CN109888271A - Positive electrode active materials and preparation method thereof, positive plate and lithium ion battery - Google Patents
Positive electrode active materials and preparation method thereof, positive plate and lithium ion battery Download PDFInfo
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Abstract
The present invention provides positive electrode active materials and preparation method thereof, positive plate and lithium ion batteries.The positive electrode active materials include: by Liα[(NixCoy)(1‑β)Aβ]OzThe crystal of formation, wherein the A includes at least one of aluminium, boron, magnesium, titanium, zirconium, 0.95≤α≤1.1,0 < β≤0.2,0.75≤x≤0.95,0.03≤y≤0.25,1.9≤z≤2.1.The positive electrode active materials stability is strong, the discharge capacity of lithium ion battery and cycle life can be made to significantly improve, and cost is relatively low, is easy to industrialization.
Description
Technical field
The present invention relates to field of material technology, and in particular, to positive electrode active materials and preparation method thereof, positive plate and lithium
Ion battery.
Background technique
Portable wireless electronic product rapidly develops, and miniaturization, lightweight and the high-energy density of power supply need
It asks and increasingly increases.In addition, in order to protect environment, with electric car, hybrid vehicle exploitation and come into operation, to big-and-middle
The demand of the good lithium ion battery of type energy-storage property also increasingly increases.Therefore, the lithium ion battery that development capacity is big, the service life is long is
One of the technical problems that are urgent to solve in the related technology.Currently, positive electrode active materials have example in the lithium ion battery of high-energy type
Such as the LiMn of spinel structure2O4, zigzag structure LiMnO2, rock salt structure LiCoO2And LiNiO2Deng, wherein due to
LiNiO2It can make lithium ion battery discharge capacity with higher, therefore it is known as the positive-active material studied extensively at present
Material, but since stability of the material in charging is poor, cause its cycle performance poor, so can not fully meet current
To the requirement of the positive electrode active materials of lithium ion battery.
Thus, the relevant technologies of existing positive electrode active materials still have much room for improvement.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is to propose that a kind of stability is strong, the discharge capacity of lithium ion battery, cycle life can be made to significantly improve, at
This is lower or is easy to the positive electrode active materials of industrialization.
In one aspect of the invention, the present invention provides a kind of positive electrode active materials for lithium ion battery.According to
The embodiment of the present invention, the positive electrode active materials include: by Liα[(NixCoy)(1-β)Aβ]OzThe crystal of formation, wherein the A
Including at least one of aluminium, boron, magnesium, titanium, zirconium, 0.95≤α≤1.1,0 < β≤0.2,0.75≤x≤0.95,0.03≤y≤
0.25,1.9≤z≤2.1.Inventors have found that the positive electrode active materials stability is strong, the electric discharge of lithium ion battery can be made to hold
Amount and cycle life significantly improve, and cost is relatively low, is easy to industrialization.
According to an embodiment of the invention, the A include the aluminium, the boron, the magnesium, the titanium, in the zirconium extremely
It is two kinds few.
According to an embodiment of the invention, the A includes the aluminium, the boron, the magnesium, the titanium, the zirconium.
According to an embodiment of the invention, the gross mass based on the positive electrode active materials, the A meets the following conditions extremely
One of few: the mass percentage of the aluminium is greater than 0 and is less than or equal to 1%；The mass percentage of the boron is greater than 0 and small
In or equal to 0.35%；The mass percentage of the magnesium is greater than 0 and is less than or equal to 0.35%；The quality percentage of the titanium contains
Amount is greater than 0 and is less than or equal to 0.5%；The mass percentage of the zirconium is greater than 0 and is less than or equal to 0.4%.
According to an embodiment of the invention, α=1, β=0.1, x=0.9, y=0.1, z=2, and it is based on the positive-active
The gross mass of material, the mass percentage of the aluminium are 0.5%, and the mass percentage of the boron is 0.02%, the magnesium
Mass percentage be 0.05%, the mass percentage of the titanium is 0.25%, and the mass percentage of the zirconium is
0.25%.
In another aspect of the invention, the present invention provides a kind of sides for preparing mentioned-above positive electrode active materials
Method.According to an embodiment of the invention, this method comprises: by NiaCob(OH)2It is mixed with lithium source, obtains the first pre-composition,
In, a+b=1, and a > 0, b > 0；First pre-composition and dopant are mixed, the second pre-composition is obtained, wherein institute
It states containing A noted earlier in dopant, and second pre-composition is made to carry out Temperature fall after calcination processing in oxygen atmosphere,
To obtain the positive electrode active materials.Inventors have found that this method is simple, convenient, and it is easy to accomplish, it is easy to industrial metaplasia
It produces, and the anode that stability is strong, significantly improves lithium ion battery discharge capacity and cycle life can effectively be prepared is lived
Property material.
According to an embodiment of the invention, this method meets at least one of the following conditions: the dopant includes Al
(OH)3、B2O3、Mg(OH)2、TiO2And Zr (OH)4At least one of；The lithium source includes LiOH, LiNO3、Li2CO3、
Li3PO4、Li2C2O4And CH3At least one of COOLi；The NiaCob(OH)2With the lithium source be according to 1:(1.005~
1.05) what molar ratio was mixed；First pre-composition and the dopant are according to 100:(1.1379~1.7747)
The ratio between parts by weight mixed；At least one of first pre-composition and second pre-composition are solid premix
Object；The temperature of the calcination processing is 500 DEG C~1000 DEG C；The time of the calcination processing is 5h~30h.
According to an embodiment of the invention, the lithium source is LiOH.
According to an embodiment of the invention, the temperature of the calcination processing is 500 DEG C~850 DEG C.
According to an embodiment of the invention, the time of the calcination processing is 4h~20h.
According to an embodiment of the invention, after obtaining the positive electrode active materials, this method further include: by the anode
Active material carries out pulverization process and screening process, and makes the anode after the pulverization process and the screening process
The granularity of active material is not more than 38 μm.
In an additional aspect of the present invention, the present invention provides a kind of positive plates for lithium ion battery.According to this hair
Bright embodiment, the positive plate include mentioned-above positive electrode active materials.Inventors have found that the positive plate can make lithium from
The discharge capacity and cycle life of sub- battery significantly improve, and cost is relatively low, is easy to industrialization, and have mentioned-above anode living
All feature and advantage of property material, no longer excessively repeat herein.
In another aspect of the invention, the present invention provides a kind of lithium ion batteries.According to an embodiment of the invention, should
Lithium ion battery includes: cathode；Anode, the anode include mentioned-above positive electrode active materials or mentioned-above anode
Piece；Battery diaphragm；And electrolyte.Inventors have found that the discharge capacity and cycle life of the lithium ion battery are high, cost compared with
It is low, be easy to industrialization, and all feature and advantage with mentioned-above positive electrode active materials or positive plate noted earlier,
This is no longer excessively repeated.
Detailed description of the invention
Fig. 1 shows the flow diagram of the method for preparing positive electrode active materials of one embodiment of the invention.
Fig. 2 shows the flow diagram of the method for preparing positive electrode active materials of another embodiment of the present invention.
Fig. 3 shows the first charge-discharge curve graph of the positive electrode active materials of the embodiment of the present invention 1.
Fig. 4 shows the cycle charge-discharge curve graph of the positive electrode active materials of the embodiment of the present invention 1.
Fig. 5 shows the first charge-discharge curve graph of the positive electrode active materials of comparative example 1 of the present invention.
Fig. 6 shows the cycle charge-discharge curve graph of the positive electrode active materials of comparative example 1 of the present invention.
Fig. 7 shows the circulation volume conservation rate test knot of the positive electrode active materials of the embodiment of the present invention 1 and comparative example 1
Fruit.
Specific embodiment
The embodiment of the present invention is described below in detail.The embodiments described below is exemplary, and is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Particular technique or condition are not specified in embodiment, according to text in the art
It offers described technology or conditions or is carried out according to product description.Reagents or instruments used without specified manufacturer,
For can be with conventional products that are commercially available.
In one aspect of the invention, the present invention provides a kind of positive electrode active materials for lithium ion battery.According to
The embodiment of the present invention, the positive electrode active materials include: by Liα[(NixCoy)(1-β)Aβ]OzThe crystal of formation, wherein the A
Including at least one of aluminium, boron, magnesium, titanium, zirconium, 0.95≤α≤1.1,0 < β≤0.2,0.75≤x≤0.95,0.03≤y≤
0.25,1.9≤z≤2.1.Inventors have found that the positive electrode active materials stability is strong, the electric discharge of lithium ion battery can be made to hold
Amount and cycle life significantly improve, and cost is relatively low, is easy to industrialization.
According to an embodiment of the invention, inventor is by having carried out a large amount of careful investigations to the ingredient of positive electrode active materials
Found with after experimental verification, with mentioned component positive electrode active materials, due in its crystal structure there are aluminium, boron, magnesium, titanium,
At least one of zirconium, can make the stability of material it is strong, to which the positive electrode active materials are when being applied to lithium ion battery,
It is moved back and forth between a positive electrode and a negative electrode conducive to lithium ion, and then the discharge capacity and cycle life of lithium ion battery can be made
It significantly improves.
According to an embodiment of the invention, inventor has found after numerous studies, anode is can be improved in mentioned-above aluminium
The capacity of material；The consistency of material can be improved in mentioned-above boron, thus stabilizing material structure；Mentioned-above magnesium can be with
Improve the circulation conservation rate of positive electrode；Mentioned-above titanium and zirconium can stablize the structural stability of positive electrode.Thus,
In the positive electrode active materials, there are at least one of aluminium, boron, magnesium, titanium, zirconium, can make the stability of material it is strong, to should
Positive electrode active materials are moved back and forth when being applied to lithium ion battery conducive to lithium ion between a positive electrode and a negative electrode, and then can be with
So that the discharge capacity and cycle life of lithium ion battery significantly improve.
According to an embodiment of the invention, further, not only may include in the positive electrode aluminium, boron, magnesium, titanium, in zirconium
At least one, and in the five kinds of described in front elements, two kinds or more of elements can also be used in combination.For example, should
A in positive electrode active materials can be aluminium and boron, be also possible to boron and zirconium, can also be aluminium, magnesium and titanium etc., above-mentioned five kinds of elements
Between can carry out flexible combination.In some embodiments of the invention, the A in the positive electrode active materials can be aluminium and
Magnesium；Aluminium, magnesium and boron；Titanium, aluminium and magnesium；Zirconium, aluminium and magnesium；Titanium, aluminium, magnesium and boron；Zirconium, aluminium, magnesium and boron；Zirconium, titanium, aluminium and boron；Zirconium,
Titanium, aluminium, magnesium and boron etc..It cooperates between above-mentioned element as a result, and plays synergistic effect, for example, aluminium and magnesium can cooperate
Improve capacity and circulation conservation rate, zirconium, titanium and aluminium can cooperate improve structural stability, zirconium, titanium, aluminium, magnesium and boron can be with
Mutual cooperation stabilizing material performance and improve capacity and circulation conservation rate etc., so as to further such that material stability
By force, to which the positive electrode active materials are when being applied to lithium ion battery, it is past between a positive electrode and a negative electrode to be further conducive to lithium ion
Movement is returned, and then can be further such that the discharge capacity and cycle life of lithium ion battery significantly improve.
According to an embodiment of the invention, further, the A includes the aluminium, the boron, the magnesium, the titanium, institute
State zirconium.Aforementioned all elements are contained in the positive electrode active materials as a result, by aluminium, boron, magnesium, five kinds of elements of titanium and zirconium it
Between cooperate play synergistic effect, for example, the capacity of positive electrode can be improved in aluminium, boron can be improved material compactness,
The structural stability of material can be improved in zirconium and titanium, and the cycle performance of material can be improved in magnesium, thus phase interworking between each component
It closes, it can be with further such that the stability of material be stronger, so that the positive electrode active materials are when being applied to lithium ion battery, into one
Step be conducive to lithium ion move back and forth between a positive electrode and a negative electrode, and then can with further such that lithium ion battery discharge capacity and
Cycle life significantly improves.
According to an embodiment of the invention, in the chemical formula Li of the positive electrode active materialsα[(NixCoy)(1-β)Aβ]OzIn, it is each
The range of parameter is 0.95≤α≤1.1,0 < β≤0.2,0.75≤x≤0.95,0.03≤y≤0.25,1.9≤z≤2.1.?
In some embodiments of the present invention, α can be specially 0.95,0.98,1,1.02,1.05 or 1.1 etc.；β can be specially
0.01,0.02,0.05,0.08,0.1,0.11,0.12,0.15,0.18 or 0.2 etc.；X can be specially 0.75,0.78,
0.8,0.82,0.84,0.86,0.88,0.9,0.92 or 0.95 etc.；Y can be specially 0.03,0.05,0.08,0.1,
0.12,0.14,0.16,0.18,0.2,0.22 or 0.25 etc.；Z can be specially 1.9,1.95,2,2.05 or 2.1 etc..By
This, for inventor by adjusting in the crystal structure of the positive electrode active materials, the proportion between various atoms is preferable, so as to
So that between the A and Ni, Co it is mutually matched preferably, the ratio between various atoms is preferably ratio, thus into one
Step enhances the stability of the positive electrode active materials crystal, and the positive electrode active materials are further sharp when being applied to lithium ion battery
Moved back and forth between a positive electrode and a negative electrode in lithium ion, so can with further such that lithium ion battery discharge capacity and circulation
Service life significantly improves；Moreover, the content of above-mentioned parameter α, β, x, y, z is more appropriate, if the too high levels of aluminium, can reduce just
The capacity of pole active material；If the content of magnesium is too low, circulation conservation rate can be reduced；If the content of zirconium and titanium is too low, can drop
The structural stability of low positive electrode active materials；The content of boron is too low, then the compactness of positive electrode active materials is poor.
According to an embodiment of the invention, further, in the positive electrode active materials, based on the positive electrode active materials
Gross mass, the mass percentage of the aluminium can be greater than 0 and be less than or equal to 1%, specifically, can be 0.1%, 0.2%,
0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1% etc.；The mass percentage of the boron can be big
In 0 and be less than or equal to 0.35%, specifically, can be 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3% or
0.35% etc.；The mass percentage of the magnesium can be greater than 0 and be less than or equal to 0.35%, specifically, can be 0.05%,
0.1%, 0.15%, 0.2%, 0.25%, 0.3% or 0.35% etc.；The mass percentage of the titanium can be greater than 0 and small
In or be equal to 0.5%, specifically, can be 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%,
0.4%, 0.45% or 0.5% etc.；The mass percentage of the zirconium can be greater than 0 and be less than or equal to 0.4%, specifically
Ground can be 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35% or 0.4% etc..Inventor as a result,
By adjusting in the crystal structure of the positive electrode active materials, the aluminium, the boron, the magnesium, the titanium, between the zirconium
Proportion, so that mutually matched preferable between the aluminium, the boron, the magnesium, the titanium, the zirconium, various originals
Ratio between son is preferably ratio, and content of the various atoms in the positive electrode active materials is also preferable, thus into one
Step enhances the stability of the positive electrode active materials crystal, and the positive electrode active materials are further sharp when being applied to lithium ion battery
Moved back and forth between a positive electrode and a negative electrode in lithium ion, so can with further such that lithium ion battery discharge capacity and circulation
Service life significantly improves；Moreover, above-mentioned five kinds of elements, i.e. aluminium, boron, magnesium, titanium, the content of zirconium are more appropriate, it is both not too high or
Will not be too low, if the too high levels of aluminium, the capacity of positive electrode active materials can be reduced；If the content of magnesium is too low, it can reduce and follow
Environmentally friendly holdup；If the content of zirconium and titanium is too low, the structural stability of positive electrode active materials can be reduced；The content of boron is too low, then
The compactness of positive electrode active materials is poor.
According to an embodiment of the invention, further, inventor shies after a large amount of careful investigations and experimental verification
Happiness ground discovery, in positive electrode active materials of the invention, as α=1, β=0.1, x=0.9, y=0.1, z=2, and based on described
The mass percentage of the gross mass of positive electrode active materials, the aluminium is 0.5%, and the mass percentage of the boron is
0.02%, the mass percentage of the magnesium is 0.05%, and the mass percentage of the titanium is 0.25%, the quality of the zirconium
When percentage composition is 0.25%, cooperates and reach more preferably between each atom in the positive electrode active materials, thus further
Enhance the stability of the positive electrode active materials crystal, which is further conducive to when being applied to lithium ion battery
Lithium ion moves back and forth between a positive electrode and a negative electrode, so can with further such that lithium ion battery discharge capacity and circulation the longevity
Life significantly improves.
In another aspect of the invention, the present invention provides a kind of sides for preparing mentioned-above positive electrode active materials
Method.According to an embodiment of the invention, referring to Fig.1, method includes the following steps:
S100: by NiaCob(OH)2It is mixed with lithium source, obtains the first pre-composition, wherein a+b=1, and a > 0, b >
0。
According to an embodiment of the invention, in the NiaCob(OH)2In, as long as meeting a+b=1, and a > 0, b > 0,
Ratio between a and b is not particularly restricted, for example, in some embodiments of the invention, the value of a can be specially 0.9,
0.8,0.7,0.6,0.5,0.4,0.3,0.2 or 0.1 etc.；Correspondingly, the value of b can be specially 0.1,0.2,0.3,0.4,
0.5,0.6,0.7,0.8 or 0.9 etc..Material source is extensive as a result, is easy to get, and cost is relatively low, and can effectively be prepared steady
The positive electrode active materials of qualitative discharge capacity and cycle life strong, that significantly improve lithium ion battery.
According to an embodiment of the invention, the lithium source may include LiOH, LiNO3、Li2CO3、Li3PO4、Li2C2O4And
CH3COOLi etc..In some embodiments of the invention, the lithium source can be specially LiOH.Material source is extensive, easy as a result,
, cost is relatively low, and in subsequent steps, by-product is less, and will not generate excessive gas and influence subsequent reactions, is conducive to
The formation of positive electrode active materials, and further can effectively be prepared that stability is strong, further obtains that lithium can be significantly improved
The discharge capacity of ion battery and the positive electrode active materials of cycle life.
According to an embodiment of the invention, the NiaCob(OH)2According to 1:(1.005~1.05 with the lithium source) rub
You are than being mixed.In some embodiments of the invention, the NiaCob(OH)2With the lithium source be according to 1:1.005,
The molar ratio of 1:1.01,1:1.015,1:1.02,1:1.025,1:1.03,1:1.035,1:1.04,1:1.045 or 1:1.05
It is mixed.The Ni as a result,aCob(OH)2Proportion between the lithium source is preferable, both not too high to lead to positive-active
Full alkali (i.e. LiOH, Li of material surface2CO3) content height, the capacity of positive electrode active materials too low will not be caused lower, thus
Conducive to the formation of positive electrode active materials, and it further can effectively be prepared that stability is strong, further obtains significantly mentioning
The discharge capacity of high-lithium ion battery and the positive electrode active materials of cycle life.
According to an embodiment of the invention, by NiaCob(OH)2The method mixed with lithium source is dry mixed, can be made
Obtain the NiaCob(OH)2Proportion between the lithium source is accurate, pre- first after preventing since lithium source is dissolved in solvent
In mixed object, the actual interpolation amount of lithium is less.
S200: first pre-composition and dopant are mixed, the second pre-composition is obtained, wherein the dopant
In contain A noted earlier, and second pre-composition is made to carry out Temperature fall after calcination processing in oxygen atmosphere, to obtain
The positive electrode active materials.
According to an embodiment of the invention, the material of the A, type, mechanism of action etc. is same as previously described, herein not
It is repeated after more.
According to an embodiment of the invention, the dopant includes Al (OH)3、B2O3、Mg(OH)2、TiO2And Zr (OH)4In
At least one.Material source is extensive as a result, is easy to get, and cost is relatively low, conducive to the formation of positive electrode active materials, and can be into one
The discharge capacity and cycle life that stability is strong, further obtains to significantly improve lithium ion battery is effectively prepared in step
Positive electrode active materials.
According to an embodiment of the invention, first pre-composition and the dopant be according to 100:(1.1379~
1.7747) what the ratio between parts by weight were mixed.In some embodiments of the invention, it first pre-composition and described mixes
Miscellaneous dose of the ratio between parts by weight can be 100:1.7747,100:1.4716 or 100:1.4410 etc..It is living to be conducive to anode as a result,
The formation of property material, in obtained positive electrode active materials, the proportion between various atoms is preferable, so that the A
Between Ni, Co it is mutually matched preferably, the ratio between various atoms is preferably ratio, to further enhance this just
The stability of pole active material crystal, the positive electrode active materials are further conducive to lithium ion and exist when being applied to lithium ion battery
It is moved back and forth between anode and cathode, and then can further obtain significantly improving the discharge capacity of lithium ion battery and follow
The positive electrode active materials in ring service life.
According to an embodiment of the invention, the method that first pre-composition and dopant are mixed is dry mixed,
The proportion between first pre-composition and dopant can be made accurate, prevented due to dissolving the first pre-composition and dopant
After solvent, there is error between the actual interpolation amount of each material and theoretical additive amount.
According to an embodiment of the invention, the temperature of the calcination processing is 500 DEG C~1000 DEG C.In some realities of the invention
It applies in example, the temperature of the calcination processing can be 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C or 1000 DEG C etc..More into
One step, the temperature of the calcination processing is 500 DEG C~850 DEG C.Easy to operate as a result, reaction condition is mild, is easy to industrialize
Production conducive to the formation of positive electrode active materials, and further can effectively be prepared that stability is strong, further obtains to show
Write the positive electrode active materials of the discharge capacity and cycle life that improve lithium ion battery；Moreover, the calcination temperature was both not too high
And lead to the wasting of resources, although will not it is too low and cause reaction be able to carry out, carry out it is more slow, production efficiency is lower.
According to an embodiment of the invention, the time of the calcination processing is 5h~30h.In some embodiments of the present invention
In, the temperature of the calcination processing can be 5h, 10h, 15h, 20h, 25h or 30h etc..Further, at the calcining
The temperature of reason is 4h~20h.It is easy to operate as a result, easy to industrialized production, conducive to the formation of positive electrode active materials, and can be with
Discharge capacity and the circulation longevity that stability is strong, further obtains to significantly improve lithium ion battery is further effectively prepared
The positive electrode active materials of life；Moreover, the calcination time both will not be too long and have caused production efficiency lower, will not be too short and cause
Although although the positive electrode active materials that preparation is formed can be realized reaction and can be realized that stability is strong, can make lithium ion battery
Discharge capacity and cycle life significantly improve progress, but in positive electrode active materials can containing other more by-products, and
Cause after being prepared into anode, effective component reduces.
In other embodiments of the invention, referring to Fig. 2, after obtaining the positive electrode active materials, this method is also
The following steps are included:
S300: carrying out pulverization process and screening process for the positive electrode active materials, and make by the pulverization process and
The granularity of the positive electrode active materials after the screening process is not more than 38 μm.
According to an embodiment of the invention, the actual conditions of the pulverization process and screening process are not particularly limited, as long as
Enable to the granularity of the positive electrode active materials after the pulverization process and the screening process i.e. no more than 38 μm
It can.In some embodiments of the invention, screening process can be carried out using the sieve of 400 mesh, specifically, by screening process
The granularity of obtained positive electrode active materials can be 1 μm, 2 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm or 38
μm etc..Thus, it is possible to remove the impurity and the larger positive-active that can not be crushed of granularity generated in the step described in front
Material is conducive to subsequent applications, and has the positive electrode active materials of above-mentioned granularity, can be further such that lithium ion battery is put
Capacitance and cycle life significantly improve.
In an additional aspect of the present invention, the present invention provides a kind of positive plates for lithium ion battery.According to this hair
Bright embodiment, the positive plate include mentioned-above positive electrode active materials.Inventors have found that the positive plate can make lithium from
The discharge capacity and cycle life of sub- battery significantly improve, and cost is relatively low, is easy to industrialization, and have mentioned-above anode living
All feature and advantage of property material, no longer excessively repeat herein.
According to an embodiment of the invention, those skilled in the art can manage in addition to mentioned-above positive electrode active materials
Solution, the positive plate can also include the other compositions, such as substrate, conductive agent, binder and thickener etc. of conventional cathode piece,
It no longer excessively repeats herein.
In another aspect of the invention, the present invention provides a kind of lithium ion batteries.According to an embodiment of the invention, should
Lithium ion battery includes: cathode；Anode, the anode include mentioned-above positive electrode active materials or mentioned-above anode
Piece；Battery diaphragm；And electrolyte.Inventors have found that the discharge capacity and cycle life of the lithium ion battery are high, cost compared with
It is low, be easy to industrialization, and all feature and advantage with mentioned-above positive electrode active materials or positive plate noted earlier,
This is no longer excessively repeated.
According to an embodiment of the invention, in addition to mentioned-above structure, the lithium ion battery other structures and component
Shape, construction, manufacturing process etc. all can be conventional shape, construction, manufacturing process, no longer excessively repeat herein.
The embodiment of the present invention is described below in detail.
Embodiment 1
By Ni0.9Co0.1(OH)2Dry mixed is carried out according to the molar ratio of 1:1.02 with LiOH, obtains the first pre-composition；It will
First pre-composition, 100 parts by weight and Al (OH)3、B2O3、Mg(OH)2、TiO2And Zr (OH)4Totally 1.7747 parts by weight carry out dry method
Mix (wherein, Al (OH)3For 1.0508 parts by weight；B2O3For 0.0163 parts by weight；Mg(OH)2For 0.0872 parts by weight；TiO2For
0.3032 parts by weight；Zr(OH)4For 0.3172 parts by weight), the second pre-composition is obtained, and make the second pre-composition in oxygen atmosphere
In, under conditions of 750 DEG C, carry out Temperature fall after calcination processing 30h, obtain positive electrode active materials, and by positive-active material
Material carries out pulverization process and screening process, is not more than the granularity of the positive electrode active materials after pulverization process and screening process
38μm。
Embodiment 2
By Ni0.9Co0.1(OH)2Dry mixed is carried out according to the molar ratio of 1:1.02 with LiOH, obtains the first pre-composition；It will
First pre-composition, 100 parts by weight and Al (OH)3、B2O3、Mg(OH)2And Zr (OH)4Totally 1.4716 parts by weight carry out dry mixed
(wherein, Al (OH)3For 1.0508 parts by weight；B2O3For 0.0163 parts by weight；Mg(OH)2For 0.0872 parts by weight；Zr(OH)4For
0.3172 parts by weight), the second pre-composition is obtained, and make the second pre-composition in oxygen atmosphere, under conditions of 750 DEG C, carried out
Temperature fall after calcination processing 30h obtains positive electrode active materials, and positive electrode active materials is carried out at pulverization process and screening
Reason makes the granularity of the positive electrode active materials after pulverization process and screening process no more than 38 μm.
Embodiment 3
By Ni0.9Co0.1(OH)2Dry mixed is carried out according to the molar ratio of 1:1.02 with LiOH, obtains the first pre-composition；It will
First pre-composition, 100 parts by weight and Al (OH)3、B2O3、Mg(OH)2Totally 1.4410 parts by weight carry out dry mixed (wherein, Al
(OH)3For 1.3117 parts by weight；B2O3For 0.0204 parts by weight；Mg(OH)2For 0.1089 parts by weight), the second pre-composition is obtained,
And make the second pre-composition in oxygen atmosphere, under conditions of 750 DEG C, Temperature fall after calcination processing 30h is carried out, anode is obtained
Active material, and positive electrode active materials are subjected to pulverization process and screening process, make after pulverization process and screening process
The granularity of positive electrode active materials is not more than 38 μm.
Comparative example 1
By Ni0.9Co0.1(OH)2Dry mixed is carried out according to the molar ratio of 1:1.02 with LiOH, obtains the first pre-composition；It will
First pre-composition in oxygen atmosphere, under conditions of 750 DEG C, carry out calcination processing 30h after Temperature fall, obtain positive-active
Material, and positive electrode active materials are subjected to pulverization process and screening process, make the anode after pulverization process and screening process
The granularity of active material is not more than 38 μm.
Experimental method is as follows:
Button cell production: being utilized respectively the positive electrode active materials that 1~embodiment of above-described embodiment 3 and comparative example 1 make,
Positive electrode active materials, carbon black, PVDF (Kynoar) and NMP (the N- crassitude for being 95:2.5:2.5:5 by mass ratio
Ketone) it is uniformly mixed, obtain slurry.The slurry is coated on the aluminium foil with a thickness of 20~40um, by vacuum drying and roll-in
It is made into positive plate, using metal lithium sheet as cathode, electrolyte ratio is the LiPF of 1.15M6/ EC:DMC (volume ratio 1:1vol%),
And assemble button cell.
It is tested at 45 DEG C using blue electric battery test system, test voltage range is 3V~4.5V；Test chemical conversion
Capacity (obtaining first charge-discharge curve graph) and 1 week, 20 weeks and 30 weeks capacity (obtaining charge and discharge cycles test curve figure).
Such as Fig. 3 and Fig. 5, wherein Fig. 3 is the first charge-discharge curve graph of embodiment 1；Fig. 5 is the charge and discharge for the first time of comparative example 1
Electric curve graph.Such as Fig. 4 and Fig. 6, wherein Fig. 4 is the charge and discharge cycles test curve of embodiment 1；Fig. 6 is the charge and discharge of comparative example 1
Electric loop test curve；Fig. 7 is the capacity retention ratio test result of 30 weeks circulations of embodiment 1 and comparative example 1.
In Fig. 4 and Fig. 6, a is the 1st week charge and discharge cycles curve graph of positive electrode active materials；B is positive electrode active materials
10th week charge and discharge cycles curve graph；C is the 20th week charge and discharge cycles curve graph of positive electrode active materials；D is positive-active material
30th week charge and discharge cycles curve graph of material.It should be noted that in Fig. 4, the charge and discharge cycles curve of positive electrode active materials
Scheme substantially overlapping (as shown in a and b).
Analysis of experimental results:
By Fig. 3 and Fig. 5 it is found that the positive electrode active materials of the embodiment of the present invention 1 specific discharge capacity with higher, for the first time
Specific discharge capacity is up to 213mAh/g；And the discharge capacity for the first time of the positive electrode active materials of comparative example 1 is only 203mAh/g.
By Fig. 4, Fig. 6 and Fig. 7 it is found that the positive electrode active materials of the embodiment of the present invention 1 can make following for lithium ion battery
The ring service life significantly improves.After charge and discharge cycles 30 weeks, capacity retention ratio is up to 98.41%；And the anode in comparative example 1 is living
Property material, charge and discharge cycles 30 enclose when, capacity retention ratio is only 50.47%.
In addition, embodiment 2 and embodiment 3 and charge and discharge cycles test curve it is similar with embodiment 1, experimental result
It is superior to the experimental result of comparative example 1.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of positive electrode active materials for lithium ion battery characterized by comprising
By Liα[(NixCoy)(1-β)Aβ]OzThe crystal of formation,
Wherein, the A includes at least one of aluminium, boron, magnesium, titanium, zirconium, and 0.95≤α≤1.1,0 < β≤0.2,0.75≤x≤
0.95,0.03≤y≤0.25,1.9≤z≤2.1.
2. positive electrode active materials according to claim 1, which is characterized in that the A includes the aluminium, the boron, described
Magnesium, the titanium, at least two in the zirconium.
3. positive electrode active materials according to claim 2, which is characterized in that the A includes the aluminium, the boron, described
Magnesium, the titanium, the zirconium.
4. positive electrode active materials according to claim 1, which is characterized in that total matter based on the positive electrode active materials
Amount, the A meet at least one of the following conditions:
The mass percentage of the aluminium is greater than 0 and is less than or equal to 1%；
The mass percentage of the boron is greater than 0 and is less than or equal to 0.35%；
The mass percentage of the magnesium is greater than 0 and is less than or equal to 0.35%；
The mass percentage of the titanium is greater than 0 and is less than or equal to 0.5%；
The mass percentage of the zirconium is greater than 0 and is less than or equal to 0.4%.
5. positive electrode active materials according to claim 3, which is characterized in that α=1, β=0.1, x=0.9, y=0.1, z
=2, and the gross mass based on the positive electrode active materials, the mass percentage of the aluminium are 0.5%, the quality hundred of the boron
Dividing content is 0.02%, and the mass percentage of the magnesium is 0.05%, and the mass percentage of the titanium is 0.25%, described
The mass percentage of zirconium is 0.25%.
6. a kind of method for preparing positive electrode active materials according to any one of claims 1 to 5 characterized by comprising
By NiaCob(OH)2It is mixed with lithium source, obtains the first pre-composition, wherein a+b=1, and a > 0, b > 0；
First pre-composition and dopant are mixed, the second pre-composition is obtained, wherein contains in the dopant and has the right
It is required that A described in any one of 1~5, and second pre-composition is made to carry out Temperature fall after calcination processing in oxygen atmosphere, with
Just the positive electrode active materials are obtained.
7. according to the method described in claim 6, it is characterized in that, meeting at least one of the following conditions:
The dopant includes Al (OH)3、B2O3、Mg(OH)2、TiO2And Zr (OH)4At least one of；
The lithium source includes LiOH, LiNO3、Li2CO3、Li3PO4、Li2C2O4And CH3At least one of COOLi, preferably institute
Stating lithium source is LiOH；
The NiaCob(OH)2According to 1:(1.005~1.05 with the lithium source) molar ratio mixed；
First pre-composition and the dopant are according to 100:(1.1379~1.7747) the ratio between parts by weight mixed
It closes；
At least one of first pre-composition and second pre-composition are solids pre-mix；
The temperature of the calcination processing is 500 DEG C~1000 DEG C, preferably 500 DEG C~850 DEG C；
The time of the calcination processing is 5h~30h, preferably 4h~20h.
8. according to the method described in claim 6, it is characterized in that, after obtaining the positive electrode active materials, further includes:
The positive electrode active materials are subjected to pulverization process and screening process, and are made by the pulverization process and the screening
The granularity of the positive electrode active materials after reason is not more than 38 μm.
9. a kind of positive plate for lithium ion battery, which is characterized in that including it is according to any one of claims 1 to 5 just
Pole active material.
10. a kind of lithium ion battery characterized by comprising
Cathode；
Anode, the anode include positive electrode active materials according to any one of claims 1 to 5 or as claimed in claim 9
Positive plate；
Battery diaphragm；And
Electrolyte.
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