CN106025361A - Low-temperature lithium ion battery - Google Patents
Low-temperature lithium ion battery Download PDFInfo
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- CN106025361A CN106025361A CN201610364127.0A CN201610364127A CN106025361A CN 106025361 A CN106025361 A CN 106025361A CN 201610364127 A CN201610364127 A CN 201610364127A CN 106025361 A CN106025361 A CN 106025361A
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- lithium
- ethylene carbonate
- ion battery
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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
- H01M10/0568—Liquid materials characterised by the solutes
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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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a low-temperature lithium ion battery and belongs to the technical field of lithium ion batteries. The low-temperature lithium ion battery is characterized in that the low-temperature lithium ion battery comprises a positive plate, a diaphragm and a negative plate which are mutually wound or laminated at intervals, wherein clearances between the positive plate, the diaphragm and the negative plate are filled with an electrolyte; the positive plate adopts a three-layered composite structure which is an intermediate positive current collector; the front side and the rear side of the positive current collector are coated with the same cathode material; the cathode material is at least one of a lithium iron phosphate material, a lithium vanadium phosphate material, a lithium ferric manganese phosphate material, a lithium cobalt oxides material, a nickel cobalt lithium manganate material, a nickel cobalt lithium aluminate material, a lithium manganate material and a nickel lithium manganate material; the positive current collector is an aluminum foil; the negative plate is a three-layered composite structure and comprises a lithium titanate material layer, a graphite material layer and a negative current collector; the lithium titanate material layer and the graphite material layer are coated on two sides of the negative current collector respectively; the negative current collector is a copper foil.
Description
Technical field
The present invention relates to a kind of low temp lithium ion battery, belong to technical field of lithium ion.
Background technology
Along with fast development and the continuous deterioration of earth environment of science and technology, the mankind are more and more higher to the demand of green energy resource product.Lithium ion battery energy density is big, and high rate performance and security performance are good, environmental protection, be widely used in electronics and new-energy automobile field, but lithium ion battery cryogenic property is poor, and especially lithium ion battery low temperature charging performance is poor.Under low temperature, lithium-ion battery electrolytes electrical conductivity is low, ohmic polarization in charging process, concentration polarization and activation polarization strengthen, and cause lithium metal to deposit so that electrolyte decomposition, electrode surface SEI film is caused to thicken, battery charge capacity and platform are extremely low, and battery charges under long-term low temperature environment and greatly have impact on the chemical property of battery, shortens the service life of battery, time even serious, the lithium metal of deposition pierces through barrier film and produces potential safety hazard.Cannot charge under lithium ion battery ultralow temperature, constrain its application in special environment field, lithium ion battery with high energy density low temperature is charged to be badly in need of a technical barrier of solution for people.
Can charge normal at low ambient temperatures to meet lithium ion battery, some attempts using lithium titanate to prepare lithium ion battery as lithium ion battery negative material in recent years, such lithium ion battery low temperature charging performance increases, but lithium titanate anode lithium ion battery energy density is little, price is high, limits the popularization of such battery.If self partial heat can will be produced in lithium ion battery with high energy density charging process, battery self ambient temperature of charging can be improved, it becomes possible to make lithium ion battery with high energy density obtain sufficient performance at low temperatures while not affecting its chemical property.It is thus possible to the charging difficult problem solved under lithium ion battery with high energy density low temperature environment.
Summary of the invention
It is an object of the invention to provide a kind of low temp lithium ion battery, solve the technical problem that lithium ion battery with high energy density can charge normal at low ambient temperatures.
For achieving the above object, the technical solution used in the present invention is:
Low-temperature lithium ion battery, including spaced winding or the positive plate of stacking, barrier film and negative plate, filling electrolyte between the gap of positive plate, barrier film and negative plate, positive plate is three-layer composite structure, structure is middle plus plate current-collecting body, same positive electrode is coated before and after plus plate current-collecting body, described positive electrode is at least one in LiFePO 4 material, lithium vanadium phosphate material, lithium ferric manganese phosphate material, cobalt acid lithium material, nickel-cobalt lithium manganate material, nickel cobalt lithium aluminate material, lithium manganate material, nickel ion doped material, and described plus plate current-collecting body is aluminium foil；
Negative plate is three-layer composite structure, and including lithium titanate material layer, graphite material and negative current collector, lithium titanate material layer and graphite material are respectively coated on the two sides of negative current collector, and negative current collector is Copper Foil.
As preferably, electrolyte is made up of solvent, electrolytic salt and additive, one or more during wherein solvent is dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl methyl carbonate (EMC), ethylene carbonate (EC), electrolytic salt is lithium hexafluoro phosphate (LiPF6), additive includes one or more in vinylethylene carbonate (VEC), ethylene carbonate (VC), fluorinated ethylene carbonate (FEC), fluorine surfactant (FS3100).
As preferably, the positive electrode of positive plate is LiFePO4 (LiFePO4), lithium iron phosphate positive material is coated uniformly on the two sides of plus plate current-collecting body layer, barrier film is 20 μ m-thick PP barrier films, the solvent of electrolyte be diethyl carbonate (DEC), Ethyl methyl carbonate (EMC), ethylene carbonate (EC) by 30:30:40 mass ratio mixing composition, electrolytic salt is lithium hexafluoro phosphate (LiPF6), electrolytic salt concentration in the electrolytic solution is 12.0%, additive is ethylene carbonate (VC), fluorinated ethylene carbonate (FEC) and fluorine surfactant (FS3100), and the adding proportion of ethylene carbonate (VC), fluorinated ethylene carbonate (FEC) and fluorine surfactant (FS3100) is respectively 2%, 2% and 0.1%.
As preferably, the positive electrode of positive plate is nickle cobalt lithium manganate (LiNi0.5Co0.2Mn0.3O2), nickle cobalt lithium manganate is coated uniformly on the two sides of aluminum foil current collector layer, solvent in electrolyte be dimethyl carbonate (DMC), Ethyl methyl carbonate (EMC), ethylene carbonate (EC) by 45:30:25 mass ratio mixing composition, electrolytic salt is lithium hexafluoro phosphate (LiPF6) concentration in the electrolytic solution is 11.5%, additive is ethylene carbonate (VC), fluorinated ethylene carbonate (FEC) and fluorine surfactant (FS3100), and ethylene carbonate (VC), fluorinated ethylene carbonate (FEC) and fluorine surfactant (FS3100) addition in the electrolytic solution are respectively 2%, 2% and 0.1%.
Advantages of the present invention with effect is:
Lithium ion battery the most of the present invention is respectively coated on lithium titanate and graphite the two sides of negative current collector in monomer battery core, without preparing lithium titanate positive plate and graphite positive plate, simplify lithium ion battery structure, existing equipment directly can be used to make, improve the equipment suitability.
Lithium ion battery monomer battery core the most of the present invention is respectively coated on lithium titanate and graphite the two sides of negative current collector, lithium ion battery is when charging, first in low voltage stage, low voltage lithium titanate anode lithium ion battery plays a role, and produce certain heat when charging, internal temperature of battery is raised, and along with cell voltage and the rising of internal temperature, high voltage graphite cathode lithium ion battery starts to play a role.So, both will not too much reduce lithium ion battery energy density, and make again lithium ion battery to charge normal at low temperatures.
Lithium ion battery monomer battery core the most of the present invention is respectively coated on lithium titanate and graphite the two sides of negative current collector, two kinds of negative material voltage complementary, it is to avoid lithium ion battery produced when using and puts, and improve security performance and the service life of battery.
Lithium ion battery management system the most of the present invention is designed as first carrying out monomer battery core electric discharge, and battery core produces certain heat in discharge process, contributes to the lifting of internal temperature of lithium ion battery, improves the charging performance under battery low temperature environment.
Accompanying drawing explanation
Fig. 1 is the 90140200-20Ah-3.2V soft bag lithium ionic cell structural representation in embodiment 1,
Fig. 2 is the 90140200-20Ah-3.2V soft bag lithium ionic cell monomer battery core section structure for amplifying schematic diagram in embodiment 1；
Fig. 3 is 90140200-20Ah-3.2V Soft Roll lithium ion single battery battery core charging and discharging curve figure under-20 DEG C of environment in embodiment 1.
Fig. 4 is 18650-2000mAh-3.6V cylindrical lithium ion battery schematic diagram in embodiment 2,
Fig. 5 is 18650-2000mAh-3.6V cylindrical lithium ion battery monomer battery core cross-section structure enlarged diagram in embodiment 2；
Fig. 6 is 18650-2000mAh-3.6V cylindrical lithium ion battery monomer battery core charging and discharging curve figure under-20 DEG C of environment in embodiment 2.
Reference: 1-1, iron phosphate lithium positive pole coating；1-2, plus plate current-collecting body；1-3, lithium titanate anode coating；1-4, graphite cathode coating；1-5, negative current collector；1-6, PP barrier film；1-7, aluminum plastic film；3-1 nickle cobalt lithium manganate positive pole coating；3-2, plus plate current-collecting body；3-3, lithium titanate anode coating；3-4, graphite cathode coating；3-5, negative current collector；3-6, PP barrier film；3-7, box hat.
Detailed description of the invention
The present invention is by the following technical solutions: lithium-ion battery monomer battery core of the present invention includes positive plate, negative plate, barrier film and electrolyte.The spaced winding of described positive plate, negative plate and barrier film or stack design, described diaphragm design is between positive plate and negative plate.Described positive plate is three-layer composite structure, positive plate includes positive electrode material layer and current collector layers, positive electrode material layer is one or more in LiFePO 4 material, lithium vanadium phosphate material, lithium ferric manganese phosphate material, cobalt acid lithium material, nickel-cobalt lithium manganate material, nickel cobalt lithium aluminate material, lithium manganate material, nickel ion doped material, plus plate current-collecting body layer is aluminium foil, and positive electrode is coated uniformly on the two sides of current collector layers and meets structure with collector formation three layers.Described negative plate is three-layer composite structure, and negative plate includes lithium titanate material layer, graphite material and negative current collector layer, and negative current collector is Copper Foil, and lithium titanate material layer and graphite material are respectively coated on the two sides formation three layers of negative current collector and meet structure.Barrier film is PP barrier film, PE barrier film, PP/PE composite diaphragm, can be according to actual battery type selecting unlike material and the barrier film of thickness.Described electrolyte is made up of solvent, electrolytic salt and additive, and wherein solvent is made up of components such as dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl methyl carbonate (EMC), ethylene carbonates (EC), and electrolytic salt is lithium hexafluoro phosphate (LiPF6), additive is made up of components such as vinylethylene carbonate (VEC), ethylene carbonate (VC), fluorinated ethylene carbonate (FEC), fluorine surfactants (FS3100).Lithium ion battery management system design is the most first discharges to lithium ion battery, carries out the charging of lithium ion battery after arriving final discharging voltage.
Embodiment 1
90140200-20Ah-3.2V soft bag lithium ionic cell monomer battery core profile is as in figure 2 it is shown, positive plate is three-layer composite structure, including LiFePO4 (LiFePO4) positive electrode material layer and aluminum foil current collector layer, lithium iron phosphate positive material is coated uniformly on the two sides of aluminum foil current collector layer.90140200-20Ah-3.2V soft bag lithium ionic cell monomer battery core negative plate is three-layer composite structure, including lithium titanate (Li2TiO3) material layer, graphite (C) material layer and negative copper foil current collector layers, lithium titanate material layer and graphite material are respectively coated on the two sides of negative copper foil collector.Barrier film is 20 μ m-thick PP barrier films, electrolyte is made up of solvent, electrolytic salt and additive, solvent be diethyl carbonate (DEC), Ethyl methyl carbonate (EMC), ethylene carbonate (EC) by 30:30:40 mass ratio form, electrolytic salt is lithium hexafluoro phosphate (LiPF6), electrolytic salinity is 12.0%, and additive is ethylene carbonate (VC), fluorinated ethylene carbonate (FEC) and fluorine surfactant (FS3100), and addition is respectively 2%, 2% and 0.1%.
This invention low form 90140200-20Ah-3.2V soft bag lithium ionic cell monomer battery core is tested, first standing 12h it is placed under-20 DEG C of temperature environments after 90140200-20Ah-3.2V soft bag lithium ionic cell monomer battery core being discharged into 1.0V, then under-20 DEG C of temperature environments, carry out constant-current constant-voltage charging, charging current is 10A, blanking voltage is 3.65V, and cut-off current is 0.4A, finally carries out constant-current discharge under-20 DEG C of environment, discharge current is 10A, and blanking voltage is 1.0V.990140200-20Ah-3.2V soft bag lithium ionic cell monomer battery core low temperature charging and discharging curve is as shown in Figure 3.Can be seen that battery core has good low temperature charge-discharge performance from 90140200-20Ah-3.2V soft bag lithium ionic cell monomer battery core low temperature charge-discharge test curve.
This lithium ion single battery core is when charging, and first it discharged by lithium ion battery management system, and in discharge process, battery core produces certain heat, contributes to charging under lithium ion battery low temperature environment.
Embodiment 2
18650-2000mAh-3.6V cylindrical lithium ion battery monomer battery core profile is as it is shown in figure 5, positive plate is three-layer composite structure, including nickle cobalt lithium manganate (LiNi0.5Co0.2Mn0.3O2) positive electrode material layer and aluminum foil current collector layer, nickle cobalt lithium manganate tertiary cathode material is coated uniformly on the two sides of aluminum foil current collector layer.18650-2000mAh-3.6V cylindrical lithium ion battery monomer battery core negative plate is three-layer composite structure, including lithium titanate (Li2TiO3) material layer, graphite (C) material layer and negative copper foil current collector layers, lithium titanate material layer and graphite material are respectively coated on the two sides of negative copper foil collector.Barrier film is 20 μ m-thick PP barrier films, electrolyte is made up of solvent, electrolytic salt and additive, solvent be dimethyl carbonate (DMC), Ethyl methyl carbonate (EMC), ethylene carbonate (EC) by 45:30:25 mass ratio form, electrolytic salt is lithium hexafluoro phosphate (LiPF6), electrolytic salinity is 11.5%, and additive is ethylene carbonate (VC), fluorinated ethylene carbonate (FEC) and fluorine surfactant (FS3100), and addition is respectively 2%, 2% and 0.1%.
This invention low form 18650-2000mAh-3.6V cylindrical lithium ion battery monomer battery core is tested, first standing 12h it is placed under-20 DEG C of temperature environments after 18650-2000mAh-3.6V cylindrical lithium ion battery monomer battery core being discharged into 1.0V, then under-20 DEG C of temperature environments, carry out constant-current constant-voltage charging, charging current is 1000mA, blanking voltage is 4.2V, and cut-off current is 40mA, finally carries out constant-current discharge under-20 DEG C of environment, discharge current is 1000mA, and blanking voltage is 1.5V.18650-2000mAh-3.6V cylindrical lithium ion battery monomer battery core low temperature charging and discharging curve is as shown in Figure 6.Can be seen that battery core has good low temperature charge-discharge performance from battery core low temperature charge-discharge test curve.
This lithium ion single battery core is when charging, and lithium ion battery management system charges after first discharging it, and in discharge process, battery core produces certain heat, contributes to charging under lithium ion battery low temperature environment.
Claims (4)
1. a low-temperature lithium ion battery, including spaced winding or the positive plate of stacking, barrier film and negative plate, filling electrolyte between the gap of positive plate, barrier film and negative plate, is characterized in that,
Positive plate is three-layer composite structure, structure is middle plus plate current-collecting body, same positive electrode is coated before and after plus plate current-collecting body, described positive electrode is at least one in LiFePO 4 material, lithium vanadium phosphate material, lithium ferric manganese phosphate material, cobalt acid lithium material, nickel-cobalt lithium manganate material, nickel cobalt lithium aluminate material, lithium manganate material, nickel ion doped material, and described plus plate current-collecting body is aluminium foil；
Negative plate is three-layer composite structure, and including lithium titanate material layer, graphite material and negative current collector, lithium titanate material layer and graphite material are respectively coated on the two sides of negative current collector, and negative current collector is Copper Foil.
Low-temperature lithium ion battery the most according to claim 1, it is characterized in that, electrolyte is made up of solvent, electrolytic salt and additive, one or more during wherein solvent is dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethylene carbonate, electrolytic salt is lithium hexafluoro phosphate, and additive includes one or more in vinylethylene carbonate, ethylene carbonate, fluorinated ethylene carbonate, fluorine surfactant.
Low-temperature lithium ion battery the most according to claim 2, it is characterized in that, the positive electrode of positive plate is LiFePO4, lithium iron phosphate positive material is coated uniformly on the two sides of plus plate current-collecting body layer, barrier film is 20 μ m-thick PP barrier films, the solvent of electrolyte is diethyl carbonate, Ethyl methyl carbonate, ethylene carbonate presses 30:30:40 mass ratio mixing composition, electrolytic salt is lithium hexafluoro phosphate, electrolytic salt concentration in the electrolytic solution is 12.0%, additive is ethylene carbonate, fluorinated ethylene carbonate and fluorine surfactant, ethylene carbonate, the adding proportion of fluorinated ethylene carbonate and fluorine surfactant is respectively 2%, 2% and 0.1%.
Low-temperature lithium ion battery the most according to claim 2, it is characterized in that, the positive electrode of positive plate is nickle cobalt lithium manganate, nickle cobalt lithium manganate is coated uniformly on the two sides of aluminum foil current collector layer, solvent in electrolyte is dimethyl carbonate, Ethyl methyl carbonate, ethylene carbonate presses 45:30:25 mass ratio mixing composition, electrolytic salt be lithium hexafluoro phosphate concentration in the electrolytic solution be 11.5%, additive is ethylene carbonate, fluorinated ethylene carbonate and fluorine surfactant, ethylene carbonate, fluorinated ethylene carbonate and fluorine surfactant addition in the electrolytic solution is respectively 2%, 2% and 0.1%.
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| CN201610364127.0A CN106025361A (en) | 2016-05-27 | 2016-05-27 | Low-temperature lithium ion battery |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106654201A (en) * | 2016-12-08 | 2017-05-10 | 深圳市鑫永丰科技有限公司 | Ternary composite material and preparation method thereof and lithium-ion battery |
| CN106784995A (en) * | 2017-01-12 | 2017-05-31 | 江苏海四达电源股份有限公司 | Electrolyte and its application and lithium ion battery |
| CN108054356A (en) * | 2017-12-06 | 2018-05-18 | 贵州梅岭电源有限公司 | A kind of high security composite positive pole lithium ion battery |
| CN109390643A (en) * | 2018-10-11 | 2019-02-26 | 南京宁智高新材料研究院有限公司 | A kind of three-diemsnional electrode heating means being cold-started at low temperature for battery |
| CN109411806A (en) * | 2018-12-11 | 2019-03-01 | 广东永邦新能源股份有限公司 | A kind of low-temperature lithium ion battery and preparation method thereof |
| CN112133885A (en) * | 2020-09-23 | 2020-12-25 | 深圳中科瑞能实业有限公司 | Battery core and secondary battery with three-layer pole piece structure |
| CN114628850A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Low-temperature lithium ion battery and charging and discharging method thereof |
| CN114634203A (en) * | 2022-02-24 | 2022-06-17 | 四川国创成电池材料有限公司 | Lithium ion battery with niobium-titanium-oxygen composite oxide cathode |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106654201A (en) * | 2016-12-08 | 2017-05-10 | 深圳市鑫永丰科技有限公司 | Ternary composite material and preparation method thereof and lithium-ion battery |
| CN106784995A (en) * | 2017-01-12 | 2017-05-31 | 江苏海四达电源股份有限公司 | Electrolyte and its application and lithium ion battery |
| CN108054356A (en) * | 2017-12-06 | 2018-05-18 | 贵州梅岭电源有限公司 | A kind of high security composite positive pole lithium ion battery |
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| CN112133885B (en) * | 2020-09-23 | 2022-08-12 | 深圳中科瑞能实业有限公司 | Battery core and secondary battery with three-layer pole piece structure |
| CN114628850A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Low-temperature lithium ion battery and charging and discharging method thereof |
| CN114634203A (en) * | 2022-02-24 | 2022-06-17 | 四川国创成电池材料有限公司 | Lithium ion battery with niobium-titanium-oxygen composite oxide cathode |
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| C06 | Publication | ||
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Application publication date: 20161012 |