CN111525095A - Lithium supplementing method for silicon-containing negative electrode material, negative electrode plate and battery - Google Patents

Lithium supplementing method for silicon-containing negative electrode material, negative electrode plate and battery Download PDF

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CN111525095A
CN111525095A CN202010238490.4A CN202010238490A CN111525095A CN 111525095 A CN111525095 A CN 111525095A CN 202010238490 A CN202010238490 A CN 202010238490A CN 111525095 A CN111525095 A CN 111525095A
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lithium
silicon
target
supplementing
substrate
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张艳芳
谭志
虞文韬
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VDL Industry Shenzhen Co Ltd
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VDL Industry Shenzhen Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/54—Controlling or regulating the coating process
    • C23C14/541—Heating or cooling of the substrates
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0423—Physical vapour deposition
    • H01M4/0426—Sputtering
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    • H01M4/00—Electrodes
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/366—Composites as layered products
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    • H01M4/00—Electrodes
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention relates to a lithium supplementing method of a silicon-containing negative electrode material, a negative electrode plate and a battery, wherein the method comprises the following steps: forming a silicon-containing negative electrode material on a current collector to obtain a substrate; preheating the substrate, and supplementing lithium to the substrate in a vacuum sputtering mode under the atmosphere of a vacuum condition; wherein the pre-heating temperature is higher than the temperature of the atmosphere and lower than the melting point of the lithium-supplement target material. According to the lithium supplement method of the silicon-containing negative electrode material, the target material is prevented from losing efficacy due to melting of the target material by heating the atmosphere of the lithium supplement chamber and controlling the temperature not to exceed the melting point of the target material; the substrate is preheated to enable the material on the target material to be plated on the substrate in a micro-melting state, so that the diffusion of target source particles on the surface of the film can be accelerated, and the uniformity and compactness of the film are improved.

Description

Lithium supplementing method for silicon-containing negative electrode material, negative electrode plate and battery
Technical Field
The invention relates to the technical field of battery production and manufacturing, in particular to a lithium supplementing method of a silicon-containing negative electrode material, a negative electrode plate and a battery.
Background
The lithium ion battery has the characteristics of high specific capacity, high voltage platform, long cycle life and the like, and is widely applied to the fields of portable electronic 3C equipment, electric automobiles, ships, space technology, biomedical engineering, logistics, national defense and military industry and the like. Development of a lithium ion battery with high energy density and high rate characteristic is always a goal pursued by people, and a negative electrode material is one of key factors for determining the characteristics of the lithium ion battery.
Silicon is taken as a negative electrode material with high specific capacity, the theoretical specific capacity of the silicon is 4200mAh/g, which is much higher than that of commercial graphite, and the silicon is widely concerned by researchers in recent years. However, the elementary silicon is accompanied by huge volume change (up to 300%) during the charging and discharging process, which causes active particles to break and pulverize, fall off from the surface of the current collector and lose electric contact, and also aggravates the side reaction between the active material and the electrolyte, finally resulting in the sharp decline of the electrode performance. This problem has greatly limited the development and practical application of silicon as a negative electrode material for lithium ion batteries.
Silica materials have the advantages of low working voltage, good safety, wide raw material sources, and the like, and thus, silica materials have become a focus of attention of researchers in recent years. The silicon oxide is also a negative electrode material containing silicon and having higher specific capacity, and compared with silicon, the volume change of the silicon oxide is smaller in the charge and discharge processes. Although volume expansion of the silicon monoxide is alleviated compared with that of the elemental silicon, there is still a problem that the active material is cracked due to stress concentration caused by volume change. Meanwhile, in order to solve the problem, lithium can be supplemented for silicon-containing cathode materials such as silicon or silicon composite materials, so that the problems of battery volume expansion and improvement of primary efficiency are solved.
The conventional lithium supplementing methods comprise a lithium powder scattering method, a lithium belt rolling method and a PVD lithium pre-supplementing method, and the lithium supplementing processes have low lithium supplementing quality and cannot meet the requirement of large-scale production.
Disclosure of Invention
Therefore, it is necessary to provide a lithium supplement method for a silicon-containing negative electrode material, a negative electrode sheet, and a battery, which can improve the lithium supplement quality.
A lithium supplementing method for a silicon-containing negative electrode material comprises the following steps:
forming a silicon-containing negative electrode material on a current collector to obtain a substrate;
preheating the substrate, and supplementing lithium to the substrate in a vacuum sputtering mode under the atmosphere of a vacuum condition; wherein the pre-heating temperature is higher than the temperature of the atmosphere and lower than the melting point of the lithium-supplement target material.
According to the lithium supplement method of the silicon-containing negative electrode material, the target material is prevented from losing efficacy due to melting of the target material by heating the atmosphere of the lithium supplement chamber and controlling the temperature not to exceed the melting point of the target material; the substrate is preheated to enable the material on the target material to be plated on the substrate in a micro-melting state, so that the diffusion of target source particles on the surface of the film can be accelerated, and the uniformity and compactness of the film are improved.
In some of these embodiments, the temperature of the atmosphere is from 30 ℃ to 130 ℃.
In some embodiments, the material of the lithium-complementary target is selected from one of metal lithium, lithium oxide, lithium nitride and lithium carbide.
In some embodiments, the number of the targets for lithium supplement is plural, and the plurality of targets are made of at least two materials, one material of the targets is selected from one of lithium metal, lithium silicon alloy, lithium boron alloy, lithium sulfur alloy, lithium oxide, lithium nitride or lithium carbide, and the other material of the targets is selected from one of silicon, carbon, silicon oxide, silicon carbide or silicon nitride.
In some embodiments, in the step of vacuum sputtering, the target is used for lithium supplement on two side surfaces of the substrate.
In some embodiments, in the step of vacuum sputtering, the substrate in the lithium replenishing region is continuously moved in a linear direction.
In some embodiments, the step of replenishing lithium is performed using a linear lithium replenishing device;
the linear lithium supplementing equipment comprises a lithium supplementing cavity, and an unreeling device, a reeling device, at least two target mounting mechanism groups and a substrate heating mechanism which are arranged in the lithium supplementing cavity;
the unreeling device unreels the substrate to be compensated with lithium;
the winding device winds the substrate after lithium supplement;
the at least two target mounting mechanism groups are arranged between the unwinding device and the winding device, wherein the at least two target mounting mechanism groups are respectively arranged corresponding to two side surfaces of the substrate between the unwinding device and the winding device; the number of the target mounting mechanisms in each group is multiple, one target is mounted on each target, and the target mounting mechanisms in the same group are sequentially distributed in a straight line in the direction from the unwinding device to the winding device; and
the substrate heating mechanism comprises a heating installation mechanism and heating sheets arranged on the heating installation mechanism, wherein the heating installation mechanism is arranged between every two adjacent target installation mechanisms in each group, and the heating sheets preheat substrates between the unwinding device and the winding device.
In some embodiments, the number of the heating installation mechanisms is multiple, and the heating installation mechanism is arranged between every two adjacent target installation mechanisms in each group.
In some embodiments, the linear lithium supplementing device further comprises a blocking mechanism and a plurality of intermediate frequency pulse power supplies;
every two adjacent target mounting mechanisms in each group form a pair, and two targets on each target mounting mechanism pair are connected with one intermediate-frequency pulse power supply;
the blocking mechanism is arranged in the lithium supplement chamber and is arranged between two adjacent pairs of target mounting mechanisms in the same group.
In some embodiments, the number of the target mounting mechanisms in each group is three or more; the number of the blocking mechanisms is multiple, and the blocking mechanisms are arranged between any two adjacent pairs of the target mounting mechanisms in each group.
In some embodiments, the blocking mechanism is a partition plate, and two side surfaces of the partition plate are respectively disposed opposite to two targets on two adjacent target mounting mechanisms.
In some embodiments, the linear lithium supplement device further comprises a chamber heating device, and the chamber heating device is used for heating the lithium supplement chamber to control the temperature of the atmosphere.
In some embodiments, the material of the target on each target mounting mechanism is metallic lithium; or two targets are arranged on each target mounting mechanism, one target is made of metal lithium, the other target is made of silicon, and the two targets are alternately arranged at intervals in the transmission direction of the substrate;
the preheating temperature is 40-170 ℃, the transmission speed of the substrate is 1 cm/h-100 m/h, and the vacuum degree of sputtering is 6 × 10-4Pa to 1.0 × 10-1Pa, and the sputtering power is 100W to 50 kW.
In some of these embodiments, the silicon-containing anode material is selected from one of silicon, silicon carbon, silicon monoxide, silicon oxide, carbon-doped silicon dioxide, silicon oxycarbide, or a combination thereof.
The negative plate is prepared by adopting the lithium supplementing method of the silicon-containing negative electrode material.
A battery contains the negative plate.
Drawings
Fig. 1 is a flowchart of a lithium supplementing method for a silicon-containing negative electrode material according to an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a linear lithium replenishing apparatus used in a lithium replenishing method according to an embodiment of the present invention;
FIG. 3 is a schematic structural diagram of a linear lithium replenishing apparatus used in a lithium replenishing method according to yet another embodiment of the present invention;
FIG. 4 is a schematic structural diagram of a blocking mechanism of a linear lithium replenishing device used in a lithium replenishing method according to yet another embodiment of the present invention;
FIG. 5 is a schematic illustration of a method for lithium replenishment of a silicon-containing negative electrode material according to an embodiment of the present invention;
fig. 6 is a schematic view of a lithium supplementing method for a silicon-containing negative electrode material according to still another embodiment of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1, an embodiment of the present invention provides a method for supplementing lithium to a silicon-containing negative electrode material, including the following steps S110 to S120:
and step S110, forming a silicon-containing negative electrode material on a current collector to obtain a substrate.
Step S120, preheating the substrate, and supplementing lithium to the substrate in a vacuum sputtering mode in an atmosphere of a vacuum condition; wherein the preheating temperature is higher than the temperature of the atmosphere and lower than the melting point of the target material for lithium supplement.
According to the lithium supplement method of the silicon-containing cathode material, the target material is prevented from losing efficacy due to melting of the target material by heating the atmosphere of the lithium supplement chamber and controlling the temperature not to exceed the melting point of the target material; the substrate is preheated to enable the material on the target material to be plated on the substrate in a micro-melting state, so that the diffusion of target source particles on the surface of the film can be accelerated, and the uniformity and compactness of the film are improved.
Compared with a vacuum evaporation coating method, the sputtering energy for vacuum sputtering lithium supplement is higher, the formed coating is nano-particle stacking, and the formed coating is compact; the film formed by the evaporation coating method has larger particles and larger gaps among the particles, and cannot effectively realize lithium ion transmission, thereby reducing the performance of the silicon-containing negative electrode material.
In some of these embodiments, the temperature of the atmosphere is from 30 ℃ to 130 ℃. The temperature range of the atmosphere can be 30-50 ℃ and 70-130 ℃.
In some embodiments, the material of the lithium-complementary target is selected from one of lithium metal, lithium silicon alloy, lithium boron alloy, lithium sulfur alloy, lithium oxide, lithium nitride and lithium carbide. Thus, the coating films of metal lithium, lithium oxide, lithium nitride or lithium carbide are respectively formed on the silicon-containing negative electrode material, and further lithium supplement is realized.
Further, the target mounting mechanisms 13 may all mount the same target, the target may be a lithium target, a lithium silicon alloy target, a lithium boron alloy target, a lithium sulfur alloy target, a lithium oxide target, a lithium nitride target, a lithium carbide target, or the like, and the types of the targets mounted on the target mounting mechanisms 13 may also be different.
In some embodiments, the number of the targets for lithium supplement is plural, and the plurality of targets are made of at least two materials, one material of the targets is selected from one of lithium metal, lithium silicon alloy, lithium boron alloy, lithium sulfur alloy, lithium oxide, lithium nitride and lithium carbide, and the other material of the targets is selected from one of silicon, carbon, silicon oxide, silicon carbide and silicon nitride. Thus, the two targets can form a coating film of lithium silicon, lithium carbon and the like on the silicon-containing negative electrode material.
In some embodiments, in the step of vacuum sputtering, the target material supplements lithium to two side surfaces of the substrate, so that the lithium supplementing coating quality is improved, and the lithium supplementing efficiency is greatly improved.
In some embodiments, during the step of vacuum sputtering, the substrate in the lithium replenishing region is continuously moved in a linear direction.
In some embodiments, the step of replenishing lithium is performed using a linear lithium replenishing apparatus. Referring to fig. 2, an embodiment of the invention provides a linear lithium replenishing apparatus 10, which includes a lithium replenishing chamber 11, and an unwinding device 121, a winding device 122, at least two target mounting mechanism sets, and a substrate heating mechanism 14, which are disposed in the lithium replenishing chamber 11.
The unwinding device 121 is used for unwinding the substrate to be compensated with lithium.
The winding device 122 is used for winding the substrate after lithium supplement.
At least two target mounting mechanism groups are arranged between the unwinding device 121 and the winding device 122, and the at least two target mounting mechanism groups are respectively used for being arranged corresponding to two side surfaces of the substrate between the unwinding device 121 and the winding device 122; the number of the target mounting mechanisms 13 in each group is plural and one target is mounted respectively, and the plural target mounting mechanisms 13 in the same group are sequentially distributed linearly in the direction from the unwinding device 121 to the winding device 122.
The substrate heating mechanism 14 includes a heating installation mechanism and a heating sheet arranged on the heating installation mechanism, the heating installation mechanism is arranged between two adjacent target installation mechanisms 13 in each group, and the heating sheet is used for preheating the substrate between the unwinding device 121 and the winding device 122.
The linear lithium supplementing device 10 unreels the substrate to be supplemented with lithium through the unreeling device 121, the reeling device 122 reels the substrate after lithium supplementation, the target installation mechanisms 13 are sequentially distributed in a linear mode in the direction from the unreeling device 121 to the reeling device 122, and the targets of the target installation mechanisms 13 supplement lithium for the substrate, so that the continuity of the lithium supplementing process of the substrate is realized, and the lithium supplementing efficiency is improved. Meanwhile, at least two target mounting mechanism groups are respectively used for being arranged corresponding to two side surfaces of the substrate between the unwinding device 121 and the winding device 122, so that lithium is simultaneously replenished to the two side surfaces of the substrate, and the lithium replenishing efficiency is further improved.
Further, the heating sheet between two adjacent target mounting mechanisms 13 is used for preheating the substrate between the unwinding device 121 and the winding device 122 during film coating, so that the lithium supplement film coating quality of the substrate can be improved.
It is understood that in some embodiments, the substrate is a current collector having a surface comprising a silicon-containing negative electrode material such as silicon, silicon monoxide, or the like. Further, the silicon-containing anode material is selected from one or a combination of silicon, silicon carbon, silicon monoxide, silicon oxide, carbon-doped silicon dioxide and silicon oxycarbide.
Further, the number of the heating installation mechanisms is plural, and accordingly, the number of the heating sheets is plural. And a heating installation mechanism is arranged between every two adjacent target installation mechanisms 13 in each group, so that the heating sheet between every two adjacent target installation mechanisms 13 is used for heating the substrate between the unwinding device 121 and the winding device 122, the substrate can be uniformly heated, and the coating quality of the substrate is further improved.
It is understood that the positions and the number of the heating installation mechanisms and the heating sheets can also be flexibly adjusted according to the needs, for example, one heating installation mechanism is arranged between every two target installation mechanisms 13, and the like.
In the present specific example, the respective target mounting mechanisms 13 of at least two target mounting mechanism groups are provided in one-to-one correspondence. Further, in this specific example, the substrate heating mechanisms 14 provided on both side surfaces of the substrate are also provided in one-to-one correspondence.
It is understood that in other examples, the target mounting mechanisms 13 of at least two target mounting mechanism sets are arranged in a staggered manner with respect to each other, as shown in fig. 3. Further, the substrate heating means 14 for providing on both side surfaces of the substrate are also disposed to be offset from each other, so that the substrate can be heated more uniformly.
In the specific example shown in fig. 2, the linear lithium replenishment apparatus 10 has at least two target mounting mechanism sets; it is understood that in other examples, the number of sets of target mounting mechanisms may be three or more, for example, two or more sets of target mounting mechanisms spaced apart and arranged in parallel on the same side surface of the substrate.
It should be noted that, in some embodiments, the linear lithium supplement device 10 further includes a chamber heating device 15, and the chamber heating device 15 is used for heating the lithium supplement chamber 11. The chamber heating device 15 controls the temperature of the atmosphere environment of the lithium supplement chamber 11, generally, the chamber heating device 15 heats the atmosphere environment of the lithium supplement chamber 11 and controls the temperature not to exceed the melting point of the target material, so as to avoid the target material from being failed due to the melting of the target material. The heating sheet heats the substrate to enable the material on the target material to be plated on the substrate in a micro-melting state, so that the diffusion of target source particles on the surface of the film can be accelerated, and the uniformity and the compactness of the film are improved.
Further, the chamber heating device 15 may be a device capable of heating such as an infrared heating device.
In some of the embodiments, the plurality of target mounting mechanisms 13 in each group are uniformly distributed in the linear direction.
Further, the unwinding device 121 has an unwinding shaft, and the winding device 122 has a winding shaft. As can be appreciated. In some embodiments, the driving directions of the unwinding device 121 and the winding device 122 can be changed, so that the unwinding device 121 becomes the winding device 122, and accordingly the winding device 122 becomes the unwinding device 121, thereby improving the flexibility.
Further, the linear lithium supplement device 10 further comprises a transmission belt, the transmission belt is disposed between the unwinding device 121 and the winding device 122, so that the unwinding device 121 transmits the substrate to the winding device 122 through the transmission belt.
Further, the winding device 122 further has a clamping plate, and the clamping plate fixes the substrate, so as to assist in winding the substrate.
In some embodiments, the linear lithium supplying apparatus 10 further includes a cooling mechanism for cooling the substrate between the unwinding device 121 and the winding device 122 to provide a constant range of temperature.
Further, a cooling mechanism is filled with cooling liquid, and the common cooling liquid is water.
In some embodiments, the linear lithium replenishing apparatus 10 further includes a vacuum pump set and a vacuum pipeline communicated with the lithium replenishing chamber 11, wherein the vacuum pump set is used for vacuumizing the lithium replenishing chamber 11 through the vacuum pipeline.
Further, the vacuum pump group includes a plurality of vacuum pumps, such as a first vacuum pump 161, a second vacuum pump 162, a third vacuum pump, and so on. In some examples, the first vacuum pump 161, the second vacuum pump 162, and the third vacuum pump may be one of a mechanical pump, a molecular pump, and a roots pump, respectively. During vacuum pumping, the mechanical pump is started to work for a period of time to reduce the air pressure in the lithium supplementing cavity 11, then the roots pump is started to further reduce the air pressure in the lithium supplementing cavity 11, and finally the molecular pump is started to further reduce the air pressure in the lithium supplementing cavity 11 so as to meet lithium supplementing operation.
The vacuum-pumping pipeline is used for exhausting the pumped air.
In some embodiments, the linear lithium replenishing apparatus 10 further includes a gas inlet device 18 communicated with the lithium replenishing chamber 11, so that after the vacuum pumping reaches a certain vacuum degree, the gas inlet device 18 can also fill protective gas such as argon into the lithium replenishing chamber 11. And then starting the target material for coating. The operations of introducing protective gas, adjusting the target material power, adjusting the transmission rate and the like can be realized by the operation table.
In a specific example, after the film coating is finished, the target material is closed, the vacuum pump set is closed, the protective gas is introduced through the gas inlet device 18 until the vacuum gauge 17 returns to normal pressure, the cavity door is opened, and the substrate after lithium supplement is taken out from the winding device 122.
In some embodiments, the linear lithium replenishing apparatus 10 further includes a vacuum gauge 17, and the vacuum gauge 17 is used for detecting the vacuum degree or the air pressure of the lithium replenishing chamber 11.
Referring to fig. 4, in some embodiments, the linear lithium replenishing apparatus 10 further includes a blocking mechanism 19 and a plurality of intermediate frequency pulse power supplies; every two adjacent target mounting mechanisms 13 in each group form a pair, two targets on each target mounting mechanism pair are connected with a medium-frequency pulse power supply, namely the two targets on each target mounting mechanism pair are controlled by the medium-frequency pulse power supply; the blocking mechanism 19 is arranged in the lithium supplement chamber 11 and between two adjacent target mounting mechanism pairs in the same group.
Therefore, two targets (namely one target pair) on one target mounting mechanism pair are controlled by one intermediate frequency pulse power supply, and the two targets on each target mounting mechanism pair realize alternate work, so that high sputtering efficiency can be provided; further, the separation mechanism 19 is arranged between two adjacent target mounting mechanism pairs in the same group, so that the sputtering interval of each target pair is limited, mutual sputtering between adjacent targets can be effectively reduced, and the problem of uneven coating caused by repeated coating of the same region of the substrate by different target pairs is avoided.
Further, the number of the target mounting mechanisms 13 in each group is three or more.
Further, the number of the blocking mechanisms 19 is plural, and the blocking mechanisms 19 are arranged between any two adjacent target mounting mechanism pairs in each group.
Specifically, in the example shown in fig. 4, from left to right, the first and second target mounting mechanisms 13 form the above-described one target mounting mechanism pair, which is denoted as a first target mounting mechanism pair; the third and fourth target mounting mechanisms 13 form the above-mentioned one target mounting mechanism pair, which is denoted as a second target mounting mechanism pair; and so on. Further, taking the first pair of target mounting mechanisms and the second pair of target mounting mechanisms as an example, the blocking mechanism 19 is provided between the first pair of target mounting mechanisms and the second pair of target mounting mechanisms.
In a specific example, the blocking mechanism 19 is a partition plate, and two side surfaces of the partition plate are respectively disposed opposite to two targets on two adjacent target mounting mechanisms 13.
In other embodiments, the linear lithium replenishment apparatus 10 further comprises a plurality of dc power supplies, each of which is connected to one of the targets on one of the target mounting mechanisms 13 for controlling one of the targets on each of the target mounting mechanisms 13.
It is understood that in some examples, the number of targets is 1 to 50.
It will be appreciated that in some examples, the thickness of the coating formed by lithium replenishment may be controlled, for example in the range of 1nm to 100 μm, for example 10nm to 20 μm.
It will be appreciated that the transport speed of the substrate can be adjusted as desired, for example in the range 1mm/h to 1000 m/h.
Referring to fig. 5, the material of the target on each target mounting mechanism is lithium metal, i.e. each target is a lithium target. Referring to fig. 6, there are two kinds of targets on each target mounting mechanism, one kind of target is made of lithium metal, the other kind of target is made of silicon, and the two kinds of targets are alternately arranged at intervals in the conveying direction of the substrate.
Further, the preheating temperature is 40-170 ℃, the conveying speed of the substrate is 1 cm/h-100 m/h, and the vacuum degree of sputtering is 6 × 10-4Pa to 1.0 × 10-1Pa, and the sputtering power is 100W to 50 kW.
Further, the preheating temperature is 110 to 170 ℃, and more preferably 120 to 170 ℃. Further, the transport speed of the substrate is preferably 1cm/h to 6m/h, preferably 5m/h to 6 m/h. Further, the linear lithium supplement device 10 preferably adopts a technical scheme that one intermediate frequency pulse power supply controls two targets on two target mounting mechanisms 13, and the sputtering power is preferably 4kW to 6 kW.
Further, in the example shown in fig. 6, when the number of the targets is 4 or more, one lithium target (Li) and one silicon target (Si) may be alternately arranged in the transport direction of the substrate, and the nano-multilayer is stacked such that the formed lithium supplement coating film is a lithium silicon single-layer alloying layer; or the lithium target material may be completely disposed at one end of the substrate close to the unwinding device 121/winding device 122, and the silicon target material may be completely disposed at one end of the substrate close to the winding device 122/unwinding device 121, which is equivalent to forming a silicon layer on the surface of the lithium layer for protection.
The invention further provides a negative electrode plate which is prepared by adopting the lithium supplementing method of the silicon-containing negative electrode material.
The embodiment of the invention also provides a battery, which contains the negative plate, so that the energy density of the battery is improved, the expansion coefficient of the battery is reduced, and the cycle performance of the battery is improved.
The following are specific examples.
Example 1
Coating the silicon monoxide negative electrode material on a copper current collector to prepare a substrate with the length of 500m, the width of 90mm and the thickness of 100 mu m (the total thickness of the negative electrode material); the substrate is installed in the linear lithium supplement apparatus as shown in fig. 2, specifically, on the unwinding device 121 and the winding device 122.
Specifically, in this example, the total number of the target mounting mechanisms is 20, and the target mounting mechanisms are divided into two target mounting mechanism groups, each of which is 10. Each target mounting mechanism is respectively provided with a target, every two adjacent target mounting mechanisms in each group form a pair, and two targets on each target mounting mechanism pair are connected with a medium-frequency pulse power supply.
Filling inert gas and vacuumizing, and vacuumizing the lithium supplementing cavity 11 by using a first vacuum pump 161 and a second vacuum pump 162 until the vacuum degree reaches 5.0X10-4After Pa, argon is filled into the lithium supplementing chamber 11 through the air inlet device 18 to be used as protective gas, and the vacuum degree in the lithium supplementing chamber 11 is measured through the vacuum gauge 17 until the vacuum degree reaches 1.0 × 10-1Pa, the preheating temperature is 130 ℃, the conveying speed of the substrate is 6m/h, and the sputtering power is 6 kW. The atmosphere temperature in the lithium replenishing chamber 11 is set at 80 ℃, the coiling speed (i.e. the conveying speed of the substrate) is set at 5m/h, vacuum sputtering is started until all the cathode materials on the unreeling device 121 are received on the unreeling device 122, and sputtering is stopped. Closing the target material, closing the vacuum pump, introducing argon gas through the gas inlet device 18 after the vacuum count value is equivalent and stable until the vacuum gauge shows normal pressure, opening the door of the lithium supplement chamber 11, and taking out the negative of the pre-lithium supplement in the winding device 122And (5) rolling the material.
Example 2
Example 2 the lithium replenishment method of example 1 was substantially the same except that the preheating temperature was 90 ℃.
Example 3
Example 3 the lithium replenishing method was substantially the same as that of example 1 except that the substrate was transported at a speed of 6m/h and the sputtering power was 3 kW.
Example 4
The embodiment 4 is basically the same as the lithium supplementing method of the embodiment 1, except that 10 lithium targets and 10 silicon targets are provided in total, and in the two target assembling mechanism sets, one lithium target and one silicon target are alternately arranged in sequence; the substrate was transported at a speed of 10m/h and the sputtering power was 10 kW.
Comparative example 1
Comparative example 1 is substantially the same as the method of supplementing lithium of example 1, except that the substrate heating mechanism in the in-line type lithium supplementing apparatus is not turned on, i.e., the preheating step in example 1 is omitted.
The negative electrode sheets prepared in examples 1 to 4 and comparative example 1 were used as negative electrodes of lithium ion batteries, and the lithium ion batteries were assembled and were respectively marked as batteries a to D. The cell size was 80mm × 30mm × 3mm (length × width × height).
The cells were prepared in the same manner as in reference cells A to D using the copper current collectors of the negative electrode material of silicon oxide not subjected to lithium supplementation in example 1 as negative electrode sheets, and were labeled as cell M, and the cell size was 80mm × 30mm × 3mm (length × width × height).
The batteries a to D and the battery M were subjected to tests of cycle performance, energy density, and expansion ratio, and the test results are shown in table 1.
Specifically, the conditions for the cycle life test of the battery were as follows: charging for 150 minutes under the condition of room temperature at 25 ℃ by a constant-current constant-voltage mode 1C charging system, discharging to 2.75V by a constant-current 1C discharging system, stopping the discharging for one cycle, finishing the test when one discharging time is less than 36 minutes, and recording the cycle number. The specific steps refer to GB-T18287-2000. The expansion ratio was calculated as: the ratio of the thickness of the battery after formation to the thickness of the battery after capacity grading.
TABLE 1
Item Number of cycles Energy density mAh/g Expansion ratio
Battery A 620 183 32％
Battery B 580 170 35％
Battery C 560 160 35％
Battery D 580 180 33％
Battery M 550 170 38％
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
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 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 (16)

1. A lithium supplementing method for a silicon-containing negative electrode material is characterized by comprising the following steps:
forming a silicon-containing negative electrode material on a current collector to obtain a substrate;
preheating the substrate, and supplementing lithium to the substrate in a vacuum sputtering mode under the atmosphere of a vacuum condition; wherein the pre-heating temperature is higher than the temperature of the atmosphere and lower than the melting point of the lithium-supplement target material.
2. The method for supplementing lithium to a silicon-containing negative electrode material according to claim 1, wherein the temperature of the atmosphere is 30 ℃ to 130 ℃.
3. The method for supplementing lithium to a silicon-containing negative electrode material according to claim 1, wherein the material of the target for supplementing lithium is selected from one of lithium metal, lithium silicon alloy, lithium boron alloy, lithium sulfur alloy, lithium oxide, lithium nitride and lithium carbide.
4. The method for replenishing lithium in a silicon-containing anode material according to claim 1, wherein the number of the targets for replenishing lithium is plural, and the plurality of targets are made of at least two materials, one of the targets is made of one of lithium metal, lithium silicon alloy, lithium boron alloy, lithium sulfur alloy, lithium oxide, lithium nitride or lithium carbide, and the other target is made of one of silicon, carbon, silicon oxide, silicon carbide or silicon nitride.
5. The method for supplementing lithium to a silicon-containing anode material according to any one of claims 1 to 4, wherein in the step of vacuum sputtering, the target supplements lithium to both side surfaces of the substrate.
6. The method for supplementing lithium to a silicon-containing negative electrode material according to claim 5, wherein in the step of vacuum sputtering, the substrate in the lithium supplementing region is continuously moved in a linear direction.
7. The method for supplementing lithium to a silicon-containing anode material according to claim 6, wherein the step of supplementing lithium is performed by using a linear lithium supplementing apparatus;
the linear lithium supplementing equipment comprises a lithium supplementing cavity, and an unreeling device, a reeling device, at least two target mounting mechanism groups and a substrate heating mechanism which are arranged in the lithium supplementing cavity;
the unreeling device unreels the substrate to be compensated with lithium;
the winding device winds the substrate after lithium supplement;
the at least two target mounting mechanism groups are arranged between the unwinding device and the winding device, wherein the at least two target mounting mechanism groups are respectively arranged corresponding to two side surfaces of the substrate between the unwinding device and the winding device; the number of the target mounting mechanisms in each group is multiple, one target is mounted on each target, and the target mounting mechanisms in the same group are sequentially distributed in a straight line in the direction from the unwinding device to the winding device; and
the substrate heating mechanism comprises a heating installation mechanism and heating sheets arranged on the heating installation mechanism, wherein the heating installation mechanism is arranged between every two adjacent target installation mechanisms in each group, and the heating sheets preheat substrates between the unwinding device and the winding device.
8. The method for supplementing lithium to a silicon-containing anode material according to claim 7, wherein the number of the heating means is plural, and the heating means is provided between every two adjacent target mounting means in each group.
9. The method for supplementing lithium to a silicon-containing anode material according to claim 7, wherein the linear lithium supplementing apparatus further comprises a blocking mechanism and a plurality of intermediate frequency pulse power supplies;
every two adjacent target mounting mechanisms in each group form a pair, and two targets on each target mounting mechanism pair are connected with one intermediate-frequency pulse power supply;
the blocking mechanism is arranged in the lithium supplement chamber and is arranged between two adjacent pairs of target mounting mechanisms in the same group.
10. The method for supplementing lithium to a silicon-containing anode material according to claim 9, wherein the number of the target mounting mechanisms in each group is three or more; the number of the blocking mechanisms is multiple, and the blocking mechanisms are arranged between any two adjacent pairs of the target mounting mechanisms in each group.
11. The method according to claim 10, wherein the blocking mechanism is a spacer, and two side surfaces of the spacer are respectively disposed opposite to two targets on two adjacent target mounting mechanisms.
12. The method for supplementing lithium to a silicon-containing anode material according to claim 7, wherein the linear lithium supplementing apparatus further comprises a chamber heating device for heating the lithium supplementing chamber to control the temperature of the atmosphere.
13. The method according to claim 12, wherein the target material of each target mounting mechanism is metallic lithium; or two targets are arranged on each target mounting mechanism, one target is made of metal lithium, the other target is made of silicon, and the two targets are alternately arranged at intervals in the transmission direction of the substrate;
the preheating temperature is 40-170 ℃, the transmission speed of the substrate is 1 cm/h-100 m/h, and the vacuum degree of sputtering is 6 × 10-4Pa to 1.0 × 10-1Pa, and the sputtering power is 100W to 50 kW.
14. The method for supplementing lithium to the silicon-containing anode material according to any one of claims 1 to 4, wherein the silicon-containing anode material is selected from one of silicon, silicon carbon, silicon monoxide, silicon oxide, carbon-doped silicon dioxide, silicon oxycarbide, or a combination thereof.
15. A negative electrode plate, characterized in that it is produced by the lithium-supplementing method of the silicon-containing negative electrode material according to any one of claims 1 to 14.
16. A battery comprising the negative electrode sheet according to claim 15.
CN202010238490.4A 2020-03-30 2020-03-30 Lithium supplementing method for silicon-containing negative electrode material, negative electrode plate and battery Pending CN111525095A (en)

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Application publication date: 20200811