CN109119632A - Positive electrode slurry, positive plate and lithium ion battery - Google Patents
Positive electrode slurry, positive plate and lithium ion battery Download PDFInfo
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- CN109119632A CN109119632A CN201710492578.7A CN201710492578A CN109119632A CN 109119632 A CN109119632 A CN 109119632A CN 201710492578 A CN201710492578 A CN 201710492578A CN 109119632 A CN109119632 A CN 109119632A
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- positive electrode
- sizing agent
- anode sizing
- lithium ion
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive 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
- 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
- H01M4/62—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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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 provides a positive electrode slurry, a positive plate and a lithium ion battery. The positive electrode slurry includes a solid component including a positive electrode material, a conductive agent, and a binder, and a solvent. The solid component also includes a positive electrode additive boric acid. The positive electrode material includes LixNiyM1‑yO2，0.9≤x≤1.1，0.6<y is less than or equal to 0.9. The boric acid serving as the positive electrode additive in the positive electrode slurry can reduce the content of impurity lithium on the surface of a positive electrode material and form a lithium fast ion conductor on the surface of the positive electrode material at the same time, thereby being beneficial to the conduction of lithium ions, improving the conductivity of the positive electrode material, reducing the polarization of a lithium ion battery, improving the capacity of the lithium ion battery and improving the cycle performance and the high-temperature storage performance of the lithium ion battery. The positive electrode additive boric acid in the positive electrode slurry can improve the phenomenon that the positive electrode slurry is easy to gel in the stirring process, reduce the requirement of the positive electrode slurry on the environmental humidity in the processing process and reduce the manufacturing cost of the lithium ion battery.
Description
Technical field
The present invention relates to field of batteries more particularly to a kind of anode sizing agents, positive plate and lithium ion battery.
Background technique
Lithium ion battery is due to having the characteristics that energy density is high, having extended cycle life, pollution-free, so that it is in consumer electricity
The fields such as sub- product, power vehicle battery and accumulation power supply have broad application prospects.
No matter in which application field, people made higher requirement the cruising ability of lithium ion battery.In order to
The energy density of lithium ion battery is improved, it is one of effective way that developing, which has the positive electrode of height ratio capacity,.Currently, nickelic contain
The tertiary cathode material of amount due to its theoretical specific capacity compared to traditional cobalt acid lithium, LiFePO4, low nickel content ternary just
Pole material is high, becomes the hot spot of research.But there are more lithias, carbon on the surface of the tertiary cathode material of high nickel content
The impurity such as sour lithium.The presence of these impurity lithiums will increase positive electrode Surface Polarization, deteriorate the capacity of lithium ion battery, reduce lithium
The energy density of ion battery influences the cycle performance and high-temperature storage performance of lithium ion battery.
In addition, the lithia on the surface of the tertiary cathode material of high nickel content is also easy to generate with the reaction of moisture in environment
Lithium hydroxide is covered on the surface of the tertiary cathode material of high nickel content, and the hydroxyl in lithium hydroxide will lead to anode sizing agent pH
Value rises, and reacts with binder (such as most common Kynoar, be abbreviated as PVDF), and PVDF is caused to take off H, de- F
Carbon-carbon double bond is formed, anode sizing agent gel is eventually led to.In tertiary cathode material process in order to improve high nickel content just
Pole slurry is easy the problem of gel, and the means mainly taken at present are the ambient humidities of strict control anode sizing agent stirring.However
In practical applications, the manufacturing cost that will lead to lithium ion battery to the strict control of ambient humidity sharply increases, and cannot achieve
Industrialized production.
Summary of the invention
In view of the problems in the background art, a purpose of the present invention is that provide a kind of anode sizing agent, positive plate and
Lithium ion battery, the anode additive boric acid in the anode sizing agent can reduce the same of the impurity lithium content on positive electrode surface
When positive electrode surface formed lithium fast-ionic conductor, facilitate the conduction of lithium ion, improve the electric conductivity of positive electrode, reduce
The polarization of lithium ion battery improves the capacity of lithium ion battery, improves the cycle performance and high temperature storage of lithium ion battery
Energy.
Another object of the present invention is to provide a kind of anode sizing agent, positive plate and lithium ion battery, the anode sizing agent
In anode additive boric acid can improve the phenomenon that being easy to happen gel in anode sizing agent whipping process, reduce anode sizing agent adding
Requirement during work to ambient humidity, reduces the manufacturing cost of lithium ion battery.
In order to achieve the above object, in one aspect of the invention, the present invention provides a kind of anode sizing agents comprising solid
Component and solvent, the solid component include positive electrode, conductive agent and binder.The solid component further includes anode
Additive boric acid.The positive electrode includes LixNiyM1-yO2, 0.9≤x≤1.1,0.6 < y≤0.9, M be selected from Co, Mn, Al,
One or more of Mg, Fe, Cr, V, Ti, Cu, B, Ca, Zn, Zr, Nb, Mo, Sr, Sb, W, Bi.
In another aspect of this invention, the present invention provides a kind of positive plate, by described according to an aspect of the present invention
Anode sizing agent is coated on plus plate current-collecting body and is formed.
In still another aspect of the invention, the present invention provides a kind of lithium ion batteries comprising by a side according to the present invention
Anode sizing agent described in face is coated on the positive plate formed on plus plate current-collecting body.
Compared with the existing technology, the invention has the benefit that
Anode additive boric acid in anode sizing agent of the invention can reduce the impurity lithium content on positive electrode surface
Lithium fast-ionic conductor is formed on positive electrode surface simultaneously, facilitates the conduction of lithium ion, improves the electric conductivity of positive electrode, is dropped
The polarization of low lithium ion battery improves the capacity of lithium ion battery, improves the cycle performance and high temperature storage of lithium ion battery
Performance.
Anode additive boric acid in anode sizing agent of the invention can improve be easy to happen in anode sizing agent whipping process it is solidifying
The phenomenon that glue, reduces anode sizing agent in process to the requirement of ambient humidity, reduces the manufacturing cost of lithium ion battery.
Detailed description of the invention
Fig. 1 is the state after anode sizing agent prepared by embodiment 1 is stood for 24 hours；
Fig. 2 is the state after anode sizing agent prepared by comparative example 1 is stood for 24 hours.
Specific embodiment
The following detailed description of anode sizing agent according to the present invention, positive plate and lithium ion battery.
Illustrate anode sizing agent according to a first aspect of the present invention first.
Anode sizing agent according to a first aspect of the present invention includes solid component and solvent, and the solid component includes anode
Material, conductive agent and binder.The solid component further includes anode additive boric acid (H3BO3).The positive electrode includes
LixNiyM1-yO2, 0.9≤x≤1.1,0.6 < y≤0.9, M be selected from Co, Mn, Al, Mg, Fe, Cr, V, Ti, Cu, B, Ca, Zn, Zr,
One or more of Nb, Mo, Sr, Sb, W, Bi.
LixNiyM1-yO2For high-nickel material, there are the impurity such as more lithia, lithium carbonate, anode slurries of the invention on surface
Anode additive H in material3BO3It can be with high-nickel material LixNiyM1-yO2Impurity lithium (such as lithium hydroxide, lithium carbonate, the oxygen on surface
Change lithium etc.) reaction, reduce impurity lithium content, simultaneous reactions product lithium borate salt (Li3BO3、LiBO2) it is lithium fast-ionic conductor,
It is distributed in the surface of high-nickel material, facilitates the conduction of lithium ion, the electric conductivity of high-nickel material is improved, reduces lithium ion battery
Polarization, improves the capacity of lithium ion battery, improves the cycle performance and high-temperature storage performance of lithium ion battery.
Anode additive H in anode sizing agent of the invention3BO3Also acid can occur with the lithium hydroxide on high-nickel material surface
Alkali neutralization reaction, reduces the pH value of anode sizing agent, improves the phenomenon that being easy to happen gel in anode sizing agent whipping process, reduces just
Pole slurry to the requirement of ambient humidity, reduces the manufacturing cost of lithium ion battery in process.
In the anode sizing agent described according to a first aspect of the present invention, the quality of boric acid can be total matter of the solid component
The 0.1%~1% of amount.Content is very few, can not effectively eliminate high-nickel material LixNiyM1-yO2The impurity lithium on surface, also can not be effective
Improve the phenomenon that being easy to happen gel in anode sizing agent whipping process；Content is excessive, and the energy for being easily reduced lithium ion battery is close
Degree, deteriorates the cycle performance and high-temperature storage performance of lithium ion battery.Preferably, the quality of boric acid can be the solid component
Gross mass 0.1%~0.5%.
In the anode sizing agent described according to a first aspect of the present invention, the additional amount of positive electrode is unrestricted, it is preferable that
The quality of the positive electrode can be the 89.5%~97.9% of the gross mass of the solid component.
In the anode sizing agent described according to a first aspect of the present invention, the additional amount of conductive agent is unrestricted, it is preferable that institute
The quality for stating conductive agent can be the 1%~5% of the gross mass of the solid component.
In the anode sizing agent described according to a first aspect of the present invention, the additional amount of binder is unrestricted, it is preferable that institute
The quality for stating binder can be the 1%~5% of the gross mass of the solid component.
In the anode sizing agent described according to a first aspect of the present invention, it is preferable that in positive electrode, M may include Co,
One of at least two and Mg, Fe, Cr, V, Ti, Cu, B, Ca, Zn, Zr, Nb, Mo, Sr, Sb, W, Bi of Mn, Al or several
Kind.
In the anode sizing agent described according to a first aspect of the present invention, it is preferable that positive electrode may include LixNiyM1-yO2,
0.9 < x < 1.1,0.6 < y < 0.9, M be selected from Co, Mn, Al, Mg, Fe, Cr, V, Ti, Cu, B, Ca, Zn, Zr, Nb, Mo, Sr, Sb, W,
One or more of Bi, it is further preferred that M may include at least two and Mg, Fe of Co, Mn, Al, Cr, V, Ti, Cu,
B, one or more of Ca, Zn, Zr, Nb, Mo, Sr, Sb, W, Bi.Specifically, LixNiyM1-yO2It can be selected from
LiNi0.8Co0.1Mn0.1O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.85Co0.15Mn0.05O2、LiNi0.85Co0.15Al0.05O2、Li
(Ni0.8Co0.1Mn0.1)0.99Mg0.01O2、Li(Ni0.8Co0.1Mn0.1)0.99Zr0.01O2One or more of.
It should be noted that the positive electrode used is not in anode sizing agent of the invention, positive plate and lithium ion battery
It is only limitted to high-nickel material LixNiyM1-yO2, it includes high-nickel material Li that positive electrode, which removes,xNiyM1-yO2Outside, it may also include other anodes
Material, such as cobalt acid lithium, LiMn2O4, LiFePO4 etc..From the point of view of the energy density for improving lithium ion battery, preferably
Li is used only in ground, positive electrodexNiyM1-yO2。
In the anode sizing agent described according to a first aspect of the present invention, the type of conductive agent is unrestricted, it is preferable that described
Conductive agent can be selected from one or more of electrically conductive graphite, conductive black, acetylene black, carbon nanotube, graphene.
In the anode sizing agent described according to a first aspect of the present invention, the type of binder is unrestricted, it is preferable that described
The optional autohemagglutination segregation vinyl fluoride (PVDF) of binder, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene-tetrafluoroethene copolymerization
Object, biasfluoroethylene-hexafluoropropylene-TFE copolymer, vinylidene fluoride pentafluor propylene copolymer ,-five fluorine third of vinylidene
Alkene-TFE copolymer, vinylidene-perfluoro methyl vinyl ether-TFE copolymer, vinylidene-chlorine trifluoro second
Alkene copolymer, polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoro second
One or more of alkene copolymer, ethylene-chlorotrifluoro-ethylene copolymer, tetrafluoraoethylene-hexafluoropropylene copolymer.
In the anode sizing agent described according to a first aspect of the present invention, the type of solvent is unrestricted, it is preferable that described molten
Agent can be N-Methyl pyrrolidone (NMP).
In the anode sizing agent described according to a first aspect of the present invention, the mass content of solid component in the anode sizing agent
It can be 50%~70%.
Secondly the positive plate of explanation according to a second aspect of the present invention is starched by the anode described according to a first aspect of the present invention
Material, which is coated on plus plate current-collecting body, to be formed.Plus plate current-collecting body can be selected from aluminium foil, nickel foil or stainless steel foil.Anode sizing agent is coated on just
Positive diaphragm can be formed by drying and removing solvent on the collector of pole.
Illustrate lithium ion battery according to a third aspect of the present invention again comprising by described according to a first aspect of the present invention
Anode sizing agent be coated on the positive plate formed on plus plate current-collecting body.Lithium ion battery further includes negative electrode tab, electrolyte, pack case
Deng electrolyte, the type of pack case are unrestricted, can be selected according to actual needs.Liquid electrolyte can be used in electrolyte
Solid electrolyte, such as inorganic solid electrolyte, polymer dielectric can also be used.Negative electrode tab includes negative current collector and sets
Cathode membrane on it is set, cathode membrane may include negative electrode material, conductive agent and binder etc..The type of negative electrode material is not
It is restricted, can be selected according to actual needs, such as negative electrode material can be common natural graphite, artificial graphite, silicon, silicon oxygen
Compound, silicon alloy, tin, tin alloy, lithium titanate etc..
The present invention and its advantages are described in detail with reference to the accompanying drawings and detailed description, but of the invention
Embodiment is without being limited thereto.
Embodiment 1
(1) preparation of anode sizing agent
Positive electrode is separately added into the ratio that the mass ratio of substance each in solid component is 93.5:3:3:0.5
LiNi0.8Co0.1Mn0.1O2, binder PVDF, conductive agent conductive black, anode additive H3BO3, after dry-mixed 15min, it is added one
Quantitative solvent NMP makes the mass content of solid component in anode sizing agent be 60%, and with the stirring of the revolving speed of 2000 turns/min
2h obtains anode sizing agent after stirring.
(2) preparation of lithium ion battery
Anode sizing agent is spread evenly across on plus plate current-collecting body aluminium foil, coating quality 0.018g/cm2, through cold after drying
The processes such as pressure, cutting, soldering polar ear obtain positive plate.
By negative electrode material artificial graphite, conductive agent acetylene black, binder butadiene-styrene rubber (SBR), thickener carboxymethyl cellulose
After plain sodium (CMC) 90:5:2:2:1 in mass ratio is thoroughly mixed uniformly in deionized water solvent system, it is coated on cathode
On copper foil of affluxion body, negative electrode tab is obtained through processes such as cold pressing, cutting, soldering polar ears after drying.
Using PE apertured polymeric film as isolation film.
Electrolyte is the LiPF of 1mol/L6Solution, organic solvent are ethylene carbonate (EC), diethyl carbonate (DEC), carbon
Dimethyl phthalate (DMC) volume ratio is the mixture of 1:1:1.
It is 2.2Ah (1C that positive plate, isolation film, negative electrode tab are assembled into capacity in the environment of ambient humidity is less than 20%
Capacity) soft bag lithium ionic cell.
Embodiment 2
(1) preparation of anode sizing agent
Positive electrode is separately added into the ratio that the mass ratio of substance each in solid component is 93.9:3:3:0.1
LiNi0.8Co0.1Mn0.1O2, binder PVDF, conductive agent conductive black, anode additive H3BO3, after dry-mixed 15min, it is added one
Quantitative solvent NMP makes the mass content of solid component in anode sizing agent be 60%, and with the stirring of the revolving speed of 2000 turns/min
2h obtains anode sizing agent after stirring.
(2) preparation of lithium ion battery
The preparation process of lithium ion battery is the same as embodiment 1.
Embodiment 3
(1) preparation of anode sizing agent
Positive electrode is separately added into the ratio that the mass ratio of substance each in solid component is 93:3:3:1
LiNi0.8Co0.1Mn0.1O2, binder PVDF, conductive agent conductive black, anode additive H3BO3, after dry-mixed 15min, it is added one
Quantitative solvent NMP makes the mass content of solid component in anode sizing agent be 60%, and with the stirring of the revolving speed of 2000 turns/min
2h obtains anode sizing agent after stirring.
(2) preparation of lithium ion battery
The preparation process of lithium ion battery is the same as embodiment 1.
Embodiment 4
(1) preparation of anode sizing agent
Positive electrode Li is separately added into the ratio that the mass ratio of substance each in solid component is 93:3:3:1
(Ni0.8Co0.1Mn0.1)0.99Mg0.01O2, binder PVDF, conductive agent conductive black, anode additive H3BO3, after dry-mixed 15min,
A certain amount of solvent NMP, which is added, makes the mass content of solid component in anode sizing agent be 70%, and is turned with 2000 turns/min
Speed stirring 2h, obtains anode sizing agent after stirring.
(2) preparation of lithium ion battery
The preparation process of lithium ion battery is the same as embodiment 1.
Embodiment 5
(1) preparation of anode sizing agent
Positive electrode Li is separately added into the ratio that the mass ratio of substance each in solid component is 93:3:3:1
(Ni0.8Co0.1Mn0.1)0.99Zr0.01O2, binder PVDF, conductive agent conductive black, anode additive H3BO3, after dry-mixed 15min,
A certain amount of solvent NMP, which is added, makes the mass content of solid component in anode sizing agent be 50%, and is turned with 2000 turns/min
Speed stirring 2h, obtains anode sizing agent after stirring.
(2) preparation of lithium ion battery
The preparation process of lithium ion battery is the same as embodiment 1.
Comparative example 1
(1) preparation of anode sizing agent
Positive electrode is separately added into the ratio that the mass ratio of substance each in solid component is 94:3:3
LiNi0.8Co0.1Mn0.1O2, binder PVDF, conductive agent conductive black, after dry-mixed 15min, a certain amount of solvent NMP, which is added, to be made
The mass content for obtaining solid component in anode sizing agent is 60%, and stirs 2h with the revolving speed of 2000 turns/min, after stirring i.e.
Obtain anode sizing agent.
(2) preparation of lithium ion battery
The preparation process of lithium ion battery is the same as embodiment 1.
Comparative example 2
(1) preparation of anode sizing agent
Positive electrode is separately added into the ratio that the mass ratio of substance each in solid component is 93:3:3:1
LiNi0.8Co0.1Mn0.1O2, binder PVDF, conductive agent conductive black, anode additive oxalic acid, after dry-mixed 15min, be added one
Quantitative solvent NMP makes the mass content of solid component in anode sizing agent be 60%, and with the stirring of the revolving speed of 2000 turns/min
2h obtains anode sizing agent after stirring.
(2) preparation of lithium ion battery
The preparation process of lithium ion battery is the same as embodiment 1.
Comparative example 3
(1) preparation of anode sizing agent
Positive electrode is separately added into the ratio that the mass ratio of substance each in solid component is 93.95:3:3:0.05
LiNi0.8Co0.1Mn0.1O2, binder PVDF, conductive agent conductive black, anode additive H3BO3, after dry-mixed 15min, it is added one
Quantitative solvent NMP makes the mass content of solid component in anode sizing agent be 60%, and with the stirring of the revolving speed of 2000 turns/min
2h obtains anode sizing agent after stirring.
(2) preparation of lithium ion battery
The preparation process of lithium ion battery is the same as embodiment 1.
Comparative example 4
(1) preparation of anode sizing agent
Positive electrode is separately added into the ratio that the mass ratio of substance each in solid component is 92:3:3:2
LiNi0.8Co0.1Mn0.1O2, binder PVDF, conductive agent conductive black, anode additive H3BO3, after dry-mixed 15min, it is added one
Quantitative solvent NMP makes the mass content of solid component in anode sizing agent be 60%, and with the stirring of the revolving speed of 2000 turns/min
2h obtains anode sizing agent after stirring.
(2) preparation of lithium ion battery
The preparation process of lithium ion battery is the same as embodiment 1.
Illustrate the test process of anode sizing agent and lithium ion battery below.
(1) anode sizing agent anti-gel is tested
The anode sizing agent of preparation is stood for 24 hours in the environment of temperature is 25 DEG C, humidity is 30%, observes anode sizing agent
State.
(2) the discharge capacity test of lithium ion battery
At 25 DEG C, by the lithium ion battery of preparation with 0.33C (1C=2.2A) constant-current charge to voltage for 4.2V, then
Constant-voltage charge stands 5min to electric current≤110mA at 4.2v.Then with 0.33C (1C=2.2A) be discharged to voltage be 2.8V,
Record the discharge capacity of lithium ion battery at this time.
The test result of table 1 embodiment 1-5 and comparative example 1-4
| Anode sizing agent stand for 24 hours after state | The discharge capacity (Ah) of lithium ion battery | |
| Embodiment 1 | Non- gel | 2.25 |
| Embodiment 2 | Non- gel | 2.24 |
| Embodiment 3 | Non- gel | 2.22 |
| Embodiment 4 | Non- gel | 2.21 |
| Embodiment 5 | Non- gel | 2.21 |
| Comparative example 1 | Gel | 2.20 |
| Comparative example 2 | Non- gel | 2.20 |
| Comparative example 3 | Non- gel | 2.20 |
| Comparative example 4 | Non- gel | 2.17 |
Fig. 1 is the state after anode sizing agent prepared by embodiment 1 is stood for 24 hours；Fig. 2 is anode sizing agent prepared by comparative example 1
State after standing for 24 hours.Anode additive H is added from the anode sizing agent that Fig. 1 and Fig. 2 can be seen that embodiment 13BO3, stand
Anode sizing agent is still able to maintain good flow regime after for 24 hours, however H is not added in the anode sizing agent of comparative example 13BO3, stand for 24 hours
The mobility of anode sizing agent is obviously deteriorated afterwards, shows gel state.This is because H3BO3It can be with nickelic tertiary cathode material table
Acid-base neutralization reaction occurs for the impurity lithium in face, reduces the pH value of anode sizing agent, improves and is easy to happen in anode sizing agent whipping process
The phenomenon that gel.
As can also be seen from Table 1, in comparative example 1, since H not being added3BO3, the impurity on nickelic tertiary cathode material surface
Lithium content is more, and the presence of these impurity lithiums will increase nickelic tertiary cathode material Surface Polarization, deteriorates the appearance of lithium ion battery
Amount, causes the discharge capacity of lithium ion battery lower.In embodiment 1-5, H3BO3It can be with nickelic tertiary cathode material surface
The reaction of impurity lithium, reduces impurity lithium content, simultaneous reactions product lithium borate salt (Li3BO3、LiBO2) it is lithium fast-ionic conductor,
It is distributed in the surface of nickelic tertiary cathode material, facilitates the conduction of lithium ion, electric conductivity is improved, reduces the pole of lithium ion battery
Change, and then effectively improves the discharge capacity of lithium ion battery.In comparative example 2, oxalic acid is added as anode additive, although its
The gelatin phenomenon of anode sizing agent can be improved to a certain extent, but nickelic tertiary cathode material surface can not be effectively reduced in it
Impurity lithium content, and even if oxalic acid reacts with impurity lithium, since reaction product itself does not have by neutralization of acid with base
Standby lithium fast-ionic conductor property, and reaction product is covered on the surface of nickelic tertiary cathode material can also hinder the biography of lithium ion
It leads, causes the discharge capacity of lithium ion battery relatively low.
In comparative example 3, H3BO3Content is very few, can not effectively eliminate the impurity lithium on nickelic tertiary cathode material surface, this
The presence of a little impurity lithiums will increase positive electrode Surface Polarization, deteriorate the discharge capacity of lithium ion battery.In comparative example 4,
H3BO3Content is excessive, is easily reduced the energy density of lithium ion battery.
According to the disclosure and teachings of the above specification, those skilled in the art can also change above embodiment
And modification.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to some modifications of the invention and
Change should also be as falling into the scope of the claims of the present invention.In addition, although having been used in this specification some specific
Term, these terms are merely for convenience of description, does not limit the present invention in any way.
Claims (10)
1. a kind of anode sizing agent, including solid component and solvent, the solid component includes positive electrode, conductive agent and glues
Tie agent；
It is characterized in that,
The solid component further includes anode additive boric acid；
The positive electrode includes LixNiyM1-yO2, 0.9≤x≤1.1,0.6 < y≤0.9, M be selected from Co, Mn, Al, Mg, Fe, Cr,
V, one or more of Ti, Cu, B, Ca, Zn, Zr, Nb, Mo, Sr, Sb, W, Bi.
2. anode sizing agent according to claim 1, which is characterized in that the quality of boric acid is the gross mass of the solid component
0.1%~1%, it is preferable that the quality of boric acid be the solid component gross mass 0.1%~0.5%.
3. anode sizing agent according to claim 1, which is characterized in that
The quality of the positive electrode is the 89.5%~97.9% of the gross mass of the solid component；
The quality of the conductive agent is the 1%~5% of the gross mass of the solid component；
The quality of the binder is the 1%~5% of the gross mass of the solid component.
4. anode sizing agent according to claim 1, which is characterized in that M include Co, Mn, Al at least two and Mg,
One or more of Fe, Cr, V, Ti, Cu, B, Ca, Zn, Zr, Nb, Mo, Sr, Sb, W, Bi.
5. anode sizing agent according to claim 1, which is characterized in that positive electrode includes LixNiyM1-yO2, 0.9 < x <
1.1,0.6 < y < 0.9, M are in Co, Mn, Al, Mg, Fe, Cr, V, Ti, Cu, B, Ca, Zn, Zr, Nb, Mo, Sr, Sb, W, Bi
It is one or more of, it is preferable that M include at least two and Mg, Fe of Co, Mn, Al, Cr, V, Ti, Cu, B, Ca, Zn, Zr, Nb,
One or more of Mo, Sr, Sb, W, Bi.
6. anode sizing agent according to claim 5, which is characterized in that LixNiyM1-yO2Selected from LiNi0.8Co0.1Mn0.1O2、
LiNi0.6Co0.2Mn0.2O2、LiNi0.85Co0.15Mn0.05O2、LiNi0.85Co0.15Al0.05O2、Li(Ni0.8Co0.1Mn0.1)0.99Mg0.01O2、Li(Ni0.8Co0.1Mn0.1)0.99Zr0.01O2One or more of.
7. anode sizing agent according to claim 1, which is characterized in that the binder is selected from poly- segregation vinyl fluoride, inclined fluorine
Ethylene-hexafluoropropylene copolymer, skewed segregation, biasfluoroethylene-hexafluoropropylene-TFE copolymer,
Vinylidene fluoride pentafluor propylene copolymer, vinylidene-pentafluoropropene-TFE copolymer, vinylidene-perfluoro-methyl second
Alkene ether-TFE copolymer, vinylidene-chlorotrifluoroethylcopolymer copolymer, polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene, tetrafluoro
Ethylene-perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoro-ethylene copolymer, tetrafluoro second
One or more of alkene-hexafluoropropylene copolymer.
8. anode sizing agent according to claim 1, which is characterized in that the solvent is N-Methyl pyrrolidone.
9. a kind of positive plate, which is characterized in that be coated on anode by anode sizing agent according to claim 1 to 8
It is formed on collector.
10. a kind of lithium ion battery, which is characterized in that including by anode sizing agent according to claim 1 to 8
It is coated on the positive plate formed on plus plate current-collecting body.
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