CN106784796A - A kind of high temperature ternary material electrokinetic cell and preparation method thereof - Google Patents

A kind of high temperature ternary material electrokinetic cell and preparation method thereof Download PDF

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Publication number
CN106784796A
CN106784796A CN201710044837.XA CN201710044837A CN106784796A CN 106784796 A CN106784796 A CN 106784796A CN 201710044837 A CN201710044837 A CN 201710044837A CN 106784796 A CN106784796 A CN 106784796A
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high temperature
ternary material
electrokinetic cell
carbonate
electrolyte
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Inventor
白思宇
林彭桃君
吴树森
武玉哲
丁蒙蒙
周皖岳
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CNSG ANHUI HONG SIFANG LITHIUM Co Ltd
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CNSG ANHUI HONG SIFANG LITHIUM Co Ltd
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Priority to CN201710044837.XA priority Critical patent/CN106784796A/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
    • H01M4/48—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/61—Types of temperature control
    • H01M10/613—Cooling or keeping cold
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/62—Heating or cooling; Temperature control specially adapted for specific applications
    • H01M10/625—Vehicles
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/653—Means for temperature control structurally associated with the cells characterised by electrically insulating or thermally conductive materials
    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/147—Lids or covers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/30—Arrangements for facilitating escape of gases
    • H01M50/394—Gas-pervious parts or elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/004—Three solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention relates to ternary material power battery technology field, a kind of high temperature ternary material electrokinetic cell, including positive pole, barrier film, negative pole, electrolyte, cover plate and shell are specifically provided, the active material of the positive pole is nickel cobalt manganese 1：1：1 type tertiary cathode material；Plus plate current-collecting body is utter misery aluminium foil；Barrier film is coated separator, and diaphragm matrix is polypropylene, and coating is ceramics；Negative pole is natural flaky graphite powder；Electrolyte includes organic solvent and additive, the organic solvent is by mass percentage the mixed solution of 30 ~ 35% ethylene carbonate, 35 ~ 40% methyl ethyl carbonate and 30 ~ 35% diethyl carbonate, additive is the mixed solution of vinylene carbonate, the 1 of 2 ~ 2.5% for accounting for organic solvent gross mass 2 ~ 2.5%, 3 acrylic carbonic acid lactones and 2 ~ 2.5% propylene sulfite；Enclosure is covered with 0.3 ~ 0.5 μm of silica gel.Product of the present invention is tested in high temperature circulation 3000 weeks and the above and passed through；Naked light is not shown in acupuncture during testing, housing does not produce blast in itself, with security higher.

Description

A kind of high temperature ternary material electrokinetic cell and preparation method thereof
Technical field
The invention belongs to ternary material electrokinetic cell field, and in particular to a kind of high temperature ternary material electrokinetic cell and its system Preparation Method.
Background technology
Petroleum resources increasingly depleted, before the arriving of next oil crisis, it is only choosing to greatly develop pure electric automobile. Tool Ministry of Industry and Information statistics, 2015, the cumulative production in pure electric coach market reached 8.8 ten thousand, increases by 584% on a year-on-year basis, compares The amount of having a net increase of of 2014 reaches 7.5 ten thousand；The pure electric coach yield of the first half of the year in 2016, up to more than 30,000, is the two of the same period last year It is many again.Because market is to the course continuation mileage requirement more and more higher of electric motor car, state aid policy is subsidized according to energy density, caused LiFePO4 will slowly withdraw from the market, and ternary lithium-ion-power cell slowly occupies the leading position of electrokinetic cell, but due to The electric automobile (bus) that situations such as ternary lithium-ion-power cell high-temperature battery flatulence, leakage already leads to different model occurs A lot of incidents of spontaneous combustion；To solve the problems, such as electric motor car applied at elevated temperature and security, the present invention provides one kind and is available for safety under high temperature The lithium-ion-power cell that property is used.
The content of the invention
Circulated at 60 DEG C of high temperature present invention aim to address existing ternary lithium ion battery, it may appear that flatulence, capacity A kind of the problems such as conservation rate can only achieve 1500 weeks, there is provided high temperature ternary material power that 3000 weeks can be reached in 60 DEG C of high temperature Battery and preparation method thereof.
The present invention is achieved by the following technical solutions：
A kind of high temperature ternary material electrokinetic cell, including positive pole, barrier film, negative pole, electrolyte, cover plate and shell, it is described
The active material of positive pole is nickel cobalt manganese 1：1：1 type tertiary cathode material；
Plus plate current-collecting body is utter misery aluminium foil；
Barrier film is coated separator, and diaphragm matrix is polypropylene, and coating is ceramics；
Negative pole is natural flaky graphite powder；
Electrolyte includes organic solvent and additive, and the organic solvent is by mass percentage 30~35% carbonic acid The mixed solution of vinyl acetate, 35~40% methyl ethyl carbonate and 30~35% diethyl carbonate, additive is molten to occupy machine The vinylene carbonate of agent gross mass 2~2.5%, 2~2.5% 1,3- acrylic-carbonic acid lactone and 2~2.5% sulfurous The mixed solution of acid propylene ester；
Enclosure is covered with 0.3~0.5 μm of silica gel.
Preferably, the aluminum foil thickness of the utter misery aluminium foil is 10~16 μm, and utter misery thickness is 0.5~2 μm.
Preferably, the thickness of the barrier film is 28~32 μm, and ceramic thickness is 3~6 μm.
Preferably, the organic solvent in the electrolyte is by mass percentage 30% ethylene carbonate, 40% The mixed solution of methyl ethyl carbonate and 30% diethyl carbonate, additive is the carbonic acid Asia second for accounting for organic solvent gross mass 2% Alkene ester, 2% 1,3- acrylic-carbonic acid lactone and 2% propylene sulfite.
Preferably, the shell is aluminum hull.
Preferably, the cover plate is also equipped with safety valve and eduction valve, and eduction valve installation site is led on the inside of Positive Poles The method for crossing ultrasonic bonding welds eduction valve and cover plate, and air guide port is on the cover board by square Positive Poles.Eduction valve inside is Silica gel material, usually in closure state, completely cuts off contact of the inside battery with air；When air pressure inside is excessive, silica gel is opened, Draw off excessive gas and may with a small amount of electrolyte.
The method for preparing the high temperature ternary material electrokinetic cell, comprises the following steps：
1), ternary material is mixed into nmp solvent, conductive agent is added, is disperseed by high speed, be made slurry and be coated in utter misery On aluminium foil, required size pole piece is cut into；
2), negative pole native graphite is mixed into solvent, conductive agent is added, is disperseed by high speed, be made slurry and be coated in collection On fluid, required size pole piece is cut into；
3) positive/negative plate is superimposed by ceramic diaphragm, battery core is made；
4), battery core is loaded in shell, electrolyte is injected, then by 45~55 DEG C of standings of high temperature, then vacuum chemical conversion, is changed Cheng Houzai is aging by 45~55 DEG C；
5) partial volume again after, aging, chemical conversion battery makes.
Preferably, step 3) battery core is superposed to zigzag lamination process.
Preferably, step 4) vacuum of vacuum chemical conversion is -0.06~-0.09kpa.
The beneficial effects of the present invention are：
Positive pole uses 111 type nickel-cobalt-manganese ternary materials, and, with respect to 523 types and 622 types, its stability is more for 111 type nickel cobalt manganeses Good, even if under 4.5V charging voltages, material need not be modified still and can have good stability, and under this condition, The gram volume of 111 types can exceed 190mAH/g.
Negative pole uses squamous native graphite, and from microstructure, native graphite is layer structure, in its SEM profile The layer structure of crystalline flake graphite is remained, wherein with the presence of a large amount of spaces, being more convenient inlaying for lithium ion.Its advantage has specific surface Product is small, and crystal structure is complete, puts a platform stable, and head fills efficiency high, and capacity is larger, closer to the theoretical gram volume of graphite. Here it is more to value its heat conductivility using native graphite.
The preparation method of the multiplex polyethylene+ceramic coating of wet method barrier film of existing market, ceramic coating main component is three Al 2 O.When moisture is entered in battery, the hydrofluoric acid that moisture is generated with electrolyte reaction, is a kind of labile acid thing Matter.Using painting ceramic diaphragm, the alundum (Al2O3) of membrane surface can neutralize the hydrofluoric acid of generation, reduce the danger of inside battery It is dangerous.Wet method film is compared compared with film by dry method in itself, with pore-size distribution evenly, and more excellent every tensile strength.It is existing The barrier film that our company is 28~32 μm using matrix thickness, ceramic thickness is 3~6 μm compared with conventional membrane (matrix thickness be 12~ 22 μm) to compare, closed pore temperature is lower, and when temperature reaches 130 DEG C, the hole in barrier film can be closed automatically, forms battery Open circuit, prevents battery from working at a higher temperature.Diaphragm matrix uses polypropylene, increases biaxial tension and shrinkage, adopts Crystal transition technique is used, then with upper ceramic layer, increases the pick up of barrier film, it is ensured that in the case of a high temperature, the liquid storage rate of electrolyte.
Electrolyte is protected using the mixed solution of boiling point ethylene carbonate, methyl ethyl carbonate and diethyl carbonate higher Electrolyte is not easy evaporation under card high temperature, and additive uses vinylene carbonate, 1,3- acrylic-carbonic acid lactone and sulfurous acid third The mixed solution of alkene ester, is prevented from coming off for graphite cathode, and electrolyte can pass freely through this structure, it is ensured that SEI at high temperature The formation of film is more stablized.
Plus plate current-collecting body uses utter misery aluminium foil, increases the conduction of collector, it is ensured that the radiating effect of collector.
When battery normal circulation works, the SEI films that are formed first of chemical conversion are destroyed, the organic solvent in electrolyte with There is charged reaction in negative pole, repair the SEI films on its surface, can again discharge gas.If battery is a complete air-tight state, The excessive gas of generation can cause battery bulging, so existing improvement project is one eduction valve of installation at cover plate, when generation gas Body is more, inside and outside pressure difference away from it is excessive when, discharge produce excessive gas.In such reaction, the gas of generation is hydrocarbon gas, Hydrocarbon gas belong to inflammable class gas, and in the state of excessive concentration, battery is short-circuited, and amount of heat is produced in the short time When, there is the possibility for producing and exploding.So, in this design while eduction valve is installed, increase a safety valve, play one Individual second class protection effect, the security during increase battery use.
Using the aluminum hull for scribbling silica gel, heat conductive silica gel is a kind of to shell with electrical insulation capability, shockproof, waterproof, absorbing Material, increased electronic product safety coefficient in use.Herein with the main reason of this material or its is excellent Thermal conductivity (thermal diffusivity).Thermal conductivity factor [W/ (mk)] after its solidification reaches 1.1~1.5, can in time by inside battery The heat of generation leads outside batteries, ensures an inside and outside good thermal conduction effect, inside battery is unlikely to generation too high Temperature.Stood after fluid injection and use high temperature ageing, it is ensured that when SEI films are preliminarily formed, increase the heat acclimation of SEI films Property.Chemical conversion ensures that during activation SEI films are finer and close using vacuum chemical conversion.
High temperature circulation test result shows that, in high temperature circulation 3000 weeks and the above, capability retention is still for product of the present invention More than 80% can be reached, test passes through；Naked light is not shown in acupuncture during testing, housing does not produce blast in itself, with higher Security.
Brief description of the drawings
Fig. 1 is the high temperature circulation figure of high temperature ternary material electrokinetic cell prepared by the embodiment of the present invention 1.
Specific embodiment
To be best understood from the present invention, with reference to embodiment and accompanying drawing, the invention will be further described, following examples Only it is that the present invention will be described rather than it is limited.
Embodiment 1：
A kind of high temperature ternary electrokinetic cell, just extremely nickel cobalt manganese 1：1：1 type tertiary cathode material, negative pole uses natural squamous Graphite, electrolyte is the mixed solution of 30% ethylene carbonate, 40% methyl ethyl carbonate and 30% diethyl carbonate, is added Plus the vinylene carbonate that agent is 2%, 2% 1,3- acrylic-carbonic acid lactone and 2% sulfurous acid propylene fat；Barrier film is painting Layer barrier film, and diaphragm matrix is polypropylene, 30 μm of thickness；Coating is ceramics；4 μm of thickness；Plus plate current-collecting body：Utter misery aluminium foil, aluminium Paper tinsel thickness is 16 μm, and utter misery thickness is 1 μm；Cover plate installs eduction valve and safety valve；Shell is aluminum hull, and internal silica gel applies thickness and is 0.5μm。
Preparation method is comprised the following steps：
1), ternary material is mixed into nmp solvent, conductive agent is added, is disperseed by high speed, be made slurry and be coated in utter misery On aluminium foil, required size pole piece is cut into；
2), negative pole native graphite is mixed into aqueous solvent, conductive agent is added, is disperseed by high speed, be made slurry and be coated in On collector, required size pole piece is cut into；
3) positive/negative plate is superimposed by ceramic diaphragm, battery core is made；
4), battery core is loaded in shell, electrolyte is injected, then by 50 DEG C of standings of high temperature, then -0.09kpa vacuums Vacuum is melted into, aging by 50 DEG C again after chemical conversion；
5) partial volume again after, aging, chemical conversion battery makes.
Embodiment 2：
A kind of high temperature ternary electrokinetic cell, just extremely nickel cobalt manganese 1：1：1 type tertiary cathode material, negative pole uses natural squamous Graphite, electrolyte is the mixed solution of 35% ethylene carbonate, 35% methyl ethyl carbonate and 30% diethyl carbonate, is added Plus the vinylene carbonate that agent is 2.5%, 2% 1,3- acrylic-carbonic acid lactone and 2% sulfurous acid propylene fat；Barrier film is Coated separator, and diaphragm matrix is polypropylene, 28 μm of thickness；Coating is ceramics；5 μm of thickness；Plus plate current-collecting body：Utter misery aluminium foil, Aluminum foil thickness is 14 μm, and utter misery thickness is 1.5 μm；Cover plate installs eduction valve and safety valve；Shell is aluminum hull, and internal silica gel applies thick It is 0.5 μm.
Preparation method is comprised the following steps：
1), ternary material is mixed into nmp solvent, conductive agent is added, is disperseed by high speed, be made slurry and be coated in utter misery On aluminium foil, required size pole piece is cut into；
2), negative pole native graphite is mixed into aqueous solvent, conductive agent is added, is disperseed by high speed, be made slurry and be coated in On collector, required size pole piece is cut into；
3) positive/negative plate is superimposed by ceramic diaphragm, battery core is made；
4), battery core is loaded in shell, electrolyte is injected, then by 45 DEG C of standings of high temperature, then -0.09kpa vacuums Vacuum is melted into, aging by 45 DEG C again after chemical conversion；
5) partial volume again after, aging, chemical conversion battery makes.
Embodiment 3：
A kind of high temperature ternary electrokinetic cell, just extremely nickel cobalt manganese 1：1：1 type tertiary cathode material, negative pole uses natural squamous Graphite, electrolyte is the mixed solution of 30% ethylene carbonate, 35% methyl ethyl carbonate and 35% diethyl carbonate, is added Plus the vinylene carbonate that agent is 2.5%, 2% 1,3- acrylic-carbonic acid lactone and 2.5% sulfurous acid propylene fat；Barrier film It is coated separator, and diaphragm matrix is polypropylene, 32 μm of thickness；Coating is ceramics；3 μm of thickness；Plus plate current-collecting body：Utter misery aluminium Paper tinsel, aluminum foil thickness is 12 μm, and utter misery thickness is 0.5 μm；Cover plate installs eduction valve and safety valve；Shell is aluminum hull, internal silica gel It is 0.3 μm to apply thickness.
Preparation method is comprised the following steps：
1), ternary material is mixed into nmp solvent, conductive agent is added, is disperseed by high speed, be made slurry and be coated in utter misery On aluminium foil, required size pole piece is cut into；
2), negative pole native graphite is mixed into aqueous solvent, conductive agent is added, is disperseed by high speed, be made slurry and be coated in On collector, required size pole piece is cut into；
3) positive/negative plate is superimposed by ceramic diaphragm, battery core is made；
4), battery core is loaded in shell, electrolyte is injected, then by 55 DEG C of standings of high temperature, then -0.06kpa vacuums Vacuum is melted into, aging by 55 DEG C again after chemical conversion；
5) partial volume again after, aging, chemical conversion battery makes.
Embodiment 4
A kind of high temperature ternary electrokinetic cell, just extremely nickel cobalt manganese 1：1：1 type tertiary cathode material, negative pole uses natural squamous Graphite, electrolyte is the mixed solution of 32% ethylene carbonate, 33% methyl ethyl carbonate and 35% diethyl carbonate, is added Plus the vinylene carbonate that agent is 2%, 2.5% 1,3- acrylic-carbonic acid lactone and 2.5% sulfurous acid propylene fat；Barrier film It is coated separator, and diaphragm matrix is polypropylene, 28 μm of thickness；Coating is ceramics；6 μm of thickness；Plus plate current-collecting body：Utter misery aluminium Paper tinsel, aluminum foil thickness is 10 μm, and utter misery thickness is 2 μm；Cover plate installs eduction valve and safety valve；Shell is aluminum hull, and internal silica gel is applied Thickness is 0.4 μm.
Preparation method is comprised the following steps：
1), ternary material is mixed into nmp solvent, conductive agent is added, is disperseed by high speed, be made slurry and be coated in utter misery On aluminium foil, required size pole piece is cut into；
2), negative pole native graphite is mixed into aqueous solvent, conductive agent is added, is disperseed by high speed, be made slurry and be coated in On collector, required size pole piece is cut into；
3) positive/negative plate is superimposed by ceramic diaphragm, battery core is made；
4), battery core is loaded in shell, electrolyte is injected, then by 50 DEG C of standings of high temperature, then -0.06kpa vacuums Vacuum is melted into, aging by 50 DEG C again after chemical conversion；
5) partial volume again after, aging, chemical conversion battery makes.
Comparative example 1
A kind of high temperature ternary electrokinetic cell, just extremely nickel cobalt manganese 1：1：1 type tertiary cathode material, negative pole uses natural squamous Graphite, electrolyte is the mixed solution of 25% ethylene carbonate, 35% methyl ethyl carbonate and 40% diethyl carbonate, is added Plus the vinylene carbonate that agent is 1.5%, 1.5% 1,3- acrylic-carbonic acid lactone and 1.5% sulfurous acid propylene fat；Every Film polypropylene, 22 μm of thickness, without ceramic coating；Plus plate current-collecting body uses 16 μm of aluminium foil, without utter misery；Cover plate installs safety valve, Eduction valve is not installed；Shell uses aluminum hull, without painting silica gel.
Preparation method is comprised the following steps：
1), ternary material is mixed into nmp solvent, conductive agent is added, is disperseed by high speed, be made slurry and be coated in aluminium foil On, cut into required size pole piece；
2), negative pole native graphite is mixed into aqueous solvent, conductive agent is added, is disperseed by high speed, be made slurry and be coated in On collector, required size pole piece is cut into；
3) positive/negative plate is superimposed by barrier film, battery core is made；
4), battery core is loaded in shell, electrolyte is injected, then normal temperature stands, then is melted into, and normal temperature is aging again after chemical conversion.
5) partial volume again after, aging, chemical conversion battery makes.
Comparative example 2
A kind of high temperature ternary electrokinetic cell, just extremely nickel cobalt manganese 5：2：3 type tertiary cathode materials, negative pole uses natural squamous Graphite, electrolyte is the mixed solution of 40% ethylene carbonate, 30% methyl ethyl carbonate and 30% diethyl carbonate, is added Plus the vinylene carbonate and 2% 1,3- acrylic-carbonic acid lactone that agent is 2.5%；Barrier film is coated separator, and diaphragm matrix It is polypropylene, 30 μm of thickness；Coating is ceramics；4 μm of thickness；Plus plate current-collecting body：Plus plate current-collecting body uses 14 μm of aluminium foil, without painting Charcoal；Cover plate installs eduction valve and safety valve；Shell is aluminum hull, and it is 0.5 μm that internal silica gel applies thickness.
Preparation method is comprised the following steps：
1), ternary material is mixed into nmp solvent, conductive agent is added, is disperseed by high speed, be made slurry and be coated in aluminium foil On, cut into required size pole piece；
2), negative pole native graphite is mixed into aqueous solvent, conductive agent is added, is disperseed by high speed, be made slurry and be coated in On collector, required size pole piece is cut into；
3) positive/negative plate is superimposed by ceramic diaphragm, battery core is made；
4), battery core is loaded in shell, electrolyte is injected, then normal temperature stands, then the chemical conversion of -0.06kpa vacuums vacuum, Normal temperature is aging again after chemical conversion；
5) partial volume again after, aging, chemical conversion battery makes.
Comparative example 3
A kind of high temperature ternary electrokinetic cell, just extremely nickel cobalt manganese 1：1：1 type tertiary cathode material, negative pole uses natural squamous Graphite, electrolyte is the mixed solution of 30% ethylene carbonate, 35% methyl ethyl carbonate and 35% diethyl carbonate, is added Plus the vinylene carbonate that agent is 2.5%；Barrier film polypropylene, 28 μm of thickness, without ceramic coating；Plus plate current-collecting body：Utter misery aluminium foil, Aluminum foil thickness is 12 μm, and utter misery thickness is 0.5 μm；Cover plate installs safety valve, does not install eduction valve；Shell is aluminum hull, internal It is 0.3 μm that silica gel applies thickness.
Preparation method is comprised the following steps：
1), ternary material is mixed into nmp solvent, conductive agent is added, is disperseed by high speed, be made slurry and be coated in utter misery On aluminium foil, required size pole piece is cut into；
2), negative pole native graphite is mixed into aqueous solvent, conductive agent is added, is disperseed by high speed, be made slurry and be coated in On collector, required size pole piece is cut into；
3) positive/negative plate is superimposed by barrier film, battery core is made；
4), battery core is loaded in shell, electrolyte is injected, then by 35 DEG C of standings, then -0.03kpa vacuum vacuum Chemical conversion, it is aging by 35 DEG C again after chemical conversion；
5) partial volume again after, aging, chemical conversion battery makes.
Ternary material electrokinetic cell prepared by embodiment 1-4 and comparative example 1-3 is carried out into high temperature circulation test, test result As shown in table 1：
The ternary material power battery at high temperature loop test result of table 1
As shown in Table 1, the high temperature ternary electrokinetic cell that embodiment 1-4 is prepared in high temperature circulation 3000 weeks and the above, Capability retention remains to reach more than 80%, and test passes through；And the ternary electrokinetic cell that comparative example 1-3 is prepared is in high temperature circulation At 1151~1300 weeks, capability retention is to drop to 80%, and flatulence occurs, and test does not pass through.
Fig. 1 is the high temperature circulation figure of high temperature ternary material electrokinetic cell prepared by the embodiment of the present invention 1, by also can be bright in figure Aobvious to find out, in high temperature circulation more than 3000 weeks, capability retention remained to reach more than 80% battery.
Ternary material electrokinetic cell acupuncture experiment prepared by embodiment 1-4 and comparative example 1-3, as a result shows：The present invention In pin prick test, constant-current charging of battery measures voltage for 3.56V to middle resultant battery to 3.60V after shelving 10min, and acupuncture makes With a diameter of 3.5mm of draw point, insertion speed 100cm/min.Draw point pierce completely after after 2s eduction valve start working, release gas Body；Battery starts bulging after 3s, has slight white cigarette to emerge；Safety valve explosion after 8s, a large amount of white dense smokes of release, whole process is held Continuous 10min or so, period simultaneously has no naked light, and housing does not produce blast in itself；The resultant battery that comparative example is prepared is in acupuncture During experiment, constant-current charging of battery measures voltage for 3.54V to 3.60V after shelving 10min, and acupuncture is a diameter of using draw point 3.5mm, insertion speed 100cm/min.Draw point pierce completely after after 1s battery start bulging；Safety valve explosion after 5s, release is big The white dense smoke of amount；Blast is produced at 7s back shrouds and case weld, there is naked light to produce at breach, with a large amount of dense smokes.Burning is held 3min is continued, sustained release 4min or so whites dense smoke after fray-out of flame.
As can be seen here, the invention provides a kind of ternary electrokinetic cell for being available for and being used safely under high temperature.
The above implementation method is only that the preferred embodiment of the present invention is described, not to model of the invention Enclose and be defined, on the premise of design spirit of the present invention is not departed from, those of ordinary skill in the art are to technical side of the invention Various modifications and improvement that case is made, all should fall into the protection domain of claims of the present invention determination.

Claims (9)

1. a kind of high temperature ternary material electrokinetic cell, including positive pole, barrier film, negative pole, electrolyte, cover plate and shell, its feature exist In：It is described
The active material of positive pole is nickel cobalt manganese 1：1：1 type tertiary cathode material；
Plus plate current-collecting body is utter misery aluminium foil；
Barrier film is coated separator, and diaphragm matrix is polypropylene, and coating is ceramics；
Negative pole is natural flaky graphite powder；
Electrolyte includes organic solvent and additive, and the organic solvent is by mass percentage 30 ~ 35% ethylene carbonate The mixed solution of ester, 35 ~ 40% methyl ethyl carbonate and 30 ~ 35% diethyl carbonate, additive is to account for organic solvent gross mass 2 The mixing of ~ 2.5% vinylene carbonate, 2 ~ 2.5% 1,3- acrylic-carbonic acid lactone and 2 ~ 2.5% propylene sulfite is molten Liquid；
Enclosure is covered with 0.3 ~ 0.5 μm of silica gel.
2. a kind of high temperature ternary material electrokinetic cell according to claim 1, it is characterised in that：The aluminium of the utter misery aluminium foil Paper tinsel thickness is 10 ~ 16 μm, and utter misery thickness is 0.5 ~ 2 μm.
3. a kind of high temperature ternary material electrokinetic cell according to claim 1, it is characterised in that：The thickness of the diaphragm matrix It is 28 ~ 32 μm to spend, and ceramic thickness is 3 ~ 6 μm.
4. a kind of high temperature ternary material electrokinetic cell according to claim 1, it is characterised in that：Having in the electrolyte Machine solvent is by mass percentage the mixing of 30% ethylene carbonate, 40% methyl ethyl carbonate and 30% diethyl carbonate Solution, additive is the vinylene carbonate for accounting for organic solvent gross mass 2%, 2% 1,3- acrylic-carbonic acid lactone and 2% Asia Sulfuric acid propylene.
5. a kind of high temperature ternary material electrokinetic cell according to claim 1, it is characterised in that：The shell is aluminum hull.
6. a kind of high temperature ternary material electrokinetic cell according to claim 1, it is characterised in that：The cover plate is also equipped with Safety valve and eduction valve.
7. prepare claim any one of 1-5 described in high temperature ternary material electrokinetic cell method, it is characterised in that including with Lower step：
1）, ternary material is mixed into nmp solvent, add conductive agent, disperseed by high speed, be made slurry and be coated in utter misery aluminium foil On, cut into required size pole piece；
2）, negative pole native graphite is mixed into solvent, add conductive agent, disperseed by high speed, be made slurry and be coated in collector On, cut into required size pole piece；
3）, by ceramic diaphragm positive/negative plate is superimposed, be made battery core；
4）, battery core loaded in shell, electrolyte is injected, then by 45 ~ 55 DEG C of high temperature standing, then vacuum chemical conversion, after chemical conversion It is aging by 45 ~ 55 DEG C again；
5) partial volume again after, aging, chemical conversion battery makes.
8. the preparation method of high temperature lithium-ion-power cell according to claim 7, it is characterised in that：Step 3）The electricity Core is superposed to zigzag lamination process.
9. the preparation method of high temperature lithium-ion-power cell according to claim 6, it is characterised in that：Step 4）It is described true Cavitation into vacuum be -0.06 ~ -0.09kpa.
CN201710044837.XA 2017-01-20 2017-01-20 A kind of high temperature ternary material electrokinetic cell and preparation method thereof Pending CN106784796A (en)

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CN109638181A (en) * 2018-11-14 2019-04-16 庐江力翔电池科技有限责任公司 A kind of VDA ternary battery square structure top cover
CN113193171A (en) * 2021-05-06 2021-07-30 合肥国轩高科动力能源有限公司 High-safety ternary lithium ion battery and preparation method thereof
CN113258128A (en) * 2021-06-28 2021-08-13 珠海冠宇电池股份有限公司 Lithium ion battery and electronic device

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CN104466304A (en) * 2014-11-13 2015-03-25 深圳鸿源博得新能源技术发展有限公司 Battery pack and method for improving thermal field consistency of battery pack
CN104795542A (en) * 2015-01-06 2015-07-22 宁波南车新能源科技有限公司 A plasma injection preparing method of a nanometer lithium ion composite anode
CN104810552A (en) * 2014-07-16 2015-07-29 万向A一二三***有限公司 High temperature electrolyte for soft packing lithium-ion battery

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CN104810552A (en) * 2014-07-16 2015-07-29 万向A一二三***有限公司 High temperature electrolyte for soft packing lithium-ion battery
CN104466304A (en) * 2014-11-13 2015-03-25 深圳鸿源博得新能源技术发展有限公司 Battery pack and method for improving thermal field consistency of battery pack
CN104795542A (en) * 2015-01-06 2015-07-22 宁波南车新能源科技有限公司 A plasma injection preparing method of a nanometer lithium ion composite anode

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109638181A (en) * 2018-11-14 2019-04-16 庐江力翔电池科技有限责任公司 A kind of VDA ternary battery square structure top cover
CN113193171A (en) * 2021-05-06 2021-07-30 合肥国轩高科动力能源有限公司 High-safety ternary lithium ion battery and preparation method thereof
CN113258128A (en) * 2021-06-28 2021-08-13 珠海冠宇电池股份有限公司 Lithium ion battery and electronic device

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