CN112542573B - Lithium battery silicon-based film negative plate and preparation method thereof - Google Patents
Lithium battery silicon-based film negative plate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a silicon-based film negative plate of a lithium battery and a preparation method thereof, wherein the silicon-based film negative plate is directly prepared by adopting a roll-to-roll magnetron sputtering technology, pulse type rapid photo-thermal annealing is introduced when a sputtered silicon or silicon oxide film is in an island-shaped film forming stage, so that the sputtered silicon or silicon oxide film is rapidly condensed into nano microspheres, and then a graphite-like carbon buffer layer is introduced to fill up and cover gaps of nano spheres, so that the expansion of a nano silicon-based material can be effectively inhibited, and the electrical conductivity of the plate is enhanced.
Description
Technical Field
The invention relates to the technical field of lithium battery negative electrode materials, in particular to a lithium battery silicon-based film negative electrode plate and a preparation method thereof.
Background
With the development of new energy lithium battery technology, more and more application occasions have high requirements on the energy density of the lithium battery. At present, the promotion of lithium cell energy density starts from the aspect of lithium cell package structure on the one hand, and another important aspect is starting from electric core, strives to improve lithium cell key material energy density. The highest capacity of the commercialized anode material is about 200mA/g, the improvement of the cathode capacity is an effective means for improving the energy density of the battery, and according to related researches, the cathode capacity is improved to 1200-1500 mAh/g, and the energy density of the battery can be improved by nearly two times. With the graphite cathode approaching 372mAh/g of theoretical capacity, research on cathode materials with higher energy density becomes inevitable, and compared with the traditional graphite electrode material, the silicon-based cathode material has higher energy density and is a hotspot for research on cathode materials.
At present, the preparation technology of the silicon-based negative electrode material is mainly to compound the silicon-based material and a carbon material to prepare a silicon-carbon or silicon-oxygen-carbon composite material, and further form a negative electrode plate on a copper foil through a traditional pole plate preparation mode of slurry coating. Since silicon undergoes large volume expansion during lithium intercalation and deintercalation, nano-crystallization of silicon material is a key technology for inhibiting the expansion. The prior preparation technology of the nano silicon-based material is difficult to realize good compatibility of small particle size, dispersibility and oxidation resistance, the particle size of Si and SiOx (SiO has the problem of oxygen loss in the magnetron sputtering process, and x is not a constant) is reduced to be less than 50nm, and good dispersion is realized, which is more difficult. Therefore, the invention provides a method for directly preparing the silicon-based negative plate of the lithium battery by adopting a magnetron sputtering technology.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a lithium battery silicon-based film negative plate and a preparation method thereof, which solve the problems of large particle size and uneven dispersion of a nano silicon-based material in the preparation process of the existing silicon-carbon negative material and can effectively reduce the expansion of the plate.
In order to achieve the purpose, the invention provides the following technical scheme: a lithium battery silicon-based film negative plate comprises a negative plate current collector and an active laminated layer deposited on the negative plate current collector, wherein the active laminated layer is formed by alternately forming a nano silicon-based thin layer and a graphite-like carbon layer.
Furthermore, the current collector of the negative plate is a copper foil, and the thickness of the copper foil is 4-10 μm.
Further, the graphite carbon-like layer coats and fills the nano silicon-based thin layer, and the nano silicon-based thin layer is annealed.
The invention also provides a preparation method of the lithium battery silicon-based film negative plate, which comprises the following steps:
s1, placing the negative plate current collector in a discharge cavity of the magnetron sputtering system;
s2, starting a silicon target or a silicon sub-oxide target to sputter to obtain a nano silicon-based thin layer, and annealing the obtained nano silicon-based thin layer;
s3, starting a graphite target, and sputtering the nano silicon-based thin layer annealed in the step S2 to obtain a graphite-like carbon layer;
s4, repeating the steps S2 and S3 to alternately sputter the nano silicon-based thin layer and the graphite-like carbon layer to form the active lamination, and obtaining the silicon-based thin film negative plate when the thickness of the active lamination is 1-4 mu m.
Further, the magnetron sputtering adopts integrated roll-to-roll magnetron sputtering, and the background vacuum in a discharge cavity of the magnetron sputtering system is less than 1.0 multiplied by 10-5Pa, the running speed of the current collector of the negative plate is 1-5 m/min.
Further, in step S2, the nano-silicon-based thin layer is Si or SiOx, where x is greater than 0 and less than 2, and the thickness of the single-layer deposition of the nano-silicon-based particle thin layer is 5nm to 10 nm.
Further, in step S2, when the silicon target is a P-type or N-type heavily doped target, dc sputtering is used, when the silicon target is an SiO target, intermediate frequency or radio frequency sputtering is used, and the sputtering power of the silicon target is 15kw to 30 kw.
Further, in the step S2, the annealing treatment is pulse-type rapid photo-thermal annealing, the temperature of the annealing treatment is 400 to 500 ℃, the temperature rise rate is 80 to 100 ℃/S, and the time is 4 to 10S.
Further, in the step S3, the sputtering power of the graphite target is 5kw to 10kw, and the thickness of the graphite-like carbon layer is 20nm to 30 nm.
Compared with the prior art, the invention has at least the following beneficial effects:
according to the silicon-based thin film negative plate of the lithium battery, the nanometer silicon-based thin layer is annealed, and the annealed nanometer silicon-based thin layer is coated and filled by the graphite-like carbon layer, so that the problem that a nanometer silicon-based material is in a good dispersion state in the process of preparing the negative plate is solved, the graphite-like carbon layer is further sputtered to enable the nanometer silicon-based thin layer to be well coated and filled in the graphite-like carbon layer, and the prepared silicon-based thin film negative plate has good conductivity and an expansion inhibiting effect.
The preparation method of the negative plate provided by the invention adopts a magnetron sputtering technology, the negative plate of the lithium battery is prepared on the flexible substrate in one step, the nanometer silicon-based thin layer is annealed, so that good dispersion is realized, the formed nanometer silicon-based particle thin layer is only 5-10 nm, the formed nanometer silicon-based particle thin layer is coated by the graphite-like carbon layer through further sputtering of the graphite-like carbon layer, and the graphite-like carbon layer has certain toughness, so that the coating and filling of the nanometer silicon-based thin layer are realized, and the volume expansion effect of the silicon-based material during lithium intercalation is buffered, and the finally prepared silicon-based film negative plate has a good expansion inhibiting effect.
Furthermore, the active lamination is formed by alternately sputtering the nano silicon-based particle thin layer and the graphite-like carbon layer, the thickness of the obtained active lamination is 1-4 mu m, the active lamination not only greatly improves the capacity of a negative electrode material, but also effectively reduces the thickness of a lithium battery silicon-based film negative plate, and indirectly improves the volume energy density and the mass energy density of a subsequent battery.
Furthermore, the invention adopts a roll-to-roll magnetron sputtering technology, can realize batch roll-to-roll production by utilizing the flexible copper foil coiled material, and is more suitable for industrial production; the pulse type rapid photo-thermal annealing is adopted, and the rapid photo-thermal annealing can realize extremely rapid temperature rise so that the island-shaped nano silicon is rapidly nucleated and condensed, the nano silicon-based material realizes good particle dispersion, and the expansion of the negative plate is further reduced.
Drawings
FIG. 1: the invention provides a basic structure of a silicon-based negative plate;
in the drawings: 1 is a negative plate current collector; 2 is a nano silicon-based thin layer; and 3 is a graphite-like carbon layer.
Detailed Description
The invention is further described with reference to the following figures and detailed description.
Example 1
Step S1, placing the copper foil coiled material with the thickness of 8 mu m in a discharge cavity of a magnetron sputtering system, and starting a vacuum-pumping system until the background vacuum is less than 1.0 multiplied by 10-5Pa。
And step S2, starting the silicon target, the rapid photo-thermal linear light source and the graphite target in sequence for sputtering, wherein the traveling speed of the copper foil is 1.5m/min, the sputtering power of the silicon target is 15kw, the power of the graphite target is 10kw, the annealing temperature is 500 ℃, the heating rate is 80 ℃/S, the time is 8S, the thickness of the silicon layer is about 5nm and the thickness of the graphite-like carbon layer is about 20nm through matching of the traveling speed and the sputtering power.
And S3, repeating the step S2, repeatedly sputtering the nano silicon-based thin layer and the graphite-like carbon layer to obtain an active lamination, and stopping sputtering when the thickness of the active lamination reaches 1 mu m to obtain the silicon film negative plate.
Example 2
Step S1, placing the copper foil coiled material with the thickness of 4 mu m in a discharge cavity of a magnetron sputtering system, starting a vacuum-pumping system until the background vacuum is less than 1.0 multiplied by 10-5Pa。
And step S2, starting the silicon target, the rapid photo-thermal linear light source and the graphite target in sequence for sputtering, wherein the traveling speed of the copper foil is 5m/min, the sputtering power of the silicon target is 22kw, the power of the graphite target is 5kw, the annealing temperature is 450 ℃, the temperature rise rate is 100 ℃/S, the annealing time is 4S, the thickness of the silicon layer is about 10nm and the thickness of the graphite-like carbon layer is about 30nm through matching of the traveling speed and the sputtering power.
And S3, repeating the step S2, repeatedly sputtering the nano silicon-based thin layer and the graphite-like carbon layer to obtain an active lamination, and stopping sputtering when the thickness of the active lamination reaches 2 mu m to obtain the silicon film negative plate.
Example 3
Step S1, placing the copper foil coiled material with the thickness of 10 mu m in a discharge cavity of a magnetron sputtering system, and starting a vacuum-pumping system until the background vacuum is less than 1.0 multiplied by 10-5Pa。
And step S2, starting the silicon target, the rapid photo-thermal linear light source and the graphite target in sequence for sputtering, wherein the traveling speed of the copper foil is 1m/min, the sputtering power of the sub-oxide target is 20kw, the power of the graphite target is 10kw, the annealing temperature is 400 ℃, the temperature rise rate is 100 ℃/S, the annealing time is 6S, the thickness of the silicon layer is about 10nm and the thickness of the graphite-like carbon layer is about 30nm through matching of the traveling speed and the sputtering power.
And S3, repeating the step S2, repeatedly sputtering the nano silicon-based thin layer and the graphite-like carbon layer to obtain an active lamination, and stopping sputtering when the thickness of the active lamination reaches 2 mu m to obtain the silicon film negative plate.
Example 4
Step S1, placing the copper foil coiled material with the thickness of 8 mu m in a discharge cavity of a magnetron sputtering system, and starting a vacuum-pumping system until the background vacuum is less than 1.0 multiplied by 10-5Pa。
And step S2, starting the silicon target, the rapid photo-thermal linear light source and the graphite target in sequence for sputtering, wherein the traveling speed of the copper foil is 2m/min, the sputtering power of the sub-oxide target is 30kw, the power of the graphite target is 10kw, the annealing temperature is 400 ℃, the temperature rise rate is 100 ℃/S, the annealing time is 10S, the thickness of the silicon layer is about 8nm and the thickness of the graphite-like carbon layer is about 25nm through matching of the traveling speed and the sputtering power.
And S3, repeating the step S2, repeatedly sputtering the nano silicon-based thin layer and the graphite-like carbon layer to obtain an active lamination, and stopping sputtering when the thickness of the active lamination reaches 4 mu m to obtain the silicon film negative plate.
In the experiment, the electrochemical evaluation is carried out on the silicon-based negative plate by using a CR2032 button cell, wherein the charging and discharging procedures are that the discharging adopts step discharging and the step discharging is sequentially 0.1C, 0.09C, … C and 0.02C. After standing for 10min, the mixture was charged at 0.1C to 2V and stopped, and the test results are shown in Table 1.
TABLE 1 negative plate electrochemical Performance test results
At present, the capacity of a negative plate prepared by matching a conventional silicon-carbon material with graphite is basically 420-500 mAh/g, the expansion rate of a manufactured soft package battery is basically 15-30%, the expansion of the battery is mainly caused by the expansion of a silicon-based negative electrode material, the expansion rate of the battery prepared by the silicon-based thin film negative electrode plate obtained by the invention can be obtained from the table 1 and is only 12% at most and 9.5% at least, and the process provided by the invention can obviously reduce the particle size of a nano silicon-based material and can well inhibit the expansion of the silicon-based material by adopting a thicker graphite-like carbon layer for coating.
Fig. 1 shows a basic structure of a silicon-based negative electrode plate, according to the basic structure, a nano silicon-based thin layer and a graphite-like carbon layer are deposited on a negative electrode plate current collector, and the nano silicon-based thin layer is coated by the graphite-like carbon layer, so that the conductivity of the silicon-based negative electrode plate is improved. Meanwhile, the silicon-based negative plate prepared by the method has higher first effect, and the capacity of the silicon-based negative plate is greatly improved, so that the energy density of the battery can be obviously improved.
Claims (7)
1. A preparation method of a lithium battery silicon-based film negative plate is characterized by comprising the following steps:
s1, placing the negative plate current collector (1) in a discharge cavity of a magnetron sputtering system;
s2, starting a silicon target or a silicon sub-oxide target to sputter to obtain a nano silicon-based thin layer (2), and annealing the obtained nano silicon-based thin layer (2);
s3, starting a graphite target, and sputtering the nano silicon-based thin layer (2) annealed in the step S2 to obtain a graphite-like carbon layer (3);
s4, repeating the steps S2 and S3 to alternately sputter the nano silicon-based thin layer (2) and the graphite-like carbon layer (3) to form an active lamination, and obtaining the lithium battery silicon-based thin film negative plate when the thickness of the active lamination is 1-4 mu m;
the magnetron sputtering adopts integrated roll-to-roll magnetron sputteringThe background vacuum in the discharge cavity of the magnetron sputtering system is less than 1.0 multiplied by 10-5Pa, the running speed of the negative plate current collector (1) is 1-5 m/min;
in the step S2, the annealing treatment is pulse type rapid photo-thermal annealing, the temperature of the annealing treatment is 400-500 ℃, the heating rate is 80-100 ℃/S, and the time is 4-10S;
in the step S2, direct current sputtering is adopted when the silicon target is a P-type or N-type heavily doped target material, and intermediate frequency or radio frequency sputtering is adopted when the silicon target is an SiO target.
2. The method for preparing the silicon-based thin film negative electrode plate for the lithium battery as claimed in claim 1, wherein in the step S2, the nano silicon-based thin layer (2) is Si or SiOx, where 0 < x < 2, and the single-layer deposition thickness of the nano silicon-based thin layer (2) is 5nm to 10 nm.
3. The method for preparing the lithium battery silicon-based film negative electrode plate as claimed in claim 1, wherein in the step S2, direct current sputtering is adopted when the silicon target is a P-type or N-type heavily doped target material, and intermediate frequency or radio frequency sputtering is adopted when the silicon target is an SiO target.
4. The method for preparing the lithium battery silicon-based thin film negative plate as claimed in claim 1, wherein in the step S3, the thickness of the graphite-like carbon layer (3) is 20nm to 30 nm.
5. The preparation method of any one of claims 1 to 4 is used for preparing the lithium battery silicon-based thin film negative plate, and the lithium battery silicon-based thin film negative plate is characterized by comprising a negative plate current collector (1) and an active laminated layer deposited on the negative plate current collector (1), wherein the active laminated layer is formed by alternately depositing nano silicon-based thin layers (2) and graphite-like carbon layers (3), and the nano silicon-based thin layers (2) are subjected to annealing treatment.
6. The lithium battery silicon-based thin film negative plate as claimed in claim 5, wherein the negative plate current collector (1) is a copper foil, and the thickness of the copper foil is 4 μm to 10 μm.
7. The lithium battery silicon-based thin film negative plate as claimed in claim 5, wherein the graphite-like carbon layer (3) coats and fills the nano silicon-based thin layer (2).
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| CN114214595B (en) * | 2021-11-04 | 2023-11-28 | 万津实业(赤壁)有限公司 | Method for plating oxide optical film on flexible substrate and optical composite component |
| CN114050233B (en) * | 2021-11-25 | 2023-03-10 | 珠海冠宇电池股份有限公司 | Negative pole piece and battery |
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