CN107316985A - The preparation method of nickel-cobalt-manganese ternary material, composite precursor and presoma - Google Patents
The preparation method of nickel-cobalt-manganese ternary material, composite precursor and presoma Download PDFInfo
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Abstract
The present invention relates to the preparation method of nickel-cobalt-manganese ternary material, composite precursor and its presoma.The preparation method, comprises the following steps, and 1) by the soluble-salt wiring solution-forming A of nickel cobalt manganese, by precipitating reagent wiring solution-forming B；2) under stirring, solution A and solution B shunting are added dropwise in same reaction vessel and obtain solution C to producing precipitation；3) process step 2) gained produce precipitation solution C, obtain nickel-cobalt-manganese ternary material precursor.The preparation method that the present invention is provided is not only it is possible to prevente effectively from introduce other impurities ion, improve the purity of resulting materials and its presoma, different metal ions distribution is more uniform in gained crystal, the difficulty of final wash can also be reduced simultaneously, cost of sewage disposal is reduced, the probability of environmental pollution is reduced.
Description
Technical field
The present invention relates to the preparation method of a kind of nickel-cobalt-manganese ternary material, composite precursor and its presoma, more particularly to
Applied to the preparation method of the nickel-cobalt-manganese ternary material in anode material for lithium-ion batteries, composite precursor and its presoma, more
It is specifically related to be applied to nickel-cobalt-manganese ternary stratified material in anode material for lithium-ion batteries, composite precursor and its presoma
Preparation method.
Background technology
Lithium battery refers to the electrochemical system of the most basic electrochemistry unit containing lithium.Lithium battery can be divided into two classes：Lithium gold
Belong to battery and lithium ion battery.Lithium ion battery does not contain the lithium of metallic state, and preparation technology is simple, and can realize and fill repeatedly
The function of electricity, with wide application field, is related to such as mobile communication, life ＆ amusement, national defense and military, Aero-Space, doctor
The various aspects such as equipment are treated, in addition to developing various portable type electronic products, also towards big-and-middle-sized energy storage device and power electric
Source direction is developed, therefore cost is low, and the high lithium ion battery of energy density has more wide DEVELOPMENT PROSPECT.
Lithium ion battery generally includes positive electrode, negative material and other inscapes.Wherein, negative material is usual
Using graphite, positive electrode generally uses LiMn2O4, cobalt acid lithium (LiCoO2), LiFePO4 (LiFePO4), nickle cobalt lithium manganate four
Plant conventional material system.Described conventional positive electrode is divided by its pattern can be divided into the positive electrode of stratiform pattern
With the positive electrode of spherical morphology, the positive electrode of two kinds of different-shapes is the research side of existing anode material for lithium-ion batteries
To.
Comparatively, cobalt acid lithium and LiFePO4 either which kind of pattern, its energy density is relatively low, and specific discharge capacity is universal
Less than 200mAhg-1, it is impossible to meet people to big-and-middle-sized energy storage device such as airplane power source and electrokinetic cell high-energy-density
Demand；But show in existing research, the nickle cobalt lithium manganate of spherical morphology is higher than 200mAhg with it-1Height ratio capacity, low cost
And the structural advantage relatively stablized is by the extensive concern of domestic and international researcher.
Nickle cobalt lithium manganate [the Li of existing spherical morphology2(NiCoMn)MO3Or Li (NiCoMn) O2] preparation key be it
Operating procedure or technological parameter in preparation process.The factor of the stability of nickle cobalt lithium manganate is influenceed to essentially consist in discharge and recharge
During whether can suppress or delay it from layer structure to the transformation of spinel structure.At present, for this problem, mainly adopt
Preparation method is coprecipitation.Coprecipitation is usually that corresponding precipitating reagent is added in metal ion solution, so that it may made
Metal ion homogeneous precipitation, reaches the mixing of atomic level, obtains the nickel-cobalt-manganese ternary material forerunner that granularity is small and is evenly distributed
Body, then mixes lithium sintering with regard to that can obtain nickel-cobalt-manganese ternary material by nickel-cobalt-manganese ternary material precursor.But using coprecipitation
Prepare during nickel-cobalt-manganese ternary material precursor to ensure the homogeneous precipitation of metal ion, it will usually adjusted by adding pH
The method of agent, complexing agent, surfactant etc. is saved to control crystal nucleation rate, growth rate and the metal ion of precipitation reaction
Homogeneous precipitation, and the conventional pH conditioning agents of these methods, such as the introducing the complexing agent, surfactant of ammoniacal liquor, not only
Foreign ion can be introduced in nickel-cobalt-manganese ternary material precursor, cause the purity of presoma in itself not enough, accelerate it and filling
The probability changed in discharge process from stratiform pattern to spinel structure, simultaneously because the introducing of foreign ion, cause metal from
Son can not realize homogeneous precipitation, but also can increase the difficulty of final wash, and cost of sewage disposal is high, causes environmental pollution and height
Cost is produced.
The content of the invention
In view of this, the present invention provides the preparation method of a kind of nickel-cobalt-manganese ternary material and its presoma, and it not only can be with
Introducing other impurities ion is prevented effectively from, different metal ions in the purity of resulting materials and its presoma, gained crystal are improved
Distribution is more uniform, while the difficulty of final wash can also be reduced, reduces cost of sewage disposal, reduces the several of environmental pollution
Rate.
To solve above technical problem, the technical scheme for the first aspect that the application is provided is to use a kind of nickel-cobalt-manganese ternary
The preparation method of material precursor, comprises the following steps,
1) by the soluble-salt wiring solution-forming A of nickel cobalt manganese, by precipitating reagent wiring solution-forming B；
2) under stirring, solution A and solution B shunting are added dropwise in same reaction vessel and obtain solution C to generation
Precipitation；
3) process step 2) gained produce precipitation solution C, obtain nickel-cobalt-manganese ternary material precursor.
It is preferred that, the step 2) in be added dropwise before, do not contained in same reaction vessel reaction bottom liquid.
It is preferred that, reaction bottom liquid includes solution A or solution B.
It is preferred that, step 2) mixing speed be 500-2000r/min.
It is preferred that, the soluble-salt of the nickel cobalt manganese is at least one of sulfate, nitrate.
It is preferred that, the precipitating reagent is at least one of sodium carbonate or sodium acid carbonate.
It is preferred that, the pH value of the solution C is that the temperature of 7-9 and/or solution C is 10-70 DEG C.
It is preferred that, the rate of addition of the solution A is V1, and the rate of addition of solution B is V2, V1=V0, V2=V0＇+kt,
Wherein V0 and V0＇ is fixed value, and t is the time, and k is variation coefficient, and k<0.
It is preferred that, V0：V0＇ is 1:(1-1.5).
It is preferred that, the step 2) in agitating solution C to produce precipitation after, after after solution A and solution B completion of dropwise addition continue
It is aged 0-24h.
It is preferred that, the nickel-cobalt-manganese ternary material precursor, nickel-cobalt-manganese ternary Material cladding presoma and nickel-cobalt-manganese ternary
The intermolecular structure of material is layer structure.
It is preferred that, the step 3) specifically include, filtration step 2) gained produce precipitation solution C, washing, it is drying precipitated
Obtain nickel-cobalt-manganese ternary material precursor.
The application also provides the technical scheme of second aspect, i.e., a kind of preparation side of nickel-cobalt-manganese ternary Material cladding presoma
Method, comprises the following steps,
Nickel-cobalt-manganese ternary material precursor is prepared according to the foregoing preparation method, in gained nickel-cobalt-manganese ternary material
The Surface coating layer of metal M of presoma hydroxide or carbonate obtains nickel-cobalt-manganese ternary Material cladding presoma；Nickel cobalt
Manganese ternary material precursor is 1 with metal M hydroxide or the mol ratio of carbonate:(0.01-0.2), metal M be Al, Si,
One or more in Zn, Zr, Ti, Sn, Mg.
The application also provides the technical scheme of the third aspect, i.e., a kind of preparation method of nickel-cobalt-manganese ternary material, including with
Lower step,
Nickel-cobalt-manganese ternary material precursor or nickel-cobalt-manganese ternary Material cladding are prepared according to the foregoing preparation method
Presoma, after the nickel-cobalt-manganese ternary material precursor of gained or nickel-cobalt-manganese ternary Material cladding presoma are mixed with lithium source,
Calcining obtains nickel-cobalt-manganese ternary material in oxygen-enriched atmosphere.
It is preferred that, the lithium source is at least one of lithium carbonate, lithium hydroxide.
It is preferred that, the nickel-cobalt-manganese ternary material precursor or nickel-cobalt-manganese ternary Material cladding presoma and mole of lithium source
Than being 1:(1.02-1.1).
It is preferred that, the calcining is calcine by steps, is followed successively by 400-700 DEG C and once calcines 2-10h, 800-1000 DEG C is secondary
Calcine 4-18h.
The preparation method for the nickel-cobalt-manganese ternary material precursor that the application is used is using the soluble-salt of nickel cobalt manganese with sinking
Agent shunting in shallow lake is added dropwise in same reaction vessel, be not the existing soluble-salt by nickel cobalt manganese generally used directly with appearance
The reaction bottom liquid placed in device such as precipitant solution is mixed, or adds other complementary solution such as pH conditioning agents, network
The mode of mixture, surfactant, the key of the preparation method of the application is not existing that a kind of addition of solution is another
In solution, but it is added dropwise to respectively in same container using two kinds of solution, so as to be obtained by the preparation method of the application
The presoma of nickel-cobalt-manganese ternary material with intermolecular layer structure and spherical morphology.
In addition, the application provides nickel-cobalt-manganese ternary Material cladding presoma and nickel also on the basis of aforementioned preparation process
The preparation method of cobalt-manganese ternary material, i.e., can be by the nickel cobalt manganese three of acquisition after foregoing acquisition nickel-cobalt-manganese ternary material precursor
After first material precursor is directly mixed with lithium source, calcining obtains nickel-cobalt-manganese ternary material in oxygen-enriched atmosphere；Also can be by nickel cobalt manganese
The Surface coating layer of metal M of ternary material precursor hydroxide or carbonate obtains nickel-cobalt-manganese ternary Material cladding forerunner
After body, then with lithium source mixed calcining obtain nickel-cobalt-manganese ternary material.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of gained nickel-cobalt-manganese ternary material precursor in embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of gained nickel-cobalt-manganese ternary material in embodiment 1；
Fig. 3 is the XRD spectra of gained nickel-cobalt-manganese ternary material in embodiment 1；
Fig. 4 is the distribution diagram of element of gained nickel-cobalt-manganese ternary material precursor in embodiment 1；
Fig. 5 is the first charge-discharge curve map of gained nickel-cobalt-manganese ternary material in embodiment 1；
Fig. 6 is the circulation figure of 1C after gained nickel-cobalt-manganese ternary material is activated through 0.1C in embodiment 1；
Fig. 7 is the scanning electron microscope (SEM) photograph of gained nickel-cobalt-manganese ternary material precursor in embodiment 6.
Embodiment
In order that those skilled in the art more fully understands technical scheme, with reference to embodiment
The present invention is described in further detail.
In this application, the form of material is the architectural feature of macroscopic view, such as liquid, particle, powder or glassy state；Thing
The pattern of matter is the microstructure presented under microscope, can be such as spherical, sheet；The structure of material refers to intermolecular
Arrangement form, such as layer structure of similar graphite, the cube crystalline structure of diamond；Nickel-cobalt-manganese ternary described herein
Material precursor, composite precursor, ternary material refer to the material with spherical morphology and intermolecular layer structure.
The preparation method of the application is essentially consisted in using existing operating procedure is different from, and is added dropwise using two kinds of solution shunts
Enter in same reaction vessel, so as to prepare the uniform nickel-cobalt-manganese ternary material precursor of Elemental redistribution.Using the application system
It can need not shift to an earlier date liquid such as precipitating reagent in placing response bottom in Preparation Method, reaction vessel, or preferably select the dropwise addition drop of solution A
Acceleration is V1, and the rate of addition of solution B is V2, V1=V0, V2=V0＇+kt, wherein V0 and V0＇ is fixed value, and t is the time,
K is variation coefficient, and k<0；Particularly preferred V0：V0＇ is 1:(1-1.5).
The application is not intended to limit the protection domain of application scheme using following specific preparation process as main explanation.
Specific preparation process：
1) it is x1 by mol ratio：x2：The soluble-salt (the application is preferably sulfate or nitrate) of x3 nickel cobalt manganese is matched somebody with somebody
The water solution A that concentration is c1mol/L is set to, precipitating reagent (the application is preferably sodium carbonate or sodium acid carbonate) is individually configured to
C2mol/L aqueous solution B.
2) the y shuntings by volume of two kinds of solution are added dropwise in the same reaction vessel for not containing reaction bottom liquid and obtain solution
C, while with speed R rotating speed agitating solution C in the same reaction vessel, precipitation can be produced in whipping process；The reaction
Bottom liquid includes solution A or solution B；
The pH value of solution C is d, and the temperature of solution C is T/ DEG C, after continue after solution A and solution B completion of dropwise addition ageing when
Between be t/h；
The rate of addition of solution A is V1, and the rate of addition of solution B is V2, V1=V0, V2=V0＇+kt, wherein V0And V0＇
It is fixed value, t is the time, k is variation coefficient, and k<0.
3) filtering gained is produced before the solution C of precipitation, washing, the drying precipitated nickel-cobalt-manganese ternary material for obtaining stratiform pattern
Drive body；
4) the nickel-cobalt-manganese ternary material precursor 3) prepared is equally divided into two parts, carried out in two ways respectively follow-up
Step, is designated as mode a and mode b；
Mode a：A nickel-cobalt-manganese ternary material precursor is pressed with lithium source (the application is preferably lithium carbonate or lithium hydroxide)
Mol ratio z is mixed, and its hybrid mode is ball milling or grinding, the T1/ DEG C of calcining t1/h in oxygen-enriched atmosphere, and T2/ DEG C is calcined t2/h, cold
But the nickel-cobalt-manganese ternary material of stratiform pattern is made afterwards.
Mode b：The surface of another nickel-cobalt-manganese ternary material precursor first coats layer of metal M hydroxide or carbonic acid
Salt obtains the nickel-cobalt-manganese ternary Material cladding presoma of stratiform pattern, and metal M is one kind in Al, Si, Zn, Zr, Ti, Sn, Mg
Or it is several；Nickel-cobalt-manganese ternary material precursor is β with metal M hydroxide or the mol ratio of carbonate；Then by gained nickel
γ is mixed cobalt-manganese ternary Material cladding presoma in molar ratio with lithium source (the application is preferably lithium carbonate or lithium hydroxide), and it is mixed
Conjunction mode is ball milling or grinding, and then T1/ DEG C of calcining t1/h, the T2/ DEG C of calcining t2/h in oxygen-enriched atmosphere, stratiform is obtained after cooling
The nickel-cobalt-manganese ternary material of pattern.
Prepared accordingly according to foregoing specific preparation process, and remove the soluble-salt of nickel cobalt manganese, precipitating reagent species
Selection is different and metal M is different with the species selection of lithium source outer, remaining parameter all same being related to, i.e. x1 is 1-2, and x2 is
1-2, x3 are 2-4, c1：C2 is 1：(1-1.5), y is 1:(1-1.1), d is 7-9, and T is 10-70 DEG C, and R is 500-2000r/
Min, t are 0-24h, V0：V0＇ is 1:(1-1.5), k is that -0.1 to -0.5, T1 is 400-700 DEG C, and t1 is 2-10h, and T2 is 800-
1000 DEG C, t2 is 4-18h, and β is 1:(1.02-1.1), γ is 1:(1.02-1.1).
The molecular formula for the nickel-cobalt-manganese ternary material precursor that the application preparation method is prepared is as follows：
(Mn1-a-bNiaCob)CO3(I)；In formula (I), 0<a<1,0≤b<1,0<a+b<1.
As soluble-salt, precipitating reagent species and the metal M for according to foregoing preparation condition, selecting different nickel cobalt manganeses and
During the species of lithium source, ternary material precursor, nickel-cobalt-manganese ternary Material cladding presoma, the nickel cobalt manganese of the corresponding nickel cobalt manganese of gained
The performance parameter of ternary material is variant, for example tap density, Elemental redistribution, first first discharge specific capacity, coulombic efficiency, work
Specific discharge capacity, capability retention after change；
Tap density refers to nickel-cobalt-manganese ternary material and its composite precursor, presoma in container under given conditions
The quality of measured unit volume, can specifically be tested using tap density tester after jolt ramming.
Elemental redistribution refers to the distributing homogeneity of contained element in material, can be detected using scanning electron microscope analysis instrument
Obtain.
The nickel-cobalt-manganese ternary material precursor that the application preparation method is prepared carries out elementary analysis, obtains its molecule
Composition, shows its molecular composition and formula (1) unanimously, the elemental analysis method of use is analyzed with XRD spectra.
The nickel-cobalt-manganese ternary material that the application preparation method is prepared as anode material for lithium-ion batteries, test from
The chemical property of sub- cell positive material, such as first discharge specific capacity, first coulombic efficiency, activation after specific discharge capacity and
Capability retention.
Wherein, when first discharge specific capacity refers to carry out discharge and recharge with 0.1C electric current, specific discharge capacity first.
When coulombic efficiency refers to carry out discharge and recharge with 0.1C electric current first, specific discharge capacity first and charging first
The ratio between specific capacity.
Specific discharge capacity refers to the specific discharge capacity after being circulated 3 times with 0.1C current charge-discharge electricity after activation.
Capability retention refers to the specific discharge capacity after being circulated 200 times under 1C current condition and first discharge specific capacity
Ratio.
Each specific performance parameter value is detected by existing usual manner and obtained above, specifically see the table below.
Embodiment 1, the soluble-salt of nickel cobalt manganese are nickel sulfate, cobaltous sulfate, manganese sulfate；Precipitating reagent is sodium carbonate；Metal M is
Al；Lithium source is lithium carbonate.Following table show the tap density of gained nickel-cobalt-manganese ternary material precursor or composite precursor, and
The correlation performance parameters obtained after gained nickel-cobalt-manganese ternary material is tested as anode material for lithium-ion batteries, gained nickel cobalt manganese three
The elemental distribution of first material precursor is as shown in figure 4, accompanying drawing 2-6 show its scanning electron microscope (SEM) photograph, XRD spectra, element point
Butut, first charge-discharge curve, activated through 0.1C after 1C circulation figure；The pattern of gained nickel-cobalt-manganese ternary material precursor is then such as
Shown in its scanning electron microscope (SEM) photograph shown in accompanying drawing 1.
Table 1：Mode a
| Tap density | First discharge specific capacity | Coulombic efficiency first | Specific discharge capacity after activation | Capability retention |
| 2.6g/cm2 | 287mAh/g | 80% | 290mAh/g | 85.3% |
Table 2：Mode b
Embodiment 2, the soluble-salt of nickel cobalt manganese are nickel nitrate, cobalt nitrate, manganese nitrate；Precipitating reagent is sodium acid carbonate；Metal M
It is Al；Lithium source is lithium carbonate.Following table show the tap density of gained nickel-cobalt-manganese ternary material precursor or composite precursor, with
And the correlation performance parameters obtained after gained nickel-cobalt-manganese ternary material is tested as anode material for lithium-ion batteries, gained nickel cobalt manganese
The elemental distribution of ternary material precursor can be with reference also to shown in Fig. 4.
Table 3：Mode a
| Tap density | First discharge specific capacity | Coulombic efficiency first | Specific discharge capacity after activation | Capability retention |
| 2.4g/cm2 | 285mAh/g | 78% | 287mAh/g | 85.4% |
Table 4：Mode b
| Tap density | First discharge specific capacity | Coulombic efficiency first | Specific discharge capacity after activation | Capability retention |
| 2.3g/cm2 | 280mAh/g | 77% | 286mAh/g | 85.2% |
Embodiment 3, the soluble-salt of nickel cobalt manganese are nickel nitrate, cobalt nitrate, manganese nitrate；Precipitating reagent is sodium acid carbonate；Metal M
It is Si；Lithium source is lithium hydroxide.Following table show the tap density of gained nickel-cobalt-manganese ternary material precursor or composite precursor,
And the correlation performance parameters obtained after gained nickel-cobalt-manganese ternary material is tested as anode material for lithium-ion batteries, gained nickel cobalt
The elemental distribution of manganese ternary material precursor can be with reference also to shown in Fig. 4.
Table 5：Mode a
| Tap density | First discharge specific capacity | Coulombic efficiency first | Specific discharge capacity after activation | Capability retention |
| 2.7g/cm2 | 289mAh/g | 81% | 290mAh/g | 85.4% |
Table 6：Mode b
| Tap density | First discharge specific capacity | Coulombic efficiency first | Specific discharge capacity after activation | Capability retention |
| 2.6g/cm2 | 286mAh/g | 80% | 289mAh/g | 85.3% |
Embodiment 4, the soluble-salt of nickel cobalt manganese are nickel nitrate, cobalt nitrate, manganese nitrate；Precipitating reagent is sodium acid carbonate；Metal M
It is Zn or Zr；Lithium source is lithium hydroxide.Following table show the jolt ramming of gained nickel-cobalt-manganese ternary material precursor or composite precursor
Density, and after gained nickel-cobalt-manganese ternary material is tested as anode material for lithium-ion batteries correlation performance parameters, institute
The elemental distribution for obtaining nickel-cobalt-manganese ternary material precursor can be with reference also to shown in Fig. 4.
Table 7：Mode a
| Tap density | First discharge specific capacity | Coulombic efficiency first | Specific discharge capacity after activation | Capability retention |
| 2.6g/cm2 | 285mAh/g | 79% | 287mAh/g | 85.3% |
Table 8：Mode b
| Tap density | First discharge specific capacity | Coulombic efficiency first | Specific discharge capacity after activation | Capability retention |
| 2.7g/cm2 | 286mAh/g | 80% | 294mAh/g | 85.4% |
Embodiment 5, the soluble-salt of nickel cobalt manganese are nickel sulfate, cobaltous sulfate, manganese sulfate；Precipitating reagent is sodium carbonate；Metal M is
Ti, Sn or Mg；Lithium source is lithium carbonate.Following table show the vibration density of gained nickel-cobalt-manganese ternary material precursor or composite precursor
Degree, and after gained nickel-cobalt-manganese ternary material is tested as anode material for lithium-ion batteries correlation performance parameters, gained
The elemental distribution of nickel-cobalt-manganese ternary material precursor can be with reference also to shown in Fig. 4.
Table 9：Mode a
| Tap density | First discharge specific capacity | Coulombic efficiency first | Specific discharge capacity after activation | Capability retention |
| 2.6g/cm2 | 287mAh/g | 80% | 290mAh/g | 85.3% |
Table 10：Mode b
| Tap density | First discharge specific capacity | Coulombic efficiency first | Specific discharge capacity after activation | Capability retention |
| 2.6g/cm2 | 287mAh/g | 80% | 290mAh/g | 85.3% |
Prepared accordingly according to foregoing specific preparation process, and except c1：c2、y、V0：V0＇, k are different outer, and remaining is related to
And all same, i.e. the soluble-salt of nickel cobalt manganese is sulfate or nitrate, and precipitating reagent is sodium carbonate or sodium acid carbonate, metal M
It is the one or more in Al, Si, Zn, Zr, Ti, Sn, Mg, lithium source is lithium carbonate or lithium hydroxide, and x1 is 1-2, and x2 is 1-2,
X3 is 2-4, and d is 7-9, and T is 10-70 DEG C, and R is 500-2000r/min, and t is 0-24h, and T1 is 400-700 DEG C, and t1 is 2-10h,
T2 is 800-1000 DEG C, and t2 is 4-18h, and β is 1:(1.02-1.1), γ is 1:(1.02-1.1).
Also according to foregoing preparation condition, different c1 are selected：c2、y、V0：V0＇, k concrete numerical value, the corresponding nickel of gained
The ternary material precursor of cobalt manganese, nickel-cobalt-manganese ternary Material cladding presoma, nickel-cobalt-manganese ternary material performance parameter it is variant,
Equally specific discharge capacity, capacity are protected for example after tap density, Elemental redistribution, first discharge specific capacity, coulombic efficiency, activation first
Holdup, each specific performance parameter value of the above is detected by existing usual manner and obtained, and specifically see the table below.
Embodiment 6, the soluble-salt of nickel cobalt manganese are in sequence than being c1：C2 is 1:1, y is 1:1, V0：V0＇ is 1:1, k
It is -0.1.Following table show the tap density of gained nickel-cobalt-manganese ternary material precursor or composite precursor, and by gained nickel
Before the correlation performance parameters that cobalt-manganese ternary material is obtained after being tested as anode material for lithium-ion batteries, gained nickel-cobalt-manganese ternary material
The elemental distribution for driving body can be with reference also to shown in Fig. 4, and the pattern of gained nickel-cobalt-manganese ternary material precursor is then such as the institute of accompanying drawing 7
Shown in its scanning electron microscope (SEM) photograph shown.
Table 11：Mode a
| Tap density | First discharge specific capacity | Coulombic efficiency first | Specific discharge capacity after activation | Capability retention |
| 2.7g/cm2 | 287mAh/g | 80% | 292mAh/g | 85.3% |
Table 12：Mode b
| Tap density | First discharge specific capacity | Coulombic efficiency first | Specific discharge capacity after activation | Capability retention |
| 2.6g/cm2 | 285mAh/g | 79% | 289mAh/g | 85.2% |
Embodiment 7, the soluble-salt of nickel cobalt manganese are in sequence than being c1：C2 is 1：1.5, y be 1：1.1, V0： V0＇ is 1：
1.5, k be -0.5.Following table show the tap density of gained nickel-cobalt-manganese ternary material precursor or composite precursor, and by institute
Obtain the correlation performance parameters obtained after nickel-cobalt-manganese ternary material is tested as anode material for lithium-ion batteries, gained nickel-cobalt-manganese ternary material
The elemental distribution of material precursor can be with reference also to shown in Fig. 4.
Table 13：Mode a
| Tap density | First discharge specific capacity | Coulombic efficiency first | Specific discharge capacity after activation | Capability retention |
| 2.5g/cm2 | 285mAh/g | 79% | 289mAh/g | 85.2% |
Table 14：Mode b
| Tap density | First discharge specific capacity | Coulombic efficiency first | Specific discharge capacity after activation | Capability retention |
| 2.6g/cm2 | 288mAh/g | 81% | 294mAh/g | 85.5% |
Embodiment 8, the soluble-salt of nickel cobalt manganese are in sequence than being c1：C2 is 1：1.2, y be 1：1.1, V0： V0＇ is 1：
1.3, k be -0.3.Following table show the tap density of gained nickel-cobalt-manganese ternary material precursor or composite precursor, and by institute
Obtain the correlation performance parameters obtained after nickel-cobalt-manganese ternary material is tested as anode material for lithium-ion batteries, gained nickel-cobalt-manganese ternary material
The elemental distribution of material precursor can be with reference also to shown in Fig. 4.
Table 15：Mode a
| Tap density | First discharge specific capacity | Coulombic efficiency first | Specific discharge capacity after activation | Capability retention |
| 2.7g/cm2 | 288mAh/g | 81% | 292mAh/g | 85.4% |
Table 16：Mode b
| Tap density | First discharge specific capacity | Coulombic efficiency first | Specific discharge capacity after activation | Capability retention |
| 2.6g/cm2 | 289mAh/g | 80% | 290mAh/g | 85.3% |
It the above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair
The limitation of the present invention, protection scope of the present invention should be defined by claim limited range.For the art
For those of ordinary skill, without departing from the spirit and scope of the present invention, some improvements and modifications can also be made, these change
Enter and retouch and also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of nickel-cobalt-manganese ternary material precursor, it is characterised in that：Comprise the following steps,
1) by the soluble-salt wiring solution-forming A of nickel cobalt manganese, by precipitating reagent wiring solution-forming B；
2) under stirring, solution A and solution B shunting are added dropwise in same reaction vessel and obtain solution C to producing precipitation；
3) process step 2) gained produce precipitation solution C, obtain nickel-cobalt-manganese ternary material precursor.
2. preparation method according to claim 1, it is characterised in that：The step 2) in be added dropwise before, it is same reaction hold
Reaction bottom liquid is not contained in device.
3. preparation method according to claim 2, it is characterised in that：Reaction bottom liquid includes solution A or solution B.
4. preparation method according to claim 1, it is characterised in that：The pH value of the solution C is 7-9 and/or solution C
Temperature is 10-70 DEG C.
5. preparation method according to claim 1, it is characterised in that：The rate of addition of the solution A is V1, solution B
Rate of addition is V2, V1=V0, V2=V0＇+kt, wherein V0 and V0＇ is fixed value, and t is the time, and k is variation coefficient, and k<
0。
6. preparation method according to claim 5, it is characterised in that：V0：V0＇ is 1:(1-1.5).
7. preparation method according to claim 1, it is characterised in that：The step 3) specifically include, filtration step 2) institute
It must produce the solution C of precipitation, washing, drying precipitated obtain nickel-cobalt-manganese ternary material precursor.
8. a kind of preparation method of nickel-cobalt-manganese ternary Material cladding presoma, it is characterised in that：Comprise the following steps,
Nickel-cobalt-manganese ternary material precursor is prepared according to preparation method described in power 1, in gained nickel-cobalt-manganese ternary material forerunner
The Surface coating layer of metal M of body hydroxide or carbonate obtains nickel-cobalt-manganese ternary Material cladding presoma；Nickel cobalt manganese three
First material precursor is 1 with metal M hydroxide or the mol ratio of carbonate:(0.01-0.2), metal M be Al, Si, Zn,
One or more in Zr, Ti, Sn, Mg.
9. a kind of preparation method of nickel-cobalt-manganese ternary material, it is characterised in that：Comprise the following steps,
Nickel-cobalt-manganese ternary material precursor or nickel-cobalt-manganese ternary Material cladding are prepared according to preparation method described in power 1 or power 8
Presoma, after the nickel-cobalt-manganese ternary material precursor of gained or nickel-cobalt-manganese ternary Material cladding presoma are mixed with lithium source,
Calcining obtains nickel-cobalt-manganese ternary material in oxygen-enriched atmosphere.
10. preparation method according to claim 9, it is characterised in that：The nickel-cobalt-manganese ternary material precursor or nickel cobalt
The mol ratio of manganese ternary material composite precursor and lithium source is 1:(1.02-1.1).
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| CN104681805A (en) * | 2013-11-28 | 2015-06-03 | 河南科隆新能源有限公司 | Ternary high-voltage positive electrode material for lithium ion battery and preparation method of ternary high-voltage positive electrode material |
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