CN109698334A - Positive plate, lithium titanate battery and preparation method thereof - Google Patents

Positive plate, lithium titanate battery and preparation method thereof Download PDF

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Publication number
CN109698334A
CN109698334A CN201811547862.0A CN201811547862A CN109698334A CN 109698334 A CN109698334 A CN 109698334A CN 201811547862 A CN201811547862 A CN 201811547862A CN 109698334 A CN109698334 A CN 109698334A
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lithium titanate
conductive carbon
coating
positive plate
adhesive
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Inventor
周奇
崔俊葳
周晓航
王耐清
易四勇
李文武
舒民
李小兵
陈小平
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Soundon New Energy Technology Co Ltd
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Soundon New Energy Technology Co Ltd
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Priority to CN201811547862.0A priority Critical patent/CN109698334A/en
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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
    • H01M4/36—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
    • 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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to a kind of positive plate, lithium titanate battery and preparation method thereof, which includes plus plate current-collecting body and the coating that is located on plus plate current-collecting body, and the raw material of the coating on plus plate current-collecting body includes outer cladding Al2O3Nickel cobalt manganese monocrystalline ternary material, conductive carbon and adhesive, outer cladding Al2O3Nickel cobalt manganese monocrystalline ternary material, conductive carbon and adhesive weight ratio be (95~98): (1~4): (1~3)；Outer cladding Al2O3Nickel cobalt manganese monocrystalline ternary material be solid nutty structure, element group become Li1.05‑ xMgxNi1‑2y‑zCoyMnyTizO2·nAl2O3, wherein 0 < x < 0.05,0 < y≤0.33,0 < z≤0.05.The positive plate and the lithium titanate battery being prepared using the positive plate, it is to be prepared using the monocrystalline ternary material of nickel cobalt manganese, be inside the particle of monocrystalline ternary material it is solid, manufactured anode pole piece compacted density is higher, helps to improve the energy density and cycle performance of battery entirety.And preparation method is simple, easily controllable, can further guarantee the quality for the product being prepared.

Description

Positive plate, lithium titanate battery and preparation method thereof
Technical field
The present invention relates to new energy fields, more particularly to a kind of positive plate, lithium titanate battery and preparation method thereof.
Background technique
Electric car is China or even the whole world solution one of energy shortage and the important invention of problem of environmental pollution, and electric Cell system is the main power resources of electric car, and power battery is the core component of battery system.Currently, answering in the market It is lithium-ion-power cell with most power batteries, power battery can be divided into ternary power battery, LiMn2O4 by material category Power battery, ferrous phosphate lithium dynamical battery, metatitanic acid lithium dynamical battery.Compared with other type power batteries, lithium titanate power Battery has apparent advantage: (1) having a safety feature, due to using the lithium titanate (Li of spinel-type4Ti5O12) it is used as cathode Material, intercalation potential is higher, and charging/discharging voltage is steady, therefore Li dendrite will not be precipitated in charge and discharge process and pierce through diaphragm, avoids Cause battery short circuit；(2) good cycle, negative electrode material volume is almost unchanged in charge and discharge process, is a kind of " zero strain " Material, structure keep complete；(3) good rate capability, lithium titanate material electrochemical diffusion coefficient is high, has three-dimensional lithium ion tunnel, It is suitble to fast charging and discharging；(4) low temperature performance well, lithium titanate material still has high lithium ion diffusion coefficient under low temperature.Exactly Due to this several big feature, so that lithium titanate battery is highly suitable for high power vehicle, such as public transport, bus road vehicle, and Mine car, excavator etc. are off-highway to use vehicle, is in addition also applied to energy storage field, plays a part of peak load shifting.
However it is short slab in lithium titanate battery application that the energy density of lithium titanate battery is low, someone passes through simple three step Hydro-thermal method has been prepared by ultra-thin Li4Ti5O12The hierarchical structure microballoon of nanometer sheet (HLTO-NS) assembling, shows good electricity Chemical property.When the constituent content of Li and Ti ratio is 1.5, pure HLTO-NS microballoon can be obtained, 1,2,5,10,15, 20, under the multiplying power of 50C, discharge capacity is respectively 179,171,167,162,159,156,50mAh/g, and wherein 1C is theoretically Specific discharge capacity is 175mAh/g.This method promotes the energy density of battery in terms of negative electrode material optimizes, but room for promotion is non- It is often limited.According to the requirement of national the year two thousand twenty estate planning, it is imperative to promote metatitanic acid lithium dynamical battery energy density.
Summary of the invention
Based on this, it is necessary to a kind of positive plate, lithium titanate battery and preparation method thereof are provided, to solve traditional lithium titanate The low problem of power battery energy density.
A kind of positive plate, including plus plate current-collecting body and the coating being located on the plus plate current-collecting body, the plus plate current-collecting body On the raw material of coating include outer cladding Al2O3Nickel cobalt manganese monocrystalline ternary material, conductive carbon and adhesive, the outer cladding Al2O3Nickel cobalt manganese monocrystalline ternary material, the conductive carbon and the adhesive weight ratio be (95~98): (1~4): (1 ~3)；
The outer cladding Al2O3Nickel cobalt manganese monocrystalline ternary material be solid nutty structure, element group becomes Li1.05-xMgxNi1-2y-zCoyMnyTizO2·nAl2O3, wherein 0 < x < 0.05,0 < y≤0.33,0 < z≤0.05.
The outer cladding Al in one of the embodiments,2O3Nickel cobalt manganese monocrystalline ternary material, the conductive carbon and The weight ratio of the adhesive is 96:2:2.
Above-mentioned positive plate uses the monocrystalline ternary material of nickel cobalt manganese, be inside the particle of monocrystalline ternary material it is solid, be made Anode pole piece compacted density it is higher, help to improve the energy density and cycle performance of battery entirety.And nickel cobalt manganese monocrystalline three The active site of first material is less, can be reduced the side reaction of particle surface and electrolyte and improves the production gas situation of battery, because This can be applied to high voltage system.
A kind of preparation method of positive plate described in any of the above embodiments, comprising the following steps:
By the outer cladding Al2O3Nickel cobalt manganese monocrystalline ternary material, the conductive carbon and the adhesive mixing, add Enter solvent, be sufficiently stirred, obtains positive coating paste；
The positive coating paste is coated on the plus plate current-collecting body, is dried, positive plate is obtained after cold pressing.
The solvent is water or N-Methyl pyrrolidone in one of the embodiments, and the positive coating paste The mass fraction of middle solvent is 40%~60%.
The surface density of the coating is 100mg/1000mm in one of the embodiments,2~300mg/1000mm2, described The compacted density of cold pressing is 3.35g/cm3~3.55g/cm3。
The temperature of the drying is 75 DEG C~85 DEG C in one of the embodiments,.
The preparation method of above-mentioned positive plate, is prepared positive coating paste by the way of physical mixed, easy to operate, It is convenient, it is suitble to large-scale industrial production.And a kind of high voltage system that can be used for can be prepared by the above method Positive plate.
A kind of lithium titanate battery, including negative electrode tab and positive plate as described in any one of the above embodiments or according to any of the above-described The positive plate that the preparation method of the positive plate is prepared.
The negative electrode tab includes the painting on negative current collector and the negative current collector in one of the embodiments, Layer；
The raw material of coating on the negative current collector includes lithium titanate, conductive carbon and adhesive, the lithium titanate, institute The weight ratio for stating conductive carbon and the adhesive is (91~96): (1~4): (1~3).
Above-mentioned high-energy density lithium titanate battery, as positive electrode, not only increases lithium titanate electricity using above-mentioned positive plate The energy density in pond, and its capacity is promoted, the production gas under high temperature is less, and capacity retention ratio is preferable.
A kind of preparation method of lithium titanate battery described in any of the above embodiments, includes the following steps:
The negative electrode tab is prepared, and the positive plate and the negative electrode tab are assembled into lithium titanate battery；
It is described prepare the negative electrode tab the following steps are included:
The lithium titanate, the conductive carbon and the adhesive are mixed, and solvent is added, is sufficiently stirred, is born Pole coating paste；
The cathode coating paste is coated on the negative current collector, after be dried, be cold-pressed, obtain the cathode Piece.
The solvent is water or N-Methyl pyrrolidone in one of the embodiments, molten in the cathode coating paste The content of agent is 40%~60%；And/or
The surface density of the coating is 100mg/1000mm2~200mg/1000mm2, the compacted density of the cold pressing is 1.60g/cm3~1.90g/cm3。
The preparation method of above-mentioned high-energy density lithium titanate battery, easy to operate, convenient, each technological parameter is easily controllable, It can be further ensured that the quality for the product that production is prepared.
Detailed description of the invention
Fig. 1 is the cycle performance comparison diagram of different lithium titanate batteries.
Specific embodiment
To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.In attached drawing Give presently preferred embodiments of the present invention.But the invention can be realized in many different forms, however it is not limited to this paper institute The embodiment of description.On the contrary, purpose of providing these embodiments is keeps the understanding to the disclosure more thorough Comprehensively.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases Any and all combinations of the listed item of pass.
The present invention relates to a kind of positive plates, including plus plate current-collecting body and the coating being located on plus plate current-collecting body, anode collection Coating on body includes outer cladding Al2O3Nickel cobalt manganese monocrystalline ternary material, conductive carbon, adhesive, wherein outer cladding Al2O3's The weight ratio of nickel cobalt manganese monocrystalline ternary material, conductive carbon and adhesive is (95~98): (1~4): (1~3).Outer cladding Al2O3Nickel cobalt manganese monocrystalline ternary material be solid nutty structure, element group become Li1.05-xMgxNi1-2y- zCoyMnyTizO2·nAl2O3, wherein 0 < x < 0.05,0 < y≤0.33,0 < z≤0.05.Preferably, outer cladding Al2O3Nickel cobalt manganese The weight ratio of monocrystalline ternary material, conductive carbon and adhesive is 96:2:2.
It is solid structure inside the particle of monocrystalline ternary material, the pressure of manufactured anode pole piece coating can be effectively improved Real density helps to improve the energy density and cycle performance of battery entirety.And the active site of nickel cobalt manganese monocrystalline ternary material It is less, the case where can be reduced the side reaction of particle surface and electrolyte and improve the production gas of battery, therefore it can be applied to high electricity Laminate system.
The present invention also provides a kind of preparation methods of positive plate comprising following steps:
Step S11: positive coating paste is prepared.
Nickel cobalt manganese monocrystalline ternary material, conductive carbon and adhesive are weighed, outer cladding Al is made2O3Nickel cobalt manganese monocrystalline ternary Material, conductive carbon, the weight ratio of adhesive are (95~98): (1~4): (1~3) is mixed, and solvent is added, makes solvent Content is 40%~60%, and mixing time 2.5h~3.5h at being 20 DEG C~50 DEG C in temperature obtains positive coating paste；
Wherein, conductive carbon is conductive carbon 1 and conductive carbon 2, and the weight ratio of conductive carbon 1 and conductive carbon 2 is preferably 1 ︰ 1；
Specifically, conductive carbon 1 can be, but not limited to be Super-P (little particle conductive black, 30~40 μm of partial size), such as It can also be CNT (carbon nanotube), conductive carbon 2 can be, but not limited to be that (bulky grain graphite powder, partial size are 6.5 μm of left sides to KS-6 It is right), such as can also be KS-15 (bulky grain graphite powder, partial size are 17.2 μm or so)；
Solvent can be, but not limited to be water, such as can also be N-Methyl pyrrolidone；
Adhesive can be, but not limited to be PVDF (Kynoar).
Step S12: being coated and dried and is cold-pressed.
The positive coating paste that step S11 is prepared is coated on plus plate current-collecting body, is 75 DEG C~85 DEG C in temperature Under be dried, positive plate is obtained after cold pressing.
Wherein, surface density when coating is 100mg/1000mm2~300mg/1000mm2, compacted density when cold pressing is 3.35g/cm3~3.55g/cm3。
The preparation method of above-mentioned positive plate, is prepared positive coating paste by the way of physical mixed, easy to operate, It is convenient.
The invention further relates to a kind of high-energy density lithium titanate batteries, including above-mentioned positive plate and negative electrode tab；Or packet The positive plate and negative electrode tab that the preparation method of above-mentioned positive plate is prepared are included, negative electrode tab includes negative current collector and cathode Coating on collector；
Wherein, the coating on negative current collector includes the raw material components of following weight ratio: lithium titanate, conductive carbon, adhesive Weight ratio be (91~96): (1~4): (1~3).
Above-mentioned high-energy density lithium titanate battery, as positive electrode, not only increases lithium titanate electricity using above-mentioned positive plate The energy density in pond, and its capacity is promoted, the production gas under high temperature is less, and capacity retention ratio is preferable.
Further, the present invention also provides a kind of preparation methods of above-mentioned high-energy density lithium titanate battery comprising such as Lower step:
Step S21: cathode coating paste is prepared.
Lithium titanate, conductive carbon and adhesive are weighed, lithium titanate, conductive carbon, the weight ratio of adhesive (91~96) are made: (1~4): (1~3) is mixed, and solvent is added, and makes the content 40%~60% of solvent, is 20 DEG C~50 DEG C in temperature Lower mixing time 4.5h~5.5h, obtains cathode coating paste；
Wherein, conductive carbon is conductive carbon 1 and conductive carbon 2, and the weight ratio of conductive carbon 1 and conductive carbon 2 is preferably 1 ︰ 1；
Specifically, conductive carbon 1 can be, but not limited to be Super-P, such as can also be CNT, conductive carbon 2 can with but it is unlimited Then KS-6, such as can also be KS-15；
Solvent can be, but not limited to be water, such as can also be N-Methyl pyrrolidone；
Adhesive can be, but not limited to be PVDF.
Step S22: preparation negative electrode tab.
The cathode coating paste that step S21 is prepared is coated on negative current collector, is dried in coating process, 75 DEG C~85 DEG C of drying temperature, coating speed 15m/min, cold pressing obtains negative electrode tab；
Wherein, the surface density of coating is 100mg/1000mm2~200mg/1000mm2, compacted density when cold pressing is 1.60g/cm3~1.90g/cm3。
Step S23: positive plate and negative electrode tab assembling prepare lithium titanate battery.
Positive plate and negative electrode tab are die cut, lamination, assembly, inject electrolyte, chemical conversion and partial volume, height is prepared Energy density lithium titanate battery.
The preparation method of the lithium titanate battery of above-mentioned high-energy density, easy to operate, convenient, each technological parameter is easy to control System, therefore it is suitble to large-scale industrial production.
The following are specific embodiment parts.
Embodiment 1
Embodiment 1 is a kind of preparation method of lithium titanate battery, and anode is designed using 4.4V, i.e. full battery upper limit voltage 2.85V is controlled, and specific production step is as follows:
Weighing nickel cobalt manganese monocrystalline ternary material, (group becomes Li1.02Mg0.03Ni0.57Co0.2Mn0.2Ti0.03O2·nAl2O3), lead Electrical carbon SP, conductive carbon KS-6 and adhesive make its weight ratio 96:1:1:2, and nickel cobalt manganese monocrystalline tertiary cathode material is placed in In agitator tank, corresponding conductive carbon and adhesive PVDF is added, 40 DEG C of whipping temp, mixing time 3 hours, obtains positive coating Slurry；
Lithium titanate, conductive carbon SP, conductive carbon KS-6 and adhesive are weighed, makes its weight ratio 95:1:1:3, by metatitanic acid Lithium is placed in agitator tank, and corresponding conductive carbon and adhesive PVDF is added, 40 DEG C of whipping temp, mixing time 5 hours, is born Pole coating paste；
Positive coating paste is evenly coated in aluminum foil current collector, surface density 200mg/1000mm2, negative electrode slurry is uniform It is coated in aluminum foil current collector, surface density 245mg/1000mm2, it is dried in coating process, 80 DEG C of drying temperature, coating speed 15m/min；
The dry anode pole piece completed is pressed into 3.4g/cm3Densification carries out pair rolls cold pressing, and cathode pole piece presses 1.70g/cm3Densification Carry out pair rolls cold pressing；
Positive plate and negative electrode tab are die cut, lamination, assembly, fluid injection, chemical conversion, the processes such as partial volume are using Soft Roll lamination system Make technique progress, obtain lithium titanate battery, is labeled as sample 1.
Outer cladding Al in the positive coating paste for the lithium titanate battery that embodiment 1 provides2O3Nickel cobalt manganese monocrystalline ternary material Material, conductive carbon and adhesive weight ratio be 96:2:2, and outer cladding Al2O3Nickel cobalt manganese monocrystalline ternary material element group As Li1.02Mg0.03Ni0.57Co0.2Mn0.2Ti0.03O2·nAl2O3.The lithium titanate battery for the specific structure that embodiment 1 provides It is intended merely to be not intended to restrict the invention, it is appreciated that in other embodiments, outside as compared with following each comparative example Coat Al2O3Nickel cobalt manganese monocrystalline ternary material, the weight ratio of conductive carbon and adhesive it is without being limited thereto, which can be (95~98): (1~4): adjustment in (1~3) range, and outer cladding Al2O3Nickel cobalt manganese monocrystalline ternary material element composition It is not limited to described above, can also be Li1.05-xMgxNi1-2y-zCoyMnyTizO2·nAl2O3, wherein x, y and z can choose full Other numerical value required enough: 0 < x < 0.05,0 < y≤0.33,0 < z≤0.05.
Comparative example 1
Comparative example 1 is a kind of preparation method of lithium titanate battery, and anode is designed using 4.2V, i.e. full battery upper limit voltage 2.65V (conventional design) is controlled, and specific production step is as follows:
Weighing nickel cobalt manganese polycrystalline ternary material, (element group becomes Li1.02Mg0.03Ni0.57Co0.2Mn0.2Ti0.03O2· nAl2O3), conductive carbon SP, conductive carbon KS-6 and adhesive, make its weight ratio 96:1:1:2, just by nickel cobalt manganese polycrystalline ternary Pole material is placed in agitator tank, is added corresponding conductive carbon and adhesive PVDF, and 40 DEG C of whipping temp, mixing time 3 hours, Positive coating paste；
Lithium titanate, conductive carbon SP, conductive carbon KS-6 and adhesive are weighed, makes its weight ratio 95:1:1:3, by metatitanic acid Lithium is placed in agitator tank, and corresponding conductive carbon and adhesive PVDF is added, 40 DEG C of whipping temp, mixing time 5 hours, is born Pole coating paste；
Positive coating paste is evenly coated in aluminum foil current collector, surface density 200mg/1000mm2, negative electrode slurry is uniform It is coated in aluminum foil current collector, surface density 245mg/1000mm2, it is dry in coating process, 80 DEG C of drying temperature, coating speed 15m/ min；
The dry anode pole piece completed is pressed into 3.4g/cm3Densification carries out pair rolls cold pressing, and cathode pole piece presses 1.70g/cm3Densification Carry out pair rolls cold pressing；
Positive plate and negative electrode tab are die cut, lamination, assembly, fluid injection, chemical conversion, the processes such as partial volume are using Soft Roll lamination system Make technique progress, obtain lithium titanate battery, is labeled as sample 2.
Comparative example 2
Comparative example 2 is a kind of preparation method of lithium titanate battery, and anode is designed using 4.4V, i.e. full battery upper limit voltage 2.85V is controlled, and specific production step is as follows:
Weigh nickel cobalt manganese polycrystalline ternary material Li1.02Mg0.03Ni0.57Co0.2Mn0.2Ti0.03O2·nAl2O3, conductive carbon SP, Conductive carbon KS-6 and adhesive make its weight ratio 96:1:1:2, and nickel cobalt manganese polycrystalline tertiary cathode material is placed in agitator tank In, corresponding conductive carbon and adhesive PVDF is added, 40 DEG C of whipping temp, mixing time 3 hours, obtains positive coating paste；
Lithium titanate, conductive carbon SP, conductive carbon KS-6 and adhesive are weighed, makes its weight ratio 95:1:1:3, by metatitanic acid Lithium is placed in agitator tank, and corresponding conductive carbon and adhesive PVDF is added, 40 DEG C of whipping temp, mixing time 5 hours, is born Pole coating paste；
Positive coating paste is evenly coated in aluminum foil current collector, surface density 200mg/1000mm2, negative electrode slurry is uniform It is coated in aluminum foil current collector, surface density 245mg/1000mm2, it is dry in coating process, 80 DEG C of drying temperature, coating speed 15m/ min；
The dry anode pole piece completed is pressed into 3.4g/cm3Densification carries out pair rolls cold pressing, and cathode pole piece presses 1.70g/cm3Densification Carry out pair rolls cold pressing；
Positive plate and negative electrode tab are die cut, lamination, assembly, fluid injection, chemical conversion, the processes such as partial volume are using Soft Roll lamination system Make technique progress, obtain lithium titanate battery, is labeled as sample 3.
Comparative example 3
Comparative example 3 is a kind of preparation method of lithium titanate battery, and anode is designed using 4.4V, i.e. full battery upper limit voltage 2.85V is controlled, and specific production step is as follows:
Weighing nickel cobalt manganese monocrystalline ternary material, (group becomes Li1.02Mg0.03Ni0.57Co0.2Mn0.2Ti0.03O2·nAl2O3), lead Electrical carbon SP, conductive carbon KS-6 and adhesive make its weight ratio 90:3:3:4, and nickel cobalt manganese monocrystalline tertiary cathode material is placed in In agitator tank, corresponding conductive carbon and adhesive PVDF is added, 40 DEG C of whipping temp, mixing time 3 hours, obtains positive coating Slurry；
Lithium titanate, conductive carbon SP, conductive carbon KS-6 and adhesive are weighed, makes its weight ratio 95:1:1:3, by metatitanic acid Lithium is placed in agitator tank, and corresponding conductive carbon and adhesive PVDF is added, 40 DEG C of whipping temp, mixing time 5 hours, is born Pole coating paste；
Positive coating paste is evenly coated in aluminum foil current collector, surface density 200mg/1000mm2, negative electrode slurry is uniform It is coated in aluminum foil current collector, surface density 245mg/1000mm2, it is dry in coating process, 80 DEG C of drying temperature, coating speed 15m/ min；
The dry anode pole piece completed is pressed into 3.4g/cm3Densification carries out pair rolls cold pressing, and cathode pole piece presses 1.70g/cm3Densification Carry out pair rolls cold pressing；
Positive plate and negative electrode tab are die cut, lamination, assembly, fluid injection, chemical conversion, the processes such as partial volume are using Soft Roll lamination system Make technique progress, obtain lithium titanate battery, is labeled as sample 4.
Comparative example 4
Comparative example 4 is a kind of preparation method of lithium titanate battery, and anode is designed using 4.4V, i.e. full battery upper limit voltage 2.85V is controlled, and specific production step is as follows:
Weigh nickel cobalt manganese monocrystalline ternary material (Li0.95Mg0.1Ni0.5Co0.2Mn0.2Ti0.1O2·nAl2O3), conductive carbon SP, Conductive carbon KS-6 and adhesive make its weight ratio 96:1:1:2, and nickel cobalt manganese monocrystalline tertiary cathode material is placed in agitator tank In, corresponding conductive carbon and adhesive PVDF is added, 40 DEG C of whipping temp, mixing time 3 hours, obtains positive coating paste；
Lithium titanate, conductive carbon SP, conductive carbon KS-6 and adhesive are weighed, makes its weight ratio 95:1:1:3, by metatitanic acid Lithium is placed in agitator tank, and corresponding conductive carbon and adhesive PVDF is added, 40 DEG C of whipping temp, mixing time 5 hours, is born Pole coating paste；
Positive coating paste is evenly coated in aluminum foil current collector, surface density 200mg/1000mm2, negative electrode slurry is uniform It is coated in aluminum foil current collector, surface density 245mg/1000mm2, it is dry in coating process, 80 DEG C of drying temperature, coating speed 15m/ min；
The dry anode pole piece completed is pressed into 3.4g/cm3Densification carries out pair rolls cold pressing, and cathode pole piece presses 1.70g/cm3Densification Carry out pair rolls cold pressing；
Positive plate and negative electrode tab are die cut, lamination, assembly, fluid injection, chemical conversion, the processes such as partial volume are using Soft Roll lamination system Make technique progress, obtain lithium titanate battery, is labeled as sample 5.
The capacity, high temperature and cycle performance of sample are tested:
1, volume test
Sample 1: full battery upper limit voltage 2.85V, corresponding anode upper limit voltage 4.4V；
Sample 2: full battery upper limit voltage 2.65V, corresponding anode upper limit voltage 4.2V.
The results are shown in Table 1 for the volume test of sample 1 and sample 2:
Table 1
Project Sample 1 Sample 2
1 36016 32174
2 36114 32129
3 36050 32558
4 35771 32417
5 36091 32049
6 36097 31956
7 35923 31877
8 35898 32547
9 36277 32134
10 36097 32362
Average value 36033 32220
The lithium titanate battery (design voltage 2.85V) for using the monocrystalline ternary material of embodiment 1 to make as shown in Table 1 holds It measures higher by 12% than battery (design voltage 2.65V) capacity for using traditional ternary polycrystalline material to prepare.
2, high temperature test
Conservation rate, recovery rate are carried out at 55 DEG C and 60 DEG C to sample 1, sample 3, sample 4 and sample 5 and produces gas situation It is tested:
Sample 1, sample 3, sample 4 and sample 5 full battery upper limit voltage 2.85V, corresponding anode upper limit voltage 4.4V.
Sample 1, sample 3, sample 4 and sample 5 test result be shown in Table 2:
Table 2
Under the conditions of identical voltage design, as shown in Table 2 the battery high-temperature capacity retention ratio of sample 1, recovery rate and produce gas Degree is better than the high-temperature behavior of sample 3, sample 4 and sample 5, illustrates using metatitanic acid made from nickel cobalt manganese monocrystalline ternary material The high-temperature behavior of lithium battery is better than lithium titanate battery made from nickel cobalt manganese polycrystalline ternary material, becomes also superior to element group Li0.95Mg0.1Ni0.5Co0.2Mn0.2Ti0.1O2·nAl2O3, wherein x, the value of y, z do not meet the following conditions simultaneously: 0 < x < 0.05,0 < y≤0.33, the lithium titanate battery of the nickel cobalt manganese monocrystalline ternary material of 0 < z≤0.05.
3, cycle performance
Cycle performance test is carried out to sample 1, sample 3, sample 4 and sample 5: pressing full battery upper limit voltage 2.85V, phase The positive upper limit voltage answered is that 4.4V carries out cycle performance test, and test result is shown in Fig. 1.
As shown in Figure 1, under the conditions of identical voltage design, 1.5C/3C under the lithium titanate battery room temperature that embodiment 1 is prepared Capacity retention ratio is better than the lithium titanate battery that comparative example 2, comparative example 3 and comparative example 4 are prepared.As it can be seen that joining in each technique In the case where as counting all, it is better than using the cycle performance of lithium titanate battery made from nickel cobalt manganese monocrystalline ternary battery material and is adopted The lithium titanate battery made from nickel cobalt manganese polycrystalline ternary material.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (10)

1. a kind of positive plate, which is characterized in that including plus plate current-collecting body and the coating that is located on the plus plate current-collecting body, it is described just The raw material of coating on the collector of pole includes outer cladding Al2O3Nickel cobalt manganese monocrystalline ternary material, conductive carbon and adhesive, institute State outer cladding Al2O3Nickel cobalt manganese monocrystalline ternary material, the conductive carbon and the adhesive weight ratio be (95~98): (1~4): (1~3)；
The outer cladding Al2O3Nickel cobalt manganese monocrystalline ternary material be solid nutty structure, element group become Li1.05- xMgxNi1-2y-zCoyMnyTizO2·nAl2O3, wherein 0 < x < 0.05,0 < y≤0.33,0 < z≤0.05.
2. positive plate according to claim 1, which is characterized in that the outer cladding Al2O3Nickel cobalt manganese monocrystalline ternary material The weight ratio of material, the conductive carbon and the adhesive is 96:2:2.
3. a kind of preparation method of positive plate of any of claims 1 or 2, which comprises the following steps:
By the outer cladding Al2O3Nickel cobalt manganese monocrystalline ternary material, the conductive carbon and the adhesive mixing, be added it is molten Agent is sufficiently stirred, and positive coating paste is obtained；
The positive coating paste is coated on the plus plate current-collecting body, is dried, positive plate is obtained after cold pressing.
4. the preparation method of positive plate according to claim 3, which is characterized in that the solvent is water or N- methyl pyrrole Pyrrolidone, and the mass fraction of solvent is 40%~60% in the positive coating paste.
5. the preparation method of positive plate according to claim 4, which is characterized in that the surface density of the coating is 100mg/ 1000mm2~300mg/1000mm2, the compacted density of the cold pressing is 3.35g/cm3~3.55g/cm3。
6. according to the preparation method of the described in any item positive plates of claim 3~5, which is characterized in that the temperature of the drying It is 75 DEG C~85 DEG C.
7. a kind of lithium titanate battery, which is characterized in that including negative electrode tab and positive plate as claimed in claim 1 or 2 or root The positive plate being prepared according to the preparation method of the described in any item positive plates of claim 3~6.
8. lithium titanate battery according to claim 7, which is characterized in that the negative electrode tab includes negative current collector and institute State the coating on negative current collector；
The raw material of coating on the negative current collector includes lithium titanate, conductive carbon and adhesive, and the lithium titanate described is led The weight ratio of electrical carbon and the adhesive is (91~96): (1~4): (1~3).
9. a kind of preparation method of lithium titanate battery described in claim 7 or 8, which comprises the steps of:
The negative electrode tab is prepared, and the positive plate and the negative electrode tab are assembled into lithium titanate battery；
It is described prepare the negative electrode tab the following steps are included:
The lithium titanate, the conductive carbon and the adhesive are mixed, and solvent is added, is sufficiently stirred, cathode painting is obtained Layer slurry；
The cathode coating paste is coated on the negative current collector, after be dried, be cold-pressed, obtain the negative electrode tab.
10. the preparation method of lithium titanate battery according to claim 9, which is characterized in that the solvent is water or N- first Base pyrrolidones, the content of solvent is 40%~60% in the cathode coating paste；And/or
The surface density of the coating is 100mg/1000mm2~200mg/1000mm2, the compacted density of the cold pressing is 1.60g/ cm3~1.90g/cm3。
CN201811547862.0A 2018-12-18 2018-12-18 Positive plate, lithium titanate battery and preparation method thereof Pending CN109698334A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110380022A (en) * 2019-06-26 2019-10-25 荆门市格林美新材料有限公司 A kind of high voltage monocrystalline nickel-cobalt-manganternary ternary anode material and preparation method
CN111129447A (en) * 2019-10-31 2020-05-08 浙江锋锂新能源科技有限公司 Ternary positive electrode material for long-cycle-life lithium storage battery and preparation method thereof
CN111403738A (en) * 2020-03-19 2020-07-10 湖北容百锂电材料有限公司 Positive electrode active material of battery cell, high-voltage high-rate battery cell and manufacturing method of battery cell
WO2021023137A1 (en) * 2019-08-08 2021-02-11 宁德时代新能源科技股份有限公司 Lithium-ion battery and device
CN112993242A (en) * 2021-05-11 2021-06-18 蜂巢能源科技有限公司 Nickel-cobalt-manganese positive electrode material and recovery method of waste nickel-cobalt-manganese positive electrode material

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110380022A (en) * 2019-06-26 2019-10-25 荆门市格林美新材料有限公司 A kind of high voltage monocrystalline nickel-cobalt-manganternary ternary anode material and preparation method
CN110380022B (en) * 2019-06-26 2022-06-10 荆门市格林美新材料有限公司 High-voltage single-crystal nickel-cobalt-manganese ternary positive electrode material and preparation method thereof
WO2021023137A1 (en) * 2019-08-08 2021-02-11 宁德时代新能源科技股份有限公司 Lithium-ion battery and device
CN111129447A (en) * 2019-10-31 2020-05-08 浙江锋锂新能源科技有限公司 Ternary positive electrode material for long-cycle-life lithium storage battery and preparation method thereof
CN111403738A (en) * 2020-03-19 2020-07-10 湖北容百锂电材料有限公司 Positive electrode active material of battery cell, high-voltage high-rate battery cell and manufacturing method of battery cell
CN112993242A (en) * 2021-05-11 2021-06-18 蜂巢能源科技有限公司 Nickel-cobalt-manganese positive electrode material and recovery method of waste nickel-cobalt-manganese positive electrode material
CN112993242B (en) * 2021-05-11 2021-10-12 蜂巢能源科技有限公司 Nickel-cobalt-manganese positive electrode material and recovery method of waste nickel-cobalt-manganese positive electrode material

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