles, the preheating temperature of a melting furnace and the stretching rate of a mechanical drum.
A high-orientation resin collector with a specific conductive path structure is formed by the melt stretching method (
According to a specific embodiment of the present disclosure, the preheating temperature of the melting furnace may be 60° C.-80° C.
According to a specific embodiment of the present disclosure, the stretching speed of the mechanical drum may be 5 m/min-30 m/min, and the stretching tension may be 40 N-80 N.
In the preparation method of the present disclosure, by controlling the stretching of the mechanical drum, the collector is stretched transversely, and the spacing distance between the particles may be controlled, thereby the width of the conductive path is controlled. In a specific embodiment of the present disclosure, the width of the conductive path is controlled to be 500 nm-5 µm.
On the other hand, the present disclosure further provides an application of the collector.
The collector of the present disclosure may be used to prepare a lithium-ion battery. While the lithium-ion battery is prepared, the design of a single cell stacked in series may save a connection electrode piece between the single batteries, improve the volume efficiency, and be suitable for vehicle use.
In the present disclosure, the resin using the conductive particles as a filler is used to prepare the collector, and the collector is characterized in that the conductive particles in the X-Y direction do not form a sufficient conductive network, but form a good conductive network in the Z direction. In this way, while a short circuit occurs, the collector is not easy to activate most of active materials in the X-Y direction so that thermal runaway does not occur easily, but may conduct electricity sufficiently in the Z direction, so that the battery may be charged and discharged normally. Thus, the battery safety is improved.
In order to have clearer understanding of technical features, purposes and beneficial effects of the present disclosure, technical schemes of the present disclosure are now described in detail below in combination with the drawings and specific embodiments. It should be understood that these embodiments are only used to describe the present disclosure and not to limit a scope of the present disclosure. In the embodiments, experimental methods without specific conditions are conventional methods and conventional conditions well-known in the field, or operated in accordance with conditions suggested by instrument manufacturers.
This embodiment provides a lithium-ion battery, and it includes:
Collector for positive electrode: in the X-Y direction, the number of the conductive particles forming the conductive path does not exceed 20% of the total number of the conductive particles (the resistivity in the X-Y direction is 5 mohm/sq); and in the Z direction, the number of the conductive particles forming the conductive path is not less than 70% of the total number of the conductive particles (the resistivity in the Z direction is 1 mohm/sq), the width of the conductive path formed by the conductive particles is 1 µm, and the distance between the adjacent conductive paths is 1 µm, it may be specifically shown in
Collector for negative electrode: in the X-Y direction, the number of the conductive particles forming the conductive path does not exceed 20% of the total number of the conductive particles (the resistivity in the X-Y direction is 5 mohm/sq); and in the Z direction, the number of the conductive particles forming the conductive path is not less than 70% of the total number of the conductive particles (the resistivity in the Z direction is 1 mohm/sq), the width of the conductive path formed by the conductive particles is 1 µm, and the distance between the adjacent conductive paths is 1 µm. The collector is prepared according to the following steps, as shown in
Acupuncture experiment: at a temperature of 20±5° C., a battery is in a full point state (SOC100), a steel needle with a diameter of 3 mm is used to penetrate rapidly in a direction perpendicular to an electrode plate, and the steel needle stays in it.
This embodiment provides a lithium-ion battery, and it includes:
Collector for positive electrode: in the X-Y direction, the number of the conductive particles forming the conductive path does not exceed 10% of the total number of the conductive particles (the resistivity in the X-Y direction is 8 mohm/sq); and in the Z direction, the number of the conductive particles forming the conductive path is not less than 70% of the total number of the conductive particles (the resistivity in the Z direction is 1 mohm/sq), the width of the conductive path formed by the conductive particles is 1 µm, and the distance between the adjacent conductive paths is 1.3 µm. The collector is prepared according to the following steps:
Collector for negative electrode: in the X-Y direction, the number of the conductive particles forming the conductive path does not exceed 10% of the total number of the conductive particles (the resistivity in the X-Y direction is 8 mohm/sq); and in the Z direction, the number of the conductive particles forming the conductive path is not less than 70% of the total number of the conductive particles (the resistivity in the Z direction is 1 mohm/sq), the width of the conductive path formed by the conductive particles is 1 µm, and the distance between the adjacent conductive paths is 1.3 µm. The collector is prepared according to the following steps:
Acupuncture experiment: at a temperature of 20±5° C., a battery is in a full point state (SOC100), a steel needle with a diameter of 3 mm is used to penetrate rapidly in a direction perpendicular to an electrode plate, and the steel needle stays in it.
This embodiment provides a lithium-ion battery, and it includes:
Collector for positive electrode: in the X-Y direction, the number of the conductive particles forming the conductive path does not exceed 20% of the total number of the conductive particles (the resistivity in the X-Y direction is 6 mohm/sq); and in the Z direction, the number of the conductive particles forming the conductive path is not less than 70% of the total number of the conductive particles (the resistivity in the Z direction is 1 mohm/sq), the width of the conductive path formed by the conductive particles is 1 µm, and the distance between the adjacent conductive paths is 1 µm. The collector is prepared according to the following steps:
Collector for negative electrode: in the X-Y direction, the number of the conductive particles forming the conductive path does not exceed 17% of the total number of the conductive particles (the resistivity in the X-Y direction is 6 mohm/sq); and in the Z direction, the part (number) of the conductive particles forming the conductive path is not less than 70% of the total number of the conductive particles (the resistivity in the Z direction is 1 mohm/sq), the width of the conductive path formed by the conductive particles is 1 µm, and the distance between the adjacent conductive paths is 1.3 µm. The collector is prepared according to the following steps:
Acupuncture experiment: at a temperature of 20±5° C., a battery is in a full point state (SOC100), a steel needle with a diameter of 3 mm is used to penetrate rapidly in a direction perpendicular to an electrode plate, and the steel needle stays in it.
This embodiment provides a lithium-ion battery, and it includes:
Collector for positive electrode: in the X-Y direction, the number of the conductive particles forming the conductive path does not exceed 20% of the total number of the conductive particles (the resistivity in the X-Y direction is 8 mohm/sq); and in the Z direction, the number of the conductive particles forming the conductive path is not less than 70% of the total number of the conductive particles (the resistivity in the Z direction is 1 mohm/sq), the width of the conductive path formed by the conductive particles is 1 µm, and the distance between the adjacent conductive paths is 1 µm. The collector is prepared according to the following steps:
Collector for negative electrode: in the X-Y direction, the number of the conductive particles forming the conductive path does not exceed 10% of the total number of the conductive particles (the resistivity in the X-Y direction is 8 mohm/sq); and in the Z direction, the number of the conductive particles forming the conductive path is not less than 70% of the total number of the conductive particles (the resistivity in the Z direction is 1 mohm/sq), the width of the conductive path formed by the conductive particles is 1 µm, and the distance between the adjacent conductive paths is 1.3 µm. The collector is prepared according to the following steps:
Acupuncture experiment: at a temperature of 20±5° C., a battery is in a full point state (SOC100), a steel needle with a diameter of 3 mm is used to penetrate rapidly in a direction perpendicular to an electrode plate, and the steel needle stays in it.
This embodiment provides a lithium-ion battery, and it includes:
Collector for positive electrode: in the X-Y direction, the number of the conductive particles forming the conductive path does not exceed 20% of the total number of the conductive particles (the resistivity in the X-Y direction is 8 mohm/sq); and in the Z direction, the number of the conductive particles forming the conductive path is not less than 70% of the total number of the conductive particles (the resistivity in the Z direction is 1 mohm/sq), the width of the conductive path formed by the conductive particles is 1 µm, and the distance between the adjacent conductive paths is 1 µm. The collector is prepared according to the following steps:
Collector for negative electrode: in the X-Y direction, the number of the conductive particles forming the conductive path does not exceed 20% of the total number of the conductive particles (the resistivity in the X-Y direction is 8 mohm/sq); and in the Z direction, the number of the conductive particles forming the conductive path is not less than 70% of the total number of the conductive particles (the resistivity in the Z direction is 1 mohm/sq), the width of the conductive path formed by the conductive particles is 1 µm, and the distance between the adjacent conductive paths is 1 µm. The collector is prepared according to the following steps:
Acupuncture experiment: at a temperature of 20±5° C., a battery is in a full point state (SOC100), a steel needle with a diameter of 3 mm is used to penetrate rapidly in a direction perpendicular to an electrode plate, and the steel needle stays in it.
This embodiment provides a lithium-ion battery, and it includes:
Collector for positive electrode: in the X-Y direction, the number of the conductive particles forming the conductive path does not exceed 20% of the total number of the conductive particles (the resistivity in the X-Y direction is 8 mohm/sq); and in the Z direction, the number of the conductive particles forming the conductive path is not less than 70% of the total number of the conductive particles (the resistivity in the Z direction is 1 mohm/sq), the width of the conductive path formed by the conductive particles is 1 µm, and the distance between the adjacent conductive paths is 1 µm. The collector is prepared according to the following steps:
Collector for negative electrode: in the X-Y direction, the number of the conductive particles forming the conductive path does not exceed 20% of the total number of the conductive particles (the resistivity in the X-Y direction is 8 mohm/sq); and in the Z direction, the number of the conductive particles forming the conductive path is not less than 70% of the total number of the conductive particles (the resistivity in the Z direction is 1 mohm/sq), the width of the conductive path formed by the conductive particles is 1 µm, and the distance between the adjacent conductive paths is 1 µm. The collector is prepared according to the following steps:
Acupuncture experiment: at a temperature of 20±5° C., a battery is in a full point state (SOC100), a steel needle with a diameter of 3 mm is used to penetrate rapidly in a direction perpendicular to an electrode plate, and the steel needle stays in it.
It may be seen from Table 1 that, the resin-based collector of the present disclosure is used, the volume energy density of Pack and the safety performance of the battery are both greatly improved (acupuncture experiment).
Filing Document | Filing Date | Country | Kind |
---|---|---|---|
PCT/CN2019/122333 | 12/2/2019 | WO |