CN113991067B - Open lithium metal negative electrode secondary battery - Google Patents
Open lithium metal negative electrode secondary battery Download PDFInfo
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- CN113991067B CN113991067B CN202111252472.2A CN202111252472A CN113991067B CN 113991067 B CN113991067 B CN 113991067B CN 202111252472 A CN202111252472 A CN 202111252472A CN 113991067 B CN113991067 B CN 113991067B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
- 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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The application relates to an open type lithium metal negative electrode secondary battery, which comprises a sealed battery shell filled with electrolyte, wherein three rolls are arranged in the sealed battery shell, the first roll is a working roll, the second roll is a positive electrode roll, the third roll is a lithium metal negative electrode roll, the three rolls are driven by one or more motors, a positive electrode belt, a lithium metal negative electrode belt and a diaphragm are wound on the working roll, the positive electrode belt, the lithium metal negative electrode belt and the diaphragm are discharged when the working roll is unreeled to rotate, and meanwhile, the positive electrode roll and the negative electrode roll are wound to rotate and are wound in the positive electrode belt and the lithium metal negative electrode belt; dendrite flattening equipment is arranged between the working roll and the lithium metal negative electrode roll, and dendrite on the surface of the lithium metal negative electrode belt is flattened through the dendrite flattening equipment when the lithium metal negative electrode belt is released and retracted to move. The battery can effectively eliminate dendrites of the lithium metal cathode.
Description
Technical Field
The application belongs to the technical field of lithium ion batteries, and particularly relates to an open type lithium metal anode secondary battery.
Background
Lithium metal negative electrode secondary batteries have very high mass specific energy, attracting many specialists' research inputs for decades. However, dendrite problems of lithium metal anodes have not been effectively solved at all times.
Dendrites grow on charging, the principle being deposition of lithium atoms. Dendrites are thought to be generated for two reasons: firstly, when the lithium metal anode belt is processed and produced, the surface layer of the lithium metal anode belt cannot be leveled to an ideal atomic level, which inevitably produces results of high atoms and low atoms. Electrons have the characteristic of collecting tips and can be collected to the place with high tips, so that a plurality of electrons are collected at the high points, and lithium positive ions are attracted to deposit immediately, so that dendrites are formed. Secondly, because lithium ions from the positive electrode can only reach the surface of the lithium metal negative electrode from the channels of the diaphragm, however, the channels are unevenly distributed on the surface of the lithium metal negative electrode, and the probability of depositing lithium ions is high in the contact place with the channels, so dendrites are necessarily formed. When the high points inherent in the lithium metal strip just hit the channels on the separator, the two reasons are concentrated together, which must accelerate dendrite growth. Some experts believe that the forces generated during dendrite growth puncture the membrane, but we do not. Our idea is that dendrites grow along lithium ion channels in the separator and strike the positive electrode creating a short circuit. If the lithium ion channels of the separator are curved, dendrite growth is also curved. Conversely, if the lithium ion channels of the separator are straight, then dendrite growth is also straight. Dendrite generation is inevitable as long as the separator exists and as long as lithium ion channels exist on the separator.
How to eliminate dendrites is a difficult problem, and the current methods of experts at home and abroad are divided into three aspects: firstly, carrying out physical doping modification on the surface of lithium metal, for example, adopting an alloy of lithium and aluminum to inhibit dendrite generation; secondly, changing the formula of the electrolyte, and dissolving dendrites through the electrolyte; and thirdly, a solid electrolyte is adopted, and physical force is adopted to block dendrites from piercing through the diaphragm. However, various studies have not been successful over the last decade, dendrites remain, and short circuits remain. Some experts believe that positively charged ions in dendrites move towards the positive electrode and electrons move towards the negative electrode during discharge, the dendrites disappear, leaving only interfacial species on the dendrite surface. When the number of dendrites increases and this occurs continuously, interfacial materials accumulate to affect lithium ion conduction. Only the phenomenon of preventing dendrite generation cannot occur, because the interface layer cannot grow on the original interface layer and only grows on the surface of the new dendrite.
It is known from the analysis of the current research state that the dendrite generation can be reduced by doping other metals on the surface of lithium metal, but this affects the conduction of lithium ions. The composition of the electrolyte is fine combination, the addition of the dissolvent to dissolve dendrites can seriously affect the conduction of ions, and the dissolved lithium remained in the electrolyte can also cause the conduction of electronic short circuit. The electrolyte is a solid electrolyte with certain hardness, which is expected to block dendrite generation, but any solid electrolyte must have ion channels, and dendrites grow along the channels, so the hardness of the electrolyte is irrelevant to blocking dendrite penetration. From the analysis of the three methods, the old thought must be abandoned, and a new way is developed. The battery which is sealed for decades is opened, the lithium metal anode belt is released at any time to repair, and an open type novel battery which can be repaired is established. The mechanical method is adopted to eliminate dendrites with mechanical properties, which are the latest and most effective directions.
Disclosure of Invention
The application aims to provide an open lithium metal negative electrode secondary battery which can effectively eliminate dendrites of a lithium metal negative electrode.
In order to achieve the above purpose, the application adopts the following technical scheme: an open lithium metal negative electrode secondary battery comprises a sealed battery shell filled with electrolyte, wherein three rolls are arranged in the sealed battery shell, the first roll is a working roll, the second roll is a positive electrode roll, the third roll is a lithium metal negative electrode roll, the three rolls are driven by one or more motors, a positive electrode belt, a lithium metal negative electrode belt and a diaphragm are wound on the working roll, the positive electrode belt, the lithium metal negative electrode belt and the diaphragm are discharged when the working roll is unreeled and rotated, and meanwhile, the positive electrode roll and the negative electrode roll are wound and rotated to roll in the positive electrode belt and the lithium metal negative electrode belt; dendrite flattening equipment is arranged between the working roll and the lithium metal negative electrode roll, and dendrite on the surface of the lithium metal negative electrode belt is flattened through the dendrite flattening equipment when the lithium metal negative electrode belt is released and retracted to move.
Further, the dendrite flattening device is a roller device, the roller device comprises an upper roller and a lower roller which are respectively arranged on the upper side and the lower side of the lithium metal negative electrode belt, and when the lithium metal negative electrode belt passes through the middle of the upper roller and the lower roller, the rollers generate pressure on the surface of the lithium metal negative electrode belt, so that dendrites on the surface of the lithium metal negative electrode belt are flattened.
Further, the dendrite flattening device is a vibrating device, the vibrating device comprises vibrating plates and fixing plates, the vibrating plates are respectively arranged on the upper side and the lower side of the lithium metal negative electrode belt, and dendrites on two surfaces of the lithium metal negative electrode belt are flattened by striking force and reaction force of the plates when the lithium metal negative electrode belt passes through the middle of the vibrating plates and the fixing plates.
Further, when the lithium metal anode belt is manufactured, the two surfaces of the lithium metal anode belt are subjected to leveling processing; the thickness of the lithium metal negative electrode belt is increased, and one lithium metal negative electrode belt and a plurality of positive electrode belt wheels are replaced to form a battery roll capable of being charged and discharged.
Further, the lithium ion battery adopts a diaphragm with a large aperture, and the diameter is larger than 100um; when the positive electrode belt is manufactured, graphene fragments are added into the positive electrode active material instead of carbon particles, so that the bending resistance of the positive electrode belt is improved.
Further, a charging counter or a battery capacity detector is arranged on the charger matched with the lithium ion battery; when the charging time reaches a set value or the charging capacity reaches a set value, the charger sends out a command for stopping charging, and the lithium metal negative electrode belt flattening system is started first to perform dendrite flattening operation when the next charging is limited, and then charging is performed.
Further, position sensing elements are arranged at two ends of the lithium metal negative electrode belt, and the lugs on the lithium metal negative electrode belt and the lugs on the positive electrode belt in the working roll are electrically connected to the outside through elastic contact between the lugs and the electric connecting sheet.
Further, a revolution counter is provided on the reels of the three rolls to issue instructions when needed to stop the paying-out and winding rotation of the three rolls in the battery.
Further, the separator is attached to both sides of the positive electrode belt and performs unreeling and reeling movements together with the positive electrode belt.
Further, the working roll, the positive electrode roll, the lithium metal negative electrode roll and the driving motor are all sealed in the battery shell, and the sealed space is filled with electrolyte or inert gas.
Further, when the lithium ion battery is applied to a high-power battery, a plurality of coils of the same kind can be arranged on the reels of the three coils so as to increase the capacity.
Compared with the prior art, the application has the following beneficial effects: an open lithium metal negative secondary battery is provided, i.e., a closed battery is changed into an open and repairable battery, using a mechanical flattening device to eliminate dendrites with mechanical properties, more effectively than all chemical elimination methods. The dendrite problem is solved, the lithium metal belt can be made thick, and a plurality of positive electrode belts are matched with one lithium metal belt in a rotating way to work, so that the specific energy of the battery can be improved in a multiplied way, and the endurance performance of the battery is equal to that of gasoline fuel. The open lithium negative electrode secondary battery can be applied to various scenes such as high-power energy storage batteries.
Drawings
Fig. 1 is a schematic structural diagram of an open lithium metal anode secondary battery according to an embodiment of the present application.
Fig. 2 is a schematic diagram of a roller apparatus flattening dendrites in an embodiment of the application.
Fig. 3 is a schematic diagram of a vibration apparatus for flattening dendrites in an embodiment of the present application.
Fig. 4 is a schematic structural diagram of an open lithium metal anode secondary battery having multiple anodes in an embodiment of the present application.
Fig. 5 is a schematic diagram of tab conduction in an embodiment of the application.
In the figure: 1-a battery housing; 2-working rolls; 3-dendrite flattening apparatus; 4-lithium metal anode tape; 5-lithium metal anode roll; 6-positive electrode roll; 7-upper rollers; 8-a lower roller; 9-vibrating plate; 10-fixing a flat plate; 11-positive external connection piece; 12-positive electrode lugs; 13-lithium negative electrode tab; 14-a negative electrode external connection piece; 15-a reel; 16-positive electrode belt.
Detailed Description
The application will be further described with reference to the accompanying drawings and examples.
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present application. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
As shown in fig. 1, the present embodiment provides an open lithium metal negative electrode secondary battery, comprising a sealed battery case filled with an electrolyte, three kinds of rolls are provided in the sealed battery case 1, the first kind of roll is a working roll 2, the second kind of roll is a positive electrode roll 6, and the third kind of roll is a lithium metal negative electrode roll 5, wherein the working roll is a chargeable and dischargeable battery roll, the three kinds of rolls are driven by one or more motors, the working roll 2 is wound with a positive electrode tape 16, a lithium metal negative electrode tape 4 and a separator, the positive electrode tape, the lithium metal negative electrode tape 4 and the separator are released when the working roll 2 is unreeled to rotate, and the positive electrode roll 6 and the negative electrode roll 5 are wound to rotate and are wound into the positive electrode tape and the lithium metal negative electrode tape 4; dendrite flattening equipment 3 is arranged between the working roll 2 and the lithium metal negative electrode roll 6, and dendrite on the surface of the lithium metal negative electrode belt is flattened through the dendrite flattening equipment 3 when the lithium metal negative electrode belt 4 is released and retracted.
In this embodiment, the dendrite flattening device may be a roller device, where the roller device includes an upper roller 7 and a lower roller 8 that are separately disposed on the upper and lower sides of the lithium metal negative electrode belt, and when the lithium metal negative electrode belt passes through the middle of the upper and lower rollers, the rollers generate pressure on the surface of the lithium metal negative electrode belt, so as to flatten dendrites on the surface of the lithium metal negative electrode belt. The dendrite flattening device can also be vibration device, the vibration device comprises a vibration flat plate 9 and a fixed flat plate 10 which are respectively arranged on the upper side and the lower side of the lithium metal negative electrode belt, and dendrites on two surfaces of the lithium metal negative electrode belt are flattened by the striking force and the reaction force of the flat plate when the lithium metal negative electrode belt passes through the middle of the vibration flat plate and the fixed flat plate.
In this embodiment, the unreeling and reeling of the lithium metal strip is driven by a micro motor inside the battery case. The electric power for flattening dendrites and the electric power for the motor are supplied from the external power during charging. Because of the low hardness of lithium metal, the power required to flatten the dendrites just produced is small, so its motor and flattening apparatus are small, and the dendrite flattening apparatus of a 10Ah cell is only half the size of a pencil. The dendrite elimination is also carried out by other methods than mechanical ones: in the manufacturing process of the lithium metal anode belt, the two surfaces of the lithium metal anode belt are subjected to leveling processing, and a diaphragm with the largest pore diameter is used. For example, the lithium metal belt is repeatedly passed between the upper and lower rollers, and the upper and lower rollers are polished like a mirror while rotating and pressing the upper and lower planes of the lithium metal belt. The two surfaces of the lithium metal strip can also be polished by selecting a suitable fiber wheel. The lithium ion battery adopts a diaphragm with a large aperture, and the diameter is larger than 100um.
In this embodiment, a charger for the lithium ion battery is provided with a charge counter or a battery capacity detector. When the charging time reaches a set value or the charging capacity reaches a set value, the charger sends out a command for stopping charging, and the lithium metal negative electrode belt flattening system is started first to perform dendrite flattening operation when the next charging is limited, and then charging is performed. When the detecting instrument of the charger considers that dendrite on the surface of the lithium metal belt needs to be flattened, the flattening equipment can automatically flatten dendrite after the charging plug is inserted. The battery of the present application does not present the difficulty of dendrites to pierce the separator. The above-mentioned prescribed value means a state in which dendrite growth has just entered the diaphragm aperture after several charges, which is an optimal state for flattening dendrite. That is, the user does not need to take care of when to flatten the lithium metal strip. The user only needs to plug in the charger when using, and the product can automatically solve the problems. The application can obviously improve the recycling times of the lithium cathode secondary battery by only polishing the surface of the lithium metal belt and then adopting the diaphragm with large aperture even if flattening equipment is not adopted. When the application is added with mechanical flattening equipment, the purpose of long-term circulation can be realized.
The lithium metal belt has small resistance to lithium ions, so that the thickness of the lithium metal negative electrode belt can be thickened when the lithium metal negative electrode belt is manufactured, and one lithium metal belt can be replaced with a plurality of positive electrode belts to form a battery roll capable of being charged and discharged, as shown in fig. 4. When the positive electrode strip in the working roll is fully charged, the working roll rotates to pay out the positive electrode strip, and the first positive electrode roll is retracted into the positive electrode strip. The second positive electrode roll then releases the positive electrode strip and the lithium metal strip is wound into a working roll, and charging is continued. When the recombined working roll is fully charged, the working roll rotates to pay out the second positive electrode belt, and the second positive electrode roll is retracted into the positive electrode belt. Finally, the above procedure is repeated to continue charging the third positive electrode roll. This is the working principle of an open lithium negative electrode multi-positive electrode secondary battery. During discharge, the multiple positive electrode rolls also work in a rotating way. The multi-anode rotation method can improve the mass specific energy of the lithium metal battery by several times, so that the endurance mileage is equal to or exceeds the gasoline fuel level.
In this embodiment, position sensing elements are provided at both ends of the lithium metal anode strip: if magnetic materials are used, instructions can be sent out when the magnetic materials are needed, and the unreeling and reeling rotation of the three rolls in the battery can be stopped.
In this embodiment, a revolution counter is provided on the reels of the three rolls to give instructions to stop the paying out and winding rotation of the three rolls in the battery when needed.
In this embodiment, the separator is attached to both sides of the positive electrode strip and performs unreeling and reeling movements together with the positive electrode strip. Therefore, the active material of the positive electrode belt can be protected from damage, and the active material can be kept in a wet state of electrolyte.
In this embodiment, the working roll, the positive electrode roll, the lithium metal negative electrode roll and the driving motor are all sealed in the battery case, and the sealed space is filled with electrolyte or inert gas.
In this example, graphene chips are added to the positive electrode active material instead of carbon particles to increase the bending resistance of the positive electrode strip when the positive electrode strip is manufactured.
In this embodiment, the tabs on the lithium metal negative electrode strip and the tabs on the positive electrode strip in the working roll are electrically connected to each other through elastic contact between the tabs and the electrical connection piece. The electrical connection pads include a positive-to-external electrical connection pad and a negative-to-external electrical connection pad, as shown in fig. 5. Elastic contact conduction is a widely applied principle in electrical equipment, and is safe and reliable in operation.
When the application is applied to a high-power battery, a plurality of coils of the same kind can be arranged on the reels of the three coils so as to increase the capacity.
The above description is only a preferred embodiment of the present application, and is not intended to limit the application in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present application still fall within the protection scope of the technical solution of the present application.
Claims (9)
1. An open lithium metal negative electrode secondary battery comprises a sealed battery shell filled with electrolyte, and is characterized in that three rolls are arranged in the sealed battery shell, wherein the first roll is a working roll, the second roll is a positive electrode roll, the third roll is a lithium metal negative electrode roll, the three rolls are driven by one or more motors, a positive electrode belt, a lithium metal negative electrode belt and a diaphragm are wound on the working roll, the positive electrode belt, the lithium metal negative electrode belt and the diaphragm are discharged when the working roll is unreeled and rotated, and meanwhile, the positive electrode roll and the lithium metal negative electrode roll are wound and rotated to retract the positive electrode belt and the lithium metal negative electrode belt; dendrite flattening equipment is arranged between the working roll and the lithium metal negative electrode roll, and dendrite on the surface of the lithium metal negative electrode belt is flattened through the dendrite flattening equipment when the lithium metal negative electrode belt is released and retracted for movement;
when the lithium metal anode belt is manufactured, the two surfaces of the lithium metal anode belt are subjected to leveling processing; the thickness of the lithium metal negative electrode belt is increased, and one lithium metal negative electrode belt and a plurality of positive electrode belt wheels are replaced to form a battery roll capable of being charged and discharged;
when the positive electrode belt in the working roll is fully charged, the working roll rotates to pay out the positive electrode belt, and meanwhile, the first positive electrode is wound into the positive electrode belt; then the second positive electrode roll releases the positive electrode belt and the lithium metal negative electrode belt to be taken in the working roll together, and charging is continued; when the recombined working roll is fully charged, the working roll rotates to release a second positive electrode belt, and the second positive electrode is wound into the positive electrode belt; finally, the above procedure is repeated to continue charging the third positive electrode roll.
2. An open lithium metal negative electrode secondary battery according to claim 1, wherein the dendrite flattening device is a roller device including an upper roller and a lower roller provided on the upper and lower sides of the lithium metal negative electrode belt, respectively, and the rollers apply pressure to the surface of the lithium metal negative electrode belt when the lithium metal negative electrode belt passes between the upper and lower rollers, thereby flattening dendrites on the surface of the lithium metal negative electrode belt.
3. The open type lithium metal negative electrode secondary battery according to claim 1, wherein the dendrite flattening device is a vibration device including vibration plates and a fixing plate separately provided on the upper and lower sides of the lithium metal negative electrode belt, and dendrites on both surfaces of the lithium metal negative electrode belt are flattened by striking force and reaction force of the plate when the lithium metal negative electrode belt passes through the middle of the vibration plate and the fixing plate.
4. The open lithium metal negative electrode secondary battery according to claim 1, wherein the open lithium metal negative electrode secondary battery employs a large-aperture separator with a diameter of more than 100um; when the positive electrode belt is manufactured, graphene fragments are added into the positive electrode active material instead of carbon particles, so that the bending resistance of the positive electrode belt is improved.
5. The open-type lithium metal anode secondary battery according to claim 1, wherein a charger for the open-type lithium metal anode secondary battery is provided with a charge counter or a battery capacity detector; when the charging time reaches a set value or the charging capacity reaches a set value, the charger sends out a command for stopping charging, and the lithium metal negative electrode belt flattening system is started first to perform dendrite flattening operation when the next charging is limited, and then charging is performed.
6. An open lithium metal negative electrode secondary battery according to claim 1, wherein position sensing elements are provided at both ends of the lithium metal negative electrode strip, tabs on the lithium metal negative electrode strip and tabs on the positive electrode strip in the working roll, and their external electrical connection is achieved by elastic contact of the tabs with the electrical connection sheet.
7. The open lithium metal negative electrode secondary battery according to claim 1, wherein a revolution counter is provided on the reels of the three rolls to instruct to stop the paying-out and winding rotation of the three rolls in the battery when necessary.
8. An open lithium metal negative electrode secondary battery according to claim 1, wherein the separator is attached to both sides of the positive electrode strip and performs unreeling and reeling movements together with the positive electrode strip.
9. The open lithium metal negative electrode secondary battery according to claim 1, wherein the working roll, the positive electrode roll, the lithium metal negative electrode roll, and the driving motor are all sealed in the battery case, and the sealed space is filled with an electrolyte or an inert gas.
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| CN202111252472.2A CN113991067B (en) | 2021-10-27 | 2021-10-27 | Open lithium metal negative electrode secondary battery |
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| KR102488680B1 (en) * | 2019-03-08 | 2023-01-17 | 주식회사 엘지에너지솔루션 | Negative Electrode for Lithium Secondary Battery, Method for Preparing the Same and Lithium Secondary Battery Comprising the Same |
| CN216903062U (en) * | 2021-10-27 | 2022-07-05 | 福州大学 | Open type lithium negative electrode secondary battery |
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