CN108461842A - A method of improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass - Google Patents
A method of improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass Download PDFInfo
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- CN108461842A CN108461842A CN201810311886.XA CN201810311886A CN108461842A CN 108461842 A CN108461842 A CN 108461842A CN 201810311886 A CN201810311886 A CN 201810311886A CN 108461842 A CN108461842 A CN 108461842A
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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
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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
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
- H01M10/486—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte for measuring temperature
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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
Abstract
The invention discloses a kind of methods improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass, including：Lithium titanate anode material is prepared using high temperature solid-state method, grinds to obtain D10=1 5um, D50=5 20um, D90=10 40um, (D90‑D10)/D50=26 cathode powder；It is conductive agent using cathode powder as active material, superconduction carbon black and carbon nanotube, Kynoar is negative electrode slurry that binder prepares solid content 35% 50%, 4000 7000mPas of viscosity；Negative electrode slurry is coated on negative current collector and obtains lithium titanate anode piece；Using ternary material as positive electrode positive plate；By N/P=0.9 0.97, positive plate, lithium titanate anode piece are prepared into battery core.The method proposed by the present invention for improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass is simple to operation, at low cost, so that battery is reacted in short circuit gently, will not fail moment.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of short circuits of raising cylindrical type lithium titanate energy storage battery core
The method of percent of pass.
Background technology
Lithium titanate battery makes by its excellent cycle performance, overlength as a kind of special battery in lithium ion battery
More and more concerns are obtained with service life and reliable security performance.The superior cycle performance of lithium titanate battery, about 30 years super
Long life meets the application demand of industrial energy storage field, and cost price is with the obvious advantage in Life cycle, and safety
Height is the good selection of energy-storage battery.But simultaneously lithium titanate battery disadvantage also clearly, as energy density is low, flatulence, price
It is high.Lithium titanate battery acquisition market approval can be supported is exactly the low cost of its safety, long-life and Life cycle,
Wherein safety all first has to consider for any a battery core.Experiment finds that lithium titanate battery is passed unlike people
It is perfectly safe as saying, unreasonable design and battery core platform selecting can equally make it become dangerous.As mentioned in the present invention
In 32131 cylindrical electrical core systems, since heat conduction, heat-sinking capability are poor so that external short circuit test when cathode generate heat
Amount cannot dissipate in time, and diaphragm is caused to melt, and then cause positive and negative anodes large area short-circuit, and positive polar decomghtion oxygen release, heat production lead to electricity
Core thermal runaway is exploded.So although 32131 cylinder systems play good inhibiting effect to metatitanic acid lithium cell flatulence, equally
Also security risk has been buried.
Invention content
Technical problems based on background technology, it is short that the present invention proposes a kind of raising cylindrical type lithium titanate energy storage battery core
The method of road percent of pass, it is simple to operation, inexpensive, it is easy to accomplish and promote, so that battery is reacted relatively gentle in short circuit,
It will not fail moment, solve the problems, such as that battery core quick heat production when external short-circuit of battery, aerogenesis lead to battery core failure explosion.
A kind of method improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass proposed by the present invention, including following step
Suddenly：
S1, lithium titanate anode material is prepared using high temperature solid-state method, lithium titanate anode material is ground to obtain cathode
Powder；Wherein, the size distribution of the cathode powder meets D10=1-5um, D50=5-20um, D90=10-40um, (D90-
D10)/D50=2-6；
S2, using the cathode powder in S1 as active material, using superconduction carbon black and carbon nanotube as conductive agent, with polyvinylidene fluoride
Alkene is that binder prepares negative electrode slurry；Wherein, the cathode powder in S1, superconduction carbon black, carbon nanotube, the weight of Kynoar
Than for 90-95：1-3：2-4：2-4；The solid content of negative electrode slurry is 35%-50%, viscosity 4000-7000mPas；
S3, it the negative electrode slurry in S2 is coated on negative current collector obtains lithium titanate anode piece；Wherein, negative electrode slurry exists
Single side surface density on negative current collector is 60-160g/m2, compacted density 1.8-2.0g/cm3；
S4, positive plate is prepared by positive electrode of ternary material；It, will be in positive plate and S3 by N/P ratios=0.9-0.97
Lithium titanate anode piece is prepared into cylindrical type lithium titanate energy storage battery core.
Preferably, in S1, the pH value of the lithium titanate anode material controls within the scope of 10.5-11.5.
Preferably, in S3, the negative current collector selects 16+2+2um utter misery aluminium foils.
Preferably, in S4, it includes preparing anode sizing agent and will be positive to prepare positive plate as positive electrode using ternary material
Slurry is coated on plus plate current-collecting body；Wherein, during preparing anode sizing agent, raw material includes ternary material, superconduction charcoal
Black, carbon nanotube and Kynoar, and ternary material, superconduction carbon black, carbon nanotube, the weight ratio of Kynoar are 92-
96：1-3：1-4：1-3.
Preferably, the ternary material is one kind in NCM111, NCM523, NCM622.
Preferably, the solid content of the anode sizing agent is 60%-70%, viscosity 4000-7000mPas；Anode sizing agent
Single side surface density control on plus plate current-collecting body is 60-160g/m2, compacted density 3.0-3.3g/cm3。
Preferably, the plus plate current-collecting body selects 16um optical aluminum foils.
Preferably, the cylindrical type lithium titanate energy storage battery core capacity of preparation is distributed within the scope of 7-10Ah, energy density distribution
Within the scope of 60-90Wh/kg.
Preferably, the control of full battery fluid injection coefficient is between 3.5-5.5g/Ah.
Preferably, full battery diaphragm selects the ceramic diaphragm of 12+4um.
Preferably, in S1, lithium titanate anode material is ground using sand mill, during grinding, adjustment
The granularity of sand mill state modulator cathode powder.
Cylindrical type lithium titanate energy storage battery core of the present invention is 32131 type cylinder of ternary-lithium titanate-system battery core.
The method of the present invention for improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass, uses high temperature solid-state method first
Lithium titanate anode material needed for being made later controls the granularity of lithium titanate anode material in specified range (i.e. D10=1-5um,
D50=5-20um, D90=10-40um, (D90-D10)/D50Between=2-6), the cathode powder of greater particle size distribution is obtained, is helped
In reduce LTO (lithium titanate) pole piece specific surface area, prevent negative plate specific surface area it is excessive, activity it is too strong bring it is unstable
Property, i.e., in short circuit, reaction is relatively gentle, will not fail moment；Secondly bulky grain internal resistance is larger, and short-circuit heat production early period is more, aerogenesis
Soon, can battery core explosion-proof valve be strutted into heat dissipation, pressure release in time, to achieve the purpose that promote safety；Control full electricity simultaneously
The design of LTO (lithium titanate) negative plate single side surface density is in 60-160g/m in pond2Between, compacted density is in 1.8-2.0g/cm3It
Between, battery core N/P (capacity of negative plates/positive electrode capacity) makes the short-circuit percent of pass of battery core up to 100% within the scope of 0.9-0.97, with
Cathode granularity D50<When 1um, short-circuit percent of pass only has 30% to compare it is found that this battery core external short circuit safety greatly promotes；
Compared with prior art, beneficial effects of the present invention are embodied in：It is simple for process, without increasing any structure member design
Or change electric core architecture design can be achieved with short-circuit safety；It adjusts LTO granularities and only changes sand mill parameter, be not necessarily to
More exchange device increases energy consumption, and size distribution is easy to adjust, and does not generate extra cost；Without changing test condition, by reducing SOC
(battery charge state) state is to sacrifice the mode of capacity to ensure that short circuit passes through, it is easy to accomplish and promote, it can be applied to reality
In industrialized production.
Description of the drawings
Fig. 1 is cylindrical type lithium titanate energy storage battery core (the i.e. LTO granularities D prepared in the embodiment of the present invention 850The three of=15um
First 622/ lithium titanate cylindrical electrical core) acceleration adiabatic calorimetry instrument test (ARC) invalid temperature curve；
Fig. 2 is LTO granularities D50The acceleration adiabatic calorimetry instrument test (ARC) of the 622/ lithium titanate cylindrical electrical core of ternary of=1um
Invalid temperature curve.
Specific implementation mode
In the following, technical scheme of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of method improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass proposed by the present invention, including following step
Suddenly：
S1, lithium titanate anode material is prepared using high temperature solid-state method, lithium titanate anode material is ground to obtain cathode
Powder；Wherein, the size distribution of the cathode powder meets D10=5um, D50=15um, D90=35um, (D90-D10)/D50=
2；
S2, using the cathode powder in S1 as active material, using superconduction carbon black and carbon nanotube as conductive agent, with polyvinylidene fluoride
Alkene is that binder prepares negative electrode slurry；Wherein, the cathode powder in S1, superconduction carbon black, carbon nanotube, the weight of Kynoar
Than being 90：2：4：4；The solid content of negative electrode slurry is 35%, viscosity 7000mPas；
S3, it the negative electrode slurry in S2 is coated on negative current collector obtains lithium titanate anode piece；Wherein, negative electrode slurry exists
Single side surface density on negative current collector is 60g/m2, compacted density 1.8g/cm3；
S4, positive plate is prepared by positive electrode of ternary material；By ratio=0.9 N/P, by the lithium titanate in positive plate and S3
Negative plate is prepared into cylindrical type lithium titanate energy storage battery core.
Embodiment 2
A kind of method improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass proposed by the present invention, including following step
Suddenly：
S1, lithium titanate anode material is prepared using high temperature solid-state method, lithium titanate anode material is ground to obtain cathode
Powder；Wherein, the size distribution of the cathode powder meets D10=1um, D50=6um, D90=37um, (D90-D10)/D50=6；
S2, using the cathode powder in S1 as active material, using superconduction carbon black and carbon nanotube as conductive agent, with polyvinylidene fluoride
Alkene is that binder prepares negative electrode slurry；Wherein, the cathode powder in S1, superconduction carbon black, carbon nanotube, the weight of Kynoar
Than being 95：1：2：2；The solid content of negative electrode slurry is 50%, viscosity 4000mPas；
S3, it the negative electrode slurry in S2 is coated on negative current collector obtains lithium titanate anode piece；Wherein, negative electrode slurry exists
Single side surface density on negative current collector is 160g/m2, compacted density 2.0g/cm3；
S4, positive plate is prepared by positive electrode of ternary material；By ratio=0.97 N/P, by the metatitanic acid in positive plate and S3
Lithium cathode sheet is prepared into cylindrical type lithium titanate energy storage battery core.
Embodiment 3
A kind of method improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass proposed by the present invention, including following step
Suddenly：
S1, lithium titanate anode material is prepared using high temperature solid-state method, lithium titanate anode material is ground to obtain cathode
Powder；Wherein, the size distribution of the cathode powder meets D10=4um, D50=7um, D90=25um, (D90-D10)/D50=3；
S2, using the cathode powder in S1 as active material, using superconduction carbon black and carbon nanotube as conductive agent, with polyvinylidene fluoride
Alkene is that binder prepares negative electrode slurry；Wherein, the cathode powder in S1, superconduction carbon black, carbon nanotube, the weight of Kynoar
Than being 91：3：3：3；The solid content of negative electrode slurry is 38%, viscosity 6600mPas；
S3, it the negative electrode slurry in S2 is coated on negative current collector obtains lithium titanate anode piece；Wherein, negative electrode slurry exists
Single side surface density on negative current collector is 80g/m2, compacted density 1.9g/cm3；
S4, positive plate is prepared by positive electrode of ternary material；By ratio=0.92 N/P, by the metatitanic acid in positive plate and S3
Lithium cathode sheet is prepared into cylindrical type lithium titanate energy storage battery core；
Wherein, in S1, the pH value control of the lithium titanate anode material is 11.5；
In S3, the negative current collector selects 16+2+2um utter misery aluminium foils；
In S4, it includes preparing anode sizing agent and being coated with anode sizing agent to prepare positive plate as positive electrode using ternary material
On plus plate current-collecting body；Wherein, during preparing anode sizing agent, raw material includes ternary material, superconduction carbon black, carbon nanometer
Pipe and Kynoar, and ternary material, superconduction carbon black, carbon nanotube, the weight ratio of Kynoar are 92：3：4：1；
The ternary material is NCM523；
The solid content of the anode sizing agent is 60%, viscosity 4000mPas；Anode sizing agent is on plus plate current-collecting body
The control of single side surface density is 86g/m2, compacted density 3.0g/cm3；
The plus plate current-collecting body selects 16um optical aluminum foils；
The cylindrical type lithium titanate energy storage battery core capacity of preparation is 7Ah, energy density 60Wh/kg；
The control of full battery fluid injection coefficient is 5.5g/Ah；
Full battery diaphragm selects the ceramic diaphragm of 12+4um.
Embodiment 4
A kind of method improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass proposed by the present invention, including following step
Suddenly：
S1, lithium titanate anode material is prepared using high temperature solid-state method, lithium titanate anode material is ground to obtain cathode
Powder；Wherein, the size distribution of the cathode powder meets D10=2um, D50=7um, D90=30um, (D90-D10)/D50=4；
S2, using the cathode powder in S1 as active material, using superconduction carbon black and carbon nanotube as conductive agent, with polyvinylidene fluoride
Alkene is that binder prepares negative electrode slurry；Wherein, the cathode powder in S1, superconduction carbon black, carbon nanotube, the weight of Kynoar
Than being 93：2：3：2；The solid content of negative electrode slurry is 46%, viscosity 4500mPas；
S3, it the negative electrode slurry in S2 is coated on negative current collector obtains lithium titanate anode piece；Wherein, negative electrode slurry exists
Single side surface density on negative current collector is 145g/m2, compacted density 1.85g/cm3；
S4, positive plate is prepared by positive electrode of ternary material；By ratio=0.95 N/P, by the metatitanic acid in positive plate and S3
Lithium cathode sheet is prepared into cylindrical type lithium titanate energy storage battery core；
Wherein, in S1, the pH value control of the lithium titanate anode material is 10.5；
In S4, it includes preparing anode sizing agent and being coated with anode sizing agent to prepare positive plate as positive electrode using ternary material
On plus plate current-collecting body；Wherein, during preparing anode sizing agent, raw material includes ternary material, superconduction carbon black, carbon nanometer
Pipe and Kynoar, and ternary material, superconduction carbon black, carbon nanotube, the weight ratio of Kynoar are 96：1：1：2；
The ternary material is NCM111；
The solid content of the anode sizing agent is 70%, viscosity 4000mPas；Anode sizing agent is on plus plate current-collecting body
The control of single side surface density is 148g/m2, compacted density 3.3g/cm3；
The plus plate current-collecting body selects 16um optical aluminum foils；
The cylindrical type lithium titanate energy storage battery core capacity of preparation is 10Ah, energy density 90Wh/kg；
The control of full battery fluid injection coefficient is 3.5g/Ah；
Full battery diaphragm selects the ceramic diaphragm of 12+4um.
Embodiment 5
A kind of method improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass proposed by the present invention, including following step
Suddenly：
S1, lithium titanate anode material is prepared using high temperature solid-state method, lithium titanate anode material is ground to obtain cathode
Powder；Wherein, the size distribution of the cathode powder meets D10=3um, D50=7um, D90=38um, (D90-D10)/D50=5；
Wherein, the pH value control of the lithium titanate anode material is 11；
S2, using the cathode powder in S1 as active material, using superconduction carbon black and carbon nanotube as conductive agent, with polyvinylidene fluoride
Alkene is that binder prepares negative electrode slurry；Wherein, the cathode powder in S1, superconduction carbon black, carbon nanotube, the weight of Kynoar
Than being 93：2：2.5：2.5；The solid content of negative electrode slurry is 39%, viscosity 5500mPas；
S3, it the negative electrode slurry in S2 is coated on negative current collector obtains lithium titanate anode piece；Wherein, negative electrode slurry exists
Single side surface density on negative current collector is 100g/m2, compacted density 1.9g/cm3；
S4, positive plate is prepared by positive electrode of ternary material；By ratio=0.97 N/P, by the metatitanic acid in positive plate and S3
Lithium cathode sheet is prepared into cylindrical type lithium titanate energy storage battery core；Wherein, it includes system to prepare positive plate as positive electrode using ternary material
For anode sizing agent and anode sizing agent is coated on plus plate current-collecting body；Wherein, during preparing anode sizing agent, raw material packet
Include ternary material, superconduction carbon black, carbon nanotube and Kynoar, and ternary material, superconduction carbon black, carbon nanotube, poly- inclined fluorine
The weight ratio of ethylene is 95：1：1：3；The ternary material is NCM622；The solid content of the anode sizing agent is 65%, and viscosity is
5000mPa·s；Single side surface density control of the anode sizing agent on plus plate current-collecting body is 101g/m2, compacted density 3.2g/cm3；
The cylindrical type lithium titanate energy storage battery core capacity of preparation is 8.7Ah, energy density 80Wh/kg；
The control of full battery fluid injection coefficient is 4.3g/Ah；
Full battery diaphragm selects the ceramic diaphragm of 12+4um.
Embodiment 6
A kind of method improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass proposed by the present invention, including following step
Suddenly：
S1, lithium titanate anode material is prepared using high temperature solid-state method, lithium titanate anode material is ground to obtain cathode
Powder；Wherein, the size distribution of the cathode powder meets D10=3um, D50=6um, D90=30um, (D90-D10)/D50=
4.5；
S2, using the cathode powder in S1 as active material, using superconduction carbon black and carbon nanotube as conductive agent, with polyvinylidene fluoride
Alkene is that binder prepares negative electrode slurry；Wherein, the cathode powder in S1, superconduction carbon black, carbon nanotube, the weight of Kynoar
Than being 90：2：4：4；The solid content of negative electrode slurry is 39%, viscosity 5500mPas；
S3, it the negative electrode slurry in S2 is coated on negative current collector obtains lithium titanate anode piece；Wherein, negative electrode slurry exists
Single side surface density on negative current collector is 69g/m2, compacted density 1.9g/cm3；
S4, positive plate is prepared by positive electrode of ternary material；By ratio=0.9 N/P, by the lithium titanate in positive plate and S3
Negative plate is prepared into cylindrical type lithium titanate energy storage battery core；
Wherein, in S1, the pH value control of the lithium titanate anode material is 11；
In S4, it includes preparing anode sizing agent and being coated with anode sizing agent to prepare positive plate as positive electrode using ternary material
On plus plate current-collecting body；Wherein, during preparing anode sizing agent, raw material includes ternary material, superconduction carbon black, carbon nanometer
Pipe and Kynoar, and ternary material, superconduction carbon black, carbon nanotube, the weight ratio of Kynoar are 92：2：4：2；
The ternary material is NCM111；
The solid content of the anode sizing agent is 65%, viscosity 5000mPas；Anode sizing agent is on plus plate current-collecting body
The control of single side surface density is 75g/m2, compacted density 3.1g/cm3；
The cylindrical type lithium titanate energy storage battery core capacity of preparation is 7Ah, energy density 65Wh/kg；
The control of full battery fluid injection coefficient is 5g/Ah；
Full battery diaphragm selects the ceramic diaphragm of 12+4um.
According to GB/T31485-2015 after cylindrical type lithium titanate energy storage battery core chemical conversion prepared by embodiment 6, partial volume《It is electronic
Automobile power accumulator safety requirements and experimental method》Battery core is charged to 100%SOC by standard testing first, then is accessed short
Road 10min, outside line internal resistance are less than 5m Ω；1h is observed, no explosion, on fire be considered as does not pass through；By testing it is found that in battery core
The maximum temperature on battery core surface has reached 120 DEG C or more when short circuit occurs, but battery core is not exploded, and explosion-proof valve 40s is opened；And
In pre-stage test, as LTO materials D50<When 1um, battery core maximum temperature will explode to battery core at 110 DEG C or so, explosion-proof valve
It opens in 1 point of half or so；It follows that the cylindrical type lithium titanate energy storage battery core external short circuit safety prepared in embodiment 6
Can be high, therefore, increase the D of LTO materials50Distribution can effectively promote the external short circuit security performance of battery core.
Embodiment 7
A kind of method improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass proposed by the present invention, including following step
Suddenly：
S1, lithium titanate anode material is prepared using high temperature solid-state method, lithium titanate anode material is ground to obtain cathode
Powder；Wherein, the size distribution of the cathode powder meets D10=5um, D50=10um, D90=40um, (D90-D10)/D50=
3.5；
S2, using the cathode powder in S1 as active material, using superconduction carbon black and carbon nanotube as conductive agent, with polyvinylidene fluoride
Alkene is that binder prepares negative electrode slurry；Wherein, the cathode powder in S1, superconduction carbon black, carbon nanotube, the weight of Kynoar
Than being 91：3：4：2；The solid content of negative electrode slurry is 39%, viscosity 5500mPas；
S3, it the negative electrode slurry in S2 is coated on negative current collector obtains lithium titanate anode piece；Wherein, negative electrode slurry exists
Single side surface density on negative current collector is 118g/m2, compacted density 1.85g/cm3；
S4, positive plate is prepared by positive electrode of ternary material；By ratio=0.95 N/P, by the metatitanic acid in positive plate and S3
Lithium cathode sheet is prepared into 32131 cylindrical type lithium titanate energy storage battery cores by winding；
Wherein, in S1, the pH value control of the lithium titanate anode material is 11；
In S4, it includes preparing anode sizing agent and being coated with anode sizing agent to prepare positive plate as positive electrode using ternary material
On plus plate current-collecting body；Wherein, during preparing anode sizing agent, raw material includes ternary material, superconduction carbon black, carbon nanometer
Pipe and Kynoar, and ternary material, superconduction carbon black, carbon nanotube, the weight ratio of Kynoar are 94：2：2：2；
The ternary material is NCM523；
The solid content of the anode sizing agent is 65%, viscosity 5000mPas；Anode sizing agent is on plus plate current-collecting body
The control of single side surface density is 120g/m2, compacted density 3.1g/cm3；
The cylindrical type lithium titanate energy storage battery core capacity of preparation is 8Ah, energy density 70Wh/kg；
The control of full battery fluid injection coefficient is 4.3g/Ah；
Full battery diaphragm selects the ceramic diaphragm of 12+4um.
According to GB/T31485-2015 after cylindrical type lithium titanate energy storage battery core chemical conversion prepared by embodiment 7, partial volume《It is electronic
Automobile power accumulator safety requirements and experimental method》Standard testing, it is first that battery core is fully charged to 100%SOC, then access
Short-circuit 10min, outside line internal resistance are less than 5m Ω；1h is observed, no explosion, on fire be considered as does not pass through；By testing it is found that battery core
The temperature on battery core surface has reached 130 DEG C or more when short-circuit, but battery core can still be opened by test, explosion-proof valve 35s；
In pre-stage test, as LTO materials D50<When 1um, when battery core short circuit the maximum temperature on battery core surface to battery core at 100 DEG C or so just
It can explode；It follows that the cylindrical type lithium titanate energy storage battery core external short circuit security performance prepared in embodiment 7 is high, because
This, increases the D of LTO materials50Distribution can effectively promote the external short circuit security performance of battery core.
Embodiment 8
A kind of method improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass proposed by the present invention, including following step
Suddenly：
S1, lithium titanate anode material is prepared using high temperature solid-state method, lithium titanate anode material is ground to obtain cathode
Powder；Wherein, the size distribution of the cathode powder meets D10=2.5um, D50=15um, D90=40um, (D90-D10)/D50
=2.5；
S2, using the cathode powder in S1 as active material, using superconduction carbon black and carbon nanotube as conductive agent, with polyvinylidene fluoride
Alkene is that binder prepares negative electrode slurry；Wherein, the cathode powder in S1, superconduction carbon black, carbon nanotube, the weight of Kynoar
Than being 93.5：1：2：3.5；The solid content of negative electrode slurry is 39%, viscosity 5500mPas；
S3, it the negative electrode slurry in S2 is coated on negative current collector obtains lithium titanate anode piece；Wherein, negative electrode slurry exists
Single side surface density on negative current collector is 129g/m2, compacted density 1.88g/cm3；
S4, positive plate is prepared by positive electrode of ternary material；By ratio=0.97 N/P, by the metatitanic acid in positive plate and S3
Lithium cathode sheet is prepared into cylindrical type lithium titanate energy storage battery core；
Wherein, in S1, the pH value control of the lithium titanate anode material is 11；
In S4, it includes preparing anode sizing agent and being coated with anode sizing agent to prepare positive plate as positive electrode using ternary material
On plus plate current-collecting body；Wherein, during preparing anode sizing agent, raw material includes ternary material, superconduction carbon black, carbon nanometer
Pipe and Kynoar, and ternary material, superconduction carbon black, carbon nanotube, the weight ratio of Kynoar are 96：1：1.5：1.5；
The ternary material is NCM622；
The solid content of the anode sizing agent is 65%, viscosity 5000mPas；Anode sizing agent is on plus plate current-collecting body
The control of single side surface density is 130g/m2, compacted density 3.2g/cm3；
The cylindrical type lithium titanate energy storage battery core capacity of preparation is 9.5Ah, energy density 85Wh/kg；
The control of full battery fluid injection coefficient is 4g/Ah；
Full battery diaphragm selects the ceramic diaphragm of 12+4um.
According to GB/T31485-2015 after cylindrical type lithium titanate energy storage battery core chemical conversion prepared by embodiment 8, partial volume《It is electronic
Automobile power accumulator safety requirements and experimental method》Battery core is charged to 100%SOC by standard testing first, then is accessed short
Road 10min, outside line internal resistance are less than 5m Ω；1h is observed, no explosion, on fire be considered as does not pass through；By testing it is found that battery core is short
The temperature on battery core surface has reached 120 DEG C or more when road, and battery core test passes through, and explosion-proof valve 32s is opened；And in pre-stage test,
As LTO materials D50<When 1um, battery core maximum temperature will explode to battery core at 100 DEG C or so, and explosion-proof valve mostly cannot be complete
Full open；It follows that the cylindrical type lithium titanate energy storage battery core external short circuit security performance prepared in embodiment 8 is high, therefore, increase
The D of big LTO materials50Distribution can effectively promote the short circuit safety energy of battery core.
In order to characterize the battery core and LTO granularities D of the preparation of embodiment 850The 622/ lithium titanate cylindrical electrical core safety of ternary of=1um
The difference of performance, respectively to the battery core and LTO granularities D of the preparation of embodiment 850The 622/ lithium titanate cylindrical electrical core of ternary of=1um is made
Acceleration adiabatic calorimetry instrument test (ARC), using the Wen Sheng of 5 DEG C/min as failure criterion, Fig. 1 is the embodiment of the present invention 8
Cylindrical type lithium titanate energy storage battery core (the i.e. LTO granularities D of middle preparation50The 622/ lithium titanate cylindrical electrical core of ternary of=15um) acceleration
Adiabatic calorimetry instrument tests (ARC) invalid temperature curve；Fig. 2 is LTO granularities D50The 622/ lithium titanate cylindrical electrical core of ternary of=1um
Adiabatic calorimetry instrument is accelerated to test (ARC) invalid temperature curve；Compare Fig. 1 and Fig. 2 it is found that bulky grain LTO battery cores invalid temperature is high
Go out 10 DEG C, it is safer, it is consistent with short-circuit test result.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of method improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass, which is characterized in that include the following steps：
S1, lithium titanate anode material is prepared using high temperature solid-state method, lithium titanate anode material is ground to obtain cathode powder；
Wherein, the size distribution of the cathode powder meets D10=1-5um, D50=5-20um, D90=10-40um, (D90-D10)/D50
=2-6；
S2, it is as conductive agent, with Kynoar as active material, using superconduction carbon black and carbon nanotube using the cathode powder in S1
Binder prepares negative electrode slurry；Wherein, the cathode powder in S1, superconduction carbon black, carbon nanotube, the weight ratio of Kynoar are
90-95：1-3：2-4：2-4；The solid content of negative electrode slurry is 35%-50%, viscosity 4000-7000mPas；
S3, it the negative electrode slurry in S2 is coated on negative current collector obtains lithium titanate anode piece；Wherein, negative electrode slurry is in cathode
Single side surface density on collector is 60-160g/m2, compacted density 1.8-2.0g/cm3；
S4, positive plate is prepared by positive electrode of ternary material；By N/P ratios=0.9-0.97, by the metatitanic acid in positive plate and S3
Lithium cathode sheet is prepared into cylindrical type lithium titanate energy storage battery core.
2. the method for improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass according to claim 1, which is characterized in that
In S1, the pH value of the lithium titanate anode material controls within the scope of 10.5-11.5.
3. the method according to claim 1 or claim 2 for improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass, feature exist
In in S3, the negative current collector selects 16+2+2um utter misery aluminium foils.
4. according to any one of the claim 1-3 methods for improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass,
It is characterized in that, in S4, it includes preparing anode sizing agent and applying anode sizing agent to prepare positive plate as positive electrode using ternary material
Cloth is on plus plate current-collecting body；Wherein, during preparing anode sizing agent, raw material includes that ternary material, superconduction carbon black, carbon are received
Mitron and Kynoar, and ternary material, superconduction carbon black, carbon nanotube, the weight ratio of Kynoar are 92-96：1-3：
1-4：1-3.
5. according to any one of the claim 1-4 methods for improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass,
It is characterized in that, the ternary material is one kind in NCM111, NCM523, NCM622.
6. the method for improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass, feature exist according to claim 4 or 5
In the solid content of the anode sizing agent is 60%-70%, viscosity 4000-7000mPas；Anode sizing agent is in plus plate current-collecting body
On single side surface density control be 60-160g/m2, compacted density 3.0-3.3g/cm3。
7. according to any one of the claim 4-6 methods for improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass,
It is characterized in that, the plus plate current-collecting body selects 16um optical aluminum foils.
8. according to any one of the claim 1-7 methods for improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass,
It is characterized in that, the cylindrical type lithium titanate energy storage battery core capacity of preparation is distributed within the scope of 7-10Ah, and energy density distribution is in 60-
Within the scope of 90Wh/kg.
9. according to any one of the claim 1-8 methods for improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass,
It is characterized in that, full battery fluid injection coefficient controls between 3.5-5.5g/Ah.
10. according to any one of the claim 1-9 methods for improving cylindrical type lithium titanate energy storage battery core short circuit percent of pass,
It is characterized in that, full battery diaphragm selects the ceramic diaphragm of 12+4um.
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