CN114695833B - Lithium dendrite suppression device, system and method for negative electrode material of lithium metal battery - Google Patents
Lithium dendrite suppression device, system and method for negative electrode material of lithium metal battery Download PDFInfo
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- CN114695833B CN114695833B CN202210195443.5A CN202210195443A CN114695833B CN 114695833 B CN114695833 B CN 114695833B CN 202210195443 A CN202210195443 A CN 202210195443A CN 114695833 B CN114695833 B CN 114695833B
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 176
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 210000001787 dendrite Anatomy 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000001629 suppression Effects 0.000 title claims description 35
- 239000007773 negative electrode material Substances 0.000 title claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 44
- 238000009792 diffusion process Methods 0.000 claims abstract description 28
- 239000007789 gas Substances 0.000 claims description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 239000004744 fabric Substances 0.000 claims description 37
- 239000002994 raw material Substances 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000010405 anode material Substances 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000010410 layer Substances 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 15
- 239000010406 cathode material Substances 0.000 abstract description 10
- 230000004888 barrier function Effects 0.000 abstract description 8
- 230000005764 inhibitory process Effects 0.000 abstract description 7
- 239000011229 interlayer Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 230000006911 nucleation Effects 0.000 abstract description 5
- 238000010899 nucleation Methods 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 208000020960 lithium transport Diseases 0.000 abstract description 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 210000002381 plasma Anatomy 0.000 description 27
- 125000004429 atom Chemical group 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 230000005684 electric field Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
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- 150000002641 lithium Chemical class 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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Classifications
-
- 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
-
- 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
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a lithium dendrite inhibition device, a lithium dendrite inhibition system and a lithium dendrite inhibition method for a lithium metal battery cathode material, which can reduce nucleation and diffusion barrier of metal lithium according to the increased lithium affinity of the material, and the expanded interlayer spacing can provide diffusion channels for lithium in the material, so that the theoretical basis of inhibiting the growth of cathode lithium dendrite by accelerating lithium transport dynamics is that a carbon atom layer is activated and expanded by adopting a high-energy medium, and the increased interlayer spacing can provide a volume diffusion channel for lithium, so that electrochemical dynamics of an electrode interface can be accelerated. The surface and the inside of the lithium metal battery cathode material treated by the high-energy medium have the functions of stably dispersing metal lithium and regulating lithium diffusion, so that the generation of lithium dendrites can be inhibited, and the cycling stability of the lithium metal battery cathode is improved.
Description
Technical Field
The invention relates to the field of new energy battery material design, in particular to a lithium dendrite suppression device, a system and a method for a lithium metal battery negative electrode material.
Background
Energy storage systems using lithium metal as the negative electrode are considered as alternatives to commercial lithium ion batteries, and due to the high specific capacity of lithium metal (3860 mA h g-1), the low redox potential (-3.040V vs. standard hydrogen electrode) characteristics, the energy density of lithium metal secondary battery systems is most considerable, becoming an effective solution for next generation high energy density batteries. Although lithium metal batteries have excellent application prospects, the deposition of lithium metal on the anode is uneven, resulting in irregular lithium dendrites formed during charging to pierce through Solid Electrolyte Interface (SEI) films, causing a series of safety problems. In addition, the growth of lithium dendrites causes the specific surface area of the metal lithium to be continuously increased, and the selectivity of side reactions with the electrolyte is increased, so that the electrolyte is irreversibly consumed, dead lithium without electronic activity is formed to influence normal electrochemical behaviors, and the capacity of the battery is continuously reduced in the daily use process. These disadvantages may reduce the stability, cycle life and safety of the lithium metal secondary battery. Therefore, there is an urgent need to solve the problem of interfacial stability of metallic lithium.
Since the surface diffusion of lithium in the anode is much faster than the bulk diffusion, tuning the diffusion/deposition of lithium at the anode surface is considered to be the dominant method to promote uniform deposition of lithium. The conventional method is to add an additive to the electrolyte or to modify the surface of the negative electrode. And Qiang Zhang (adv. Funct. Mater.2017,27,1605989) adding fluoroethylene carbonate into the carbonate electrolyte to induce formation of a compact and stable SEI layer, which is beneficial to obtaining uniform Li deposition morphology. The Yi Cui team (Nano lett.2015,15,5,2910-2916) places a three-dimensional (3D) oxidized polyacrylonitrile nanofiber network on top of the current collector, and polymer fibers containing polar surface functional groups can guide the uniform deposition of lithium metal on the surface. The patent CN202011629545.0 performs multi-level functional modification on the negative electrode, and uses a lithium-philic metal layer and a preparation artificial lithium ion diffusion layer to inhibit the generation of lithium dendrites. These results indicate that modifying the surface of the negative electrode or the electrolyte can improve the performance thereof, but these methods often have problems of complicated process, uneven thickness of the modification layer, difficulty in utilizing bulk diffusion paths of materials, insufficient stability of SEI formed during the cycling process, and the like.
Disclosure of Invention
The invention aims to provide a lithium dendrite suppression device, a lithium dendrite suppression system and a lithium dendrite suppression method for a lithium metal battery anode material, wherein the lithium metal battery anode material (carbon cloth) is subjected to plasma treatment, so that element doping and structural defection can be carried out on the surface and the inside of the anode material, and the affinity between the carbon cloth and lithium is improved.
In order to solve at least one of the above problems, a first aspect of the present invention provides a lithium dendrite suppression apparatus of a negative electrode material of a lithium metal battery, comprising:
a housing into which a lithium metal battery negative electrode element can be placed; and
And the high-energy medium forming component can form a high-energy medium in the shell, so that the anode material atoms of the anode element of the lithium metal battery are in an activated expansion state, and further form a bulk diffusion channel of lithium metal so as to inhibit the lithium dendrites.
Further, the high energy medium forming assembly includes: a gas pipeline, a high-frequency alternating current power supply and a heating and cooling plate;
the gas pipeline comprises a gas inlet and two outlets, wherein one outlet is connected with a vacuum pump, the other outlet is connected with a vent valve, and the gas inlet is connected with a gas cylinder;
The high-frequency alternating current power supply is coupled with the gas inlet end of the gas pipeline and the inner wall of the high-energy medium forming assembly, wherein the inner wall of the high-energy medium forming assembly is coupled with a grounding wire;
And two ends of the plasma component are respectively provided with a heating and cooling plate, and the heating and cooling plates are coupled with a temperature control system.
Further, the lithium dendrite suppression apparatus further includes:
The support assembly and the high-energy medium forming assembly are coaxially arranged by taking the gas pipeline as an axis, wherein the lithium metal battery cathode element can be arranged on the support assembly.
Further, a plurality of through holes are arranged on a part of the pipeline of the gas pipeline, which is positioned in the plasma component.
Further, a flow controller is arranged at the inlet of the gas pipeline.
Further, the upper surface and the lower surface of the supporting component are provided with a pressure sensor.
Further, the high energy medium may be one of nitrogen, oxygen, and ammonia.
In a second aspect, the present invention provides a lithium dendrite suppression system for a negative electrode material of a lithium metal battery, comprising: lithium dendrite suppression device, raw material column and product column of lithium metal battery cathode material;
the raw material column conveys the lithium metal battery negative electrode element to the lithium dendrite suppression device so as to enable negative electrode material atoms of the lithium metal battery negative electrode element to be in an activated expansion state, and further form a lithium metal bulk diffusion channel so as to suppress the lithium dendrite;
the support assembly conveys the expanded lithium metal battery negative electrode element to the product column.
In a third aspect, the present invention provides a lithium dendrite suppression method of a negative electrode material of a lithium metal battery, including:
The negative electrode element of the lithium metal battery is put into a shell through a raw material column;
And forming a high-energy medium in the shell, so that anode material atoms of the anode element of the lithium metal battery are in an activated expansion state, and further forming a bulk diffusion channel of lithium metal so as to inhibit the lithium dendrite.
Further, the lithium dendrite suppression method further includes:
And doping a modifying medium in gaps among negative electrode material atoms of the negative electrode element of the lithium metal battery so as to improve the affinity between the negative electrode element of the lithium metal battery and lithium.
The beneficial effects of the invention are that
The invention provides a lithium dendrite inhibition device, a lithium dendrite inhibition system and a lithium dendrite inhibition method for a lithium metal battery cathode material, which can reduce nucleation and diffusion barrier of metal lithium according to the increased lithium affinity of the material, and the expanded interlayer spacing can provide diffusion channels for lithium in the material, so that the theoretical basis of inhibiting the growth of cathode lithium dendrite by accelerating lithium transport dynamics is that a carbon atom layer is activated and expanded by adopting a high-energy medium, and the increased interlayer spacing can provide a volume diffusion channel for lithium, so that electrochemical dynamics of an electrode interface can be accelerated. The surface and the inside of the lithium metal battery cathode material treated by the high-energy medium have the functions of stably dispersing metal lithium and regulating lithium diffusion, so that the generation of lithium dendrites can be inhibited, and the cycling stability of the lithium metal battery cathode is improved.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained from them without inventive effort for a person skilled in the art.
Fig. 1 is a schematic diagram of the overall structure of a lithium dendrite suppression apparatus for a negative electrode material of a lithium metal battery according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a lithium dendrite suppression system of a negative electrode material of a lithium metal battery according to an embodiment of the present invention.
Description of the drawings: 1. a housing; 2. a high energy medium forming assembly; 21. heating the cooling plate; 3. a support assembly, a4 raw material column; 5. a product column; 6, a high-frequency alternating current power supply; 7. an optical sensor; 8. a gas cylinder; 9. a flow controller; 10. a vacuum pump; 11 exhaust valve; 12. and driving the motor.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
For convenience of description, the description of "first", "second", etc. in this application is provided for descriptive purposes only and is not to be construed as indicating or implying a relative importance or the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
In order to solve the defects of the existing lithium metal battery in the method or process for inhibiting lithium dendrite, and the device easy to produce and enlarge does not appear yet.
Based on this, the present invention provides a lithium dendrite suppression device of a negative electrode material of a lithium metal battery, as shown in fig. 1, comprising:
a housing into which a lithium metal battery negative electrode element can be placed; and
And the high-energy medium forming component can form a high-energy medium in the in-vivo so as to enable negative electrode material atoms of the negative electrode element of the lithium metal battery to be in an expanded state, thereby forming a bulk diffusion channel of lithium metal so as to inhibit the lithium dendrite.
It can be understood that the negative electrode element of the lithium metal battery is carbon cloth, the high-energy medium forming component 2 is preferably a plasma reactor, carbon is arranged in the lithium dendrite suppression device, the plasma reactor is started to generate plasma, the plasma continuously impacts the carbon cloth from inside and outside, element doping and defection are carried out on the surface and the inside of the carbon cloth material, and a bulk diffusion channel of lithium metal is opened. Preferably, the wall of the shell and the high-energy medium forming assembly 2 is made of ceramic or an insulating material such as polymethyl methacrylate to resist plasma erosion, and an aluminum material with an anodized inner surface can be selected.
In some embodiments, as shown in fig. 1, the high energy medium forming assembly includes: a gas pipeline, a high-frequency alternating current power supply and a heating and cooling plate;
the gas pipeline comprises a gas inlet and two outlets, wherein one outlet is connected with a vacuum pump, the other outlet is connected with a vent valve, and the gas inlet is connected with a gas cylinder;
The high-frequency alternating current power supply is coupled with the gas inlet end of the gas pipeline and the inner wall of the high-energy medium forming assembly, wherein the inner wall of the high-energy medium forming assembly is coupled with a grounding wire;
And two ends of the plasma component are respectively provided with a heating and cooling plate, and the heating and cooling plates are coupled with a temperature control system.
It can be understood that the high-energy medium forming component 2 takes a gas pipeline as an axis, the wall of the inner wall of the high-energy medium forming component is coupled with a conducting wire which is grounded, two exhaust holes are formed below the gas pipeline, one exhaust hole is connected with the vacuum pump 10, the other exhaust hole is connected with the exhaust valve 11, and the gas inlet of the gas pipeline is connected with the gas cylinder 8; the high-frequency alternating current power supply 6 is coupled with the hollow circular tube of the gas inlet of the gas pipeline and the inner wall of the high-energy medium forming assembly 2, and is used for applying a high-frequency alternating current electric field to the inside of the high-energy medium forming assembly 2 to form a high-energy medium, the high-frequency alternating current power supply 6 needs to support radio frequency, and the general alternating current frequency needs to meet the radio frequency range, preferably 10-1000kHz; whereas the high frequency ac power supply power is typically between 50W and 50kW, depending on the size of the apparatus and the processing requirements. The temperature control function of the high-energy medium forming assembly 2 is realized by two heating and cooling plates 21 thermally coupled to the upper and lower cover plates of the high-energy medium forming assembly, for controlling the temperature of the cavity of the high-energy medium forming assembly 2, and is controlled by a control system. The high energy medium forming assembly 2 is preferably a plasma reactor, and the heating and cooling plate 21 is generally formed by combining a plurality of physical layers, namely a sandwich structure of a thermal gasket, a heater block, a thermal partition and a cooling block, and provides a heating and cooling operation for a reactor chamber, and is combined with a thermal sensor arranged in the chamber to form a temperature control system. Typically, the temperature of the plasma reactor chamber is controlled to 20-200 ℃, and higher temperatures are required to ensure stability of the material in the plasma atmosphere, without limitation.
In some embodiments, as shown in fig. 1, the lithium dendrite suppression apparatus further includes:
The support assembly and the high-energy medium forming assembly are coaxially arranged by taking the gas pipeline as an axis, wherein the lithium metal battery cathode element can be arranged on the support assembly.
It will be appreciated that the support assembly 3 is built in the high-energy medium forming assembly 2, and may be a processing drum coaxially arranged with the high-energy medium forming assembly, and adopts a columnar support for conveying the processed lithium metal battery cathode element (carbon cloth), and preferably, the support assembly 3 in the high-energy medium forming assembly 2 is made of corundum or polytetrafluoroethylene. All the support columns of the support assembly 3 are changed into porous cylinder support wall surfaces, and the material is preferably polytetrafluoroethylene.
In some other embodiments, as shown in fig. 1, a plurality of through holes are provided in a portion of the gas line located inside the plasma assembly.
It will be appreciated that under the action of the high-frequency alternating current electric field between the high-energy medium forming component 2 and the gas pipeline thereof, the gas can be ionized, so that the plasma formed by ionization can be modified by materials, in some preferred embodiments, the gas pipeline in the high-energy medium forming component 2 is made of aluminum, the hollow round tube at the gas inlet of the surface anodic oxidation treatment is made of aluminum, and the surface anodic oxidation treatment is performed, so that the ionization is more sufficient, the modification effect is better, and a plurality of through holes uniformly distributed in the position intervals of the gas pipeline in the high-energy medium forming component 2 are used for uniformly inputting the gas into the high-energy medium forming component 2. In a specific embodiment, a flow controller 9 is arranged at the inlet of the gas pipeline, and the flow rate and the gas pressure of the gas conveyed into the high-energy medium forming assembly 2 are regulated and controlled through the flow controller 9 and a vacuum pump 10. The gas used in the high-energy medium can be a purer single gas such as nitrogen, oxygen, ammonia and the like, or can be a corresponding gas diluted by rare gas, and the invention is not limited.
In some other embodiments, the support assembly is provided with a pressure sensor on the upper and lower surfaces.
It can be understood that an elastic device is arranged between the upper cover and the lower cover of the supporting component 3 and the gas pipeline, so that the initial winding of the carbon cloth is facilitated, the stress condition of the carbon cloth in the process of rotating and conveying a plurality of cylinders is controlled, the carbon cloth is prevented from being damaged due to overlarge stress, and the pressure sensor is arranged at the elastic device; the pressure sensor is coupled with a controller, and the opening or closing of the driving motor and the high-frequency alternating current power supply 6 is regulated according to the stress value of the elastic device output by the pressure sensor.
In some specific embodiments, the lithium dendrite suppressing device casing 1 is provided with a motor driving sealing port, which can separate an internal plasma environment from an external environment, and the upper surface of the casing 1 is provided with a casing cover with good switchable tightness, which is used for adding raw materials, taking out products, winding carbon cloth before processing starts, periodically checking and maintaining, and the like.
In a preferred embodiment, the high energy medium forming assembly 2 is evacuated for more than 20 minutes before the gas is fed into the high energy medium forming assembly 2 to ensure that no other gas remains; after the high-energy medium forming assembly 2 is filled with gas, the pressure in the high-energy medium forming assembly 2 is controlled to be 1-30Pa.
The invention also provides a lithium dendrite suppression system of the lithium metal battery cathode material, as shown in fig. 2, comprising: lithium dendrite suppression device, raw material column and product column of lithium metal battery cathode material;
the raw material column conveys the lithium metal battery negative electrode element to the lithium dendrite suppression device so as to enable negative electrode material atoms of the lithium metal battery negative electrode element to be in an activated expansion state, and further form a lithium metal bulk diffusion channel so as to suppress the lithium dendrite;
The expanded lithium metal battery negative electrode element is transferred to the product column by the lithium metal battery negative electrode element.
It can be understood that the raw material column 4 and the product column 5 are respectively positioned at the right rear and the right front of the high-energy medium forming assembly 2 and are coupled and driven with the variable frequency motor; an optical sensor 7 is arranged in the lithium dendrite suppression system near the raw material column 4 and the product column 5 and is used for identifying the critical allowance of the carbon cloth on the raw material column so as to switch the driving motor 12 of the raw material column 4 and the product column 5 and reversely convey the carbon cloth, and plasma processing is repeatedly carried out; the high energy medium treatment time is controlled by the drive motor 12 of the product column 5, typically the time required for one revolution of the product column 5 is controlled to be 0.1-10 minutes, and in some preferred embodiments, the high energy medium treatment time is 1-100 minutes.
In some specific embodiments, the cathode material of the lithium metal battery is produced by conveying commercial carbon cloth from the raw material column 4 to the supporting component 3 to the product column 5 in a roll-to-roll manner, forming a radial high-frequency alternating current electric field between the high-energy medium forming component shell 2 and a central gas pipeline which are coupled by the high-frequency alternating current power supply 6 in the high-energy medium forming component 2, ionizing gas input from the porous gas pipeline to form plasma, and continuously impacting the carbon cloth on the supporting component 3 from inside and outside by the repeated alternating electric field to modify the carbon cloth; the system is temperature controlled through a heating and cooling plate 21 thermally coupled with the upper cover plate and the lower cover plate of the high-energy medium forming assembly; regulating and controlling the flow rate and the air pressure of the air conveyed into the high-energy medium forming assembly 2 through the flow controller 9 and the vacuum pump 10; the driving motor 12 is used for adjusting the rotating speed of the product column 5 and controlling the residence time of the carbon cloth in the high-energy medium forming assembly 2; the optical sensor 7 is used for detecting the carbon cloth allowance of the raw material column 4, and when the position of insufficient allowance is detected, the driving motor 12 of the product column 5 is automatically closed or the driving motor 12 of the raw material column 4 is switched to be opened, and the carbon cloth is reversely conveyed for repeated treatment and modification.
In the embodiment of the invention, the specific flow of the whole system operation is as follows: firstly, a raw material column 4 is put into the high-energy medium forming assembly 2, carbon cloth is wound around a supporting assembly 3 and a product column 5, and the cover sealing on the upper surface of the shell 1 is closed. The controller in the system determines whether carbon cloth is wound on the supporting component 3 in the high-energy medium forming component 2 according to stress data fed back by the pressure sensor, then generates a control instruction, if the fact that the carbon cloth is wound is determined, controls the vacuum pump 10 to be opened for vacuumizing the high-energy medium forming component 2 for more than 20 minutes, simultaneously opens the temperature control system for preheating, sets the gas flow according to prompts, sets the rotating speed and the number of circulation turns after the pressure of the reaction system is stabilized within a range of 1-30Pa (namely, switches the driving motor 12 after the optical sensor 7 recognizes that the residual carbon cloth of the raw material column is smaller than a critical value, takes the product column 5 as the raw material column 4, reverses the circulation times of processing the carbon cloth), starts the driving motor of the raw material column 4, synchronously starts the high-frequency alternating current power supply 6, and starts plasma modification. If no carbon cloth is wound, a buzzing warning sound is sent out to prompt and confirm the loading of the carbon cloth. After the treatment is completed, the controller automatically turns off the driving motor 12, the high-frequency alternating current power supply 6 and the temperature control system and gives out buzzing prompt sound, an operator turns off the air cylinder 8 and the vacuum pump 10, and the exhaust valve is opened to enable the internal pressure of the reactor to be consistent with the external pressure, so that the product column 5 can be taken out.
The invention also provides a lithium dendrite inhibition method of the lithium metal battery cathode material, which comprises the following steps:
Placing a lithium metal battery cathode element into a shell;
And forming a high-energy medium in the shell, so that anode material atoms of the anode element of the lithium metal battery are in an activated expansion state, and further forming a bulk diffusion channel of lithium metal so as to inhibit the lithium dendrite.
It can be understood that the negative electrode element of the lithium metal battery is carbon cloth, the high-energy medium forming component is preferably a plasma reactor, carbon is arranged in the plasma reactor, the plasma reactor is started to generate plasma, the plasma continuously impacts the carbon cloth from inside and outside, element doping and defection are carried out on the surface and the inside of the carbon cloth material, and the bulk diffusion channel of lithium metal is opened, so that the bulk diffusion channel of lithium metal is formed, and lithium dendrite is restrained.
In some embodiments, the lithium dendrite suppression method further includes:
And doping a modifying medium in gaps among negative electrode material atoms of the negative electrode element of the lithium metal battery so as to improve the affinity between the negative electrode element of the lithium metal battery and lithium.
It can be understood that the carbon cloth is modified by utilizing the plasma atmosphere generated by ionized gas of the high-frequency alternating current battery, and element doping and atomic level defect sites can be introduced on the surface and inside of the carbon cloth, so that the affinity between a carbon atomic layer and lithium is greatly enhanced, and the nucleation and diffusion energy barrier of lithium can be reduced; in addition, the inner atomic layer of the carbon cloth modified by the plasmas can generate the conditions of expansion of a structural layer and expansion of an interlayer distance due to the introduction of high-energy ions, thereby providing possibility for bulk transportation of lithium in the carbon cloth material and reducing migration energy barriers in the layer.
The invention provides a lithium dendrite suppression device, a system and a method for a lithium metal battery cathode material, which are characterized in that a high-energy medium is arranged to form a component, a supporting component, a raw material column and a product column, the theoretical basis of lithium dendrite suppression by combining lithium affinity modification of a cathode current collector is utilized, a carbon cloth is modified by utilizing a plasma atmosphere generated by ionized gas of a high-frequency alternating current battery, element doping and atomic level defect sites can be introduced on the surface and the inside of the carbon cloth, so that the affinity between a carbon atomic layer and lithium is greatly enhanced, and the nucleation and diffusion energy barrier of lithium can be reduced; in addition, the inner atomic layer of the carbon cloth modified by the plasmas can generate the conditions of expansion of a structural layer and expansion of an interlayer distance due to the introduction of high-energy ions, thereby providing possibility for bulk transportation of lithium in the carbon cloth material and reducing migration energy barriers in the layer. In general, plasma modified carbon cloths can reduce the nucleation and diffusion energy barrier of lithium by providing a lithium-philic site, and possess large carbon atom layer spacing, which can reduce the migration energy barrier of lithium in the bulk phase. The plasma treatment does not introduce impurity contamination from chemical treatments and the rotation of the processing bowl provides a more uniform and controlled treatment effect with negligible impact on the structural strength, conductivity, etc. of the electrode itself under appropriate process conditions.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present specification. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example.
Furthermore, the various embodiments or examples described in this specification and the features of the various embodiments or examples may be combined and combined by those skilled in the art without contradiction. The above description is merely an embodiment of the present specification and is not intended to limit the present specification. Various modifications and changes may be made to the embodiments herein by those skilled in the art. Any modification, equivalent replacement, improvement, or the like, which is made within the spirit and principle of the embodiments of the present specification, should be included in the scope of the claims of the embodiments of the present specification.
Claims (8)
1. A lithium dendrite suppression device for a negative electrode material of a lithium metal battery, comprising:
a housing into which a lithium metal battery negative electrode element can be placed; and
The high-energy medium forming component can form a high-energy medium in the shell to enable negative electrode material atoms of the negative electrode element of the lithium metal battery to be in an expanded state, so that a bulk diffusion channel of lithium metal is formed to inhibit the lithium dendrite; the negative electrode material is carbon cloth;
the high energy medium forming assembly includes: a gas pipeline, a high-frequency alternating current power supply and a heating and cooling plate;
the gas pipeline comprises a gas inlet and two outlets, wherein one outlet is connected with a vacuum pump, the other outlet is connected with a vent valve, and the gas inlet is connected with a gas cylinder;
The high-frequency alternating current power supply is coupled with the gas inlet end of the gas pipeline and the inner wall of the high-energy medium forming assembly, wherein the inner wall of the high-energy medium forming assembly is coupled with a grounding wire;
Two ends of the high-energy medium forming component are respectively provided with a heating and cooling plate, and the heating and cooling plates are coupled with a temperature control system;
The lithium dendrite suppression apparatus further includes:
The support assembly and the high-energy medium forming assembly are coaxially arranged by taking the gas pipeline as an axis, wherein the lithium metal battery cathode element can be arranged on the support assembly.
2. The lithium dendrite suppressing device of claim 1, wherein a part of the gas pipe located inside the high-energy medium forming component is provided with a plurality of through holes.
3. The lithium dendrite suppression apparatus of claim 1, wherein a flow controller is provided at the inlet of the gas conduit.
4. The lithium dendrite suppressing device of claim 1, wherein a pressure sensor is provided between the upper and lower covers of the support assembly and the gas line.
5. The lithium dendrite suppression apparatus of claim 1, wherein the high energy medium can be one of nitrogen, oxygen, and ammonia.
6. A lithium dendrite suppression system for a negative electrode material of a lithium metal battery, comprising: a raw material column, a product column, and a lithium dendrite suppression apparatus of the lithium metal battery anode material according to any one of claims 1 to 5;
the raw material column conveys the lithium metal battery negative electrode element to the lithium dendrite suppression device so as to enable negative electrode material atoms of the lithium metal battery negative electrode element to be in an activated expansion state, and further form a lithium metal bulk diffusion channel so as to suppress the lithium dendrite;
the support assembly conveys the expanded lithium metal battery negative electrode element to the product column.
7. A lithium dendrite suppression method of a lithium metal battery anode material using the lithium metal battery anode material lithium dendrite suppression apparatus according to claim 1, comprising:
Conveying the lithium metal battery cathode element into a shell through a raw material column;
And forming a high-energy medium in the shell, so that anode material atoms of the anode element of the lithium metal battery are in an activated expansion state, and further forming a bulk diffusion channel of lithium metal so as to inhibit the lithium dendrite.
8. The lithium dendrite suppression method of claim 7, further comprising:
And doping a modifying medium in gaps among negative electrode material atoms of the negative electrode element of the lithium metal battery so as to improve the affinity between the negative electrode element of the lithium metal battery and lithium.
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