CN116169249A - Negative electrode plate, secondary battery and electric equipment - Google Patents
Negative electrode plate, secondary battery and electric equipment Download PDFInfo
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- CN116169249A CN116169249A CN202310425649.7A CN202310425649A CN116169249A CN 116169249 A CN116169249 A CN 116169249A CN 202310425649 A CN202310425649 A CN 202310425649A CN 116169249 A CN116169249 A CN 116169249A
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- 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
- H01M2004/027—Negative 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
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- 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)
Abstract
The invention discloses a negative plate, which comprises a negative current collector and a negative active layer arranged on at least one side surface of the negative current collector, wherein a negative active substance in the negative active layer is graphite; the negative electrode sheet satisfies: k is more than 5 and less than 80; wherein, the liquid crystal display device comprises a liquid crystal display device,
OI is the ratio of the peak area of the characteristic diffraction peak of the graphite 004 surface to the peak area of the characteristic diffraction peak of the graphite 110 surface in the X-ray diffraction spectrum of the negative plate; PD is the compaction density of the negative plate, and the unit is g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the C is the coating density of the negative electrode active layer, and the unit is g/1540.25mm 2 The method comprises the steps of carrying out a first treatment on the surface of the D90 is particle size corresponding to the cumulative volume percentage of the negative electrode active material reaching 90%, and the unit is mu m; BET is the specific surface area of the negative electrode active material, in m 2 And/g. The invention also discloses a secondary battery and electric equipment. The negative electrode plate can improve the quick charge capacity, the cycle life and the safety performance of the secondary battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a negative electrode plate, a secondary battery and electric equipment.
Background
For lithium ion batteries, a negative electrode active material with small particle size and large specific surface area is generally adopted in the existing quick charge technology, and then a pole piece with low surface density, low compaction and low OI value (the ratio of the peak area of the characteristic diffraction peak of the graphite 004 surface to the peak area of the characteristic diffraction peak of the graphite 110 surface in an X-ray diffraction spectrum) is matched to improve the dynamic performance of the battery. However, the negative electrode active material with small particle size and large specific surface area can cause side reaction of the electrode plate to increase, and the cycle performance of the battery is affected. And if the pole piece adopts low compaction density and low surface density, the battery energy density can be reduced.
Therefore, how to increase the energy density of the battery and improve the dynamics and cycle performance of the battery is an urgent problem to be solved at present.
Disclosure of Invention
The invention aims to provide a negative plate which can improve the dynamics and the cycle performance of a battery.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a negative plate, which comprises a negative current collector and a negative active layer arranged on at least one side surface of the negative current collector, wherein a negative active substance in the negative active layer is graphite;
the negative electrode sheet satisfies: k is more than 5 and less than 80;
wherein ,
;
OI is the ratio of the peak area of the characteristic diffraction peak of the graphite 004 surface to the peak area of the characteristic diffraction peak of the graphite 110 surface in the X-ray diffraction spectrum of the negative plate;
PD is the compaction density of the negative plate, and the unit is g/cm 3 ；
C is the coating surface density of the negative electrode active layer, and the unit is g/1540.25mm 2 ；
D90 is particle size corresponding to the cumulative volume percentage of the negative electrode active material reaching 90%, and the unit is mu m;
BET is the specific surface area of the negative electrode active material, in m 2 /g。
Further, the value range of the OI is 5-30.
Further, the PD has a value ranging from 0.8 to 1.75g/cm 3 。
Further, the method comprises the steps of,the value range of the C is 0.03-0.2 g/1540.25mm 2 。
Further, the D90 has a value ranging from 20 to 60 μm.
Further, the BET value ranges from 0.5 to 3.0. 3.0 m 2 /g。
Further, the negative electrode active layer comprises a negative electrode active material, a conductive agent and a binder, wherein the weight ratio of the negative electrode active material to the conductive agent to the binder is 85-98:1-15:1-5.
The second aspect of the invention provides a secondary battery, which comprises a positive plate, a negative plate, a separation film, electrolyte and a shell, wherein the separation film is used for separating the positive plate from the negative plate, and the shell is used for packaging the positive plate, the negative plate, the separation film and the electrolyte, wherein the negative plate is the negative plate.
Further, the positive plate comprises a positive current collector and a positive active layer arranged on at least one side surface of the positive current collector; the positive electrode active layer comprises a positive electrode active material, a conductive agent and a binder, wherein the weight ratio of the positive electrode active material to the conductive agent to the binder is 93-98:0-5:1-5.
The third aspect of the invention provides electric equipment, which comprises the secondary battery.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, parameters such as orientation OI, compaction density PD, coating surface density C, D particle size, specific surface area BET and the like in the negative plate are related and a parameter K is defined, when the K value is controlled to be more than 5 and less than 80, the negative plate with excellent dynamic performance can be obtained, and the secondary battery using the negative plate has excellent dynamic performance and cycle performance.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Aiming at the defects of the prior art, the invention provides a negative electrode plate with high dynamic performance, and a secondary battery manufactured by the negative electrode plate has the advantages of high charging rate and long cycle life.
The negative electrode plate with high dynamic performance comprises a negative electrode current collector and a negative electrode active layer arranged on at least one side surface of the negative electrode current collector, wherein a negative electrode active substance in the negative electrode active layer is graphite.
In the present application, parameters are defined
，
Wherein OI is the ratio of the peak area of the characteristic diffraction peak of the graphite 004 surface to the peak area of the characteristic diffraction peak of the graphite 110 surface in the X-ray diffraction pattern of the negative plate;
PD is the compaction density of the negative plate, and the unit is g/cm 3 ；
C is the coating surface density of the negative electrode active layer, and the unit is g/1540.25mm 2 ；
D90 is particle size corresponding to the cumulative volume percentage of the negative electrode active material reaching 90%, and the unit is mu m;
BET is the specific surface area of the negative electrode active material, in m 2 /g。
In the above relation, several key physical parameters affecting the fast charge performance of the lithium ion battery are involved, and in order to pursue the fast charge performance of the battery, the following conditions are required to be satisfied by the negative electrode: firstly, the coating surface density C of the negative plate is as small as possible, so that the congestion of lithium ion transmission between the positive electrode and the negative electrode can be reduced, and the average distance of lithium ion transmission between the positive electrode and the negative electrode can be reduced; secondly, the specific surface area BET of the negative electrode active material is as large as possible, so that the number of channels of lithium ions in the embedded negative electrode plate layer can be increased; thirdly, the cathode particles are as small as possible, that is, the D90 representing the particle diameter is as small as possible, so that the diffusion distance of lithium ions in the cathode particles can be increased. In addition, the compaction density and the orientation OI of the pole piece also have a certain influence on the quick charge performance. However, the range of values of the above parameters is also limited.
Through long-term research, the inventors establish a relation between the particle size parameter D90 and the specific surface area BET of the negative electrode active material in the negative electrode sheet and the OI value, the compacted density PD and the coating surface density C of the electrode sheet, and define a parameter K. And a large number of experiments show that when the parameter K of the negative electrode plate is controlled to meet the condition that K is more than 5 and less than 80, the secondary battery prepared from the electrode plate can be ensured to have higher rate capability, quick charge capability, cycle life and safety performance.
In this application, OI represents the orientation of graphite in the electrode. After the graphite is made into the electrode slice, the arrangement direction (orientation) of the graphite lamellar structure has a great influence on the migration of lithium ions. Ideally, when the graphite layer structure is completely perpendicular to the plane direction of the electrode plate, the path of lithium ions inserted into the negative electrode plate can be ensured to be short enough, and the diffusion of the lithium ions is most beneficial, so that lithium precipitation and poor circulation capacity caused by overlong lithium insertion path are reduced; however, it is difficult to realize the preparation, and it is generally only possible to control the orientation of the graphite electrode within a certain range.
The orientation of the graphite electrode can be tested by adopting an X-ray diffraction method, and the principle is as follows: when the diffraction pattern test is carried out on the electrode slice sample which is horizontally placed, the diffraction signals of the 110 crystal face can be acquired from the graphite which is perpendicular to the electrode slice in the layered structure, and the diffraction signals of the 002 crystal face and the 004 crystal face are from the graphite which is parallel to the electrode slice in the layered structure, so that the orientation of the graphite electrode can be described by the ratio of the diffraction peak intensity (or integral area) of the 002 crystal face or the 004 crystal face to the diffraction peak intensity (or integral area) of the 110 crystal face. In the application, the orientation OI of the graphite electrode is represented by a characteristic diffraction peak S of a graphite 004 surface in an X-ray diffraction spectrum of a negative plate 004 Peak area S of characteristic diffraction peak with 110 plane 110 Ratio S 004 /S 110 To represent.
In this application, PD is the compacted density of the negative electrode sheet. When the lithium ion battery is charged and discharged, lithium ions are extracted and intercalated between the anode material and the cathode material, and the extraction and intercalation processes of the lithium ions are closely related to the compaction density of the pole pieces. On one hand, as the compaction density of the pole piece is increased, the contact between the anode active material particles is gradually tight, the electronic conductive network in the pole piece is perfect, and the internal resistance is reduced; however, if the compaction density is too high, the pole piece can rebound in the circulation process, so that a contact chain between the conductive agent and the adhesive and the anode active material is broken, and the anode active material particles are mutually stripped, thereby increasing the resistance of charge transmission and further deteriorating the rate performance and the circulation performance of the battery. On the other hand, the compaction density of the negative electrode plate is improved, the porosity in the electrode plate is reduced continuously, the liquid retention amount of electrolyte in the electrode plate is reduced continuously, the ionic conductivity of the electrode plate is reduced, the conductive network is deteriorated, and the internal resistance of the battery is increased. Therefore, the proper compaction density is selected, so that the rebound of the negative plate can be reduced, and the power performance of the battery can be ensured.
In this application, C is the coated surface density of the anode active layer. The coating surface density of the pole piece has great influence on the quick charge performance of the lithium ion battery. As the areal density of the electrode sheet increases, the specific energy of the battery increases, but a thicker SEI film is generated, resulting in an increase in interfacial resistance, thereby reducing the diffusion rate of lithium ions, and when a large current is charged, lithium ions are not easily extracted from the negative electrode sheet, easily polarization is caused, and reversible lithium ions are reduced, thereby resulting in capacity degradation, which is disadvantageous for rapid battery charging. On the other hand, as the surface density of the pole piece increases, the porosity of the pole piece also decreases, the liquid retention amount of the pole piece continuously decreases, the ionic conductivity of the pole piece decreases, the conductive network becomes worse, and the internal resistance of the battery increases; and causes the intercalation/deintercalation path of lithium ions in the electrode to be prolonged and the resistance to be increased, thus deteriorating the cycle performance. Therefore, the proper surface density is selected, so that the internal resistance of the resistor can be reduced, and the discharge specific capacity and the cycle performance of the battery can be ensured.
In the present application, D90 is the particle diameter corresponding to the cumulative volume percentage of the anode active material reaching 90%. The specific surface area of the cathode active material with small particle size is larger, the contact area with the electrolyte is larger, so that the diffusion path of lithium ions is shortened, the deintercalation of lithium ions in the material under high current density is facilitated, and therefore, the cathode active material with small particle size is beneficial to improving the rate capability of the battery. Meanwhile, as the particle diameter of the anode active material particles increases, the ion transport distance is also reduced, and thus battery power performance can also be improved. However, when the particle diameter of the anode active material is too small, the difficulty of dispersion of the slurry increases accordingly, so that the manufacturing cost increases accordingly. Therefore, the D90 particle size of the anode active material is selected properly, so that the lithium ion battery can be ensured to have excellent power performance and multiplying power performance, the service life of the lithium ion battery can be prolonged, and the manufacturing cost can be controlled.
In the present application, BET is the specific surface area of the anode active material, and it is related to factors such as the compacted density and porosity of the electrode sheet, in addition to the particle size of the anode active material. The larger the specific surface area of the negative electrode active material, the more contact with the conductive carbon is made, and a good conductive network is maintained. When the specific surface area is increased, a decrease in material density is unavoidable, and thus the electrode density is reduced, so that it is not unrestricted to increase the specific surface area of the anode active material. Of course, if a nano-sized anode active material is used, the electrode density may be significantly reduced, and although the rate performance may be improved, the safety performance of the battery may be affected, such as an increase in side reactions with an electrolyte, and an increase in difficulty in dispersion of slurry in a pulping process.
The parameters in the relation are mutually restricted, and meanwhile, the requirements of the fast charge performance and the cycle life on physical properties are different, so that the requirements of the fast charge and the life of the battery are met, balance design is carried out on the physical properties parameters and the pole piece design parameters, the value of a formula K formed by the parameters is in the range of 5-80, the cycle performance can be ensured on the basis of meeting the fast charge, and the lithium ion battery with excellent fast charge capacity, high cycle life and safety performance can be prepared.
In the present application, the orientation OI of the graphite electrode preferably satisfies: OI is more than or equal to 5 and less than or equal to 30. When the OI value is within the above range, the path of lithium ions inserted into the negative electrode sheet can be ensured to be short enough, so that lithium precipitation and deterioration of cycle ability caused by overlong lithium insertion path are reduced. In some embodiments of the present application, OI may be 5, 8, 10, 12, 15, 18, 20, 22, 25, 28, 30, or any range between the above values.
In the present application, the compacted density PD of the negative electrode sheet preferably satisfies: 0.8 g/cm 3 ≤PD≤1.75g/cm 3 . When the PD of the negative electrode sheet is controlled within the above range, it is possible to prevent the lithium intercalation path from increasing due to a low compacted density, and to reduce the deactivation of the active material due to an excessive compacted density. In some embodiments of the present application, the PD may be 0.8 g/cm 3 、1.0 g/cm 3 、1.2 g/cm 3 、1.4 g/cm 3 、1.5 g/cm 3 、1.6 g/cm 3 、1.75 g/cm 3 Or any range between the above values.
In the present application, the coating surface density C of the negative electrode sheet preferably satisfies: 0.03g/1540.25mm 2 ≤PD≤0.2 g/1540.25mm 2 . In some embodiments of the present application, C may be 0.03, 0.05, 0.06, 0.08, 0.1, 0.12, 0.15, 0.16, 0.18, 0.2 g/1540.25mm 2 Or any range between the above values.
In the present application, the particle diameter D90 of the anode active material preferably satisfies: 20. PD is less than or equal to 60 mu m. When the D90 particle size of the anode active material is controlled within the range, larger particle size particles of the anode active material can be ensured to be within a reasonable range, and the reduction of the dynamic performance of the pole piece caused by the growth of a lithium intercalation path of the large particle material is avoided. In some embodiments of the present application, D90 may be 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, or any range between the above values.
In the present application, the specific surface area BET of the anode active material preferably satisfies: 0.5 m is m 2 /g≤BET≤3.0 m 2 And/g. When the BET of the negative electrode active material is controlled within the range, the side reaction of the electrode plate and the reduction of the battery cycle performance caused by the overlarge specific surface area are avoided on the premise of ensuring that the electrode plate has good dynamic performance. In some embodiments of the present application, the BET may be 0.5 m 2 /g、1.0 m 2 /g、1.5 m 2 /g、2.0 m 2 /g、2.5 m 2 /g、3.0 m 2 /g, or any range between the above values.
In the present application, the particle diameter D90 of the negative electrode active material can be measured by a particle size distribution laser diffraction method (see, specifically, GB/T19077-2016) using a laser diffraction particle size distribution measuring instrument, and the average particle diameter is represented by the median D90 of the volume distribution.
The OI value of the negative plate can be obtained by using an X-ray powder diffractometer, and according to the rule of X-ray diffraction analysis and the lattice parameter measurement method JISK0131-1996 and JB/T4220-2011 of graphite, an X-ray diffraction spectrogram is obtained, and then the OI value=S 004 /S 110, wherein ,S004 Peak area of characteristic diffraction peak of graphite 004 face, S 110 Peak area of the characteristic diffraction peak of the graphite 110 face.
The compaction density pd=m/V of the negative plate, m represents the weight of the negative plate, V represents the volume of the negative plate, m can be obtained by weighing with an electronic balance having an accuracy of 0.01g or more, and the volume V of the negative plate can be obtained by multiplying the surface area of the negative plate by the thickness of the negative plate, wherein the thickness can be measured with a screw micrometer having an accuracy of 0.5 μm.
It is understood that in the negative electrode sheet of the present application, the negative electrode active layer includes a conductive agent and a binder in addition to the negative electrode active material (graphite). The conductive agent and the binder can be selected according to requirements, for example, the conductive agent can be selected from conductive carbon black (SP), carbon Nanotube (CNT), acetylene black, graphene, ketjen black, carbon nanofiber and the like; the binder may be selected from polyacrylonitrile, polyvinylidene fluoride (PVDF), polyvinyl alcohol, sodium carboxymethylcellulose (CMC), polymethacrylate, polyacrylic acid, sodium polyacrylate, polyacrylamide, polyamide, polyimide, polyacrylate, styrene Butadiene Rubber (SBR), sodium alginate, chitosan, polyethylene glycol, guar gum, etc. In some embodiments of the present application, the weight part ratio of the negative electrode active material and the conductive agent binder may be 85-98:1-15:1-5.
In the application, the negative plate can be prepared by the following preparation process:
(1) Stirring: dissolving a negative electrode active material, a conductive agent and a binder in a solvent according to a certain proportion to prepare uniformly dispersed negative electrode slurry;
(2) Coating: uniformly coating the negative electrode slurry on a negative electrode current collector, and sufficiently drying the negative electrode current collector by an oven to remove a solvent;
(3) Cold pressing: cold-pressing the dried negative plate under a certain pressure;
(4) Cutting: cutting the cold-pressed negative electrode plate, and cutting the negative electrode plate to a specified size for later use.
In the above step (1), the D90 particle diameter and specific surface area BET of the anode active material are adjusted by selecting the anode active material graphite; in the step (2), the coating surface density C is adjusted by controlling the coating process; in the above step (3), the compacted density PD is adjusted by controlling the cold pressing process.
The OI value of the negative electrode sheet is related to various factors such as the orientation of graphite powder, the particle diameter of powder D90, the compaction density PD of the negative electrode sheet, and the like. Therefore, the required OI value of the negative plate can be obtained by controlling the orientation of the graphite powder, the D90 particle size, the compaction density and other means. In addition, in the coating process of the anode slurry, the OI value of the pole piece can be changed by artificially inducing the arrangement of graphite on the anode current collector through a magnetic field induction technology.
On the basis of the negative plate, the invention further provides a secondary battery, which comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the diaphragm is arranged to isolate the positive plate from the negative plate. The secondary battery can be a square battery or a cylindrical or soft package battery; the battery can be a lithium ion battery or a sodium ion battery. Wherein, positive plate, barrier film and negative plate stack in proper order, form naked electric core through coiling or lamination mode. And filling the bare cell into a shell, and then injecting electrolyte to obtain the secondary battery.
In the secondary battery, the positive plate comprises a positive current collector and a positive active coating layer arranged on at least one side surface of the positive current collector, wherein the positive active coating layer comprises a positive active material, a conductive agent and a binder. Taking a lithium ion battery as an example, the active material in the positive electrode active coating can be one or more of lithium iron phosphate, lithium manganese iron phosphate, ternary material, lithium cobaltate and lithium manganate. In some embodiments of the present application, the ratio of the parts by weight of the positive electrode active material, the conductive agent, and the binder may be 93-98:0-5:1-5. The conductive agent and the binder may be selected according to the need.
In the above secondary battery, the separator may be selected according to actual needs. For example, the separator may be selected from polyethylene film, polypropylene film, polyvinylidene fluoride film, nonwoven fabric, etc. While the release film may have a different coating thereon, such as an alumina coating, a boehmite coating, a PVDF coating, and the like.
In the above secondary battery, the electrolyte includes a lithium salt solute and a solvent. The kind of lithium salt and solvent is not particularly limited, and may be selected according to actual requirements. For example lithium salts optionally LiPF 6 、LiTFSi、LiBF 4 Etc. Illustratively, in some embodiments of the present application, it may be selected to mix Ethylene Carbonate (EC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC) in a volume ratio of 1:1:1 to obtain an organic solvent, followed by a substantially dry lithium salt LiPF 6 Dissolving in the mixed organic solvent to prepare the electrolyte with the concentration of 1.2 mol/L.
The invention further provides electric equipment, which comprises the secondary battery.
In some embodiments, the powered device of the present application includes, but is not limited to, a backup power source, a motor, an electric car, an electric motorcycle, a moped, a bicycle, an electric tool, a household large-scale battery, and the like.
The present invention will be further described with reference to specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the present invention and practice it.
The experimental methods used in the following examples are conventional methods unless otherwise specified, and materials, reagents, etc. used, unless otherwise specified, are commercially available.
Example 1
1. Preparation of positive electrode sheet
Positive electrode active material LiFePO 4 The conductive agent CNT, SP and binder PVDF are added into a stirring tank according to the mass ratio of 96 percent to 0.5 percent to 1.5 percent to 2 percent, and then the materials are addedNMP was added and mixed with stirring to form a uniform positive electrode slurry. And then, coating the positive electrode slurry on a positive electrode current collector aluminum foil, drying, tabletting and cutting to obtain a positive electrode plate P. The positive plate has a compacted density of 2.5g/cm 3 。
2. Preparation of negative electrode sheet
Adding graphite as a cathode active material, a conductive agent SP, a binder CMC and SBR into a stirring tank according to the mass ratio of 96 percent to 1 percent to 0-2 percent, adding deionized water, and stirring and mixing to obtain uniform cathode slurry. And then, coating the negative electrode slurry on a negative electrode current collector copper foil, and tabletting and slitting after drying to obtain a negative electrode plate N. Wherein the graphite used had a D90 particle size of 20. Mu.m, and a specific surface area BET of 1.2. 1.2 g/m 2 The coating surface density C of the pole piece is controlled to be 0.1 g/1540.25mm 2 A compaction density PD of 0.95 g/cm 3 The OI value of the pole piece is 5.6.
3. Preparing an electric core:
(1) Full cell
And (3) winding or laminating the positive plate P, the negative plate N and the diaphragm, performing formation and capacity division through baking and liquid injection, and performing normal-temperature 1C/1C cycle test on the prepared battery cell.
(2) Three-electrode battery
And (3) winding or laminating the positive plate P, the negative plate N and the diaphragm, placing the thin copper wire coated by the diaphragm between the positive electrode and the negative electrode to be led out as a nickel strap for the three electrodes, and then plating lithium on the copper wire in the battery core to finish the preparation of the three-electrode battery.
Examples 2 to 15, comparative examples 1 to 6
Examples 1 to 15, comparative examples 1 to 6 were prepared by the same method as in example 1, and parameters of the anode active material and the anode coating layer in each example are shown in table 1.
Electrochemical performance test
1. 1C/1C cycle test
The following tests were carried out at 25 ℃):
a) Clamping the battery by using a 2-piece clamping tool, wherein the initial clamping force is 300kgf;
b) 1C constant-current and constant-voltage charging to 3.65V, and cut-off current is 0.05C;
c) Standing for 30min;
d) Constant-current discharging of 1C to 2.5V;
e) Standing for 30min;
f) Repeating the steps b) -e) 1500 times, and calculating the ratio of the 1500 th time capacity to the 1 st time capacity to obtain the 1500 week capacity retention rate.
2. Three electrode rate test
The following tests were carried out at 25 ℃):
a) 1C is discharged to 2.5V;
b) Standing for 30min;
c) And (3) performing a lithium-ion battery charging rate test: charging the battery to 3.65V with a certain multiplying power until the difference value between the potential of the negative electrode and the potential of the reference electrode is less than or equal to 0V, and recording the multiplying power as the lithium separating multiplying power of the three electrodes;
d) Standing for 30min;
e) 1C was discharged to 2.5V.
TABLE 1
As can be seen from the data in table 1, in examples 1 to 15, by adjusting the D90 particle diameter, the specific surface area BET, the OI value of the graphite electrode, the smear surface density C and the compaction density PD of the negative electrode sheet, when the K value was in the range of 5 to 80, the capacity retention rate of the obtained battery in 1500 weeks was 80% or more, and the lithium separation rate of the three electrodes was 1.4C or more, which showed good cycle performance and rate performance.
In comparative examples 1 to 6, when the K value was 5 or more and 80 or more, the cycle performance and the rate performance of the battery were both poor, the capacity retention rate at 1500 cycles was lower than 76%, and the three-electrode lithium-separating rate was lower than 1.3C.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. The negative electrode plate is characterized by comprising a negative electrode current collector and a negative electrode active layer arranged on at least one side surface of the negative electrode current collector, wherein a negative electrode active substance in the negative electrode active layer is graphite;
the negative electrode sheet satisfies: k is more than 5 and less than 80, and the unit is 25480.29 g 2.5 *m -5.5 ；
wherein ,
;
OI is the ratio of the peak area of the characteristic diffraction peak of the graphite 004 surface to the peak area of the characteristic diffraction peak of the graphite 110 surface in the X-ray diffraction spectrum of the negative plate;
PD is the compaction density of the negative plate, and the unit is g/cm 3 ；
C is the coating surface density of the negative electrode active layer, and the unit is g/1540.25mm 2 ；
D90 is particle size corresponding to the cumulative volume percentage of the negative electrode active material reaching 90%, and the unit is mu m;
BET is the specific surface area of the negative electrode active material, in m 2 /g。
2. The negative electrode sheet according to claim 1, wherein the OI has a value in the range of 5 to 30.
3. The negative electrode sheet according to claim 1, wherein the PD has a value in the range of 0.8 to 1.75g/cm 3 。
4. The negative electrode sheet according to claim 1, wherein the value of C is in the range of 0.03 to 0.2 g/1540.25mm 2 。
5. The negative electrode sheet according to claim 1, wherein the D90 has a value in the range of 20 to 60 μm.
6. The negative electrode sheet according to claim 1, wherein the BET has a value in the range of 0.5 to 3.0. 3.0 m 2 /g。
7. The negative electrode sheet according to claim 1, wherein the negative electrode active layer comprises a negative electrode active material, a conductive agent and a binder, and the weight ratio of the negative electrode active material, the conductive agent and the binder is 85-98:1-15:1-5.
8. The secondary battery is characterized by comprising a positive plate, a negative plate, a separation film, electrolyte and a shell, wherein the separation film is used for separating the positive plate from the negative plate, and the shell is used for packaging the positive plate, the negative plate, the separation film and the electrolyte, and the negative plate is the negative plate according to any one of claims 1-7.
9. The secondary battery according to claim 8, wherein the positive electrode sheet comprises a positive electrode current collector and a positive electrode active layer provided on at least one side surface of the positive electrode current collector; the positive electrode active layer comprises a positive electrode active material, a conductive agent and a binder, wherein the weight ratio of the positive electrode active material to the conductive agent to the binder is 93-98:0-5:1-5.
10. A powered device comprising the secondary battery of claim 8 or 9.
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