CN113991067A - Open lithium metal negative electrode secondary battery - Google Patents
Open lithium metal negative electrode secondary battery Download PDFInfo
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- CN113991067A CN113991067A CN202111252472.2A CN202111252472A CN113991067A CN 113991067 A CN113991067 A CN 113991067A CN 202111252472 A CN202111252472 A CN 202111252472A CN 113991067 A CN113991067 A CN 113991067A
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- lithium metal
- metal negative
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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 invention relates to an open lithium metal negative secondary battery, which comprises a sealed battery shell filled with electrolyte, wherein three types of coils are arranged in the sealed battery shell, the first type of coil is a working coil, the second type of coil is a positive coil, the third type of coil is a lithium metal negative coil, the three types of coils 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 coil, the positive electrode belt, the lithium metal negative electrode belt and the diaphragm are discharged when the working coil is unwound and rotated, and the positive electrode coil and the negative electrode coil are wound and rotated to take in the positive electrode belt and the lithium metal negative electrode belt; and a dendrite flattening device is arranged between the working roll and the lithium metal negative pole roll, and when the lithium metal negative pole belt is released and retracted to move, the dendrite flattening device flattens dendrites on the surface of the lithium metal negative pole belt. The battery can effectively eliminate the dendrite of the lithium metal negative electrode.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to an open lithium metal negative electrode secondary battery.
Background
Lithium metal negative electrode secondary batteries have very high mass specific energy, and have attracted many experts' research efforts for over a decade. However, the dendrite difficulty of lithium metal negative electrodes has not been effectively solved.
Dendrites grow upon charging, the principle being the deposition of lithium atoms. Research suggests that dendrites are produced by two causes: one is that when the lithium metal negative electrode strip is processed and produced, the surface layer of the lithium metal negative electrode strip cannot be flattened at an ideal atomic level, which inevitably results in high atoms and low atoms. The electrons have the sharp concentration characteristic and can be firstly concentrated to a high false sharp place, so that a plurality of electrons are firstly concentrated on a high point, lithium positive ions are immediately attracted to deposit, and dendritic crystals are formed. Secondly, because the lithium ions from the positive electrode can only reach the surface of the lithium metal negative electrode from the channels of the diaphragm, but the channels are unevenly distributed on the surface of the lithium metal negative electrode, the probability of lithium ion deposition is high at any place contacting with the channels, and thus dendrites are inevitably formed. When the inherently high point on the lithium metal strip just hits the channel in the separator, the combination of these two causes necessarily accelerates dendrite growth. Some experts believe that the forces generated by dendrite growth puncture the membrane, but we do not. Our idea is that dendrites grow along lithium ion channels in the separator, and encounter the positive electrode to generate a short circuit phenomenon. If the lithium ion channel of the separator is curved, the dendrite growth is also curved. Conversely, if the lithium ion channels of the separator are straight, the growth of dendrites is also straight. So that dendrite generation is inevitable as long as the lithium ion channel on the separator exists, as long as the separator exists.
How to eliminate the dendrite problem, the current methods of experts at home and abroad are divided into three aspects: the method comprises the following steps of carrying out physical doping modification on the surface of lithium metal, for example, inhibiting dendritic crystal generation by adopting an alloy of lithium and aluminum; secondly, changing the formula of the electrolyte, and dissolving the dendritic crystal by the electrolyte; thirdly, solid electrolyte is adopted, and physical force is adopted to prevent the dendrite from breaking through the diaphragm. However, various studies have not been successful in the last decade, dendrites still exist, and short circuits still occur. Some experts believe that when positively charged ions in dendrites move to the positive electrode and electrons move to the negative electrode during discharge, the dendrites disappear and only interface substances on the surface of the dendrites are left. When the number of dendrites increases and this continues to occur, interfacial material accumulates and affects the conduction of lithium ions. The phenomenon can not occur only when the dendrite is prevented from generating because the interface layer can not grow on the original interface layer and only can grow on the surface of the new dendrite.
By analyzing the current research state, doping other metals on the surface of lithium metal can reduce the generation of dendrite, but the conduction of lithium ions can be influenced. The electrolyte is a fine composition, the addition of a solute to dissolve dendrites can seriously affect the conduction of ions, and the remaining of dissolved lithium in the electrolyte can also cause electronic short circuit conduction. The electrolyte is solid electrolyte with certain hardness, and is expected to block the generation of dendrite, but any solid electrolyte must have an ion channel, and the dendrite grows along the channel, so the hardness of the electrolyte is irrelevant to the penetration of the dendrite. From the analysis of the three methods, the old thinking must be abandoned and a new approach is made. The battery which is closed for decades is opened, and the lithium metal negative electrode belt is released at any time for repairing, so that the novel open type battery which can be repaired is established. It is the latest and most efficient direction to use mechanical methods to eliminate dendrites with mechanical properties.
Disclosure of Invention
The present invention is directed to an open lithium metal negative electrode secondary battery that can effectively eliminate dendrites of a lithium metal negative electrode.
In order to achieve the purpose, the invention adopts the technical scheme that: an open lithium metal negative secondary battery comprises a sealed battery shell filled with electrolyte, wherein three types of coils are arranged in the sealed battery shell, the first type of coil is a working coil, the second type of coil is a positive coil, the third type of coil is a lithium metal negative coil, the three types of coils are driven by one or more motors, a positive strip, a lithium metal negative strip and a diaphragm are wound on the working coil, the positive strip, the lithium metal negative strip and the diaphragm are discharged when the working coil is unwound and rotated, and the positive coil and the negative coil rotate to wind in the positive strip and the lithium metal negative strip; and a dendrite flattening device is arranged between the working roll and the lithium metal negative pole roll, and when the lithium metal negative pole belt is released and retracted to move, the dendrite flattening device flattens dendrites on the surface of the lithium metal negative pole belt.
Further, the dendrite flattening equipment is roller equipment, the roller equipment 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 pole belt, and when the lithium metal negative pole 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 pole belt, so that dendrites on the surface of the lithium metal negative pole belt are flattened.
Further, dendrite flattening equipment is vibrating equipment, vibrating equipment is including dividing the vibration flat board and the fixed flat board of locating the lithium metal negative pole upper and lower downside, the lithium metal negative pole takes when passing through in the middle of vibration flat board, the fixed flat board, and the flat hitting power of flat board and reaction force flatten the dendrite on lithium metal negative pole and take two surfaces.
Further, when the lithium metal negative electrode belt is produced, two surfaces of the lithium metal negative electrode belt are subjected to flattening processing; the thickness of the lithium metal negative electrode belt is increased, and a lithium metal negative electrode belt and a plurality of positive electrode belts are alternately formed into a battery roll which can be charged and discharged.
Furthermore, the lithium ion battery adopts a diaphragm with large aperture, and the diameter of the diaphragm is larger than 100 um; when the positive electrode belt is manufactured, graphene fragments are added into a positive electrode active material instead of carbon particles so as to increase the bending resistance of the positive electrode belt.
Furthermore, 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 a command of stopping charging, and the lithium metal negative pole belt flattening system is started firstly to perform dendrite flattening operation when the next charging is limited, and then the charging is performed.
Furthermore, position sensing elements are arranged at two ends of the lithium metal negative pole belt, and the external electric connection of the lug on the lithium metal negative pole belt and the lug on the positive pole belt in the working roll is realized through the elastic contact of the lugs and the electric connection sheet.
Further, the reels of the three types of rolls are provided with revolution counters to send instructions when needed to stop the pay-out and take-up rotation of the three types of rolls in the battery.
Furthermore, the diaphragm is attached to two sides of the positive pole belt and performs unreeling and reeling motions together with the positive pole belt.
Further, the working roll, the positive roll, the lithium metal negative roll and the driving motor are sealed in the battery case, 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 same-type coils can be arranged on the reels of the three coils so as to increase the capacity.
Compared with the prior art, the invention has the following beneficial effects: an open lithium metal negative electrode secondary battery is provided, that is, a closed battery is changed into an open and repairable battery, and a mechanical flattening device is adopted to eliminate dendrites with mechanical properties, which is more effective than all chemical elimination methods. The problem of dendrite is solved, the battery can be thick with lithium metal strap, let many positive pole areas, alternate the work of a lithium metal strap of cooperation, the specific energy of improvement battery that like this can the multiple makes its duration equal to gasoline fuel. The open type lithium cathode secondary battery can be applied to various scenes such as a high-power energy storage battery and the like.
Drawings
Fig. 1 is a schematic structural view of an open lithium metal negative electrode secondary battery according to an embodiment of the present invention.
FIG. 2 is a schematic diagram of a roller apparatus flattening dendrites in an embodiment of the present invention.
Fig. 3 is a schematic diagram of a vibrating device for flattening dendrites in an embodiment of the present invention.
Fig. 4 is a schematic diagram of a structure in which an open lithium metal negative secondary battery has multiple positive electrodes according to an embodiment of the present invention.
Fig. 5 is a schematic diagram of the conduction of the tab in the embodiment of the invention.
In the figure: 1-a battery case; 2, working volume; 3-dendrite flattening equipment; 4-lithium metal negative electrode tape; 5-lithium metal negative pole roll; 6-positive pole roll; 7, rolling a roller; 8, rolling a lower roller; 9-vibrating the flat plate; 10, fixing the flat plate; 11-positive external electrical connection piece; 12-positive pole tab; 13-lithium negative electrode tab; 14-negative external electrical connection piece; 15-a reel; 16-positive electrode strip.
Detailed Description
The invention is further explained below with reference to the drawings and the embodiments.
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. 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 example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As shown in fig. 1, the present embodiment provides an open lithium metal negative secondary battery, which includes a sealed battery case filled with an electrolyte, three types of rolls are disposed in the sealed battery case 1, the first type of roll is a working roll 2, the second type of roll is a positive roll 6, the third type of roll is a lithium metal negative roll 5, wherein the working roll is a battery roll that can be charged and discharged, the three types of rolls are driven by one or more motors, a positive strip 16, a lithium metal negative strip 4 and a diaphragm are wound on the working roll 2, the positive strip, the lithium metal negative strip 4 and the diaphragm are released when the working roll 2 is unwound and rotated, and the positive strip 6 and the lithium metal negative strip 4 are retracted when the positive roll 6 and the negative roll 5 are wound and rotated; and a dendrite flattening device 3 is arranged between the working roll 2 and the lithium metal negative pole roll 6, and when the lithium metal negative pole belt 4 is released and retracted to move, the dendrite flattening device 3 flattens dendrites on the surface of the lithium metal negative pole belt.
In this embodiment, the dendrite flattening device may be a roller device, the roller device includes an upper roller 7 and a lower roller 8 respectively disposed on the upper and lower sides of the negative strip of lithium metal, and the rollers press the surface of the negative strip of lithium metal when the negative strip of lithium metal passes through the middle of the upper and lower rollers, so as to flatten dendrites on the surface of the negative strip of lithium metal. The dendrite flattening equipment can also be vibration equipment, the vibration equipment 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 a lithium metal negative pole belt, and when the lithium metal negative pole belt passes through the middle of the vibration flat plate and the fixed flat plate, the flat plate striking force and the reaction force flatten the dendrite on the two surfaces of the lithium metal negative pole belt.
In this embodiment, the unwinding and winding of the lithium metal strip are driven by a micro motor inside the battery case. The power for flattening the dendrite and the power for the motor are supplied by external power during charging. Because of the low hardness of lithium metal, the power required to flatten the freshly produced dendrites is small, so its motor and flattening equipment is small, and a 10Ah cell dendrite flattening equipment is only half a pencil in size. Elimination of dendrites can be achieved in addition to mechanical methods: in the production and manufacturing process of the lithium metal negative electrode strip, two surfaces of the lithium metal negative electrode strip are subjected to flattening processing, and a diaphragm with the largest pore diameter is used. For example, the lithium metal strip is passed repeatedly between the upper and lower rollers, and the upper and lower rollers are polished like a mirror while pressing the upper and lower planes of the lithium metal strip. Suitable fiber wheels may also be selected to polish both surfaces of the lithium metal strip. The lithium ion battery adopts a diaphragm with large aperture, and the diameter is larger than 100 um.
In this embodiment, a charging counter or a battery capacity detector is disposed on the charger used with the lithium ion battery. When the charging time reaches a set value or the charging capacity reaches a set value, the charger sends a command of stopping charging, and the lithium metal negative pole belt flattening system is started firstly to perform dendrite flattening operation when the next charging is limited, and then the charging is performed. When a detection instrument of the charger considers that the dendritic crystal on the surface of the lithium metal strip needs to be flattened, the flattening equipment can automatically flatten the dendritic crystal after the charging plug is plugged. The battery of the present invention does not experience the difficulty of dendrites breaking through the separator. The above-mentioned predetermined value means a state where the dendrite growth just enters the membrane pores after several charges, which is an optimum state for flattening the dendrite. That is, the user does not have to be aware of when to perform the flattening process of the lithium metal strip. The user only needs to plug in the charger when using, and the problem just can be solved automatically to this product. The invention can obviously improve the cycle use times of the lithium cathode secondary battery by only polishing the surface of the lithium metal belt without adopting a flattening device and then adopting a diaphragm with large aperture. When the invention is added with mechanical flattening equipment, the purpose of long-term circulation can be realized.
The lithium metal strip has a small resistance to lithium ions, so that the thickness of the lithium metal strip can be increased when the lithium metal negative electrode strip is manufactured, and a lithium metal strip can be alternately combined with a plurality of positive electrode strips to form a battery roll which can be charged and discharged, as shown in fig. 4. When the positive tape in the working roll is charged, the working roll will rotate to pay out the positive tape, while the first positive roll will take in the positive tape. The second positive coil then releases the positive strip and takes up the lithium metal strip into the working coil, and continues charging. When the recombined working roll is fully charged, the working roll rotates to pay out the second positive pole strip, and the second positive pole roll takes in the positive pole strip. Finally, the above-described process is repeated to continue the charging of the third positive electrode roll. This is the operating principle of the open lithium negative multi-positive secondary battery. The multiple positive electrode rolls are alternately operated in this way during discharging. The multi-anode rotation method can improve the mass specific energy of the lithium metal battery of the invention by times, so that the endurance mileage is equal to or exceeds the level of gasoline fuel.
In this embodiment, position sensing elements are provided at both ends of the lithium metal negative electrode strip: for example, the magnetic object can send out an instruction when needed to stop the unwinding and winding rotation of the three types of rolls in the battery.
In this embodiment, the reels of the three types of rolls are provided with revolution counters to issue instructions to stop the pay-out and take-up rotation of the three types of rolls in the battery when necessary.
In this embodiment, the separator is attached to both sides of the positive electrode tape, and performs unwinding and winding movements together with the positive electrode tape. This can protect the active material of the positive electrode strip from being damaged and also can keep the active material in a wet state of the electrolyte.
In this embodiment, the working roll, the positive roll, the lithium metal negative roll, and the driving motor are sealed in the battery case, and the sealed space is filled with an electrolyte or an inert gas.
In this example, graphene chips were added to the positive electrode active material instead of carbon particles to increase the bending resistance of the positive electrode tape when manufacturing the positive electrode tape.
In the embodiment, the tab on the lithium metal negative electrode belt and the tab on the positive electrode belt in the working roll are electrically connected to each other through the elastic contact of the tabs and the electric connection sheets. The electrical connection tabs include positive to external electrical connection tabs and negative to external electrical connection tabs as shown in fig. 5. Elastic contact conduction is a commonly applied principle in electrical equipment, and the operation is safe and reliable.
When the invention is applied to high-power batteries, a plurality of same-type coils can be arranged on the reels of the three coils so as to increase the capacity.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (10)
1. An open lithium metal negative secondary battery comprises a sealed battery shell filled with electrolyte, and is characterized in that three types of coils are arranged in the sealed battery shell, wherein the first type of coil is a working coil, the second type of coil is a positive coil, the third type of coil is a lithium metal negative coil, the three types of coils 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 coil, the positive electrode belt, the lithium metal negative electrode belt and the diaphragm are discharged when the working coil is unwound and rotated, and the positive electrode coil and the negative electrode coil are wound and rotated to take in the positive electrode belt and the lithium metal negative electrode belt; and a dendrite flattening device is arranged between the working roll and the lithium metal negative pole roll, and when the lithium metal negative pole belt is released and retracted to move, the dendrite flattening device flattens dendrites on the surface of the lithium metal negative pole belt.
2. The open lithium metal negative secondary battery of claim 1, wherein the dendrite flattening device is a roller device including an upper roller and a lower roller respectively disposed on the upper and lower sides of the lithium metal negative strip, and the rollers press the surface of the lithium metal negative strip when the lithium metal negative strip passes through the middle of the upper and lower rollers, thereby flattening dendrites on the surface of the lithium metal negative strip.
3. The open lithium metal negative electrode secondary battery according to claim 1, wherein the dendrite flattening device is a vibrating device, the vibrating device comprises a vibrating plate and a fixing plate respectively disposed on the upper and lower sides of the lithium metal negative electrode belt, and the striking force and the reaction force of the vibrating plate and the fixing plate flatten dendrites on both surfaces of the lithium metal negative electrode belt when the lithium metal negative electrode belt passes through the middle of the vibrating plate and the fixing plate.
4. The open lithium metal negative electrode secondary battery according to claim 1, wherein the lithium metal negative electrode strip is manufactured by flattening both surfaces thereof; the thickness of the lithium metal negative electrode belt is increased, and a lithium metal negative electrode belt and a plurality of positive electrode belts are alternately formed into a battery roll which can be charged and discharged.
5. The open lithium metal negative electrode secondary battery according to claim 1, wherein the lithium ion battery employs a large-aperture separator with a diameter of more than 100 um; when the positive electrode belt is manufactured, graphene fragments are added into a positive electrode active material instead of carbon particles so as to increase the bending resistance of the positive electrode belt.
6. The open lithium metal negative electrode secondary battery according to claim 1, wherein a charger for use with 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 a command of stopping charging, and the lithium metal negative pole belt flattening system is started firstly to perform dendrite flattening operation when the next charging is limited, and then the charging is performed.
7. The open lithium metal negative electrode secondary battery as claimed in claim 1, wherein position sensing elements are provided at both ends of the lithium metal negative electrode strip, and the tab of the lithium metal negative electrode strip and the tab of the positive electrode strip in the working roll are electrically connected to each other by elastic contact of the tabs with the electrical connection sheet.
8. The open lithium metal negative electrode secondary battery according to claim 1, wherein the winding shaft of the three types of rolls is provided with a revolution counter to instruct, when necessary, the unwinding and winding of the three types of rolls in the battery to be stopped.
9. The open lithium metal negative electrode secondary battery of claim 1, wherein the separator is attached to both sides of the positive electrode tape and performs unwinding and winding movements together with the positive electrode tape.
10. The open lithium metal negative secondary battery according to claim 1, wherein the working roll, the positive roll, the lithium metal negative roll and the driving motor are 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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