CN110400961A - High temperature resistant type lithium ion battery and preparation method thereof - Google Patents
High temperature resistant type lithium ion battery and preparation method thereof Download PDFInfo
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- CN110400961A CN110400961A CN201810379730.5A CN201810379730A CN110400961A CN 110400961 A CN110400961 A CN 110400961A CN 201810379730 A CN201810379730 A CN 201810379730A CN 110400961 A CN110400961 A CN 110400961A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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 invention discloses a kind of high temperature resistant type lithium ion batteries comprising shell is provided with electrolyte and battery core in the shell, and the electrolyte includes electrolyte, organic solvent and nitrile additive.The invention also discloses the preparation methods of above-mentioned high temperature resistant type lithium ion battery.A kind of high temperature resistant type lithium ion battery of the present invention and preparation method thereof, by the way that nitrile additive is added into electrolyte, is able to suppress the flatulence of lithium titanate, improves the high temperature resistance of battery；By the way that battery core is designed as the excessive form of positive electrode capacity, oxygenolysis of the electrolyte under high potential can be alleviated, inhibit to produce gas, further increase the chemical property of battery.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of high temperature resistant type lithium ion battery and its preparation side
Method.
Background technique
Lithium ion battery is big with its specific energy, operating voltage is high, self-discharge rate is small, the advantages such as small in size, light-weight, from it
Since birth, revolutionary variation just has been brought to energy storage field, is widely used in various portable electronic devices and electronic
In automobile；However as the improvement of people's living standards, more stringent requirements are proposed to lithium ion battery for higher user experience:
Quality is lighter, uses time longer, high temperature resistant etc.；New more excellent performance of electrode is had to look for solve the above-mentioned problems
Material.
Spinel type lithium titanate Li4Ti5O12Because having zero strain, three-dimensional lithium ion diffusion admittance, desolvation can be low
Feature as the lithium ion battery of negative electrode material there is excellent security performance, excellent high rate performance, overlength to recycle using it
Service life, superelevation low temperature charging performance the advantages that, but its platform voltage is up to 1.5V vs.Li+/Li, therefore uses conventional three-way
Material is that the lithium titanate battery energy density of positive electrode is lower；On the other hand, Li4Ti5O12The interface pair occurred with electrolyte
Reaction is easy to cause the generation of flatulence, and as the temperature rises, interface side reaction accelerates, and high temperature flatulence is more obvious, and then deteriorates
The high temperature storage and high temperature cyclic performance of battery, these limit the large-scale application of lithium titanate anode material.
Summary of the invention
The object of the present invention is to provide a kind of high temperature resistant type lithium ion batteries and preparation method thereof, can effectively solve the problem that and adopt
The problem of lithium ion battery for using lithium titanate as negative electrode material is easy to happen flatulence and then influences battery chemistries performance.
The first technical solution of the present invention are as follows:
A kind of high temperature resistant type lithium ion battery comprising shell is provided with electrolyte and battery core, the electricity in the shell
Solving liquid includes electrolyte, organic solvent and nitrile additive.
The characteristics of the first technical solution of the invention, also resides in:
The battery core includes positive plate, negative electrode tab and the diaphragm for separating positive plate and negative electrode tab；The positive plate packet
The anode sizing agent for including carbon-coated aluminum foils plus plate current-collecting body and being coated on, the anode sizing agent include positive active material nickel mangaic acid
Lithium, positive conductive agent and positive electrode binder；The negative electrode tab includes carbon-coated aluminum foils negative current collector and the cathode that is coated on
Slurry, the negative electrode slurry include negative electrode active material lithium titanate, cathode conductive agent and negative electrode binder.
The positive conductive agent is made of at least one of superconduction graphite, acetylene black, graphene, carbon nanotube；It is described
Cathode conductive agent is made of at least one of superconduction graphite, acetylene black, graphene, carbon nanotube；The positive electrode binder is
The mixture or Kynoar of sodium carboxymethylcellulose and butadiene-styrene rubber；The negative electrode binder is Kynoar.
The electrolyte is lithium hexafluoro phosphate, difluorine oxalic acid boracic acid lithium, at least one in two lithium trifluoromethanesulp,onylimides
Kind；The organic solvent is ethylene carbonate, in fluorinated ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate
At least one；The nitrile additive is 1,3,6 hexane, three nitrile, succinonitrile, adiponitrile, methoxyacetyl nitrile, five fluorine ethoxies
At least one of three phosphonitrile of basic ring.
The diaphragm is PP type diaphragm or polyvinylidene fluoride alkenes diaphragm.
The PP type diaphragm is that single layer PP diaphragm or bilayer PP/PE diaphragm or three layers of PP/PE/PP diaphragm or ceramics apply
Layer one of PP diaphragm or PVDF coating PP diaphragm；The polyvinylidene fluoride alkenes diaphragm is that PVDF diaphragm or cellulose are compound
PVDF diaphragm.
The shell is shell with square aluminum or cylinder aluminum hull or one of cylindrical steel shell or aluminum plastic film.
Second of technical solution of the present invention are as follows:
A kind of preparation method of above-mentioned high temperature resistant type lithium ion battery, specifically includes the following steps:
Step 1, preparation battery core；
Electrolyte, organic solvent and nitrile additive are uniformly mixed obtained electrolyte by step 2；
Battery core prepared by the step 1 is encased in shell by step 3, and the step 2 is then injected into shell and is made
Electrolyte and sealing, finally at room temperature carry out preliminary filling chemical conversion, obtain high temperature resistant type lithium ion battery.
The characteristics of second of technical solution of the invention, also resides in:
In the step 1, the preparation method of the battery core specifically includes the following steps:
Step 1.1, according to mass percent 90-96:2-5:2-5 by nickel ion doped, positive conductive agent and positive electrode binder
It is uniformly mixed, obtains the first mixture；The positive electrode binder is the mixture or poly- of sodium carboxymethylcellulose and butadiene-styrene rubber
Vinylidene；
Step 1.2, when the positive electrode binder is the mixture of sodium carboxymethylcellulose and butadiene-styrene rubber, to the step
Deionized water is added in rapid 1.1 the first mixtures obtained；When the positive electrode binder is Kynoar, Xiang Suoshu step
N-Methyl pyrrolidone is added in 1.1 the first mixtures obtained；Then viscosity is adjusted to 6000-8000cP, and is adjusted and contained admittedly
Anode sizing agent is made to 50-60% in amount；
Step 1.3, by anode sizing agent made from the step 1.2 be coated on carbon-coated aluminum foils plus plate current-collecting body on after through overdrying
Positive plate is made in dry, roll-in and cutting；
Step 1.4 mixes lithium titanate, cathode conductive agent and negative electrode binder according to mass percent 85-92:4-8:4-7
It closes uniformly, obtains the second mixture；
N-Methyl pyrrolidone is added in the second mixture that step 1.5, Xiang Suoshu step 1.4 obtain, then adjusts viscous
It spends to 8000-10000cP, and adjusts solid content to 40-50%, negative electrode slurry is made；
Step 1.6, by negative electrode slurry made from the step 1.5 be coated on carbon-coated aluminum foils negative current collector on after through overdrying
Negative electrode tab is made after dry, roll-in and cutting；
Step 1.7, by negative electrode tab made from positive plate made from the step 1.3 and the step 1.6 according to diaphragm, just
Battery core is made in the sequence assembling of pole piece, diaphragm, negative electrode tab, makes the ratio N/P 0.5- of the capacity of negative plates and positive electrode capacity
0.99。
In the step 2, the hybird environment of the electrolyte, organic solvent and nitrile additive is less than for relative humidity
1% inert gas environment, the concentration of the electrolyte are 1-2mol/L, and the volume ratio that the nitrile additive is added is 1-
5%.
In the step 3, the fluid injection coefficient of the injection electrolyte is 2-10g/Ah.
In the step 3, the specific steps of the preliminary filling chemical conversion are as follows:
Step 3.1, with 0.01C electric current constant-current charge to 3.5V, then with 0.01C electric current constant-current discharge to 1.5V；
Step 3.2, with 0.1C electric current constant-current charge to 3.5V, then with 0.1C electric current constant-current discharge to 1.5V；
Step 3.3, with 0.5C electric current constant-current charge to 3.5V, then with 0.5C electric current constant-current discharge to 1.5V；
Step 3.4, with 1C electric current constant-current charge to 3.5V, then with 1C electric current constant-current discharge to 3.0V.
Compared with prior art, a kind of high temperature resistant type lithium ion battery of the present invention and preparation method thereof, by electrolyte
Middle addition nitrile additive, is able to suppress the flatulence of lithium titanate, improves the high temperature resistance of battery；By the way that battery core design is positive
Capacity excessive form in pole can alleviate oxygenolysis of the electrolyte under high potential, inhibit to produce gas, further increase battery
Chemical property.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of high temperature resistant type lithium ion battery of the embodiment of the present invention；
Fig. 2 is 55 DEG C of 2C of the lithium ion battery and comparative example of nickel ion doped and lithium titanate made from the embodiment of the present invention 1
Charge and discharge cycles capacity retention ratio correlation curve.
In figure, 1. shells, 2. positive plates, 3. negative electrode tabs, 4. diaphragms, 5. anode ears, 6. negative electrode lugs.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
The embodiment of the present invention provides a kind of high temperature resistant type lithium ion battery comprising shell 1 is provided in the shell 1
Electrolyte and battery core, the battery core include positive plate 2, negative electrode tab 3 and the diaphragm 4 for separating positive plate 2 Yu negative electrode tab 3, just
It is provided with anode ear 5 on pole piece 2, negative electrode lug 6 is provided in negative electrode tab 3；The positive plate 2 includes carbon-coated aluminum foils plus plate current-collecting body
With the anode sizing agent being coated on, the negative electrode tab 3 includes carbon-coated aluminum foils negative current collector and the cathode being coated on slurry
Material；The electrolyte includes electrolyte, organic solvent and nitrile additive.
The anode sizing agent includes positive active material nickel ion doped, positive conductive agent and positive electrode binder；The cathode
Slurry includes negative electrode active material lithium titanate, cathode conductive agent and negative electrode binder.
The positive conductive agent is made of at least one of superconduction graphite, acetylene black, graphene, carbon nanotube；It is described
Cathode conductive agent is made of at least one of superconduction graphite, acetylene black, graphene, carbon nanotube；The positive electrode binder is
The mixture or Kynoar of sodium carboxymethylcellulose and butadiene-styrene rubber；The negative electrode binder is Kynoar.
The electrolyte is lithium hexafluoro phosphate, difluorine oxalic acid boracic acid lithium, at least one in two lithium trifluoromethanesulp,onylimides
Kind；The organic solvent is ethylene carbonate, in fluorinated ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate
At least one；The nitrile additive is 1,3,6 hexane, three nitrile, succinonitrile, adiponitrile, methoxyacetyl nitrile, five fluorine ethoxies
At least one of three phosphonitrile of basic ring.
The diaphragm 4 is PP type diaphragm or polyvinylidene fluoride alkenes diaphragm.
The PP type diaphragm is that single layer PP diaphragm or bilayer PP/PE diaphragm or three layers of PP/PE/PP diaphragm or ceramics apply
Layer one of PP diaphragm or PVDF coating PP diaphragm；The polyvinylidene fluoride alkenes diaphragm is that PVDF diaphragm or cellulose are compound
PVDF diaphragm.
The shell 1 is shell with square aluminum or cylinder aluminum hull or one of cylindrical steel shell or aluminum plastic film.
The embodiment of the present invention also provides a kind of preparation method of above-mentioned high temperature resistant type lithium ion battery, specifically includes following step
It is rapid:
Step 1 mixes nickel ion doped, positive conductive agent and positive electrode binder according to mass percent 90-96:2-5:2-5
It closes uniformly, obtains the first mixture；The positive electrode binder is the mixture or poly- inclined of sodium carboxymethylcellulose and butadiene-styrene rubber
Vinyl fluoride；When positive electrode binder is the mixture of sodium carboxymethylcellulose and butadiene-styrene rubber, add in the first mixture of Xiang Suoshu
Enter deionized water；When positive electrode binder is Kynoar, N-Methyl pyrrolidone is added in the first mixture of Xiang Suoshu；So
Viscosity is adjusted afterwards to 6000-8000cP, and adjusts solid content to 50-60%, obtains anode sizing agent；Anode sizing agent is coated on
Positive plate is made by drying, roll-in and cutting after on carbon-coated aluminum foils plus plate current-collecting body；
Step 2 mixes lithium titanate, cathode conductive agent and negative electrode binder according to mass percent 85-92:4-8:4-7
Uniformly, the second mixture is obtained；N-Methyl pyrrolidone is added into second mixture, then adjusts viscosity to 8000-
10000cP, and solid content is adjusted to 40-50%, obtain negative electrode slurry；Negative electrode slurry is coated on carbon-coated aluminum foils negative pole currect collecting
Negative electrode tab is made after drying, roll-in and cutting after on body；
Step 3, by negative electrode tab made from positive plate made from the step 1 and the step 2 according to diaphragm, positive plate,
Battery core is made in the sequence assembling of diaphragm, negative electrode tab, makes the ratio N/P 0.5-0.99 of capacity of negative plates and positive electrode capacity；
Electrolyte, organic solvent and nitrile additive are uniformly mixed obtained electrolyte by step 4；It is the electrolyte, organic
The hybird environment of solvent and nitrile additive is inert gas environment of the relative humidity less than 1%, and the concentration of the electrolyte is
1-2mol/L, the volume ratio that the nitrile additive is added are 1-5%；
Battery core made from the step 3 is encased in shell by step 5, then the electricity made from injection step 4 into shell
Solution liquid simultaneously seals, and finally carries out preliminary filling chemical conversion at room temperature, obtains high temperature resistant type lithium ion battery；The injection electrolyte
Fluid injection coefficient is 2-10g/Ah；
The specific steps of the preliminary filling chemical conversion are as follows:
Step 501, with 0.01C electric current constant-current charge to 3.5V, then with 0.01C electric current constant-current discharge to 1.5V；
Step 502, with 0.1C electric current constant-current charge to 3.5V, then with 0.1C electric current constant-current discharge to 1.5V；
Step 503, with 0.5C electric current constant-current charge to 3.5V, then with 0.5C electric current constant-current discharge to 1.5V；
Step 504, with 1C electric current constant-current charge to 3.5V, then with 1C electric current constant-current discharge to 3.0V.
Embodiment 1:
Step 1, according to mass percent 90:5:5 by nickel ion doped, positive conductive agent acetylene black and positive electrode binder carboxylic first
Base sodium cellulosate is uniformly mixed with the mixture of butadiene-styrene rubber, then addition deionized water adjusting viscosity to 6000cP, and is adjusted
Solid content obtains anode sizing agent to 60%；By drying, roll-in after anode sizing agent is coated on carbon-coated aluminum foils plus plate current-collecting body
And it cuts and positive plate is made；
Step 2 gathers lithium titanate, cathode conductive agent carbon nanotube and negative electrode binder partially according to mass percent 85:8:7
Vinyl fluoride is uniformly mixed, and adds N-Methyl pyrrolidone, then adjusts viscosity to 8000cP, and adjusts solid content to 50%,
Obtain negative electrode slurry；It is made after drying, roll-in and cutting after negative electrode slurry is coated on carbon-coated aluminum foils negative current collector
Negative electrode tab；
Step 3, using ceramic coating PP diaphragm, by cathode made from positive plate made from the step 1 and the step 2
Piece assembles according to the sequence of diaphragm, positive plate, diaphragm, negative electrode tab and battery core is made, and makes the ratio N/P of capacity of negative plates and positive electrode capacity
It is 0.5；
Step 4, be by concentration two lithium trifluoromethanesulp,onylimide of electrolyte of 2mol/L, organic solvent ethylene carbonate,
Five fluorine ethoxy basic ring of nitrile additive, three phosphonitrile, the methoxyacetyl nitrile of diethyl carbonate, methyl ethyl carbonate and volume ratio for 5%
Obtained electrolyte is uniformly mixed under inert gas environment of the relative humidity less than 1%；
Battery core made from the step 3 is encased in shell by step 5, then according to fluid injection coefficient 5g/Ah into shell
Electrolyte 100g made from injection step 4 is simultaneously sealed, and finally carries out preliminary filling chemical conversion, the specific steps of preliminary filling chemical conversion at room temperature
Are as follows:
Step 501, with 0.01C electric current constant-current charge to 3.5V, then with 0.01C electric current constant-current discharge to 1.5V；
Step 502, with 0.1C electric current constant-current charge to 3.5V, then with 0.1C electric current constant-current discharge to 1.5V；
Step 503, with 0.5C electric current constant-current charge to 3.5V, then with 0.5C electric current constant-current discharge to 1.5V；
Step 504, with 1C electric current constant-current charge to 3.5V, then with 1C electric current constant-current discharge to 3.0V.
Embodiment 2:
Step 1, according to mass percent 96:2:2 by nickel ion doped, positive conductive agent superconduction graphite and positive electrode binder carboxylic
Sodium carboxymethylcellulose pyce is uniformly mixed with the mixture of butadiene-styrene rubber, then addition deionized water adjusting viscosity to 8000cP, and is adjusted
Solid content is saved to 50%, obtains anode sizing agent；By drying, roller after anode sizing agent is coated on carbon-coated aluminum foils plus plate current-collecting body
Positive plate is made in pressure and cutting；
Lithium titanate, cathode conductive agent acetylene black and negative electrode binder are gathered inclined fluorine according to mass percent 92:4:4 by step 2
Ethylene is uniformly mixed, and adds N-Methyl pyrrolidone, then adjusting viscosity to 10000cP, and adjusts solid content to 40%, is obtained
To negative electrode slurry；It is made negative after drying, roll-in and cutting after negative electrode slurry is coated on carbon-coated aluminum foils negative current collector
Pole piece；
Step 3, using single layer PP diaphragm, positive plate made from the step 1 and negative electrode tab made from the step 2 are pressed
Obtained battery core is assembled according to the sequence of diaphragm, positive plate, diaphragm, negative electrode tab, makes the ratio N/P of capacity of negative plates and positive electrode capacity
0.99；
Step 4, the electrolyte lithium hexafluoro phosphate, organic solvent fluorinated ethylene carbonate and the volume ratio that are 1mol/L by concentration
For 1% 1,3,6 hexane of nitrile additive, three nitrile, succinonitrile mixes under inert gas environment of the relative humidity less than 1%
Even obtained electrolyte；
Battery core made from the step 3 is encased in shell by step 5, then according to fluid injection coefficient 2g/Ah into shell
Electrolyte 100g made from injection step 4 is simultaneously sealed, and finally carries out preliminary filling chemical conversion, the specific steps of preliminary filling chemical conversion at room temperature
Are as follows:
Step 501, with 0.01C electric current constant-current charge to 3.5V, then with 0.01C electric current constant-current discharge to 1.5V；
Step 502, with 0.1C electric current constant-current charge to 3.5V, then with 0.1C electric current constant-current discharge to 1.5V；
Step 503, with 0.5C electric current constant-current charge to 3.5V, then with 0.5C electric current constant-current discharge to 1.5V；
Step 504, with 1C electric current constant-current charge to 3.5V, then with 1C electric current constant-current discharge to 3.0V.
Embodiment 3:
Step 1, according to mass percent 92:3:3 by nickel ion doped, positive conductive agent graphene and positive electrode binder carboxylic first
Base sodium cellulosate is uniformly mixed with the mixture of butadiene-styrene rubber, then addition deionized water adjusting viscosity to 7000cP, and is adjusted
Solid content obtains anode sizing agent to 55%；By drying, roll-in after anode sizing agent is coated on carbon-coated aluminum foils plus plate current-collecting body
And it cuts and positive plate is made；
Step 2 gathers lithium titanate, cathode conductive agent superconduction graphite and negative electrode binder partially according to mass percent 90:6:6
Vinyl fluoride is uniformly mixed, and adds N-Methyl pyrrolidone, then adjusts viscosity to 9000cP, and adjusts solid content to 45%,
Obtain negative electrode slurry；It is made after drying, roll-in and cutting after negative electrode slurry is coated on carbon-coated aluminum foils negative current collector
Negative electrode tab；
Step 3, using the double-deck PP/PE diaphragm, by cathode made from positive plate made from the step 1 and the step 2
Piece assembles according to the sequence of diaphragm, positive plate, diaphragm, negative electrode tab and battery core is made, and makes the ratio N/P of capacity of negative plates and positive electrode capacity
It is 0.6；
Step 4, the electrolyte difluorine oxalic acid boracic acid lithium, the organic solvent ethylene carbonate, fluoro that are 1.5mol/L by concentration
Nitrile additive adiponitrile that ethylene carbonate and volume ratio are 2%, methoxyacetyl nitrile are in inertia of the relative humidity less than 1%
Obtained electrolyte is uniformly mixed under gaseous environment；
Battery core made from the step 3 is encased in shell by step 5, then according to fluid injection coefficient 10g/Ah to shell
Electrolyte 100g made from middle injection step 4 is simultaneously sealed, and finally carries out preliminary filling chemical conversion, the specific steps of preliminary filling chemical conversion at room temperature
Are as follows:
Step 501, with 0.01C electric current constant-current charge to 3.5V, then with 0.01C electric current constant-current discharge to 1.5V；
Step 502, with 0.1C electric current constant-current charge to 3.5V, then with 0.1C electric current constant-current discharge to 1.5V；
Step 503, with 0.5C electric current constant-current charge to 3.5V, then with 0.5C electric current constant-current discharge to 1.5V；
Step 504, with 1C electric current constant-current charge to 3.5V, then with 1C electric current constant-current discharge to 3.0V.
Embodiment 4:
Step 1 gathers nickel ion doped, positive conductive agent carbon nanotube and positive electrode binder according to mass percent 93:4:3
Then vinylidene is added N-Methyl pyrrolidone and adjusts viscosity to 6500cP, and adjusts solid content to 58%, obtain positive slurry
Material；Positive plate is made by drying, roll-in and cutting after anode sizing agent is coated on carbon-coated aluminum foils plus plate current-collecting body；
Lithium titanate, cathode conductive agent graphene and negative electrode binder are gathered inclined fluorine according to mass percent 87:5:5 by step 2
Ethylene is uniformly mixed, and adds N-Methyl pyrrolidone, then adjusting viscosity to 8500cP, and adjusts solid content to 48%, is obtained
To negative electrode slurry；It is made negative after drying, roll-in and cutting after negative electrode slurry is coated on carbon-coated aluminum foils negative current collector
Pole piece；
Step 3, using three layers of PP/PE/PP diaphragm, will be born made from positive plate made from the step 1 and the step 2
Pole piece assembles according to the sequence of diaphragm, positive plate, diaphragm, negative electrode tab and battery core is made, and makes the ratio of capacity of negative plates and positive electrode capacity
N/P is 0.7；
Step 4, two lithium trifluoromethanesulp,onylimide of electrolyte by concentration is 1.8mol/L, organic solvent ethylene carbonate
The nitrile additive 1 that ester, fluorinated ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and volume ratio are 3%,
3,6 hexane, three nitrile, succinonitrile, adiponitrile are uniformly mixed obtained electrolyte under inert gas environment of the relative humidity less than 1%；
Battery core made from the step 3 is encased in shell by step 5, then according to fluid injection coefficient 3g/Ah into shell
Electrolyte 100g made from injection step 4 is simultaneously sealed, and finally carries out preliminary filling chemical conversion, the specific steps of preliminary filling chemical conversion at room temperature
Are as follows:
Step 501, with 0.01C electric current constant-current charge to 3.5V, then with 0.01C electric current constant-current discharge to 1.5V；
Step 502, with 0.1C electric current constant-current charge to 3.5V, then with 0.1C electric current constant-current discharge to 1.5V；
Step 503, with 0.5C electric current constant-current charge to 3.5V, then with 0.5C electric current constant-current discharge to 1.5V；
Step 504, with 1C electric current constant-current charge to 3.5V, then with 1C electric current constant-current discharge to 3.0V.
Embodiment 5:
Step 1 gathers nickel ion doped, positive conductive agent acetylene black and positive electrode binder partially according to mass percent 94:3:4
Then vinyl fluoride is added N-Methyl pyrrolidone and adjusts viscosity to 7500cP, and adjusts solid content to 55%, obtain positive slurry
Material；Positive plate is made by drying, roll-in and cutting after anode sizing agent is coated on carbon-coated aluminum foils plus plate current-collecting body；
Step 2 gathers lithium titanate, cathode conductive agent carbon nanotube and negative electrode binder partially according to mass percent 90:8:7
Vinyl fluoride is uniformly mixed, and adds N-Methyl pyrrolidone, then adjusts viscosity to 9500cP, and adjusts solid content to 50%,
Obtain negative electrode slurry；It is made after drying, roll-in and cutting after negative electrode slurry is coated on carbon-coated aluminum foils negative current collector
Negative electrode tab；
Step 3, using PVDF coating PP diaphragm, by cathode made from positive plate made from the step 1 and the step 2
Piece assembles according to the sequence of diaphragm, positive plate, diaphragm, negative electrode tab and battery core is made, and makes the ratio N/P of capacity of negative plates and positive electrode capacity
It is 0.85；
Step 4, be by concentration two lithium trifluoromethanesulp,onylimide of electrolyte of 2mol/L, organic solvent ethylene carbonate,
Diethyl carbonate, methyl ethyl carbonate and volume ratio are 4.5% nitrile additive, five fluorine ethoxy basic ring, three phosphonitrile, methoxyacetyl nitrile
Obtained electrolyte is uniformly mixed under inert gas environment of the relative humidity less than 1%；
Battery core made from the step 3 is encased in shell by step 5, then according to fluid injection coefficient 9g/Ah into shell
Electrolyte 100g made from injection step 4 is simultaneously sealed, and finally carries out preliminary filling chemical conversion, the specific steps of preliminary filling chemical conversion at room temperature
Are as follows:
Step 501, with 0.01C electric current constant-current charge to 3.5V, then with 0.01C electric current constant-current discharge to 1.5V；
Step 502, with 0.1C electric current constant-current charge to 3.5V, then with 0.1C electric current constant-current discharge to 1.5V；
Step 503, with 0.5C electric current constant-current charge to 3.5V, then with 0.5C electric current constant-current discharge to 1.5V；
Step 504, with 1C electric current constant-current charge to 3.5V, then with 1C electric current constant-current discharge to 3.0V.
Embodiment 6:
Step 1 gathers nickel ion doped, positive conductive agent superconduction graphite and positive electrode binder according to mass percent 95:5:5
Then vinylidene is added N-Methyl pyrrolidone and adjusts viscosity to 7500cP, and adjusts solid content to 53%, obtain positive slurry
Material；Positive plate is made by drying, roll-in and cutting after anode sizing agent is coated on carbon-coated aluminum foils plus plate current-collecting body；
Lithium titanate, cathode conductive agent acetylene black and negative electrode binder are gathered inclined fluorine according to mass percent 90:5:6 by step 2
Ethylene is uniformly mixed, and adds N-Methyl pyrrolidone, then adjusting viscosity to 9800cP, and adjusts solid content to 45%, is obtained
To negative electrode slurry；It is made negative after drying, roll-in and cutting after negative electrode slurry is coated on carbon-coated aluminum foils negative current collector
Pole piece；
Step 3, using PVDF diaphragm, by negative electrode tab made from positive plate made from the step 1 and the step 2 according to
Battery core is made in the sequence assembling of diaphragm, positive plate, diaphragm, negative electrode tab, makes the ratio N/P of capacity of negative plates and positive electrode capacity
0.75；
Step 4, the electrolyte difluorine oxalic acid boracic acid lithium, the organic solvent fluorinated ethylene carbonate, carbon that are 2mol/L by concentration
Nitrile additive succinonitrile that dimethyl phthalate and volume ratio are 2.5%, adiponitrile are in inert gas ring of the relative humidity less than 1%
Obtained electrolyte is uniformly mixed under border；
Battery core made from the step 3 is encased in shell by step 5, then according to fluid injection coefficient 8g/Ah into shell
Electrolyte 100g made from injection step 4 is simultaneously sealed, and finally carries out preliminary filling chemical conversion, the specific steps of preliminary filling chemical conversion at room temperature
Are as follows:
Step 501, with 0.01C electric current constant-current charge to 3.5V, then with 0.01C electric current constant-current discharge to 1.5V；
Step 502, with 0.1C electric current constant-current charge to 3.5V, then with 0.1C electric current constant-current discharge to 1.5V；
Step 503, with 0.5C electric current constant-current charge to 3.5V, then with 0.5C electric current constant-current discharge to 1.5V；
Step 504, with 1C electric current constant-current charge to 3.5V, then with 1C electric current constant-current discharge to 3.0V.
Lithium ion battery negative material in the prior art mostly uses all kinds of Carbon Materials, generally using negative in this kind of battery
Pole capacity excess (i.e. capacity of negative plates/positive electrode capacity ratio N/P > 1) is to inhibit the generation of Li dendrite during the charging process；And titanium
Acid lithium battery is up to 1.5V vs.Li+/Li due to the charge and discharge platform current potential of Li4Ti5O12, it is not necessary that uses capacity of negative plates
Excessive mode.
To promote nickel ion doped/lithium titanate battery high-temperature storage performance, high temperature cyclic performance, the present invention is arranged by following
Apply implementation: optimization battery core design, using the excessive design method of positive electrode capacity；Using the high voltage withstanding electrolysis additive of nitrile；
Using the strong diaphragm of inoxidizability.
The present invention is mainly reflected in compared to traditional nickel ion doped/lithium titanate battery, technical advantage:
On the one hand, optimization battery core design, is prepared into nickel ion doped/lithium titanate battery of positive electrode capacity excessive (N/P < 1), energy
Enough alleviate oxygenolysis of the electrolyte under high potential, inhibits to produce gas；On the other hand, by the way that nitrile addition is added into electrolyte
Agent is able to suppress the flatulence of LTO (Li4Ti5O12), improves the chemical property of battery；Nitrile organic solvent has wider electricity
Hydrofluoric acid and gold can be complexed in-CN the group of the good characteristics such as chemical window, high anode stability, low-viscosity and higher boiling, nitrile
Belong to ion, weaken the oxidation of cathode metal ion pair electrolyte, and can be reacted with the trace water in electrolyte, reduces electricity
The content for solving the water and hydrofluoric acid in liquid, stablizes electrolyte.
High temperature resistant type lithium ion battery made from 1-9 of the embodiment of the present invention and comparative example are subjected to high temperature storage and height below
The comparative experiments of warm cycle performance:
Comparative example:
A kind of capacity is the nickel ion doped and lithium titanate flexible-packed battery of 20Ah comprising positive plate, negative electrode tab, diaphragm,
Electrolyte and laminated aluminum film；The ratio N/P of the capacity of negative plates of battery and positive electrode capacity is 1.50 when battery core designs；Positive plate by
Carbon-coated aluminum foils collector and the anode sizing agent being coated on form, and 90:5:5 is by nickel ion doped, conductive agent by mass percentage
Acetylene black, binder CMC+SBR after mixing, add solvent deionized water, adjust viscosity to 6000cP, solid content is extremely
60%；After slurry is coated on carbon-coated aluminum foils, pole piece obtains the anode pole piece of required dimensions through drying, roll-in, cutting；It presses
Lithium titanate, conductive agent carbon nanotube, binder PVDF after mixing, are added Solvents N-methyl by mass percent 85:8:7
Pyrrolidones NMP adjusts viscosity to 8000cP, solid content to 50%；By slurry be coated on carbon-coated aluminum foils after, pole piece through drying,
Roll-in, cutting obtain the cathode pole piece of required dimensions；It is negative according to diaphragm-anode pole piece-diaphragm-using single layer PE diaphragm
The sequence pole group unit of pole pole piece assembles naked battery core；The additive-free electrolyte 100g of 2mol/L, electricity are injected by fluid injection coefficient 5g/Ah
Solving liquid group becomes electrolyte two (trimethyl fluoride sulfonyl) imine lithium, organic solvent ethylene carbonate, diethyl carbonate, methyl ethyl carbonate
Ester；After the completion of naked battery core fluid injection, battery is at room temperature according to progress preliminary filling chemical conversion the step of being identical with the embodiment of the present invention.
The high temperature storage and high temperature cyclic performance data comparison of embodiment 1-9 and comparative example are as shown in table 1:
Table 1
As shown in Table 1, after 2000 (55 DEG C) of 2C high temperature circulations, using nickel ion doped/lithium titanate of embodiment 1-9
The capacity retention ratio of battery is 95% or more, and the capacity retention ratio of comparative example is only 85%；The high temperature storage of embodiment 1-9 is held
Measuring conservation rate is 97% or more, and the high temperature storage capacity retention ratio of comparative example is 90%.
It is analyzed by the above correlation data it is found that excessively being set by carrying out positive electrode capacity to nickel ion doped/lithium titanate battery
Meter and addition nitrile additive, high temperature cyclic performance and high temperature storage that battery can be significantly improved using the strong diaphragm of inoxidizability
Performance.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with scope of protection of the claims
Subject to.
Claims (10)
1. a kind of high temperature resistant type lithium ion battery, which is characterized in that it includes shell, and electrolyte and electricity are provided in the shell
Core, the electrolyte include electrolyte, organic solvent and nitrile additive.
2. high temperature resistant type lithium ion battery according to claim 1, which is characterized in that the battery core includes positive plate, bears
Pole piece and diaphragm for separating positive plate and negative electrode tab；The positive plate includes carbon-coated aluminum foils plus plate current-collecting body and is coated in it
On anode sizing agent, the anode sizing agent includes positive active material nickel ion doped, positive conductive agent and positive electrode binder；It is described
Negative electrode tab includes carbon-coated aluminum foils negative current collector and the negative electrode slurry that is coated on, and the negative electrode slurry includes negative electrode active material
Matter lithium titanate, cathode conductive agent and negative electrode binder.
3. high temperature resistant type lithium ion battery according to claim 2, which is characterized in that the positive conductive agent is by superconduction stone
At least one of ink, acetylene black, graphene, carbon nanotube composition；The cathode conductive agent is by superconduction graphite, acetylene black, stone
At least one of black alkene, carbon nanotube composition；The positive electrode binder is the mixing of sodium carboxymethylcellulose and butadiene-styrene rubber
Object or Kynoar；The negative electrode binder is Kynoar.
4. high temperature resistant type lithium ion battery according to any one of claim 1-3, which is characterized in that the electrolyte is
At least one of lithium hexafluoro phosphate, difluorine oxalic acid boracic acid lithium, two lithium trifluoromethanesulp,onylimides；The organic solvent is carbonic acid
At least one of vinyl acetate, fluorinated ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate；The nitrile adds
Add agent at least one in 1,3,6 hexane, three nitrile, succinonitrile, adiponitrile, methoxyacetyl nitrile, five fluorine ethoxy basic rings, three phosphonitrile
Kind.
5. the lithium ion battery according to claim 4 based on nickel ion doped and lithium titanate, which is characterized in that the diaphragm
For PP type diaphragm or polyvinylidene fluoride alkenes diaphragm；The PP type diaphragm is single layer PP diaphragm or bilayer PP/PE diaphragm
Or three layers of PP/PE/PP diaphragm or one of ceramic coating PP diaphragm or PVDF coating PP diaphragm；The polyvinylidene fluoride alkenes every
Film is PVDF diaphragm or the compound PVDF diaphragm of cellulose.
6. a kind of preparation method of the high temperature resistant type lithium ion battery as described in any one of claim 1-5, which is characterized in that tool
Body the following steps are included:
Step 1, preparation battery core；
Electrolyte, organic solvent and nitrile additive are uniformly mixed obtained electrolyte by step 2；
Battery core prepared by the step 1 is encased in shell by step 3, and electricity made from the step 2 is then injected into shell
Solution liquid simultaneously seals, and finally carries out preliminary filling chemical conversion at room temperature, obtains high temperature resistant type lithium ion battery.
7. the preparation method of high temperature resistant type lithium ion battery according to claim 6, which is characterized in that in the step 1,
The preparation method of the battery core specifically includes the following steps:
Step 1.1 mixes nickel ion doped, positive conductive agent and positive electrode binder according to mass percent 90-96:2-5:2-5
Uniformly, the first mixture is obtained；The positive electrode binder is the mixture of sodium carboxymethylcellulose and butadiene-styrene rubber or gathers inclined fluorine
Ethylene；
Step 1.2, when the positive electrode binder is the mixture of sodium carboxymethylcellulose and butadiene-styrene rubber, Xiang Suoshu step
Deionized water is added in 1.1 the first mixtures obtained；When the positive electrode binder is Kynoar, Xiang Suoshu step
N-Methyl pyrrolidone is added in 1.1 the first mixtures obtained；Then viscosity is adjusted to 6000-8000cP, and is adjusted and contained admittedly
Anode sizing agent is made to 50-60% in amount；
Step 1.3, by anode sizing agent made from the step 1.2 be coated on carbon-coated aluminum foils plus plate current-collecting body on after by drying,
Positive plate is made in roll-in and cutting；
Step 1.4 mixes lithium titanate, cathode conductive agent and negative electrode binder according to mass percent 85-92:4-8:4-7
It is even, obtain the second mixture；
Step 1.5, Xiang Suoshu step 1.4 obtain the second mixture in N-Methyl pyrrolidone is added, then adjust viscosity to
8000-10000cP, and solid content is adjusted to 40-50%, negative electrode slurry is made；
Step 1.6, by negative electrode slurry made from the step 1.5 be coated on carbon-coated aluminum foils negative current collector on after by drying,
Negative electrode tab is made after roll-in and cutting；
Step 1.7, by negative electrode tab made from positive plate made from the step 1.3 and the step 1.6 according to diaphragm, anode
Battery core is made in the sequence assembling of piece, diaphragm, negative electrode tab, makes the ratio N/P 0.5-0.99 of the capacity of negative plates and positive electrode capacity.
8. the preparation method of high temperature resistant type lithium ion battery according to claim 6, which is characterized in that in the step 2,
The hybird environment of the electrolyte, organic solvent and nitrile additive is inert gas environment of the relative humidity less than 1%, described
The concentration of electrolyte is 1-2mol/L, and the volume ratio that the nitrile additive is added is 1-5%.
9. the preparation method of high temperature resistant type lithium ion battery according to claim 6, which is characterized in that in the step 3,
The fluid injection coefficient of the injection electrolyte is 2-10g/Ah.
10. the preparation method of high temperature resistant type lithium ion battery according to claim 6, which is characterized in that the step 3
In, the specific steps of the preliminary filling chemical conversion are as follows:
Step 3.1, with 0.01C electric current constant-current charge to 3.5V, then with 0.01C electric current constant-current discharge to 1.5V；
Step 3.2, with 0.1C electric current constant-current charge to 3.5V, then with 0.1C electric current constant-current discharge to 1.5V；
Step 3.3, with 0.5C electric current constant-current charge to 3.5V, then with 0.5C electric current constant-current discharge to 1.5V；
Step 3.4, with 1C electric current constant-current charge to 3.5V, then with 1C electric current constant-current discharge to 3.0V.
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