CN113299974A - Battery with a battery cell - Google Patents
Battery with a battery cell Download PDFInfo
- Publication number
- CN113299974A CN113299974A CN202110570155.9A CN202110570155A CN113299974A CN 113299974 A CN113299974 A CN 113299974A CN 202110570155 A CN202110570155 A CN 202110570155A CN 113299974 A CN113299974 A CN 113299974A
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- CN
- China
- Prior art keywords
- coating
- mass
- battery
- coating layer
- thickness
- Prior art date
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- Pending
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- 239000000919 ceramic Substances 0.000 description 1
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- 239000011593 sulfur Substances 0.000 description 1
Images
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The application provides a battery, battery include positive plate and electrolyte, and positive plate includes the anodal mass flow body, and the surface of the anodal mass flow body is equipped with first coating, is equipped with the second coating on the first coating, and the battery satisfies following relation:
eta is viscosity of the electrolyte, D501Is the median particle diameter of the first coating layer, D502Is the median particle diameter, T, of the second coating layer1Is the thickness of the first coating, T2Is the thickness of the second coating. By enabling the battery to satisfy the relational expression, the diffusion distance of lithium ions in a solid phase can be shortened, so that the direct current resistance of the battery in a low-temperature low-charge state is reduced, and the charge and discharge performance of the battery is improved.
Description
Technical Field
The present application relates to the field of lithium ion batteries, and more particularly, to a battery.
Background
Since the commercialization of lithium ion batteries, lithium ion batteries have been widely used in consumer electronics, electric vehicles, electric tools, and the like, due to their advantages of high voltage platform, high energy density, high output power, long cycle life without memory effect, and environmental friendliness. At present, the lithium ion battery has the problems of weak discharge capacity and poor charge-discharge performance under a low-temperature low-charge state.
Content of application
The embodiment of the application provides a battery, and solves the problem that a lithium ion battery is poor in charging and discharging performance under a low-temperature low-charge state.
In order to achieve the above object, in a first aspect, an embodiment of the present application provides a battery, including a negative electrode sheet, a separator, a positive electrode sheet, and an electrolyte;
the positive plate comprises a positive current collector, a first coating is arranged on the surface of the positive current collector, and a second coating is arranged on the first coating;
the battery satisfies the following relationship:
eta is viscosity of the electrolyte, D501Is the median particle diameter of the first coating layer, D502Is the median particle diameter, T, of the second coating layer1Is the thickness of the first coating, T2Is the thickness of the second coating.
Optionally, the median particle size of the second coating layer is smaller than the median particle size of the first coating layer, and the thickness of the second coating layer is smaller than the thickness of the first coating layer.
Optionally, the ratio of the thickness of the second coating layer to the thickness of the first coating layer is less than one third.
Optionally, the first coating has a median particle size in a range from 10 μm to 20 μm;
the median particle diameter of the second coating layer ranges from 1 μm to 10 μm.
Optionally, the thickness of the first coating layer ranges from 30 μm to 100 μm;
the thickness of the second coating layer ranges from 10 μm to 30 μm.
Optionally, the first coating comprises a first active substance, a first conductive agent and a first adhesive, the mass of the first active substance accounts for 95% -98.5% of the mass of the first coating, the mass of the first conductive agent accounts for 0.5% -3% of the mass of the first coating, and the mass of the first adhesive accounts for 1% -2% of the mass of the first coating;
the second coating comprises a second active substance, a second conductive agent and a second adhesive, wherein the mass of the second active substance accounts for 95-98.5% of the mass of the second coating, the mass of the second conductive agent accounts for 0.5-3% of the mass of the second coating, and the mass of the second adhesive accounts for 1-2% of the mass of the second coating.
Optionally, the mass of the first conductive agent is 0.5-3% of the mass of the first coating;
the mass of the second conductive agent is 0.5-3% of the mass of the second coating.
Optionally, the mass of the first adhesive is 1% -2% of the mass of the first coating;
the mass of the second adhesive is 1% -2% of the mass of the second coating.
Optionally, the viscosity η of the electrolyte ranges from 3 to 10cP at a temperature of 25 ℃.
Optionally, the electrolyte includes an organic solvent, a lithium salt and an additive, the organic solvent includes a cyclic solvent and a chain solvent, and a mass ratio of the cyclic solvent to the chain solvent is in a range of 0.25 to 1.
In the embodiment of this application, the battery includes positive plate and electrolyte, and positive plate includes the anodal mass flow body, and the surface of the anodal mass flow body is equipped with first coating, is equipped with the second coating on the first coating, and the battery satisfies following relation:
eta is viscosity of the electrolyte, D501Is the median particle diameter of the first coating layer, D502Is the median particle diameter, T, of the second coating layer1Is the thickness of the first coating layer,T2is the thickness of the second coating. By enabling the battery to satisfy the relational expression, the diffusion distance of lithium ions in a solid phase can be shortened, so that the direct current resistance of the battery in a low-temperature low-charge state is reduced, and the charge and discharge performance of the battery is improved.
Drawings
For a clear explanation of the technical solutions in the embodiments of the present application, the drawings of the specification are described below, it is obvious that the following drawings are only embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to the listed drawings without any inventive effort.
Fig. 1 is a schematic structural diagram of a positive electrode sheet provided in an embodiment of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. On the basis of the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without any creative effort belong to the protection scope of the present application.
Referring to fig. 1, an embodiment of the present application provides a battery including a negative electrode sheet, a separator, a positive electrode sheet, and an electrolyte;
the positive plate comprises a positive current collector 3, a first coating 1 is arranged on the surface of the positive current collector 3, and a second coating 2 is arranged on the first coating 1;
the battery satisfies the following relational expression:
eta is viscosity of the electrolyte, D501Median particle diameter, D50, of the first coating 12Is the median particle diameter, T, of the second coating layer 21Is the thickness, T, of the first coating layer 12Is the thickness of the second coating 2.
Specifically, the first coating layer 1 and the second coating layer 2 may be disposed along the length direction of the battery. The positive current collector 3 may further have a blank foil area, where the surface of the positive current collector 3 is not covered by the first coating 1 and the second coating 2. The positive current collector 3 may be a homogeneous aluminum foil having a thickness of 8 to 15 μm, or an aluminum foil having a carbon-coated bottom layer.
The first coating layer 1 and the second coating layer 2 may be simultaneously applied to the surface of the positive current collector 3 using a dual die coating head die coater. The surface of the positive current collector 3 comprises a first surface of the positive current collector and a second surface of the positive current collector, and the first surface of the positive current collector and the second surface of the positive current collector are two opposite surfaces of the positive current collector 3. At least one of the first surface of the positive current collector and the second surface of the positive current collector is coated with a first coating 1 and a second coating 2. After coating, rolling and cutting, the battery can be prepared. The resistivity rho of the pole piece can be tested by adopting a pole piece internal resistance instrument, the rho of the battery is less than or equal to 2500 omega.m, and further, the rho can be less than or equal to 1000 omega.m.
The positive plate, the diaphragm and the negative plate can be sequentially stacked and wound into a battery winding core.
It should be understood that the lower the viscosity of the electrolyte is, the more favorable the Charge and discharge performance of the battery is, but in the solvent of the low-viscosity electrolyte, the content of the chain-like organic solvent is higher, the oxidation potential is correspondingly lower, and under the high-temperature high-Charge State (SOC), the gas generation of the battery is easily caused by the too low viscosity of the electrolyte, and the high-temperature cycle and high-temperature storage gas generation performance of the battery are reduced.
The median particle size of the second coating layer 2 is smaller than that of the first coating layer 1, so that the diffusion distance of lithium ions in a solid phase can be shortened, the direct current resistance of the battery in a low-temperature low-charge state is reduced, and the charge and discharge performance of the battery is improved. The median particle size of the first coating 1 is relatively large, so that the battery has good high-temperature cycle and high-temperature storage gas generation performance, and can bear capacity exertion in a high charge state. Therefore, the influences of small median particle size, large specific surface, high content, more contact reaction sites with electrolyte and easy side reaction at high temperature on the battery are reduced.
In summary, the thickness, particle size, and electrolyte viscosity of the first coating layer 1 and the second coating layer 2 collectively affect the battery performance. Experimental research shows that under the condition that the expression is less than 1, the high-temperature gas production performance of the battery is very poor. In the case where the above expression is greater than 5, the discharge resistance of the battery at low SOC is significantly increased, even by more than about 20% to about 50%, and the charge-discharge performance of the battery at low temperature is poor. Under the condition that the battery meets the relational expression, the battery has better charge and discharge performance at low temperature and better high-temperature cycle and high-temperature storage gas generation performance, thereby obtaining excellent battery performance.
In the embodiment of this application, the battery includes positive plate and electrolyte, and positive plate includes the anodal mass flow body, and the surface of the anodal mass flow body is equipped with first coating, is equipped with the second coating on the first coating, and the battery satisfies following relation:
eta is viscosity of the electrolyte, D501Is the median particle diameter of the first coating layer, D502Is the median particle diameter, T, of the second coating layer1Is the thickness of the first coating, T2Is the thickness of the second coating. By enabling the battery to satisfy the relational expression, the diffusion distance of lithium ions in a solid phase can be shortened, so that the direct current resistance of the battery in a low-temperature low-charge state is reduced, and the charge and discharge performance of the battery is improved. In addition, the battery can improve the charge and discharge performance of the battery, and simultaneously has better high-temperature cycle and high-temperature storage gas production performance.
It should be noted that the manufacturing method of the battery provided by the embodiment of the application is simple, the existing production equipment and production line can be adopted for production, the production equipment and the production line do not need to be greatly modified, and the production cost is low.
Optionally, the median particle diameter of the second coating layer 2 is smaller than that of the first coating layer 1, and the thickness of the second coating layer 2 is smaller than that of the first coating layer 1. By making the median particle size of the second coating layer 2 smaller than that of the first coating layer 1, the diffusion distance of lithium ions in a solid phase can be further shortened, so that the direct current resistance of the battery in a low-temperature low-charge state is further reduced, and the charge and discharge performance of the battery is improved.
Optionally, the ratio of the thickness of the second coating layer 2 to the thickness of the first coating layer 1 is less than one third.
Further, the median particle diameter of the first coating layer 1 ranges from 10 μm to 20 μm;
the median particle diameter of the second coating layer 2 ranges from 1 μm to 10 μm.
Further, the thickness of the first coating layer 1 ranges from 30 μm to 100 μm;
the thickness of the second coating layer 2 ranges from 10 μm to 30 μm.
Specifically, the median particle diameter of the first coating layer 1 is larger than that of the second coating layer 2, and the thickness of the first coating layer 1 is larger than that of the second coating layer 2, so that the first coating layer 1 has better high-temperature performance and can provide main capacity volatilization. The smaller median particle size of the second coating layer 2 compared to the median particle size of the first coating layer 1, and the thinner thickness of the second coating layer 2, provide the main volume evaporation at low charge state. The areal density of the second coating 2 may range from 3mg/cm2-10mg/cm2The areal density of the first coating layer 1 may range from 5mg/cm2-20mg/cm2。
Optionally, the first coating 1 includes a first active substance, a first conductive agent and a first adhesive, where the mass of the first active substance accounts for 95% to 98.5% of the mass of the first coating 1, the mass of the first conductive agent accounts for 0.5% to 3% of the mass of the first coating 1, and the mass of the first adhesive accounts for 1% to 2% of the mass of the first coating 1;
the second coating 2 comprises a second active substance, a second conductive agent and a second adhesive, wherein the mass of the second active substance accounts for 95-98.5% of the mass of the second coating 2, the mass of the second conductive agent accounts for 0.5-3% of the mass of the second coating 2, and the mass of the second adhesive accounts for 1-2% of the mass of the second coating 2.
Specifically, the first active material may be a lithium-containing compound with a layered structure, a spinel structure or an olivine structure, or may be a mixture of one or more of lithium cobaltate, lithium manganate, lithium iron phosphate, lithium nickel manganate or lithium nickel manganese cobaltate. Similarly, the second active material may be a lithium-containing compound with a layered structure, a spinel structure or an olivine structure, or may be a mixture of one or more of lithium cobaltate, lithium manganate, lithium iron phosphate, lithium nickel manganate or lithium nickel manganese cobaltate. The first active material and the second active material may be the same material or different materials.
The first conductive agent is selected from substances which have conductive characteristics and do not participate in chemical reaction in the battery, and can include but not limited to carbon black materials, such as carbon black, conductive carbon black, acetylene black, ketjen black and the like, conductive fiber materials, such as carbon fibers, carbon nanotubes, metal fibers and the like, and graphite materials, such as natural graphite, graphene and the like. Similarly, the second conductive agent is selected from substances having conductive properties and not participating in chemical reactions in the battery, and may include, but is not limited to, carbon black materials, such as carbon black, conductive carbon black, acetylene black, ketjen black, and the like, conductive fiber materials, such as carbon fibers, carbon nanotubes, metal fibers, and the like, and graphite materials, such as natural graphite, graphene, and the like. The first conductive agent and the second conductive agent may be the same substance or may be different substances.
The first adhesive is selected from substances which can have adhesive properties and do not participate in chemical reactions in the battery, and may include, but is not limited to, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl fiber, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, styrene-butadiene rubber (SBR), fluorinated rubber, ethylene-vinyl acetate copolymer, polyurethane, and a mixture of one or more of copolymers thereof. Similarly, the second binder may include, but is not limited to, a mixture of one or more of polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl fiber, regenerated cellulose, polyvinyl pyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, Styrene Butadiene Rubber (SBR), fluorinated rubber, ethylene-vinyl acetate copolymer, polyurethane, and copolymers thereof. The first adhesive and the second adhesive may be the same or different.
Optionally, the mass of the first conductive agent is 0.5-3% of the mass of the first coating 1;
the mass of the second conductive agent is 0.5-3% of the mass of the second coating 2.
Further, the mass of the first conductive agent is 0.5-1.5% of the mass of the first coating layer 1, and the mass of the second conductive agent is 0.5-1.5% of the mass of the second coating layer 2. By limiting the contents of the first conductive agent and the second conductive agent, the battery can have a better conductive effect.
Optionally, the mass of the first adhesive is 1-2% of the mass of the first coating 1;
the mass of the second adhesive is 1-2% of the mass of the second coating 2.
Further, the mass of the first adhesive is 1-1.5% of the mass of the first coating layer 1, and the mass of the second adhesive is 1-1.5% of the mass of the second coating layer 2. By limiting the contents of the first adhesive and the second adhesive, the battery can have a better adhesive effect.
Optionally, the viscosity η of the electrolyte ranges from 3 to 10cP at a temperature of 25 ℃. The lower the viscosity of the electrolyte is, the more favorable the charge and discharge performance of the battery is, and the charge and discharge performance of the battery can be further improved by limiting the value range of the viscosity of the electrolyte to be 3-6 cP.
Optionally, the electrolyte includes an organic solvent, a lithium salt and an additive, the organic solvent includes a cyclic solvent and a chain solvent, and a mass ratio of the cyclic solvent to the chain solvent is in a range of 0.25 to 1.
The organic solvent comprises one or more substances produced by mixing of conventional organic solvents such as cyclic carbonate, chain carbonate and carboxylic ester. Organic solvents include, but are not limited to: carbonic acidEthylene Ester (EC), Propylene Carbonate (PC), γ -butyrolactone (GBL), Butylene Carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), Ethyl Methyl Carbonate (EMC), Methyl Propyl Carbonate (MPC), Ethyl Propyl Carbonate (EPC), fluoroethylene carbonate (FEC), Methyl Formate (MF), Ethyl Formate (EF), Methyl Acetate (MA), Ethyl Acetate (EA), Propyl Acetate (PA), Methyl Propionate (MP), Ethyl Propionate (EP), Propyl Propionate (PP), Methyl Butyrate (MB), Ethyl Butyrate (EB), Sulfolane (SL), dimethylsulfone (MSM), methylethylsulfone (EMS), diethylsulfone (ESE), Tetrahydrofuran (THF), Ethylene Sulfite (ES) and Propylene Sulfite (PS). The weight ratio of the cyclic solvent to the chain solvent is in the range of 0.2 to 0.5, and further, the weight ratio of the cyclic solvent to the chain solvent may be in the range of 0.25 to 0.4. At 25 ℃, the viscosity of the electrolyte is between 3 and 10cP, and further, the viscosity of the electrolyte can be between 4 and 7 cP. The conductivity of the electrolyte is 5-12 mS-cm-1Further, the conductivity of the electrolyte is 7-10 mS-cm-1. The viscosity and conductivity of the electrolyte can be determined by methods known in the art. For example, a conductivity meter may be used to measure the conductivity of the electrolyte and a viscosity meter may be used to measure the viscosity of the electrolyte.
The lithium salt includes at least one of an inorganic lithium salt and an organic lithium salt. The inorganic lithium salt includes at least one of lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium hexafluoroarsenate (LiAsF6), lithium difluorophosphate (LiPO2F2) lithium perchlorate (LiClO 4). The organic lithium salt includes at least one of lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiODFB), lithium bis (fluorosulfonyl) imide (LiFSI), and lithium bis (trifluoromethanesulfonyl) imide (LiTFSI). These salts may be used as a lithium salt solute or as a lithium salt solvent. The concentration of the electrolyte lithium salt in the electrolyte solution may be in the range of 0.5mol/L to 1.5mol/L, and further, the concentration of the electrolyte lithium salt in the electrolyte solution may be in the range of 0.8mol/L to 1.2 mol/L.
The additive comprises one or more of fluorine-containing compounds, sulfur-containing compounds and unsaturated double bond-containing compounds. The following substances can be selected in particular and are not limited thereto: fluoroethylene carbonate, ethylene sulfite, propane sultone, N-methyl pyrrolidone, N-methyl formamide, N-methyl acetamide, acetonitrile, acrylonitrile, gamma-butyrolactone and methyl sulfide.
The following describes the battery provided in the examples of the present application with reference to specific experiments.
The procedure for example 1 was as follows:
1. manufacture of positive plate
The first active material LiCoO 2D 50 is 15.4um, the second active material LiCoO 2D 50 is 7.3um, the binder PVDF and the conductive agent are dissolved in N-methyl pyrrolidone (NMP) according to the mass ratio of 97:1.5:1.5 and uniformly stirred to prepare slurry. Coating the aluminum foil on the same side by using a coating machine with a dual-mode coating head device, wherein the coating layer with small slurry feeding particle size is arranged on the upper layer and the particle size is larger than the lower layer, the median of the coating surface density of the lower layer is 12.56mg/cm2, the median of the coating surface density of the upper layer is 4.18g/cm2, the coating tolerance is controlled according to +/-1.5 wt%, the coating speed is 8m/min, the wet double-layer membrane is dried after coating, then the wet double-layer membrane is coated on the other side of the aluminum foil in the same way, dried, rolled and cut to prepare the positive plate of the lithium ion battery; the manufacturing process is a conventional procedure in the field, and the adopted process parameters (such as stirring parameters, coating speed, rolling speed and pressure), slurry characteristics and pole piece design are conventional values in the field.
2. Manufacture of negative plate
Dissolving graphite serving as a negative electrode active material, SBR serving as a binder and CMC serving as a thickening agent in deionized water according to a mass ratio of 97:1.5:1.5, uniformly stirring to prepare slurry, simultaneously coating the prepared slurry on one side of a copper foil by using a coating machine of a single-mode head coating device, coating and drying the other side of the copper foil in the same manner after drying, rolling, slitting and the like on a dried membrane, thereby completing the preparation of the negative electrode plate.
3. Preparation of the electrolyte
Uniformly mixing ethylene carbonate, propyl propionate and dimethyl carbonate according to the volume ratio of 25:25:50 to obtain the organic solvent. In an argon atmosphere glove box with the water content of less than 10ppm, 1mol/L of LiPF6 is dissolved in the organic solvent and is uniformly mixed to obtain the electrolyte.
4. Lithium ion battery fabrication
And winding the prepared positive plate, the prepared negative plate and the prepared diaphragm by using a winding machine to prepare a winding core of a winding structure, selecting a base material, ceramic and glued composite diaphragm for the diaphragm, packaging by adopting an aluminum-plastic film, baking for 48 hours in a vacuum state to remove moisture, injecting electrolyte, and forming and sorting the battery to obtain the square soft package lithium ion battery, which is recorded as C1.
5. Direct Current Resistance (DCR) test of lithium ion battery
The fresh lithium ion secondary battery is placed for 5 minutes at 25 ℃, is subjected to constant current charging to 4.4V at the rate of 1C, is subjected to constant voltage charging until the current is less than or equal to 0.05C, and the state of charge (SOC) of the battery is 100 percent, is placed for 5 minutes, is subjected to constant current discharging at the rate of 1C, and is adjusted to 20 percent. The lithium ion secondary battery with 20% SOC was left at 25 ℃ for 10 minutes, and was discharged at 0.1C rate for 10 seconds, and the final voltage V1 and 1C rate for 360 seconds were obtained, and the final voltage V2 were obtained. It is noted that 25 ℃ 10% SOC 1C rate discharge 360s DCR ═ V1-V2)/(1C-0.1C.
Different from the 25 ℃ 10% SOC 1C multiplying power discharge 360s DCR test of the lithium ion secondary battery, the direct current impedance test of the lithium ion secondary battery at 0 ℃, 20% and 1C multiplying power discharge 360s has the discharge temperature of 0 ℃.
6. 60 ℃ storage expansion test of lithium ion battery
The fresh lithium ion secondary battery is placed aside for 5 minutes at 25 ℃, and is charged to 4.4V at a constant current of 1C rate, and then is charged at a constant voltage until the current is less than or equal to 0.05C, and the state of charge (SOC) of the battery is 100 percent. The cell thickness T3 was tested with 600g PPG. The fully charged battery was placed in an oven at 60 ℃ and stored for 35 days, after which the battery was taken out and tested for battery thickness T4. The lithium ion secondary battery has 100% SOC and the percentage of gas generation after 35 days of storage at 60 ℃ (T4-T3)/T3 is 100%.
7. Thickness test of active material on upper and lower layers of positive electrode
Thickness T of the first coating1And the thickness T of the second coating layer2The following test adopts a scanning electron microscope SEM method to measure the section of the anode plate,the thickness of the first and second coating layers was measured separately for 10 zones and averaged.
The procedure for comparative example 1 was as follows:
comparative example 1 differs from example 1 in that: the coating is a single layer, and the coating comprises an active substance (graphite: SiOx: 19:1), a binder SBR, a thickening agent CMC, a conductive agent SP and a conductive agent CNT according to a mass ratio of 96.9:1.8:0.8:0.45: 0.05. And coating the active slurry according to the surface density of 8.26mg/cm2, drying, coating the other side of the membrane copper foil according to the same surface density, and then forming a lithium ion battery with the positive plate, the diaphragm, the aluminum plastic bag and the electrolyte, wherein the lithium ion battery is marked as C7.
The manufacturing processes of examples 2 to 10, comparative example 3 and comparative example 4 were identical to example 1, and the manufacturing process of comparative example 2 was identical to comparative example 1 except for the differences shown in table 1.
TABLE 1
Through experiments, the experimental results shown in the table 2 are obtained:
TABLE 2
In the context of Table 2, the following examples are,
as can be seen from table 2, the battery provided in the embodiment of the present application has a small dc resistance at a low temperature and a low state of charge, and has good charge and discharge properties. In addition, the expansion rate of the battery provided by the embodiment of the application is small, which shows that the battery provided by the embodiment of the application has better high-temperature cycle and high-temperature storage gas production performance while the charge and discharge performance of the battery is improved.
While the present embodiments have been described with reference to the accompanying drawings, it is to be understood that the invention is not limited to the precise embodiments described above, which are meant to be illustrative and not restrictive, and that various changes may be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The battery is characterized by comprising a negative plate, a diaphragm, a positive plate and electrolyte;
the positive plate comprises a positive current collector, a first coating is arranged on the surface of the positive current collector, and a second coating is arranged on the first coating;
the battery satisfies the following relationship:
eta is viscosity of the electrolyte, D501Is the median particle diameter of the first coating layer, D502Is the median particle diameter, T, of the second coating layer1Is the thickness of the first coating, T2Is the thickness of the second coating.
2. The battery of claim 1, wherein the median particle size of the second coating layer is less than the median particle size of the first coating layer, and the thickness of the second coating layer is less than the thickness of the first coating layer.
3. The battery of claim 1, wherein the ratio of the thickness of the second coating to the thickness of the first coating is less than one third.
4. The battery of claim 1, wherein the first coating has a median particle size in a range of 10 μ ι η to 20 μ ι η;
the median particle diameter of the second coating layer ranges from 1 μm to 10 μm.
5. The battery of claim 1, wherein the first coating has a thickness in a range of 30 μ ι η to 100 μ ι η;
the thickness of the second coating layer ranges from 10 μm to 30 μm.
6. The battery according to claim 1, wherein the first coating layer comprises a first active material, a first conductive agent and a first binder, the mass of the first active material accounts for 95-98.5% of the mass of the first coating layer, the mass of the first conductive agent accounts for 0.5-3% of the mass of the first coating layer, and the mass of the first binder accounts for 1-2% of the mass of the first coating layer;
the second coating comprises a second active substance, a second conductive agent and a second adhesive, wherein the mass of the second active substance accounts for 95-98.5% of the mass of the second coating, the mass of the second conductive agent accounts for 0.5-3% of the mass of the second coating, and the mass of the second adhesive accounts for 1-2% of the mass of the second coating.
7. The battery of claim 6, wherein the mass of the first conductive agent is 0.5% to 3% of the mass of the first coating layer;
the mass of the second conductive agent is 0.5-3% of the mass of the second coating.
8. The battery of claim 6, wherein the mass of the first binder is 1% to 2% of the mass of the first coating layer;
the mass of the second adhesive is 1% -2% of the mass of the second coating.
9. The battery of claim 1, wherein the viscosity η of the electrolyte ranges from 3 to 10cP at a temperature of 25 degrees.
10. The battery according to claim 1, wherein the electrolyte comprises an organic solvent, a lithium salt and an additive, wherein the organic solvent comprises a cyclic solvent and a chain solvent, and the mass ratio of the cyclic solvent to the chain solvent is in a range of 0.25 to 1.
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