CN111900501A - Lithium supplement additive and preparation method and application thereof - Google Patents
Lithium supplement additive and preparation method and application thereof Download PDFInfo
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- CN111900501A CN111900501A CN202010799978.4A CN202010799978A CN111900501A CN 111900501 A CN111900501 A CN 111900501A CN 202010799978 A CN202010799978 A CN 202010799978A CN 111900501 A CN111900501 A CN 111900501A
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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
- H01M10/42—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
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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
Abstract
The invention provides a lithium supplement additive and a preparation method and application thereof, and the lithium supplement additive comprises Li3x+ yNxFaClbBrcIdWherein x is not less than 1 and is an integer, a is not less than 0, b is not less than 0, c is not less than 0, d is not less than 0, y is a + b + c + d, and y is not less than 1 and is an integer. The lithium supplement additive is high in stability, active lithium can be supplemented for the lithium ion battery in a safe mode, and the first charge-discharge efficiency, the energy density and the cycle life of the lithium ion battery are obviously improved.
Description
Technical Field
The invention relates to a lithium supplement additive, a preparation method and application thereof, and belongs to the technical field of lithium ion batteries.
Background
Lithium ion batteries are very widely used secondary batteries. Graphite is mainly used as a negative electrode material of the lithium ion battery in the current market. With the increasing demand for energy density of lithium ion batteries, higher capacity negative electrode materials such as silicon-based negative electrodes, tin-based negative electrodes, hard carbon negative electrodes, and the like are also gradually used in lithium ion batteries. However, the cathode materials with higher capacity, such as silicon-based cathodes, tin-based cathodes, and hard carbon cathodes, generally have the disadvantage of low first charge-discharge efficiency, and the capacity exertion and the improvement of the actual energy density of the full battery are seriously affected.
In view of the above circumstances, a negative electrode lithium supplement technology is often used to solve the above problems. The lithium supplement of the negative electrode is to supplement lithium into the negative electrode piece, and the following specific implementation forms are mainly adopted: (1) mechanically pressing and supplementing lithium through a metal lithium foil and a negative plate; (2) spraying lithium powder on the surface of the negative plate to supplement lithium; (3) preparing lithium powder into slurry and coating the slurry on the surface of the negative plate; (4) depositing lithium on the surface of the negative plate in a vacuum thermal evaporation mode; (5) embedding lithium into the negative plate in an electroplating or electrodeposition mode; (6) mixing the negative electrode material with lithium metal powder, and performing ball milling, or heating and melting the lithium metal, and then mixing the molten lithium metal with the negative electrode material, and directly supplementing lithium to the negative electrode material; (7) firstly, preparing lithium silicide powder LixSi, and then mixing the lithium silicide powder and a negative electrode material for lithium supplement. However, the operation of lithium supplement to the negative electrode is generally complicated and has serious safety hazards, so technicians are studying the lithium supplement to the positive electrode plate.
The positive electrode is supplemented with lithium mainly by lithium-rich positive electrode materials such as Li1+xNi0.5Mn1.5O4、Li2NiO2、Li5FeO4、Li3N、Li2O2、Li2And S and the like are added into the positive plate for lithium supplement. In the positive electrode lithium-supplementing material, Li1+xNi0.5Mn1.5O4、Li2NiO2、Li5FeO4The lithium-rich metal oxide has a low lithium-replenishing capacity, and some substances that do not contribute to the positive electrode capacity remain in the positive electrode sheet after lithium replenishment. Li2S is high in lithium supplement capacity, but elemental sulfur remains in the positive plate after lithium supplement, and the performance of the lithium battery is adversely affected. Li2O2The lithium supplement capacity is higher, but oxygen is generated in the lithium supplement process, and the safety is poor. Li3The lithium supplement capacity of N is high, nitrogen generated in the lithium supplement process is safer gas, the nitrogen can be removed in the production process of the battery, and other substances cannot be remained in the anode after lithium supplement. However, it is not limited to，Li3The N powder has poor chemical stability when exposed to air, is easily converted into lithium carbonate in the air, releases ammonia gas, has the risk of combustion, and prevents the possibility of application of lithium supplement.
Disclosure of Invention
The invention provides a lithium supplement additive which is high in stability, can supplement active lithium for a lithium ion battery in a relatively safe mode, and obviously improves the first charge-discharge efficiency, the energy density and the cycle life of the lithium ion battery.
The invention provides a preparation method of a lithium supplement additive, which has the advantages of high safety coefficient, simplicity and easiness in operation.
The invention provides a positive plate which comprises the lithium supplement additive, so that the positive plate can safely and efficiently realize lithium supplement operation on a lithium ion battery, and the first charge-discharge efficiency, the energy density and the cycle life of the lithium ion battery are obviously improved.
The invention provides a lithium ion battery, which comprises the positive plate, so that the lithium ion battery has the characteristics of excellent first charge-discharge efficiency, high energy density and long cycle life.
The invention provides a lithium supplement additive, which comprises Li3x+yNxFaClbBrcIdWherein x is not less than 1 and is an integer, a is not less than 0, b is not less than 0, c is not less than 0, d is not less than 0, y is a + b + c + d, and y is not less than 1 and is an integer.
The lithium supplement additive is prepared by the following steps:
under an inert atmosphere, Li3Mixing N with lithium halide, and calcining at the temperature of 400-1000 ℃ to obtain the lithium supplement additive;
wherein the lithium halide is at least one selected from the group consisting of lithium fluoride, lithium chloride, lithium bromide and lithium iodide.
The lithium supplement additive, wherein the time of the calcination treatment is 0.5-12 h.
The lithium supplement additive as described above, wherein the average particle size D50 of the lithium supplement additive is 0.1 to 50 μm.
The invention also provides a preparation method of the lithium supplement additive, which comprises the following steps: under an inert atmosphere, Li3Mixing N with lithium halide, and calcining at the temperature of 400-1000 ℃ to obtain the lithium supplement additive;
wherein the lithium halide is at least one selected from the group consisting of lithium fluoride, lithium chloride, lithium bromide and lithium iodide.
The invention also provides a positive plate, which comprises a current collector and a positive active layer arranged on at least one surface of the current collector;
wherein the positive electrode active layer comprises the lithium supplement additive.
The positive electrode sheet as described above, wherein the lithium supplement additive is present in the positive electrode active layer in an amount of 1 to 10% by mass.
The invention also provides a positive plate, which comprises a current collector, a positive active layer arranged on at least one surface of the current collector, and a lithium supplement layer arranged on at least one surface of the positive active layer;
wherein the lithium supplement layer comprises the lithium supplement additive of any one of the above.
The positive electrode plate as described above, wherein the lithium supplement additive is included in the lithium supplement layer in an amount of 50 to 99.9% by mass.
The invention also provides a lithium ion battery, which comprises the positive plate.
The lithium supplement additive has high chemical stability and good safety in the air, and therefore, the lithium supplement additive can be used as a safe and efficient positive electrode lithium supplement additive. In the application process, the lithium supplement additive can continuously release lithium ions, so that the first charge-discharge efficiency of the lithium ion battery is optimized, the energy density of the lithium ion battery is effectively improved, and the cycle life of the lithium ion battery is prolonged. In addition, the lithium supplement additive can be compatible with the existing lithium ion battery production process, is convenient to use and is convenient for large-scale popularization and utilization.
The preparation method of the lithium supplement additive provided by the invention has the characteristics of simple conditions, no need of assistance of large instruments and high safety coefficient.
The positive plate provided by the invention comprises the lithium supplement additive, so that the positive plate has the characteristics of safety and high efficiency in lithium supplement, and is beneficial to improving the first charge-discharge efficiency, the energy density and the cycle life of the lithium ion battery.
The lithium ion battery provided by the invention comprises the positive plate, so that the first charge-discharge efficiency, the energy density and the cycle life of the lithium ion battery are remarkably improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a lithium supplement additive, which comprises Li3x+yNxFaClbBrcIdWherein x is not less than 1 and is an integer, a is not less than 0, b is not less than 0, c is not less than 0, d is not less than 0, y is a + b + c + d, and y is not less than 1 and is an integer.
The lithium supplement additive shown in the molecular formula at least contains one of F, Cl, Br and I, namely a, b, c and d are not 0 at the same time. The lithium supplement additive has excellent chemical stability and high safety performance in the air, and can not cause the risk of fire, thereby being safely used. In addition, the lithium supplement additive is used as a positive electrode lithium supplement raw material to be applied to the lithium ion battery, so that the first charge-discharge efficiency of the lithium ion battery can be obviously improved, and the energy density and the cycle life of the lithium ion battery are optimized. The inventor analyzes that the lithium supplement additive is possibly applied to the lithium ion battery, and when the lithium ion battery is charged and discharged for the first time and the whole application process, the additive can continuously release lithium ions to enter the anode, so that the active lithium of the lithium ion battery is supplemented, and the first charge and discharge efficiency, the energy density and the cycle life of the lithium ion battery are improved.
In addition, the lithium supplement capacity can be changed due to different compositions of the lithium supplement additive, and the composition of the lithium supplement additive can be adjusted according to target requirements.
The lithium supplement additive can be prepared by a method comprising the following steps of:
under an inert atmosphere, Li3Mixing N with lithium halide, and calcining at the temperature of 400-1000 ℃ to obtain the lithium supplement additive;
wherein the lithium halide is at least one selected from the group consisting of lithium fluoride, lithium chloride, lithium bromide and lithium iodide.
It should be noted that the entire preparation process of the lithium supplement additive needs to be carried out under an inert atmosphere. The present invention does not limit the kind of the inert atmosphere, and may be at least one of argon, nitrogen, helium, neon, krypton, and xenon.
Mixing raw materials for preparing a lithium supplement additive under an inert atmosphere to obtain a mixture, wherein the raw materials comprise Li3N and at least one of lithium fluoride, lithium chloride, lithium bromide, and lithium iodide. The mixture is calcined at the temperature of 400-1000 ℃, and the calcined product is the lithium supplement additive of the invention. The calcination may be carried out in a high-temperature heating furnace such as a muffle furnace.
During the preparation, the mixture may be subjected to a milling treatment before calcination, which may be carried out in a mechanical milling device, to ensure a sufficient mixture between the raw materials. In addition, the grinding treatment may be followed by a tabletting treatment of the ground mixture and a subsequent calcining treatment of the tabletted mixture.
The invention is not limited by the ratio between the individual raw materials, theoretically, x mol Li3N, a mol of lithium fluoride, b mol of lithium chloride, c mol of lithium bromide and d mol of lithium iodide are subjected to the reaction to obtain the molecular formula Li3x+yNxFaClbBrcIdWherein x is an integer of 1 or more, a is an integer of 0 or more, b is an integer of 0 or more, c is an integer of 0 or more, d is an integer of 0 or more, y is a + b + c + d, and y is an integer of 1 or more.
It can be understood that in order to enhance the lithium supplement effect as much as possible, the lithium ion battery is supplemented with more active lithium, i.e., Li3The amount of the substance of N is generally greater than the amount of the substance of lithium halide employed.
In the embodiment of the invention for preparing the lithium supplement additive, the time of the calcination treatment needs to be controlled to be not less than 0.5h, and can be controlled to be in the range of 0.5-12 h.
After the calcination treatment is finished, the calcined product can be ground to obtain the lithium supplement additive with the average particle size D50 of 0.1-50 μm, so that the subsequent application of the lithium supplement additive is facilitated.
The invention also provides a preparation method of the lithium supplement additive, which comprises the following steps: under an inert atmosphere, Li3Mixing N with lithium halide, and calcining at the temperature of 400-1000 ℃ to obtain the lithium supplement additive; wherein the lithium halide is at least one selected from the group consisting of lithium fluoride, lithium chloride, lithium bromide and lithium iodide.
The whole preparation process of the lithium supplement additive is carried out under the protection of inert atmosphere.
In the practice of the invention, x molLi is first introduced under an inert atmosphere3And mixing N with a mol of lithium fluoride, b mol of lithium chloride, c mol of lithium bromide and d mol of lithium iodide to obtain a mixture. And then, introducing inert gas into the high-temperature heating furnace, and calcining the mixture in the high-temperature heating furnace at 400-1000 ℃, wherein the calcined product is the lithium supplement additive.
Further, the calcining treatment also comprises grinding the mixture, tabletting and calcining the flaky mixture.
Further, after the calcination treatment, the calcination product is cooled to room temperature and crushed and ground to obtain the lithium supplement additive with the proper particle size.
Wherein the time of the calcination treatment is 0.5-12 h.
The invention also provides a positive plate, which comprises a current collector and a positive active layer arranged on at least one surface of the current collector, wherein the positive active layer comprises the lithium supplement additive.
Specifically, the positive electrode slurry containing the lithium supplement additive is coated on at least one surface of the current collector, and after the solvent is evaporated to dryness, the positive electrode sheet is obtained through rolling and cutting. The positive electrode slurry comprises a positive electrode active material, a conductive agent, a binder and a solvent in addition to a lithium supplement additive.
In the preparation process, the anode active material, the lithium supplement additive, the conductive agent, the binder and the solvent are mixed and stirred to obtain anode slurry with a uniform system. And then coating the positive slurry on at least one surface of the current collector, and rolling and cutting after the solvent is evaporated to dryness to obtain the positive plate. The lithium supplement additive can be added at any node, for example, the lithium supplement additive can be mixed with other substances and then added with a solvent for stirring to prepare the anode slurry, and the invention does not have too much limitation as to the adding sequence of the lithium supplement additive and other substances; or adding the lithium supplement additive after mixing other substances with the solvent, and stirring to prepare the anode slurry.
The current collector of the present invention may employ a positive electrode metal current collector commonly used in the art, such as aluminum foil.
The present invention is not limited to the selection of the positive electrode active material, and may be LiCoO2、LiFePO4、LiNi0.3Co0.3Mn0.3O2、LiNi0.5Co0.3Mn0.2O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.8Co0.15Al0.05O2、LiNi0.5Mn1.5O4At least one of (1); the conductive agent is at least one selected from Acetylene Black (AB), conductive carbon black (Super-P), Ketjen Black (KB), Carbon Nanotubes (CNT) and graphene; the binder is selected from at least one of polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC) and Sodium Alginate (SA); the solvent is selected from N-methyl pyrroleAt least one of an alkanone (NMP), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), acetonitrile, tetrahydrofuran, toluene, xylene.
In addition, the thickness of the current collector and the thickness of the positive active layer may be specifically determined according to the requirements, and the present invention is not limited.
Further, in order to ensure the lithium supplement effect, the mass fraction of the lithium supplement additive in the positive electrode active layer cannot be lower than 0.01%. In a preferred embodiment, the lithium supplement additive is present in an amount of 1 to 10% by mass based on the total mass of the positive electrode active layer.
The positive plate provided by the invention has higher gram capacity due to the inclusion of the lithium supplement additive, and the first charge-discharge efficiency, the energy density and the cycle life of the lithium ion battery can be obviously improved when the positive plate is applied to the lithium ion battery.
The invention also provides a positive plate, which comprises a current collector, a positive active layer arranged on at least one surface of the current collector, and a lithium supplement layer arranged on at least one surface of the positive active layer. Wherein the lithium supplement layer comprises the lithium supplement additive.
Specifically, the lithium supplement slurry containing the lithium supplement additive is coated on at least one surface of the positive active layer, and after the solvent is evaporated to dryness, the positive plate is rolled and cut to obtain the positive plate. The lithium supplement slurry comprises a polymer and a solvent besides the lithium supplement additive.
In the preparation process, the lithium supplement additive, the polymer and the solvent are mixed and stirred to obtain the lithium supplement slurry with a uniform system. And then, coating the lithium supplementing slurry on at least one surface of the positive active layer, and rolling and cutting after the solvent is evaporated to dryness to obtain the positive plate. Wherein, the polymer can be at least one selected from polyvinylidene fluoride (PVDF binder), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polyethylene oxide (or polyethylene glycol), polyacrylonitrile, polyacrylate, polycarbonate, polyvinyl acetal, polystyrene, nitrile rubber and polyamide; the solvent may be at least one selected from the group consisting of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), acetonitrile, tetrahydrofuran, toluene, xylene.
In addition, conductive carbon black can be further included in the lithium supplement layer. Namely, the conductive carbon black is added into a system of a lithium supplement additive, a polymer and a solvent to obtain a lithium supplement slurry containing the conductive carbon black, so that a lithium supplement layer containing the conductive carbon black is further obtained. The addition of the conductive carbon black is helpful for improving the conductivity of the lithium supplement layer, thereby increasing the speed of lithium supplement.
The current collector of the present invention may employ a positive electrode metal current collector commonly used in the art, such as aluminum foil.
The positive active layer of the invention comprises a positive active material, a conductive agent and a binder. Specifically, the positive electrode active material, the conductive agent, the binder and the solvent are mixed to prepare positive electrode slurry, the positive electrode slurry is coated on at least one surface of the current collector, and the positive electrode active layer is obtained after the solvent is evaporated to dryness. The selection of the positive electrode active material, the conductive agent, the binder and the solvent is the same as that of the positive electrode plate, and the details are not repeated here.
In addition, the thickness of the current collector, the thickness of the positive active layer, and the thickness of the lithium supplement layer may be specifically determined according to the requirements, and the present invention is not limited thereto.
Further, in order to ensure the lithium supplementing effect, the mass fraction of the lithium supplementing additive in the lithium supplementing layer cannot be lower than 0.01%. In a preferred manner, the mass fraction of the lithium-supplementing additive is 50 to 99.9%, optionally 90 to 99%, based on the total mass of the lithium-supplementing layer.
The positive plate provided by the invention has higher gram capacity due to the inclusion of the lithium supplement additive, and the first charge-discharge efficiency, the energy density and the cycle life of the lithium ion battery can be obviously improved when the positive plate is applied to the lithium ion battery.
The invention also provides a lithium ion battery which comprises any one of the positive plate.
It can be understood that the lithium ion battery of the present invention includes, in addition to the positive electrode sheet, a negative electrode sheet, an electrolyte, and a separator, wherein the separator is spaced between the positive electrode sheet and the negative electrode sheet, and the electrolyte is filled between the positive electrode sheet and the negative electrode sheet.
The negative plate specifically comprises a negative current collector and a negative active layer arranged on the surface of the negative current collector. When the negative plate is prepared, the negative active material, the conductive agent and the binder can be dispersed in a proper amount of deionized water, and the mixture is fully stirred and mixed to form uniform negative slurry; and uniformly coating the negative electrode slurry on the negative electrode current collector layer, and drying, rolling and slitting to obtain the negative electrode sheet.
The anode active material of the present invention may be a carbon-containing material, a silicon-containing anode material, or a tin-containing anode material, or a mixture thereof at an arbitrary ratio. The carbonaceous negative electrode material includes at least one of artificial graphite, hard carbon, soft carbon, and the like; the silicon-containing anode material includes: silica, silicon, etc.; the negative electrode material containing tin includes: tin, tin oxide, and the like. The material of the negative electrode current collector may be at least one of copper foil, nickel foam, and copper foam. The conductive agent may be at least one selected from natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, and graphene. The binder may be at least one selected from the group consisting of carboxymethyl cellulose, styrene-butadiene rubber, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymer, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyamideimide, polyvinyl alcohol, and sodium polyacrylate.
The electrolyte selection is not strictly limited in the present invention, and may include one or more of the solvents commonly used in the current lithium battery electrolytes, and the electrolyte lithium salts commonly used in the current lithium ion electrolytes, such as: the solvent may be ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate (FEC), dimethyl carbonate (DMC), diethyl carbonate (DEC), difluoroethylene carbonate (DFEC), dipropyl carbonate, methylethyl carbonate (EMC), ethyl acetate, ethyl propionate, propyl acetate, propyl propionate, sulfolane, γ -butyrolactone, etc.; the lithium salt is selected from lithium hexafluorophosphate (LiPF)6) One or more of lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI).
The material selection of the diaphragm is not strictly limited, and the diaphragm can be a commonly used diaphragm material in the current lithium battery, such as one of a polypropylene diaphragm (PP), a polyethylene diaphragm (PE), a polypropylene/polyethylene double-layer composite film (PP/PE), a polyimide electrostatic spinning diaphragm (PI), a polypropylene/polyethylene/polypropylene three-layer composite film (PP/PE/PP), a cellulose non-woven fabric diaphragm and a diaphragm with a ceramic coating.
When the lithium ion battery is prepared, the positive plate, the diaphragm and the negative plate are wound or laminated to obtain a bare cell, and the bare cell is packaged into an aluminum-plastic film bag which is formed in a stamping mode in advance. And (3) after the packaged battery is dried at 85 ℃, injecting the electrolyte into the dried battery, and finishing the preparation of the lithium battery after the battery is laid aside, formed and secondarily sealed.
The lithium ion battery provided by the invention has significant advantages in energy density and cycle life because the lithium ion battery comprises the positive plate.
The lithium supplement additive and the lithium ion battery according to the present invention will be described in detail below with reference to specific embodiments. Unless otherwise specified, the chemical materials and instruments used in the following examples and comparative examples are all conventional chemical materials and conventional instruments, and are commercially available.
Example 1
The preparation method of the lithium supplement additive of the embodiment comprises the following steps:
weighing 2mol of Li in a nitrogen atmosphere3N, 3mol LiF is added into a double-planet ball mill to be fully ground and mixed into uniform powder, the rotating speed is set to be 500r/min, and the grinding time is 2 h. The powder obtained from the grinding was compressed into tablets on a powder tablet press under a nitrogen atmosphere, with a pressure set at 33 MPa. And (3) placing the obtained tablets in a high-temperature tube furnace by using a nickel boat, introducing nitrogen into the furnace, setting the furnace temperature to 800 ℃ and the heating rate to 10 ℃/min, heating to the set temperature, then calcining at constant temperature for 4h, and cooling to room temperature to obtain a calcined product. Adding the calcined product into a high-energy ball mill in nitrogen atmosphere, fully grinding and crushing the calcined product into uniform powder, setting the rotating speed to 2000 revolutions per minute, and grinding the powderAfter 4.5h, the Li lithium supplement additive of the embodiment is obtained9N2F3The average particle diameter D50 measured by a laser particle sizer is 1.5 mu m, and is marked as a lithium supplement additive 1 #.
And (3) testing chemical stability: the lithium supplement additive No. 1 is exposed to air with the relative humidity of 40% (room temperature and 25 ℃), and after 1h, no obvious change and no obvious irritant gas are generated.
And (3) testing lithium supplement capacity: stirring 90 parts by mass of a lithium supplement additive 1#, 5 parts by mass of an acetylene black conductive agent, 5 parts by mass of a PVDF binder and 60 parts by mass of an N-methylpyrrolidone (NMP) solvent for 4 hours under vacuum by a double planetary stirrer under the conditions of revolution of 40r/min and rotation of 3000r/min to disperse the materials into uniform slurry, coating the uniform slurry on an aluminum foil current collector with the thickness of 12 mu m, drying the aluminum foil current collector at 130 ℃, and coating one side of the aluminum foil current collector to ensure that the surface density of coating paste is 0.005g/cm2The membrane is compacted under 40MPa by a tablet press, and then is punched into small wafers by a 12mm circular punching machine, and the small wafers are matched with a diaphragm small wafer with the diameter of 16.5mm (a wet-process diaphragm ND12 produced by Shanghai Enjie New Material science and technology Co., Ltd., the thickness is 12 mu m) and a pure metal lithium small wafer with the diameter of 14mm (a lithium wafer is used as a negative electrode by Tianjin Lizhong Li industries Co., Ltd., the thickness is 0.2 mm), an electrolyte (1mol/L LiPF6 EC/DMC (volume ratio is 1:1)), a 2025 type stainless steel gasket, a 2025 type stainless steel shrapnel and a 2025 type button battery case, so as to assemble the 2025 type button battery. The first charging capacity Q of the assembled button cell is tested by a charging and discharging tester of blue-electricity electronic corporation of Wuhan city, and the charging system is as follows: the charging is carried out to 4.2V by a constant current of 1mA, then the charging is terminated by 4.2V and a constant voltage until the current is reduced to 0.05mA, and the initial charging capacity Q is recorded to 5.5 mAh. The unit mass lithium supplement capacity L/(0.6 × 3.1415926 × 0.005 × 0.9) ═ 1081 mAh/g.
Example 2
The preparation method of the lithium supplement additive of the embodiment comprises the following steps:
weighing 3mol of Li in an argon atmosphere3N, 1mol LiF is added into a sand mill to be fully ground and mixed into uniform powder, the rotating speed is set to be 1000 r/min, and the grinding time is 0.5 h. Grinding under argon atmosphereThe resulting powder was compressed into tablets on a powder tablet press with a pressure set at 50 MPa. And (3) placing the obtained zirconia ceramic boat for tabletting (the surface of which is plated with a LiF protective layer) in a high-temperature box type furnace, introducing argon into the furnace, setting the furnace temperature at 1000 ℃, heating the furnace at 20 ℃/min, heating to the set temperature, calcining at the constant temperature for 0.5h, and cooling to the room temperature to obtain a calcined product. Adding the calcined product into a grinder to fully grind and crush the calcined product into uniform powder under the argon atmosphere, setting the rotating speed to 800 revolutions per minute, and grinding the powder for 2.5 hours to obtain the Li lithium supplement additive of the embodiment7N3F, the average particle diameter D50 of the lithium ion battery is 11 μm measured by a laser particle sizer and is marked as a lithium supplement additive 2 #.
And (3) testing chemical stability: the lithium supplement additive No. 2 is exposed to air with the relative humidity of 40% (room temperature and 25 ℃), and after 1h, no obvious change and no obvious irritant gas are generated.
And (3) testing lithium supplement capacity: the test method was the same as that in example 1. Record the first charge Q7.41 mAh. The lithium supplement capacity per unit mass L is 1456 mAh/g.
Example 3
The preparation method of the lithium supplement additive of the embodiment comprises the following steps:
under argon atmosphere, weighing 1mol of Li3N, 1mol LiF is added into a double-planet ball mill to be fully ground and mixed into uniform powder, the rotating speed is set to be 300 r/min, and the grinding time is 4 h. The powder obtained from the grinding was compressed into tablets on a powder tablet press under an argon atmosphere, with the pressure set at 100 MPa. And (3) placing the obtained tablets in a high-temperature tube furnace by using a nickel boat, introducing nitrogen into the furnace, setting the furnace temperature at 400 ℃ and the heating rate at 5 ℃/min, heating to the set temperature, then calcining at the constant temperature for 12h, and cooling to the room temperature to obtain a calcined product. Adding the calcined product into a mechanical crusher in a nitrogen atmosphere, and sufficiently crushing the calcined product into uniform powder, wherein the rotating speed is set to 300 revolutions per minute, and the crushing time is 0.5h, so that the lithium supplement additive Li of the embodiment is obtained4NF, the average grain diameter D50 of the powder measured by a laser particle sizer is 50 μm, and is marked as a lithium supplement additive 3 #.
And (3) testing chemical stability: the lithium supplement additive No. 3 is exposed to air with the relative humidity of 40% (room temperature and 25 ℃), and after 1h, no obvious change and no obvious irritant gas are generated.
And (3) testing lithium supplement capacity: the test method was the same as that in example 1. The first charge Q was recorded as 6.69 mAh. The lithium supplement capacity L per unit mass is 1314 mAh/g.
Example 4
The preparation method of the lithium supplement additive of the embodiment comprises the following steps:
under argon atmosphere, weighing 1mol of Li3N, 3mol LiF is added into a double-planet ball mill to be fully ground and mixed into uniform powder, the rotating speed is set to be 600 revolutions per minute, and the grinding time is 1.5 hours. The powder obtained from the grinding was compressed into tablets on a powder tablet press under an argon atmosphere, with a pressure set at 20 MPa. And (3) placing the obtained tablets in a high-temperature tube furnace by using a nickel boat, introducing nitrogen into the furnace, setting the furnace temperature at 750 ℃ and the heating rate at 15 ℃/min, heating to the set temperature, then calcining at the constant temperature for 1.5h, and cooling to the room temperature to obtain a calcined product. Adding the calcined product into a double-planet ball mill in a nitrogen atmosphere, fully grinding and crushing the calcined product into uniform powder, setting the rotating speed to be 1000 revolutions per minute, and grinding the powder for 8.5 hours to obtain the lithium supplement additive Li of the embodiment6NF3The average particle diameter D50 measured by a laser particle sizer is 5.5 mu m, and is marked as a lithium supplement additive No. 4.
And (3) testing chemical stability: the lithium supplement additive No. 4 is exposed to air with the relative humidity of 40% (room temperature and 25 ℃), and after 1h, no obvious change and no obvious irritant gas are generated.
And (3) testing lithium supplement capacity: the test method was the same as that in example 1. Record the first charge Q3.61 mAh. The lithium supplement capacity L per unit mass is 710 mAh/g.
Example 5
The preparation method of the lithium supplement additive of the embodiment comprises the following steps:
weighing 2mol of Li in a nitrogen atmosphere3Adding N, 3mol LiCl into a double planetary ball mill, fully grinding and mixingSynthesizing uniform powder, setting the rotating speed to be 500r/min, and grinding for 2 h. The powder obtained from the grinding was compressed into tablets on a powder tablet press under a nitrogen atmosphere, with a pressure set at 33 MPa. And (3) placing the obtained tablets in a high-temperature tube furnace by using a nickel boat, introducing nitrogen into the furnace, setting the furnace temperature at 600 ℃ and the heating rate at 10 ℃/min, heating to the set temperature, then calcining at constant temperature for 4h, and cooling to room temperature to obtain a calcined product, wherein the gas flow rate is 100 ml/min. Adding the calcined product into a sand mill in a nitrogen atmosphere, fully grinding and crushing the calcined product into uniform powder, setting the rotating speed to 4000 revolutions per minute, and grinding for 6 hours to obtain the lithium supplement additive Li of the embodiment9N2Cl3The average particle diameter D50 measured by a laser particle sizer is 0.1 μm, and is marked as a lithium supplement additive No. 5.
And (3) testing chemical stability: the lithium supplement additive No. 5 is exposed to air with the relative humidity of 40% (room temperature and 25 ℃), and after 1h, no obvious change and no obvious irritant gas are generated.
And (3) testing lithium supplement capacity: the test method was the same as that in example 1. Record the first charge Q4.13 mAh. And the lithium supplement capacity L per unit mass is 812 mAh/g.
Example 6
The preparation method of the lithium supplement additive of the embodiment comprises the following steps:
weighing 2mol of Li in a nitrogen atmosphere3N, 2mol LiF and 1mol LiCl are added into a double-planet ball mill to be fully ground and mixed into uniform powder, the rotating speed is set to be 450 r/min, and the grinding time is 2 h. The powder obtained from the grinding was compressed into tablets on a powder tablet press under a nitrogen atmosphere, with a pressure set at 33 MPa. And (3) placing the obtained tablets in a high-temperature tube furnace by using a nickel boat, introducing nitrogen into the furnace, setting the furnace temperature to 800 ℃ and the heating rate to 10 ℃/min, heating to the set temperature, then calcining at the constant temperature for 2.5h, and cooling to the room temperature to obtain a calcined product, wherein the gas flow rate is 100 ml/min. Adding the calcined product into a high-energy ball mill in a nitrogen atmosphere, fully grinding and crushing the calcined product into uniform powder, setting the rotating speed to 900 revolutions per minute, and grinding the powder for 3.5 hours to obtain the lithium supplement additive Li of the embodiment9N2F2Cl, the average grain diameter D50 of the lithium ion battery is 20 μm measured by a laser particle sizer and is marked as the lithium supplement additive 6 #.
And (3) testing chemical stability: the lithium supplement additive No. 6 is exposed to air with the relative humidity of 40% (room temperature and 25 ℃), and after 1h, no obvious change and no obvious irritant gas are generated.
And (3) testing lithium supplement capacity: the test method was the same as that in example 1. Record the first charge Q4.96 mAh. The lithium-supplementing capacity per unit mass is 975 mAh/g.
Example 7
The preparation method of the lithium supplement additive of the embodiment comprises the following steps:
weighing 2mol of Li in a nitrogen atmosphere3N, 1mol LiF and 1mol LiCl are added into a double-planet ball mill to be fully ground and mixed into uniform powder, the rotating speed is set to be 450 r/min, and the grinding time is 2 h. The powder obtained from the grinding was compressed into tablets on a powder tablet press under a nitrogen atmosphere, with a pressure set at 33 MPa. And (3) placing the obtained tablets in a high-temperature tube furnace by using a nickel boat, introducing nitrogen into the furnace, setting the furnace temperature to 800 ℃ and the heating rate to 10 ℃/min, heating to the set temperature, then calcining at the constant temperature for 2.5h, and cooling to the room temperature to obtain a calcined product, wherein the gas flow rate is 100 ml/min. Adding the calcined product into a high-energy ball mill in a nitrogen atmosphere, fully grinding and crushing the calcined product into uniform powder, setting the rotating speed to be 1500 revolutions per minute, and grinding the powder for 3 hours to obtain the lithium supplement additive Li of the embodiment8N2FCl, the average grain diameter D50 is 8 μm measured by laser particle size analyzer, and is marked as No. 7 of lithium supplement additive.
And (3) testing chemical stability: the lithium supplement additive No. 7 is exposed to air with the relative humidity of 40% (room temperature and 25 ℃), and after 1h, no obvious change and no obvious irritant gas are generated.
And (3) testing lithium supplement capacity: the test method was the same as that in example 1. Record the first charge Q5.90 mAh. The lithium supplement capacity L per unit mass is 1159 mAh/g.
Example 8
The preparation method of the lithium supplement additive of the embodiment comprises the following steps:
weighing 5mol of Li in a nitrogen atmosphere3N, 1mol of LiF, 1mol of LiCl and 1mol of LiBr are added into a double-planet ball mill to be fully ground and mixed into uniform powder, the rotating speed is set to be 450 r/min, and the grinding time is 2 h. The powder obtained from the grinding was compressed into tablets on a powder tablet press under a nitrogen atmosphere, with a pressure set at 33 MPa. And (3) placing the obtained tablets in a high-temperature tube furnace by using a nickel boat, introducing nitrogen into the furnace, setting the furnace temperature to 800 ℃ and the heating rate to 10 ℃/min, heating to the set temperature, then calcining at the constant temperature for 2.5h, and cooling to the room temperature to obtain a calcined product, wherein the gas flow rate is 100 ml/min. Adding the calcined product into a high-energy ball mill in a nitrogen atmosphere, fully grinding and crushing the calcined product into uniform powder, setting the rotating speed to 1600 revolutions per minute, and grinding the powder for 3.2 hours to obtain the lithium supplement additive Li of the embodiment18N5FClBr, the average particle diameter D50 of the lithium ion battery is 7 μm measured by a laser particle sizer, and the lithium ion battery is marked as a lithium supplement additive No. 8.
And (3) testing chemical stability: the lithium supplement additive No. 8 is exposed to air with the relative humidity of 40% (room temperature and 25 ℃), and after 1h, no obvious change and no obvious irritant gas are generated.
And (3) testing lithium supplement capacity: the test method was the same as that in example 1. Record the first charge Q ═ 6.17 mAh. The unit mass lithium supplement capacity L is 1213 mAh/g.
Example 9
The preparation method of the positive plate of the embodiment comprises the following steps:
92 parts by mass of a nickel-cobalt-manganese ternary positive electrode material (Ningbo-bai New energy science and technology Co., Ltd., nickel-cobalt lithium manganate, NCM811, specific capacity of 191mAh/g), 5 parts by mass of a lithium supplement additive 1#, 1 part by mass of an acetylene black conductive agent, 0.5 part by mass of a carbon nanotube conductive agent, 1.5 parts by mass of a PVDF binder and 50 parts by mass of a solvent NMP are stirred by a double planetary stirrer for 4 hours under vacuum conditions of revolution of 30r/min and autorotation of 2000r/min to be dispersed into uniform positive electrode slurry, the uniform positive electrode slurry is coated on an aluminum foil with the thickness of 9 mu m, then a current collector is dried at 125 ℃, rolled under 35 tons of pressure and cut into positive electrode sheets.
The pole piece surface of the positive pole piece Z1 of the embodiment is denseThe degree is 18mg/cm2The compacted density is 3.45g/cm3。
Example 10
The method for preparing the positive electrode sheet Z2 in this example is basically the same as the method for preparing the positive electrode sheet Z2 in example 9, except that: 92 parts by mass of the nickel-cobalt-manganese ternary positive electrode material in example 9 was adjusted to 96 parts by mass of the nickel-cobalt-manganese ternary positive electrode material, and 5 parts by mass of the lithium supplement additive 1# was adjusted to 1 part by mass of the lithium supplement additive 4 #.
Example 11
The method for preparing the positive electrode sheet Z3 in this example is basically the same as the method for preparing the positive electrode sheet Z3 in example 9, except that: the lithium supplement additive # 1 in example 9 was adjusted to be a lithium supplement additive # 3.
Example 12
The method for preparing the positive electrode sheet Z4 in this example is basically the same as the method for preparing the positive electrode sheet Z4 in example 9, except that: 92 parts by mass of the nickel-cobalt-manganese ternary positive electrode material in example 9 was adjusted to 85 parts by mass of the nickel-cobalt-manganese ternary positive electrode material, and 5 parts by mass of the lithium supplement additive 1# was adjusted to 12 parts by mass of the lithium supplement additive 4 #.
Example 13
The method for preparing the positive electrode sheet Z5 in this example is basically the same as the method for preparing the positive electrode sheet Z5 in example 9, except that: 92 parts by mass of the nickel-cobalt-manganese ternary positive electrode material in example 9 was adjusted to 90 parts by mass of the nickel-cobalt-manganese ternary positive electrode material, and 5 parts by mass of the lithium supplement additive 1# was adjusted to 7 parts by mass of the lithium supplement additive 5 #.
Example 14
The method for preparing the positive electrode sheet Z6 in this example is basically the same as the method for preparing the positive electrode sheet Z6 in example 9, except that: 92 parts by mass of the nickel-cobalt-manganese ternary positive electrode material in example 9 was adjusted to 91 parts by mass of the nickel-cobalt-manganese ternary positive electrode material, and 5 parts by mass of the lithium supplement additive 1# was adjusted to 6 parts by mass of the lithium supplement additive 6 #.
Example 15
The method for preparing the positive electrode sheet Z7 in this example is basically the same as the method for preparing the positive electrode sheet Z7 in example 9, except that: 92 parts by mass of the nickel-cobalt-manganese ternary positive electrode material in example 9 was adjusted to 88 parts by mass of the nickel-cobalt-manganese ternary positive electrode material, and 5 parts by mass of the lithium supplement additive 1# was adjusted to 9 parts by mass of the lithium supplement additive 7 #.
Example 16
The method for preparing the positive electrode sheet Z8 in this example is basically the same as the method for preparing the positive electrode sheet Z8 in example 9, except that: 92 parts by mass of the nickel-cobalt-manganese ternary positive electrode material in example 9 was adjusted to 90 parts by mass of the nickel-cobalt-manganese ternary positive electrode material, and 5 parts by mass of the lithium supplement additive 1# was adjusted to 7 parts by mass of the lithium supplement additive 8 #.
Example 17
The preparation method of the positive plate of the embodiment comprises the following steps:
97 parts by mass of a nickel-cobalt-manganese ternary positive material (Nipponbo New energy science and technology Co., Ltd., nickel-cobalt lithium manganate, NCM811, specific capacity 191mAh/g), 1 part by mass of an acetylene black conductive agent, 0.5 part by mass of a carbon nanotube conductive agent, 1.5 parts by mass of a PVDF binder and 50 parts by mass of NMP (N-methyl pyrrolidone) as a solvent are stirred by a double planetary stirrer for 4 hours under the conditions of revolution of 30r/min and rotation of 2000r/min in vacuum, dispersed into uniform positive slurry, coated on an aluminum foil with the thickness of 9 mu m, dried at 125 ℃ (formation of a positive active layer), rolled under the pressure of 35 tons and cut. At this time, the surface density of the positive electrode active layer was 17mg/cm2The compacted density is 3.45g/cm3。
Stirring 95 parts by mass of lithium supplement additive 1#, 5 parts by mass of PVDF binder and 60 parts by mass of N-methylpyrrolidone (NMP) solvent for 4 hours under vacuum by a double planetary stirrer under the conditions of revolution of 40r/min and rotation of 3000r/min to disperse the lithium supplement slurry into uniform lithium supplement slurry, and then coating the lithium supplement slurry on the surface of the positive electrode active layer, wherein the coating surface density is 1mg/cm2After drying the solvent (forming a lithium supplement layer), the positive electrode sheet Z9 of this example was obtained.
Example 18
Compared with example 17, the lithium supplement layer of the positive electrode sheet Z10 of the present example is different from example 17 in that the preparation method of the lithium supplement layer of the positive electrode sheet Z10 of the present example includes: dissolving 90 parts by mass of lithium supplement additive 1#, 10 parts by mass of PVDF binder and 60 parts by mass of N-methylpyrrolidone (NMP)Stirring for 4h under vacuum by a double planetary stirrer under the conditions of revolution of 40r/min and rotation of 3000r/min to disperse the lithium supplementing slurry into uniform lithium supplementing slurry, and coating the lithium supplementing slurry on the surface of the active layer of the positive electrode, wherein the coating surface density is 1.5mg/cm2。
Example 19
Compared with example 17, the lithium supplement layer of the positive electrode sheet Z11 of the present example is different from example 17 in that the preparation method of the lithium supplement layer of the positive electrode sheet Z11 of the present example includes: stirring 90 parts by mass of lithium supplement additive 1#, 5 parts by mass of acetylene black conductive agent, 5 parts by mass of PVDF binder (average molecular weight 100 ten thousand) and 60 parts by mass of N-methylpyrrolidone (NMP) solvent for 4 hours under vacuum by a double planetary stirrer under the conditions of revolution of 40r/min and rotation of 3000r/min to disperse the lithium supplement slurry into uniform lithium supplement slurry, and then coating the lithium supplement slurry on the surface of an anode active layer, wherein the coating surface density is 2mg/cm2。
Example 20
Compared with example 17, the lithium supplement layer of the positive electrode sheet Z12 of the present example is different from example 17 in that the preparation method of the lithium supplement layer of the positive electrode sheet Z12 of the present example includes: stirring 92 parts by mass of lithium supplement additive 1#, 2 parts by mass of acetylene black conductive agent, 2 parts by mass of carbon nano tube conductive agent, 4 parts by mass of PVDF binder and 60 parts by mass of N-methylpyrrolidone (NMP) solvent for 4 hours under vacuum by a double planetary stirrer under the conditions of revolution of 40r/min and rotation of 3000r/min to disperse the lithium supplement slurry into uniform lithium supplement slurry, and then coating the lithium supplement slurry on the surface of the positive electrode active layer, wherein the coating surface density is 1.5mg/cm2。
Example 21
Compared with example 17, the lithium supplement layer of the positive electrode sheet Z13 of the present example is different from example 17 in that the preparation method of the lithium supplement layer of the positive electrode sheet Z13 of the present example includes: stirring 99 parts by mass of lithium supplement additive 1#, 1 part by mass of polyethylene oxide (PEO, average molecular weight of 700 ten thousand) and 200 parts by mass of acetonitrile solvent for 4h under vacuum by a double-planet stirrer under the conditions of revolution of 40r/min and rotation of 3000r/min to disperse the lithium supplement slurry into uniform lithium supplement slurry, and then coating the lithium supplement slurry on the surface of the collection active layer, wherein the coating surface density is 1.5mg/cm2。
Example 22
Compared with example 17, the lithium supplement layer of the positive electrode sheet Z14 of the present example is different from example 17 in that the preparation method of the lithium supplement layer of the positive electrode sheet Z14 of the present example includes: 94 parts by mass of lithium supplement additive 1#, 4 parts by mass of polycarbonate (polypropylene carbonate, average molecular weight 40 ten thousand), 1 part by mass of acetylene black conductive agent, 1 part by mass of carbon nano tube conductive agent and 80 parts by mass of DMF solvent are stirred for 4 hours under the conditions of revolution of 40r/min and rotation of 3000r/min by a double-planet stirrer in vacuum to be dispersed into uniform lithium supplement slurry, and then the lithium supplement slurry is coated on the surface of an anode active layer, wherein the coating surface density is 1.5mg/cm2。
Comparative example 1
The preparation method of the positive electrode Z1a sheet of the comparative example comprises the following steps:
97 parts by mass of a nickel-cobalt-manganese ternary positive electrode material (Ningbo-bai New energy science and technology Co., Ltd., nickel-cobalt lithium manganate, NCM811, specific capacity 191mAh/g), 1 part by mass of an acetylene black conductive agent, 0.5 part by mass of a carbon nanotube conductive agent, 1.5 parts by mass of a PVDF binder and 50 parts by mass of a solvent NMP are stirred by a double planetary stirrer under vacuum conditions of revolution of 30r/min and rotation of 2000r/min for 4 hours to be dispersed into uniform slurry, the uniform slurry is coated on an aluminum foil current collector with the thickness of 9 mu m, and then the aluminum foil current collector is dried at 125 ℃, rolled under the pressure of 35 tons and cut into positive electrode sheets. The pole piece surface density of the positive pole piece is 18mg/cm2The compacted density is 3.45g/cm3。
Comparative example 2
The preparation method of the positive electrode sheet Z2a of the comparative example comprises the following steps:
92 parts by mass of nickel-cobalt-manganese ternary cathode material (Ningbo-bai new energy science and technology, Co., Ltd., lithium nickel-cobalt-manganese oxide, NCM811, specific capacity 191mAh/g) and 5 parts by mass of Li3N powder (commercially available, having an average particle diameter of 18 μm), 1 part by mass of acetylene black conductive agent, 0.5 part by mass of carbon nanotube conductive agent, 1.5 parts by mass of PVDF binder, and 50 parts by mass of NMP as a solvent were stirred by a double planetary mixer under vacuum for 4 hours under conditions of revolution at 30r/min and rotation at 2000r/min to disperse the mixture into a uniform slurry, which was then coatedDrying the obtained product on an aluminum foil current collector with the thickness of 9 mu m at 125 ℃, rolling the obtained product under the pressure of 35 tons, and cutting the obtained product into positive plates. The pole piece surface density of the positive pole piece is 18mg/cm2The compacted density is 3.45g/cm3。
Wherein Li3N powder (commercially available, average particle size 18 μm) chemical stability test: mixing Li3The N powder was exposed to air at a relative humidity of 40% (room temperature 25 ℃ C.), and after 1h, Li3The N powder changed from a purple red to a grey white color and was generated with ammonia gas, which had an irritating odor.
Test examples
The positive electrode sheets Z1-Z14 in the examples and the positive electrode sheets Z1a-Z2a in the comparative examples are respectively matched with a negative electrode sheet, a Polyethylene (PE) porous diaphragm (a wet-process diaphragm ND12 produced by Shanghai Enjie New Material science and technology Limited, and the thickness of the diaphragm is 12 μm), a lithium ion battery electrolyte (an LBC445B33 model electrolyte of Shenzhen Xinjiang science and technology Limited), a positive electrode tab (an aluminum tab of Licheng Delixin electronics Limited, Hongkong) and a negative electrode tab (a nickel tab of Licheng Delixin electronics Limited), and the lithium ion batteries are prepared by a conventional lithium ion battery preparation process and are marked as lithium ion batteries C1-C14 and C1a-C2 a.
The preparation method of the negative plate comprises the following steps: 50 parts by mass of artificial graphite (an artificial graphite material LKP-G5 of Shanghai fir Technology Co., Ltd., a specific capacity of 355mAh/G), 44 parts by mass of a silica negative electrode material (a silica negative electrode material SO1600 of Liyang Tianmu Pilot cell materials Technology Co., Ltd., a specific capacity of 1600mAh/G), 2.0 parts by mass of a carbon black conductive agent, 1.0 part by mass of a carbon nanotube conductive agent, 2.5 parts by mass of an SBR binder, 0.5 part by mass of carboxymethyl cellulose and 100 parts by mass of solvent water, stirring for 4h under vacuum with revolution of 30r/min and rotation of 1500r/min by a double planetary stirrer, dispersing into uniform slurry, coating on the surface of 6 μm copper foil, and then drying at 110 ℃, rolling under 40 tons of pressure, and finally cutting into the negative plate with the required size, wherein the surface density of the negative plate is 5 mg/cm.2The compacted density of the pole piece is 1.69g/cm3。
The energy density and the cycle life of the lithium ion battery are detected by the following detection method:
1. first charge-discharge efficiency detection
Charging the battery to 4.25V at 25 deg.C with 0.5C constant current, then charging with constant voltage until the current is reduced to 0.02C, standing for 5min, discharging the battery to 2.5V with 0.5C constant current, and recording the first charge capacity Q of the batteryCharging deviceAnd first discharge capacity QPutCalculating the first charge-discharge efficiency eta of the battery as EPut/ECharging deviceX 100%. The results are shown in Table 1.
2. Energy density detection
Charging the battery to 4.25V at 25 deg.C with 0.5C constant current by using battery charge-discharge tester, then charging with constant voltage until the current is reduced to 0.02C, standing for 5min, discharging the battery to 2.5V with 0.5C constant current, and recording the first discharge capacity Q of the batteryPutAnd first discharge energy EPutWeighing the cell, recording the weight as W, and calculating the energy density ED as EPutand/W. The results are shown in Table 1.
1. Cycle life detection
Using a battery charge-discharge tester to perform charge-discharge cycle test on the battery at 25 ℃, wherein the charge-discharge system comprises the following steps: charging to 4.25V at 0.5C constant current, then charging at constant voltage until the current is reduced to 0.02C, standing for 5min, discharging the battery to 2.5V at 0.5C constant current for 1 cycle, and setting the cycle number of the battery charge-discharge tester to 5000 times. The capacity of the battery decays continuously as the battery cycles, and the number of cycles that the battery undergoes when the capacity decays to 80% of the first discharge capacity qrad is recorded as the cycle life of the battery. The results are shown in Table 1.
TABLE 1
As can be seen from Table 1: compared with a comparative example, the positive plate containing the lithium supplement additive is used in the lithium ion battery, so that the first charge-discharge efficiency and the energy density of the lithium ion battery can be obviously improved, and the cycle life of the lithium ion battery is prolonged.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The lithium supplement additive is characterized in that the lithium supplement additive consists of Li3x+yNxFaClbBrcIdWherein x is not less than 1 and is an integer, a is not less than 0, b is not less than 0, c is not less than 0, d is not less than 0, y is a + b + c + d, and y is not less than 1 and is an integer.
2. The lithium supplement additive according to claim 1, wherein the lithium supplement additive is prepared by a method comprising the following steps:
under an inert atmosphere, Li3Mixing N with lithium halide, and calcining at the temperature of 400-1000 ℃ to obtain the lithium supplement additive;
wherein the lithium halide is at least one selected from the group consisting of lithium fluoride, lithium chloride, lithium bromide and lithium iodide.
3. The lithium supplement additive according to claim 2, wherein the calcination treatment time is 0.5 to 12 hours.
4. The lithium supplement additive according to any one of claims 1 to 3, wherein the lithium supplement additive has an average particle size D50 of 0.1 to 50 μm.
5. A method for preparing the lithium supplement additive according to any one of claims 1 to 4, comprising the steps of: under an inert atmosphere, Li3Mixing N and lithium halide, and calcining at 400-1000 deg.C to obtain the final productThe lithium supplement additive;
wherein the lithium halide is at least one selected from the group consisting of lithium fluoride, lithium chloride, lithium bromide and lithium iodide.
6. The positive plate is characterized by comprising a current collector and a positive active layer arranged on at least one surface of the current collector;
wherein the positive electrode active layer comprises the lithium supplement additive according to any one of claims 1 to 4.
7. The positive electrode sheet according to claim 6, wherein the mass fraction of the lithium supplement additive in the positive electrode active layer is 1 to 10%.
8. The positive plate is characterized by comprising a current collector, a positive active layer arranged on at least one surface of the current collector, and a lithium supplement layer arranged on at least one surface of the positive active layer;
wherein the lithium supplement layer comprises the lithium supplement additive of any one of claims 1-4.
9. The positive electrode sheet according to claim 8, wherein the lithium supplement layer contains 50 to 99.9 mass% of the lithium supplement additive.
10. A lithium ion battery, characterized in that it comprises the positive electrode sheet according to any one of claims 6 to 9.
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