CN105514424A - Lithium ion battery and preparation method thereof - Google Patents
Lithium ion battery and preparation method thereof Download PDFInfo
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- CN105514424A CN105514424A CN201510884304.3A CN201510884304A CN105514424A CN 105514424 A CN105514424 A CN 105514424A CN 201510884304 A CN201510884304 A CN 201510884304A CN 105514424 A CN105514424 A CN 105514424A
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- 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
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M10/058—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
-
- 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 provides a lithium ion battery. The lithium ion battery is characterized in that a current collector of a positive plate of the lithium ion battery is coated with a paste layer, and the paste layer comprises lithium iron phosphate, carbon nanotubes, organolithium and PVDF (polyvinylidene fluoride). The invention further provides a preparation method of the lithium ion battery. The preparation method comprises the following steps that lithium iron phosphate, the carbon nanotubes, organolithium and PVDF are weighed in mass ratio, and NMP (N-methylpyrolidone) is weighed quantitatively; part of NMP is taken out, PVDF is dissolved in the part of NMP, and a glue solution is prepared; the carbon nanotubes and organolithium are added to residual NMP, the mixture is subjected to high-speed dispersion and then subjected to ultrasonic dispersion, lithium iron phosphate is added, the mixture is subjected to second high-speed dispersion, and dispersed paste is prepared; the glue solution is added to the dispersed paste for high-speed mixed dispersion, and positive electrode paste is prepared; the current collector is coated with the positive electrode paste, and the positive plate is prepared; the battery is prepared through assembly. The lithium ion battery has the advantages that exertion of capacity density of the positive electrode is integrated while the electrical conductivity of the battery is improved, the capacity of the lithium ion battery is increased, and the rate capability and the cycle performance of the lithium ion battery are enhanced.
Description
Technical field
The invention belongs to field of lithium ion battery, particularly relate to a kind of lithium ion battery and preparation method thereof.
Background technology
Power lithium-ion battery to be widely used in electric automobile, commercial car as the new generation of green energy and to obtain the consistent favorable comment of clients and be more and more subject to liking of clients.Quick charge, far away, the life-span long developing direction being undoubtedly electric automobile future of continuing a journey.This will have excellent high rate performance and cycle performance by demanded driving force ion battery, have higher energy density simultaneously.LiFePO4 as lithium-ion-power cell material, have nontoxic, pollution-free, security performance is good, raw material sources is extensive, low price, etc. advantage, be that other material cannot be compared.But in the lithium ion battery taking LiFePO4 as raw material, LiFePO4 exists that poorly conductive, lithium ion diffusion velocity are slow, high power charging-discharging time actual specific capacity low problem, become a difficult point of restriction lithium-ion-power cell industry development.
The method of current raising LiFePO4 Li-like ions battery high rate performance is mainly by adding conductive agent and optimizing battery design, and in positive electrode, add conductive agent be the most frequently used, effect the best way.Current conductive agent mainly contains SP (carbon black conductive agent) and KS-6 (graphite agent) compound, SP and KS-6 conductivity is general, conductivity is poor compared with carbon nano-tube, affect the high rate performance of battery, and conductive agent proportion is many, have impact on the ratio that active material is shared in pole piece, thus affect capacity boost; SP is small particle diameter conductive agent, hinders mass transfer, affects effective performance of positive electrode capacity, and finally affects the raising of lithium ion battery energy density; In the charge and discharge process of battery, lithium ion can be consumed because of the continuous formation-destruction-formation of SEI film (solid electrolyte interface film), finally affects cycle life.
Summary of the invention
Technical problem to be solved by this invention is that the conductivity of raising LiFePO4 Li-like ions battery takes into account the performance of positive pole gram volume simultaneously, improves the capacity of lithium ion battery, strengthens high rate performance and the cycle performance of lithium ion battery.
For solving the problems of the technologies described above, the invention provides a kind of lithium ion battery, comprise a positive plate, a negative plate, a barrier film, electrolyte and battery container, it is characterized in that, described positive plate comprises a collector, described collector is coated with pulp layer, and the composition of described pulp layer comprises LiFePO4, carbon nano-tube, organolithium and PVDF; The mass ratio of described LiFePO4, carbon nano-tube, organolithium, PVDF is: 91-96.4:1.5-4.5:0.1-1:2-4.
Further, the mass ratio of described LiFePO4, carbon nano-tube, organolithium, PVDF is: 95:2:0.5:2.5.
Further, described organolithium comprises at least one in lithium methide, butyl lithium, s-butyl lithium, just base lithium, phenyl lithium.
For solving the problems of the technologies described above, present invention also offers a kind of preparation method of lithium ion battery, comprising the following steps:
(1) take LiFePO4, carbon nano-tube, organolithium and PVDF in mass ratio, and take NMP (1-METHYLPYRROLIDONE) according to quantity; Take out a part of NMP, PVDF is dissolved in wherein, is mixed with glue;
(2) carbon nano-tube, organolithium are joined in residue NMP, first high speed dispersion, then carry out ultrasonic disperse, then add LiFePO4 and carry out second time high speed dispersion again, obtained dispersed paste;
(3) glue is joined in dispersed paste carry out mixed at high speed dispersion, obtained anode sizing agent;
(4) anode sizing agent is coated on collector, obtained positive plate;
(5) battery is assembled;
The mass ratio of described LiFePO4, carbon nano-tube, organolithium, PVDF is: 91-96.4:1.5-4.5:0.1-1:2-4.
Further, the mass ratio of described LiFePO4, carbon nano-tube, organolithium, PVDF is: 95:2:0.5:2.5.
Further, take NMP in described step (1) according to quantity and refer to that NMP is 40%-50%:1 with the mass ratio of the four kinds of solid matters taken.
Further, described gelatin concentration is 5%-20%.
Further, the condition of the high speed dispersion in described step (2) is: vacuum condition, revolution 20-45rpm (revolutions per minute), rotation 1000-2500rpm; The time of described high speed dispersion is 0.8-1.2h; The time of described second time high speed dispersion is 3.5-4.5h.
Further, the frequency of described ultrasonic disperse is 15-20KHz, and power is 200-300W, and the time of described ultrasonic disperse is 25-35min.
Further, the condition of the mixed at high speed dispersion in described step (3) is: vacuum condition, revolution 20-45rpm, rotation 1000-2500rpm; The time of described mixed at high speed dispersion is 1.8-2.3h.
Compared with prior art, beneficial effect is in the present invention: a kind of lithium ion battery provided by the invention, and the composition of the pulp layer in battery anode slice comprises LiFePO4, carbon nanotube conducting agent, organolithium, binding agent PVDF.Carbon nano-tube enhances the conductivity between LiFePO4, between active material particle and collector, thus reduces the polarization produced because of electronics local accumulation in the electrodes, improves the conductivity of battery; The conductivity of carbon nano-tube is more excellent than SP, KS-6 simultaneously, the content of conductive agent can be reduced, battery is made to have higher capacity, and the toughness that carbon nano-tube is very strong makes conductive agent and positive active material close contact, thus provide passage extremely easily for electronics transport in the electrodes, improve the cycle performance of battery.In cell reaction, the lithium ion of organolithium can compensate the lithium ion because formation SEI film and carbon nano-defects cause embedding lithium and consume, and improves the gram volume of battery.The conductivity improving battery takes into account the performance of positive pole gram volume simultaneously, improves the capacity of lithium ion battery, enhances high rate performance and the cycle performance of lithium ion battery.
Accompanying drawing explanation
Fig. 1 is that the positive plate SEM in the embodiment of the present invention schemes.
Fig. 2 is lithium ion battery in the embodiment of the present invention and traditional lithium-ion battery gram volume comparison diagram.
Fig. 3 a is lithium ion battery in the embodiment of the present invention and traditional lithium-ion battery multiplying power charging curve comparison diagram; Fig. 3 b is lithium ion battery of the present invention and traditional lithium-ion battery rate discharge curves comparison diagram.
Fig. 4 is lithium ion battery in the embodiment of the present invention and traditional lithium-ion battery cyclic curve comparison diagram.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The positive plate of lithium ion battery of the present invention is made up of LiFePO4, carbon nanotube conducting agent, organolithium, binding agent PVDF and collector.Carbon nano-tube is the One-dimensional Quantum wire with excellent conductive performance, can strengthen between LiFePO4, conductivity between active material particle and collector, thus reduce the polarization produced because of electronics local accumulation in the electrodes, be conducive to the conductivity improving battery, carbon nano-tube compares SP simultaneously, KS-6 has more excellent conductivity, the content of conductive agent can be reduced, promote the content of active material, thus make battery have higher capacity, and carbon nano-tube has very strong toughness, its distinctive fibre structure can be formed solid conductive network and be caught firmly by both positive and negative polarity active material, make conductive agent and positive active material close contact, thus provide passage extremely easily for electronics transport in the electrodes, improve the cycle performance of battery.In cell reaction, the lithium ion of organolithium can compensate the lithium ion because formation SEI film and carbon nano-defects cause embedding lithium and consume, and improves the gram volume of battery.Carbon nano tube surface defect is few, lack active group, solubility in various solvent is all very low, be difficult to dispersion, activated carbon nano-tube is carried out often through surperficial organic active agent such as interpolation neopelex, sodium dodecyl sulfate etc., add organolithium and not only can compensate lithium ion consumption, surfactant effect can also be played simultaneously.
Prepare lithium battery according to technical scheme of the present invention, step is as follows:
(1) be 91-96.4:1.5-4.5:0.1-1:2-4 according to the mass ratio of LiFePO4, carbon nano-tube, lithium methide, PVDF, take each component, take nmp solvent according to quantity, the NMP taken is 40%-50%:1 with the ratio of four kinds of solid matter mass simultaneously;
(2) take out PVDF and part NMP, be mixed with the glue that mass fraction is 5%-20%, scattered rear stand-by;
(3) carbon nano-tube, lithium methide are joined in residue NMP, be 45Hz at rotation frequency under vacuum condition, revolution is high speed dispersion 0.8-1.2h under 40Hz, then through ultrasonic disperse 25-35min, ultrasonic disperse process conditions are 15-20KHz, power 200-300W, then adds LiFePO4 and carries out second time high speed dispersion 3.5-4.5h;
(4) glue is added scattered slurry high speed mixing dispersion 1.8-2.3h;
(5) coating of obtained anode sizing agent is obtained positive plate on a current collector;
(6) battery is assembled into by the positive plate obtained and graphite cathode sheet, barrier film, electrolyte, battery container.
Obtained positive plate, lithium ion battery and conventional batteries are carried out dependence test, demonstrates technique effect of the present invention.
Here is a specific embodiment of the present invention.
Embodiment
Prepare lithium battery according to technical scheme of the present invention, step is as follows:
(1) take each component according to 95% LiFePO4,2% carbon nano-tube, 0.5% lithium methide, 2.5%PVDF, take nmp solvent according to quantity, the NMP taken is 45% of four kinds of solid matter mass simultaneously;
(2) take out PVDF and part NMP, be mixed with the glue that mass fraction is 10%, scattered rear stand-by;
(3) carbon nano-tube, lithium methide are joined in residue NMP, be 45Hz at rotation frequency under vacuum condition, revolution is high speed dispersion 1h under 40Hz, then through ultrasonic disperse 30min, ultrasonic disperse process conditions are 15-20KHz, power 200-300W, then adds LiFePO4 and carries out second time high speed dispersion 4h;
(4) glue is added scattered slurry high speed mixing dispersion 2h;
(5) obtained anode sizing agent is applied on aluminium foil again obtain positive plate;
(6) battery is assembled into by the positive plate obtained and graphite cathode sheet, barrier film, electrolyte, battery container.
Obtained positive plate, lithium ion battery and conventional batteries are carried out dependence test, result is as follows: Fig. 1 positive plate SEM of the present invention schemes (electronic scanning video picture figure), from figure, we can see that carbon nano-tube can be good at being distributed in whole pole piece, mainly because organolithium has the effect of surperficial organic active agent, can activated carbon nano-tube, well distribution is in the slurry in pulping process to make carbon nanometer.Fig. 2 lithium ion battery of the present invention and traditional lithium-ion battery gram volume comparison diagram, from figure, we can find out that lithium ion battery gram volume of the present invention performance is higher than the battery of conventional conductive agent.Fig. 3 a and Fig. 3 b is lithium ion battery of the present invention and traditional lithium-ion battery rate charge-discharge curve comparison figure, and from figure, we can find out that lithium ion cell charging constant current ratio of the present invention, electric discharge intermediate value current potential are higher, and high rate performance is more excellent.Fig. 4 is lithium ion battery of the present invention and traditional lithium-ion battery cyclic curve comparison diagram, and from figure, we can find out that lithium ion battery 3C (coulomb) the of the present invention 200 weeks capability retentions that circulate are higher, and cycle life is longer.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a lithium ion battery, comprise a positive plate, a negative plate, a barrier film, electrolyte and battery container, it is characterized in that, described positive plate comprises a collector, described collector is coated with pulp layer, and the composition of described pulp layer comprises LiFePO4, carbon nano-tube, organolithium and PVDF; The mass ratio of described LiFePO4, carbon nano-tube, organolithium, PVDF is: 91-96.4:1.5-4.5:0.1-1:2-4.
2. lithium ion battery as claimed in claim 1, it is characterized in that, the mass ratio of described LiFePO4, carbon nano-tube, organolithium, PVDF is: 95:2:0.5:2.5.
3. lithium ion battery as claimed in claim 1, it is characterized in that, described organolithium comprises at least one in lithium methide, butyl lithium, s-butyl lithium, just base lithium, phenyl lithium.
4. the preparation method of a kind of lithium ion battery as described in claims 1 to 3 any one, is characterized in that, comprise the following steps:
(1) take LiFePO4, carbon nano-tube, organolithium and PVDF in mass ratio, and take NMP according to quantity; Take out a part of NMP, PVDF is dissolved in wherein, is mixed with glue;
(2) carbon nano-tube, organolithium are joined in residue NMP, first high speed dispersion, then carry out ultrasonic disperse, then add LiFePO4 and carry out the dispersion of second time mixed at high speed again, obtained dispersed paste;
(3) glue is joined in dispersed paste carry out high speed dispersion, obtained anode sizing agent;
(4) anode sizing agent is coated on collector, obtained positive plate;
(5) battery is assembled;
The mass ratio of described LiFePO4, carbon nano-tube, organolithium, PVDF is: 91-96.4:1.5-4.5:0.1-1:2-4.
5. the preparation method of lithium ion battery as claimed in claim 4, it is characterized in that, the mass ratio of described LiFePO4, carbon nano-tube, organolithium, PVDF is: 95:2:0.5:2.5.
6. the preparation method of lithium ion battery as claimed in claim 4, is characterized in that, takes NMP according to quantity and refer to that NMP is 40%-50%:1 with the mass ratio of the four kinds of solid matters taken in described step (1).
7. the preparation method of lithium ion battery as claimed in claim 4, it is characterized in that, the concentration of described glue is 5%-20%.
8. the preparation method of lithium ion battery as claimed in claim 4, it is characterized in that, the condition of the high speed dispersion in described step (2) is: vacuum condition, revolution 20-45rpm, rotation 1000-2500rpm; The time of described high speed dispersion is 0.8-1.2h; The time of described second time high speed dispersion is 3.5-4.5h.
9. the preparation method of lithium ion battery as claimed in claim 4, it is characterized in that, the frequency of described ultrasonic disperse is 15-20KHz, and power is 200-300W, and the time of described ultrasonic disperse is 25-35min.
10. the preparation method of lithium ion battery as claimed in claim 4, is characterized in that, the condition of the mixed at high speed dispersion in described step (3) is: vacuum condition, revolution 20-45rpm, rotation 1000-2500rpm; The time of described mixed at high speed dispersion is 1.8-2.3h.
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| CN110943218A (en) * | 2019-10-30 | 2020-03-31 | 天津力神电池股份有限公司 | Positive electrode slurry, preparation method thereof, positive plate and lithium iron phosphate battery |
| CN111082023A (en) * | 2019-12-30 | 2020-04-28 | 山东精工电子科技有限公司 | Preparation method and application of positive electrode material with high-conductivity tubular network structure |
| CN114725395A (en) * | 2022-04-26 | 2022-07-08 | 蜂巢能源科技股份有限公司 | Electrode and preparation method thereof |
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Application publication date: 20160420 |
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