CN104347867B - A kind of anode material of lithium battery and preparation method thereof - Google Patents
A kind of anode material of lithium battery and preparation method thereof Download PDFInfo
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- CN104347867B CN104347867B CN201310319817.0A CN201310319817A CN104347867B CN 104347867 B CN104347867 B CN 104347867B CN 201310319817 A CN201310319817 A CN 201310319817A CN 104347867 B CN104347867 B CN 104347867B
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- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- 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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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention provides a kind of anode material of lithium battery and preparation method thereof, comprise the following steps：S1, by 5 ~ 25h of solution A and aqueous slkali coprecipitation reaction；S2, toward being at the uniform velocity pumped into solution B in solution A, and after entirety and aqueous slkali are proceeded into coprecipitation reaction, termination while solution B is pumped into it is dried to obtain presoma；S3, presoma mixed with lithium salts, anode material of lithium battery is obtained after sintering；Ni, Co, Mn mol ratio in solution A=（1‑2x）：x：X, 0 ＜ x≤0.25；Ni, Co, Mn mol ratio in solution B=（1‑2y）：y：Y, 0.25≤y ＜ 0.5.The anode material of lithium battery that the present invention is provided is while have the advantages that high power capacity, high thermal stability, high circulation performance, high electrochemical performance and low cost.
Description
Technical field
The invention belongs to field of lithium ion secondary, more particularly to a kind of anode material of lithium battery and preparation method thereof.
Background technology
Due to LiCoO2、LiNiO2、LiMnO2There is very strong complementarity, exploitation binary or ternary in structure and performance
Composite positive pole, improve material chemical property turn into research Main way.Co and Mn are incorporated into simultaneously
LiNiO2Layer structure among the LiNi that is formed1-x-yCoxMnyO2Ternary transition metal composite oxides show compared with
LiCoO2More excellent chemical property, it is considered to be most possibly substitute LiCoO2Positive electrode.
High-nickel material in nickel-cobalt-manganese ternary material, can be because of its electrolyte because top layer has the tetravalence nickel element of high price
Decompose, always cause poor heat endurance, thus can not apply.Sun yangkook are prepared for a kind of possessing core shell structure
There are graded elemental concentrations in nickel-cobalt-manganese ternary material, this material, wherein Ni is gradually decreased, and Mn in outermost two microns
Gradually increase with Co.But the ternary material of the core shell structure is after the sintering, meeting between the kernel of material and outer gradient top layer
Obvious boundary is produced, causes core can occur because of the difference of the inside and outside structure coefficient of expansion in sintering and cyclic process
Separation and rupture between shell, destroy material structure, it is difficult to reach preferable cycle performance and thermal stability.In addition, this boundary
Limit also can limiting lithium ion diffusion, reduce material chemical property.
The content of the invention
The present invention, which solves nickel-cobalt-manganese ternary material internal in the prior art, to be had obvious boundary, is difficult to reach and preferably follows
The technical problem of ring performance, thermal stability and chemical property.
The invention provides a kind of preparation method of anode material of lithium battery, comprise the following steps：
S1, first solution A and aqueous slkali constant speed be pumped into reaction vessel, carry out coprecipitation reaction；
S2, after step S1 carries out 5 ~ 25h, be at the uniform velocity pumped into solution B into solution A, and will be mixed while solution B is pumped into
Close solution entirety to be pumped into reaction vessel with aqueous slkali constant speed, proceed before being dried to obtain after coprecipitation reaction, reaction terminating
Drive body；
S3, the obtained presomas of step S2 are mixed with lithium salts, the anode material of lithium battery is obtained after sintering；
The solution A be the mixed solution containing water soluble nickel salt, water-soluble manganese salt and water soluble cobaltous salt, wherein Ni, Co,
Mn mol ratio=（1-2x）：x：X, wherein 0 ＜ x≤0.25；
The solution B be the mixed solution containing water soluble nickel salt, water-soluble manganese salt and water soluble cobaltous salt, wherein Ni, Co,
Mn mol ratio=（1-2y）：y：Y, wherein 0.25≤y ＜ 0.5；And solution A is different with solution B；
The aqueous slkali is the aqueous solution containing precipitating reagent and complexing agent；The precipitating reagent is in water soluble hydroxide
One or more, complexing agent is ammoniacal liquor.
Present invention also offers a kind of anode material of lithium battery, the anode material of lithium battery is provided by the present invention to be prepared
Method is prepared；The anode material of lithium battery have in kernel-gradient shell double-layer structure, the gradient shell by it is interior extremely
Outer nickel content is gradually reduced, and manganese cobalt content gradually rises.
The preparation method for the anode material of lithium battery that the present invention is provided, presoma is prepared by two step coprecipitations, wherein
First step coprecipitation process forms the kernel of the positive electrode, and it is nickelic low cobalt manganese material；Then second step coprecipitation process
In by controlling the concentration of nickel cobalt manganese in reaction system, form the gradient shell of the concentration in gradient distribution of three kinds of elements, the ladder
Being outside one's consideration, nickel concentration is gradually reduced shell from the inside to the outside, cobalt and manganese concentration gradually rise, and is not present between the gradient shell and kernel
Substantially boundary, the situation that can be prevented effectively from nucleocapsid separation or rupture when its follow-up sintering prepares positive electrode occurs, also will not lithium
The abjection and insertion of ion so that there is high power capacity, high thermal stability, high circulation simultaneously using the lithium battery of the positive electrode
The advantage of energy, high electrochemical performance and low cost.
Brief description of the drawings
Fig. 1 is the structural representation for the reaction unit that presoma is prepared in embodiment 1.
Fig. 2 is the co-precipitation presoma S1 prepared in embodiment 1 section SEM figures.
Fig. 3 is the content distribution of elements figure of the co-precipitation presoma S1 prepared in embodiment 1 nickel cobalt manganeses from the inside to the outside.
Fig. 4 is the XRD test charts for the anode material of lithium battery S10 that embodiment 1 is prepared.
In figure, 1 --- the first container, 2 --- second container, 3 --- the 3rd container, 4 --- reaction vessel, 5 --- production
Thing collection vessel, 6 --- the first pump, 7 --- the second pump, 8 --- the 3rd pump.
Embodiment
The invention provides a kind of preparation method of anode material of lithium battery, comprise the following steps：
S1, first solution A and aqueous slkali constant speed be pumped into reaction vessel, carry out coprecipitation reaction；
S2, after step S1 carries out 5 ~ 25h, be at the uniform velocity pumped into solution B into solution A, and will be mixed while solution B is pumped into
Close solution entirety to be pumped into reaction vessel with aqueous slkali constant speed, proceed before being dried to obtain after coprecipitation reaction, reaction terminating
Drive body；
S3, the obtained presomas of step S2 are mixed with lithium salts, the anode material of lithium battery is obtained after sintering；
The solution A be the mixed solution containing water soluble nickel salt, water-soluble manganese salt and water soluble cobaltous salt, wherein Ni, Co,
Mn mol ratio=（1-2x）：x：X, wherein 0 ＜ x≤0.25；
The solution B be the mixed solution containing water soluble nickel salt, water-soluble manganese salt and water soluble cobaltous salt, wherein Ni, Co,
Mn mol ratio=（1-2y）：y：Y, wherein 0.25≤y ＜ 0.5；And solution A is different with solution B；
The aqueous slkali is the aqueous solution containing precipitating reagent and complexing agent；The precipitating reagent is in water soluble hydroxide
One or more, complexing agent is ammoniacal liquor.
The nickel-cobalt-manganese ternary material for possessing core shell structure that in the prior art prepared by Sun yangkook, the kernel of the material
There is obvious boundary between shell, therefore can be because of the inside and outside structure coefficient of expansion in sintering and cyclic process
It is different and slight crack occur, so that material structure is destroyed, so as to be difficult to reach preferable cycle performance and thermal stability.In addition,
This boundary also can limiting lithium ion diffusion, so as to reduce the chemical property of material.
And be then to prepare presoma by two step coprecipitations in the present invention, specifically, first directly by nickelic low cobalt manganese salt
First step co-precipitation is carried out with aqueous slkali, the kernel of the positive electrode is formed, it is nickelic low cobalt manganese material.Then in second step
In coprecipitation process, the concentration of nickel cobalt manganese in control reaction system, in nickelic core surface formation gradient shell, the gradient shell
Middle nickel, cobalt, the concentration in gradient distribution of three kinds of elements of manganese, i.e. the gradient shell from the inside to the outside nickel concentration gradually reduce, cobalt and manganese
Concentration gradually rises；And because the solution A that gradient shell and kernel are used in co-precipitation is identical, therefore intermediate layer with it is interior
Substantially boundary is not present between core, the separation of nucleocapsid when its follow-up sintering prepares positive electrode or rupture on the one hand can be prevented effectively from
Situation occur, on the other hand also will not lithium ion abjection and insertion, using the positive electrode lithium battery simultaneously there is Gao Rong
The advantage of amount, high circulation performance, high electrochemical performance and low cost.
Meanwhile, in the present invention, the solution A is the mixing containing water soluble nickel salt, water-soluble manganese salt and water soluble cobaltous salt
The mol ratio of solution, wherein Ni, Co, Mn=（1-2x）：x：X, wherein 0 ＜ x≤0.25；Ie in solution A is nickelic low manganese cobalt liquor.
In step S1, directly solution A and aqueous slkali are co-precipitated, nickelic low manganese cobalt material is formed.In this step S1, coprecipitation reaction
Time is 5 ~ 25h, that is, passes through solution A（It is nickelic low manganese cobalt liquor）A period of time first is co-precipitated with aqueous slkali, is formed nickelic
Low manganese cobalt inner core.Under preferable case, in step S1, the time of coprecipitation reaction is 10 ~ 15h.By controlling co-precipitation anti-
It is the time answered, actual then be coprecipitation reaction time, the average grain of obtained kernel as previously described in order to control the size of kernel
Footpath is 1 ~ 10 micron, preferably 4 ~ 8 microns.
It is used as a kind of preferred embodiment of the present invention, x=0.1, Ni, Co, Mn mol ratio=8 in ie in solution A：1：1.
Preparation in accordance with the present invention, after solution A and aqueous slkali co-precipitation a period of time form nickelic kernel, so
Afterwards toward solution B is at the uniform velocity pumped into solution A, that is, form the mixed solution of solution A and solution B.Wherein, solution A is as previously described height
The low manganese cobalt liquor of nickel；And solution B be the mixed solution containing water soluble nickel salt, water-soluble manganese salt and water soluble cobaltous salt, wherein Ni,
Co, Mn mol ratio=（1-2y）：y：Y, wherein 0.25≤y ＜ 0.5；Ie in solution B relative solutions A is low nickel and high manganese cobalt liquor.Cause
This, toward during being pumped into solution B in solution A, nickel content is gradually reduced in its mixed solution system formed, and manganese cobalt contains
Amount then gradually rises.Therefore, by the mixed solution integrally and in aqueous slkali coprecipitation process, outside the gradient of core surface formation
Nickel content is gradually reduced shell from the inside to the outside, and manganese cobalt content gradually rises, and real on the interface intersected with kernel of the gradient shell
Border is still solution A and alkali solution precipitate product, hence in so that obvious interface is not present between gradient shell and kernel.Cause
This, in the presoma ultimately formed, although it is from the inside to the outside kernel-gradient shell double-layer structure, but due in gradient shell
The graded of constituent content so that obvious decomposition is not present between nickelic kernel and gradient shell, in follow-up sintering not
Nucleocapsid separation rupture can be produced, will not also cause the diffusion of lithium ion to be blocked.
The positive electrode that the preparation method provided by the present invention is prepared, its nickel element concentration reduction from the inside to the outside,
Cobalt and the rise of manganese element concentration, and internal nickel element content is high, can obtain higher capacity；The higher cobalt energy of outside content
Preferable layer structure is provided, the relatively low cobalt of internal content can reduce the cost of material；The higher manganese element of outside content is higher,
Good thermal stability can be provided, hence in so that the lithium battery anode material that the preparation method provided using the present invention is prepared
Material can have high power capacity and security performance simultaneously.
Under preferable case, in the present invention, solution A is calculated with the integral molar quantity of Ni, Co, Mn contained by it, and solution B is with it
Contained Ni, Co, Mn integral molar quantity is calculated, toward being pumped into before solution B in solution A in step S2, solution A and solution B
Mol ratio=1：5~5：1.
In the present invention, Ni, Co, Mn total mol concentration are 0.5 ~ 3.0mol/L in solution A.Ni, Co, Mn in solution B
Total mol concentration is 0.5 ~ 3.0mol/L.
Under preferable case, in step S2, Ni, Co, Mn total mol concentration M1 and rubbing for precipitating reagent in solution A and solution B
Your concentration M2 ratio M1：M2=1:3~3:1, wherein the molar concentration M2 of precipitating reagent is with OH-Meter.Under preferable case, M1：M2=1:
1。
Similarly it is preferred that in the case of, in step S2, Ni, Co, Mn total mol concentration M1 and complexing in solution A and solution B
The molar concentration M3 of agent ratio M1：M3=1:0.25~1:3, the molar concentration M3 of its complexing agent is with NH3Meter.Preferable case
Under, M1：M3=1:0.5.
In the present invention, the water soluble nickel salt can use the water-soluble salt of nickel common in the art, such as optional bin cure
One or more in sour nickel, nickel nitrate, nickel acetate, nickel chloride, but it is not limited to this.Similarly, the water-soluble manganese salt can
One or more in manganese sulfate, manganese nitrate, manganese acetate, manganese chloride, but it is not limited to this.The water soluble cobaltous salt is optional
One or more from cobaltous sulfate, cobalt nitrate, cobalt acetate, cobalt chloride, but it is not limited to this.
As it was previously stated, the precipitating reagent is water soluble hydroxide.Under preferable case, the precipitating reagent may be selected from hydroxide
One or more in sodium, lithium hydroxide, potassium hydroxide, but it is not limited to this.
In the present invention, the speed that the speed and solution B being pumped into for solution A in reaction vessel are pumped into solution A does not have
There is particular determination；Under preferable case, the speed and solution B for being pumped into solution A are pumped into speed in solution A without too fast.
In step S2, the time for proceeding coprecipitation reaction is more than 0 ~ 20h.As long as step S2's is total to i.e. in the present invention
The precipitation reaction time is more than 0, you can in nickelic core surface formation gradient shell.Under preferable case, in step S2, proceed
The time of coprecipitation reaction is 2 ~ 20h, and the thickness for the gradient shell being correspondingly formed is 0.1 ~ 5 micron.
The co-precipitation of the step of the above two is fully completed, i.e., after reaction terminating, then product system is filtered, drying process.
Under preferable case, drying temperature is 20 ~ 200 DEG C.Spherical ternary hydroxide, i.e. presoma are obtained after drying.
The method according to the invention, then mixes presoma with lithium salts, and anode material of lithium battery is can obtain after sintering.
The species of wherein lithium salts is known to those skilled in the art, for example may be selected from lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate,
One or more in lithium chloride.Under preferable case, the mol ratio of presoma and lithium salts is 1:0.8~1:1.5, more preferably 1:1
~1:1.1。
The sintering is preferred to use double sintering mode；Specifically, first paragraph sintering temperature is 350 ~ 550 DEG C, during sintering
Between be 1 ~ 10h, preferably 4h.Second segment sintering temperature is 700 ~ 1000 DEG C, and sintering time is 4 ~ 40h, preferably 12h.Pass through
Double sintering, can effectively prevent from destroying the pattern of presoma during vigorous reaction.
Present invention also offers a kind of anode material of lithium battery, the anode material of lithium battery is provided by the present invention to be prepared
Method is prepared；The anode material of lithium battery have in kernel-gradient shell double-layer structure, the gradient shell by it is interior extremely
Outer nickel content is gradually reduced, and manganese cobalt content gradually rises.The anode material of lithium battery that the present invention is provided is while have high power capacity, height
Heat endurance, high circulation performance, high electrochemical performance and inexpensive advantage.
As it was previously stated, the anode material of lithium battery that the present invention is provided has nickelic kernel-gradient shell double-layer structure, wherein
Kernel is the lithium compound of nickelic low manganese cobalt, and gradient shell is nickel, manganese, the lithium compound of cobalt element concentration gradient distribution（By interior
Gradually reduced to outer nickel content, and manganese cobalt content then gradually rises）.
In order that technical problem solved by the invention, technical scheme and beneficial effect are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only to explain
The present invention, is not intended to limit the present invention.
Embodiment 1
（1）As shown in figure 1, loading 2mol/L solution A 1 in second container 2, the solution A 1 is nickel sulfate, sulfuric acid
The aqueous solution of manganese and cobaltous sulfate, mol ratio Ni：Co：Mn=8：1：1；Load 2mol/L solution B 1 into the first container 1, it is described
Solution B 1 is the aqueous solution of nickel sulfate, manganese sulfate and cobaltous sulfate, mol ratio Ni：Co：Mn=4：3：3.Load into the 3rd container 3
Aqueous slkali, aqueous slkali is that the concentration of sodium hydroxide in the mixed system of sodium hydroxide and ammoniacal liquor, aqueous slkali is 2mol/L, ammoniacal liquor
Concentration is 1mol/L；
（2）The first pump 6 is closed, the second pump 7 and the 3rd pump 8 are opened, first by the solution A 1 and the 3rd held in second container 2
The aqueous slkali constant speed held in container 3, which is pumped into reaction vessel 4, is reacted, and the reaction time is 10h；Now in second container 2
The volume of solution B 1 of the remaining solution A 1 with being held in the first container 1 is equal；
（3）It is then turned on the first pump 6 and the solution B 1 held in first container 1 is at the uniform velocity pumped into remaining solution A 1（I.e.
Two containers 2）In, and the second pump 7 and the 3rd pump 8 are opened simultaneously, by the mixed solution system in second container 2 and the 3rd container 3
In aqueous slkali constant speed be pumped into reaction vessel 4 and reacted, the reaction time is 10h；
（4）By step（3）Obtained reaction product is dried at 100 DEG C, and collects and had in product collecting container 5
There is the co-precipitation presoma S1 of kernel-gradient shell double-layer structure, its chemical formula is Ni0.70Co0.15Mn0.15(OH)2；Then will
The co-precipitation presoma S1 is with lithium hydroxide with 1：After 1 mixed in molar ratio, 4h is sintered at 480 DEG C, 780 are then heated to
DEG C, continue to sinter 12h, obtain the anode material of lithium battery S10 of the present embodiment, its chemical formula is LiNi0.70Co0.15Mn0.15O2。
Embodiment 2
The anode material of lithium battery S20 of the present embodiment is prepared using step same as Example 1, difference is：
Step（1）In, solution A 2 is the aqueous solution of nickel nitrate, manganese nitrate and cobalt nitrate, mol ratio Ni：Co：Mn=5：2.5：
2.5, the concentration of solution A 2 is 3mol/L；Solution B 2 is the aqueous solution of nickel nitrate, manganese nitrate and cobalt nitrate, mol ratio Ni：Co：Mn
=1：4.5：4.5, the concentration of solution B 2 is 0.6mol/L；
Step（2）In, the reaction time is 15h；Now in second container 2 remaining solution A 2 with being held in the first container 1
Solution B 2 volume it is equal；
Step（3）In, the reaction time is 2h.
By above-mentioned steps, the co-precipitation presoma S2 with kernel-gradient shell double-layer structure of the present embodiment is obtained
（Its chemical formula is Ni0.50Co0.25Mn0.25(OH)2）With anode material of lithium battery S20（Its chemical formula is
LiNi0.50Co0.25Mn0.25O2）.
Embodiment 3
The anode material of lithium battery S30 of the present embodiment is prepared using step same as Example 1, difference is：
Step（1）In, solution A 3 is the aqueous solution of nickel acetate, manganese acetate and cobalt acetate, mol ratio Ni：Co：Mn=9：0.5：
0.5, the concentration of solution A 3 is 0.5mol/L；Solution B 3 is the aqueous solution of nickel acetate, manganese acetate and cobalt acetate, mol ratio Ni：Co：
Mn=5：2.5：2.5, the concentration of solution B 3 is 2.5mol/L；
Step（2）In, the reaction time is 5h；Now held in second container 2 in the remaining container 1 of solution A 3 and first
The volume of solution B 3 is equal；
Step（3）In, the reaction time is 20h.
By above-mentioned steps, the co-precipitation presoma S3 with kernel-gradient shell double-layer structure of the present embodiment is obtained
（Its chemical formula is Ni0.60Co0.20Mn0.20(OH)2）With the anode material of lithium battery S30 of the present embodiment（Its chemical formula is
LiNi0.60Co0.20Mn0.20O2）.
Embodiment 4
The anode material of lithium battery S40 of the present embodiment is prepared using step same as Example 1, difference is：
Step（4）In, using the lithium hydroxide of lithium chloride alternate embodiment 1, and with kernel-gradient shell double-layer structure
Co-precipitation presoma S4 and lithium chloride mol ratio be 1：1.1.
By above-mentioned steps, the co-precipitation presoma S4 of the present embodiment is obtained（Its chemical formula is Ni0.70Co0.15Mn0.15
(OH)2）With anode material of lithium battery S40（Its chemical formula is LiNi0.70Co0.15Mn0.15O2）.
Comparative example 1
（1）As shown in figure 1, loading 2mol/L solution A 1 in second container 2, the solution A 1 is nickel sulfate, sulfuric acid
The aqueous solution of manganese and manganese sulfate, mol ratio Ni：Co：Mn=8：1：1；Load aqueous slkali into the 3rd container 3, aqueous slkali is hydrogen-oxygen
The concentration for changing sodium hydroxide in the mixed system of sodium and ammoniacal liquor, aqueous slkali is 2mol/L, and the concentration of ammoniacal liquor is 1mol/L.
（2）The aqueous slkali constant speed held in the container 3 of solution A 1 and the 3rd held in second container 2 is pumped into reaction vessel
Reacted in 4, after reaction 20h, dried at 100 DEG C and collection obtains being co-precipitated presoma DS1 in product collecting container 5,
Its chemical formula is Ni0.8Co0.1Mn0.1(OH)2。
（3）By step（2）Obtained co-precipitation presoma DS1 is with lithium hydroxide with 1：After 1 mixed in molar ratio, 480
4h is sintered at DEG C, 780 DEG C are then heated to, continues to sinter 12h, obtains the anode material of lithium battery DS10 of this comparative example, it is changed
Formula is LiNi0.8Co0.1Mn0.1O2。
Performance test
1st, SEM/EDS is tested
The obtained co-precipitation presoma S1 with kernel-gradient double-layer structure of embodiment 1 is first dispersed in epoxy resin
In, it is polished after solidification, the co-precipitation presoma S1 for semiglobe of dishing out, then using field emission scanning electron microscope（FESEM）
S1 section pattern is tested, while detecting nickel cobalt manganese constituent content variation tendencies of the S1 from core center to ball edge with EDS.Survey
Test result is as shown in Figures 2 and 3.
Note：Total content in Fig. 3 using three kinds of elements of nickel cobalt manganese is counted as 1.0, and wherein abscissa is from co-precipitation presoma
Distance of the core center to test position（That is radius）.
As shown in Figure 2, the co-precipitation presoma S1 that the preparation method provided using the present invention is prepared does not have from the inside to the outside
With the presence of obvious boundary, that is, the anode material of lithium battery S10 obtained also exists without obvious boundary from the inside to the outside.
From the figure 3, it may be seen that the co-precipitation presoma S1 that the preparation method provided using the present invention is prepared, radius is 0-3
Micron（That is kernel）Region is nickelic low manganese cobalt distribution（Mol ratio Ni：Co：Mn=8：1：1）；Radius is 3-5 microns（I.e. outside gradient
Shell）Region is nickel cobalt manganese constituent content distribution gradient, from mol ratio Ni：Co：Mn=8：1：1 graded is to Ni：Co：Mn=4：
3：3, i.e. nickel content are gradually reduced, and cobalt manganese content gradually rises.
2nd, XRD is tested
Using Rigaku SmartLab models X-ray diffraction powder tester to lithium battery made from embodiment 1
Positive electrode S10 carries out XRD tests, uses Cu-K β targets during test, and it is 2 θ angles from 10 ° to 80 °, sweep speed that test is interval
10 seconds are spent to be every.Test result is as shown in Figure 4.
As shown in Figure 4, although use anode material of lithium battery that the preparation method that provides of the present invention prepares its for nickel
Cobalt-manganese ternary composite positive pole, but it still has and LiNiO2Identical layer structure.
3rd, charge-discharge test
By embodiment 1-4 and the difference of comparative example 1 obtained positive electrode S10-S40 and DS10, respectively with conductive agent acetylene
Black, binding agent PVDF in mass ratio 85：10：After 5 ratio mixing, NMP is used to be dispersed into slurry for solvent, then at 20 DEG C very
Each powder is ground after sky drying 24h and sieved, under 2MPa pressure by powder pressing on disk nickel screen, positive pole, electricity is used as
Solution liquid is 1mol/L LiPF6/EC-DEC-EMC（Volume ratio 2:1:3）, CR2016 models button electricity is assembled into glove box
Pond.Then in battery performance detection device（Guangzhou Lan Qi Co., Ltds, model BK-6016AR/2）It is upper to carry out.Test condition：With
1mA/cm2（0.5C）Electric current constant-current charge and electric discharge are carried out to each battery between 3.0~4.4 V.
High temperature test is carried out at 55 DEG C, and test equipment is Giant Force Instrument Enterprise Co.,
LTD., model ETH-408-60-CP-SD.
Test result is as shown in table 1.
Table 1
。
The anode material of lithium battery of the invention provided is can be seen that while having high power capacity, height from the test result of upper table 1
Heat endurance, high circulation performance, high electrochemical performance and inexpensive advantage, hence it is evident that better than the sample of comparative example.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modifications, equivalent substitutions and improvements made within refreshing and principle etc., should be included in the scope of the protection.
Claims (11)
1. a kind of preparation method of anode material of lithium battery, it is characterised in that comprise the following steps：
S1, first solution A and aqueous slkali constant speed be pumped into reaction vessel, carry out coprecipitation reaction；
S2, after step S1 carries out 5~25h, be at the uniform velocity pumped into solution B into solution A, and will be mixed while solution B is pumped into
Solution is overall to be pumped into reaction vessel with aqueous slkali constant speed, and forerunner is dried to obtain after proceeding coprecipitation reaction, reaction terminating
Body；
S3, the obtained presomas of step S2 are mixed with lithium salts, the anode material of lithium battery is obtained after sintering；
The solution A is mixed solution containing water soluble nickel salt, water-soluble manganese salt and water soluble cobaltous salt, wherein Ni, Co, Mn
Mol ratio=(1-2x)：x：X, wherein 0 ＜ x≤0.1；
The solution B is mixed solution containing water soluble nickel salt, water-soluble manganese salt and water soluble cobaltous salt, wherein Ni, Co, Mn
Mol ratio=(1-2y)：y：Y, wherein 0.25≤y ＜ 0.3；And solution A is different with solution B；
The aqueous slkali is the aqueous solution containing precipitating reagent and complexing agent；The precipitating reagent in water soluble hydroxide one
Plant or a variety of, complexing agent is ammoniacal liquor.
2. preparation method according to claim 1, it is characterised in that in step S1, time of coprecipitation reaction for 10~
15h。
3. preparation method according to claim 1, it is characterised in that solution A is always rubbed with Ni, Co, Mn's contained by it
You are calculated amount, and solution B is calculated with the integral molar quantity of Ni, Co, Mn contained by it, in step S2 toward be pumped into solution A solution B it
Before, mol ratio=1 of solution A and solution B：5~5：1.
4. preparation method according to claim 1, it is characterised in that in step S2, proceed coprecipitation reaction when
Between be 2~20h, drying temperature be 20~200 DEG C.
5. preparation method according to claim 1, it is characterised in that Ni, Co, Mn total mol concentration are 0.5 in solution A
~3.0mol/L；Ni, Co, Mn total mol concentration are 0.5~3.0mol/L in solution B.
6. preparation method according to claim 1 or 5, it is characterised in that in step S2, Ni in solution A and solution B, Co,
Mn total mol concentration M1 and the molar concentration M2 of precipitating reagent ratio M1：M2=1:3~3:1, wherein precipitating reagent is mole dense
M2 is spent with OH-Meter.
7. preparation method according to claim 1 or 5, it is characterised in that in step S2, Ni in solution A and solution B, Co,
Mn total mol concentration M1 and the molar concentration M3 of complexing agent ratio M1：M3=1:0.25~1:3, mole of its complexing agent
Concentration M3 is with NH3Meter.
8. preparation method according to claim 1, it is characterised in that the water soluble nickel salt be selected from nickel sulfate, nickel nitrate,
One or more in nickel acetate, nickel chloride；The one kind of water-soluble manganese salt in manganese sulfate, manganese nitrate, manganese acetate, manganese chloride
Or it is a variety of；One or more of the water soluble cobaltous salt in cobaltous sulfate, cobalt nitrate, cobalt acetate, cobalt chloride；The precipitating reagent
One or more in sodium hydroxide, lithium hydroxide, potassium hydroxide.
9. preparation method according to claim 1, it is characterised in that in step S3, the mol ratio of presoma and lithium salts is
1:0.8~1:1.5；One or more of the lithium salts in lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium chloride.
10. the preparation method according to claim 1 or 9, it is characterised in that described to be sintered to double sintering in step S3；
First paragraph sintering temperature is 350~550 DEG C, and sintering time is 1~10h；Second segment sintering temperature is 700~1000 DEG C, sintering
Time is 4~40h.
11. a kind of anode material of lithium battery, it is characterised in that the anode material of lithium battery is by any one of claim 1-10 institutes
The preparation method stated is prepared；The anode material of lithium battery has kernel-gradient shell double-layer structure, the gradient shell
In from the inside to the outside nickel content gradually reduce, manganese cobalt content gradually rises.
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| CN107265519B (en) * | 2017-06-23 | 2019-01-25 | 海南大学 | A kind of application for improving lithium ion cell positive gradient distribution material precursor and synthesizing the method and its presoma of particle size uniformity |
| CN107331858B (en) * | 2017-06-23 | 2019-08-09 | 海南大学 | A kind of lithium ion battery tertiary cathode gradient distribution material precursor and its application |
| CN108039481A (en) * | 2017-12-25 | 2018-05-15 | 湖北环天高科新能源有限公司 | A kind of fluorine-containing power battery positive electrode |
| CN108054375A (en) * | 2017-12-25 | 2018-05-18 | 湖北环天高科新能源有限公司 | A kind of power battery positive electrode |
| CN108039480A (en) * | 2017-12-25 | 2018-05-15 | 湖北环天高科新能源有限公司 | Power battery positive electrode |
| CN109273701B (en) * | 2018-11-23 | 2022-03-18 | 中南大学 | High-nickel core-shell structure gradient nickel-cobalt-manganese ternary cathode material and preparation method thereof |
| CN109694102A (en) * | 2018-12-17 | 2019-04-30 | 肇庆遨优动力电池有限公司 | A kind of lithium-rich manganese-based anode material and preparation method thereof |
| CN111916713B (en) * | 2020-08-20 | 2022-10-04 | 黑龙江科技大学 | High-voltage lithium nickel manganese oxide positive electrode material with core-multilayer shell structure and preparation method thereof |
| CN112054183A (en) * | 2020-09-03 | 2020-12-08 | 深圳澳睿新能源科技有限公司 | Method for preparing material with component gradient characteristic and application of material in battery |
| CN114275825B (en) * | 2021-11-29 | 2024-03-26 | 蜂巢能源科技有限公司 | Precursor, preparation method, positive electrode material comprising precursor, positive electrode and battery |
| CN114349071A (en) * | 2021-12-22 | 2022-04-15 | 广州大学 | Synthesis method of high-nickel cobalt-rich cathode material with single crystal core-shell structure |
| CN114649525B (en) * | 2022-03-02 | 2023-06-02 | 南通金通储能动力新材料有限公司 | Lithium-rich manganese-based@ternary composite precursor, positive electrode material and preparation method of positive electrode material |
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