CN108448056A - A kind of preparation method of high-energy density anode pole piece and its lithium ion battery - Google Patents
A kind of preparation method of high-energy density anode pole piece and its lithium ion battery Download PDFInfo
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- CN108448056A CN108448056A CN201810215009.2A CN201810215009A CN108448056A CN 108448056 A CN108448056 A CN 108448056A CN 201810215009 A CN201810215009 A CN 201810215009A CN 108448056 A CN108448056 A CN 108448056A
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- pole piece
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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 invention discloses the preparation methods of a kind of high-energy density anode pole piece and its lithium ion battery, are made of collector, positive electrode active materials, conductive agent, binder, and the positive electrode active materials are cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2), LiMn2O4 (LiMn2O4), nickle cobalt lithium manganate (LiNi(1‑x‑y)CoxMnyO2), nickel cobalt lithium aluminate (LiNi(1‑x‑y)CoxAlyO2), rich lithium manganese (xLi [Li1/3Mn2/3]O2·(1–x)LiMO2, M is transition metal) in two kinds；The mass ratio of the positive electrode active materials, conductive agent, binder:93‑99：0.5‑4：0.5‑3；The mass ratio of described two positive electrode active materials is 30 85:15‑70；The present invention is different according to the performance of two kinds of positive electrode active materials, the advantages of adjusting the two ratio, can effectively play two kinds of positive electrode active materials, realizes the purpose maximized favourable factors and minimized unfavourable ones；Lithium battery prepared by the present invention can also significantly improve the cycle performance and security performance of battery, meet market demands while promoting energy density.
Description
Technical field
The present invention be a kind of lithium ion battery preparing technical field more particularly to a kind of high-energy density anode pole piece and
The preparation method of its lithium ion battery.
Background technology
As fuel-engined vehicle is constantly universal, it is daily that the atmosphere pollution caused by motor vehicle exhaust emission has seriously affected the mankind
Life, so it is one of the effective measures for reducing carbon emission amount and improving environment for human survival to greatly develop new-energy automobile.It is existing
Stage, national governments are just putting into effect the development that relevant policies carry forward vigorously new-energy automobile industry in succession.2017, India, Norway,
France and Britain have announced, will gradually eliminate fuel vehicle, are replaced with more clean electric or hybrid automobile.Norway sets
The fixed deadline date is 2025, and India is the year two thousand thirty, and Britain and method state are all the year two thousand forties.Although China does not provide the combustion that prohibits selling also
The specific time of oily vehicle, but " double integrator " policy carried out at present according to China, it can be seen that enter new energy vapour comprehensively
The vehicle epoch are a matter of time.
Lithium ion battery has many advantages, such as high-energy density, high voltage, low self-discharge, memory-less effect, long circulation life,
It is the key technology for developing new energy.However, compared with traditional fuel vehicle, lower energy density and mileage travelled, greatly
The earth limits the popularization of new-energy automobile.In order to promote the development of newly energy automobile, China to propose the energy density of power battery
New target call, in the year two thousand twenty, single battery energy density will reach 350wh/kg, system energy densities 250wh/kg, institute
To develop the most important thing that high energy density cells have become promotion new-energy automobile industry development.However, cannot blindness list
Pure pursuit high-energy density, while developing high-energy density, the deserved more concerns of security performance of battery.
Nickelic positive electrode has the characteristics that height ratio capacity, is the popular material of current exploitation lithium ion battery with high energy density
Material, however, that there is also capacity retention ratios is low for nickelic positive electrode, the poor disadvantage of thermal stability reduces the peace of lithium ion battery
Full performance, so the security performance for improving ion battery is the key that one of exploitation lithium ion battery with high energy density.Proprietary term
For a kind of lithium ion battery (application publication number of high-energy density：CN105470559A), which disclose a kind of high-energy
Density lithium ion battery, positive electrode used in the lithium ion battery is LiFePO4 series, wherein made battery core is most
High-energy density also only has 160wh/kg, energy density much to can not meet current demand；In addition, the battery core is before dispensing
It needs two positive electrode carrying out ball milling mixing, is unfavorable for actual industrialization batch production.
Invention content
The purpose of the present invention is to provide the preparation method of a kind of high-energy density anode pole piece and its lithium ion battery, solutions
The problem of being proposed in certainly above-mentioned background.
To achieve the above object, the present invention provides the following technical solutions：
A kind of high-energy density anode pole piece, is made of collector, positive electrode active materials, conductive agent, binder, it is described just
Pole active material is cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2), LiMn2O4 (LiMn2O4), nickle cobalt lithium manganate (LiNi(1-x-y)
CoxMnyO2), nickel cobalt lithium aluminate (LiNi(1-x-y)CoxAlyO2), rich lithium manganese (xLi [Li1/3Mn2/3]O2·(1–x)LiMO2, M was
Cross metal) in two kinds, the mass ratioes of described two positive electrode active materials is 0.17~5.67:1.
As the further scheme of the present invention, the mass ratio of described two positive electrode active materials is 0.25~4:1.
As the further scheme of the present invention, the mass ratio of described two positive electrode active materials is 0.375~3.67:1.
As the further scheme of the present invention, the mass ratio of described two positive electrode active materials is 0.66~-1.5:1.
As the present invention further scheme, the positive electrode active materials, conductive agent, binder mass ratio:93-99：
0.5-4：0.5-3.
A kind of preparation method of lithium ion battery, includes the preparation of anode pole piece and cathode pole piece, preparation method include with
Lower step：(1) anode pole piece is prepared, binder, conductive agent, blended anode active material is molten according to quality proportioning mixing addition
Agent, stirring at normal temperature 120-240min, vacuum degassing bubble obtain anode sizing agent；Prepared anode sizing agent is uniformly coated on utter misery
On aluminium foil positive and negative, aluminium foil both sides reserve sky foil as pole-piece pole-ear position, tab welding are used for, by being made after roll-in, cross cutting
Made positive plate is placed and is preserved under vacuum condition, for use by positive plate；(2) cathode pole piece is prepared, by binder, conduction
Agent, negative electrode active material are mixed according to quality proportioning is added solvent, and stirring at normal temperature 120-240min, vacuum degassing bubble obtains cathode
Slurry, the negative electrode binder, conductive agent, active material mass ratio be 93-97,0.5-4,0.8-3；The cathode that will have been configured
Slurry is uniformly coated on copper foil positive and negative, and copper foil both sides reserve sky foil as pole-piece pole-ear and are, is used for tab welding, is passed through roller
Negative plate is made after pressure, cross cutting, made negative plate is placed and is preserved under vacuum condition, for use；(3) battery core is made：It will just
Pole pole piece, cathode pole piece, diaphragm are fabricated to naked battery core by the way of lamination, after short-circuit test, through tab welding, top side seal,
After baking, fluid injection, chemical conversion, the forming of two envelopes, partial volume, it is fabricated to soft bag lithium ionic cell.
As the present invention further scheme, the negative electrode active material be graphite, carbonaceous mesophase spherules, hard carbon, soft carbon,
One or more of silicon-carbon/silica.
As the further scheme of the present invention, the conductive agent is carbon black, electrically conductive graphite, carbon fiber, carbon nanotube, stone
One or more of black alkene.
In the present invention, using the different positive electrode active materials of two kinds of performances, and by adjusting the two ratio, mix and match,
The complementation for effectively realizing two kinds of positive electrode active materials, to achieve the purpose that maximize favourable factors and minimize unfavourable ones.Lithium battery prepared by the present invention
The cycle performance and security performance of battery can also be significantly improved while promoting energy density.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) present invention is different according to the performance of two kinds of positive electrode active materials, both adjustment ratio, mix and match, Ke Yiyou
Effect ground plays the advantage of two kinds of positive electrode active materials respectively the shortcomings that making up other side, to realize the purpose maximized favourable factors and minimized unfavourable ones.
(2) lithium battery prepared by the present invention can also significantly improve battery while promoting energy density
Cycle performance and security performance, meet market demands.
(3) present invention is mixed two kinds of positive electrode active materials by different proportion, easy to operate, is differed with conventional production practices
Less, feasibility is strong, easily realizes industrialization.
Specific implementation mode
Embodiment 1
By taking the manufacturing process of the soft bag lithium ionic cell of model 465473 as an example, the specific manufacturing process of the battery is such as
Under：
1, anode pole piece makes：
First, positive electrode binder Kynoar (PVDF) is dispersed in solvent N-methyl pyrilidone (NMP),
The glue that solid content is 6% is made；Then, positive conductive agent SP and CNT conduction slurries are separately added into glue, are in rotating speed
Under conditions of 3000rpm, blended anode active material is then NCA (nickel cobalt aluminic acids by weight by stirring at normal temperature 240min
Lithium)：LiNi0.5Co0.2Mn0.3O2=8：2 are added thereto, wherein each material mass percentage ratio is NCA：
LiNi0.5Co0.2Mn0.3O2：SP：CNT：PVDF=78%：19.5%：0.5%：1.0%：1.0%, it is 2500rpm's in rotating speed
Under the conditions of, 30min is steeped in stirring at normal temperature 210min, vacuum degassing, is 6000-by the way that NMP is added to adjust slurry viscosity
12000mPa.s, solid content are 62% -70%；Finally, prepared anode sizing agent is uniformly coated on utter misery aluminium foil positive and negative
On, aluminium foil both sides reserve sky foil as pole-piece pole-ear position, tab welding are used for, by the way that positive plate is made after roll-in, cross cutting, by institute
Manufactured positive plate is placed to be preserved under vacuum condition, for use.
2, negative plate makes：
First, sodium carboxymethylcellulose (CMC) is evenly dispersed in deionized water, the glue that solid content is 1.2% is made
Liquid, conductive agent SP are added in glue, under conditions of rotating speed is 2100rpm, stirring at normal temperature 180min, then by cathode graphite
It is added, under conditions of rotating speed is 2400rpm, SBR suspensions are finally added slurry, stirred at a slow speed by stirring at normal temperature 210min
It mixes, vacuumizes bubble removing, wherein each material mass percentage ratio is C：SP：CMC：SBR=95%：1.5%：1.0%：2.5%,
It is 2000-5000mPa.s by the way that deionized water is added to adjust viscosity, solid content is 42%-50%；Finally, it will configure
Negative electrode slurry is uniformly coated on copper foil positive and negative, and copper foil both sides reserve sky foil as pole-piece pole-ear and are, is used for tab welding, is led to
Negative plate is made after crossing roll-in, cross cutting, made negative plate is placed and is preserved under vacuum condition, for use.
3, battery core makes
Anode pole piece, cathode pole piece, diaphragm are fabricated to naked battery core by the way of lamination, after short-circuit test, through lug
After welding, top side seal, baking, fluid injection, chemical conversion, the forming of two envelopes, partial volume, it is 2Ah, the Soft Roll of model 465473 to be fabricated to capacity
Lithium ion battery.
Example 2：By taking the manufacturing process of the soft bag lithium ionic cell of model 465473 as an example, compared with example 1, difference
It is in the quality proportioning difference in each substance of anode pole piece, each material mass percentage ratio is NCA：LiNi0.5Co0.2Mn0.3O2：
SP：CNT：PVDF=68.25%：29.25%：0.5%：1%：1.0%, other all sames.
Example 3：By taking the manufacturing process of the soft bag lithium ionic cell of model 465473 as an example, compared with example 1, difference
It is in the quality proportioning difference in each substance of anode pole piece, each material mass percentage ratio is NCA：LiNi0.5Co0.2Mn0.3O2：
SP：CNT：PVDF=58.5%：39%：0.5%：1%：1.0%, other all sames.
Example 4：By taking the manufacturing process of the soft bag lithium ionic cell of model 465473 as an example, compared with example 1, difference
It is in the quality proportioning difference in each substance of anode pole piece, each material mass percentage ratio is NCA：LiNi0.5Co0.2Mn0.3O2：
SP：CNT：PVDF=48.75%：48.75%：0.5%：1%：1.0%, other all sames.
Example 5：By taking the manufacturing process of the soft bag lithium ionic cell of model 465473 as an example, compared with example 1, difference
It is in the quality proportioning difference in each substance of anode pole piece, each material mass percentage ratio is NCA：LiNi0.5Co0.2Mn0.3O2：
SP：CNT：PVDF=39%：58.5%：0.5%：1%：1.0%, other all sames.
Example 6：By taking the manufacturing process of the soft bag lithium ionic cell of model 465473 as an example, compared with example 1, difference
It is in the quality proportioning difference in each substance of anode pole piece, each material mass percentage ratio is NCA：LiNi0.5Co0.2Mn0.3O2：
SP：CNT：PVDF=29.25%：68.25%：0.5%：1%：1.0%, other all sames.
Example 7：By taking the manufacturing process of the soft bag lithium ionic cell of model 465473 as an example, compared with example 1, difference
It is in the quality proportioning difference in each substance of anode pole piece, each material mass percentage ratio is NCA：LiNi0.5Co0.2Mn0.3O2：
SP：CNT：PVDF=19.5%：78%：0.5%：1%：1.0%, other all sames.
Comparative example 1：It is different compared with example 1 by taking the manufacturing process of the soft bag lithium ionic cell of model 465473 as an example
Place is that the quality proportioning of each substance of anode pole piece is different, and each material mass percentage ratio is NCA：SP：CNT：PVDF=
97.5%：0.5%：1%：1.0%, other all sames.
Comparative example 2：It is different compared with example 1 by taking the manufacturing process of the soft bag lithium ionic cell of model 465473 as an example
Place is that the quality proportioning of each substance of anode pole piece is different, and each material mass percentage ratio is LiNi0.5Co0.2Mn0.3O2：SP：
CNT：PVDF=97.5%：0.5%：1%：1.0%, other all sames.
The electrical property of different positive electrode active materials mixing proportion battery cores in examples detailed above is compared below, is summarized such as table
Shown in 1：
As it can be seen from table 1 the cycle performance between example 1-7 is not much different, but energy density but has bigger difference,
Phase difference is 18Wh/Kg；Comparative example 1 and comparative example 1, though it can be found that single NCA has higher energy density,
It is that cycle performance is poor；Comparison example 7 and comparative example 2, it can be found that the positive electrode active materials of blending are than single
LiNi0.5Co0.2Mn0.3O2It is about 15Wh/Kg to have higher energy density, difference, and cycle performance difference between the two is not
Greatly.By comparing above, it can be found that the positive electrode active materials of blending can neutralize the advantage and disadvantage of single positive electrode active materials, raise
It is long to keep away short, while improving energy density, improve the cycle performance of battery core.
The security performance of different positive electrode active materials mixing proportion battery core in examples detailed above is compared below, summarize as
Shown in table 2：
From table 2 it can be seen that example 1, example 2 are compared with comparative example 1, the security performance of positive electrode active materials battery core is blended
There is larger promotion, in conjunction with table 1 it can be found that while improving battery core cycle performance, significantly improves the peace of battery core
Full performance, while battery core energy density is not much different.
The better embodiment of this patent is explained in detail above, but this patent is not limited to above-mentioned embodiment party
Formula, one skilled in the relevant art within the scope of knowledge, can also be under the premise of not departing from this patent objective
It makes a variety of changes.
Claims (8)
1. a kind of high-energy density anode pole piece, including collector, positive electrode active materials, conductive agent, binder, feature exist
In the positive electrode active materials are cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2), LiMn2O4 (LiMn2O4), nickle cobalt lithium manganate
(LiNi(1-x-y)CoxMnyO2), nickel cobalt lithium aluminate (LiNi(1-x-y)CoxAlyO2), rich lithium manganese (xLi [Li1/3Mn2/3]O2·(1–x)
LiMO2, M is transition metal) in two kinds, the mass ratioes of described two positive electrode active materials is 0.17~5.67:1.
2. high-energy density anode pole piece according to claim 1, which is characterized in that described two positive electrode active materials
Mass ratio is 0.25~4:1.
3. high-energy density anode pole piece according to claim 1, which is characterized in that described two positive electrode active materials
Mass ratio is 0.375~3.67:1.
4. high-energy density anode pole piece according to claim 1, which is characterized in that described two positive electrode active materials
Mass ratio is 0.66~1.5:1.
5. high-energy density anode pole piece according to claim 1, which is characterized in that the positive electrode active materials, conduction
Agent, binder mass ratio:93-99：0.5-4：0.5-3.
6. a kind of preparation method of lithium ion battery, includes the preparation of anode pole piece and cathode pole piece, which is characterized in that it is described just
Pole pole piece is anode pole piece as claimed in claim 1 or 2, and the preparation method comprises the following steps：(1) anode pole piece is prepared,
Binder, conductive agent, blended anode active material are mixed according to quality proportioning, solvent is added, stirring at normal temperature 120-240min,
Vacuum degassing is steeped, and anode sizing agent is obtained；Prepared anode sizing agent is uniformly coated on utter misery aluminium foil positive and negative, aluminium foil both sides are stayed
Go out sky foil as pole-piece pole-ear position, tab welding is used for, by the way that positive plate is made after roll-in, cross cutting, by made positive plate
It places and is preserved under vacuum condition, for use；(2) cathode pole piece is prepared, by binder, conductive agent, negative electrode active material according to quality
Solvent, stirring at normal temperature 120-240min is added in proportioning mixing, and vacuum degassing bubble obtains negative electrode slurry, the negative electrode binder, conduction
Agent, active material mass ratio be 93-97,0.5-4,0.8-3；The negative electrode slurry configured is uniformly coated on copper foil positive and negative
On, copper foil both sides reserve sky foil as pole-piece pole-ear and are, tab welding are used for, by the way that negative plate is made after roll-in, cross cutting, by institute
Manufactured negative plate is placed to be preserved under vacuum condition, for use；(3) battery core is made：Anode pole piece, cathode pole piece, diaphragm are used
The mode of lamination is fabricated to naked battery core, after short-circuit test, through tab welding, top side seal, baking, fluid injection, chemical conversion, the forming of two envelopes,
After partial volume, it is fabricated to soft bag lithium ionic cell.
7. the preparation method of lithium ion battery according to claim 3, which is characterized in that the negative electrode active material is stone
One or more of ink, carbonaceous mesophase spherules, hard carbon, soft carbon, silicon-carbon/silica.
8. the preparation method of lithium ion battery according to claim 3, which is characterized in that the conductive agent be carbon black,
One or more of electrically conductive graphite, carbon fiber, carbon nanotube, graphene.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109411716A (en) * | 2018-09-18 | 2019-03-01 | 深圳市优特利电源有限公司 | Based lithium-ion battery positive plate and preparation method thereof and lithium ion battery |
| CN111900363A (en) * | 2020-08-21 | 2020-11-06 | 珠海冠宇电池股份有限公司 | Positive active material, and pole piece and lithium ion battery containing positive active material |
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| CN106229477A (en) * | 2016-08-12 | 2016-12-14 | 中航锂电（洛阳）有限公司 | Positive electrode active materials, preparation method and application |
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| CN101752550A (en) * | 2008-12-10 | 2010-06-23 | 深圳市比克电池有限公司 | Method for confecting lithium ion battery anode sizing agent |
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| CN109411716A (en) * | 2018-09-18 | 2019-03-01 | 深圳市优特利电源有限公司 | Based lithium-ion battery positive plate and preparation method thereof and lithium ion battery |
| CN111900363A (en) * | 2020-08-21 | 2020-11-06 | 珠海冠宇电池股份有限公司 | Positive active material, and pole piece and lithium ion battery containing positive active material |
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