CN105304934B - Positive pole is modified high security lithium ion battery - Google Patents
Positive pole is modified high security lithium ion battery Download PDFInfo
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- CN105304934B CN105304934B CN201510730102.3A CN201510730102A CN105304934B CN 105304934 B CN105304934 B CN 105304934B CN 201510730102 A CN201510730102 A CN 201510730102A CN 105304934 B CN105304934 B CN 105304934B
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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
- 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
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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
- 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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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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Abstract
The present invention relates to a kind of positive pole to be modified high security lithium ion battery, it is characterised in that containing the dynamic protective agent of heat in its anode plate, when the battery is warming up to certain temperature, the heat moves protective agent and carries out cross-linking reaction with barrier thermal runaway.The dynamic protective agent of heat, the dynamic protective agent of heat is such as formula(I)Shown BMI A, or such as formula(II)The BMI B of structure, or such as formula(III)Bismaleimide amine oligomer C, or such as formula(IV)Shown bismaleimide amine oligomer D:It can receive a variety of modifications, alternative including alkoxy-modified, acyl modified etc., various in style, be easy to selection to use;The security performance of the battery is strengthened, and manufacture method is also fairly simple.
Description
Technical field
The present invention is to be related to a kind of positive pole to be modified high security lithium ion battery, has hot start peace more particularly to one kind
The high security secondary lithium battery of full mechanism.
Background technology
Lithium ion battery has found broad application on the 3C Products such as computer, communication and consumer electronics, electric car,
The utilization in large-scale energy storage field is also being popularized, still, the high voltage withstanding organic electrolyte used due to lithium-ion battery systems
Solvent has stronger combustibility, and high-capacitance positive/negative active material can decompose to give off big calorimetric when temperature rises
Amount so that in not caused heat when deployed, may ignite lithium battery organic solvent, have higher danger, or even rise
It is hot fried;In addition, lithium ion battery in charge and discharge process, disintegration or generation phase change due to cathode material structure, all can
Deviate from the oxygen in cathode material structure, and these abjection oxygen can the effect of reacting with electrolyte, make internal temperature of battery wink
Between raise, cause the safety problem of lithium rechargeable battery, therefore researcher, more and more pay attention to therefore such lithium battery applications
Product is to the thermal runaway of the very fast heat release of internal short-circuit caused by accident puncture or external impacts destructive factor and battery explosion etc.
The risk of phenomenon avoids.The battery that high security becomes high voltage, high-energy-density and high power capacity must pull against and solve
Problem, the electric car especially on the way walked --- electric car easily becomes battery extrusion by being hit caused by traffic accident
Shape.
It is to make surface modification to anode material of lithium battery to lift the security practice mostly in known references and patent, such as profit
LiMO is coated on metal oxide or metal fluoride2(M represents transition metal) surface, the method can lift material structure
Stability, the thermal discharge between material and electrolyte is reduced, reaches security improvement purpose, but, introduce metal oxide or metal
The diaphragm that fluoride is formed in electrode material surface, itself does not have hot start security mechanism, and can not effectively press down yet
Deoxidation phenomenon processed, its to the internal short-circuit that triggers by plus environmental factor, such as it is unexpected puncture or external impacts are destroyed, trigger wink
Between high fever and cause the risk reduction still not yet in effect of battery explosion.
Patent CN 101807724 provides a kind of lithium battery with the dynamic protective effect of heat, and the battery is using span
Carry out the security that acid imide oligomer improves battery as the dynamic protective agent of heat, but it is clear that the BMI oligomer is deposited
It is relatively low in solubility and apply it is inconvenient the problem of.
The content of the invention
It is an object of the invention to provide a kind of positive pole to be modified high security lithium ion battery, can receive a variety of modifications,
It is alternative including alkoxy-modified, it is acyl modified etc., it is various in style, be easy to selection use;The security performance of the battery obtains
It is also fairly simple to reinforcing, manufacture method.
To achieve these goals, the technical proposal of the invention is realized in this way:A kind of positive pole is modified high security lithium
Ion battery, including:
(A)Anode plate
(B)Negative plates
(C)Barrier film
(D)Electrolyte
Wherein cell positive material contained by anode plate is LiMn2O4、LiFePO4Or LiNixCoyMnzO3(X+y+z=1,
0≤x, y, z≤0), including LiMnO2、LiCoO2And ternary material LiNi1/3Co1/3Mn1/3O3Deng;Battery negative plate institute
It is carbon containing cell negative electrode material, including hard carbon, carbonaceous mesophase spherules(MCMB), graphite etc., or Li4Ti5O12;Anode plate and
Conductive additive used in negative plates is carbon black, graphite or acetylene black, graphene, CNT, gas-phase growth of carbon fibre
(VGCF)Deng binding agent is Kynoar PVDF, carboxyl methyl cellulose or styrene butadiene rubber sbr;
It is characterized in that:Anode plate material surface is coated with one layer of heat and moves protective agent, and the hot dynamic temperature is 80 DEG C -280
℃;It is formula that the heat, which moves protective agent,(I)Shown BMI A, or formula(II)The BMI B of structure, or
Formula(III)Bismaleimide amine oligomer C, or formula(IV)Shown bismaleimide amine oligomer D, A, B and C or
Contain phenol epoxide in D, a variety of modifications can be received, it is alternative including alkoxy-modified, it is acyl modified etc., it is various in style,
It is easy to selection to use:
Wherein, R1, R2=H, either R or-C (O)-R, R CxHy, x=1 ~ 9, y=3 ~ 19
Usually, R is methyl(-CH3), ethyl(-C2H5),(-C3H8), (- C4H9), (- C5H11), (- C6H13), (-
C7H15), (C8H17), (- C9H19), phenyl(-C6H5,), benzyl(-C7H7,), the stupid base of first(-
C7H7,), ethylbenzene(-C8H9,)Deng.
Positive electrode content is 70% ~ 92% by weight percentage in described anode plate;Binder content is 3% ~ 10%;
Conductive additive content is 5 ~ 10%;The dynamic protection agent content of heat is 0.1% ~ 10%.
The positive effect of the present invention is that electrode anode material, conductive additive and the dynamic protective agent of above-mentioned heat are passed through into bonding
Anode plate is made in agent, either using being coated on anode plate surface or the surface coated on barrier film and positive contact, by
When heat reaches certain temperature, the heat moves protective agent and crosslinks reaction, so as to hinder the generation of thermal runaway;The safety of the battery
Performance is strengthened, and manufacture method is also fairly simple.
Brief description of the drawings
Fig. 1:BMI A molecule cross-link schematic diagrames.
Embodiment
The present invention will be further described with reference to the accompanying drawings and examples, in following specific experiment examples, provides
A large amount of concrete details are in order to the more deep understanding present invention.It is however, aobvious and easy to those skilled in the art
See, the present invention can be carried out without one or more of these details.
Embodiment 1
Positive electrode:LiFePO4/PVDF/VGCF=90/4/6;
Negative material:Graphite/PVDF/VGCF=91/4/5;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery 10Ah.
Comparative example of the present embodiment as following examples.
Positive electrode:LiFePO4In/PVDF/VGCF/A=90/4/5/1, A, R1, R2For H;
Negative material:Graphite/PVDF/VGCF=80/10/10;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 6Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 2 is not on fire.
Embodiment 2
Positive electrode:LiNi1/3Co1/3Mn1/3In/PVDF/VGCF/A=70/10/10/10, A, R1, R2For phenyl(-
C6H5);
Negative material:Graphite/PVDF/VGCF=91/4/5;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 8Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 3 is not on fire.
Embodiment 3
Positive electrode:LiCoO2In/PVDF/VGCF/A=90/4/5.9/0.1, A, R1, R2For acetyl group(-C(O)CH3);
Negative material:MCMB/PVDF/VGCF=90/4/6;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 6Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 4 is not on fire.
Embodiment 4
Positive electrode:LiFePO4In/PVDF/VGCF/A=90/4/5/1, A, R1, R2For methyl(-CH3);
Negative material:MCMB/PVDF/VGCF=91/4/5;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 6Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 5 is not on fire.
Embodiment 5
Positive electrode:LiMn2O4In/PVDF/VGCF/A=90/4/4/2, A, R1, R2For nonyl(-C9H19);
Negative material:Graphite/PVDF/VGCF=91/4/5;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 6Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 6 is not on fire.
Embodiment 6
Positive electrode:LiNi1/2Co1/2O3In/PVDF/VGCF/A=85/5/5/5, A, R1, R2For capryl(-C(O)
C9H19);
Negative material:Graphite/PVDF/VGCF=91/4/5;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 6Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 7 is not on fire.
Embodiment 7
Positive electrode:LiFePO4In/PVDF/VGCF/B=90/4/5/1, B, R1, R2For H;
Negative material:Graphite/PVDF/VGCF=80/10/10;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 6Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 8 is not on fire.
Embodiment 8
Positive electrode:LiNi1/3Co1/3Mn1/3In/PVDF/VGCF/B=70/10/10/10, B, R1, R2For phenyl(-
C6H5);
Negative material:Graphite/PVDF/VGCF=91/4/5;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 8Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 9 is not on fire.
Embodiment 9
Positive electrode:LiCoO2In/PVDF/VGCF/B=90/4/5.9/0.1, B, R1, R2For acetyl group(-C(O)CH3);
Negative material:MCMB/PVDF/VGCF=90/4/6;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 6Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 10 is not on fire.
Embodiment 10
Positive electrode:LiFePO4In/PVDF/VGCF/B=90/4/5/1, B, R1, R2For methyl(-CH3);
Negative material:MCMB/PVDF/VGCF=91/4/5,
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 6Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 11 is not on fire.
Embodiment 11
Positive electrode:LiMn2O4In/PVDF/VGCF/B=90/4/4/2, B, R1, R2For nonyl(-C9H19);
Negative material:Graphite/PVDF/VGCF=91/4/5;
Barrier film:PP microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 6Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 6 is not on fire.
Embodiment 12
Positive electrode:LiNi1/2Co1/2O3In/PVDF/VGCF/B=85/5/5/5, B, R1, R2For capryl(-C(O)
C9H19);
Negative material:Graphite/PVDF/VGCF=91/4/5;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 6Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 13 is not on fire.
Embodiment 13
Positive electrode:LiFePO4In/PVDF/VGCF/C=90/4/5/1, C, R1, R2For H;
Negative material:Graphite/PVDF/VGCF=80/10/10;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 6Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 14 is not on fire.
Embodiment 14
Positive electrode:LiNi1/3Co1/3Mn1/3In/PVDF/VGCF/C=70/10/10/10, C, R1, R2For phenyl(-
C6H5);
Negative material:Li4Ti5O12/PVDF/VGCF=91/4/5;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 8Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 15 is not on fire.
Embodiment 15
Positive electrode:LiCoO2In/PVDF/VGCF/C=90/4/5.9/0.1, C, R1, R2For acetyl group(-C(O)CH3);
Negative material:MCMB/PVDF/VGCF=90/4/6;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 6Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 16 is not on fire.
Embodiment 16
Positive electrode:LiFePO4In/PVDF/VGCF/C=90/4/5/1, C, R1, R2For methyl(-CH3);
Negative material:MCMB/PVDF/VGCF=91/4/5;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 6Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 17 is not on fire.
Embodiment 17
Positive electrode:LiMn2O4In/PVDF/VGCF/C=90/4/4/2, C, R1, R2For nonyl(-C9H19);
Negative material:Graphite/PVDF/VGCF=91/4/5;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 6Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 6 is not on fire.
Embodiment 18
Positive electrode:LiNi1/2Co1/2O3In/PVDF/VGCF/C=85/5/5/5, C, R1, R2For capryl(-C(O)
C9H19);
Negative material:Graphite/PVDF/VGCF=91/4/5;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 6Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 19 is not on fire.
Embodiment 19
Positive electrode:LiFePO4In/PVDF/VGCF/D=90/4/5/1, D, R1, R2For H;
Negative material:Graphite/PVDF/VGCF=80/10/10;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 6Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 20 is not on fire.
Embodiment 20
Positive electrode:LiNi1/3Co1/3Mn1/3In/PVDF/VGCF/D=70/10/10/10, D, R1, R2For phenyl(-
C6H5);
Negative material:Graphite/PVDF/VGCF=91/4/5;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 8Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 21 is not on fire.
Embodiment 21
Positive electrode:LiCoO2In/PVDF/VGCF/D=90/4/5.9/0.1, D, R1, R2For acetyl group(-C(O)CH3);
Negative material:MCMB/PVDF/VGCF=90/4/6;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 6Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 22 is not on fire.
Embodiment 22
Positive electrode:LiFePO4In/PVDF/VGCF/D=90/4/5/1, D, R1, R2For methyl(-CH3);
Negative material:MCMB/PVDF/VGCF=91/4/5,
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 6Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 23 is not on fire.
Embodiment 23
Positive electrode:LiMn2O4In/PVDF/VGCF/D=90/4/4/2, D, R1, R2For nonyl(-C9H19);
Negative material:Graphite/PVDF/VGCF=91/4/5;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 6Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 24 is not on fire.
Embodiment 24
Positive electrode:LiNi1/2Co1/2O3In/PVDF/VGCF/D=85/5/5/5, D, R1, R2For capryl(-C(O)
C9H19);
Negative material:Graphite/PVDF/VGCF=91/4/5;
Barrier film:PE microporous barriers;
Electrolyte:1M LiPF6, solvent EC/DMC/EMC(v/v/v=1/1/1).
Battery types:Soft-package battery, 6Ah.
Do puncture experiment simultaneously with comparative example, comparative example is on fire, and embodiment 25 is not on fire.
Claims (5)
1. a kind of positive pole is modified high security lithium ion battery, including:
(A)Anode plate
(B)Negative plates
(C)Barrier film
(D)Electrolyte
Wherein cell positive material contained by anode plate is LiMn2O4、LiFePO4、LiMnO2、LiCoO2Or ternary material LiNi1/ 3Co1/3Mn1/3O2;Cell negative electrode material contained by battery negative plate is carbon, or Li4Ti5O12;Anode plate and negative plates institute
Conductive additive is carbon black, graphite, graphene, CNT, gas-phase growth of carbon fibre VGCF;Binding agent is polyvinylidene fluoride
Alkene PVDF, carboxyl methyl cellulose or styrene butadiene rubber sbr;
It is characterized in that:Anode plate is made by binding agent in positive electrode, conductive additive and the dynamic protective agent of heat, or
The dynamic protective agent of heat is coated on anode plate surface, hot dynamic temperature is 80 DEG C -280 DEG C;It is formula that the heat, which moves protective agent,(I)Shown
BMI A, or formula(II)The BMI B of structure, or formula(III)Bismaleimide amine oligomer C,
Or formula(IV)Shown bismaleimide amine oligomer D,
Wherein, R1, R2=H, either R or-C (O)-R, R CxHy, x=1 ~ 9, y=3 ~ 19.
2. a kind of positive pole according to claim 1 is modified high security lithium ion battery, it is characterised in that described negative pole
Material includes graphite, hard carbon, carbonaceous mesophase spherules MCMB.
3. a kind of positive pole according to claim 1 is modified high security lithium ion battery, it is characterised in that described carbon black
For acetylene black.
4. positive pole according to claim 1 is modified high security lithium ion battery, it is characterised in that described R is-CH3 ,-
C2H5 ,-C3H8 ,-C4H9 ,-C5H11 ,-C6H13 ,-C7H15 ,-C8H17 ,-C9H19,Non- title -1, 1Non- title -2,Non- title -3。
5. positive pole according to claim 1 is modified high security lithium ion battery, it is characterised in that described anode plate
In by weight percentage positive electrode content be 70% ~ 92%;Binder content is 3% ~ 10%;Conductive additive content is 5 ~ 10%;
The dynamic protection agent content of heat is 0.1% ~ 10%.Its percentage sum is equal to 100%.
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CN109216702A (en) * | 2018-08-20 | 2019-01-15 | 珠海光宇电池有限公司 | Oligomer protective layer and preparation method thereof and lithium ion battery |
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