CN116190549A - Lithium supplementing method for battery and battery prepared by adopting lithium supplementing method - Google Patents

Lithium supplementing method for battery and battery prepared by adopting lithium supplementing method Download PDF

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CN116190549A
CN116190549A CN202211648006.0A CN202211648006A CN116190549A CN 116190549 A CN116190549 A CN 116190549A CN 202211648006 A CN202211648006 A CN 202211648006A CN 116190549 A CN116190549 A CN 116190549A
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lithium
supplementing
battery
electrode
ion battery
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周槐
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Dongguan Weike Battery Co ltd
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Dongguan Weike Battery Co ltd
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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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • 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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Abstract

The invention provides a battery lithium supplementing method and a battery prepared by adopting the same, comprising the following steps: preparing a semi-finished lithium ion battery and preparing a lithium supplementing electrode; and placing the lithium supplementing electrode in an air bag filled with protective gas, and then supplementing lithium to the semi-finished lithium ion battery. The method can accurately control the coulomb efficiency improvement amplitude and avoid excessive lithium supplementation; lithium supplementing of the lithium battery by using lithium powder can be avoided, and compared with a main flow process, the process safety can be improved; substantially no degradation to battery performance; the lithium ion battery is obtained by adopting the lithium supplementing method. The lithium supplementing electrode can supplement lithium to the positive electrode and the negative electrode respectively; the lithium source is lithium sheet; the lithium supplementing electrode is placed in the air bag, and the air bag is reserved during formation; and the lithium supplementing step is to supplement lithium after formation, and the lithium supplementing amount is calculated through current and time.

Description

Lithium supplementing method for battery and battery prepared by adopting lithium supplementing method
Technical Field
The invention belongs to the technical field of ion batteries, and particularly relates to a battery lithium supplementing method and a battery prepared by adopting the same.
Background
Along with the technical development of 3C digital products, the volume energy density of the lithium ion battery is also higher and higher, so that the high development of a silicon carbon negative electrode is promoted, the silicon carbon negative electrode has a gram capacity far higher than that of a graphite material, but the problem of low coulomb efficiency of the first charge and discharge exists due to the characteristics of the material, and the problem of low coulomb efficiency of the lithium ion battery is solved in the prior art mainly in two directions: 1. a positive electrode lithium supplementing additive; 2. and supplementing lithium to the negative electrode plate process.
CN109004304a, "soft-package lithium ion battery lithium supplementing method, lithium ion battery preparation method and middle lithium supplementing battery", disclosed in chinese patent application, is an electrolyte-containing air bag formed by placing a lithium supplementing electrode in a battery cell package, i.e. the lithium supplementing electrode is also in the air bag, but also contains electrolyte, and lithium is not directly supplemented by using a lithium sheet; chinese patent application CN109103419A (lithium ion battery negative electrode lithium supplementing electrode) and preparation method thereof, wherein an organic film layer is coated on the surface of a pre-lithium electrode, and the organic film layer is formed by dissolving electrolyte lithium salt in an organic solvent.
The method has the problems of high cost, high safety risk, performance degradation, unstable coulomb efficiency improvement and the like.
Disclosure of Invention
The invention aims to develop a battery lithium supplementing method and a battery prepared by the method, so that the discharge capacity of the lithium battery is improved, the safety risk is reduced, and meanwhile, the lithium supplementing amount can be accurate.
The invention provides a battery lithium supplementing method, which comprises the following steps: preparing a semi-finished lithium ion battery and preparing a lithium supplementing electrode; and placing the lithium supplementing electrode in an air bag filled with protective gas, and then supplementing lithium to the semi-finished lithium ion battery.
Further, the method for preparing the semi-finished lithium ion battery comprises the following steps:
step 1: providing a current collector, and coating active material materials on the current collector in a gap or continuous coating mode to respectively prepare a positive electrode precursor and a negative electrode precursor;
step 2: manufacturing a positive electrode precursor and a negative electrode precursor manufactured in the step 1 into a lug or a multi-lug structure to obtain a positive electrode plate and a negative electrode plate;
step 3: the manufactured positive plate and the manufactured negative plate are respectively manufactured into a positive bare cell and a negative bare cell with a diaphragm in a winding mode; the diaphragm is made by a wet process;
step 4: packaging the positive electrode bare cell and the negative electrode bare cell by using an aluminum plastic film, and baking;
step 5: and (5) injecting liquid after baking to obtain the semi-finished lithium ion battery.
In the step 1, the positive electrode precursor is prepared by mixing LCO/sodium cobaltate, SP and PVDF according to a ratio of 97:2:1 in the mass ratio of NMP, stirring for 8-10h to uniformly disperse the mixture, and obtaining mixed slurry; coating the mixed slurry on the surface of a current collector aluminum foil at a single-sided surface density of 4m/min, drying at 80-120 ℃, and then rolling at normal temperature for 1-48h to prepare the positive electrode precursor.
In the step 1, the negative electrode precursor is prepared into tablets by mixing graphite, silicon oxide, SP, a dispersing agent (CMC) and a binder (SBR) according to the following ratio of 87.3:10:0.3:1.1:1.3, dissolving the mixture in deionized water, and stirring for 8-10 hours to uniformly disperse the mixture to obtain mixed slurry; and (3) coating the mixed slurry on the surface of a current collector copper foil at a single-sided surface density of 4m/min, drying at 100+/-5 ℃, and then carrying out rolling treatment at normal temperature for 1-48h to prepare the anode precursor.
In the step 4, the aluminum plastic film is DNP113um.
In the step 4, the baking temperature is 85+/-1 ℃ and the baking time is 24-72 hours.
Further, the method for preparing the lithium supplementing electrode comprises the following steps:
manufacturing three electrode lugs in a glove box, and baking the materials in an inert gas environment; fixing the lithium sheet and the tab together in a diaphragm winding mode to obtain a lithium supplementing electrode; the diaphragm is made by a wet process.
In the method for preparing the lithium-supplementing electrode, the baking temperature is 85+/-1 ℃ and the time is 24-72 hours.
In the method for preparing the lithium-supplementing electrode, the inert atmosphere is argon atmosphere.
Further, the lithium supplementing process comprises the following steps:
(1) Placing the lithium supplementing electrode at the relative position of a seal of the semi-finished lithium ion battery;
(2) Packaging the lithium supplementing electrode by adopting an air bag filled with protective gas;
(3) The battery is placed on a charging and discharging device for lithium supplement after standing and formation, and charging and discharging are carried out to complete the electricity supplement.
In the step (3), the battery is subjected to secondary sealing, capacity separation and edge folding processes after the battery is charged, and the manufacturing is completed.
In the step (3), during charge and discharge, the Ni tab is in butt joint with the positive electrode of the device, the lithium supplementing electrode is in butt joint with the negative electrode and/or the positive electrode of the charge and discharge device, the device adopts a discharge step, the discharge current is 0.1C, and the discharge capacity is designed to be 3-6% of the design capacity of the battery.
Further, the semi-finished lithium ion battery is replaced by a semi-finished sodium ion battery, and the lithium supplementing method is replaced by a sodium supplementing method.
In a second aspect, the present invention provides a lithium ion battery obtained by the above lithium supplementing method.
Further, the lithium supplementing method is replaced by a sodium supplementing method, and the lithium ion battery is replaced by a sodium ion battery.
The method can accurately control the coulomb efficiency improvement amplitude and avoid excessive lithium supplementation; lithium supplementing of the lithium battery by using lithium powder can be avoided, and compared with a main flow process, the process safety can be improved; has no deterioration to battery performance.
The lithium supplementing electrode can supplement lithium to the positive electrode and the negative electrode respectively; the lithium source is lithium sheet; the lithium supplementing electrode is placed in the air bag, and the air bag is reserved during formation; and the lithium supplementing step is to supplement lithium after formation, and the lithium supplementing amount is calculated through current and time.
Drawings
FIG. 1 is a schematic diagram of a lithium-ion-supplementing electrode according to example 1 of the present invention,
in the figure, 1, a lithium sheet, 2, a diaphragm, 3 and an aluminum tab;
fig. 2 is a schematic structural diagram of the embodiment 1 of the present invention in which the lithium-compensating electrode is placed at a relative position of a seal for encapsulation;
in the figure, 4, a positive electrode lug, 5, a negative electrode lug, 6, a battery cell main body, 7, a lithium supplementing electrode, 8, a top seal, 9, a seal, 10, a side seal, 11 and an air bag.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present invention clearer, the present invention will be further described in detail with reference to examples. It should be understood that the embodiments described in this specification are only for explaining the present invention, and are not intended to limit the present invention, and specific parameter settings and the like of the embodiments may be selected according to the circumstances without materially affecting the results.
In the embodiment of the invention, the formation of the battery means that the battery activates positive and negative electrode substances in the battery core in a charging and discharging mode, so that the self-discharging performance, the charging and discharging performance and the storage performance of the battery are improved; capacity grading refers to grading the battery capacity by testing the battery capacity and other electrical performance parameters after the battery is manufactured.
In the embodiment of the invention, LCO is lithium cobaltate.
In the embodiment of the invention, SP is styrenated phenol.
In the embodiment of the invention, PVDF is polyvinylidene fluoride.
In an embodiment of the invention, NMP is N-methylpyrrolidone.
In the embodiment of the invention, the dispersing agent is CMC and carboxymethyl cellulose.
In the embodiment of the invention, the binder is SBR, styrene-butadiene latex binder.
In the embodiment of the invention, the NMP is dissolved in NMP, and the use amount of NMP is based on the complete dissolution of LCO/sodium cobaltate, SP and PVDF.
In the embodiment of the invention, the graphite, the silicon oxide, the SP, the dispersing agent and the binding agent are completely dissolved in deionized water.
In the embodiment of the invention, LCO, sodium cobaltate, SP, PVDF, graphite, silica, SP, CMC and SBR are commercially available analytical pure reagents.
In the embodiment of the invention, the aluminum plastic film is DNP113um.
In the embodiment of the invention, the high-temperature baking temperature is 85+/-1 ℃ and the time is 24-72h.
In the embodiment of the invention, the inert atmosphere is argon atmosphere.
Example 1
Preparing and tabletting a positive electrode precursor: LCO, SP, PVDF was prepared as follows 97:2:1 in the mass ratio of NMP, fully stirring for 10 hours to uniformly disperse, coating the mixed slurry on the surface of an aluminum foil at the single-sided surface density of 4m/min, drying at 80 ℃, and carrying out rolling treatment at normal temperature for 5 hours;
preparing and tabletting the cathode precursor: graphite, silica, SP, dispersant (CMC), binder (SBR) according to 87.3:10:0.3:1.1:1.3, dissolving the mixture in deionized water, stirring for 10 hours to uniformly disperse the mixture, coating the mixed slurry on the surface of a copper foil at a single-sided surface density of 4m/min, drying the copper foil at 100+/-5 ℃, and carrying out normal-temperature rolling treatment for 5 hours;
pole pieces are manufactured by adopting middle pole lugs;
manufacturing the manufactured pole piece and diaphragm into a bare cell by winding;
packaging by using an aluminum plastic film, and baking at a high temperature; the high-temperature baking temperature is 85+/-1 ℃ and the time is 24 hours;
manufacturing a three-electrode tab in a glove box, wherein the materials are required to be baked at a high temperature in an inert gas environment, the temperature is 85+/-1 ℃, and the time is 24 hours; the lithium sheet and the tab are fixed together by a diaphragm winding mode to manufacture a lithium supplementing electrode, and the structure is shown in figure 1;
after the battery is filled with liquid, the lithium supplementing electrode is placed at a relative position for packaging, and the structure is shown in figure 2;
standing the battery, forming, placing the battery on a special charging and discharging device for supplementing lithium, wherein the Ni electrode lug is in butt joint with the positive electrode of the device, the lithium supplementing electrode is in butt joint with the negative electrode of the device, the device adopts a discharging step, the discharging current is 0.1C, and the discharging capacity is designed to be 3% of the design capacity of the battery;
and after the electricity is supplemented, the battery is subjected to normal secondary sealing, capacity division, edge folding and other processes to finish the manufacturing.
Example 2
Preparing and tabletting a positive electrode precursor: LCO, SP, PVDF was prepared as follows 97:2:1 in the mass ratio of NMP, fully stirring for 10 hours to uniformly disperse, coating the mixed slurry on the surface of an aluminum foil at the single-sided surface density of 4m/min, drying at 90 ℃, and carrying out normal-temperature rolling treatment for 15 hours;
preparing and tabletting the cathode precursor: graphite, silica, SP, dispersant (CMC), binder (SBR) according to 87.3:10:0.3:1.1:1.3, dissolving the mixture in deionized water, stirring for 8 hours to uniformly disperse the mixture, coating the mixed slurry on the surface of a copper foil at a single-sided surface density of 4m/min, drying the copper foil at 100+/-5 ℃, and carrying out normal-temperature rolling treatment for 15 hours;
pole pieces are manufactured by adopting middle pole lugs;
manufacturing the manufactured pole piece and diaphragm into a bare cell by winding;
packaging by using an aluminum plastic film, and baking at a high temperature; the high-temperature baking time is 36h;
manufacturing three-electrode tabs in a glove box, wherein the materials are required to be baked at a high temperature in an inert gas environment, and the high-temperature baking time is 36 hours; fixing the lithium sheet and the tab together by a diaphragm winding mode to manufacture a lithium supplementing electrode (figure 1);
after the battery is filled with the liquid, the lithium supplementing electrode is placed at a relative position for packaging;
standing the battery, forming, placing the battery on a special charging and discharging device for supplementing lithium, wherein the Ni electrode lug is in butt joint with the positive electrode of the device, the lithium supplementing electrode is in butt joint with the negative electrode of the device, the device adopts a discharging step, the discharging current is 0.1C, and the discharging capacity is designed to be 6% of the design capacity of the battery;
and after the electricity is supplemented, the battery is subjected to normal secondary sealing, capacity division, edge folding and other processes to finish the manufacturing.
Example 3
Preparing and tabletting a positive electrode precursor: LCO, SP, PVDF was prepared as follows 97:2:1 in the mass ratio of NMP, fully stirring for 10 hours to uniformly disperse, coating the mixed slurry on the surface of an aluminum foil at the single-sided surface density of 4m/min, drying at 120 ℃, and carrying out normal-temperature rolling treatment;
preparing and tabletting the cathode precursor: graphite, silica, SP, dispersant (CMC), binder (SBR) according to 87.3:10:0.3:1.1:1.3, dissolving the mixture in deionized water, stirring for 9 hours to uniformly disperse the mixture, coating the mixed slurry on the surface of a copper foil at a single-sided surface density of 4m/min, drying the copper foil at 100+/-5 ℃, and carrying out normal-temperature rolling treatment;
pole pieces are manufactured by adopting middle pole lugs;
manufacturing the manufactured pole piece and diaphragm into a bare cell by winding;
packaging by using an aluminum plastic film, and baking at a high temperature; the high-temperature baking time is 48 hours;
manufacturing three-electrode tabs in a glove box, wherein the materials are required to be baked at a high temperature in an inert gas environment, and the high-temperature baking time is 48 hours; fixing the lithium sheet and the tab together by a diaphragm winding mode to manufacture a lithium supplementing electrode as shown in figure 1;
after the battery is filled with the liquid, the lithium supplementing electrode is placed at a relative position for packaging;
standing the battery, forming, placing the battery on a special charging and discharging device for supplementing lithium, wherein an Al electrode lug and a lithium supplementing electrode are respectively in butt joint with the device, the device adopts a discharging process step, the discharging current is 0.1C, and the discharging capacity is designed to be 6% of the design capacity of the battery;
and after the electricity is supplemented, the battery is subjected to normal secondary sealing, capacity division, edge folding and other processes to finish the manufacturing.
Comparative example 1
Preparing and tabletting a positive electrode precursor: LCO, SP, PVDF was prepared as follows 97:2:1 in the mass ratio of NMP, fully stirring for 10 hours to uniformly disperse, coating the mixed slurry on the surface of an aluminum foil at the single-sided surface density of 4m/min, drying at 80-120 ℃, and rolling at normal temperature;
preparing and tabletting the cathode precursor: preparing a negative electrode material: graphite, silica, SP, dispersant (CMC), binder (SBR) according to 87.3:10:0.3:1.1:1.3, dissolving the raw materials in deionized water, stirring for 10 hours to uniformly disperse the raw materials, coating the mixed slurry on the surface of a copper foil at a single-sided surface density of 4m/min, and drying and rolling at the temperature of 100+/-5 ℃ at normal temperature;
pole pieces are manufactured by adopting middle pole lugs;
manufacturing the manufactured pole piece and diaphragm into a bare cell by winding;
packaging by using an aluminum plastic film, and baking;
after the battery is injected with the liquid, the battery is subjected to aging, packaging, formation, secondary packaging, capacity division and edge folding procedures to finish the manufacturing;
i.e. the original steps 5-7 are omitted.
Table 1 differences between examples and comparative examples:
Figure BDA0004010590930000081
as can be seen from table 1, the new process can significantly improve the first efficiency of the full cell.
In contrast to patent CN109004304 a: the lithium sheet is used as a lithium source, the film forming effect of the cathode during the first charging of the formation is not affected in the lithium supplementing step after the formation of the battery, meanwhile, the air bag with the lithium supplementing electrode is cut off after the secondary sealing, the air bag can be reserved for collecting harmful gas generated during the formation, the high-temperature performance of the battery is improved, the lithium supplementing structure is more advantageous in high-temperature storage, meanwhile, the lithium supplementing structure is used for supplementing lithium by adding the lithium supplementing electrode in a mode of connecting the anode and the cathode with the lithium supplementing electrode in a charging and discharging mode, the electric quantity of the lithium supplementing can be accurately controlled by controlling the current and the time, meanwhile, the anode and the lithium supplementing electrode can be connected, and the lithium supplementing is carried out on the anode, and the result is shown in the table 2:
TABLE 2
Figure BDA0004010590930000091
Calculating accurate lithium supplement:
the capacity of the lithium supplementing step can be calculated according to the following formula by controlling the current and time of the lithium supplementing electrode and the positive electrode or negative electrode connecting circuit:
lithium supplementing capacity q=lithium supplementing current I for lithium supplementing time T;
the unit of lithium supplementing current is mA, the unit of lithium supplementing time is h, and the unit of lithium supplementing capacity is mAh;
in contrast to patent CN109103419 a: according to the invention, lithium is supplemented by introducing the lithium supplementing electrode, the theoretical calculation of the electric quantity of the lithium supplementing can be performed through current and time, the lithium supplementing precision is higher, multiple coating is not needed, and the manufacturing period and cost are more advantageous.
Example 4
Preparing and tabletting a positive electrode precursor: LCO, SP, PVDF was prepared as follows 97:2:1 in the mass ratio of NMP, fully stirring for 10 hours to uniformly disperse, coating the mixed slurry on the surface of an aluminum foil at the single-sided surface density of 4m/min, drying at 80 ℃, and carrying out normal-temperature rolling treatment for 8 hours;
preparing and tabletting the cathode precursor: graphite, silica, SP, dispersant (CMC), binder (SBR) according to 87.3:10:0.3:1.1:1.3, dissolving the mixture in deionized water, stirring for 10 hours to uniformly disperse the mixture, coating the mixed slurry on the surface of a copper foil at a single-sided surface density of 4m/min, drying the copper foil at 100+/-5 ℃, and carrying out normal-temperature rolling treatment for 8 hours;
adopting a multipolar lug structure to manufacture pole pieces;
manufacturing the manufactured pole piece and diaphragm into a bare cell by winding;
packaging by using an aluminum plastic film, and baking at a high temperature; the high-temperature baking temperature is 85+/-1 ℃ and the time is 72 hours;
manufacturing a three-electrode tab in a glove box, wherein the materials are required to be baked at a high temperature in an inert gas environment, the temperature is 85+/-1 ℃, and the time is 72 hours; fixing the lithium sheet and the tab together in a diaphragm winding mode to manufacture a lithium supplementing electrode;
after the battery is filled with the liquid, the lithium supplementing electrode is placed at a relative position for packaging;
standing the battery, forming, placing the battery on a special charging and discharging device for supplementing lithium, wherein the Ni electrode lug is in butt joint with the positive electrode of the device, the lithium supplementing electrode is in butt joint with the negative electrode of the device, the device adopts a discharging step, the discharging current is 0.1C, and the discharging capacity is designed to be 3% of the design capacity of the battery;
and after the electricity is supplemented, the battery is subjected to normal secondary sealing, capacity division, edge folding and other processes to finish the manufacturing.
Example 5
Preparing and tabletting a positive electrode precursor: LCO, SP, PVDF was prepared as follows 97:2:1 in the mass ratio of NMP, fully stirring for 10 hours to uniformly disperse, coating the mixed slurry on the surface of an aluminum foil at the single-sided surface density of 4m/min, drying at 80 ℃, and carrying out rolling treatment at normal temperature for 9 hours;
preparing and tabletting the cathode precursor: graphite, silica, SP, dispersant (CMC), binder (SBR) according to 87.3:10:0.3:1.1:1.3, dissolving the mixture in deionized water, stirring for 10 hours to uniformly disperse the mixture, coating the mixed slurry on the surface of a copper foil at a single-sided surface density of 4m/min, drying the copper foil at 100+/-5 ℃, and carrying out normal-temperature rolling treatment for 9 hours;
adopting a multipolar lug structure to manufacture pole pieces;
manufacturing the manufactured pole piece and diaphragm into a bare cell by winding;
packaging by using an aluminum plastic film, and baking at a high temperature; the high-temperature baking temperature is 85+/-1 ℃ and the time is 30 hours;
manufacturing a three-electrode tab in a glove box, wherein the materials are required to be baked at a high temperature in an inert gas environment, the temperature is 85+/-1 ℃, and the time is 30 hours; fixing the lithium sheet and the tab together in a diaphragm winding mode to manufacture a lithium supplementing electrode;
after the battery is filled with the liquid, the lithium supplementing electrode is placed at a relative position for packaging;
standing the battery, forming, placing the battery on a special charging and discharging device for supplementing lithium, wherein the Ni electrode lug is in butt joint with the positive electrode of the device, the lithium supplementing electrode is in butt joint with the negative electrode of the device, the device adopts a discharging step, the discharging current is 0.1C, and the discharging capacity is designed to be 3% of the design capacity of the battery;
and after the electricity is supplemented, the battery is subjected to normal secondary sealing, capacity division, edge folding and other processes to finish the manufacturing.
Example 6
Preparing and tabletting a positive electrode precursor: LCO, SP, PVDF was prepared as follows 97:2:1 in the mass ratio of NMP, fully stirring for 10 hours to uniformly disperse, coating the mixed slurry on the surface of an aluminum foil at the single-sided surface density of 4m/min, drying at 80 ℃, and rolling at normal temperature for 10 hours;
preparing and tabletting the cathode precursor: graphite, silica, SP, dispersant (CMC), binder (SBR) according to 87.3:10:0.3:1.1:1.3, dissolving the mixture in deionized water, stirring for 10 hours to uniformly disperse the mixture, coating the mixed slurry on the surface of a copper foil at a single-sided surface density of 4m/min, drying the copper foil at 100+/-5 ℃, and carrying out normal-temperature rolling treatment for 10 hours;
adopting a multipolar lug structure to manufacture pole pieces;
manufacturing the manufactured pole piece and diaphragm into a bare cell by winding;
packaging by using an aluminum plastic film, and baking at a high temperature; the high-temperature baking temperature is 85+/-1 ℃ and the time is 24 hours;
manufacturing a three-electrode tab in a glove box, wherein the materials are required to be baked at a high temperature in an inert gas environment, the temperature is 85+/-1 ℃, and the time is 24 hours; fixing the lithium sheet and the tab together in a diaphragm winding mode to manufacture a lithium supplementing electrode;
after the battery is filled with the liquid, the lithium supplementing electrode is placed at a relative position for packaging;
standing the battery, forming, placing the battery on a special charging and discharging device for supplementing lithium, wherein the Ni electrode lug is in butt joint with the positive electrode of the device, the lithium supplementing electrode is in butt joint with the negative electrode of the device, the device adopts a discharging step, the discharging current is 0.1C, and the discharging capacity is designed to be 3% of the design capacity of the battery;
and after the electricity is supplemented, the battery is subjected to normal secondary sealing, capacity division, edge folding and other processes to finish the manufacturing.
In summary, the lithium supplementing electrode manufactured by the invention can supplement lithium to the positive electrode and the negative electrode respectively; the lithium source is lithium sheet; the lithium supplementing electrode is placed in the air bag, and the air bag is reserved during formation; and the lithium supplementing step is to supplement lithium after formation, and the lithium supplementing amount is calculated through current and time. The method can accurately control the coulomb efficiency improvement amplitude and avoid excessive lithium supplementation; lithium supplementing of the lithium battery by using lithium powder can be avoided, and compared with a main flow process, the process safety can be improved; has no deterioration to battery performance. In addition, the invention can be equally applied to sodium supplement of sodium batteries, and the related principles and processes are the same.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

1. A method of battery lithium replenishment comprising: preparing a semi-finished lithium ion battery and preparing a lithium supplementing electrode; and placing the lithium supplementing electrode in an air bag filled with protective gas, and then supplementing lithium to the semi-finished lithium ion battery.
2. The method for lithium replenishment of a battery according to claim 1, wherein the method for producing a semi-finished lithium ion battery comprises:
step 1: providing a current collector, and coating active material materials on the current collector in a gap or continuous coating mode to respectively prepare a positive electrode precursor and a negative electrode precursor;
step 2: manufacturing a positive electrode precursor and a negative electrode precursor manufactured in the step 1 into a lug or a multi-lug structure to obtain a positive electrode plate and a negative electrode plate;
step 3: the manufactured positive plate and the manufactured negative plate are respectively manufactured into a positive bare cell and a negative bare cell with a diaphragm in a winding mode; the diaphragm is made by a wet process;
step 4: packaging the positive electrode bare cell and the negative electrode bare cell by using an aluminum plastic film, and baking;
step 5: and (5) injecting liquid after baking to obtain the semi-finished lithium ion battery.
3. The method of claim 2, wherein in step 1, the positive electrode precursor is prepared by mixing LCO/sodium cobaltate, SP and PVDF according to a ratio of 97:2:1 in the mass ratio of NMP, stirring for 8-10h to uniformly disperse the mixture, and obtaining mixed slurry; coating the mixed slurry on the surface of a current collector aluminum foil at a single-sided surface density of 4m/min, drying at 80-120 ℃, and then rolling at normal temperature for 1-48h to prepare the positive electrode precursor.
4. The method of claim 2, wherein in step 1, the negative electrode precursor is prepared into tablets by mixing graphite, silica, SP, dispersant (CMC), and binder (SBR) according to a ratio of 87.3:10:0.3:1.1:1.3, dissolving the mixture in deionized water, and stirring for 8-10 hours to uniformly disperse the mixture to obtain mixed slurry; and (3) coating the mixed slurry on the surface of a current collector copper foil at a single-sided surface density of 4m/min, drying at 100+/-5 ℃, and then carrying out rolling treatment at normal temperature for 1-48h to prepare the anode precursor.
5. The method for supplementing lithium to a battery according to claim 2, wherein in the step 4, the aluminum plastic film is DNP113um; the baking temperature is 85+/-1 ℃ and the baking time is 24-72 hours.
6. The method for supplementing lithium to a battery according to claim 1, wherein the method for preparing a lithium supplementing electrode comprises:
manufacturing three electrode lugs in a glove box, and baking the materials in an inert gas environment; fixing the lithium sheet and the tab together in a diaphragm winding mode to obtain a lithium supplementing electrode; the diaphragm is made by a wet process.
7. The method of claim 1, wherein the lithium supplementing process comprises:
(1) Placing the lithium supplementing electrode at the relative position of a seal of the semi-finished lithium ion battery;
(2) Packaging the lithium supplementing electrode by adopting an air bag filled with protective gas;
(3) The battery is placed on a charging and discharging device for lithium supplement after standing and formation, and charging and discharging are carried out to complete the electricity supplement.
8. The method of claim 7, wherein in step (3), during charging and discharging, the Ni tab is in butt joint with the positive electrode of the device, the lithium-supplementing electrode is in butt joint with the negative electrode and/or the positive electrode of the charging and discharging device, the device adopts a discharging step, the discharging current is 0.1C, and the discharging capacity is designed to be 3-6% of the designed capacity of the battery.
9. The method of claim 1, wherein the semi-finished lithium ion battery is replaced with a semi-finished sodium ion battery, and the method of lithium supplementation is replaced with a method of sodium supplementation.
10. A battery prepared by a battery lithium supplementing method, characterized in that the battery lithium supplementing method of claims 1-8 is adopted to prepare a lithium ion battery.
CN202211648006.0A 2022-12-21 2022-12-21 Lithium supplementing method for battery and battery prepared by adopting lithium supplementing method Pending CN116190549A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117766847A (en) * 2024-01-04 2024-03-26 博研嘉信(北京)科技有限公司 Long-cycle polymer lithium ion battery and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117766847A (en) * 2024-01-04 2024-03-26 博研嘉信(北京)科技有限公司 Long-cycle polymer lithium ion battery and preparation method thereof

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