CN214848694U - Device for coating lithium on negative pole piece - Google Patents
Device for coating lithium on negative pole piece Download PDFInfo
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- CN214848694U CN214848694U CN202120997269.7U CN202120997269U CN214848694U CN 214848694 U CN214848694 U CN 214848694U CN 202120997269 U CN202120997269 U CN 202120997269U CN 214848694 U CN214848694 U CN 214848694U
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
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Images
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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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- Secondary Cells (AREA)
Abstract
The utility model provides a device for coating lithium on a negative pole piece, which comprises a shell injected with electrolyte, wherein at least one guide roller is arranged in the shell, a feeding conductive roller is arranged outside the shell, and the negative pole piece bypasses the feeding conductive roller and the guide roller and is immersed in the electrolyte; the shell is internally provided with a lithium source immersed in electrolyte, the lithium source is electrically connected with the feeding conductive roller, and a circuit for electrically connecting the lithium source with the feeding conductive roller is provided with a current regulator. The primary battery is formed by communicating the negative pole piece with the lithium source, and the current between the negative pole piece and the lithium source is adjusted, so that the lithium coating amount of the negative pole piece is controlled, an SEI (solid electrolyte interphase) film is formed, the lithium coating is uniform, and the method has the characteristics of simple preparation method, uniform lithium coating, continuous production and the like.
Description
Technical Field
The utility model belongs to the technical field of the battery, especially, relate to a device that covers lithium to negative pole piece.
Background
The negative pole piece of the traditional lithium ion battery consists of a current collector, an active substance, a conductive agent, a thickening agent and a binder. The preparation process of the negative pole piece comprises the following steps: firstly, uniformly dispersing an active substance, a conductive agent and a binder into a solvent by a mechanical method to form slurry with good rheological property and stability; and uniformly coating the dispersed slurry on a current collector in a transfer and extrusion coating mode, and baking to obtain a dry negative pole piece with a certain negative active material loading capacity.
However, when the battery manufactured by the negative electrode plate is activated in formation and is recycled, side reactions can cause loss of a part of lithium source in the electrolyte, so that the first effect of the battery is low, and the cycle performance is reduced quickly.
The lithium ion battery is widely applied in the fields of electronics and new energy automobiles, the energy density and the cycle life of the battery are important concerns, and the first charging efficiency, the energy density and the cycle life of the battery can be improved by a method of coating lithium on a negative pole piece in advance. At present, lithium foil or lithium powder is attached to a negative electrode plate in a physical mode mainly by adopting a calendaring and laminating mode, then the calendered and laminated negative electrode plate is assembled into a battery, and laminated lithium is diffused into the negative electrode plate by standing at high temperature, however, the requirement of physical lithium coating on the lithium foil and the lithium powder is very strict, the uniformity of lithium coating on the negative electrode plate cannot be accurately controlled, and how to perform uniform lithium coating on the negative electrode plate becomes a technical difficulty.
CN111276669A discloses a prelithiation process of a negative electrode plate, which includes: mixing 80-98% of a negative electrode active material, 0.5-8% of a binder and 0.5-10% of a conductive agent to obtain a mixed material, and coating the mixed material on the surface of a current collector to obtain an initial negative electrode piece; covering the initial negative pole piece with the lithium foil or the lithium alloy coated with the base layer, and transferring the lithium foil or the lithium alloy to the surface and the inside of the initial negative pole piece through the micro-needle to obtain the lithium-coated metalA negative pole piece; the mode of microneedle transfer is selected from one or more times of rolling, squeezing or squeezing-standing; the density of the micro-needle is 10-10000 needles/cm2And rolling the lithium-coated metal negative pole piece, and soaking the rolled lithium-coated metal negative pole piece in electrolyte to obtain a pre-lithiated negative pole piece. The method does not introduce any toxic substance, has short process time and rich controllable parameters, but still has the problem that the uniformity of the lithium coating cannot be accurately controlled.
CN109449375A discloses a lithium supplement negative pole piece and a preparation method thereof, wherein the lithium supplement negative pole piece comprises a pole piece and a lithium supplement coating coated on the outer side of the pole piece, and the lithium supplement coating contains lithium metal powder, ceramic powder and/or inorganic salt powder. The preparation method comprises the following steps: mixing lithium metal powder, ceramic powder and/or inorganic salt powder under a protective atmosphere to obtain mixed powder, mixing the mixed powder, a binder and an organic solvent to obtain slurry, and coating the slurry on the surface of a negative pole piece to obtain the lithium-supplement negative pole piece. The lithium supplementing method can accurately control the lithium supplementing quantity, and the problem that the lithium covering uniformity cannot be controlled still exists.
CN112310484A discloses a pole piece lithium supplementing device and a pole piece lithium supplementing method, wherein the pole piece lithium supplementing device comprises a lithium material coating mechanism and a rolling mechanism. The lithium material coating mechanism is used for coating lithium material on the surface of the base material passing through the lithium material coating mechanism. The roll pressing mechanism comprises a first laminating roller and a second laminating roller which are oppositely arranged, and the first laminating roller and the second laminating roller are used for rolling a pole piece passing through between the first laminating roller and the second laminating roller and the base material coated with the lithium material, so that the lithium material on the base material is transferred to the pole piece. In the process of the substrate conveying, the lithium material coating mechanism coats the lithium material on the surface of the substrate passing through the lithium material coating mechanism, so that a lithium film with smaller thickness is formed on the surface of the substrate, the lithium supplementing efficiency of the pole piece is improved, and the problem that the lithium coating uniformity cannot be controlled still exists.
The existing lithium coating devices for the negative pole piece have the problems of complex process, non-uniform lithium coating, high cost and the like, so that the problem that how to ensure the uniform lithium coating of the negative pole piece under the conditions of simple process and low cost in the preparation process of the negative pole piece becomes the problem which needs to be solved urgently at present.
SUMMERY OF THE UTILITY MODEL
Not enough to prior art exists, the utility model aims to provide a device that covers lithium to negative pole piece forms the primary cell through negative pole piece and lithium source intercommunication to adjust the electric current size between negative pole piece and the lithium source, realize covering the lithium volume to the negative pole piece and control, and form the SEI membrane, it is even to make to cover the lithium, the battery after the equipment can directly adopt the electric current charge more than 0.1C, have preparation method simple, cover characteristics such as lithium is even and can serialization production.
To achieve the purpose, the utility model adopts the following technical proposal:
the utility model provides a device for coating lithium on a negative pole piece, which comprises a shell injected with electrolyte, wherein at least one guide roller is arranged in the shell, a feeding conductive roller is arranged outside the shell, and the negative pole piece bypasses the feeding conductive roller and the guide roller and is immersed in the electrolyte; the shell is internally provided with a lithium source immersed in electrolyte, the lithium source is electrically connected with the feeding conductive roller, and a circuit for electrically connecting the lithium source with the feeding conductive roller is provided with a current regulator.
In the utility model, the negative pole piece is connected with the lithium source through the feeding conductive roller to form a primary battery, the current between the negative pole piece and the feeding conductive roller is adjusted through the current adjuster, and the lithium is uniformly distributed on the surfaces of the two sides of the negative pole piece by electrochemical lithium coating, and the lithium coating amount can be accurately controlled by adjusting the size and time of the current; furthermore, as the electrochemical lithium coating is adopted, the side reaction is simultaneously carried out on the interface of the negative pole piece in contact with the electrolyte to form an SEI film, so that the consumption of active lithium in the electrolyte and the positive pole material is reduced during the formation of the battery, the first coulomb efficiency and the later cycle performance of the battery are effectively improved, and the method has the characteristics of simple preparation method, uniform lithium coating, continuous production and the like.
It should be noted that, the present invention does not have specific requirements and special limitations on the form of the current regulator, and those skilled in the art can reasonably select the form of the current regulator according to design needs, and the current regulator capable of regulating the current magnitude in the circuit can be used in the present invention, and the current regulator can be an active device, for example, a dc power supply analyzer, and can also be a passive device, for example, the current regulator is a rheostat.
It should be noted that the external circuit current flows through the negative electrode plate, the current regulator and the lithium source in sequence, and the current direction in the electrolytic cell is just opposite.
As a preferred technical scheme of the utility model, the casing in be provided with supersonic generator.
The utility model discloses a set up supersonic generator in the casing, make the electrolyte concentration distribution in the casing even to further improve the homogeneity that covers the lithium in-process.
The lithium source includes a lithium block and/or a lithium plate.
The feeding conductive roller comprises an upper feeding roller and a lower feeding roller, the upper feeding roller and the lower feeding roller are pressed on the negative pole piece, and the lithium source is electrically connected with the upper feeding roller.
And the feeding upper roller and the feeding lower roller are both made of conductive rubber.
The conductive rubber is prepared by uniformly distributing conductive particles such as silver-plated glass, silver-plated aluminum, silver and the like in silicone rubber, and contacting the conductive particles through pressure to achieve good conductive performance.
The guide rollers are arranged in the shell in a staggered mode, and the negative pole pieces are wound around the guide rollers and are arranged in a snake shape in the shell.
The guide rollers are arranged on two sides of the lithium source in a staggered mode, and the negative pole pieces are arranged on two sides of the lithium source in a snake shape.
The negative pole piece bypasses the guide roller, and the negative pole piece moves in a snake shape along the vertical direction.
As a preferred technical scheme of the utility model, be provided with level sensor on the casing, level sensor is used for detecting the liquid level height of electrolyte in the casing.
The shell is externally connected with a liquid storage tank for storing electrolyte, and a pipeline for connecting the liquid storage tank and the shell is provided with an electromagnetic valve.
And a compression pump is also arranged on a pipeline connecting the liquid storage tank and the shell.
The device also comprises a controller, wherein the controller is respectively and independently electrically connected with the electromagnetic valve, the compression pump, the liquid level sensor and the current regulator, and is used for receiving signals sent by the liquid level sensor and feeding back and regulating the opening of the electromagnetic valve, the opening of the compression pump and the current of the current regulator.
The utility model discloses an electrolyte height in the controller control casing, when level sensor detected the liquid level height of electrolyte and was less than topmost layer guide roll cross-section circle minimum place horizontal plane, controller feedback control solenoid valve and compression pump were opened, were pour into electrolyte into to the casing by the liquid storage pot to the liquid level that makes electrolyte is less than topmost layer guide roll cross-section circle maximum place horizontal plane.
Illustratively, the utility model provides a method for adopting foretell device that covers lithium to negative pole piece, the method specifically include following step:
coating, rolling and vacuum drying are sequentially carried out on a current collector, and the density of the coated double-coated surface is 80-400 g/m2The compacted density of the rolled negative pole piece is 1.3-1.6 g/cm3The vacuum drying temperature is 80-180 ℃, the vacuum degree is 10-200 Pa, the time is 6-24 h, and the moisture mass content of the dried negative pole piece is 80-150 ppm;
(II) winding the negative pole piece onto a guide roller through a feeding conductive roller, immersing the negative pole piece into an electrolyte, communicating the negative pole piece with a lithium source through the feeding conductive roller to form a primary battery, regulating the current between the negative pole piece and the lithium source by a current regulator under a protective atmosphere to electrochemically coat lithium on the negative pole piece, wherein the regulating step comprises at least two times of current regulation, the range of the current regulation is 0.005-1C, the time is 0-3 h, the current and the time of the current regulation are sequentially increased each time, and after ultrasonic cleaning, the negative pole piece is prepared, wherein the lithium coating amount of the negative pole piece is less than or equal to 20%, and the preferred amount is 6-20%.
The lithium coating amount is the content of lithium coated/the content of lithium theoretically capable of being intercalated in the negative electrode.
Compared with the prior art, the beneficial effects of the utility model are that:
in the utility model, the negative pole piece is connected with the lithium source through the feeding conductive roller to form a primary battery, the current between the negative pole piece and the feeding conductive roller is adjusted through the current adjuster, and the lithium is uniformly distributed on the surfaces of the two sides of the negative pole piece by electrochemical lithium coating, and the lithium coating amount can be accurately controlled by adjusting the size and time of the current; furthermore, as the electrochemical lithium coating is adopted, the side reaction is simultaneously carried out on the interface of the negative pole piece in contact with the electrolyte to form an SEI film, so that the consumption of active lithium in the electrolyte and the positive pole material is reduced during the formation of the battery, the first coulomb efficiency and the later cycle performance of the battery are effectively improved, and the method has the characteristics of simple preparation method, uniform lithium coating, continuous production and the like.
Drawings
Fig. 1 is a schematic structural diagram of a device for coating lithium on a negative electrode plate according to an embodiment of the present invention.
Wherein, 1-shell; 2-a lithium source; 3-an electrolyte; 4-feeding a conductive roller; 5-a current regulator; 6-a liquid storage tank; 7-an electromagnetic valve; 8-a liquid level sensor; 9-a guide roller; 10-compression pump.
Detailed Description
It is to be understood that in the description of the present invention, the terms "central," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in the orientation or positional relationship indicated in the drawings for the purpose of convenience and simplicity of description, and are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are not to be construed as limiting the present invention.
It should be noted that, unless explicitly stated or limited otherwise, the terms "disposed," "connected" and "connected" in the description of the present invention are to be construed broadly, and may for example be fixedly connected, detachably connected or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.
The technical solution of the present invention will be further explained by the following embodiments.
In a specific embodiment, the utility model provides a device for coating lithium on a negative pole piece, as shown in fig. 1, the device comprises a shell 1 filled with electrolyte 3, at least one guide roller 9 is arranged in the shell 1, a feeding conductive roller 4 is arranged outside the shell 1, and the negative pole piece bypasses the feeding conductive roller 4 and the guide roller 9 and is immersed in the electrolyte 3; the shell 1 is also internally provided with a lithium source 2 immersed in the electrolyte 3, the lithium source 2 is electrically connected with the feeding conductive roller 4, a current regulator 5 is arranged on a circuit electrically connected with the lithium source 2 and the feeding conductive roller 4, and the current flows through the negative pole piece, the current regulator 5 and the lithium source 2 in sequence.
In the utility model, the negative pole piece is connected with the lithium source 2 through the feeding conductive roller 4 to form a primary battery, the current between the negative pole piece and the feeding conductive roller 4 is adjusted through the current adjuster 5, and the lithium is evenly distributed on the surfaces of the two sides of the negative pole piece by using the electrochemical lithium coating, and the lithium coating amount can be accurately controlled by adjusting the size and time of the current; furthermore, as the electrochemical lithium coating is adopted, the side reaction is simultaneously carried out on the interface of the negative pole piece in contact with the electrolyte 3 to form an SEI film, so that the consumption of active lithium in the electrolyte 3 and the positive pole material is reduced during the formation of the battery, the first coulomb efficiency and the later cycle performance of the battery are effectively improved, and the method has the characteristics of simple preparation method, uniform lithium coating, continuous production and the like.
Further, be provided with supersonic generator in the casing 1, the utility model discloses a set up supersonic generator in casing 1, make 3 concentration distribution of electrolyte in the casing 1 even to further improve the homogeneity that covers the lithium in-process.
Further, the lithium source 2 comprises a lithium block and/or a lithium plate, the feeding conductive roller 4 comprises a feeding upper roller and a feeding lower roller, the feeding upper roller and the feeding lower roller are in press fit with the negative pole piece, the lithium source 2 is electrically connected with the feeding upper roller, and the feeding upper roller and the feeding lower roller are made of conductive rubber.
Further, the guide roll 9 sets up in the casing 1 is crisscross, and the negative pole piece is snakelike arranging in casing 1 around guide roll 9, and further, guide roll 9 all staggers the arranging in the both sides of lithium source 2, and the negative pole piece all is snakelike arranging in the both sides of lithium source 2, and the negative pole piece is around guide roll 9, and the negative pole piece is snakelike motion along vertical direction.
Still be provided with level sensor 8 on the casing 1, level sensor 8 is used for detecting the liquid level height of electrolyte 3 in the casing 1. The shell 1 is externally connected with a liquid storage tank 6 for storing electrolyte 3, a solenoid valve 7 is arranged on a pipeline connecting the liquid storage tank 6 and the shell 1, and a compression pump 10 is also arranged on a pipeline connecting the liquid storage tank 6 and the shell 1.
Further, the device also comprises a controller, the controller is respectively and independently electrically connected with the electromagnetic valve 7, the compression pump 10, the liquid level sensor 8 and the current regulator 5, and the controller is used for receiving a signal sent by the liquid level sensor 8 and feeding back and regulating the opening of the electromagnetic valve 7, the opening of the compression pump 10 and the current of the current regulator 5.
Illustratively, the utility model provides a method for adopting foretell device that covers lithium to negative pole piece, the method specifically include following step:
coating, rolling and vacuum drying are sequentially carried out on a current collector, and the density of the coated double-coated surface is 80-400 g/m2The compacted density of the rolled negative pole piece is 1.3-1.6 g/cm3The vacuum drying temperature is 80-180 ℃, the vacuum degree is 10-200 Pa, the time is 6-24 h, and the moisture mass content of the dried negative pole piece is 80-150 ppm;
(II) winding the negative pole piece onto a guide roller 9 through a feeding conductive roller 4, immersing the negative pole piece into an electrolyte 3, communicating the negative pole piece with a lithium source 2 through the feeding conductive roller 4 to form a primary battery, regulating the current between the negative pole piece and the lithium source 2 by a current regulator 5 under the protective atmosphere of nitrogen and/or argon to electrochemically coat lithium on the negative pole piece, wherein the regulating step comprises at least two times of current regulation, the range of the current regulation is 0.005-1C, the time is 0-3 h, the current and the time of the current regulation are sequentially increased each time, and after ultrasonic cleaning, the lithium-coated negative pole piece is obtained, the lithium coating amount of the lithium-coated negative pole piece is less than or equal to 20%, and the preferred lithium coating amount is 6-20%.
And assembling the negative pole piece battery into a battery, and sequentially carrying out formation and capacity grading after the battery is packaged, wherein the charging interval is 4-6 min in the formation process. The formation current is more than or equal to 0.1C when the formation process is started.
In the following examples and comparative examples, the area of the negative electrode sheet immersed in the electrolyte was 600mm x 50mm, and the gram volume of graphite was 343 mAh/g.
Example 1
The embodiment provides a method for coating lithium on a negative electrode plate by using a device for coating lithium on a negative electrode plate, which is provided in a specific embodiment, and the method specifically includes the following steps:
coating, rolling and vacuum drying a current collector in sequence, wherein the density of the coated double-coated surface is 150g/m2The compacted density of the rolled negative pole piece is 1.5g/cm3The temperature of vacuum drying is 130 ℃, the vacuum degree is 100Pa, the time is 15h, and the moisture mass content of the dried negative pole piece is 110 ppm;
(II) winding the negative pole piece onto a guide roller 9 through a feeding conductive roller 4, immersing the negative pole piece into an electrolyte 3, communicating the negative pole piece with a lithium source 2 through the feeding conductive roller 4 to form a primary battery, regulating the current between the negative pole piece and the lithium source 2 to electrochemically coat lithium on the negative pole piece in a nitrogen atmosphere, wherein the regulating step of the current regulator 5 comprises three times of current regulation, the first time of current regulation is 0.05C, the time is 72s, the second time of current regulation is 0.1C, the time is 324s, the third time of current regulation is 0.5C, the time is 576s, after ultrasonic cleaning, obtaining the lithium-coated negative pole piece, and the lithium coating amount of the lithium-coated negative pole piece is 9%.
The embodiment also provides a battery, which comprises the lithium-coated negative pole piece, the battery is formed to reach 30% SOC, the interval in the charging process is 5min, the formation is divided into two steps, the current of the first formation is 0.1C, the time is 2160s, the current of the second formation is 0.5C, and the time is 1080 s.
Example 2
The embodiment provides a method for coating lithium on a negative electrode plate by using a device for coating lithium on a negative electrode plate, which is provided in a specific embodiment, and the method specifically includes the following steps:
coating, rolling and vacuum drying a current collector in sequence, wherein the density of the coated double-coated surface is 96g/m2The compacted density of the rolled negative pole piece is 1.3g/cm3The vacuum drying temperature is 80 ℃, the vacuum degree is 200Pa, the time is 24 hours, and the moisture mass content of the dried negative pole piece is 120 ppm;
(II) winding the negative pole piece onto a guide roller 9 through a feeding conductive roller 4, immersing the negative pole piece into an electrolyte 3, communicating the negative pole piece with a lithium source 2 through the feeding conductive roller 4 to form a primary battery, regulating the current between the negative pole piece and the lithium source 2 to electrochemically coat lithium on the negative pole piece under the argon atmosphere, wherein the regulating step of the current regulator 5 comprises two current regulation steps, the first current regulation is 0.1C for 360s, the second current regulation is 0.5C for 864s, and after ultrasonic cleaning, the lithium-coated negative pole piece is obtained, and the lithium coating amount of the lithium-coated negative pole piece is 13%.
The embodiment also provides a battery, which comprises the lithium-coated negative electrode plate obtained in the above way, the battery is formed to reach 30% SOC, the interval in the charging process is 5min, the formation is divided into two steps, the current for the first formation is 0.1C, the time is 2520s, the current for the second formation is 0.5C, and the time is 720 s.
Example 3
The embodiment provides a method for coating lithium on a negative electrode plate by using a device for coating lithium on a negative electrode plate, which is provided in a specific embodiment, and the method specifically includes the following steps:
coating, rolling and vacuum drying a current collector in sequence, wherein the density of the coated double-coated surface is 200g/m2The compacted density of the rolled negative pole piece is 1.6g/cm3The temperature of vacuum drying is 180 ℃, the vacuum degree is 10Pa, the time is 6 hours, and the moisture mass content of the dried negative pole piece is 150 ppm;
(II) winding the negative pole piece onto a guide roller 9 through a feeding conductive roller 4, immersing the negative pole piece into an electrolyte 3, communicating the negative pole piece with a lithium source 2 through the feeding conductive roller 4 to form a primary battery, regulating the current between the negative pole piece and the lithium source 2 to electrochemically coat lithium on the negative pole piece in a nitrogen atmosphere, wherein the regulating step of the current regulator 5 comprises two current regulation steps, the first current regulation is 0.1C for 360s, the second current regulation is 0.5C for 1152s, and after ultrasonic cleaning, the lithium-coated negative pole piece is obtained, and the lithium coating amount of the lithium-coated negative pole piece is 17%.
The embodiment also provides a battery, the battery comprises the negative pole piece coated with lithium, the battery is formed to reach 30% SOC, the interval in the charging process is 5min, the formation is divided into two steps, the current of the first formation is 0.1C, the time is 2880s, the current of the second formation is 0.5C, and the time is 360 s.
Example 4
The embodiment provides a method for coating lithium on a negative electrode plate by using a device for coating lithium on a negative electrode plate, which is provided in a specific embodiment, and the method specifically includes the following steps:
coating, rolling and vacuum drying a current collector in sequence, wherein the density of the coated double-coated surface is 100g/m2The compacted density of the rolled negative pole piece is 1.5g/cm3The temperature of vacuum drying is 150 ℃, the vacuum degree is 100Pa, the time is 12h, and the moisture content of the dried negative pole pieceThe amount content is 80 ppm;
(II) winding the negative pole piece onto a guide roller 9 through a feeding conductive roller 4, immersing the negative pole piece into an electrolyte 3, communicating the negative pole piece with a lithium source 2 through the feeding conductive roller 4 to form a primary battery, regulating the current between the negative pole piece and the lithium source 2 to electrochemically coat lithium on the negative pole piece under argon, wherein the step of regulating the current regulator 5 comprises two current regulation steps, the first current regulation is 0.1C for 360s, the second current regulation is 0.5C for 1368s, and after ultrasonic cleaning, the lithium-coated negative pole piece is obtained, and the lithium coating amount of the lithium-coated negative pole piece is 20%.
The embodiment also provides a battery, which comprises the lithium-coated negative pole piece, the battery is formed to reach 30% SOC, the interval in the charging process is 5min, the formation is only one step, the current of the formation is 0.1C, and the time is 3600 s.
Example 5
The embodiment provides a method for coating lithium on a negative electrode plate by using the device for coating lithium on a negative electrode plate provided in a specific embodiment, which is different from embodiment 1 in that the first current is adjusted to be 0.05C for 72s, the second current is adjusted to be 0.1C for 324s, the third current is adjusted to be 0.5C for 360s, the lithium coating amount of the lithium-coated negative electrode plate is 6%, and other preparation steps and parameters are completely the same as those of embodiment 1.
The embodiment also provides a battery, which comprises the lithium-coated negative pole piece, the battery is formed to reach 30% SOC, the interval in the charging process is 5min, the formation is divided into two steps, the current of the first formation is 0.1C, the time is 1440s, the current of the second formation is 0.5C, and the time is 1440 s.
Example 6
This example provides a method for coating lithium on a negative electrode plate by using the apparatus for coating lithium on a negative electrode plate provided in an embodiment, which is different from example 1 in that the first current is adjusted to 0.003C, and the rest of the parameters are identical to those in example 1.
Example 7
This example provides a method for coating lithium on a negative electrode plate by using the apparatus for coating lithium on a negative electrode plate provided in a specific embodiment, which is different from example 1 in that the third current is adjusted to 1.2C, and the rest of the parameters are identical to those in example 1.
Comparative example 1
This comparative example provides a method of making a negative electrode tab, which differs from example 1 in that step (ii) is not performed.
The negative pole piece provided by the comparative example is not coated with lithium, so that the formation can not be started from the current of 0.1C, the battery formation reaches 30% SOC, the interval in the charging process is 5min, the formation is divided into two steps, the current of the first formation is 0.05C and the time is 720s, the current of the second formation is 0.5C and the time is 2088 s.
Comparative example 2
The comparative example provides a lithium coating method for a negative electrode plate, compared with example 1, the difference is that step (II) is conventional rolling lithium coating for the lithium plate, and the lithium coating method specifically comprises the following steps:
coating, rolling and vacuum drying a current collector in sequence, wherein the density of the coated double-coated surface is 150g/m2The compacted density of the rolled negative pole piece is 1.5g/cm3The temperature of vacuum drying is 130 ℃, the vacuum degree is 100Pa, the time is 15h, and the moisture mass content of the dried negative pole piece is 20 ppm;
and (II) pressing the lithium sheet onto the surface of the negative pole piece in a rolling manner to obtain the lithium-coated negative pole piece, wherein the lithium coating amount of the lithium-coated negative pole piece is 9%.
Wherein, the assembling method of the battery in the above examples and comparative examples comprises: correspondingly welding positive and negative electrode tabs at exposed foil positions of the positive electrode piece and the negative electrode piece, and sequentially aligning the diaphragm, the negative electrode piece, the diaphragm and the positive electrode piece from bottom to top, wherein the diaphragm exceeds the negative electrode piece, the negative electrode piece exceeds the positive electrode piece, the coiled diaphragm exceeds the negative electrode piece by 0.5-1.5 circles, and the negative electrode piece exceeds the positive electrode piece by 1.5-2.0 circles. Then the components are wound into a winding core with a fixed size, a negative coating area at the winding position of the winding core completely covers a positive coating area, and a winding core positive lug which is wound is welded with a top cover assembly; filling liquid into the battery, placing the winding core with the top cover assembly welded thereon into a steel shell, welding a negative electrode tab with the steel shell, and then injecting electrolyte 3 into the steel shell; and (3) packaging the battery, namely packaging the top cover assembly and the steel shell, standing for a certain time after packaging, and completely soaking the winding core by the electrolyte 3.
The formation parameters of the examples and the comparative examples are shown in table 1, and the formed battery is subjected to capacity grading at room temperature, is stood for 30min, is charged to 3.65V at a constant current of 0.5C, is stood for 5min, is further charged at a constant voltage of 3.65V until the current is reduced to 0.05C, is stood for 5min, and is then discharged to 2.5V at a constant current of 0.5C.
After the batteries prepared in the above examples and comparative examples were subjected to capacity grading, the first coulombic efficiency and the capacity retention rate at 45 ℃ after 1000 cycles of 1C charge/1C discharge were measured, and the test results are shown in table 2.
TABLE 1
TABLE 2
| Lithium content/% | First coulomb efficiency% | Capacity retention ratio/%) | |
| Example 1 | 9 | 95.2 | 94.8 |
| Example 2 | 13 | 96.1 | 94.3 |
| Example 3 | 17 | 96.6 | 94.0 |
| Example 4 | 20 | 97.2 | 93.8 |
| Example 5 | 6 | 93.8 | 92.6 |
| Example 6 | 8.9 | 94.2 | 92.6 |
| Example 7 | 11.3 | 93.7 | 93.4 |
| Comparative example 1 | 0 | 85.3 | 89.5 |
| Comparative example 2 | 9 | 90.3 | 89.6 |
From the above table, it can be seen that:
(1) embodiment 1 compares with embodiment 6, 7, and embodiment 1's first coulombic efficiency, capacity retention rate are superior to embodiment 6, 7, can see from this that, the utility model discloses a control current intensity and time in the current regulation to covering lithium volume and carrying out accurate control, and can guarantee to cover the homogeneity of lithium, if current regulation is less than 0.005C, then there is the covering lithium that needs for a long time, influence pole piece preparation efficiency; if the current is adjusted to be larger than 1.2C, the current is too large in the lithium coating process, so that an SEI film is formed compactly, the resistance of a pole piece is increased, the multiplying power of the battery is influenced, and the lithium coating effect is poor.
(2) Embodiment 1 compares with comparative example 1, 2, and the first coulombic efficiency, the capacity retention ratio of embodiment 1 are superior to comparative example 1, 2, can see from this, the utility model discloses in, the negative pole piece is connected with lithium source 2 through feeding conducting roller 4, forms the galvanic cell, adjusts the electric current between negative pole piece and the feeding conducting roller 4 through current regulator 5, utilizes the electrochemistry to cover lithium, makes lithium evenly distributed at the both sides surface of negative pole piece to can be through the size and the time of adjusting the electric current, to covering lithium volume accurate control; furthermore, as the electrochemical lithium coating is adopted, the side reaction is simultaneously carried out on the interface of the negative pole piece in contact with the electrolyte 3 to form an SEI film, so that the consumption of active lithium in the electrolyte 3 and the positive pole material is reduced during the formation of the battery, the first coulomb efficiency and the later cycle performance of the battery are effectively improved, and the method has the characteristics of simple preparation method, uniform lithium coating, continuous production and the like.
The applicant states that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and those skilled in the art should understand that any changes or substitutions easily conceivable by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure scope of the present invention.
Claims (10)
1. The device for coating the lithium on the negative pole piece is characterized by comprising a shell, at least one guide roller is arranged in the shell, a feeding conductive roller is arranged outside the shell, and the negative pole piece bypasses the feeding conductive roller and the guide roller and is immersed in the electrolyte;
the shell is internally provided with a lithium source immersed in electrolyte, the lithium source is electrically connected with the feeding conductive roller, and a circuit for electrically connecting the lithium source with the feeding conductive roller is provided with a current regulator.
2. The device for coating lithium on the negative pole piece is characterized in that an ultrasonic generator is arranged in the shell.
3. The device for coating lithium on the negative pole piece is characterized in that the lithium source comprises a lithium block and/or a lithium plate.
4. The device for coating lithium on the negative pole piece according to claim 1, wherein the feeding conductive roller comprises an upper feeding roller and a lower feeding roller, the upper feeding roller and the lower feeding roller press-fit the negative pole piece, and the lithium source is electrically connected with the upper feeding roller;
and the feeding upper roller and the feeding lower roller are both made of conductive rubber.
5. The device for coating lithium on the negative pole piece according to claim 1, wherein the guide rollers are staggered in the shell, and the negative pole pieces are arranged in a snake shape in the shell around the guide rollers.
6. The device for coating lithium on the negative pole piece according to claim 5, wherein the guide rollers are arranged in a staggered manner on both sides of the lithium source, and the negative pole piece is arranged in a serpentine manner on both sides of the lithium source.
7. The device for coating lithium on the negative pole piece is characterized in that the negative pole piece bypasses the guide roller and moves in a snake shape along the vertical direction.
8. The device for coating lithium on the negative pole piece is characterized in that a liquid level sensor is arranged on the shell and used for detecting the liquid level height of electrolyte in the shell.
9. The device for coating lithium on the negative pole piece is characterized in that the shell is externally connected with a liquid storage tank for storing electrolyte, and a pipeline for connecting the liquid storage tank with the shell is provided with an electromagnetic valve;
and a compression pump is also arranged on a pipeline connecting the liquid storage tank and the shell.
10. The device for coating lithium on the negative electrode plate of claim 9, further comprising a controller, wherein the controller is electrically connected to the solenoid valve, the compression pump, the liquid level sensor and the current regulator independently, and is configured to receive a signal from the liquid level sensor and perform feedback regulation on the opening of the solenoid valve, the opening of the compression pump and the current of the current regulator.
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| CN113224259A (en) * | 2021-05-11 | 2021-08-06 | 湖北亿纬动力有限公司 | Device for coating lithium on negative pole piece, lithium coating method, negative pole piece and battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113224259A (en) * | 2021-05-11 | 2021-08-06 | 湖北亿纬动力有限公司 | Device for coating lithium on negative pole piece, lithium coating method, negative pole piece and battery |
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