CN117154014A - Positive plate and application thereof - Google Patents

Positive plate and application thereof Download PDF

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Publication number
CN117154014A
CN117154014A CN202310096661.8A CN202310096661A CN117154014A CN 117154014 A CN117154014 A CN 117154014A CN 202310096661 A CN202310096661 A CN 202310096661A CN 117154014 A CN117154014 A CN 117154014A
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positive electrode
electrode active
positive
lithium
active material
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林超旺
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Honor Device Co Ltd
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Honor Device Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The application provides a positive plate and application thereof, wherein the positive plate comprises a positive current collector, a first positive active layer and a second positive active layer which are sequentially stacked, and the thickness of the first positive active layer is more than or equal to 0.5 mu m; in the first positive electrode active material of the first positive electrode active layer, the molar ratio of lithium element to active metal element is greater than 1; and the full electrical resistance R of the positive plate is not lower than 1 omega. The special composition of the positive plate and the proper resistance of the pole piece can effectively and stably improve the needling test passing rate of the lithium ion battery on the premise of ensuring the energy density of the lithium ion battery.

Description

Positive plate and application thereof
Technical Field
The application relates to a positive plate, in particular to a positive plate and application thereof, and belongs to the technical field of secondary batteries.
Background
With the advent of electronics, digitization and intellectualization, more and more products rely on energy storage devices such as batteries and power supplies. In this development surge, lithium ion batteries have been rapidly developed due to their high energy density, good service life, and excellent environmental friendliness.
In the development of lithium ion batteries, the safety performance of the use process of the lithium ion batteries is inevitably required to be focused. Along with the popularization of lithium ion batteries, the problem of battery stamping and burning caused by disassembly and collision on the market is caused at random, so that users pay more and more attention to the safety performance of the batteries. The needling test of the battery is to evaluate the safety performance of the battery under the condition of extrusion or disassembly or collision based on external force, and the needling test is to fully charge the battery with a certain current, then penetrate the battery with a fixed speed by adopting a nail with a certain diameter, and take whether smoke, fire, combustion and explosion of the battery as test criteria.
At present, the improvement measures aiming at needling mainly prevent short circuit occurrence by coating a ceramic layer on the surface of a negative electrode, or ensure that the short circuit mainly occurs between the empty current collectors of the positive electrode and the negative electrode by prolonging the empty current collectors of the positive electrode and the negative electrode, but greatly lose the energy density of the battery. In addition, at present, a layer of gummed paper is attached to the surface of the empty current collector to avoid the burrs of the empty current collector from piercing the diaphragm, and the gummed paper can reduce the probability of short circuit of the empty current collector of the positive and negative pole plates, so that the improvement measures for enabling the short circuit to occur between the empty current collectors of the positive and negative poles are often unstable in effect, and the reproducibility of the test result is poor.
Disclosure of Invention
The application provides a positive plate and application thereof, wherein the positive plate has special composition and proper pole piece resistance, and can effectively and stably improve the needling test passing rate of a lithium ion battery on the premise of ensuring the energy density of the lithium ion battery.
The first aspect of the application provides a positive plate, which comprises a positive current collector, a first positive active layer and a second positive active layer which are sequentially stacked, wherein the thickness of the first positive active layer is more than or equal to 0.5 mu m;
in the first positive electrode active material of the first positive electrode active layer, the molar ratio of lithium element to active metal element is greater than 1;
and the full electrical resistance R of the positive plate is not lower than 1 omega.
The thickness of the first positive electrode active layer in the positive electrode plate is more than or equal to 0.5 mu m, and the full-charge resistance is not lower than 1 omega, so that the positive electrode plate has lower short-circuit current. When the battery works under severe conditions such as impact and needling, even if a short circuit occurs between the anode and the cathode, the heat generating power in the short circuit process is greatly reduced due to low short circuit current, the safety of the short circuit process is ensured, the capability of the battery for passing needling test is improved, the short circuit phenomenon is mild and controllable, and the probability of the battery for generating fire and explosion is reduced. In addition, the special structural composition and chemical composition of the positive plate can ensure that more active lithium ions exist in the lithium ion battery, thereby being beneficial to considering the energy density of the lithium ion battery.
In one possible implementation, R.ltoreq.50Ω.
In one possible implementation, the first positive electrode active material includes a chemical composition of Li x A y T z A compound of (a);
where x/y > 1, element A comprises at least one of Fe, ni, co, mn, cu, zn, cr, al and element T comprises at least one of O, cl, S, F, P.
In one possible implementation, the second positive active material includes at least one of lithium cobaltate, lithium manganate, lithium nickel cobalt manganate, lithium iron phosphate, lithium iron manganese phosphate, lithium vanadyl phosphate, lithium-rich manganese-based material, lithium nickel cobalt aluminate, and lithium titanate.
In one possible implementation manner, in the secondary positive electrode active material, a molar ratio of lithium element to active metal element is 1 or less.
In one possible implementation, the gram capacity of the first positive electrode active material is greater than the gram capacity of the second positive electrode active material.
In one possible implementation, the delithiation potential of the first positive electrode active material is less than the delithiation potential of the second positive electrode active material.
In one possible implementation, the first positive electrode active layer has a thickness of 0.5 to 10 μm.
In one possible implementation, the first positive electrode active layer further includes a binder and a conductive agent, and the mass ratio of the binder to the conductive agent is (6:1) - (1:3).
In one possible implementation, the powder resistivity of the first positive electrode active material is not less than 1Ω.
In one possible implementation, the powder resistivity of the first positive electrode active material is 10 to 200Ω.
A second aspect of the application provides a lithium ion battery comprising the positive electrode sheet of the first aspect. The lithium ion battery has excellent performance in energy density and safety performance.
A third aspect of the application provides an electronic device comprising the lithium ion battery of the second aspect. The electronic equipment has excellent standby time and safety performance and high user satisfaction.
Drawings
FIG. 1 is a schematic view of a positive plate according to the present application;
FIG. 2a is a schematic diagram of the present application prior to a needling test of the cells;
fig. 2b is a schematic diagram of the present application after a needling test of the cells.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present application more apparent, the technical solutions in the embodiments of the present application will be clearly and completely described in the following in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
As shown in fig. 1, a first aspect of the present application provides a positive electrode sheet, which includes a positive electrode current collector 10, a first positive electrode active layer 1, and a second positive electrode active layer 2, which are sequentially stacked, wherein the thickness of the first positive electrode active layer is 0.5 μm or more; in the first positive electrode active material of the first positive electrode active layer 1, the molar ratio of lithium element to active metal element is greater than 1; the full-charge resistance R of the positive plate is not lower than 1Ω.
The positive electrode collector 10 of the positive electrode sheet includes two surfaces which are disposed opposite to each other and have the largest area, and the present application is called a functional surface. The first positive electrode active layer 1 and the second positive electrode active layer 2 of the positive electrode plate are sequentially arranged on the functional surface of the positive electrode current collector 10, wherein the first positive electrode active layer 1 is arranged on the functional surface, and the second positive electrode active layer 2 is arranged on the surface, far away from the positive electrode current collector 10, of the first positive electrode active layer 1. In addition to the first positive electrode active layer 1 and the second positive electrode active layer 2 shown in fig. 1 being provided on the two functional surfaces of the positive electrode current collector 10, respectively, in another embodiment, the first positive electrode active layer 1 and the second positive electrode active layer 2 may be provided on only one functional surface of the positive electrode current collector 10. The positive current collector 10 may be an aluminum foil, a nickel foil, or the like, which are common in the art, and the present patent uses an aluminum foil as the positive current collector.
Specifically, the first positive electrode active layer 1 includes a first positive electrode active material, a conductive agent, and a binder; the second positive electrode active layer 2 includes a second positive electrode active material, a conductive agent, and a binder. The present application is not limited to the choice of the conductive agent in the first positive electrode active layer 1 and the conductive agent in the second positive electrode active layer 2, and for example, both may be independently selected from at least one of conductive carbon black, acetylene black, ketjen black, conductive graphite, conductive carbon fiber, carbon nanotube, single-walled carbon nanotube, multi-arm carbon nanotube, carbon fiber; the present application is also not limited to the selection of the binder in the first positive electrode active layer 1 and the binder in the second positive electrode active layer 2, and illustratively, both may be independently selected from at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and lithium Polyacrylate (PAALi).
In the positive plate, the first positive electrode active material and the second positive electrode active material are used for providing lithium ions which are transferred and released between the positive electrode and the negative electrode for the lithium ion battery, so that the charge and discharge of the lithium ion battery are realized. It can be understood that the first positive electrode active material and the second positive electrode active material each include lithium element, and in addition, include at least one of active metal elements commonly used in the art, such as Mg, fe, co, cu, zn, cr, ti, mn, al, te, W, ni, nb, zr, la, ce, sr, Y, K and the like. The molar ratio of the sum of lithium element and total active metal element in the first positive electrode active material is greater than 1, so that the first positive electrode active material can provide more lithium ions for the lithium ion battery in the first cycle as a lithium-rich material, thereby being beneficial to enabling the lithium ion battery comprising the positive electrode plate to have higher energy density. The present application is not limited to the selection of the second positive electrode active material, and may be the same as or different from the first positive electrode active material.
In addition to optimizing the energy density of the lithium ion battery by the positive electrode sheet having the above chemical composition and structural composition, the positive electrode sheet of the present application has a full electrical resistance R of not less than 1 Ω. The inventor finds that under the action of external forces such as impact, collision and the like, the positive plate can obviously reduce the probability of ignition and explosion of the lithium ion battery, and particularly can obviously and stably improve the passing rate of the needling test when the needling test is carried out on the lithium ion battery. The inventors speculate that the reason may be that the higher full electrical resistance of the electrode sheet including the first positive electrode active layer having a thickness of not less than 0.5 μm can reduce the heat generation power during the short circuit of the battery, and thus can make the short circuit phenomenon mild and controllable, and reduce the probability of the occurrence of fire and explosion phenomena of the battery. Compared with a method for generating short circuit between the positive and negative empty current collectors covered by gummed paper, the positive plate of the application has higher efficiency and higher stability for improving the safety performance of the lithium ion battery.
It is worth mentioning that in the practical application process, the full-charge resistance of the positive plate can be adjusted according to the application requirement and the application environment of the battery, so that the lithium ion battery can be more adaptive to the current application. For example, the full electrical resistance R can be reduced as much as possible on the basis of not lower than 1Ω for consumer batteries, while the full electrical resistance R can be moderately raised on the basis of not lower than 1Ω for power batteries, so as to further ensure safety.
The full-charge resistor is the resistor of the positive electrode sheet obtained by disassembling the lithium ion battery when the battery is subjected to constant-current-constant-voltage charging until the SOC is 100%. The specific constant-current constant-voltage charging system is not excessively limited by the application.
In addition, the preparation method of the positive plate is not excessively limited. For example, the prepared first positive electrode slurry is coated on the functional surface of the positive electrode current collector 10, and then dried, and then a second positive electrode slurry is coated on the surface of the dried first positive electrode active layer 1, and then dried to obtain a second positive electrode active layer 2, and then after-treatment such as pressing, cutting and the like, the positive electrode sheet of the application is obtained. Of course, in the preparation process, relevant parameters need to be controlled to make the positive plate have a full electrical resistance of not less than 1Ω, for example, the full electrical resistance R is adjusted by controlling the selection between the first positive electrode active material and the second positive electrode active material, and mutual matching, and the like.
Further, considering the related electrical properties of the lithium ion battery including rate capability, low temperature cycle capability and the like, the full electrical resistance R of the positive plate is less than or equal to 50Ω. The inventors found that when the full electrical resistance R is too high, the resistance inside the battery cell increases, so that the electrical performance of the battery is lowered to some extent. Therefore, when the full electrical resistance is not higher than 50Ω, the positive electrode sheet can make the lithium ion battery simultaneously excellent in safety performance, energy density and electrical performance.
In one embodiment, the first positive electrode active material comprises a chemical composition of Li x A y T z A compound of (a); where x/y > 1, x > 1, element A comprises at least one of Fe, ni, co, mn, cu, zn, cr, al and element T comprises at least one of O, cl, S, F, P.
In one embodiment, the second positive active material includes at least one of lithium cobaltate, lithium manganate, lithium nickel cobalt manganate, lithium iron phosphate, lithium manganese iron phosphate, lithium vanadyl phosphate, lithium-rich manganese-based material, lithium nickel cobalt aluminate, and lithium titanate, and the present application is not limited thereto.
In order to further ensure the energy density of the lithium ion battery, a first positive electrode active material with higher gram capacity than a second positive electrode active material can be selected, and the energy density of the lithium ion battery is further improved by improving the first effect of the lithium ion battery.
As described above, the first positive electrode active material is a lithium-rich material. Therefore, in order to maximize the initial efficiency of the lithium ion battery, the first positive electrode active material and the second positive electrode active material which are more adaptive can be selected by taking the delithiation potential as a parameter. Specifically, the lithium removal potential of the first positive electrode active material is lower than that of the second positive electrode active material, so that the first positive electrode active material can release more lithium ions in the first charging process, and the energy density of the lithium ion battery is further improved by improving the first effect.
In the practice of the present application, the thickness of the first positive electrode active layer is generally controlled to be 0.5 μm or more. The thickness of the first positive electrode active layer is reasonably controlled, and the performance of the lithium ion battery is further improved. The inventor researches find that as the first positive electrode active layer is increased within a certain range, the safety performance of the lithium ion battery is gradually improved, and the energy density firstly presents an increasing trend and then basically keeps unchanged or slightly reduces. Therefore, in view of better performance of the lithium ion battery, the back of the first positive electrode active layer is generally controlled to be 0.5 to 10 μm.
Of course, the use of different first or second positive electrode active materials, conductive agents or binders in the positive electrode sheet, and even the use of different negative electrode active materials, electrolytes or separators, can have an impact on the final performance of the lithium ion battery. Therefore, in general, when the thickness of the first positive electrode active layer is controlled to be 0.5 to 3 μm, the performance of the lithium ion battery can be substantially optimized.
The application is not limited by the adjustment mode of the full-electric resistance R of the positive plate, and the implementation mode of R is more than or equal to 1 omega or more than or equal to 1 omega and less than or equal to 50 omega.
In one embodiment, the full electrical resistance R may be adjusted by adjusting the mass ratio of the conductive agent and the binder in the first positive electrode active layer. Specifically, when the mass ratio of the binder and the conductive agent in the first positive active layer is (6:1) to (1:3), the limitation of the full electric resistance R of the positive electrode sheet of the present application can be achieved. Further, when the mass ratio (3:1) - (1:1) of the binder and the conductive agent in the first positive active layer is good for further reducing the internal resistance of the battery cell on the premise of considering the passing rate of the needling test.
It is known in the art that, in order to improve the cycle performance or the rate performance of a battery, a carbon coating treatment or a trace metal (for example, mg, ti, al, ni, cu, cr, pt, la, nb) or trace metal element oxide doping treatment is often performed on the positive electrode active material, and different carbon coating amounts or trace element doping amounts affect the powder conductivity of the positive electrode active material. In another embodiment, the full electrical resistance R may be adjusted by the powder resistivity of the first positive electrode active material. Specifically, when the powder resistivity of the first positive electrode active material is not lower than 1Ω, it is possible to realize r++1Ω. Further, when the powder resistivity of the first positive electrode active material is 10 to 200Ω,1Ω.ltoreq.r.ltoreq.50Ω.
The positive plate provided by the application can provide more lithium ions and has higher full-charge resistance, so that the safety performance of the lithium ion battery can be stably improved on the premise of not reducing the energy density of the lithium ion battery, and particularly, the needling test has stable and excellent passing rate.
A second aspect of the present application provides a lithium ion battery comprising the positive electrode sheet of the first aspect.
In addition to the positive electrode sheet, the lithium ion battery includes a negative electrode sheet, an electrolyte, and a separator. The diaphragm is positioned between the anode and the cathode, and electrolyte fills the battery cell. The specific structure of the lithium ion battery is not different from the structure of the existing lithium ion battery in the field, and is not described here again.
The application does not limit the selection of the negative plate, the electrolyte and the diaphragm too much.
In one embodiment, the negative electrode sheet precursor includes a negative electrode current collector and a negative electrode active layer disposed on at least one functional surface of the current collector. The negative electrode current collector may be aluminum foil, among others, which is common in the art. The anode active layer includes an anode active material, a binder, and a conductive agent. The negative electrode active material is, for example, an amorphous carbon material, specifically, a hard carbon material, a soft carbon material, or the like, and further, the negative electrode active material is selected from a hard carbon material such as resin carbon, organic polymer pyrolytic carbon, carbon black, or the like. The conductive agent is at least one selected from, but not limited to, super-P, conductive carbon black, carbon nanotubes, acetylene black. The binder is selected from, but not limited to, one selected from polyvinylidene fluoride (PVDF) or polyethylene oxide (PEO).
In one embodiment, the separator may be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene, and polyvinylidene fluoride.
In a specific embodiment, the electrolyte comprises at least an organic solvent and a lithium salt, wherein the organic solvent can be at least one selected from ethylene carbonate, butylene carbonate, propylene carbonate, ethylmethyl carbonate, ethylene vinyl carbonate fluoroethylene carbonate, fluoroethylmethyl carbonate, difluoroethylene carbonate, fluorodimethylcarbonate, dimethylcarbonate, diethyl carbonate, dipropyl carbonate; the lithium salt may include, but is not limited to, at least one selected from lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI).
The lithium ion battery of the present application includes the aforementioned positive electrode sheet, and thus has excellent performance in terms of safety performance and energy density.
A third aspect of the present application provides an electronic device, where the electronic device may include, but is not limited to, a mobile or stationary terminal with a battery, such as a cell phone, tablet, notebook, ultra-mobile personal computer, UMPC, handheld computer, intercom, netbook, POS, personal digital assistant (personal digital assistant, PDA), wearable device, virtual reality device, base station, energy storage device, etc.
The electronic equipment of the application uses the lithium ion battery as a driving source or an energy storage unit, so that the standby time and the safety performance are excellent, and the user satisfaction is high.
The positive electrode sheet and the lithium ion battery according to the present application will be described in detail with reference to specific examples.
Example 1
The preparation method of the positive plate comprises the following steps:
1) The first positive electrode active slurry (including 96wt% li) was applied using aluminum foil as the positive electrode current collector 1.5 FePO 4 3wt% PVDF and 1wt% conductive carbon black) are uniformly coated on the two functional surfaces of the aluminum foil, and a first positive electrode active layer is formed after drying at 85 ℃; wherein Li is 1.5 FePO 4 The carbon inclusion amount was 3wt%, and 2000ppm of Mg element (doping amount based on atomic weight of Fe) was doped therein.
2) The second positive electrode active paste (including 97.8wt% LiCoO) was continuously applied to both surfaces of the first positive electrode active layer 2 0.8wt% PVDF and 1.4wt% conductive carbon black) and drying at 85 ℃ to form a second positive electrode active layer; wherein LiCoO 2 The gram capacity of (C) is 176mAh/g.
3) And (3) carrying out cold pressing, cutting and slitting on the structure in the step (2) in sequence to obtain the positive plate of the embodiment, wherein the thickness of the first positive electrode active layer is 2 mu m, and the thickness of the second positive electrode active layer is 104 mu m.
The relevant parameters of the positive plate of this example are shown in table 1.
Example 2
The preparation method of the positive electrode sheet of this example is substantially the same as that of example 1, except that Li is used 2 MnO 3 Replacement of Li 1.5 FePO 4 . The relevant parameters of the positive plate of this example are shown in table 1.
Example 3
The preparation method of the positive electrode sheet of this example is substantially the same as that of example 1, except that Li is used 2.5 CuO 2 Replacement of Li 1.5 FePO 4 . The relevant parameters of the positive plate of this example are shown in table 1.
Example 4
The preparation method of the positive electrode sheet of this example is substantially the same as that of example 1, except that Li is used 2 Mn 0.5 Ni0.5O 3 Replacement of Li 1.5 FePO 4 . The relevant parameters of the positive plate of this example are shown in table 1.
Example 5
The preparation method of the positive electrode sheet of this example is basically the same as that of example 1, except that in the first positive electrode active slurry, the mass ratio of PVDF to conductive carbon black is 6:1. the relevant parameters of the positive plate of this example are shown in table 1.
Example 6
The preparation method of the positive electrode sheet of this example is basically the same as that of example 1, except that in the first positive electrode active slurry, the mass ratio of PVDF to conductive carbon black is 5:1. the relevant parameters of the positive plate of this example are shown in table 1.
Example 7
The preparation method of the positive electrode sheet of this example is basically the same as that of example 1, except that in the first positive electrode active slurry, the mass ratio of PVDF to conductive carbon black is 4:1. the relevant parameters of the positive plate of this example are shown in table 1.
Example 8
The preparation method of the positive electrode sheet of this example is basically the same as that of example 1, except that in the first positive electrode active slurry, the mass ratio of PVDF to conductive carbon black is 2:1. the relevant parameters of the positive plate of this example are shown in table 1.
Example 9
The preparation method of the positive electrode sheet in this example is basically the same as that in example 1, except that in the first positive electrode active slurry, the mass ratio of PVDF to conductive carbon black is 1:1. the relevant parameters of the positive plate of this example are shown in table 1.
Example 10
The preparation method of the positive electrode sheet in this example is basically the same as that in example 1, except that in the first positive electrode active slurry, the mass ratio of PVDF to conductive carbon black is 1:2. the relevant parameters of the positive plate of this example are shown in table 1.
Example 11
The preparation method of the positive electrode sheet in this example is basically the same as that in example 1, except that in the first positive electrode active slurry, the mass ratio of PVDF to conductive carbon black is 1:3. the relevant parameters of the positive plate of this example are shown in table 1.
Example 12
The preparation method of the positive electrode sheet of this example is substantially the same as that of example 1, except that in the first positive electrode active slurry, li 1.5 FePO 4 The carbon inclusion amount of (2) was adjusted from 3wt% to 4wt%, and the Mg doping amount was kept constant at 2000ppm, thereby obtaining a first positive electrode active material having a powder resistivity of 5 Ω. The relevant parameters of the positive plate of this example are shown in table 1.
Example 13
The preparation method of the positive electrode sheet of this example is substantially the same as that of example 1, except that in the first positive electrode active slurry, li 1.5 FePO 4 The carbon inclusion amount of (2) was adjusted from 3wt% to 4.5wt%, and the Mg doping amount was kept constant at 2000ppm, thereby obtaining a first positive electrode active material having a powder resistivity of 3Ω. The relevant parameters of the positive electrode sheet of this example are shown in table 1.
Example 14
The preparation method of the positive electrode sheet of this example is substantially the same as that of example 1, except that in the first positive electrode active slurry, li 1.5 FePO 4 The carbon inclusion amount of (2) was adjusted from 3wt% to 5wt%, and the Mg doping amount was kept constant at 2000ppm, thereby obtaining a first positive electrode active material having a powder resistivity of 1Ω. The relevant parameters of the positive plate of this example are shown in table 1.
Example 15
The preparation method of the positive electrode sheet of this example is substantially the same as that of example 1, except that in the first positive electrode active slurry, li 1.5 FePO 4 The carbon inclusion amount of (2) was adjusted from 3wt% to 2.7wt%, and the Mg doping amount was reduced to 1500ppm, thereby obtaining a first positive electrode active material having a powder resistivity of 20Ω. The relevant parameters of the positive plate of this example are shown in table 1.
Example 16
The preparation method of the positive electrode sheet of this example is substantially the same as that of example 1, except that in the first positive electrode active slurry, li 1.5 FePO 4 The carbon inclusion amount of the alloy is adjusted from 3wt% to 2.3wt%, and the doping amount of Mg is reduced to 1300ppmAnd a first positive electrode active material having a powder resistivity of 50Ω was obtained. The relevant parameters of the positive electrode sheet of this example are shown in table 1.
Example 17
The preparation method of the positive electrode sheet of this example is substantially the same as that of example 1, except that in the first positive electrode active slurry, li 1.5 FePO 4 The carbon inclusion amount of (2) was adjusted from 3wt% to 2.0wt%, and the Mg doping amount was reduced to 1300ppm, thereby obtaining a first positive electrode active material having a powder resistivity of 100 Ω. The relevant parameters of the positive electrode sheet of this example are shown in table 1.
Example 18
The preparation method of the positive electrode sheet of this example is substantially the same as that of example 1, except that in the first positive electrode active slurry, li 1.5 FePO 4 The carbon inclusion amount of (2) was adjusted from 3wt% to 1.5wt%, and the Mg doping amount was reduced to 1000ppm, thereby obtaining a first positive electrode active material having a powder resistivity of 150Ω. The relevant parameters of the positive electrode sheet of this example are shown in table 1.
Example 19
The preparation method of the positive electrode sheet of this example is substantially the same as that of example 1, except that in the first positive electrode active slurry, li 1.5 FePO 4 The carbon inclusion amount of (2) was adjusted from 3wt% to 1.0wt%, and the Mg doping amount was reduced to 1000ppm, thereby obtaining a first positive electrode active material having a powder resistivity of 200Ω. The relevant parameters of the positive electrode sheet of this example are shown in table 1.
Example 20
The method of producing the positive electrode sheet of this example was substantially identical to that of example 1, except that the thickness of the first positive electrode active layer was made 1 μm by reducing the mass of the first positive electrode slurry. The relevant parameters of the positive plate of this example are shown in table 1.
Example 21
The method of producing the positive electrode sheet of this example was substantially identical to that of example 1, except that the thickness of the first positive electrode active layer was made 0.5 μm by reducing the mass of the first positive electrode slurry. The relevant parameters of the positive plate of this example are shown in table 1.
Example 22
The method of manufacturing the positive electrode sheet of this example was substantially identical to that of example 1, except that the thickness of the first positive electrode active layer was made 3 μm by increasing the mass of the first positive electrode slurry. The relevant parameters of the positive plate of this example are shown in table 1.
Example 23
The method of producing the positive electrode sheet of this example was substantially identical to that of example 1, except that the thickness of the first positive electrode active layer was made 5 μm by increasing the mass of the first positive electrode slurry. The relevant parameters of the positive plate of this example are shown in table 1.
Example 24
The method of producing the positive electrode sheet of this example was substantially identical to that of example 1, except that the thickness of the first positive electrode active layer was made 10 μm by increasing the mass of the first positive electrode slurry. The relevant parameters of the positive plate of this example are shown in table 1.
Example 25
The preparation method of the positive electrode sheet of this comparative example was substantially the same as in example 1, except that Li was used 1.2 Ni 1/3 Co 1/ 3 Mn 1/3 O 2 Replacement of Li 1.5 FePO 4 . The relevant parameters of the positive plate of this comparative example are shown in Table 1.
Example 26
The preparation method of the positive plate of the comparative example is basically the same as that of example 1, except that in the first positive electrode active slurry, the mass ratio of PVDF to conductive carbon black is 7:1. the relevant parameters of the positive plate of this comparative example are shown in Table 1.
Example 27
The preparation method of the positive electrode sheet of this comparative example was substantially the same as in example 1, except that Li in the first positive electrode active slurry 1.5 FePO 4 The carbon inclusion amount of (2) was adjusted from 3wt% to 0.8wt%, and the Mg doping amount was reduced to 800ppm, thereby obtaining a first positive electrode active material having a powder resistivity of 250Ω. The relevant parameters of the positive electrode sheet of this example are shown in table 1.
Example 28
The method of preparing the positive electrode sheet of this comparative example was substantially identical to that of example 1, except that the thickness of the first positive electrode active layer was 15 μm by increasing the mass of the first positive electrode slurry. The relevant parameters of the positive plate of this comparative example are shown in Table 1.
Comparative example 1
The preparation method of the positive plate of the comparative example comprises the following steps: the second positive electrode active slurry in example 1 (including 97.8wt% LiCoO) was applied as a positive electrode current collector using aluminum foil 2 0.8wt% pvdf and 1.4wt% conductive carbon black) was directly coated on both functional surfaces of the aluminum foil, and then dried at 85 ℃, followed by cold pressing, cutting and slitting in sequence. The positive electrode sheet of this comparative example (only one positive electrode active layer per functional performance of the current collector) was obtained, and the thickness of the single-layer positive electrode active layer was 107 μm. The relevant parameters of the positive plate of this comparative example are shown in Table 1.
Comparative example 2
The preparation method of the positive plate of the comparative example comprises the following steps:
1) The first positive electrode active paste (including 96wt% LiFePO) was applied using aluminum foil as the positive electrode current collector 4 1% conductive carbon black: 3% PVDF) is uniformly coated on the two functional surfaces of the aluminum foil, and a first positive electrode active layer is formed after drying at 85 ℃;
2) The second positive electrode active slurry of example 1 (including 97.8wt% LiCoO) was continuously coated on both surfaces of the first positive electrode active layer 2 0.8wt% PVDF and 1.4wt% conductive carbon black) and drying at 85 ℃ to form a second positive electrode active layer;
3) And (3) carrying out cold pressing, cutting and slitting on the structure in the step (2) in sequence to obtain the positive plate of the comparative example, wherein the thickness of the first positive electrode active layer is 2 mu m, and the thickness of the second positive electrode active layer is 104 mu m.
The relevant parameters of the positive plate of this comparative example are shown in Table 1.
Comparative example 3
The preparation method of the positive plate of the comparative example is basically the same as that of example 1, except that in the first positive electrode active slurry, the mass ratio of PVDF to conductive carbon black is 1:4. the relevant parameters of the positive plate of this comparative example are shown in Table 1.
Comparative example 4
The preparation method of the positive electrode sheet of this comparative example was substantially the same as in example 1, except that Li in the first positive electrode active slurry 1.5 FePO 4 Is coated with carbonThe amount was adjusted from 3wt% to 6wt%, and the doping amount of Mg was kept constant at 2000ppm, thereby obtaining a first positive electrode active material having a powder resistivity of 0.5 Ω. The relevant parameters of the positive electrode sheet of this example are shown in table 1.
Comparative example 5
The method of preparing the positive electrode sheet of this comparative example was substantially identical to that of example 1, except that the thickness of the first positive electrode active layer was made 0.2 μm by reducing the mass of the first positive electrode slurry. The relevant parameters of the positive plate of this comparative example are shown in Table 1.
Test examples
The positive electrode sheets of the embodiment and the comparative example are respectively welded and rubberized with the negative electrode sheets and then wound, the positive electrode sheets and the negative electrode sheets are separated by a diaphragm to form a bare cell, and the bare cell is subjected to the procedures of top sealing, side sealing, code spraying, vacuum drying, electrolyte injection, high-temperature standing, formation, air extraction, side cutting, capacity, high-temperature standing, edge folding and the like to obtain the cells of the embodiment and the comparative example.
The preparation method of the negative plate comprises the following steps: the preparation method comprises the steps of adopting copper foil as a negative electrode current collector, coating negative electrode active slurry (comprising 97.7wt% of graphite, 1.2wt% of CMC and 1.1wt% of SBR) on two functional surfaces of the copper foil, drying at 85 ℃, and then sequentially carrying out cold pressing, cutting and slitting to obtain a negative electrode plate.
The battery core and the first positive electrode active material prepared by the method are subjected to detection of the following parameters, and the results are shown in table 1.
1. Energy density W test
And standing the cell in an environment of 25+/-3 ℃ for 2 hours, charging to cut-off voltage of 4.48V by constant current of 0.5 ℃, then testing at constant voltage until current is reduced to 0.025 ℃ and standing for 10 minutes, and discharging to 3.0V by current cross current of 0.2 ℃ to obtain the discharge energy of the cell.
The cell was charged to a shipment voltage of 4.0V, then the thickness of the cell was measured with PPG, the length and width of the cell were measured with a fixed force caliper, and the cell energy density was calculated as follows. When the energy density W of the battery cell is more than or equal to 680Wh/L, the energy density of the battery cell is proved to be excellent.
Energy density w=discharge energy/(cell length width thickness)
2. Internal resistance R1 of battery cell
And standing the battery cell in an environment with the temperature of 25+/-3 ℃ for more than 12 hours, and then measuring the internal resistance R1 of the battery cell by adopting a HIOKI internal resistance tester, wherein the internal resistance frequency is set to be 1KHz, and the measurement accuracy is +/-0.01 mohm. When the internal resistance R1 of the battery cell is less than or equal to 30mohm, the battery cell is proved to have excellent electrical performance.
3. Needling test
The specific operation is shown in fig. 2a and 2 b. Taking 10 cells B of each example and comparative example, standing the cells B in an environment of 25+/-3 ℃ for 2 hours, charging to cut-off voltage of 4.48V at constant current of 0.5C, and testing at constant voltage until the current is reduced to 0.025C. And then the charged battery cell B is subjected to needling test by adopting a steel needle A with the diameter of 4+/-0.06 mm, the taper of 15+/-2 degrees and the total length of 100mm at normal temperature, the needling speed is 30mm/s, the needling position is the middle of the battery cell B, and the penetrating depth is based on the condition that the steel nail A penetrates through the battery cell B. When the passing rate is more than or equal to 5/10 (namely, at least 5 samples of 10 samples do not catch fire, explode and the like), the needling test is qualified.
4. Pole piece full-electricity internal resistance R test
Placing the battery cell in an environment of 25+/-3 ℃ for 2 hours, charging to cut-off voltage of 4.48V at constant current of 0.5 ℃, then testing at constant voltage until current is reduced to 0.025 ℃ for 10 minutes, taking out the positive plate after disassembly, preparing a sample with the diameter of 14mm by adopting a punching machine, testing the full-pole electrical resistance R of the sample by adopting a meta-energy technology BER2500, setting the testing pressure to be 5MPa, and measuring the accuracy to be 0.5%FS.
5. Powder conductivity test
And pressing 5+/-1 g of the first positive electrode active material powder into a small disc with the diameter of 2mm by a tablet press, then testing the conductivity of the small disc by adopting a four-probe resistance meter, testing a 16pcs sample, and taking the average value as the conductivity of the first positive electrode active material.
6. Lithium removal potential test
After the positive electrode active material to be detected is prepared into a button cell by taking a lithium sheet as a counter electrode, the cell is charged and discharged by current of 0.01C, and the potential reaching the rated gram capacity is the delithiation potential of the positive electrode active material. And respectively testing the lithium removal potential of the first positive electrode active material and the lithium removal potential of the second positive electrode active material, and comparing the lithium removal potential of the first positive electrode active material and the lithium removal potential of the second positive electrode active material with each other, wherein the lithium removal potential of the first positive electrode active material is larger than the lithium removal potential of the second positive electrode active material when C is larger than C, and the lithium removal potential of the first positive electrode active material is smaller than the lithium removal potential of the second positive electrode active material when C is smaller than C.
TABLE 1
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As can be seen from table 1, the positive electrode sheet of the present application has excellent performance in terms of the needling performance passing rate and energy density, compared to the comparative example.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.

Claims (13)

1. The positive plate is characterized by comprising a positive current collector, a first positive active layer and a second positive active layer which are sequentially stacked, wherein the thickness of the first positive active layer is more than or equal to 0.5 mu m;
in the first positive electrode active material of the first positive electrode active layer, the molar ratio of lithium element to active metal element is greater than 1;
and the full electrical resistance R of the positive plate is not lower than 1 omega.
2. The positive electrode sheet according to claim 1, wherein R is 50 Ω or less.
3. The positive electrode sheet according to claim 1, wherein the first positive electrode active material comprises a chemical composition of Li x A y T z A compound of (a);
where x/y > 1, element A comprises at least one of Fe, ni, co, mn, cu, zn, cr, al and element T comprises at least one of O, cl, S, F, P.
4. The positive electrode sheet according to claim 1, wherein the second positive electrode active material includes at least one of lithium cobaltate, lithium manganate, lithium nickel cobalt manganate, lithium iron phosphate, lithium manganese iron phosphate, lithium vanadyl phosphate, lithium-rich manganese-based material, lithium nickel cobalt aluminate, and lithium titanate.
5. The positive electrode sheet according to claim 1 or 4, wherein a molar ratio of lithium element to active metal element in the secondary positive electrode active material is 1 or less.
6. The positive electrode sheet according to any one of claims 1 to 5, wherein the gram capacity of the first positive electrode active material is larger than the gram capacity of the second positive electrode active material.
7. The positive electrode sheet according to any one of claims 1 to 6, wherein the delithiation potential of the first positive electrode active material is smaller than the delithiation potential of the second positive electrode active material.
8. The positive electrode sheet according to any one of claims 1 to 7, wherein the thickness of the first positive electrode active layer is 0.5 to 10 μm.
9. The positive electrode sheet according to claim 1, wherein the first positive electrode active layer further comprises a binder and a conductive agent in a mass ratio of (6:1) to (1:3).
10. The positive electrode sheet according to claim 1 or 9, wherein the powder resistivity of the first positive electrode active material is not lower than 1Ω.
11. The positive electrode sheet according to claim 10, wherein the powder resistivity of the first positive electrode active material is 10 to 200 Ω.
12. A lithium ion battery comprising the positive electrode sheet according to any one of claims 1 to 11.
13. An electronic device comprising the lithium-ion battery of claim 12.
CN202310096661.8A 2023-01-17 2023-01-17 Positive plate and application thereof Pending CN117154014A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040234850A1 (en) * 2001-04-10 2004-11-25 Yusuke Watarai Lithium ion polymer secondary battery, electrode and method for synthesizing polymer compound in binder used in adhesion layer thereof
CN112467107A (en) * 2020-11-25 2021-03-09 珠海冠宇动力电池有限公司 High-safety positive plate and lithium ion battery thereof
CN114497566A (en) * 2022-01-25 2022-05-13 珠海冠宇电池股份有限公司 Positive plate and lithium ion battery
CN114497447A (en) * 2022-01-25 2022-05-13 珠海冠宇电池股份有限公司 Positive plate and lithium ion battery
CN115066767A (en) * 2021-03-23 2022-09-16 珠海冠宇电池股份有限公司 Positive plate and lithium ion battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040234850A1 (en) * 2001-04-10 2004-11-25 Yusuke Watarai Lithium ion polymer secondary battery, electrode and method for synthesizing polymer compound in binder used in adhesion layer thereof
CN112467107A (en) * 2020-11-25 2021-03-09 珠海冠宇动力电池有限公司 High-safety positive plate and lithium ion battery thereof
CN115066767A (en) * 2021-03-23 2022-09-16 珠海冠宇电池股份有限公司 Positive plate and lithium ion battery
CN114497566A (en) * 2022-01-25 2022-05-13 珠海冠宇电池股份有限公司 Positive plate and lithium ion battery
CN114497447A (en) * 2022-01-25 2022-05-13 珠海冠宇电池股份有限公司 Positive plate and lithium ion battery

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