CN108011074A - A kind of pole piece preparation method for improving lithium titanate battery security performance - Google Patents

A kind of pole piece preparation method for improving lithium titanate battery security performance Download PDF

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Publication number
CN108011074A
CN108011074A CN201711054178.4A CN201711054178A CN108011074A CN 108011074 A CN108011074 A CN 108011074A CN 201711054178 A CN201711054178 A CN 201711054178A CN 108011074 A CN108011074 A CN 108011074A
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CN
China
Prior art keywords
composite material
pole piece
conductive composite
lithium titanate
polymer base
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201711054178.4A
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Chinese (zh)
Inventor
王金龙
汪涛
杨尘
朱春林
段锐
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy Co Ltd
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Publication date
Application filed by Hefei Guoxuan High Tech Power Energy Co Ltd filed Critical Hefei Guoxuan High Tech Power Energy Co Ltd
Priority to CN201711054178.4A priority Critical patent/CN108011074A/en
Publication of CN108011074A publication Critical patent/CN108011074A/en
Pending legal-status Critical Current

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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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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

Abstract

The invention discloses a kind of pole piece preparation method for improving lithium titanate battery security performance, including：Prepare polymer base conductive composite material；Two surfaces of the polymer base conductive composite material coated in collector are obtained into polymer base conductive composite material coating；Battery core pole piece is made in the electrode coated slurry of collection liquid surface for being coated with polymer base conductive composite material coating.Pole piece preparation method provided by the invention can improve the security performance of tertiary cathode lithium titanate anode system battery, when substantial amounts of heat is produced inside battery short circuit battery core, on the one hand the resistivity of conducing composite material in itself can be increased, slow down the electronics conduction between positive and negative anodes, on the other hand conducing composite material volume accelerated expansion can be made, make to produce mechanical stress between coating and collector and separate, so as to block the electronics between positive and negative anodes to conduct, prevent inside vigorous reaction excessive heat production during battery short circuit and cause thermal runaway to ultimately result in battery explosion or on fire.

Description

A kind of pole piece preparation method for improving lithium titanate battery security performance
Technical field
The present invention relates to technical field of lithium batteries, more particularly to a kind of pole piece for improving lithium titanate battery security performance to prepare Method.
Background technology
As people increasingly pay attention to environmental protection and the further of the non-renewable energy resources deposit such as oil reduces, newly The development of the regenerative resource industry such as energy rises to national strategy in China.In recent years, lithium ion battery is excellent by its Different chemical property rapidly becomes the first choice of new-energy automobile power battery energy-storage system, and developing prospect is wide.
However, since lithium battery energy density is high, activity is stronger, this is a double-edged sword, with dynamic lithium battery energy Also it is given to bring of a relatively high security risk using process while density the more carries the more high, as battery is running into acupuncture, squeezing Light when pressure, external short circuit, high temperature then to occur battery anti-explosion valve leakage, battery can occur on fire under serious conditions, even Explosion.At present, mainly by set explosion-proof valve, set at cover board connection sheet thermistor, electrolyte add fire retardant or Pole piece coats the modes such as one layer of flame retardant coating, and security lifting of these safe designs to battery is that there are certain side Help, but its protection has certain hysteresis quality can not realize in battery since the reason starting stage such as short circuit is protected.
The content of the invention
Based on technical problem existing for background technology, the present invention proposes a kind of pole for improving lithium titanate battery security performance Piece preparation method, its pole piece prepared can significantly improve the security performance of lithium titanate battery.
A kind of pole piece preparation method for improving lithium titanate battery security performance proposed by the present invention, the lithium titanate battery are Tertiary cathode-lithium titanate anode system, comprises the following steps：
S1, prepare polymer base conductive composite material；
S2, by the polymer base conductive composite material in S1 coated in collector surface obtain polymer-matrix electric conduction it is compound Material coating；
S3, in the electrode coated slurry of collection liquid surface for being coated with polymer base conductive composite material coating be made battery core pole Piece.
Preferably, the active material of the tertiary cathode is LiNixCoyMn1-x-yO2, wherein, 0<x<1、0<y<1；The titanium The active material of sour cathode of lithium is Li4Ti5O12Or Li4Ti5O12The material of doping vario-property.
Preferably, the raw material of the polymer base conductive composite material include epoxy resin, conducting filler, third phase and Curing agent；The conducting filler is polypyrrole, one or more mixing in carbon black, SP, carbon nano-fiber, graphene Thing；The third phase is ethylene-octene copolymer, the copolymerization of ethylene-vinyl acetate copolymer, ethylene methyl methacrylate One or more kinds of mixtures in thing, ethylene-ethyl acrylate copolymer；The curing agent is polyethylene polyamine, second two One or more kinds of mixtures in amine, polyamide.
Preferably, in the raw material of polymer base conductive composite material, the weight content of conducting filler is 20- 40wt%；The weight content of third phase is 1-8wt%.
Preferably, in S2, the thickness of the polymer base conductive composite material coating is 1.5 ± 0.5 μm.
Relative to the prior art, pole piece prepared by the present invention is characterized in that the polymer-matrix electric conduction composite wood of collection liquid surface Expect prepared by coating, third phase material is introduced to build coating monolithic conductive network channel by polymer matrix of epoxy resin, it is conductive Filler material meeting precedence partition strengthens susceptibility of the coating to temperature at third phase and basal body interface.Normally make in battery The electric conductivity of coating is lifted under the conditions of, but works as battery in the case where the abnormal extreme case such as internal short-circuit or external short circuit occurs, Cause inside battery meeting heat production heating, this polymer base conductive composite material coating can perceive at the first time, polymer-matrix electric conduction The electrical conductivity of composite coating can be reduced with the rise of temperature, while in pole piece coating layer of active substance play can occur for temperature rise Make composite conducting polymer material coating volumetric expansion before strong reaction, on the one hand can cut off the conductive network in coating, the opposing party Face produces sufficiently large stress between collector and itself due to the difference of cubical expansivity makes itself and collector, activity Matter coatings depart from, finally thoroughly cut off short-circuit loop in time, avoid reaction from being further exacerbated by and produce thermal runaway generation it is quick-fried It is fried, significantly improve the security performance of battery.
Brief description of the drawings
Fig. 1 is the schematic diagram of pole piece prepared by the present invention；
Fig. 2 is the electricity that battery, the pole pieces of 6 preparation of comparative example implementation that pole piece prepared by the embodiment of the present invention 5 makes make The surface temperature rise curve comparison figure in pond.
Embodiment
Fig. 1 is the schematic diagram of pole piece prepared by the present invention；As shown in Figure 1, the pole piece includes anode sizing agent, cathode size Active material layer 1, polymer base conductive composite material coating 2 and the collector 3 of formation, and polymer base conductive composite material applies Layer 2 is between collector 3 and active material layer 1.
In the following, technical scheme is described in detail by specific embodiment.
Embodiment 1
A kind of pole piece preparation method for improving lithium titanate battery security performance proposed by the present invention, the lithium titanate battery are Tertiary cathode-lithium titanate anode system, comprises the following steps：
S1, prepare polymer base conductive composite material；
S2, by the polymer base conductive composite material in S1 coated in collector surface obtain polymer-matrix electric conduction it is compound Material coating；
S3, in the electrode coated slurry of collection liquid surface for being coated with polymer base conductive composite material coating be made battery core pole Piece.
Embodiment 2
A kind of pole piece preparation method for improving lithium titanate battery security performance proposed by the present invention, the lithium titanate battery are Tertiary cathode-lithium titanate anode system, comprises the following steps：
S1, prepare polymer base conductive composite material；Wherein, the raw material of the polymer base conductive composite material includes ring Oxygen tree fat, conducting filler, third phase and curing agent；The conducting filler is carbon black；The third phase is total to for ethylene-octene Polymers；The curing agent is polyethylene polyamine；Conducting filler, the weight content of third phase are respectively that polymer-matrix electric conduction is compound 40wt%, 8wt% of material weight；
S2, by the polymer base conductive composite material in S1 coated in collector surface obtain polymer-matrix electric conduction it is compound Material coating；Wherein, the thickness of the polymer base conductive composite material coating is 2 μm；
S3, in the electrode coated slurry of collection liquid surface for being coated with polymer base conductive composite material coating be made battery core pole Piece.
The active material of the tertiary cathode is LiNi0.6Co0.2Mn0.2O2；The active material of the lithium titanate anode is Li4Ti5O12。
Embodiment 3
A kind of pole piece preparation method for improving lithium titanate battery security performance proposed by the present invention, the lithium titanate battery are Tertiary cathode-lithium titanate anode system, comprises the following steps：
S1, prepare polymer base conductive composite material；Wherein, the raw material of the polymer base conductive composite material includes ring Oxygen tree fat, conducting filler, third phase and curing agent；The conducting filler is carbon black；The third phase is total to for ethylene-octene Polymers；The curing agent is polyethylene polyamine；Conducting filler, the weight content of third phase are respectively that polymer-matrix electric conduction is compound 20wt%, 8wt% of material weight；
S2, by the polymer base conductive composite material in S1 coated in collector two surfaces obtain polymer-matrix electric conduction Composite coating；Wherein, the thickness of the polymer base conductive composite material coating is 1 μm；
S3, in the electrode coated slurry of collection liquid surface for being coated with polymer base conductive composite material coating be made battery core pole Piece.
The active material of the tertiary cathode is LiNi0.6Co0.2Mn0.2O2；The active material of the lithium titanate anode is Li4Ti5O12。
Embodiment 4
A kind of pole piece preparation method for improving lithium titanate battery security performance proposed by the present invention, the lithium titanate battery are Tertiary cathode-lithium titanate anode system, comprises the following steps：
S1, prepare polymer base conductive composite material；Wherein, the raw material of the polymer base conductive composite material includes ring Oxygen tree fat, conducting filler, third phase and curing agent；The conducting filler is carbon black；The third phase is total to for ethylene-octene Polymers；The curing agent is polyethylene polyamine；Conducting filler, the weight content of third phase are respectively that polymer-matrix electric conduction is compound 30wt%, 8wt% of material weight；
S2, by the polymer base conductive composite material in S1 coated in collector two surfaces obtain polymer-matrix electric conduction Composite coating；Wherein, the thickness of the polymer base conductive composite material coating is 1.5 μm；
S3, in the electrode coated slurry of collection liquid surface for being coated with polymer base conductive composite material coating be made battery core pole Piece.
The active material of the tertiary cathode is LiNi0.5Co0.2Mn0.3O2；The active material of the lithium titanate anode is Li4Ti5O12The material of doping vario-property.
Embodiment 5
A kind of pole piece preparation method for improving lithium titanate battery security performance proposed by the present invention, the lithium titanate battery are Tertiary cathode-lithium titanate anode system, comprises the following steps：
S1, prepare polymer base conductive composite material；Wherein, the raw material of the polymer base conductive composite material includes ring Oxygen tree fat, conducting filler, third phase and curing agent；The conducting filler is carbon black；The third phase is total to for ethylene-octene Polymers；The curing agent is polyethylene polyamine；Conducting filler, the weight content of third phase are respectively that polymer-matrix electric conduction is compound 35wt%, 5wt% of material weight；
S2, by the polymer base conductive composite material in S1 be coated in collector two surfaces, polymerize after drying Thing based conductive composite material coating；Wherein, the thickness of the polymer base conductive composite material coating is 1.5 μm；
S3, one be coated with polymer base conductive composite material coating collection liquid surface coating anode sizing agent cathode is made Pole piece, anode pole is made in another collection liquid surface coating cathode size for being coated with polymer base conductive composite material coating Piece.
Embodiment 6
Pole piece preparation method of the embodiment of the present invention, including：2 μ m-thicks are coated in aluminium foil surface and apply layer of charcoal, then starch cathode Material, cathode size are coated in layer of charcoal and obtain pole piece.
The pole piece that pole piece prepared by embodiment 5 is prepared with embodiment 6 makes through overbaking, roll-in, cutting, winding respectively Into battery, and battery surface temperature rise when testing external short-circuit of battery is tested, and the results are shown in Figure 2 for it, can by Fig. 2 Know, battery prepared by battery made of 5 pole piece of embodiment and 6 pole piece of comparative example quickly rises in short-circuit test temperature early period Height, nearby starts to distinguish, battery temperature ascending curve made of 5 pole piece of embodiment becomes gentle, at 130 DEG C at 120 DEG C There is downward trend, the polymer-matrix electric conduction material coating of 5 battery core pole piece of embodiment starts swollen in temperature rise effect lower volume at this time It is swollen make active material peeled off with collector to be formed open circuit prevent battery further react, prevent thermal runaway and cause to explode；And Battery made of 6 pole piece of comparative example is not enough to prevent pole piece due to no protective coating although explosion-proof valve is opened Electrochemical reaction, when temperature continues rise and can melt membrane to cause the direct contact short circuit of positive and negative anodes pole piece, ultimately results in thermal runaway And produce battery and smolder, explode, it follows that by preparing one layer of polymeric base between collector and positive and negative anodes active coating Conducing composite material coating can greatly improve the security performance of lithium titanate battery.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto, Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.

Claims (5)

1. a kind of pole piece preparation method for improving lithium titanate battery security performance, the lithium titanate battery is tertiary cathode-metatitanic acid Cathode of lithium system, it is characterised in that comprise the following steps：
S1, prepare polymer base conductive composite material；
S2, by the polymer base conductive composite material in S1 coated in collector surface obtain polymer base conductive composite material Coating；
S3, in the electrode coated slurry of collection liquid surface for being coated with polymer base conductive composite material coating be made battery core pole piece.
2. the pole piece preparation method of lithium titanate battery security performance is improved according to claim 1, it is characterised in that described three The active material of first cathode is LiNixCoyMn1-x-yO2, wherein, 0<x<1、0<y<1；The active material of the lithium titanate anode is Li4Ti5O12Or Li4Ti5O12The material of doping vario-property.
3. the pole piece preparation method according to claim 1 or claim 2 for improving lithium titanate battery security performance, it is characterised in that institute Stating the raw material of polymer base conductive composite material includes epoxy resin, conducting filler, third phase and curing agent；The conduction is filled out Charge is polypyrrole, one or more mixtures in carbon black, SP, carbon nano-fiber, graphene；The third phase is second Alkene-octene copolymer, ethylene-vinyl acetate copolymer, ethylene methyl methacrylate copolymer, ethylene-ethylacrylate One or more kinds of mixtures in copolymer；The curing agent for polyethylene polyamine, ethylenediamine, one kind in polyamide or The a variety of mixture of person.
4. the pole piece preparation method of lithium titanate battery security performance is improved according to claim 3, it is characterised in that polymerizeing In the raw material of thing based conductive composite material, the weight content of conducting filler is 20-40wt%；The weight content of third phase is 1- 8wt%.
5. the pole piece preparation method of lithium titanate battery security performance, its feature are improved according to any one of claim 1-4 It is, in S2, the thickness of the polymer base conductive composite material coating is 1.5 ± 0.5 μm.
CN201711054178.4A 2017-10-31 2017-10-31 A kind of pole piece preparation method for improving lithium titanate battery security performance Pending CN108011074A (en)

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Application publication date: 20180508