CN109428051A - Lithium ion battery and positive plate thereof - Google Patents

Lithium ion battery and positive plate thereof Download PDF

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Publication number
CN109428051A
CN109428051A CN201710768080.9A CN201710768080A CN109428051A CN 109428051 A CN109428051 A CN 109428051A CN 201710768080 A CN201710768080 A CN 201710768080A CN 109428051 A CN109428051 A CN 109428051A
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positive electrode
positive
material layer
electrode material
ion battery
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史东洋
金海族
卜祥艳
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology 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
    • H01M4/131—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention discloses a lithium ion battery positive plate, whichThe method comprises the following steps: the positive current collector comprises a positive current collector body, a first positive electrode material layer distributed on one surface of the positive current collector body, and a second positive electrode material layer distributed on the other surface of the positive current collector body, wherein the first positive electrode material layer comprises a first positive electrode active substance, the second positive electrode material layer comprises a second positive electrode active substance, and the general formula of the first positive electrode active substance is LiaNixCoyM(1‑x‑y)O2Wherein M is selected from at least one of Mn, Al, Zr, Ti, V, Mg, Fe, Mo and B, a is more than or equal to 0.95 and less than or equal to 1.2, and a is more than or equal to 0<x<1，0<y<1, and x + y<1, the second positive electrode active material is selected from LiCoO2、LiNiO2、LiMnO2、LiFea1Mn1‑a1PO4Carbon coated LiFea1Mn1‑ a1PO4、Li2MnSiO4、Li2FeSiO4、LiNi0.5Mn1.5O4At least one of (1), wherein 0<a1 is less than or equal to 1. Compared with the prior art, the first positive electrode material layer containing the lithium nickel oxide material is coated on one surface of the positive electrode current collector of the positive plate, and the second positive electrode material layer with good thermal stability is coated on the other surface of the positive electrode current collector, so that the capacity of the obtained battery is high, and the risk of nail penetration of the battery is low.

Description

Lithium ion battery and its positive plate
Technical field
The invention belongs to field of batteries, it is more particularly related to a kind of lithium ion battery and its positive plate.
Background technique
With the fast development of science and technology and the continuous deterioration of earth environment, demand of the mankind to green energy resource product is also more next It is higher.Lithium ion battery energy density is big, high rate performance and has a safety feature, environmentally protective, is therefore widely used in electronic Automotive field.But the continuation of the journey problem of lithium ion battery is to hinder a big bottleneck of Development of Electric Vehicles, to solve the problems, such as continuation of the journey The energy density of battery must be just promoted, higher energy density is the premise realizing electric car and being widely applied.
Ternary material is pacified due to its energy density with higher by extensive concern, but with the battery that ternary material is anode Full performance is to be improved.Solution common at present is to mix ternary material with the active material of some better heat stabilities Improve the security performance of battery, but active material only carries out simple physical mixed by this method, due to different materials Between granule-morphology and granular size difference, be difficult to be uniformly mixed, it is relatively low to eventually result in battery capacity, and polarization is uneven, interior Hinder the problems such as bigger than normal.
In view of this, it is necessory to provide a kind of lithium ion battery and its positive plate with desired Safety performance.
Summary of the invention
It is an object of the invention to: overcome the deficiencies of the prior art and provide a kind of lithium ion with desired Safety performance Battery and its positive plate.
To achieve the goals above, the present invention provides a kind of based lithium-ion battery positive plates comprising: plus plate current-collecting body, The first positive electrode material layer being distributed in plus plate current-collecting body one side, and the second positive material being distributed on plus plate current-collecting body another side The bed of material, the first positive electrode material layer include the first positive active material, and the second positive electrode material layer includes the second positive active material, institute The general formula for stating the first positive active material is LiaNixCoyM(1-x-y)O2, wherein M is selected from Mn, Al, Zr, Ti, V, Mg, Fe, Mo, B At least one of, 0.95≤a≤1.2,0 < x < 1,0 < y < 1, and x+y < 1, second positive active material are selected from LiCoO2、 LiNiO2、LiMnO2、LiFea1Mn1-a1PO4, carbon-coated LiFea1Mn1-a1PO4、Li2MnSiO4、Li2FeSiO4、 LiNi0.5Mn1.5O4At least one of, wherein 0 < a1≤1.
As a kind of improvement of based lithium-ion battery positive plate of the present invention, first positive active material is selected from LiNi0.33Co0.33Mn0.33O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.5Co0.25Mn0.25O2、LiNi0.6Co0.2Mn0.2O2、 LiNi0.8Co0.1Mn0.1O2、LiNi0.85Co0.1Mn0.05O2、LiNi0.8Co0.15Al0.05O2At least one of.
As a kind of improvement of based lithium-ion battery positive plate of the present invention, second positive active material is selected from LiCoO2、 LiNiO2、LiMnO2、LiFea1Mn1-a1PO4, carbon-coated LiFea1Mn1-a1PO4At least one of, wherein 0 < a1≤1.
As a kind of improvement of based lithium-ion battery positive plate of the present invention, first positive electrode material layer with a thickness of 35 μm~ 140μm。
As a kind of improvement of based lithium-ion battery positive plate of the present invention, first positive electrode material layer with a thickness of 60 μm~ 110μm。
As a kind of improvement of based lithium-ion battery positive plate of the present invention, second positive electrode material layer with a thickness of 50 μm~ 180μm。
As a kind of improvement of based lithium-ion battery positive plate of the present invention, second positive electrode material layer with a thickness of 75 μm~ 125μm。
Positive electrode material layer is too thin, relatively difficult to achieve in technique, because the thickness of positive electrode material layer has to be larger than active material list The partial size of particle；Positive electrode material layer is too thick, and the gram volume that will affect active material plays, and keeps battery capacity relatively low, and resistance is bigger than normal, Eventually lead to cycle performance of battery variation.
As a kind of improvement of based lithium-ion battery positive plate of the present invention, first positive electrode material layer further include conductive agent and The mass ratio of binder, first positive active material, conductive agent and bonding agent is 90%~99.4%:0.3%~5%: 0.3%~5%.
As a kind of improvement of based lithium-ion battery positive plate of the present invention, second positive electrode material layer further include conductive agent and The mass ratio of binder, second positive active material, conductive agent and bonding agent is 90%~99.4%:0.3%~5%: 0.3%~5%.
As a kind of improvement of based lithium-ion battery positive plate of the present invention, the surface density of first positive electrode material layer is 6.5mg/cm2~30mg/cm2, preferably 10mg/cm2~23mg/cm2, the surface density of second positive electrode material layer is 7.0mg/cm2~28mg/cm2, preferably 10mg/cm2~20mg/cm2。
When surface density is too small, coating process is difficult to realize；When surface density is too big, cell dynamics poor performance is low Warm DC internal resistance deteriorates obvious, material circulation degradation.
As a kind of improvement of based lithium-ion battery positive plate of the present invention, the conductive agent is selected from conductive black (SP), carbon is received At least one of mitron (CNT), electrically conductive graphite (KS-6).
As a kind of improvement of based lithium-ion battery positive plate of the present invention, the plus plate current-collecting body is aluminium foil.
To achieve the goals above, it the present invention provides a kind of lithium ion battery, including positive plate, negative electrode tab, is interval in Isolation film and electrolyte between positive plate and negative electrode tab, the positive plate are positive plate above-mentioned.
As a kind of improvement of lithium ion battery of the present invention, the negative electrode tab includes negative current collector and is distributed in cathode collection Negative electrode material layer on fluid, the negative electrode material layer include negative electrode active material, conductive agent, binder and thickener, described Negative electrode active material, conductive agent, binder and thickener weight ratio be 90%~99%:0.1%~3%:0.1%~8%: 0.1%~3%.
As a kind of improvement of lithium ion battery of the present invention, the negative electrode active material be selected from graphite, Si/C composite material, At least one of SiO, carbonaceous mesophase spherules, graphene, petroleum coke, carbon fiber, thermal decomposed resins carbon.
As a kind of improvement of lithium ion battery of the present invention, the battery is coiled battery or laminated battery plate.
Compared with the existing technology, lithium ion battery and its positive plate of the present invention have following technical effect that
1) in the battery comprising above-mentioned positive plate, battery core first positive electrode material layer and during winding or lamination Two positive electrode material layers are spaced each other appearance, and when thermal runaway occurs for battery, the high stability material in the second positive electrode material layer can It is dissipated to next layer to obstruct the further thermal expansion of the first positive electrode material layer of easy thermal runaway, reduces heat diffusion, the safety of battery Performance greatly promotes；
2) there can be mixing non-uniformity problem in stirring to avoid conventional hybrid anode, be effectively improved conventional hybrid just The problems such as pole battery polarization is uneven, internal resistance is big, capacity is relatively low.
Detailed description of the invention
With reference to the accompanying drawings and detailed description, lithium ion battery of the present invention and its positive plate are described in detail, Wherein:
Fig. 1 is the structural schematic diagram of lithium ion battery takeup type battery core of the present invention.
Fig. 2 is the structural schematic diagram of lithium ion battery lamination formula battery core of the present invention.
Appended drawing reference:
10- positive plate；100- plus plate current-collecting body；The first positive electrode material layer of 100a-；The second positive electrode material layer of 100b-；
20- negative electrode tab；200- negative current collector；202- negative electrode material layer；
30- isolation film.
Specific embodiment
In order to be more clear goal of the invention of the invention, technical solution and advantageous effects, below in conjunction with attached drawing and Specific embodiment, the present invention will be described in further detail.It should be understood that embodiment described in this specification is In order to explain the present invention, it is not intended to limit the present invention.
It please refers to shown in Fig. 1 and Fig. 2, lithium ion battery of the present invention includes positive plate 10, negative electrode tab 20, is interval in positive plate Isolation film 30 and electrolyte between 10 and negative electrode tab 20, positive plate 10 include plus plate current-collecting body 100, plus plate current-collecting body 100 One side be equipped with the first positive electrode material layer 100a, another side is equipped with the second positive electrode material layer 100b, and negative electrode tab 20 includes negative Pole collector 200 and the negative electrode material layer 202 being distributed on negative current collector 200.
Embodiment 1:
The preparation of positive plate 10
By the first positive active material LiNi0.8Co0.1Mn0.1O2, conductive agent (SP), binder (PVDF) is by weight 97: After 2:1 is thoroughly mixed uniformly in N-Methyl pyrrolidone dicyandiamide solution, coated on the plus plate current-collecting body with a thickness of 13 μm In the one side of 100 aluminium foils, drying obtains the first positive electrode material layer 100a with a thickness of 50 μm.By the second positive active material LiFePO4, conductive agent (SP), binder (PVDF) sufficiently stir in N-Methyl pyrrolidone dicyandiamide solution by weight 95:4:1 Mix after mixing, coated in the other one side with a thickness of 13 μm of 100 aluminium foil of plus plate current-collecting body, drying, obtain with a thickness of Then 80 μm of the second positive electrode material layer 100b obtains anode pole piece 10 by cold pressing.Wherein the face of the first positive electrode material layer is close Degree is 10g/cm2, the surface density of the second positive electrode material layer is 12.5g/cm2。
The preparation of negative electrode tab 20
Negative electrode active material artificial graphite, conductive agent (SP), binder butadiene-styrene rubber (SBR), thickening agent carboxymethyl is fine After the plain sodium (CMC) of dimension is thoroughly mixed in deionized water solvent system uniformly according to weight ratio 96:1:2:1, it is coated on thickness Degree is on 8 μm of 200 copper foil of negative current collector is two-sided, and drying, cold pressing obtain cathode pole piece 20.
Electrolyte preparation
By ethylene carbonate (EC), methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) according to mass ratio EC:EMC:DEC It is mixed for 30:50:20, obtains organic solvent.Then by lithium salts LiPF6It is dissolved in mixed organic solvents, wherein LiPF6 Concentration be 1.0M.
Lithium ion battery preparation
Using the PE porous polymer film of 12 μ m thicks as isolation film 30, positive plate 10, isolation film 30, negative electrode tab 20 are pressed Sequence is folded, and is in isolation film 30 among positive plate 10 and negative electrode tab 20 and is played the role of isolation, and is wound and obtained naked battery core. Naked battery core is placed in aluminum plastic film or aluminum hull, the basic electrolyte prepared and encapsulation, chemical conversion is injected, obtains lithium ion battery.
Embodiment 2
Embodiment 2 is substantially the same manner as Example 1, the difference is that, the first positive active material is LiNi0.8Co0.1Mn0.1O2, the second positive active material is LiMnO2, the first positive electrode material layer is with a thickness of 80 μm, the second positive material Thickness of feed layer is 80 μm, and the surface density of the first positive electrode material layer is 16g/cm2, the surface density of the second positive electrode material layer is 20g/ cm2。
Embodiment 3
Embodiment 3 is substantially the same manner as Example 1, the difference is that, the first positive active material is LiNi0.8Co0.1Mn0.1O2, the second positive active material is LiFe0.2Mn0.8PO4, the first positive electrode material layer is with a thickness of 35 μm, second For positive electrode material layer with a thickness of 120 μm, the surface density of the first positive electrode material layer is 6.5g/cm2, the surface density of the second positive electrode material layer For 20g/cm2。
Embodiment 4
Embodiment 4 is substantially the same manner as Example 1, the difference is that, the first positive active material is LiNi0.8Co0.1Mn0.1O2, the second positive active material is LiFe0.5Mn0.5PO4, the first positive electrode material layer is with a thickness of 80 μm, second For positive electrode material layer with a thickness of 125 μm, the surface density of the first positive electrode material layer is 8g/cm2, the surface density of the second positive electrode material layer is 7g/cm2。
Embodiment 5
Embodiment 5 is substantially the same manner as Example 1, the difference is that, the first positive active material is LiNi0.8Co0.1Mn0.1O2, the second positive active material is carbon-coated LiFe0.8Mn0.2PO4, the first positive electrode material layer with a thickness of 70 μm, for the second positive electrode material layer with a thickness of 180 μm, the surface density of the first positive electrode material layer is 15g/cm2, the second positive electrode material layer Surface density be 15g/cm2。
Embodiment 6
Embodiment 6 is substantially the same manner as Example 1, the difference is that, the first positive active material is LiNi0.8Co0.1Mn0.1O2, the second positive active material is Li2MnSiO4, for the first positive electrode material layer with a thickness of 90 μm, second is positive Layer thickness is 100 μm, and the surface density of the first positive electrode material layer is 18g/cm2, the surface density of the second positive electrode material layer is 25g/cm2。
Embodiment 7
Embodiment 7 is substantially the same manner as Example 1, the difference is that, the first positive active material is LiNi0.33Co0.33Mn0.33O2, the second positive active material is Li2FeSiO4, the first positive electrode material layer is with a thickness of 100 μm, second For positive electrode material layer with a thickness of 80 μm, the surface density of the first positive electrode material layer is 20g/cm2, the surface density of the second positive electrode material layer is 20g/cm2。
Embodiment 8
Embodiment 8 is substantially the same manner as Example 1, the difference is that, the first positive active material is LiNi0.8Co0.1Mn0.1O2, the second positive active material is LiNi0.5Mn1.5O4, the first positive electrode material layer is with a thickness of 140 μm, second For positive electrode material layer with a thickness of 80 μm, the surface density of the first positive electrode material layer is 23g/cm2, the surface density of the second positive electrode material layer is 10g/cm2。
Embodiment 9
Embodiment 9 is substantially the same manner as Example 1, the difference is that, the first positive active material is LiNi0.8Co0.1Mn0.1O2, the second positive active material is LiFePO4And LiMnO2(mass ratio 1:1), the first positive electrode material layer With a thickness of 80 μm, for the second positive electrode material layer with a thickness of 60 μm, the surface density of the first positive electrode material layer is 16g/cm2, the second anode The surface density of material layer is 28g/cm2。
Embodiment 10
Embodiment 10 is substantially the same manner as Example 1, the difference is that, the first positive active material is LiNi0.8Co0.1Mn0.1O2, the second positive active material is LiFePO4And LiMnO2(mass ratio 1:2), the first positive electrode material layer With a thickness of 60 μm, for the second positive electrode material layer with a thickness of 100 μm, the surface density of the first positive electrode material layer is 12g/cm2, the second anode The surface density of material layer is 25g/cm2。
Embodiment 11
Embodiment 11 is substantially the same manner as Example 1, the difference is that, the first positive active material is LiNi0.33Co0.33Mn0.33O2, the second positive active material is LiFe0.2Mn0.8PO4And Li2MnSiO4(mass ratio 1:1), the One positive electrode material layer is with a thickness of 80 μm, and for the second positive electrode material layer with a thickness of 75 μm, the surface density of the first positive electrode material layer is 30g/ cm2, the surface density of the second positive electrode material layer is 15g/cm2。
Embodiment 12
Embodiment 12 is substantially the same manner as Example 1, the difference is that, the first positive active material is LiNi0.6Co0.2Mn0.2O2, the second positive active material is LiFePO4, the first positive electrode material layer is with a thickness of 80 μm, the second positive material Thickness of feed layer is 100 μm, and the surface density of the first positive electrode material layer is 25g/cm2, the surface density of the second positive electrode material layer is 15g/ cm2。
Embodiment 13
Embodiment 13 is substantially the same manner as Example 1, the difference is that, the first positive active material is LiNi0.5Co0.2Mn0.3O2, the second positive active material is LiFePO4, the first positive electrode material layer is with a thickness of 60 μm, the second positive material Thickness of feed layer is 50 μm, and the surface density of the first positive electrode material layer is 16g/cm2, the surface density of the second positive electrode material layer is 18g/ cm2。
Embodiment 14
Embodiment 14 is substantially the same manner as Example 1, the difference is that, the first positive active material is LiNi0.8Co0.15Al0.05O2, the second positive active material is LiFePO4, the first positive electrode material layer is with a thickness of 110 μm, and second just Pole layer thickness is 100 μm, and the surface density of the first positive electrode material layer is 10g/cm2, the surface density of the second positive electrode material layer is 20g/cm2。
Embodiment 15
Embodiment 15 is substantially the same manner as Example 1, the difference is that, the first positive active material is LiNi0.5Co0.2Al0.3O2, the second positive active material is LiFePO4, the first positive electrode material layer is with a thickness of 80 μm, the second positive material Thickness of feed layer is 100 μm, and the surface density of the first positive electrode material layer is 16g/cm2, the surface density of the second positive electrode material layer is 20g/ cm2。
Embodiment 16
Embodiment 16 is substantially the same manner as Example 1, the difference is that, the first positive active material is LiNi0.8Co0.1Mn0.1O2And LiNi0.8Co0.15Al0.05O2(mass ratio 1:1), the second positive active material are LiFePO4, the One positive electrode material layer is with a thickness of 80 μm, and for the second positive electrode material layer with a thickness of 100 μm, the surface density of the first positive electrode material layer is 16g/ cm2, the surface density of the second positive electrode material layer is 15g/cm2。
Embodiment 17
Embodiment 17 is substantially the same manner as Example 1, the difference is that, the first positive active material is LiNi0.8Co0.1Mn0.05Zr0.05O2, the second positive active material is LiNiO2, the first positive electrode material layer is with a thickness of 75 μm, second For positive electrode material layer with a thickness of 100 μm, the surface density of the first positive electrode material layer is 15g/cm2, the surface density of the second positive electrode material layer For 15g/cm2。
Comparative example 1:
Positive plate preparation
By positive active material LiNi0.8Co0.1Mn0.1O2, conductive agent (SP), binder (PVDF) is by weight 97:2:1 After being thoroughly mixed in N-Methyl pyrrolidone dicyandiamide solution uniformly, coated on the plus plate current-collecting body aluminium foil with a thickness of 13 μm It is two-sided on, drying, cold pressing obtain anode pole piece, wherein the thickness of the positive electrode material layer on two sides is all 80 μm, and surface density is all 16g/cm2。
Negative electrode tab preparation
By active material artificial graphite, conductive agent (SP), binder butadiene-styrene rubber (SBR), thickener carboxymethyl cellulose After sodium (CMC) is thoroughly mixed in deionized water solvent system uniformly according to weight ratio 96:1:2:1, it is coated on a thickness of 8 μm negative current collector copper foil it is two-sided on, drying, cold pressing obtain cathode pole piece.
Electrolyte preparation
By ethylene carbonate (EC), methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) according to mass ratio EC:EMC:DEC It is mixed for 30:50:20, obtains organic solvent.Then by lithium salts LiPF6It is dissolved in mixed organic solvents, wherein LiPF6 Concentration be 1.0M.
Lithium ion battery preparation
Using the PE porous polymer film of 12 μ m thicks as isolation film, positive plate, isolation film, negative electrode tab are folded in order It is good, it is in isolation film among positive and negative anodes and plays the role of isolation, and wind and obtain naked battery core.By naked battery core be placed in aluminum plastic film or In aluminum hull, the basic electrolyte prepared and encapsulation, chemical conversion are injected, lithium ion battery is obtained.
Comparative example 2
Comparative example 2 and comparative example 1 are essentially identical, the difference is that, positive active material LiFePO4, wherein two sides The thickness of positive electrode material layer be all 100 μm, surface density is all 20g/cm2。
Comparative example 3:
Comparative example 3 and comparative example 1 are essentially identical, the difference is that by positive active material LiNi0.8Co0.1Mn0.1O2With LiFePO4(mass ratio 1:1), conductive agent (SP), binder (PVDF) are molten in N-Methyl pyrrolidone by weight 96:3:1 After being thoroughly mixed in agent system uniformly, on two-sided coated on the plus plate current-collecting body aluminium foil with a thickness of 13 μm, drying, cold pressing Obtain anode pole piece, wherein the thickness of the positive electrode material layer on two sides is all 100 μm, and surface density is all 20g/cm2。
Embodiment 2~17 and the test of comparative example 1~3 are substantially the same manner as Example 1, the substance of each embodiment and comparative example Type and content are as shown in table 1~2.
1 embodiment 1~17 of table and related species and content in comparative example 1~3
2 embodiment 1~17 of table and related species and content in positive electrode material layer thickness in comparative example 1~3, cathode
Lithium ion battery safety performance test
Above-mentioned each group battery is completely filled according to following process: with 1C constant-current charge to 4.2V, then extremely with 4.2V constant-voltage charge Cut-off current 0.05C, and stand 5 minutes.Drift bolt test is done according to the standard of GBT, test result is as shown in table 3.
Cycle performance of lithium ion battery test
The battery being prepared is subjected to following tests respectively:
At 25 DEG C, by battery with 1C constant-current charge to 4.2V, then constant-voltage charge to electric current is 0.05C, then permanent with 1C Stream is discharged to 2.8V, at this time to recycle for the first time, carries out cycle charging/electric discharge according to above-mentioned condition, records 500 cycle charge-discharges The capacity retention ratio of battery afterwards.Each cycle performance of battery test result is referring to table 3.
3 embodiment 1~17 of table and battery structure and the performance test results in comparative example 1~3
Interpretation of result
It can be seen that from the comparison of embodiment 1~17 and comparative example 1~3 when the plus plate current-collecting body aluminium foil in comparative example 1 Two-sided while coating contains positive electrode active materials LiNi0.8Co0.1Mn0.1O2Material layer when, the drift bolt risk of battery is 6 grades, full The requirement of foot HL≤4 that national standard is not examined by force；When the two-sided of the plus plate current-collecting body aluminium foil in comparative example 2 while coating contains anode Active material LiFePO4Material layer when, although the drift bolt risk of battery drops to 4 grades, can satisfy HL≤4 that national standard is examined by force It is required that but battery capacity it is lower, only 40Ah；When the two-sided of the plus plate current-collecting body aluminium foil in comparative example 3 while coating is containing just Pole active material LiNi0.8Co0.1Mn0.1O2:LiFePO4When the mixed material layer of=1:1 (mass ratio), the drift bolt risk of battery is 5 grades, it can not meet the requirement for HL≤4 that national standard is examined by force.And when the one side of 100 aluminium foil of plus plate current-collecting body in embodiment 1~17 It coats the first positive electrode material layer 100a containing lithium nickel oxide material and another side coats the activity containing better heat stability When the second positive electrode material layer 100b of material (such as LFP), battery capacity is high, and battery capacity conservation rate remains to after circulation 500 times It is maintained at 80% or more, and either coiled battery or laminated battery plate, the drift bolt risk of battery is all 4 grades, is had Preferable test result.
Shown by comparative analysis: lithium nickel oxide can be effectively reduced just using the battery of positive plate 10 of the present invention production Pole material (such as LiNi0.8Co0.1Mn0.1O2) system drift bolt risk, drift bolt risk is reduced to 4 grades by 6 grades, meets national standard and examine by force It is required that and battery capacity it is high, meet the requirement of energy density.
In conjunction with above description it is found that compared with the existing technology, lithium ion battery and its positive plate of the present invention have following skill Art effect:
1) in the battery comprising above-mentioned positive plate, battery core first positive electrode material layer and during winding or lamination Two positive electrode material layers are spaced each other appearance, and when thermal runaway occurs for battery, the high stability material in the second positive electrode material layer can It is dissipated to next layer to obstruct the further thermal expansion of the first positive electrode material layer of easy thermal runaway, reduces heat diffusion, the safety of battery Performance greatly promotes；
2) there can be mixing non-uniformity problem in stirring to avoid conventional hybrid anode, be effectively improved conventional hybrid just The problems such as pole battery polarization is uneven, internal resistance is big, capacity is relatively low.
According to above-mentioned principle, the present invention can also carry out change and modification appropriate to above-mentioned specific embodiment.Therefore, The invention is not limited to the specific embodiments disclosed and described above, should also be as falling to some modifications and changes of the invention Enter in scope of protection of the claims of the invention.In addition, although being used some specific terms in this specification, these Term merely for convenience of description, does not limit the present invention in any way.

Claims (10)

1. a kind of based lithium-ion battery positive plate comprising: plus plate current-collecting body, first be distributed in plus plate current-collecting body one side anode Material layer, and the second positive electrode material layer being distributed on plus plate current-collecting body another side, the first positive electrode material layer include the first anode Active material, the second positive electrode material layer include the second positive active material, which is characterized in that first positive active material General formula is LiaNixCoyM(1-x-y)O2, wherein M is selected from least one of Mn, Al, Zr, Ti, V, Mg, Fe, Mo, B, 0.95≤a ≤ 1.2,0 < x < 1,0 < y < 1, and x+y < 1, second positive active material are selected from LiCoO2、LiNiO2、LiMnO2、 LiFea1Mn1-a1PO4, carbon-coated LiFea1Mn1-a1PO4、Li2MnSiO4、Li2FeSiO4、LiNi0.5Mn1.5O4In at least one Kind, wherein 0 < a1≤1.
2. based lithium-ion battery positive plate according to claim 1, which is characterized in that first positive active material is selected from LiNi0.33Co0.33Mn0.33O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.5Co0.25Mn0.25O2、LiNi0.6Co0.2Mn0.2O2、 LiNi0.8Co0.1Mn0.1O2、LiNi0.85Co0.1Mn0.05O2、LiNi0.8Co0.15Al0.05O2At least one of.
3. based lithium-ion battery positive plate according to claim 1, which is characterized in that second positive active material is selected from LiCoO2、LiNiO2、LiMnO2、LiFea1Mn1-a1PO4, carbon-coated LiFea1Mn1-a1PO4At least one of, wherein 0 < a1 ≤1。
4. based lithium-ion battery positive plate according to claim 1, which is characterized in that the thickness of first positive electrode material layer It is 35 μm~140 μm.
5. based lithium-ion battery positive plate according to claim 1, which is characterized in that the thickness of first positive electrode material layer It is 60 μm~110 μm.
6. based lithium-ion battery positive plate according to claim 1, which is characterized in that the thickness of second positive electrode material layer It is 50 μm~180 μm.
7. based lithium-ion battery positive plate according to claim 1, which is characterized in that the thickness of second positive electrode material layer It is 75 μm~125 μm.
8. based lithium-ion battery positive plate according to claim 1, which is characterized in that the face of first positive electrode material layer is close Degree is 6.5mg/cm2~30mg/cm2, preferably 10mg/cm2~23mg/cm2, the surface density of second positive electrode material layer is 7.0mg/cm2~28mg/cm2, preferably 10mg/cm2~20mg/cm2。
9. a kind of lithium ion battery, including positive plate, negative electrode tab, the isolation film being interval between positive plate and negative electrode tab, and Electrolyte, which is characterized in that the positive plate is positive plate according to any one of claims 1 to 8.
10. lithium ion battery according to claim 9, which is characterized in that the battery is coiled battery or stacked Battery.
CN201710768080.9A 2017-08-31 2017-08-31 Lithium ion battery and positive plate thereof Pending CN109428051A (en)

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Application publication date: 20190305