CN113422000B - Electrochemical device and electronic device - Google Patents

Electrochemical device and electronic device Download PDF

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CN113422000B
CN113422000B CN202110687690.2A CN202110687690A CN113422000B CN 113422000 B CN113422000 B CN 113422000B CN 202110687690 A CN202110687690 A CN 202110687690A CN 113422000 B CN113422000 B CN 113422000B
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active material
material layer
lithium
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coating
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CN113422000A (en
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韩翔龙
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Ningde Amperex Technology 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
    • H01M4/131—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
    • 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
    • H01M4/136—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
    • 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
    • H01M2004/026—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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The present application provides an electrochemical device and an electronic device, the electrochemical device including: a positive electrode including: a positive electrode current collector, a first active material layer, and a second active material layer; the first active material layer is positioned between the positive electrode current collector and the second active material layer; the first active material layer contains lithium manganate and lithium iron phosphate, and the second active material layer contains lithium nickel cobalt manganate. The safety performance can be guaranteed while the cost is reduced.

Description

Electrochemical device and electronic device
Technical Field
The present disclosure relates to electrochemical technologies, and particularly to an electrochemical device and an electronic device.
Background
The price of ternary materials used in the positive electrode of an electrochemical device (such as a lithium ion battery) is high, and in order to reduce the cost, some electrochemical devices adopt lithium manganate with low price as a positive electrode material, however, the lithium manganate is easy to react with HF in an electrolyte to dissolve Mn into the electrolyte, and the Mn is deposited to a negative electrode through an electrochemical reaction in the use process, and finally an SEI (solid electrolyte interphase) film of the negative electrode is damaged, and lithium is precipitated in the charging and discharging process, and the lithium is ignited seriously.
Disclosure of Invention
In some embodiments, the present application provides an electrochemical device comprising:
a positive electrode including: a positive electrode current collector, a first active material layer, and a second active material layer; the first active material layer is positioned between the positive electrode current collector and the second active material layer;
the first active material layer contains lithium manganate and lithium iron phosphate, and the second active material layer contains lithium nickel cobalt manganate. In some embodiments, at least a portion of the lithium iron phosphate is located on a surface of the lithium manganate.
In some embodiments, the lithium manganate is contained in the first active material layer in an amount of more than 80% by mass and less than 100% by mass.
In some embodiments, the second active material layer further includes at least one of lithium iron phosphate or a lithium rich manganese based material.
In some embodiments, the weight per unit area of the first active material layer on one side of the positive electrode current collector is a g/cm 2 (ii) a The weight of the second active material layer per unit area on one side of the positive current collector is b g/cm 2 ；0.016<a+b<0.026。
In some embodiments, the weight per unit area of the first active material layer on one side of the positive electrode current collector is a g/cm 2 (ii) a The weight of the second active material layer per unit area on one side of the positive current collector is bg/cm 2 ；a≥2.5×b。
In some embodiments, 10 xb ≧ a ≧ 4 xb.
In some embodiments, the lithium manganate is MnO 2 And (3) preparing the lithium manganate.
In some embodiments, the electrochemical device further includes a negative electrode including a negative electrode current collector and a negative electrode active material layer, the negative electrode active material layer including: at least one of Sn, sb, lithium titanate, a tin-based compound, a silicon-based compound, artificial graphite, natural graphite, soft carbon, hard carbon, mesocarbon microbeads or graphene.
The present application also provides an electronic device comprising the electrochemical device of any one of the above.
In some embodiments of the present application, an electrochemical device comprises: a positive electrode including: a positive electrode current collector, a first active material layer, and a second active material layer; the first active material layer is positioned between the positive electrode current collector and the second active material layer; the first active material layer contains lithium manganate and lithium iron phosphate, and the second active material layer contains lithium nickel cobalt manganate. The safety performance can be guaranteed while the cost is reduced.
Drawings
The above and other features, advantages, and aspects of embodiments of the present disclosure will become more apparent by referring to the following detailed description when taken in conjunction with the accompanying drawings. Throughout the drawings, the same or similar reference numbers refer to the same or similar elements. It should be understood that the drawings are schematic and that elements and elements are not necessarily drawn to scale.
Fig. 1 is a schematic diagram of a positive electrode of an embodiment of the disclosure.
Fig. 2 is a schematic view of another positive electrode of an embodiment of the present disclosure.
Fig. 3 is a schematic of the cycle capacity retention of example 1 and comparative example 1 of the present disclosure.
Fig. 4 is a schematic of the cycle capacity retention of example 2 and comparative example 2 of the present disclosure.
Fig. 5 is a schematic of the cycle capacity retention of example 3 and comparative example 3 of the present disclosure.
Fig. 6 is a graph illustrating capacity fade during storage for example 4 and comparative example 4 of the present disclosure.
Fig. 7 is a schematic of the cycle capacity retention of example 5 and comparative example 5 of the present disclosure.
Detailed Description
Embodiments of the present application will be described in more detail below. While certain embodiments of the present application have been illustrated, it should be understood that the present application may be embodied in various forms and should not be construed as limited to the embodiments set forth herein, but rather these embodiments are provided for a more thorough and complete understanding of the present application. It should be understood that the embodiments of the present application are for illustrative purposes only and are not intended to limit the scope of the present application.
To reduce the cost of electrochemical devices (e.g., lithium ion batteries), some technologies employ MnO 2 Lithium manganate prepared for raw materials is used as a positive electrode material of an electrochemical device, but the lithium manganate reacts with HF in an electrolyte in the using process to dissolve out Mn, and finally an SEI (solid electrolyte interphase) film of a negative electrode is damagedIn some technologies, the mass percentage of the low-cost lithium manganate needs to be controlled below 80%. In other techniques, mn is used which is relatively costly 3 O 4 The prepared lithium manganate with low Mn dissolution risk can be used independently in the two-wheel vehicle market at present, but the lithium manganate has high cost, low gram-volume and limited application.
In some embodiments, the present application provides an electrochemical device comprising: as shown in fig. 2, the positive electrode includes: a positive electrode collector 10, a first active material layer 11, and a second active material layer 12; the positive current collector 10 may be made of copper foil, aluminum foil, steel sheet, etc., and the first active material layer 11 is located between the positive current collector 10 and the second active material layer 12; the first active material layer contains lithium manganate (MnO may be used) 2 The second active material of the prepared lithium manganate comprises nickel cobalt lithium manganate.
In some embodiments, the first active material layer 11 and the second active material layer 12 of the positive electrode may have different compositions, and the use of lithium manganate in the first active material layer 11 may reduce the manufacturing cost of the positive electrode, and since the first active material layer 11 is located between the positive electrode collector 10 and the second active material layer 12, the second active material layer 12 may protect the first active material layer 11, reduce the contact of the first active material layer with the electrolytic solution, and may reduce the elution of Mn from the lithium manganate in the first active material layer 11 due to the influence of HF in the electrolytic solution. In addition, lithium nickel cobalt manganese oxide is added into the second active material layer 12, the lithium nickel cobalt manganese oxide in the second active material layer 12 can effectively absorb HF and is not easy to dissolve out Mn, so that the problem that Mn dissolved out due to contact of lithium manganese oxide in the first active material layer 11 and HF can be further reduced, the stability of the second active material layer 12 is guaranteed, safety performance is improved, the gram volume of lithium nickel cobalt manganese oxide is higher than that of lithium manganese oxide, and the whole gram volume of the positive electrode can also be improved. Some embodiments of the present disclosure ensure the safety of an electrochemical device while reducing the cost of the electrochemical device.
In some embodiments of the present application, the positive electrode of the electrochemical device may have a double-layer coating structure, the manufacturing cost is reduced by the first active material layer 11, and the contact of lithium manganate and HF in the first active material layer 11 is reduced by the second active material layer 12, increasing safety performance. In some embodiments of the application, the low-cost advantage of lithium manganate and the high stability advantage of nickel cobalt lithium manganate can be utilized, the cost can be reduced through a double-layer coating mode, and the controllable risk of Mn dissolution can be ensured.
In some embodiments of the present application, the first active material layer 11 further includes lithium iron phosphate. In some embodiments, lithium iron phosphate is less likely to cause a problem of atom elution in the electrolyte solution, and has good stability, and the addition of lithium iron phosphate to the first active material layer 11 can improve the stability of the entire first active material layer.
In some embodiments of the present application, at least a portion of the lithium iron phosphate is located on a surface of the lithium manganate. In some embodiments, referring to fig. 2, the lithium iron phosphate is adsorbed on the surface of lithium manganate to reduce the contact between lithium manganate and the electrolyte, so as to protect lithium manganate, reduce the corrosion of HF to lithium manganate, further inhibit the dissolution of Mn from lithium manganate, and improve the safety of the positive electrode.
In some embodiments of the present application, the mass percentage content of lithium manganese oxide in the first active material layer 11 is more than 80% and less than 100%; the mass percentage content of lithium iron phosphate in the first active material layer 11 is less than 20%. In some embodiments, the manufacturing cost of lithium manganate is relatively low, the manufacturing cost of the first active material layer 11 can be reduced in the case where the lithium manganate is high in mass percentage, and aggregation of lithium iron phosphate can be reduced and agglomeration of lithium iron phosphate can be suppressed in the case where the lithium iron phosphate is low in mass percentage. The mass percentage content of a certain component in the first active material layer 11 is equal to the ratio of the mass of the component to the total mass of the first active material layer 11.
In some embodiments of the present application, the second active material layer 12 further includes at least one of lithium iron phosphate or a lithium-rich manganese-based material. In some embodiments, lithium iron phosphate and the lithium-rich manganese-based material have better electrolyte stability and safety, and the lithium iron phosphate and the lithium-rich manganese-based material are added to the second active material layer 12, so that on one hand, lithium manganate in the first active material layer 11 can be protected from corrosion of HF, on the other hand, the safety of the ternary material lithium nickel cobalt manganese in the second active material layer 12 is lower than that of lithium iron phosphate, and the lithium iron phosphate and the lithium-rich manganese-based material in the second active material layer 12 can also stabilize the second active material layer 12, thereby improving the safety and stability of the whole positive electrode. In some embodiments of the present application, the characteristic that lithium iron phosphate and lithium nickel cobalt manganese oxide are difficult for Mn to dissolve out is utilized, a double-layer coating mode can be adopted, the second active material layer 12 contains lithium nickel cobalt manganese oxide, lithium iron phosphate and other non-lithium manganese oxide materials, the first active material layer 11 contains a mixture of lithium iron phosphate and lithium manganese oxide, lithium iron phosphate is utilized as a small particle to be adsorbed on the surface of lithium manganese oxide, and the corrosion of HF to lithium manganese oxide is reduced.
In some embodiments of the present application, the weight per unit area of the first active material layer 11 on one side of the positive electrode current collector 10 is a g/cm 2 (ii) a The weight per unit area of the second active material layer 12 on one surface of the positive electrode collector 10 is b g/cm 2 ；0.016<a+b<0.026. In some embodiments, the sum of the weights per unit area of the first active material layer 11 and the second active material layer 12 on one surface of the positive electrode current collector 10 may not be too high or too low, and too high may cause the active material layers on the positive electrode current collector 10 to fall off, or too much binder needs to be added to the positive electrode to cause a decrease in conductivity, and too low may cause a decrease in the volumetric energy density of the positive electrode as a whole.
In some embodiments of the present application, the weight per unit area of the first active material layer 11 on one side of the positive electrode current collector is a g/cm 2 (ii) a The weight of the second active material layer 12 per unit area on one surface of the positive electrode current collector is bg/cm 2 (ii) a a is more than or equal to 2.5 multiplied by b. In some embodiments, the price of lithium manganate in the first active material layer 11 is low, the cost of the positive electrode can be significantly reduced by adopting lithium manganate in the first active material layer 11, the cost of lithium nickel cobalt manganese in the second active material layer 12 is higher than that of lithium manganate, and it is limited that a is greater than or equal to 2.5 × b, so that the positive electrode can be ensured to have a significant cost advantage. The applicant finds out through experimental research that the examples 1-5 can achieve better experimental results,that is, when the weight per unit area of the first active material layer on the single surface of the positive electrode current collector and the weight per unit area of the second active material layer on the single surface of the positive electrode current collector satisfy the ranges defined in examples 1 to 5, the experimental results are superior.
In some embodiments, (10 xb) ≧ a ≧ 4 xb, the positive electrode has a significant cost advantage, and the volumetric energy density of the positive electrode as a whole is superior. Further, in some embodiments, (9.5 xb) ≧ a ≧ 4.25 xb), the positive electrode has a significant cost advantage, and the volumetric energy density of the positive electrode as a whole is superior.
In some embodiments of the present application, the electrochemical device further includes a negative electrode including a negative electrode current collector and a negative electrode active material layer, the negative electrode current collector may employ an aluminum foil, a copper foil, or the like, and the negative electrode active material layer includes: at least one of Sn, sb, lithium titanate, a tin-based compound, a silicon-based compound, artificial graphite, natural graphite, soft carbon, hard carbon, mesocarbon microbeads or graphene. In some embodiments, the negative electrode further comprises a conductive agent, a thickening agent and a binder, the conductive agent can adopt conductive graphite, the thickening agent can adopt sodium carboxymethyl cellulose, and the binder can adopt styrene butadiene rubber.
In some embodiments of the present disclosure, an electrochemical device comprises: an isolation film; the separator includes: at least one of a polypropylene single-layer diaphragm, a polyethylene single-layer diaphragm, a polypropylene/polyethylene/polypropylene three-layer composite diaphragm, a diaphragm with a nano ceramic impregnated coating taking polyethylene terephthalate non-woven fabrics as a base material, or a diaphragm coated with polyolefin mixed resin on a porous base material.
In some embodiments of the present disclosure, the electrochemical device includes an electrolyte including a solvent and a lithium salt, wherein the solvent is selected from one or more of dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl Methyl Carbonate (EMC), ethyl Propyl Carbonate (EPC), ethyl butyl carbonate (BEC), dipropyl carbonate (DPC), ethylene Carbonate (EC), propylene Carbonate (PC), butylene Carbonate (BC), γ -butyrolactone (γ -BL), vinylene Carbonate (VC), propylene Sulfite (PS); the lithium salt is selected from lithium hexafluorophosphate (LiPF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium perchlorate (LiClO) 4 ) Lithium trifluoromethanesulfonate (CF) 3 SO 3 Li) or several kinds in any proportion.
In some embodiments of the present application, the electrochemical device is a wound lithium ion battery or a stacked lithium ion battery.
In some embodiments of the present application, the electrochemical device may be a lithium ion battery, and the lithium ion battery may be a secondary battery (e.g., a lithium ion secondary battery), a primary battery (e.g., a lithium primary battery, etc.), and the like, but is not limited thereto.
Embodiments of the present application also provide an electronic device including the electrochemical device described above. The electronic device of the embodiment of the present application is not particularly limited, and may be any electronic device known in the art. In some embodiments, the electronic device may include, but is not limited to, a notebook computer, a pen-input computer, a mobile computer, an electronic book player, a portable phone, a portable facsimile, a portable copier, a portable printer, a head-mounted stereo headset, a video recorder, a liquid crystal television, a handheld cleaner, a portable CD player, a mini-disc, a transceiver, an electronic organizer, a calculator, a memory card, a portable recorder, a radio, a backup power source, an electric motor, an automobile, a motorcycle, a moped, a bicycle, a lighting fixture, a toy, a game machine, a clock, an electric tool, a flashlight, a camera, a large household battery, and the like.
The present application will be better illustrated by the following examples, in which a lithium ion battery is used as an example.
The following describes a method of testing various parameters of the present application.
And (3) cycle testing: the lithium ion battery was charged to 4.2V at 25 ℃, 45 ℃ or 60 ℃ with a constant current of 0.5C. Then, the mixture was charged at a constant voltage of 4.2V until the current became 0.05C, and the mixture was allowed to stand for 5min. Then discharging to 2.8V with constant current of 1.0C, and standing for 2min. This was taken as a cycle and the discharge capacity C was recorded 0 The cycle was repeated 1000 times according to the above cycle,recording discharge capacity C once per 100 cycles, and calculating cycle capacity retention rate C/C 0 X 100%, the amount of Mn eluted was measured after the end of 1000 cycles.
And (3) testing the calendar life: charging the lithium ion battery to 100%, standing at 70 +/-2 ℃, and charging the lithium ion battery to 4.2V at a constant current of 0.5 ℃. Then charging with constant voltage of 4.2V until the current is 0.05C, standing for 5min, fully charging and standing for 24h; then discharging to 2.8V with constant current of 1.0C, and standing for 2min. One cycle was set as such, and the discharge capacity C was recorded 0 The cycles were repeated 100 times in accordance with the above, the discharge capacity C was recorded every 1 cycle, and the cycle capacity retention rate C/C was calculated 0 X 100%, mn elution amount was measured after 80 cycles were completed.
Example 1
Preparation of the positive electrode: lithium manganate, lithium iron phosphate, conductive carbon black, carbon nano tubes and polyvinylidene fluoride are mixed according to the weight ratio of 86.4:9.6:0.8:0.8:2.4 in N-methylpyrrolidone solution to form positive electrode slurry 1. An aluminum foil is used as a positive current collector (16 μm), and the positive slurry 1 is coated on the positive current collector to form a coating 1. Preparing nickel cobalt lithium manganate, conductive carbon black, a carbon nano tube and polyvinylidene fluoride according to a weight ratio of 96:0.8:0.8:2.4 in N-methylpyrrolidone solution to form positive electrode slurry 2. And coating the positive electrode slurry 2 on the coating 1 to form a coating 2, and drying, cold pressing and cutting to obtain the positive electrode. The weight ratio of the coating 1 to the coating 2 is 9:1, coat weight of coating 1 was 0.293g/1540mm 2 I.e. 0.019g/cm 2 The weight ratio of lithium manganate to lithium iron phosphate in the coating layer 1 is 8:1, coating 1 has a thickness of 0.145mm after cold pressing and coating 2 has a coating weight of 0.033g/1540mm 2 I.e. 0.002g/cm 2 The thickness of the coating 2 after cold pressing is 0.025mm. In this embodiment, the weight per unit area of the first active material layer on the single surface of the positive electrode collector and the weight per unit area of the second active material layer on the single surface of the positive electrode collector satisfy a =9.5 × b.
Preparation of a negative electrode: mixing artificial graphite (V) Negative pole 0.1V), styrene-butadiene rubber and sodium carboxymethylcellulose according to the weight ratio97.7:1.0: the proportion of 1.3 is dissolved in deionized water to form cathode slurry. The copper foil is used as a negative current collector (8 mu m), and the negative slurry is coated on the negative current collector (coating weight is 0.127g/1540 mm) 2 I.e. 0.008g/cm 2 ) And drying, cold pressing and cutting to obtain the cathode.
Preparing an electrolyte: in an environment with a water content of less than 10ppm, mixing lithium hexafluorophosphate with a nonaqueous organic solvent (ethylene carbonate (EC): diethyl carbonate (DEC): propylene Carbonate (PC): propyl propionate: vinylene Carbonate (VC) =20, weight ratio) in a ratio of 10:90 are formulated to form an electrolyte.
Preparing an isolating membrane: selecting single-layer polypropylene (PP) as a diaphragm, and having air permeability of 76secs/100cm 3
Preparing a lithium ion battery: and stacking the negative electrode, the positive electrode and the isolating film in sequence to enable the isolating film to be positioned between the positive electrode and the negative electrode to play a role of isolation, and then winding the components into an electrode assembly. The electrode assembly was then packed in an aluminum plastic film pouch and, after dehydration at 80 ℃, a dry electrode assembly was obtained. And then injecting the electrolyte into a dry electrode assembly, and completing the preparation of the lithium ion battery through the working procedures of vacuum packaging, standing, formation, shaping and the like.
Comparative example 1
Comparative example 1 differs from example 1 only in the preparation of the positive electrode and the remaining steps are the same.
Preparing a positive electrode: lithium manganate, conductive carbon black, carbon nano tubes and polyvinylidene fluoride according to the weight ratio of 96:0.8:0.8:2.4, and dissolving in N-methyl pyrrolidone solution to form anode slurry. Coating the anode slurry on an aluminum foil, and drying, cold pressing and cutting to obtain the anode
The results of the performance test of example 1 and comparative example 1 are shown in fig. 3, and it can be seen from fig. 3 that the cycle performance of example 1 at 25 ℃ is significantly better than that of comparative example 1, the elution amount of Mn after 1000 cycles of example 1 is 300ppm, and the elution amount of Mn of comparative example 1 is 800ppm. This is probably because the double coating was used in example 1, and the lithium nickel cobalt manganese oxide in the coating layer 2 in example 1 protected the lithium manganese oxide in the coating layer 1, and the contact of the lithium manganese oxide in the coating layer 1 with the electrolyte was reduced, thereby reducing the elution of Mn. While the positive electrode in comparative example 1 has only the coating 1 and no coating 2, the lithium manganate is corroded by HF in the electrolyte to cause serious elution of Mn, resulting in a decrease in cycle performance.
Example 2
Preparation of the positive electrode: lithium manganate, lithium iron phosphate, conductive carbon black, carbon nanotubes and polyvinylidene fluoride according to the weight ratio of 91.2:4.8:0.8:0.8:2.4 in N-methylpyrrolidone solution to form positive electrode slurry 1. The positive electrode slurry 1 was coated on a positive electrode current collector using an aluminum foil as the positive electrode current collector (16 μm) to form a coating layer 1. Preparing nickel cobalt lithium manganate, lithium iron phosphate, conductive carbon black, a carbon nano tube and polyvinylidene fluoride according to the weight ratio of 91.2:4.8:0.8:0.8:2.4 in N-methylpyrrolidone solution to form positive electrode slurry 2. And coating the positive electrode slurry 2 on the coating 1, and drying, cold pressing and cutting to obtain the positive electrode. The weight ratio of the coating 1 to the coating 2 is 85:15, coat weight of coat 1 was 0.293g/1540mm 2 I.e. 0.019g/cm 2 The ratio of lithium manganese oxide to lithium iron phosphate in the coating 1 is 95:5, the thickness of the coating 1 after cold pressing is 0.134mm, and the coating weight of the coating 2 is 0.049g/1540mm 2 I.e. 0.003g/cm 2 The thickness of the coating 2 after cold pressing is 0.031mm. In this embodiment, the weight per unit area of the first active material layer on the single surface of the positive electrode collector and the weight per unit area of the second active material layer on the single surface of the positive electrode collector satisfy a =6.3 × b.
Preparation of a negative electrode: mixing artificial graphite (V) Minus 1 0.1V), si (V) Minus 2 0.6V), styrene butadiene rubber and sodium carboxymethyl cellulose in a weight ratio of 92.8:4.9:1.0:1.3 (corresponding to a weight ratio of artificial graphite to Si of 95.
Preparing an electrolyte: the same as in example 1.
Preparing an isolating membrane: selecting single-layer Polyethylene (PE) as a diaphragm, coating ceramic on one side of the diaphragm, and ensuring that the air permeability is 85secs/100cm 3 。
Preparing a lithium ion battery: the same as in example 1.
Comparative example 2
Comparative example 2 is different from example 2 only in the preparation of the positive electrode, and the rest is the same.
Preparation of the positive electrode: lithium manganate, conductive carbon black, carbon nanotubes and polyvinylidene fluoride according to the weight ratio of 95.7:0.9:0.9:2.5 is dissolved in the N-methyl pyrrolidone solution to form the anode slurry. Coating the anode slurry on an aluminum foil, and drying, cold pressing and cutting to obtain the anode.
The results of the performance tests of example 2 and comparative example 2 are shown in fig. 4, and it can be seen from fig. 4 that the cycle performance of example 2 is significantly better than that of comparative example 2, the elution amount of Mn of example 2 after 600 cycles is 400ppm, and the elution amount of Mn of comparative example 2 is 1200ppm. The elution amount of Mn in example 2 was significantly less than that in comparative example 2.
Example 3:
preparation of the positive electrode: lithium manganate, lithium iron phosphate, conductive carbon black, carbon nano tubes and polyvinylidene fluoride according to the weight ratio of 81.6:14.4:0.8:0.8:2.4 in N-methylpyrrolidone solution to form positive electrode slurry 1. An aluminum foil is used as a positive current collector (16 μm), and the positive slurry 1 is coated on the positive current collector to form a coating 1. Preparing nickel cobalt lithium manganate, lithium iron phosphate, a lithium-rich manganese base, conductive carbon black, a carbon nano tube and polyvinylidene fluoride according to the weight ratio of 86.4:4.8:4.8:0.8:0.8:2.4 in N-methylpyrrolidone solution to form positive electrode slurry 2. And coating the positive electrode slurry 2 on the coating 1 to form a coating 2, and drying, cold pressing and cutting to obtain the positive electrode. The weight ratio of the coating 1 to the coating 2 is 85:15 coat weight of coating 1 was 0.293g/1540mm 2 I.e. 0.019g/cm 2 The ratio of lithium manganese oxide to lithium iron phosphate in the coating 1 is 95:5, the thickness of coating 1 after cold pressing is 0.134mm, and the coating weight of coating 2 is 0.049g/1540mm 2 I.e. 0.003g/cm 2 The thickness of the coating 2 after cold pressing is 0.031mm. In this embodiment, the weight per unit area of the first active material layer on the single surface of the positive electrode collector and the weight per unit area of the second active material layer on the single surface of the positive electrode collector satisfy a =9.5 × b.
Of negative electrodesPreparation: mixing natural graphite (V) Negative pole 0.1V), artificial graphite (V) Negative pole 0.1V), styrene butadiene rubber and sodium carboxymethyl cellulose are dissolved in the deionized water according to the weight ratio of 30.7. The copper foil is adopted as a negative current collector, and the negative slurry is coated on the copper foil of the negative current collector (the coating weight is 0.080 kg/m) 2 ) And drying, cold pressing and cutting to obtain the cathode.
Preparing an electrolyte: lithium hexafluorophosphate was formulated with a nonaqueous organic solvent (ethylene carbonate (EC): diethyl carbonate (DEC): propylene Carbonate (PC): methyl ethyl carbonate (EMC): vinylene Carbonate (VC) =20, in a weight ratio of 28.
Preparing the isolating membrane by selecting a polypropylene/polyethylene/polypropylene three-layer composite membrane, coating ceramic on one surface of the membrane, and enabling the air permeability to be 200secs/100cm 3 。
Preparing a lithium ion battery: the same as in example 1.
Comparative example 3
Comparative example 3 is different from example 3 only in the preparation of the positive electrode, and the rest is the same.
Preparation of the positive electrode: lithium manganate, conductive carbon black, carbon nanotubes and polyvinylidene fluoride according to the weight ratio of 95.7:0.9:0.9:2.5 is dissolved in the N-methyl pyrrolidone solution to form the anode slurry. And coating the positive electrode slurry on a positive electrode current collector, and drying, cold pressing and cutting to obtain the positive electrode.
The results of the performance tests of example 3 and comparative example 3 are shown in FIG. 5, with 1000 cycles of Mn elution of 200ppm for example 3 and 1600ppm for comparative example 3. This is because the double-layer coating method adopted in example 3 reduces the contact of lithium manganate in the coating layer 1 with the electrolyte, thereby suppressing elution of Mn from the coating layer 1.
Example 4:
preparation of the positive electrode: lithium manganate, conductive carbon black, carbon nano tubes and polyvinylidene fluoride are mixed according to the weight ratio of 96.6:1.0:0.8: the positive electrode slurry 1 was formed by dissolving the positive electrode slurry in an N-methylpyrrolidone solution at a ratio of 1.6. The positive electrode slurry 1 was coated on a positive electrode current collector using an aluminum foil as the positive electrode current collector (16 μm), to form a coating layer 1. Preparing nickel cobalt lithium manganate, lithium iron phosphate, conductive carbon black, carbon nano tubes and polyvinylidene fluoride according to the weight ratio of 86.4:9.6:0.8:0.8:2.4 in N-methylpyrrolidone solution to form positive electrode slurry 2. And coating the positive electrode slurry 2 on the coating 1 to form a coating 2, and drying, cold pressing and cutting to obtain the positive electrode.
The weight ratio of the coating 1 to the coating 2 is 80:20, coat weight of coating 1 was 0.260g/1540mm 2 I.e. 0.017g/cm 2 The ratio of lithium manganate to lithium iron phosphate in the coating 1 is 85:15, the thickness of the coating 1 after cold pressing is 0.130mm, and the coating weight of the coating 2 is 0.065g/1540mm 2 I.e. 0.004g/cm 2 The thickness of the coating 2 after cold pressing is 0.038mm. In this embodiment, the weight per unit area of the first active material layer on the single surface of the positive electrode collector and the weight per unit area of the second active material layer on the single surface of the positive electrode collector satisfy a =4.25 × b.
Preparing a negative electrode: the same as in example 1.
Preparing an electrolyte: the same as in example 1.
Preparing an isolating membrane: selecting a polypropylene/polyethylene/polypropylene three-layer composite diaphragm, coating ceramic on one side, and having the air permeability of 200secs/100cm 3 。
Preparing a lithium ion battery: the same as in example 1.
Comparative example 4
Comparative example 4 is different from example 4 only in the preparation of the positive electrode.
Preparation of the positive electrode: mnO of 2 The prepared lithium manganate, the conductive carbon black, the carbon nano tube and the polyvinylidene fluoride are mixed according to the weight ratio of 95.7:0.9:0.9:2.5 is dissolved in the N-methyl pyrrolidone solution to form the anode slurry. Coating the anode slurry on an aluminum foil, and drying, cold pressing and cutting to obtain the anode.
The results of the performance tests of example 4 and comparative example 4 are shown in fig. 6, and it can be seen from fig. 6 that the storage performance of the lithium ion battery of example 4 is better than that of the lithium ion battery of comparative example 4, the Mn dissolution at 50 calendar life of example 4 is 1000ppm, and the Mn dissolution at 50 calendar life of comparative example 4 is 2500ppm, because the coating 2 protects the lithium manganate in the coating 1 and reduces the Mn dissolution in the double-layer coating manner adopted in example 4.
Example 5:
preparation of the positive electrode: lithium manganate, conductive carbon black, carbon nanotubes and polyvinylidene fluoride are mixed according to the weight ratio of 96.1:1.5:0.8: the positive electrode slurry 1 was formed by dissolving the positive electrode slurry in an N-methylpyrrolidone solution at a ratio of 1.6. The positive electrode slurry 1 was coated on a positive electrode current collector using an aluminum foil as the positive electrode current collector (16 μm) to form a coating layer 1. Lithium nickel cobalt manganese oxide, a lithium-rich manganese-based material, conductive carbon black, a carbon nano tube and polyvinylidene fluoride according to the weight ratio of 86.4:9.6:0.8:0.8:2.4 in N-methylpyrrolidone solution to form positive electrode slurry 2. And coating the positive electrode slurry 2 on the coating 1 to form a coating 2, and drying, cold pressing and cutting to obtain the positive electrode. The weight ratio of the coating 1 to the coating 2 is 80:20, coat weight of coat 1 was 0.260g/1540mm 2 I.e. 0.017g/cm 2 The ratio of lithium manganate to lithium iron phosphate in the coating 1 is 85:15, the thickness of the coating 1 after cold pressing is 0.128mm, and the coating weight of the coating 2 is 0.065g/1540mm 2 I.e. 0.004g/cm 2 The thickness of the coating 2 after cold pressing is 0.038mm. In this embodiment, the weight per unit area of the first active material layer on the single surface of the positive electrode collector and the weight per unit area of the second active material layer on the single surface of the positive electrode collector satisfy a =4.25 × b.
Preparation of a negative electrode: mixing artificial graphite (V) Negative pole 0.08V), styrene butadiene rubber and sodium carboxymethyl cellulose according to the weight ratio of 97.7:1.0: the ratio of 1.3 was dissolved in deionization to form a negative electrode slurry. Copper foil is adopted as a negative current collector (8 mu m), and the negative slurry is coated on the negative current collector (coating weight is 0.085 kg/m) 2 ) And drying, cold pressing (the thickness of a pole piece is 0.12 mm), and cutting to obtain the negative electrode.
Preparing an electrolyte: in an environment with a water content of less than 10ppm, mixing lithium hexafluorophosphate with a nonaqueous organic solvent (ethylene carbonate (EC): diethyl carbonate (DEC): propylene Carbonate (PC): ethyl Methyl Carbonate (EMC) =10, weight ratio) in a 12.5:87.5 to form an electrolyte.
Preparing an isolating membrane: the same as in example 1.
Preparing a lithium ion battery: the same as in example 1.
Comparative example 5
Comparative example 5 is different from example 5 only in the preparation of the positive electrode, and the rest is the same.
Preparation of the positive electrode: mnO of 2 The prepared lithium manganate, the conductive carbon black, the carbon nano tube and the polyvinylidene fluoride are mixed according to the weight ratio of 95:1.1:1.4:2.5 is dissolved in the N-methyl pyrrolidone solution to form the anode slurry. Coating the anode slurry on an aluminum foil, and drying, cold pressing and cutting to obtain the anode.
The results of the performance tests of example 5 and comparative example 5 are shown in FIG. 7, where the 300 cycles of Mn elution of example 5 is 500ppm and the 300 cycles of Mn elution of comparative example 5 is 900ppm. In example 5, the coating 2 protects the lithium nickel manganese cobalt and the lithium-rich manganese-based material in the coating 1 by means of double-layer coating, so that the elution of lithium manganese in the coating 1 is suppressed, and the elution amount of Mn is reduced.
Although the subject matter has been described in language specific to structural features and/or methodological acts, it is to be understood that the subject matter defined in the appended claims is not necessarily limited to the specific features or acts described above. Rather, the specific features and acts described above are disclosed as example forms of implementing the claims.

Claims (9)

1. An electrochemical device, comprising:
a positive electrode, the positive electrode comprising: a positive electrode current collector, a first active material layer, and a second active material layer; the first active material layer is positioned between the positive electrode current collector and the second active material layer;
the first active material layer contains lithium manganate and lithium iron phosphate, the second active material contains lithium nickel cobalt manganese oxide, at least part lithium iron phosphate is located the surface of lithium manganate, in the first active material layer the mass percent content of lithium iron phosphate is less than 20%.
2. The electrochemical device according to claim 1,
the mass percentage content of the lithium manganate in the first active material layer is more than 80% and less than 100%.
3. The electrochemical device according to claim 1,
the second active material layer further includes at least one of lithium iron phosphate or a lithium-rich manganese-based material.
4. The electrochemical device according to claim 1,
the weight of the first active material layer per unit area on the single surface of the positive current collector is ag/cm 2 ；
The weight of the second active material layer per unit area on one surface of the positive current collector is bg/cm 2 ；
0.016<a+b<0.026。
5. The electrochemical device according to claim 1,
the weight of the first active material layer per unit area on one surface of the positive current collector is ag/cm 2 ；
The weight of the second active material layer per unit area on one surface of the positive current collector is bg/cm 2 ；
a≥2.5×b。
6. The electrochemical device according to claim 5, wherein 10 xb ≧ a ≧ 4 xb.
7. The electrochemical device of claim 1, wherein said lithium manganate is formed using MnO 2 And (3) preparing the lithium manganate.
8. The electrochemical device according to claim 1, further comprising a negative electrode including a negative electrode current collector and a negative electrode active material layer, the negative electrode active material layer comprising: at least one of Sn, sb, lithium titanate, a tin-based compound, a silicon-based compound, artificial graphite, natural graphite, soft carbon, hard carbon, mesocarbon microbeads or graphene.
9. An electronic device comprising the electrochemical device according to any one of claims 1 to 8.
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