CN115117425A - Lithium ion secondary battery and preparation method and application thereof - Google Patents
Lithium ion secondary battery and preparation method and application thereof Download PDFInfo
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- CN115117425A CN115117425A CN202110285318.9A CN202110285318A CN115117425A CN 115117425 A CN115117425 A CN 115117425A CN 202110285318 A CN202110285318 A CN 202110285318A CN 115117425 A CN115117425 A CN 115117425A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 45
- 239000007774 positive electrode material Substances 0.000 claims abstract description 30
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- 229910013716 LiNi Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
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- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
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- FVCJARXRCUNQQS-UHFFFAOYSA-N trimethylsilyl dihydrogen phosphate Chemical compound C[Si](C)(C)OP(O)(O)=O FVCJARXRCUNQQS-UHFFFAOYSA-N 0.000 description 1
- IIVDETMOCZWPPU-UHFFFAOYSA-N trimethylsilyloxyboronic acid Chemical compound C[Si](C)(C)OB(O)O IIVDETMOCZWPPU-UHFFFAOYSA-N 0.000 description 1
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention relates to the field of lithium ion batteries, and discloses a lithium ion secondary battery and a preparation method and application thereof. The lithium ion secondary battery comprises a positive plate and a negative plate, wherein the positive plate contains a positive active material, and the positive active material contains Mg 2+ Doped lithium nickel cobalt aluminate material and coating on Mg 2+ Doped nickelZnO on the surface of the lithium cobalt aluminate material, wherein the content of ZnO is 0.1-2 wt% based on the total weight of the positive electrode active material, and Mg 2+ The content of the doped lithium nickel cobalt aluminate material is 98-99.9 wt%. The lithium ion secondary battery has a discharge capacity of more than or equal to 2700mAh under the condition of 0.2C, a specific energy of more than or equal to 240Wh/kg and a longer cycle life.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a lithium ion secondary battery and a preparation method and application thereof.
Background
Rechargeable electric tools are becoming more popular, and the power batteries that provide power for electric tools mainly include nickel-cadmium, nickel-hydrogen and lithium ion batteries.
With the increasing attention of people on environmental protection, nickel-cadmium batteries with heavy metal cadmium pollution are increasingly limited. The nickel-metal hydride battery has low energy density, short service life, memory effect and high manufacturing cost, so that the application of the nickel-metal hydride battery is limited. The lithium ion battery has excellent performance, long high-rate discharge cycle life, no memory effect, no pollution, high specific power/energy, excellent cost performance and wide application prospect in the electric tool industry.
The basic requirements of lithium ion batteries for electric tools are as follows: firstly, the safety and the reliability are realized, and the fire and the explosion do not occur when the device is used by mistake; the internal resistance of the battery is required to be as small as possible, and enough energy or power can be released at a high multiplying power (more than 5C) within a wide environment temperature range; thirdly, the energy density is higher and the service life is acceptable; fourthly, the lithium ion battery has better cost performance compared with other types of secondary batteries.
In the process of developing and improving specific energy while ensuring battery performance, cylindrical batteries are receiving more and more attention, and 18650 type cylindrical batteries are widely used due to size standardization, high product maturity and mature process equipment. Currently, a cylindrical battery for 18650 type electric tools in the market adopts a system of an NCM (lithium nickel cobalt manganese oxide battery) or NCA (lithium nickel cobalt aluminate battery) anode and a graphite cathode, and the 0.2C capacity is mainly 1300mAh-2500 mAh.
With the increasing use requirements of users, there is a strong demand for high-power, high-specific energy and long-cycle lithium ion secondary batteries to meet the expanding application markets (e.g., garden tools, home appliances, etc.).
Therefore, it is of great importance to research and develop lithium ion secondary batteries having high discharge capacity and long cycle life.
Disclosure of Invention
The invention aims to overcome the defects of low discharge capacity and poor cycle performance of the lithium ion secondary battery in the prior art, and provides the lithium ion secondary battery, and the preparation method and the application thereof.
In order to achieve the above object, a first aspect of the present invention provides a lithium ion secondary battery comprising a positive electrode sheet containing a positive electrode active material, and a negative electrode sheet, wherein the positive electrode active material contains Mg 2+ Doped lithium nickel cobalt aluminate material and coating on Mg 2+ ZnO on the surface of the doped nickel cobalt lithium aluminate material, wherein the content of ZnO is 0.1-2 wt% based on the total weight of the positive active material, and Mg 2+ The content of the doped lithium nickel cobalt aluminate material is 98-99.9 wt%.
A second aspect of the present invention provides a method for manufacturing the aforementioned lithium-ion secondary battery, wherein the method includes:
(1) carrying out sheet-making winding, assembling and liquid injection on the positive plate, the negative plate, the diaphragm and the electrolyte to obtain a battery to be formed;
(2) and sequentially carrying out formation and aging on the battery to be formed to obtain the lithium ion secondary battery.
In a third aspect, the present invention provides a use of the lithium ion secondary battery in a rechargeable electric tool.
Through the technical scheme, the discharge capacity of the lithium ion secondary battery provided by the invention under the condition of 0.2C is more than or equal to 2700mAh, the specific energy is more than or equal to 240Wh/kg, 4A charging is carried out, 10A, 20A and 30A discharging is carried out, and the initial capacities of 80%, 70% and more than 60% are respectively maintained after 600 times of circulation. In addition, the lithium ion secondary battery provided by the invention has excellent electrochemical performance and safety performance.
Drawings
Fig. 1 is a schematic flow chart of a method for manufacturing a lithium ion secondary battery of the present invention;
fig. 2 is a schematic diagram of a cell structure of the lithium ion secondary battery of the present invention;
fig. 3 is a schematic diagram showing the relationship between cycle number and energy retention rate when the lithium ion secondary battery prepared in example 1 of the present invention is charged at a constant current of 4A, discharged at a constant current of 10A to 2.5V;
fig. 4 is a schematic diagram showing the relationship between cycle number and energy retention rate when the lithium ion secondary battery prepared in example 1 of the present invention is charged at a constant current of 4A, discharged at a constant current of 20A to 2.5V;
fig. 5 is a schematic diagram showing the relationship between cycle number and energy retention rate when the lithium ion secondary battery prepared in example 1 of the present invention is charged at a constant current of 4A, discharged at a constant current of 30A to 2.5V.
Description of the reference numerals
1 negative electrode tab 2 insulating spacer 3 casing
4 diaphragm 5 negative plate 6 positive plate
7 insulating pad 8 positive lug 9 block
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention provides, in a first aspect, a lithium ion secondary battery comprising a positive electrode sheet containing a positive electrode active material, and a negative electrode sheet, wherein the positive electrode active material contains Mg 2+ Doped lithium nickel cobalt aluminate material and coating on Mg 2+ ZnO on the surface of the doped nickel cobalt lithium aluminate material, wherein the content of ZnO is 0.1-2 wt% based on the total weight of the positive active material, and Mg 2+ The content of the doped lithium nickel cobalt aluminate material is 98-99.9 wt%.
The inventors of the present invention have surprisingly found that: adopts metal oxide coating and ion doping technology, firstly uses ion doping technology to obtain Mg 2+ Doping nickel cobalt lithium aluminate material, and coating the doped nickel cobalt lithium aluminate material with ZnO. Mg (magnesium) 2+ The nickel-cobalt lithium aluminate material is doped, so that the migration channel of lithium ions in the crystal lattice of the ternary material is expanded, the conductivity of the material is improved, and the rate capability of the battery is improved. The ZnO coating can improve the interface condition of the active material and the electrolyte, inhibit the adverse reaction of the interface, and improve the high discharge capacity, specific energy and cycle life of the material.
Further, a silica-graphite composite material is used as a negative electrode active material, and graphite (carbon) coating is performed on the silica. On one hand, SiO particles are used as active substances to provide lithium storage capacity; on the other hand, the graphite can buffer the volume change of SiO particles in the charging and discharging processes, improve the conductivity of the SiO material and avoid the agglomeration of the SiO particles in the charging and discharging cycles. Thus, the silica-graphite composite combines the advantages of both, exhibiting high discharge capacity, specific energy and long cycle life.
According to the present invention, the total amount of the positive electrode active material is preferablyThe content of ZnO is 0.2 to 1.5 weight percent based on the weight, and Mg 2+ The content of the doped lithium nickel cobalt aluminate material is 98.5-99.8 wt%; in the present invention, the ZnO and the Mg are mixed 2+ The content of the doped lithium nickel cobalt aluminate material is limited in the range, so that the power performance and the cycle performance of the material can be better improved.
According to the present invention, Mg is added to the positive electrode active material based on the total weight of the positive electrode active material 2+ The doping amount is 0.01-0.05 wt%, preferably 0.01-0.04 wt%. In the present invention, Mg is added 2+ The doping amount is limited within the range, so that the cycle life of the material can be better prolonged.
According to the invention, preferably, said Mg 2+ The expression of the doped lithium nickel cobalt aluminate material is LiNi 0.8 Co 0.1 Al 0.08 Mg 0.02 O 2 。
According to the present invention, the positive electrode active material has a particle diameter of 5 to 20 μm and a specific surface area of 0.5 to 1.5m 2 G, the gram capacity is 200-208 mAh/g; preferably, the positive electrode active material has a particle size of 5 to 15 μm and a specific surface area of 0.7 to 1.4m 2 G, the gram capacity is 202-206 mAh/g.
According to the invention, the positive plate also comprises a positive conductive agent, a positive binder and a positive additive, and based on the total weight of the positive plate, the content of the positive active material is 91.5-98.95 wt%, the content of the positive conductive agent is 0.5-3 wt%, the content of the positive additive is 0.05-1.5 wt%, and the content of the positive binder is 0.5-4 wt%; preferably, the content of the positive electrode active material is 95-96.5 wt%, the content of the positive electrode conductive agent is 1.5-2 wt%, the content of the positive electrode additive is 0.5-1 wt%, and the content of the positive electrode binder is 1.5-2 wt% based on the total weight of the positive electrode sheet. In the present invention, the content ranges of the positive electrode active material, the positive electrode conductive agent, the positive electrode binder, and the positive electrode additive are defined within the foregoing ranges, and the specific capacity and power performance of the battery can be improved.
According to the present invention, the positive electrode conductive agent is selected from one or more of SP (SUPER-P), Ketjen black, KS-6 and acetylene black; preferably, the conductive agent is SP (SUPER-P). Wherein the conductive agent SUPER-P has a particle size of 30-40nm and is small-particle conductive carbon black. The Ketjen black has a particle size of 30-50nm and is a type of superconducting carbon black. KS-6 has a particle size of about 6.5 μm and is a large particle graphite powder. The acetylene black has a particle size of 35-45nm, is carbon black, and is characterized by being between SUPER-P and KS-6.
According to the invention, the positive electrode binder is selected from one or more of polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), Polyimide (PI) and polyacrylic acid (PAA); preferably, the positive electrode binder is polyvinylidene fluoride (PVDF).
According to the invention, the positive electrode additive is lithium carbonate (Li) 2 CO 3 )。
According to the invention, the negative plate contains a negative active material, and the negative active material contains a silica-graphite composite material; preferably, the negative active material contains silicon oxide and graphite coated on the surface of the silicon oxide; preferably, the content of the silica is 3 to 15 wt% and the content of the graphite is 85 to 97 wt%, based on the total weight of the anode active material; more preferably, the content of the silica is 5 to 10 wt% and the content of the graphite is 90 to 95 wt%, based on the total weight of the anode active material; still more preferably, the content of the silica is 6 to 7 wt% and the content of the graphite is 93 to 94 wt%, based on the total weight of the anode active material. In the present invention, the content of the silica and the graphite is limited to the foregoing range, which has advantages in that good cycle performance can be obtained, and the capacity does not vary too much due to too high or too low amount of SiO, thereby affecting battery performance.
According to the invention, the particle size of the silica is 2-10 μm and the specific surface area is 0.5-2.0m 2 G, the gram capacity is 1550-; preferably, the particle size of the silicon monoxide is 4-7 μm, and the specific surface area is 1-1.5m 2 The gram capacity is 1600-1630 mAh/g. In the present invention, the particle diameter, specific surface area and gram volume of the silica are defined within the foregoing ranges, and there is an advantage in thatThe reaction activity of the material is ensured in a reasonable range, and the properties of the material, such as circulation and the like, cannot be influenced by side reaction increase caused by overlarge specific surface area.
According to the invention, the particle size of the graphite is 3-15 μm, and the specific surface area is 1.0-2.5m 2 (ii)/g; preferably, the graphite has a particle size of 7 to 12 μm and a specific surface area of 1.5 to 2.0m 2 (ii) in terms of/g. In the present invention, the particle size and specific surface area of the graphite are limited to the above ranges, which has the advantages that sufficient reactivity and power performance of the material can be ensured, and side reactions on the surface of the negative electrode are not increased due to an excessively large specific surface area.
According to the invention, the negative plate also contains a negative conductive agent and a negative binder, and based on the total weight of the negative plate, the content of the negative active material is 92-98 wt%, the content of the negative conductive agent is 0.5-2 wt%, and the content of the negative binder is 1.5-6 wt%; preferably, the content of the negative active material is 95.5 to 97.5 wt%, the content of the negative conductive agent is 1 to 1.5 wt%, and the content of the negative binder is 1.5 to 3 wt%, based on the total weight of the negative electrode sheet. In the invention, the contents of the negative electrode active material, the negative electrode conductive agent and the negative electrode binder are limited within the ranges, so that the ionic conductivity and the conductivity of the negative electrode plate can be ensured, and the specific capacity of the negative electrode plate cannot be reduced due to the excessive conductive agent and the negative electrode binder.
According to the invention, the negative electrode conductive agent is single-walled Carbon Nanotubes (CNT) and/or Super-P; preferably, the negative electrode conductive agent is a composite conductive agent of a single-walled carbon nanotube and Super-P, and the weight ratio of the single-walled carbon nanotube to the Super-P is 1: (10-100); preferably 1: (15-50). In the invention, the composite conductive agent is adopted, and the electronic conductivity is enhanced compared with that of a single conductive agent.
According to the invention, the negative electrode binder is a composite binder of sodium carboxymethyl cellulose and styrene butadiene rubber, and the weight ratio of the sodium carboxymethyl cellulose to the styrene butadiene rubber is 1: (1-10), preferably 1: ((2-6)).
According to the invention, the negative plate is a double-tab. In the invention, it should be explained that the bipolar tab refers to ultrasonic welding of two aluminum strips with a specification of 4mm x 0.1mm at the blank position of the negative plate, and the unipolar tab refers to ultrasonic welding of 1 nickel strip with a specification of 4mm x 0.1mm at the blank position of the positive plate.
According to the present invention, the lithium ion secondary battery includes a separator, which is a ceramic separator; preferably, the diaphragm comprises PP/PE/PP (polypropylene/polyethylene/polypropylene) and Al coated on the surface of the PP/PE/PP 2 O 3 (ii) a Preferably, the Al 2 O 3 The thickness of the coating is 1-4 um.
According to the invention, the total thickness of the separator is 12 to 16 μm.
According to the present invention, the lithium ion secondary battery further includes an electrolyte, wherein the electrolyte includes a lithium salt, an electrolyte solvent, and an additive selected from at least one of TMSB (trimethylsilylborate)), TMSP (trimethylsilylphosphate), and LiTFSI (lithium bistrifluoromethanesulfonylimide).
A second aspect of the present invention provides a method for manufacturing the aforementioned lithium ion secondary battery, wherein the method includes:
(1) the positive plate, the negative plate, the diaphragm and the electrolyte are subjected to sheet-making winding, assembly and liquid injection to obtain a battery to be formed;
(2) and sequentially carrying out formation and aging on the battery to be formed to obtain the lithium ion secondary battery.
According to a preferred embodiment of the present invention, the method for manufacturing a lithium ion secondary battery includes:
(1) preparing a positive plate: using N-methyl pyrrolidone (NMP) as a solvent, preparing a positive binder into glue with the solid content of 6-9 wt%, adding a positive conductive agent and a positive active material into the glue, uniformly stirring to obtain slurry, adding NMP to adjust the solid content of the slurry to 65-75 wt% and the viscosity to 4000-5500mPa.s to obtain positive slurry, coating the positive slurry on a positive current collector, and then rolling and dividing to obtain a positive plate;
preparing a negative plate: preparing a negative electrode binder into glue with the solid content of 1.0-3.5 wt% by taking water as a solvent, adding a negative electrode conductive agent and a negative electrode active material into the glue, uniformly stirring to obtain slurry, adding water to adjust the solid content of the slurry to be 35-50 wt% and the viscosity to be 2000-3500mPa.s to obtain negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector, and then rolling and dividing to obtain a negative electrode sheet;
(2) carrying out sheet-making winding, assembling and liquid injection on the positive plate, the negative plate, the diaphragm and the electrolyte to obtain a battery to be formed;
(3) and sequentially carrying out formation and aging on the battery to be formed to obtain the high-power 18650 lithium ion battery.
(4) Wherein, in the step (3), the formation conditions include: (a) charging for 1h at 0.05 ℃ under constant current until the cut-off voltage is 3.65V; b) charging for 1h at a constant current of 0.1 ℃ until the cut-off voltage is 3.65V;
(5) preferably, in step (3), the aging conditions include: placing the formed battery into an oven at 40-60 ℃ for standing for 24-36 h.
According to the present invention, room temperature means 23. + -. 2 ℃ unless otherwise specified.
In a third aspect, the present invention provides a use of the lithium ion secondary battery in a rechargeable power tool.
It should be noted that 18650 type lithium ion secondary battery according to the present invention means a cylindrical lithium ion battery having an outer diameter and a height of 18mm and 65mm, respectively, that is, "18" means a diameter of 18mm, "65" means a length of 65mm, and "0" means a cylindrical battery.
According to the invention, the 18650 type electric tool can be used as a charging electric tool, can be used as a power supply of a garden tool and/or a household appliance, and has wide application prospect and commercial prospect.
Additional features and advantages of the invention will be described in detail in the detailed description which follows.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
the cycle life data is measured by a BTS series battery test cabinet of Shenzhen New Wille electronics Limited;
the super carbon black of the positive and negative electrode conductive agents is a product sold in Belgium Extra high company with the model number SP.
The lithium carbonate as the positive electrode additive is a commercial product with the specification of battery grade of Jiangxi Jianfeng lithium industry company in Jiangxi.
The positive electrode binder polyvinylidene fluoride is commercially available from sulva chemical company, belgium as model PVDF 5130.
The negative electrode conductive agent carbon nano tube is a commercial product of LB212 model of Zhenjiang Tiannai company
The negative electrode binder styrene-butadiene rubber was commercially available from LG chemical corporation of korea under the model number B81.
Example 1
This example is to illustrate a 18650 type lithium ion secondary battery prepared by the method of the present invention.
The preparation was carried out according to the flow diagram of the preparation method of the lithium ion secondary battery shown in fig. 1:
(1) preparation of positive and negative pole pieces
1. Composition of the positive electrode powder:
positive electrode active material: 96.0 wt% ZnO coated Mg 2+ Doped polycrystalline NCA material (particle size 10.2 μm, specific surface area 0.86 m) 2 G, gram capacity 203.5mAh/g, zinc oxide coating amount of 1 percent, Mg 2+ The doping amount is 0.02%);
positive electrode conductive agent: 1.9 wt% SP;
and (3) a positive electrode additive: 0.2 wt% Li 2 CO 3 ；
Positive electrode binder: 1.9 wt% PVDF binder;
taking the total weight of the anode powder as a reference, the anode active material is as follows: positive electrode conductive agent: and (3) a positive electrode additive: the content ratio of the positive electrode binder is 96.0 wt%: 1.9 wt%: 0.2 wt%: 1.9 wt%;
preparing a positive plate: bonding PVDF by using NMP as solventPreparing glue with the solid content of 8 wt% by using the agent, adding a positive electrode conductive agent, a positive electrode additive and a positive electrode active material into the glue, uniformly stirring to obtain slurry, adding NMP (N-methyl pyrrolidone) to adjust the solid content of the slurry to 71.9% and the viscosity to 5000mPa.s to obtain positive electrode slurry (positive electrode slurry); the positive electrode slurry was coated on an aluminum foil having a thickness of 16 μm and an areal density of 133.2g/cm 2 Rolling the thickness of the coated and dried positive plate to 97 mu m by using a double-roller rolling machine, then cutting the rolled positive plate by using a slitting machine, reserving a tab welding position on the positive plate to obtain the positive plate, putting the cut positive plate into a high-vacuum degree oven, and controlling the moisture content of the positive plate to be less than 150 ppm;
2. composition of the negative electrode powder:
negative electrode active material: silica (SiO) -graphite composite material, wherein 7.0 wt% of Silica (SiO) material (particle diameter 5 μm, specific surface area 1.19 m) 2 1620mAh/g gram capacity), 93.0 wt% natural graphite (11.2 μm particle diameter, 1.26m specific surface area) 2 /g)；
Negative electrode conductive agent: a composite conductive agent of single-walled CNT (carbon nanotube) and SP (the weight ratio of single-walled CNT to SP is 1: 15);
negative electrode binder: a composite binder of CMC and SBR (the weight ratio of CMC to SBR is 1: 2);
taking the total weight of the negative electrode powder as a reference, the negative electrode active material: negative electrode conductive agent: the content ratio of the negative electrode binder is 95.5 wt%: 1.5 wt%: 3.0 wt%;
preparing a negative plate: preparing a negative electrode binder into glue with solid content of 3.0 wt% by taking water as a solvent, adding a negative electrode conductive agent and a negative electrode active material into the glue, uniformly stirring to obtain slurry, adding water to adjust the solid content of the slurry to be 45% and the viscosity to be 3000mPa.s, and obtaining negative electrode slurry (negative electrode slurry mixture); coating the negative electrode slurry on a copper foil with the thickness of 10 mu m, and rolling the coated and dried negative electrode sheet to the thickness of 101 mu m by using a double-roller rolling machine, wherein the surface density is 68.8g/cm 2 Then, a slitting machine is used for slitting the rolled negative plate, and two tab connecting positions are reserved on the negative plateAnd placing the obtained negative pole pieces to be bipolar lug pole pieces, putting the cut negative pole pieces into a high-vacuum oven, and controlling the moisture content of the negative pole pieces to be less than 250 ppm.
(2) Preparing an electrolyte: the electrolyte solvent is prepared from Ethylene Carbonate (EC), dimethyl carbonate (DMC) and Ethyl Methyl Carbonate (EMC) according to the weight ratio of 2: 1: 15 volume ratio of the electrolyte is LiPOF 6 (ii) a In the electrolyte, Li + The concentration was 1.5mol/L, the concentration of Vinylene Carbonate (VC) was 2.0 wt%, and the concentration of fluoroethylene carbonate (FEC) was 10 wt%.
(3) The diaphragm is Al with a thickness of 16 μm 2 O 3 Coated ceramic diaphragm (Al) 2 O 3 The coating layer thickness was 4 μm).
(4) Winding the negative electrode plate 5, the diaphragm 4, the positive electrode plate 6 and the diaphragm in sequence by using a sheet-making winder to prepare a battery cell as shown in FIG. 2; then, sequentially loading the lower insulating gasket 2, the battery cell and the upper insulating gasket 7 into a steel shell (namely, a shell 3 in fig. 2), and performing procedures of resistance welding of a negative electrode tab 1 at the bottom of the steel shell, rolling a groove and short circuit detection to obtain the battery cell to be injected with liquid; injecting electrolyte under the environment with the dew point temperature of minus 45 ℃, then welding the positive lug 8 and the cap 9 by adopting a laser welding mode, sealing to prepare a 18650 lithium ion battery, then cleaning the sealed battery, coating antirust oil, and standing at normal temperature;
(4) the battery after will shelve carries out formation and ageing in proper order, and wherein, the condition of formation includes: charging at 0.05C for 1h until the cut-off voltage is 3.65V, and then charging at 0.1C for 3.65V until the battery voltage after formation is less than 3.65V; the aging conditions include: and (3) placing the formed battery into an oven at 60 ℃, standing for 24 hours, and obtaining a finished battery after aging, wherein the finished battery is marked as A1.
The 18650 type lithium ion secondary battery a1 prepared in example 1 was tested for performance.
(1) Capacity testing
The finished cell a1 was tested for discharge capacity at 23 ℃ under conditions of 0.2C and 1C, respectively.
The discharge capacity under the condition of 0.2C is 2715mAh, the specific discharge capacity under the condition of 0.2C is 248Wh/kg, and the discharge capacity under the condition of 1C is 2621 mAh.
(2) High current cycle performance test
The cell was subjected to 4A constant current charging at room temperature, constant voltage charging to 4.2V with a current of 100mA, and then constant current discharging to 2.5V with 10A, 20A, and 30A, and cyclic charging and discharging were performed, and as a result, as shown in fig. 3, 4, and 5: the energy retention rates after 600 cycles were 87.02%, 73.99%, 64.33%, respectively.
(3) Safety performance testing
After full charge, the device can not be ignited or exploded under the test conditions of short circuit, overcharge and the like.
Example 2
This example is to illustrate a 18650 type lithium ion secondary battery prepared by the method of the present invention.
A 18650 type lithium ion secondary battery was prepared in the same manner as in example 1, except that: the composition of the positive electrode powder and the negative electrode powder is the same as that in example 1, and the contents of the positive electrode powder and the negative electrode powder are different, specifically:
composition of the positive electrode powder: based on the total weight of the anode powder, 95.0 wt% of ZnO coated Mg 2+ Doped polycrystalline NCA material, 1.5 wt% of positive electrode conductive agent SP and 0.2 wt% of positive electrode additive Li 2 CO 3 3.3 wt% PVDF binder;
composition of the negative electrode powder: taking the total weight of the negative electrode powder as a reference, 96.5 wt% of a negative electrode active material, namely a silicon oxide (SiO) -graphite composite material, 1 wt% of a negative electrode conductive agent, namely a single-wall CNT and SP composite conductive agent, and 2.5 wt% of a negative electrode binder CMC/SBR;
otherwise, a 18650 lithium ion battery, labeled as a2, was obtained in the same manner as in example 1.
The performance of the finished cell a2 was tested in the same manner as in example 1 and the results were as follows:
(1) the 18650 cylindrical lithium ion secondary battery a2 made in this example had a discharge capacity of 2745mAh at 0.2C, a specific discharge capacity of 250Wh/kg at 0.2C, and a discharge capacity of 2689mAh at 1C.
(2) The battery is subjected to 4A constant current charging at room temperature, then is subjected to constant voltage charging to 4.2V by 100mA current, and then is subjected to constant current discharging to 2.5V by 10A, 20A and 30A, and is subjected to cyclic charging and discharging, wherein the energy conservation rates after the cyclic charging and discharging are respectively 85.60%, 70.23% and 61.53% after the cyclic charging and discharging are respectively carried out for 600 times.
(3) After full charge, the device can not be ignited or exploded under the test conditions of short circuit, overcharge and the like.
Example 3
This example is to illustrate a 18650 type lithium ion secondary battery prepared by the method of the present invention.
The preparation was carried out according to the flow diagram of the preparation method of the lithium ion secondary battery shown in fig. 1:
a 18650 type lithium ion secondary battery was prepared in the same manner as in example 1, except that: the components are the same as those in the embodiment 1, and the contents of the anode powder and the cathode powder are different, specifically:
the positive electrode powder comprises the following components: based on the total weight of the anode powder, 96.5 wt% of ZnO coated Mg 2+ Doped polycrystalline NCA material, 1.5 wt% of positive electrode conductive agent SP and 0.2 wt% of positive electrode additive Li 2 CO 3 1.8 wt% of a PVDF binder;
composition of the negative electrode powder: based on the total weight of the negative electrode powder, 97.5 wt% of a negative electrode active material, namely a silicon oxide (SiO) -graphite composite material, 1.0 wt% of a negative electrode conductive agent, namely a single-wall CNT and SP composite conductive agent, and 1.5 wt% of a negative electrode binder CMC/SBR;
otherwise, a 18650 lithium ion battery, labeled as a3, was obtained in the same manner as in example 1.
The performance of the finished cell a3 was tested in the same manner as in example 1 and the results were as follows:
(1) the 18650 cylindrical lithium ion secondary battery a3 made in this example had a discharge capacity of 2736mAh at 0.2C, a specific discharge capacity of 244Wh/kg at 0.2C, and a discharge capacity of 2649mAh at 1C.
(2) The battery is subjected to 4A constant current charging at room temperature, then is subjected to constant voltage charging to 4.2V by 100mA current, and then is subjected to constant current discharging to 2.5V by 10A, 20A and 30A, and is subjected to cyclic charging and discharging, wherein the energy conservation rates after the cyclic charging and discharging are 83.78%, 75.56% and 62.22% respectively after the cyclic charging and discharging are performed for 600 times.
Example 4
This example is to illustrate a 18650 type lithium ion secondary battery prepared by the method of the present invention.
The lithium ion secondary battery was prepared according to the flow chart of the preparation method of the lithium ion secondary battery shown in fig. 1:
a 18650 type lithium ion secondary battery was prepared in the same manner as in example 1, except that: the contents of Silica (SiO) and graphite are different from those of example 1, and specifically, the Silica (SiO) -graphite composite material contains 10 wt% of Silica (SiO) material and 90 wt% of natural graphite;
otherwise, a 18650 lithium ion battery, labeled a4, was obtained in the same manner as in example 1.
The test results are:
(1) the 18650 lithium ion battery made in this example has a discharge capacity of 2689mAh at 0.2C, a specific discharge capacity of 241wh/kg at 0.2C, and a discharge capacity of 2593mAh at 1C.
(2) The battery is subjected to 4A constant current charging at room temperature, then is subjected to constant voltage charging to 4.2V by 100mA current, and then is subjected to constant current discharging to 2.5V by 10A, 20A and 30A, and is subjected to cyclic charging and discharging, wherein the energy conservation rates after the cyclic charging and discharging are respectively 80.05%, 71.96% and 60.99% after the cyclic charging and discharging are respectively carried out for 600 times.
Example 5
This example is to illustrate a 18650 type lithium ion secondary battery prepared by the method of the present invention.
The lithium ion secondary battery was prepared according to the flow chart of the preparation method of the lithium ion secondary battery shown in fig. 1:
a 18650 type lithium ion secondary battery was prepared in the same manner as in example 1, except that: equal weight of SP was used instead of single-walled CNT and SP composite conductive agent in the negative electrode of example 1;
otherwise, a 18650 lithium ion battery, labeled a5, was obtained in the same manner as in example 1.
The test results are:
(1) the 18650 lithium ion battery a6 made in this example has a discharge capacity of 2712mAh at 0.2C, a specific discharge capacity of 244Wh/Kg at 0.2C, and a discharge capacity of 2626mAh at 1C.
(2) The battery is subjected to 4A constant current charging at room temperature, then is subjected to constant voltage charging to 4.2V by 100mA current, and then is subjected to constant current discharging to 2.5V by 10A, 20A and 30A, and is subjected to cyclic charging and discharging, wherein the energy conservation rates after the cyclic charging and discharging are respectively 72.31%, 68.36% and 60.66% after the cyclic charging and discharging are respectively carried out for 600 times.
Example 6
This example is to illustrate a 18650 type lithium ion secondary battery prepared by the method of the present invention.
The preparation was carried out according to the flow diagram of the preparation method of the lithium ion secondary battery shown in fig. 1:
a 18650 type lithium ion secondary battery was prepared in the same manner as in example 1, except that: in the slitting step, a tab splicing position is reserved on the positive and negative pole pieces, the obtained positive and negative pole pieces are both single-pole tab pieces,
otherwise, a 18650 lithium ion battery, labeled a6, was obtained in the same manner as in example 1.
The test results are as follows:
(1) the 18650 lithium ion battery made by the embodiment has a discharge capacity of 2682mAh under the condition of 0.2C, a discharge specific capacity of 238Wh/Kg under the condition of 0.2C and a discharge capacity of 2578mAh under the condition of 1C.
(2) The battery is subjected to 4A constant current charging at room temperature, then is subjected to constant voltage charging to 4.2V by 100mA current, and then is subjected to constant current discharging to 2.5V by 10A, 20A and 30A, and is subjected to cyclic charging and discharging, wherein the energy conservation rates after 600 cycles are 66.31%, 51.29% and 44.13% respectively.
Example 7
This example is to illustrate a 18650 type lithium ion secondary battery prepared by the method of the present invention.
The preparation was carried out according to the flow diagram of the preparation method of the lithium ion secondary battery shown in fig. 1:
a 18650 type lithium ion secondary battery was prepared in the same manner as in example 1, except that: the components are the same as those in the embodiment 1, and the contents of the anode powder and the cathode powder are different, specifically:
the positive electrode powder comprises the following components: based on the total weight of the anode powder, 94.5 wt% of ZnO coated Mg 2+ Doped polycrystalline NCA material, 1.5 wt% of positive electrode conductive agent SP and 0.2 wt% of positive electrode additive Li 2 CO 3 3.8 wt% of PVDF binder;
composition of the negative electrode powder: based on the total weight of the negative electrode powder, 97.5 wt% of a negative electrode active material silicon oxide (SiO) -graphite composite material, 1.0 wt% of a negative electrode conductive agent single-wall CNT and SP composite conductive agent and 1.5 wt% of a negative electrode binder CMC/SBR;
otherwise, a 18650 lithium ion battery, labeled as a7, was obtained in the same manner as in example 1.
The performance of the finished cell a7 was tested in the same manner as in example 1 and the results were as follows:
(1) the 18650 cylindrical lithium ion secondary battery a7 manufactured in this example had a discharge capacity of 2696mAh at 0.2C, a specific discharge capacity of 238Wh/kg at 0.2C, and a discharge capacity of 2617mAh at 1C.
(2) The battery is subjected to 4A constant current charging at room temperature, then is subjected to constant voltage charging to 4.2V by 100mA current, and then is subjected to constant current discharging to 2.5V by 10A, 20A and 30A, and is subjected to cyclic charging and discharging, wherein the energy conservation rates after the cyclic charging and discharging are respectively 78.38%, 65.86% and 52.42% after the cyclic charging and discharging are respectively carried out for 600 times.
Example 8
This example is to illustrate a 18650 type lithium ion secondary battery prepared by the method of the present invention.
The lithium ion secondary battery was prepared according to the flow chart of the preparation method of the lithium ion secondary battery shown in fig. 1:
a 18650 type lithium ion secondary battery was fabricated in the same manner as in example 1, except that: the components of the positive electrode powder and the negative electrode powder are the same as those in the embodiment 1, and the contents of the positive electrode powder and the negative electrode powder are different, specifically:
the positive electrode powder comprises the following components: taking the total weight of the anode powder as a reference, 97.0 wt% of ZnO coated Mg 2+ Doped polycrystalline NCA material, 1.5 wt% of positive electrode conductive agent SP and 0.2 wt% of positive electrode additive Li 2 CO 3 1.3 wt% of a PVDF binder;
composition of the negative electrode powder: based on the total weight of the negative electrode powder and 1, 97.5 wt% of a negative electrode active material silicon oxide (SiO) -graphite composite material, 1.0 wt% of a negative electrode conductive agent single-wall CNT and SP composite conductive agent and 1.5 wt% of a negative electrode binder CMC/SBR;
otherwise, a 18650 lithium ion battery, labeled as A8, was obtained in the same manner as in example 1.
The performance of the finished cell A8 was tested in the same manner as in example 1 and the results were as follows:
(1) the 18650 cylindrical lithium ion secondary battery A8 made in this example had a discharge capacity of 2716mAh at 0.2C, a specific discharge capacity of 248Wh/kg at 0.2C, and a discharge capacity of 2637mAh at 1C.
(2) The battery is subjected to 4A constant current charging at room temperature, then is subjected to constant voltage charging to 4.2V by 100mA current, and then is subjected to constant current discharging to 2.5V by 10A, 20A and 30A, and is subjected to cyclic charging and discharging, wherein the energy conservation rates after the cyclic charging and discharging are respectively 73.58%, 67.96% and 50.12% after the cyclic charging and discharging are respectively carried out for 600 times.
Comparative example 1
A 18650 type lithium ion secondary battery was prepared in the same manner as in example 1, except that: the "Silica (SiO) -graphite composite material" in example 1 was replaced with an equal weight of "graphite material";
otherwise, a 18650 lithium ion battery was obtained, designated as DA1, in the same manner as in example 1.
The test results are as follows:
(1) the 18650 lithium ion battery made in this example has a discharge capacity of 2632mAh at 0.2C, a discharge specific capacity of 235Wh/kg at 0.2C, and a discharge capacity of 2469mAh at 1C.
(2) The battery is subjected to 4A constant current charging at room temperature, then is subjected to constant voltage charging to 4.2V by 100mA current, and then is subjected to constant current discharging to 2.5V by 10A, 20A and 30A, and is subjected to cyclic charging and discharging, wherein the energy conservation rates after the cyclic charging and discharging are respectively 78.37%, 60.53% and 56.36% after the cyclic charging and discharging are respectively carried out for 600 times.
Comparative example 2
A 18650 type lithium ion secondary battery was prepared in the same manner as in example 1, except that: the NCA product (particle size: 13.5 μm, specific surface area: 0.72 m) of type S900 manufactured by Hubei 2 G, gram capacity 200.3mAh/g), no zinc oxide coating, no Mg 2+ Doping, and the rest are the same as the example 1, so as to obtain a 18650 lithium ion battery, which is marked as DA 2;
(1) the 18650 lithium ion battery made in this example had a discharge capacity of 2701mAh at 0.2C, a specific discharge capacity of 240Wh/kg at 0.2C, and a discharge capacity of 2619mAh at 1C.
(2) The battery is charged with 4A constant current at room temperature, charged with 100mA current to 4.2V at constant voltage, discharged with 10A, 20A and 30A constant current to 2.5V, and subjected to cyclic charge and discharge, wherein the energy conservation rates after 600 cycles are 80.60%, 73.23% and 68.53% respectively.
Comparative example 3
A 18650 type lithium ion secondary battery was fabricated in the same manner as in example 1, except that: the "ZnO-coated Mg" in example 1 was replaced with "NCM 811" of equal weight 2+ Doped polycrystalline NCA material ";
otherwise, a 18650 lithium ion battery was obtained, designated as DA3, in the same manner as in example 1.
The test results are:
(1) the 18650 lithium ion battery made by the comparative example has a discharge capacity of 2660mAh under the condition of 0.2C, a discharge specific capacity of 241Wh/kg under the condition of 0.2C and a discharge capacity of 2502mAh under the condition of 1C.
(2) The battery is subjected to 4A constant current charging at room temperature, then is subjected to constant voltage charging to 4.2V by 100mA current, and then is subjected to constant current discharging to 2.5V by 10A, 20A and 30A, and is subjected to cyclic charging and discharging, wherein the energy conservation rates after 600 cycles are respectively 76.03%, 61.25% and 53.09%.
Comparative example 4
A 18650 type lithium ion secondary battery was prepared in the same manner as in example 1, except that:
positive electrode active material: ZnO coated Mg 2+ The doped polycrystalline NCA material is different, specifically, the grain diameter is 4 μm, and the specific surface area is 1.86m 2 G, gram capacity 203mAh/g, coating amount of 1.0 wt%, Mg 2+ The doping amount is 0.02 wt%.
Otherwise, a 18650 lithium ion battery was obtained, designated as DA4, in the same manner as in example 1.
The test results are:
(1) the 18650 lithium ion battery made by the comparative example has a discharge capacity of 2705mAh under the condition of 0.2C, a discharge specific capacity of 243Wh/Kg under the condition of 0.2C and a discharge capacity of 2602mAh under the condition of 1C.
(2) The battery is subjected to 4A constant current charging at room temperature, then is subjected to constant voltage charging to 4.2V by 100mA current, and then is subjected to constant current discharging to 2.5V by 10A, 20A and 30A, and is subjected to cyclic charging and discharging, wherein the energy conservation rates after 600 cycles are 78.53%, 67.25% and 63.09% respectively.
Comparative example 5
A 18650 type lithium ion secondary battery was prepared in the same manner as in example 1, except that:
negative electrode active material: the Silica (SiO) -graphite composite material is different, specifically, the particle diameter of the Silica (SiO) material is 1 μm, and the specific surface area is 3.15m 2 G, the gram volume is 1625 mAh/g; the natural graphite has a particle diameter of 11.3 μm and a specific surface area of 1.25m 2 /g。
Otherwise, a 18650 lithium ion battery was obtained, designated as DA5, in the same manner as in example 1.
The test results are:
(1) the 18650 lithium ion battery made by the comparative example has a discharge capacity of 2702mAh under the condition of 0.2C, and has a discharge capacity of 242Wh/kg under the condition of 0.2C and a discharge capacity of 2616mAh under the condition of 1C.
(2) The battery is subjected to 4A constant current charging at room temperature, then is subjected to constant voltage charging to 4.2V by 100mA current, and then is subjected to constant current discharging to 2.5V by 10A, 20A and 30A, and is subjected to cyclic charging and discharging, wherein the energy conservation rates after 600 cycles are 77.83%, 67.65% and 64.79% respectively.
In conclusion, it can be seen from the above results that the 18650 type cylindrical lithium ion secondary battery prepared in embodiments 1 to 8 of the present invention by using modified positive and negative electrode materials, using a specific chemical system, simultaneously matching with a specific electrolyte and a separator, and using a specific preparation process has excellent electrochemical performance and safety performance, the 0.2C capacity is not less than 2700mAh at 23 ℃, the energy retention ratio of 4A charging 10A discharging cycle 600 times is not less than 80%, the energy retention ratio of 4A charging 20A discharging cycle 600 times is not less than 70%, the energy retention ratio of 4A charging 30A discharging cycle 600 times (cut-off at 75 ℃) is not less than 60%, and the specific energy of the single battery is not less than 240Wh/kg, and can be used as a power supply for electric tools, garden tools and household appliances, and has broad application prospects and commercial prospects.
In addition, in example 4 in which "the Silicon (SiO) oxide-graphite composite material contains 10 wt% of the Silicon (SiO) oxide material and 90 wt% of the natural graphite", the discharge capacity, specific energy and cycle life were slightly inferior to those of example 1 in comparison with "the Silicon (SiO) oxide-graphite composite material contains 7 wt% of the Silicon (SiO) oxide material and 93 wt% of the natural graphite", because the expansion of the negative electrode during charge and discharge was enhanced with the increase of the silicon oxide content, thereby reducing the cycle performance of the battery.
In addition, the conductive agent SP is adopted in the example 5, but the compound conductive agent is not adopted, and the discharge capacity, the specific energy and the cycle life are poorer than those of the example 1 due to the reduction of the electronic conductivity.
In addition, the unipolar lug is adopted in the example 6, and the internal resistance of the battery is obviously increased due to the adoption of the structure mode of the unipolar lug, so that the power performance and the cycle performance of the battery are reduced, and the discharge capacity, the specific energy and the cycle life are poorer compared with those of the example 1.
In addition, the "contents of the positive electrode powder and the negative electrode powder" used in examples 7 and 8 were out of the preferable range with respect to examples 1 to 3, and as a result, the discharge capacity, specific energy, and cycle life were slightly inferior to those of example 1.
In addition, comparative example 1 resulted in a significant decrease in the gram capacity of the negative electrode due to the replacement of the silica in the composite negative electrode material with an equal weight of graphite. In order to meet the capacity requirement of the battery, the compaction density of the positive electrode and the negative electrode needs to be obviously increased, so that the power performance and the cycle performance of the battery are reduced.
In addition, comparative example 2 does not use zinc oxide (ZnO) coating and Mg for the NCA material 2+ Doping causes increased surface side reactions of the material during cycling and reduced power performance of the material, thereby reducing the power performance and cycling performance of the cell.
In addition, comparative example 3 exhibited Mn during cycling due to polymorph NCM811 2+ The dissolution of (b) results in deterioration of material stability, and thus, reduction of battery cycle performance.
In addition, comparative example 4 has an increased specific surface area of the material due to the decrease in the particle size of the positive electrode material, which also leads to an increase in side reactions of the electrolyte on the surface of the positive electrode, thereby decreasing the cycle performance of the battery.
In addition, comparative example 5 has a significant increase in specific surface area due to a decrease in particle size of the silica, and thus causes an increase in side reactions on the surface of the negative electrode during cycling, thereby decreasing the cycle performance of the battery.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A lithium ion secondary battery comprising a positive electrode sheet containing a positive electrode active material and a negative electrode sheet, characterized in that the positive electrode active material contains Mg 2+ Doped lithium nickel cobalt aluminate material and coating Mg 2+ Doped nickel cobalt lithium aluminate material surfaceBased on the total weight of the positive electrode active material, the content of ZnO is 0.1-2 wt%, and the Mg 2+ The content of the doped lithium nickel cobalt aluminate material is 98-99.9 wt%.
2. The lithium ion secondary battery according to claim 1, wherein the ZnO is contained in an amount of 0.2 to 1.5 wt% based on the total weight of the positive electrode active material, and the Mg 2+ The content of the doped lithium nickel cobalt aluminate material is 98.5-99.8 wt%.
3. The lithium ion secondary battery according to claim 1 or 2, wherein Mg is based on the total weight of the positive electrode active material 2+ The doping amount is 0.01-0.05 wt%, preferably 0.01-0.04 wt%.
4. The lithium ion secondary battery according to any one of claims 1 to 3, wherein the positive electrode active material has a particle diameter of 5 to 20 μm and a specific surface area of 0.5 to 1.5m 2 The gram capacity is 200-208 mAh/g.
5. The lithium ion secondary battery according to any one of claims 1 to 4, wherein the positive electrode sheet further comprises a positive electrode conductive agent, a positive electrode binder and a positive electrode additive, and the content of the positive electrode active material is 91.5 to 98.95 wt%, the content of the positive electrode conductive agent is 0.5 to 3 wt%, the content of the positive electrode additive is 0.05 to 1.5 wt%, and the content of the positive electrode binder is 0.5 to 4 wt%, based on the total weight of the positive electrode sheet.
6. The lithium ion secondary battery according to claim 1, wherein the negative electrode sheet contains a negative electrode active material;
preferably, the negative active material contains silicon oxide and graphite coated on the surface of the silicon oxide;
preferably, the content of the silica is 3 to 15 wt% and the content of the graphite is 85 to 97 wt%, based on the total weight of the anode active material;
preferably, the particle size of the silica is 2-10 μm, and the specific surface area is 0.5-2m 2 The gram capacity is 1550 and 1650 mAh/g;
preferably, the graphite has a particle size of 3 to 15 μm and a specific surface area of 1 to 2.5m 2 /g。
7. The lithium ion secondary battery according to claim 1 or 6, wherein the negative electrode sheet further comprises a negative electrode conductive agent and a negative electrode binder, and the content of the negative electrode active material is 92 to 98 wt%, the content of the negative electrode conductive agent is 0.5 to 2 wt%, and the content of the negative electrode binder is 1.5 to 6 wt%, based on the total weight of the negative electrode sheet.
8. The lithium ion secondary battery according to any one of claims 1 to 7, wherein the lithium ion secondary battery comprises a separator;
preferably, the diaphragm comprises PP/PE/PP and Al coated on the surface of the PP/PE/PP 2 O 3 ；
Preferably, Al of the surface of the separator 2 O 3 The thickness of the coating is 1-4 um;
preferably, the total thickness of the separator is 12 to 16 μm.
9. A method for manufacturing a lithium ion secondary battery according to any one of claims 1 to 8, characterized in that the method comprises:
(1) carrying out sheet-making winding, assembling and liquid injection on the positive plate, the negative plate, the diaphragm and the electrolyte to obtain a battery to be formed;
(2) and sequentially carrying out formation and aging on the battery to be formed to obtain the lithium ion secondary battery.
10. Use of a lithium ion secondary battery according to any one of claims 1 to 8 in rechargeable power tools.
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| WO2024158346A1 (en) * | 2023-01-25 | 2024-08-02 | Centrum Pre Vyuzitie Pokrocilych Materialov Slovenskej Akademie Vied, Verejna Vyskumna Institucia | A negative electrode for a rechargeable li-ion battery, its production method, and a rechargeable li-ion battery |
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