CN114709362A - Laser preparation method and manufacturing equipment for lithium ion battery cathode material sandwich structure - Google Patents

Laser preparation method and manufacturing equipment for lithium ion battery cathode material sandwich structure Download PDF

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Publication number
CN114709362A
CN114709362A CN202111553608.3A CN202111553608A CN114709362A CN 114709362 A CN114709362 A CN 114709362A CN 202111553608 A CN202111553608 A CN 202111553608A CN 114709362 A CN114709362 A CN 114709362A
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powder
laser
lithium ion
ion battery
sandwich structure
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李波
罗准
姚建华
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a laser preparation method of a lithium ion battery cathode material sandwich structure, which comprises the following steps: preprocessing a substrate; placing the substrate in a protective gas atmosphere, and performing powder paving and laser sintering for multiple times to obtain a sandwich structure cathode; drying, cutting and assembling the sandwich structure cathode into a lithium ion battery, and detecting the electrochemical performance of the lithium ion battery; the invention also includes a preparation apparatus comprising: the powder distributing and spreading device comprises a shell, a powder spreading part, a position adjusting mechanism and a lifting mechanism; the laser sintering device comprises a laser and a pump source device; the protective gas device comprises a gas supply part and a gas pipe; and the control device is arranged on the shell and comprises a human-computer interaction interface and a controller. The beneficial effects of the invention are: the sandwich structure cathode is prepared by compounding different materials, and the prepared sandwich structure cathode material has long cycle life and excellent electrochemical performance by combining the excellent performances of different materials.

Description

Laser preparation method and manufacturing equipment for lithium ion battery cathode material sandwich structure
Technical Field
The invention relates to the field of lithium ion battery electrode production, in particular to a laser preparation method and manufacturing equipment for a lithium ion battery cathode material sandwich structure.
Background
Batteries have been used as electrical energy storage devices for over 200 years, ranging from initially non-rechargeable batteries (e.g., zinc manganese dry cells) to rechargeable batteries (e.g., lead-acid batteries, nickel metal hydride batteries, nickel cadmium batteries) to more recently lithium ion batteries. Lithium ion battery technology was studied from the 60's of the world and was commercialized to the market by sony corporation of japan in 1992. With the increasing demand for mobile electronic devices and lithium ion batteries, problems have arisen in the manufacture of lithium ion battery cathodes with high efficiency and low cost. For example, due to the low theoretical capacity and complicated fabrication process of commercial graphite negative electrodes, which have increasingly limited capabilities, the demand for high operating voltage, long cycle life, low self-discharge, light weight Lithium Ion Batteries (LIBs) has been steadily increasing. Therefore, it is necessary and a great challenge to develop a method for efficiently preparing a negative electrode of a lithium ion battery and to develop an advanced negative electrode material. In order to meet the demand for high-performance lithium ion batteries, a great deal of research has been conducted to develop lithium ion batteries having higher energy density and power density.
The negative electrode material is a carrier of lithium ions and electrons in the charging process of the lithium battery and plays a role in storing and releasing energy; in the cost of the battery, the negative electrode material accounts for 5% -15%, which is one of the important raw materials of the lithium ion battery, the current commercialized negative electrode material of the lithium battery mainly comprises modified natural graphite and artificial graphite, although the preparation technology is quite mature, the theoretical specific capacity of the negative electrode material is only 372mAh/g, and the demand of the market on the high-capacity lithium ion battery is difficult to meet, so the current silicon-based negative electrode with higher gram capacity is developed. Silicon has ultrahigh theoretical lithium intercalation capacity which is about ten times of that of carbon materials, and has the advantages of charge-discharge platform similar to graphite, low price, rich sources and the like. But in addition to poor electronic and ionic conductivity, silicon can undergo severe volume changes (> 400%) during the process of lithium intercalation, which in turn leads to material pulverization, loss of electrical contact with the current collector and the conductive agent, and rapid capacity fade. In addition, the unstable solid electrolyte interface film (SEI film) on the silicon surface also severely limits its cycle life. In the process of lithium intercalation and deintercalation, along with the expansion and contraction of silicon, the SEI film on the silicon surface is continuously deformed and cracked, and a new SEI film is formed on the exposed silicon surface, so that the SEI film is gradually accumulated and thickened, the diffusion of lithium ions to silicon particles is greatly hindered, and the lithium intercalation capacity of active substances is reduced. In addition, the selection of the nano-scale silicon particles can inhibit material pulverization and reduce capacity attenuation, but the nano-scale particles are easy to agglomerate and have no obvious effect of inhibiting the thickening of an SEI film, so that the electrochemical performance of the nano-scale silicon particles is still to be improved.
Disclosure of Invention
In order to overcome the defects of poor volume expansion, poor conductivity and the like of silicon serving as a lithium ion battery cathode material, the invention provides a laser preparation method and manufacturing equipment of a lithium ion battery cathode material sandwich structure.
In order to achieve the purpose, the invention adopts the technical scheme that:
the laser preparation method of the lithium ion battery cathode material sandwich structure is characterized by comprising the following steps of:
1) pretreating the substrate to remove impurities on the surface of the lithium ion battery cathode material;
2) placing the substrate in a protective gas atmosphere, and then performing powder paving and laser sintering on the surface of the substrate for multiple times to obtain a sandwich structure cathode; the powder paved on the surface of the substrate is negative electrode material powder;
3) drying the sandwich structure cathode;
4) cutting the cathode of the sandwich structure into electrode plates with the same specification, selecting the electrode plates with uniform quality to be directly used as the cathode of the lithium ion battery, and assembling the cathode, the electrolyte, the diaphragm and the elastic sheet into the lithium ion battery in sequence;
5) and immersing the prepared lithium ion battery into electrolyte, and detecting the electrochemical performance of the lithium ion battery after the lithium ion battery is fully soaked.
Preferably, the negative electrode material powder is one or a combination of two or more of a carbon-based material, a silicon-based material, a tin-based material, and a cobalt-based material. More preferably, the carbon-based material is graphite; the silicon-based material is silicon oxide. For example, graphite has excellent conductivity and a layered structure, can improve the conductivity and the absorption volume expansion of silicon, is compounded with silicon to prepare a graphite and silicon sandwich structure, is used as a lithium ion battery cathode material, has excellent charge-discharge long cycle life and excellent electrochemical performance, and has the advantages of high efficiency and high quality.
Preferably, the protective gas is argon, and the gas flow is 15L/min.
Preferably, the laser wavelength of the substrate during laser sintering is 532nm, the pulse frequency is 1 kHz-30 kHz, the pulse width is 1-100 ns, and the single pulse energy is 0.1-10 multiplied by 10-4J, laser scanning speed of 10-350 mms-1And the laser is perpendicular to the substrate.
Preferably, the powder spreading mode of the substrate is repeated in parallel, and the powder spreading speed is 0.5-2 m2Min; the number of powder laying layers is 1-5, the thickness of each powder layer is 20-100 mu m, and the thickness of the whole sandwich structure cathode is 50-500 mu m.
The manufacturing equipment constructed by the laser preparation method of the lithium ion battery cathode material sandwich structure is characterized by comprising the following steps of:
the powder distributing and spreading device comprises a shell, a powder spreading part, a position adjusting mechanism and a lifting mechanism, wherein the inner cavity of the shell is divided into a working cavity and a laser generating cavity through a transverse partition plate, and an operation opening is formed in the transverse partition plate; the powder spreading part is arranged in the working cavity of the shell, a plurality of independent powder spreading cavities are arranged in the powder spreading part, and each powder spreading cavity is provided with at least one powder spreading outlet capable of controlling the powder discharging speed; the position adjusting mechanism is arranged in the working cavity, and an adjusting end of the position adjusting mechanism is connected with the powder spreading part and used for driving the powder spreading part to perform reciprocating powder spreading movement in the shell; the lifting mechanism is arranged in the laser generating cavity, and a lifting platform capable of passing through an operation port is arranged at the top of the lifting mechanism;
the laser sintering device comprises a laser and a pump source, the laser is used for powder sintering and is arranged at the inner top of the shell, and a light outlet of the laser is aligned with the lifting platform assembly; the pump source device mainly generates laser and is arranged in the laser generation cavity, and a light outlet of the pump source device is connected with a light inlet of the laser through an optical fiber for transmitting the laser;
the protective gas device comprises a gas supply part and a gas pipe, wherein the gas supply part is arranged in the laser generating cavity and is communicated with the working cavity through the gas pipe;
and the control device is arranged on the shell and comprises a human-computer interaction interface and a controller, the controller is arranged in the human-computer interaction interface, a signal transmission port of the controller is electrically connected with the signal transmission port of the human-computer interaction interface, and a signal output port of the controller is electrically connected with the laser, the pump source device, the position adjusting mechanism and the control end of the lifting mechanism respectively.
Further, the shell comprises an upper shell and a lower shell, a bottom plate of the upper shell is a diaphragm plate for separating the upper shell from the lower shell, the front end of the upper shell is pivoted with a door body assembly, and an operation opening is formed in the bottom plate of the upper shell; the lower shell is arranged at the bottom of the upper shell, a bottom supporting platform and a supporting column are arranged in the lower shell, the bottom supporting platform is connected below the bottom plate of the upper shell through the supporting column, and a space for containing a pump source device is reserved between the bottom supporting platform and the bottom plate of the lower shell.
Further, the powder spreading part comprises a powder dividing box, a powder spreading box and a powder flow control device, a plurality of independent powder dividing cavities are arranged in the powder dividing box, and a powder dividing outlet is formed in the bottom of each powder dividing cavity; the powder spreading box is arranged right below the powder dividing box, the powder spreading box is provided with a plurality of independent powder spreading cavities which correspond to the powder dividing cavities one by one, a powder spreading outlet is arranged at the bottom of the powder spreading cavity, and the top of the powder spreading cavity is provided with an opening and used for receiving powder falling from the powder dividing outlet; and a powder flow control device is arranged at the powder distribution outlet and/or the powder laying outlet and used for controlling the powder outlet speed.
Furthermore, be equipped with the powder chamber of spreading of a plurality of funnel types side by side in the powder box, correspond the branch powder chamber of dividing the powder box respectively, just the powder that divides the powder box to hold is just fit for once spreading the powder.
Further, the powder flow control device comprises a rotating motor and a pair of baffle plates, and the two baffle plates are respectively and rotatably arranged at the powder distributing outlet and/or the powder spreading outlet through rotating shafts; the output end of the rotating motor is connected with the end part of the rotating shaft and used for driving the two blocking pieces to synchronously rotate so as to jointly open or close the powder distributing outlet and/or the powder spreading outlet, and therefore the flow of powder is controlled.
Furthermore, two baffle sheets can be spliced into a V-shaped structure.
Further, the laser is a nanosecond pulse laser.
Further, the position adjusting mechanism comprises a driving motor and a lead screw, the lead screw is rotatably and horizontally arranged in the working cavity of the shell, and the end part of the lead screw is connected with the power output end of the driving motor; the lead screw is arranged in the internal thread hole of the powder paving box in a penetrating mode, and the external thread of the lead screw is meshed with the internal thread of the internal thread hole and used for driving the powder paving box to move axially along the lead screw.
Furthermore, the lifting mechanism mainly controls the ascending and descending of the substrate, has higher precision requirement, calculates the moving distance in micron order, and comprises a supporting table, a hydraulic cylinder and a lifting table, wherein the supporting table is arranged at the top of the bottom supporting table; the hydraulic cylinder is vertically arranged on the support table and keeps the lifting end of the hydraulic cylinder vertically and upwardly telescopic, so that the up-and-down movement of the substrate is realized; the lifting platform is horizontally arranged at the lifting end of the hydraulic cylinder, the outer contour of the lifting platform is smaller than the operation opening, and the lifting platform can conveniently pass through the operation opening.
Further, the gas supply part is a gas cylinder filled with protective gas, such as argon gas and other protective gas; the gas cylinder is communicated with the gas working cavity through a gas pipe; the gas working cavity is mainly used for preparing materials and preventing the materials from being influenced by air impurities.
The use method of the manufacturing equipment comprises the following steps:
1) pretreating the substrate to remove impurities on the surface of the lithium ion battery cathode material;
2) the equipment self-checks to judge whether the experimental conditions are met; the equipment self-checking mainly comprises the steps of checking whether the protective gas is sufficient or not, whether the light emitting of a laser is normal or not, whether a water cooling machine works normally or not and the like;
3) injecting different types of battery negative electrode material powder into corresponding powder dividing cavities of the powder dividing boxes, and setting the powder flow rate; the powder type is mainly common anode material powder, such as carbon-based material (graphite, etc.), silicon-based material (silicon oxide, etc.), tin-based material, cobalt-based material, etc.;
4) opening the protective gas and setting the gas flow;
5) setting parameters such as laser parameters, powder laying rate, the number of powder laying layers and the preparation thickness of the sandwich structure cathode on a human-computer interaction interface;
6) the controller receives the quality of the human-computer interaction interface, controls the powder laying part to act to carry out first-layer powder laying and laser sintering on the substrate, and then the substrate descends according to a preset distance;
7) the powder spreading part continues to operate, the substrate is subjected to the spreading and the laser sintering of the other powder of the second layer, and the substrate descends according to the preset distance;
8) repeatedly carrying out powder laying, laser sintering and substrate descending for a set distance on the substrate until the preparation of the sandwich structure cathode material is completed;
9) and performing processes of punching, screening, assembling, testing and the like on the prepared sandwich structure cathode material.
Argon is selected as the protective gas in the step 4), and the gas flow is 15L/min;
in the step 5), the selected laser is a nanosecond pulse laser, the laser wavelength is 532nm, the pulse frequency is 1 kHz-30 kHz, the pulse width is 1-100 ns, and the single pulse energy is 0.1-10 multiplied by 10-4J, laser scanning speed of 10-350 mms-1The laser is vertical to the substrate; the powder spreading mode is parallel repetition, and the powder spreading speed is 0.5-2 m2Min; the number of powder laying layers can be set according to experimental requirements, the thickness of each layer is 20-100 mu m, and the number of layers is generally 1-5; the thickness of the sandwich structure cathode is generally 50 to 500 μm.
And 6), uniformly paving a layer of powder layer with a set thickness on the substrate by the powder under the action of a powder paving device, and sintering the powder on the substrate by a laser device without difference.
In step 6), after the first layer is sintered, the substrate sinks for a certain distance under the control of a hydraulic device, and specifically, the dropping distance is the thickness of the set powder sintered monolayer.
In step 7), the powder for the second sintering may be different from or the same as the powder material for the first layer.
In step 7), when different powders are sintered, the power output by the laser is adjusted accordingly in the setting due to the different properties of the powders.
In the step 8), powder laying and laser sintering are generally repeated for 2-5 times, and the number of layers of the interlayer structure is generally 2-5.
In the step 9), the prepared sandwich structure cathode is cut into electrode plates with the same specification by a slicing machine, then the electrode plates are weighed, the electrode plates with uniform quality are selected as experimental objects, the electrode plates are sent into a glove box to be assembled, the prepared battery shell, electrolyte, a diaphragm, an elastic sheet and the like are assembled in sequence, finally the battery shell, the electrolyte, the diaphragm, the elastic sheet and the like are placed on a packaging machine to be compacted, the prepared battery is placed for one night to be fully soaked by the electrolyte, and then an electrochemical tester is used for testing the electrochemical performance of the prepared battery, so that a test result is obtained.
The principle of the invention is as follows: the single-layer cathode material is prepared by using a laser sintering technology, powder is spread on the previous layer of material by a powder spreading device, then laser sintering is carried out, and the powder spreading and sintering process is repeated to prepare the sandwich structure cathode material.
Compared with the prior art, the invention has the following beneficial effects:
(1) the composite material can be processed by a laser technology by combining the excellent performances of various materials, and compared with the traditional technology, the composite material has the advantages of simple process and obvious effect;
(2) corresponding parameters can be set according to the requirements of an experimenter to manufacture the sandwich structure cathode which meets the design requirements of the experimenter;
(3) the time consumption is short, the condition requirement is low, and a large amount of sandwich structure cathode materials can be prepared in a short time;
(4) the batch custom-made production of the lithium ion battery sandwich structure cathode material can be met, and the efficiency is obviously improved.
Drawings
FIG. 1 is a schematic diagram of the operation of the process of the present invention;
FIG. 2a is a schematic structural view of the manufacturing apparatus according to the present invention;
FIG. 2b is a schematic structural view of the manufacturing apparatus of the present invention;
FIG. 2c is a schematic perspective view of the manufacturing apparatus of the present invention;
FIG. 2d is a schematic structural view of a housing of the manufacturing apparatus of the present invention;
FIG. 2e is a schematic view of the internal structure of the housing of the manufacturing apparatus of the present invention;
FIG. 3a is a schematic view of the internal structure of the manufacturing apparatus according to the present invention;
FIG. 3b is a second schematic view of the internal structure of the manufacturing apparatus according to the present invention;
FIG. 4a is a schematic structural view of a powder laying box of the preparation device of the present invention;
FIG. 4b is a front view of a powder laying box of the manufacturing apparatus of the present invention;
FIG. 4c is a front view of the powder laying box of the manufacturing apparatus of the present invention;
FIG. 4d is a bottom view of the powder laying box of the manufacturing apparatus of the present invention;
FIG. 4e is a cross-sectional view A-A of FIG. 4 b;
FIG. 5a is a structural view of a powder flow control apparatus of the manufacturing apparatus of the present invention;
FIG. 5b is a front view of a powder flow control apparatus of the manufacturing apparatus of the present invention;
FIG. 5c is a front view of a powder flow control apparatus of the manufacturing apparatus of the present invention;
FIG. 5d is a bottom view of the powder flow control device of the manufacturing apparatus of the present invention;
FIG. 5e is a cross-sectional view B-B of FIG. 5 c;
6a, 6b and 6c are structural diagrams of the powder box and the powder laying box of the invention at different angles;
FIG. 6d is a front view of the compact and powder laying box of the present invention;
FIG. 6e is a top view of the compact and compact case of the present invention;
FIG. 6f is a bottom view of the compact and powder spreading box of the present invention;
FIG. 6g is a side view of the compact and compact case of the present invention;
FIG. 6h is a cross-sectional view C-C of FIG. 6 d;
FIG. 7 shows the cycle life times and coulombic efficiency of an electrode prepared by the process of the present invention at 1A/g in an electrochemical tester;
FIG. 8 is a graph of the rate performance of an electrode prepared according to the process of the present invention in an electrochemical tester.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
With reference to the accompanying drawings:
embodiment 1a laser preparation process method of a lithium ion battery negative electrode material sandwich structure, which is described in the invention, comprises the following steps:
1) cleaning a metal foil serving as a substrate for one hour by using alcohol and deionized water, and removing impurities on the surface of the metal foil; the metal foil is copper foil, the purity reaches 99.99%, and the thickness is about 50 μm;
2) opening equipment, whether check out test set can normally work, pack into the branch powder box respectively with silicon oxide powder and graphite powder in, paste the copper foil after will handling on the elevating platform, close the working chamber door, be full of the argon gas with the working chamber, set up all kinds of parameters at operating panel, the laser parameter is: 532nm wavelength, 30000Hz pulse frequency, 10ns pulse width and 1.5X 10 single pulse energy-4J, scanning the surface at a speed of 100mm/s by using laser, enabling the laser to be perpendicular to the copper foil, and performing powder paving and sintering for multiple times to obtain the cathode with the sandwich structure;
3) putting the sandwich structure into a vacuum drying oven to be dried for 12 hours at 120 ℃;
4) cutting the dried negative electrode material into a circular sheet with the diameter of 14mm by using a slicer, directly using the circular sheet as a negative electrode of a lithium ion battery without adopting a binder and a conductive agent, using a celgard 2050 diaphragm and a dissolved EC/DMC/DEC, 1: 2 vol% of 1M LiPF6As an electrolyte, a button cell is assembled in a glove box filled with argon, and an electrochemical performance test is carried out.
Embodiment 2a manufacturing apparatus constructed by the laser preparation method of a lithium ion battery negative electrode material sandwich structure according to the present invention includes:
the powder distributing and spreading device 1 comprises a shell 11, a powder spreading part 12, a position adjusting mechanism 13 and a lifting mechanism 14, wherein the inner cavity of the shell 11 is divided into a working cavity and a laser generating cavity through a transverse partition plate, and an operation opening is formed in the transverse partition plate; the powder spreading part 12 is arranged in the working cavity of the shell, a plurality of independent powder spreading cavities are arranged in the powder spreading part, and each powder spreading cavity is provided with at least one powder spreading outlet capable of controlling the powder discharging speed; the position adjusting mechanism 13 is arranged in the working cavity, and an adjusting end of the position adjusting mechanism is connected with the powder spreading part and used for driving the powder spreading part to perform reciprocating powder spreading movement in the shell; the lifting mechanism 14 is arranged in the laser generating cavity, and a lifting platform capable of passing through an operation port is arranged at the top of the lifting mechanism 14;
the laser sintering device 2 comprises a laser 21 and a pump source 22, wherein the laser 21 is used for powder sintering and is arranged at the inner top of the shell, and a light outlet of the laser 21 is aligned with the lifting platform assembly; the pump source 22 mainly generates laser light and is arranged in the laser generation cavity, and a light outlet of the pump source 22 is connected with a light inlet of the laser 21 through an optical fiber 23 for transmitting the laser light;
the protective gas device 3 comprises a gas supply part 31 and a gas pipe 32, the gas supply part is arranged in the laser generating cavity, and the gas supply part is communicated with the working cavity through the gas pipe;
and the control device 4 is arranged on the shell and comprises a human-computer interaction interface 41 and a controller, the controller is arranged in the human-computer interaction interface, a signal transmission port of the controller is electrically connected with the signal transmission port of the human-computer interaction interface, and a signal output port of the controller is electrically connected with the laser, the pump source device, the position adjusting mechanism and the control end of the lifting mechanism respectively.
Further, the housing 11 includes an upper housing 111 and a lower housing 112, a bottom plate of the upper housing 111 is a diaphragm plate for separating the upper housing from the lower housing, a door body assembly 113 is pivotally connected to a front end of the upper housing 111, and an operation opening is formed in the bottom plate of the upper housing 111; the lower casing 112 is arranged at the bottom of the upper casing, a bottom support platform 114 and a support column 115 are arranged in the lower casing, the bottom support platform 114 is connected below the bottom plate of the upper casing 111 through the support column 115, and a space for accommodating a pumping source is reserved between the bottom support platform 114 and the bottom plate of the lower casing 112.
The powder spreading part 12 comprises a powder dividing box 121, a powder spreading box 122 and a powder flow control device 123, wherein a plurality of independent powder dividing cavities are formed in the powder dividing box 121, and a powder dividing outlet is formed in the bottom of each powder dividing cavity; the powder spreading box 122 is arranged right below the powder dividing box, the powder spreading box 122 is provided with a plurality of independent powder spreading cavities which correspond to the powder dividing cavities one by one, a powder spreading outlet is arranged at the bottom of each powder spreading cavity, and the top of each powder spreading cavity is provided with an opening and used for receiving powder falling from the powder dividing outlet; and a powder flow control device 123 is arranged at the powder distribution outlet and/or the powder laying outlet and used for controlling the powder outlet speed.
Spread the powder chamber that is equipped with a plurality of funnel types side by side in the powder box 122, correspond the branch powder chamber of dividing the powder box respectively, just divide the powder that powder box held to be fit for once spreading the powder.
The powder flow control device 123 comprises a rotating motor 1231 and a pair of blocking pieces 1232, and the two blocking pieces are respectively and rotatably installed at the powder distributing outlet and/or the powder spreading outlet through rotating shafts; the output end of the rotating motor is connected with the end part of the rotating shaft and used for driving the two blocking pieces to synchronously rotate so as to jointly open or close the powder distributing outlet and/or the powder spreading outlet, and therefore the flow of powder is controlled.
The two baffle sheets can be spliced into a V-shaped structure.
The laser is a nanosecond pulse laser.
The position adjusting mechanism 13 comprises a driving motor 131 and two lead screws 132, the two lead screws 132 are parallel to each other and are rotatably and horizontally arranged in two opposite inner side walls of the working cavity of the shell, and the end part of each lead screw 132 is connected with the power output end of the driving motor 131; the screw 132 is inserted into the internal thread hole of the powder laying box 122, and the external thread of the screw 132 is engaged with the internal thread of the internal thread hole to drive the powder laying box to move along the axial direction of the screw.
The lifting mechanism 14 is mainly used for controlling the ascending and descending of the substrate, has high precision requirement, calculates the moving distance by micron level, and comprises a support table 141, a hydraulic cylinder 142 and a lifting table 143, wherein the support table 141 is arranged at the top of the bottom support table 114; the hydraulic cylinder 142 is vertically arranged on the support table 141, and the lifting end of the hydraulic cylinder 142 is kept to vertically extend upwards, so that the substrate can move up and down; the lifting platform 143 is horizontally arranged at the lifting end of the hydraulic cylinder, and the outer contour of the lifting platform is slightly smaller than the operation opening, so that the lifting platform can conveniently pass through the operation opening.
The gas supply part 31 is a gas cylinder filled with protective gas, such as argon; the gas cylinder is communicated with the gas working cavity through a gas pipe 32; the gas working cavity is mainly used for preparing materials and preventing the materials from being influenced by air impurities.
Referring to fig. 8, it can be seen that: electrochemical tests on the sandwich electrode resulted in excellent electrochemical performance. Under the current density of 1A/g, after 1000 times of circulation, the discharge capacity of the electrode with the sandwich structure can still be kept at 1253.8mAh/g, and the coulombic efficiency is always kept above 99%.
Referring to fig. 7, it can be seen that: electrochemical testing of the sandwich electrode resulted in excellent electrochemical performance, with the lower line indicating capacity; the upper line represents coulombic efficiency. The sandwich structure electrode shows excellent speed performance under different current densities, and the sandwich structure electrode still has higher speed performance when an overlarge current density test is carried out and then a small current density test is carried out.
The embodiments described in this specification are merely illustrative of implementations of the inventive concept and the scope of the present invention should not be considered limited to the specific forms set forth in the embodiments but includes equivalent technical means as would be recognized by those skilled in the art based on the inventive concept.

Claims (10)

1. The laser preparation method of the lithium ion battery cathode material sandwich structure is characterized by comprising the following steps of:
1) pretreating the substrate to remove impurities on the surface of the lithium ion battery cathode material;
2) placing the substrate in a protective gas atmosphere, and then performing powder paving and laser sintering on the surface of the substrate for multiple times to obtain a sandwich structure cathode; the powder paved on the surface of the substrate is negative electrode material powder;
3) drying the sandwich structure cathode;
4) cutting the cathode of the sandwich structure into electrode plates with the same specification, selecting the electrode plates with uniform quality to be directly used as the cathode of the lithium ion battery, and assembling the cathode, the electrolyte, the diaphragm and the elastic sheet into the lithium ion battery in sequence;
5) and immersing the prepared lithium ion battery into electrolyte, and detecting the electrochemical performance of the lithium ion battery after the lithium ion battery is fully soaked.
2. The laser preparation method of the sandwich structure of the lithium ion battery cathode material according to claim 1, characterized in that: the negative electrode material powder is one or a combination of two or more of a carbon-based material, a silicon-based material, a tin-based material and a cobalt-based material.
3. The laser preparation method of the sandwich structure of the lithium ion battery cathode material according to claim 1, characterized in that: the protective gas is argon, and the gas flow is 15L/min.
4. The laser preparation method of the sandwich structure of the lithium ion battery cathode material according to claim 1, characterized in that: the laser wavelength of the substrate during laser sintering is 532nm, the pulse frequency is 1 kHz-30 kHz, the pulse width is 1-100 ns, and the single pulse energy is 0.1-10 multiplied by 10-4J, laser scanning speed of 10-350 mms-1And the laser is perpendicular to the substrate.
5. The laser preparation method of the sandwich structure of the lithium ion battery cathode material according to claim 1, characterized in that: the powder spreading mode of the substrate is repeated in parallel, and the powder spreading speed is 0.5-2 m2Min; the number of powder laying layers is 1-5, the thickness of each powder layer is 20-100 mu m, and the thickness of the whole sandwich structure cathode is 50-500 mu m.
6. The manufacturing equipment constructed by the laser preparation method of the lithium ion battery cathode material sandwich structure according to any one of claims 1 to 5 is characterized by comprising the following steps:
the powder distributing and spreading device comprises a shell, a powder spreading part, a position adjusting mechanism and a lifting mechanism, wherein the inner cavity of the shell is divided into a working cavity and a laser generating cavity through a transverse partition plate, and an operation opening is formed in the transverse partition plate; the powder spreading part is arranged in the working cavity of the shell, a plurality of independent powder spreading cavities are arranged in the powder spreading part, and each powder spreading cavity is provided with at least one powder spreading outlet capable of controlling the powder discharging speed; the position adjusting mechanism is arranged in the working cavity, and an adjusting end of the position adjusting mechanism is connected with the powder spreading part and used for driving the powder spreading part to perform reciprocating powder spreading movement in the shell; the lifting mechanism is arranged in the laser generating cavity, and a lifting platform capable of passing through an operation port is arranged at the top of the lifting mechanism;
the laser sintering device comprises a laser and a pump source, the laser is arranged at the inner top of the shell, and a light outlet of the laser is aligned with the lifting platform assembly; the pump source device is arranged in the laser generation cavity, and a light outlet of the pump source device is connected with a light inlet of the laser device through an optical fiber;
the protective gas device comprises a gas supply part and a gas pipe, the gas supply part is arranged in the laser generation cavity, and the gas supply part is communicated with the working cavity through the gas pipe;
and the control device is arranged on the shell and comprises a human-computer interaction interface and a controller, the controller is arranged in the human-computer interaction interface, a signal transmission port of the controller is electrically connected with the signal transmission port of the human-computer interaction interface, and a signal output port of the controller is electrically connected with the laser, the pump source device, the position adjusting mechanism and the control end of the lifting mechanism respectively.
7. The manufacturing apparatus of claim 6, wherein: the shell comprises an upper shell and a lower shell, a bottom plate of the upper shell is a diaphragm plate for separating the upper shell from the lower shell, the front end of the upper shell is pivoted with a door body assembly, and an operation opening is formed in the bottom plate of the upper shell; the lower shell is arranged at the bottom of the upper shell, a bottom supporting platform and a supporting column are arranged in the lower shell, the bottom supporting platform is connected below the bottom plate of the upper shell through the supporting column, and a space for containing a pump source device is reserved between the bottom supporting platform and the bottom plate of the lower shell.
8. The manufacturing apparatus according to claim 7, wherein: the powder spreading part comprises a powder dividing box, a powder spreading box and a powder flow control device, wherein a plurality of independent powder dividing cavities are formed in the powder dividing box, and a powder dividing outlet is formed in the bottom of each powder dividing cavity; the powder spreading box is arranged right below the powder dividing box, the powder spreading box is provided with a plurality of independent powder spreading cavities which correspond to the powder dividing cavities one by one, a powder spreading outlet is arranged at the bottom of the powder spreading cavity, and the top of the powder spreading cavity is provided with an opening and used for receiving powder falling from the powder dividing outlet; and a powder flow control device is arranged at the powder distribution outlet and/or the powder laying outlet and used for controlling the powder outlet speed.
9. The manufacturing apparatus according to claim 8, wherein: the position adjusting mechanism comprises a driving motor and a lead screw, the lead screw is rotatably and horizontally arranged in the working cavity of the shell, and the end part of the lead screw is connected with the power output end of the driving motor; the lead screw is arranged in the internal thread hole of the powder paving box in a penetrating mode, and the external thread of the lead screw is meshed with the internal thread of the internal thread hole and used for driving the powder paving box to move axially along the lead screw.
10. The manufacturing apparatus according to claim 9, wherein: the lifting mechanism comprises a supporting platform, a hydraulic cylinder and a lifting platform, and the supporting platform is arranged at the top of the bottom supporting platform; the hydraulic cylinder is vertically arranged on the support table and keeps the lifting end of the hydraulic cylinder vertically extending upwards; the lifting platform is horizontally arranged at the lifting end of the hydraulic cylinder, and the outer contour of the lifting platform is smaller than the operation opening.
CN202111553608.3A 2021-12-17 2021-12-17 Laser preparation method and manufacturing equipment for lithium ion battery cathode material sandwich structure Pending CN114709362A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007052934A (en) * 2005-08-15 2007-03-01 Sony Corp Method of manufacturing electrode for battery and manufacturing device
JP2020136211A (en) * 2019-02-25 2020-08-31 国立大学法人長岡技術科学大学 Manufacturing method of secondary battery
CN113078291A (en) * 2021-03-26 2021-07-06 珠海冠宇电池股份有限公司 Negative plate, preparation method thereof and battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007052934A (en) * 2005-08-15 2007-03-01 Sony Corp Method of manufacturing electrode for battery and manufacturing device
JP2020136211A (en) * 2019-02-25 2020-08-31 国立大学法人長岡技術科学大学 Manufacturing method of secondary battery
CN113078291A (en) * 2021-03-26 2021-07-06 珠海冠宇电池股份有限公司 Negative plate, preparation method thereof and battery

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