CN107910507A - A kind of tertiary cathode material - Google Patents
A kind of tertiary cathode material Download PDFInfo
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- CN107910507A CN107910507A CN201711032416.1A CN201711032416A CN107910507A CN 107910507 A CN107910507 A CN 107910507A CN 201711032416 A CN201711032416 A CN 201711032416A CN 107910507 A CN107910507 A CN 107910507A
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- tertiary cathode
- cathode material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
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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
Abstract
The present invention provides a kind of tertiary cathode material, passes through a certain amount of LiFePO 4 of blending thereto, the power-performance and security performance of raising ternary material cathode lithium-ion-power cell.
Description
Technical field
The invention belongs to battery material technical field, and in particular to a kind of tertiary cathode material containing LiFePO 4.
Background technology
With the development of society, the energy, environmental problem increasingly become the significant problem for influencing human survival and development.For
This problem is tackled, new energy industry emerges rapidly.In recent years, the electric automobile row under the market demand and government guidance effect
Industry has swift and violent development, and the requirement to power battery is also continuously improved.It is higher energy density, more power density, safer
Power battery into whole new-energy automobile industry pursuit.
It is a kind of new lithium ion power battery cathode material with the tertiary cathode material that nickel cobalt manganese material (NCM) is representative
Material.NCM is nickle cobalt lithium manganate Li (NixCoyMn1-x-y)O2Abbreviation, its presoma is using nickel salt, cobalt salt, manganese salt as raw material system
, the ratio of nickel cobalt manganese can be adjusted according to actual needs.Compared to traditional lithium system battery material (such as cobalt acid lithium)
Speech, NCM has the advantages such as cost is low, operating temperature is high, gram volume is high, has extended cycle life, but its security performance is poor, have impact on
The application and popularization of ternary material cathode lithium-ion-power cell.And the security performance of battery is directly related to the excellent of vehicle performance
It is bad, or even influence whether the property and life security of car owner.
The content of the invention
In view of this, the present invention is directed to propose a kind of tertiary cathode material, sub- by a certain amount of phosphoric acid of blending thereto
Iron lithium (LFP), improves the power-performance and security performance of ternary material cathode lithium-ion-power cell.
The tertiary cathode material of the present invention, including nickle cobalt lithium manganate and the phosphoric acid Asia for accounting for nickle cobalt lithium manganate quality 0.5-10%
Iron lithium.
Wherein, the particle mean size of the nickle cobalt lithium manganate is 5 ± 2 μm, the particle mean size of the LiFePO 4 for 0.7 ±
0.2μm。
The tertiary cathode material of the present invention including following raw materials by being made：100 parts of nickle cobalt lithium manganate, LiFePO 4
0.5-10 parts, 0.5-5 parts of binding agent, 0.5-10 parts of conductive agent, 10-60 parts of solvent.In case of need, can be with raw material
Add some other auxiliary agents, such as antioxidant, activator.
Wherein, the binding agent is the one or more in PVDF, CMC, polyacrylate and SBR, and the conductive agent is
One or more in acetylene black, SUPER P Li, carbon nanotubes, the solvent are N-methyl pyrrolidones (NMP), deionization
Water, methyl ethyl ketone, the one or more in isopropanol.
Present invention also offers a kind of anode pole piece of tertiary cathode material, it is made of above-mentioned tertiary cathode material.Into one
Step, the anode pole piece of the tertiary cathode material are made by following methods：By nickle cobalt lithium manganate, LiFePO 4, binding agent, lead
After electric agent, solvent mix homogenate in proportion, coating on metal foil, it is dry after by rolling, being die cut, lamination, encapsulation, fluid injection,
The processes such as high temperature is melted into advance, high temperature ageing, room temperature aging, partial volume, obtain anode pole piece.
The present invention has higher energy density, energy density is up to 250Wh/KG, with reference to warp using NCM as material of main part
The close pile structure theoretical model of six sides of allusion quotation, can effective land productivity to the gap filling LiFePO 4 little particle of NCM material granules
With space, cathode compacted density is improved, so as to lift the volume energy density of battery.LiFePO 4 has preferable electric conductivity
Can, by short grained filling, further enhance the contact action between particle so that pole piece resistivity can significantly drop
It is low, lift battery core power-performance.In addition, LiFePO 4 acupuncture, extrude, the security such as overcharge in terms of there is relatively low temperature
Rise, so as to significantly improve the security performance of battery core.
Relative to the prior art, the present invention has the advantage that：A certain amount of phosphoric acid of blending in cathode ternary material (NCM)
Ferrous lithium, significantly improves the power-performance and security performance of battery core.The safety of cathode blending LiFePO 4 (LFP) battery core afterwards
Performance significantly improves, and acupuncture percent of pass is from when being not added with<5%, after bringing up to addition>95%, battery core surface temperature during acupuncture
Rising when addition LiFePO 4 (LFP) is relatively not added with afterwards reduces about 52%；After adding LiFePO 4 (LFP), temperature drop is overcharged
Low about 10%, overcharging crest voltage reduces about 23%；Other security performances such as extruding, short circuit, thermal shock are also improved significantly.
Brief description of the drawings
The attached drawing for forming the part of the present invention is used for providing a further understanding of the present invention, schematic reality of the invention
Apply example and its explanation is used to explain the present invention, do not form inappropriate limitation of the present invention.In the accompanying drawings：
The SEM that Fig. 1 is pure LFP and NCM schemes；Wherein, a) pure LFP；B) pure NCM；
Fig. 2 is NCM and the SEM of LFP blendings schemes；
Fig. 3 is that the NCM and EDS after LFP blendings schemes；Wherein, a) sample SEM schemes, b) distribution diagram of element, c) element percentage
Than；
Fig. 4 is addition LFP and is not added with LFP positive plate resistivity contrasts；
Fig. 5 is cathode addition LFP and is not added with LFP acupuncture curve comparison figures；Wherein, a) cathode adds LFP, b) cathode is not
Add LFP；
Fig. 6 is that cathode addition LFP overcharges curve comparison figure with being not added with LFP；In, a) cathode addition LFP, b) cathode do not add
Add LFP.
Embodiment
The present invention is described more detail below.
Make anode pole piece respectively using the formula in table 1 as raw material, and using same cathode pole piece with it is made just
Finished product battery core is made in pole pole piece jointly.The production method of anode pole piece is, after each component raw material is mixed homogenate, coated in aluminium foil
On, it is dry after by rolling, being die cut, lamination, encapsulation, fluid injection, high temperature be melted into advance, high temperature ageing, room temperature aging, the work such as partial volume
Sequence, finished product battery core is made with cathode pole piece zoarium.
Table 1
Microstructure observing is carried out under Electronic Speculum using the anode pole piece sample of embodiment 1, and with the SEM of pure LFP and NCM
Contrast, as a result as shown in Figs. 1-2.Meanwhile EDS analyses are coordinated to the sample of NCM and LFP blendings, the results are shown in Figure 3.By
The analysis of SEM and EDS is it is known that short grained LFP is dispersed between the NCM gaps of bulky grain, contact action between particle
Increase, compaction increase.
Resistivity measurement is carried out using the sample of embodiment 2 and comparative example, four probe test results (Fig. 4) show that LFP is mixed
Sample resistivity after mixing substantially reduces, the half of resistivity about before blending.
The contrast test of acupuncture experiment is carried out using the sample of embodiment 3 and comparative example.Test the temperature at 20 DEG C ± 5 DEG C
Lower progress, measures battery core voltage using universal meter, battery core is fixed on fixture, thermocouple is placed in battery core centre of surface, makes pin
Thorn drill bit is through battery core and starts timing, observes temperature and voltage change.Testing result is as shown in Figure 5.Added in cathode raw material
After LFP, can surface of stability temperature rise within a certain period of time, embody good anti-safety of acupuncture.
Overcharge safety test is carried out using the sample of embodiment 4 and comparative example.After battery core is discharged, with the electric current pair of 1C
Battery core charges, and current reduction records charging process voltage, electric current and temperature change to close to 0 after the about 60min that charges.Inspection
The results are shown in Figure 6 for survey.After adding LFP in cathode raw material, uprushing for voltage and temperature can effectively be avoided by overcharging moment, be embodied
Good overcharge safety.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on, should all be included in the protection scope of the present invention god.
Claims (8)
1. a kind of tertiary cathode material, including nickle cobalt lithium manganate and the LiFePO 4 for accounting for nickle cobalt lithium manganate quality 0.5-10%.
2. tertiary cathode material according to claim 1, it is characterised in that the particle mean size of the nickle cobalt lithium manganate is 5
± 2 μm, the particle mean size of the LiFePO 4 is 0.7 ± 0.2 μm.
3. tertiary cathode material according to claim 1, it is characterised in that by being made including following raw materials：Nickel cobalt manganese
Sour 100 parts of lithium, 0.5-10 parts of LiFePO 4,0.5-5 parts of binding agent, 0.5-10 parts of conductive agent, 10-60 parts of solvent.
4. tertiary cathode material according to claim 1, it is characterised in that the binding agent is PVDF, CMC, polypropylene
Acid esters and the one or more in SBR.
5. tertiary cathode material according to claim 1, it is characterised in that the conductive agent is acetylene black, SUPER P
One or more in Li, carbon nanotubes.
6. tertiary cathode material according to claim 1, it is characterised in that the solvent is N-methyl pyrrolidones, is gone
Ionized water, methyl ethyl ketone, the one or more in isopropanol.
7. a kind of anode pole piece of tertiary cathode material, is made of claim 1-6 any one of them tertiary cathode materials.
8. the preparation method of anode pole piece described in claim 7, comprises the following steps：By nickle cobalt lithium manganate, LiFePO 4, glue
After knot agent, conductive agent, solvent mix homogenate in proportion, coat on metal foil, by rolling, being die cut, lamination, envelope after drying
The processes such as dress, fluid injection, high temperature are melted into advance, high temperature ageing, room temperature aging, partial volume, obtain anode pole piece.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711032416.1A CN107910507A (en) | 2017-10-27 | 2017-10-27 | A kind of tertiary cathode material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711032416.1A CN107910507A (en) | 2017-10-27 | 2017-10-27 | A kind of tertiary cathode material |
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| Publication Number | Publication Date |
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| CN107910507A true CN107910507A (en) | 2018-04-13 |
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| CN201711032416.1A Pending CN107910507A (en) | 2017-10-27 | 2017-10-27 | A kind of tertiary cathode material |
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| CN102544498A (en) * | 2012-03-12 | 2012-07-04 | 安徽安凯汽车股份有限公司 | Cathode material of lithium ion battery |
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| CN106992297A (en) * | 2016-01-20 | 2017-07-28 | 深圳市雄韬电源科技股份有限公司 | A kind of preparation method and application of ternary battery composite anode material |
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Patent Citations (10)
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|---|---|---|---|---|
| CN101281987A (en) * | 2008-05-22 | 2008-10-08 | 上海南都能源科技有限公司 | Ferrous phosphate lithium-based polyalcohol lithium battery and method for manufacturing the same |
| CN102386409A (en) * | 2011-11-03 | 2012-03-21 | 湖南丰源业翔晶科新能源股份有限公司 | Paste for cathode of lithium iron phosphate lithium ion battery |
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Application publication date: 20180413 |