CN102916177B - Nickel cobalt manganese hydroxide precursor and preparation method thereof - Google Patents
Nickel cobalt manganese hydroxide precursor and preparation method thereof Download PDFInfo
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Abstract
The invention provides a nickel cobalt manganese hydroxide precursor represented by a general formula (I). The hydroxide precursor is an orderly accumulated sphere with a page-like structure composed of a plurality of layers of sheets. The invention further provides a preparation method of the nickel cobalt manganese hydroxide precursor. In the process of preparing the nickel cobalt manganese hydroxide precursor, a sodium hydroxide solution, an ammonia water solution and a mixed solution of nickel salt, cobalt salt and manganese salt are reacted; and the nickel cobalt manganese hydroxide precursor which is the orderly accumulated sphere with the page-like structure is obtained by controlling pH and the amount of the ammonia water solution in the reaction process and adding an additive for adjusting particle morphology in the reaction process at the same time. The experimental results show that the nickel cobalt manganese hydroxide precursor prepared by the invention has better spherical morphology, uniform particle and good particle mobility; therefore, the nickel cobalt manganese hydroxide precursor is beneficial to diffusing lithium ion in the subsequent sintering process.
Description
Technical field
The present invention relates to technical field of energy material preparation, especially nickel cobalt manganese hydroxide precursor and preparation method thereof.
Background technology
Lithium ion battery has the advantages such as high-energy, long-life, memory-less effect and low stain, is widely used in the multiple fields such as mobile phone, computer, digital product, instrument and meter, electric tool, electric bicycle, electric automobile, national defence.At present, the positive electrode that lithium ion battery adopts mainly contains cobalt acid lithium, LiFePO4, LiMn2O4 and nickle cobalt lithium manganate etc., wherein, the maximum positive electrode of occupation rate of market is cobalt acid lithium, but cobalt security performance that is little, expensive as strategic resources reserves and the sour lithium of cobalt is poor, limits further developing of this material.And nickle cobalt lithium manganate has that specific capacity is high, Heat stability is good and the advantage such as cheap, is the one of most potentiality in anode material for lithium-ion batteries, has good application prospect at the dynamic field such as electric motor car, electric tool.
At present, nickle cobalt lithium manganate (LiNi is prepared
xco
ymn
1-x-yo
2) common method have high temperature solid-state method and co-precipitation-high temperature solid-state method.High temperature solid-state method is that nickel source, cobalt source, manganese source, lithium source ball milling evenly, then are carried out high-temperature calcination.The shortcoming of the method is difficult to nickel cobalt manganese three kinds of elements to mix, therefore the synergy of three can not just be given full play to, and the pattern of the material of preparation is difficult to control, the powder body material of usual synthesis is made up of random particle, the bulk density of this material is low, poor fluidity, is unfavorable for the making of positive electrode.Another kind method is co-precipitation-high temperature solid-state method, namely first prepares nickel cobalt manganese hydroxide precursor by coprecipitation, then adds lithium source sintering, obtains nickle cobalt lithium manganate.In the sintering process of the method after adding lithium source, substantially pattern and the granularity of presoma is not changed, and the pattern of nickel-cobalt lithium manganate material, granularity play a part key in many performances of lithium ion battery, then the method synthesizes the ideal preparation method of nickle cobalt lithium manganate, synthesize the nickel cobalt manganese hydroxide precursor with suitable pattern and granularity and become the key affecting nickle cobalt lithium manganate performance, therefore the preparation method of researcher to nickel magnesium cobalt hydroxide presoma starts deep research.Such as, publication number is the preparation method that the Chinese patent of CN1622371A discloses a kind of anode material for lithium-ion batteries high density spherical nickel-cobalt LiMn2O4, nickel salt, cobalt salt, manganese source mixed aqueous solution and NaOH, ammonia spirit pump are first injected in the reactor be with and stirred by the preparation method of this invention nickel cobalt manganese hydroxide precursor respectively continuously, regulate the flow of nickel cobalt-manganese salt mixed aqueous solution and ammonia spirit, control reaction condition and obtain spherical or class spherical Ni
1/3co
1/3mn
1/3(OH)
2presoma.Publication number is that the Chinese patent of CN101202343 discloses lithium ion battery positive pole material cobalt nickel oxide manganses lithium and preparation method thereof; the preparation method of the presoma that this invention relates to is: with the soluble-salt of nickel, cobalt and manganese for raw material; with ammoniacal liquor or ammonium salt for complexing agent; NaOH is precipitation reagent; adding water soluble dispersant; adding water soluble antioxidant or use inert gas control and protection; by solution with and the mode of flowing is added to reaction kettle for reaction; basic treatment; ageing; Separation of Solid and Liquid, washing drying obtains nickel cobalt manganese hydroxide precursor.Although above-mentioned disclosed patent can obtain spherical nickel-cobalt manganese hydroxide precursor, all the surface topography of spherical precursor is not controlled, thus be unfavorable for the diffusion of lithium ion in sintering process.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of nickel cobalt manganese hydroxide precursor and preparation method thereof, prepared the nickel cobalt manganese hydroxide precursor of special appearance by method provided by the invention, thus made the nickel cobalt manganese hydroxide precursor of preparation be conducive to the diffusion of lithium ion in follow-up sintering process.
In view of this, the invention provides one and there is the nickel cobalt manganese hydroxide precursor represented with general formula (I),
Ni
xCo
yMn
1-x-y（OH）
2 （Ⅰ）；
Wherein, 0 < x < 1,0 < y < 1, x+y < 1;
Described nickel cobalt manganese hydroxide precursor be composite wafer form reference book page structure pile up in order spherical.
Preferably, the thickness of described thin slice is 30 ~ 100nm.
Present invention also offers the preparation method that one has the nickel cobalt manganese hydroxide precursor represented with general formula (I), comprise the following steps:
Nickel salt, manganese salt and cobalt salt are mixed, obtain mixed solution, in described mixed solution, the total concentration of nickel salt, manganese salt and cobalt salt is 1 ~ 2mol/L, in described nickel salt, in nickel ion, cobalt salt, in cobalt ions and manganese salt, the mol ratio of manganese ion is x:y:1-x-y, wherein 0 < x < 1,0 < y < 1, x+y < 1;
Additive is mixed with described mixed solution, obtain the first mixed solution, described additive is triethanolamine, shitosan, HPMA or polyacrylic acid, and the ratio of the molal quantity of described additive and described nickel ion, cobalt ions and manganese ion total mole number is 0.005 ~ 0.1:1;
The ammonia spirit be sodium hydroxide solution and the concentration of 2 ~ 10mol/L by described first mixed solution, concentration being 5 ~ 10mol/L mixes, obtain the second mixed solution, the molal quantity of described ammoniacal liquor and the ratio of described nickel ion, cobalt ions and manganese ion total mole are 1 ~ 10:1, the flow of described sodium hydroxide solution is regulated to make the pH of described second mixed solution be 9 ~ 13, ageing after described second mixed solution reaction, obtains having the nickel cobalt manganese hydroxide precursor represented with general formula (I);
Ni
xCo
yMn
1-x-y（OH）
2 （Ⅰ）；
Wherein, 0 < x < 1,0 < y < 1, x+y < 1.
Preferably, described nickel salt is one or more in nickelous sulfate, nickel nitrate and nickel chloride.
Preferably, described manganese salt is one or more in manganese sulfate, manganese nitrate and manganese chloride.
Preferably, described cobalt salt is one or more in cobaltous sulfate, cobalt nitrate and cobalt chloride.
Preferably, described reaction is carried out under protective atmosphere.
Preferably, described protective atmosphere is nitrogen or argon gas.
Preferably, the time of described reaction is 4 ~ 24h.
Preferably, the time of described ageing is 24 ~ 72h.
The invention provides a kind of nickel cobalt manganese hydroxide precursor and preparation method thereof.In the process preparing nickel cobalt manganese hydroxide precursor, the mixed solution of sodium hydroxide solution, ammonia spirit and nickel salt, cobalt salt and manganese salt reacts by the present invention, by the pH in control course of reaction and ammonia spirit amount, in course of reaction, with the addition of the additive having and regulate granule-morphology simultaneously, obtain the nickel cobalt manganese hydroxide precursor of the spherical structure of the structurally ordered accumulation of reference book laminated.Experimental result shows, the spherical morphology of nickel cobalt manganese hydroxide precursor prepared by the present invention is better, and uniform particles, mobility of particle is good, thus in follow-up sintering process, have the diffusion utilizing lithium ion.
Accompanying drawing explanation
Fig. 1 is Ni prepared by the embodiment of the present invention 3
0.5co
0.3mn
0.2(OH)
2high power stereoscan photograph;
Ni prepared by Fig. 2 embodiment of the present invention 3
0.5co
0.3mn
0.2(OH)
2low power stereoscan photograph;
Ni prepared by Fig. 3 comparative example 1 of the present invention
1/3co
1/3mn
1/3(OH)
2high power stereoscan photograph.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses one and there is the nickel cobalt manganese hydroxide precursor represented with general formula (I), described nickel cobalt manganese hydroxide precursor be composite wafer form reference book page structure pile up in order spherical;
Ni
xCo
yMn
1-x-y（OH）
2 （Ⅰ）；
Wherein, 0 < x < 1,0 < y < 1, x+y < 1;
The thickness of described thin slice is preferably 30 ~ 100nm, is more preferably 50 ~ 80nm.Nickel cobalt manganese hydroxide precursor of the present invention has special secondary spherical structure, and it is spherical for what be made up of special laminated structure, and reference book page structure is piled up, thus is more conducive to the diffusion of lithium ion in sintering process.
In order to obtain the nickel cobalt manganese hydroxide precursor of above-mentioned pattern, the invention also discloses the preparation method of above-mentioned nickel cobalt manganese hydroxide precursor, comprising the following steps:
Nickel salt, manganese salt and cobalt salt are mixed, obtain mixed solution, in described mixed solution, the total concentration of nickel salt, manganese salt and cobalt salt is 1 ~ 2mol/L, in described nickel salt, in nickel ion, cobalt salt, in cobalt ions and manganese salt, the mol ratio of manganese ion is x:y:1-x-y, wherein 0 < x < 1,0 < y < 1, x+y < 1;
Mixed with described mixed solution by additive, obtain the first mixed solution, the ratio of the molal quantity of described additive and described nickel ion, cobalt ions and manganese ion total mole number is 0.005 ~ 0.1:1;
The ammonia spirit be sodium hydroxide solution and the concentration of 2 ~ 10mol/L by described first mixed solution, concentration being 5 ~ 10mol/L mixes, obtain the second mixed solution, the molal quantity of described ammoniacal liquor and the ratio of total mole of described nickel ion, cobalt ions and manganese ion are 1 ~ 10:1, the flow of described sodium hydroxide solution is regulated to make the pH of described second mixed solution be 9 ~ 13, ageing after described second mixed solution reaction, obtains having the nickel cobalt manganese hydroxide precursor of the atomic ratio composition represented with general formula (I);
Ni
xCo
yMn
1-x-y（OH）
2 （Ⅰ）；
Wherein, 0 < x < 1,0 < y < 1, x+y < 1.
Prepare in the process of nickel cobalt manganese hydroxide precursor above-mentioned, first nickel salt, cobalt salt and manganese salt are mixed, obtain mixed solution; Then in mixed solution, add additive, obtain the first mixed solution; And prepare sodium hydroxide solution and ammonia spirit; Finally the first mixed solution, sodium hydroxide solution and ammonia spirit are mixed, three reacts, in the process of above-mentioned three kinds of solution mixing, control the addition of ammoniacal liquor and regulate the flow of sodium hydroxide solution, reaction terminates rear ageing, thus obtains having the nickel cobalt manganese hydroxide precursor represented with general formula (I).In course of reaction, by controlling the pH of the concentration of above-mentioned solution, the addition of ammoniacal liquor and the stage of reaction, and with the addition of the additive regulating granule-morphology, thus obtain the nickel cobalt manganese hydroxide precursor that reference book page structure piles up the spherical structure of formation in order.
According to the present invention, first nickel salt, manganese salt and cobalt salt are mixed, obtain mixed solution.In described mixed solution, the total concentration of nickel salt, manganese salt and cobalt salt is 1 ~ 2mol/L, in described nickel salt, in nickel ion, cobalt salt, in cobalt ions and manganese salt, the mol ratio of manganese ion is x:y:1-x-y, wherein 0 < x < 1,0 < y < 1, x+y < 1.Described nickel salt is preferably soluble nickel salt, is more preferably one or more in nickelous sulfate, nickel nitrate and nickel chloride; Described cobalt salt is preferably soluble cobalt, is more preferably one or more in cobaltous sulfate, cobalt nitrate and cobalt chloride; Described manganese salt is preferably soluble manganese salt, is more preferably one or more in manganese sulfate, manganese nitrate and manganese chloride.
After the mixed solution of nickel salt, cobalt salt and manganese salt has been prepared, additive is added in described mixed solution.Described additive is as the particular matter regulating nickel cobalt manganese hydroxide precursor pattern, and its consumption is also regulate pattern essential condition.The consumption of described additive is 0.5 ~ 10% of nickel ion, cobalt ions and manganese ion total mole number in described first mixed solution, is more preferably 2 ~ 7%.Described additive is triethanolamine, shitosan, HPMA or polyacrylic acid.
Preferably, the present invention has prepared sodium hydroxide solution that concentration is 2 ~ 10mol/L and concentration is the ammonia spirit of 5 ~ 10mol/L.
The ammonia spirit mixing of to be the sodium hydroxide solution of 2 ~ 10mol/L and concentration by described first mixed solution, concentration be 5 ~ 10mol/L, obtains the second mixed solution.In the second mixed solution, described NaOH is as precipitation reagent, and described ammoniacal liquor is as complexing agent, because the solubility of compound is determined, and need the nickel cobalt manganese hydroxide precursor obtaining special appearance, therefore, present invention defines the concentration of described precipitation reagent and described complexing agent.In the process of preparation second mixed solution, the ratio controlling the molal quantity of ammoniacal liquor and the total mole number of described nickel ion, cobalt ions and manganese ion is 1 ~ 10:1, is more preferably 3 ~ 8:1; Regulate sodium hydroxide solution flow to control the pH of the second mixed solution for 9 ~ 13 simultaneously.Ageing after described second mixed solution reaction, preferably, in the process of described ageing, the pH controlling reactant liquor is identical with the pH in course of reaction, obtains nickel cobalt manganese hydroxide precursor after ageing.The time of described reaction is preferably 4 ~ 24h, is more preferably 8 ~ 20h, most preferably is 10 ~ 15h, and the time of described ageing is preferably 12 ~ 72h, is more preferably 24 ~ 36h.
In preparation second mixed solution process, the first mixed solution, sodium hydroxide solution and ammonia spirit mix by the present invention, obtain the second mixed solution.The present invention does not select traditional direct mode nickel salt, manganese salt, cobalt salt, additive, sodium hydroxide solution and ammonia spirit mixed, according to meeting direct generating nickel cobalt manganese precipitation of hydroxide after above-mentioned traditional approach mixing, this precipitation is loose structure, can not obtain special secondary spherical nickel cobalt manganese hydroxide precursor.Therefore, first the present invention has prepared mixed solution, then has prepared the first mixed solution, finally the first mixed solution, sodium hydroxide solution and ammonia spirit is mixed, thus obtains the second mixed solution.
According to the present invention, the process preparing nickel cobalt manganese hydroxide precursor can be prepared according to the following reaction formula:
xNi
2+（aq）+yCo
2+（aq）+（1-x-y）Mn
2++zNH
3·H
2O→[Ni
xCo
yMn
1-x-y（NH
3）
n 2+]（aq）+nH
2O+（z-n）NH
3·H
2O（aq） （1）；
[Ni
xCo
yMn
1-x-y（NH
3）
n 2+]（aq）+2OH
-+nH
2O→Ni
xCo
yMn
1-x-y（OH）
2（s）↓+nNH
3·H
2O（aq） （2）；
From above-mentioned reaction equation, nickel ion, manganese ion and cobalt ions first with ammoniacal liquor effect, the ammonium salt of generating nickel cobalt manganese, nickel cobalt manganese ammonium salt again with the effect of precipitation reagent NaOH, thus nickel cobalt manganese hydroxide precursor is precipitated out, obtain nickel cobalt manganese hydroxide precursor.In above-mentioned course of reaction, [Ni in additive meeting influence process (2) added
xco
ymn
1-x-y(NH
3)
n 2+] form with alkali reaction the process precipitated, thus affect the pattern of product.
Nickel cobalt manganese hydroxide precursor prepared by the present invention has the atomic ratio composition represented with general formula (I); According to the difference of selected nickel element, cobalt element and manganese element molal quantity, can prepare but be not limited to 333,532,424,114 type nickel-cobalt-manganese ternary hydroxide presomas, it is respectively Ni
1/3co
1/3mn
1/3(OH)
2, Ni
0.5co
0.3mn
0.2(OH)
2, Ni
0.4co
0.2mn
0.4(OH)
2, Ni
1/6co
1/6mn
4/6(OH)
2.
The invention provides a kind of nickel cobalt manganese hydroxide precursor and preparation method thereof.In the process preparing nickel cobalt manganese hydroxide precursor, sodium hydroxide solution, ammonia spirit and nickel cobalt-manganese salt solution react by the present invention, by the pH in control course of reaction and ammonia spirit amount, in course of reaction, with the addition of the additive having and regulate granule-morphology simultaneously, obtain the nickel cobalt manganese hydroxide precursor of the spherical structure of the structurally ordered accumulation of reference book laminated.Experimental result shows, the spherical morphology of nickel cobalt manganese hydroxide precursor prepared by the present invention is better, and uniform particles, mobility of particle is good, thus is conducive to the diffusion of lithium ion in follow-up sintering process.
In order to understand the present invention further, be described in detail to nickel cobalt manganese hydroxide precursor provided by the invention and preparation method thereof below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1
(1) prepare the mixed solution of nickelous sulfate, cobaltous sulfate, manganese sulfate, the mol ratio of described nickelous sulfate, cobaltous sulfate and manganese sulfate is 1/3:1/3:1/3, and in mixed solution, the total concentration of nickelous sulfate, cobaltous sulfate and manganese sulfate is 2mol/L;
(2) in mixed solution, the triethanolamine of 2% of nickelous sulfate, cobaltous sulfate and manganese sulfate total mole number is added;
(3) compound concentration is the sodium hydroxide pellets agent solution of 5mol/L;
(4) compound concentration is the ammonia spirit of 5mol/L;
(5) joined continuously by above-mentioned three kinds of solution in the reactor of band stirring, the addition controlling ammoniacal liquor is NH
3h
2o:(Ni+Co+Mn)=1:1; Regulate sodium hydroxide pellets agent solution flow with control ph for 11, logical argon shield in course of reaction, ageing 36h after reaction 20h, controls ageing process pH consistent with course of reaction; Be separated also washing reaction thing and obtain that there is the nickel cobalt manganese hydroxide represented with general formula (II): Ni
1/3co
1/3mn
1/3(OH)
2(II).
Nickel cobalt manganese hydroxide precursor molecular formula prepared by said process is Ni
1/3co
1/3mn
1/3(OH)
2, it is spherical that the structurally ordered accumulation of its reference book laminated being the composite wafer being 30nm by sheet thickness is formed is formed, and particle is relatively uniform, good sphericity, and mobility of particle is good.
Embodiment 2
(1) prepare the mixed solution of nickel chloride, cobalt chloride, manganese chloride, the mol ratio of described nickel chloride, cobalt chloride and manganese chloride is 1/3:1/3:1/3, and in mixed solution, the total concentration of nickel chloride, cobalt chloride and manganese chloride is 2mol/L;
(2) in mixed solution, the HPMA of 5% of nickel chloride, cobalt chloride and manganese chloride total mole number is added;
(3) compound concentration is the sodium hydroxide pellets agent solution of 10mol/L;
(4) compound concentration is the ammonia spirit of 8mol/L;
(5) joined continuously by above-mentioned three kinds of solution in the reactor of band stirring, the addition controlling ammoniacal liquor is NH
3h
2o:(Ni+Co+Mn)=8:1; Regulate sodium hydroxide pellets agent solution flow with control ph for 10, logical nitrogen protection in course of reaction, ageing 48h after reaction 20h, controls ageing process pH consistent with course of reaction; Be separated also washing reaction thing and obtain that there is the nickel cobalt manganese hydroxide represented with general formula (II): Ni
1/3co
1/3mn
1/3(OH)
2(II).
Nickel cobalt manganese hydroxide precursor prepared by said process, it is spherical that the structurally ordered accumulation of its reference book laminated being the composite wafer being 55nm by sheet thickness is formed is formed, and particle is relatively uniform, good sphericity, and mobility of particle is good.
Embodiment 3
(1) prepare the mixed solution of nickelous sulfate, cobaltous sulfate, manganese sulfate, the mol ratio of described nickelous sulfate, cobaltous sulfate and manganese sulfate is 0.5:0.3:0.2, and in mixed solution, the total concentration of nickelous sulfate, cobaltous sulfate and manganese sulfate is 2mol/L;
(2) in mixed solution, the HPMA of 3% of nickelous sulfate, cobaltous sulfate and manganese sulfate total mole number is added;
(3) compound concentration is the sodium hydroxide pellets agent solution of 5mol/L;
(4) compound concentration is the ammonia spirit of 5mol/L;
(5) joined continuously by above-mentioned three kinds of solution in the reactor of band stirring, the addition controlling ammoniacal liquor is NH
3h
2o:(Ni+Co+Mn)=2:1; Regulate sodium hydroxide pellets agent solution flow with control ph for 11, logical argon shield in course of reaction, ageing 24h after reaction 18h, controls ageing process pH consistent with course of reaction; Be separated also washing reaction thing and obtain that there is the nickel cobalt manganese hydroxide represented with general formula (III): Ni
0.5co
0.3mn
0.2(OH)
2(III).
Nickel cobalt manganese hydroxide precursor prepared by said process, it is spherical that the structurally ordered accumulation of its reference book laminated being the composite wafer being 30nm by sheet thickness is formed is formed, and particle is relatively uniform, good sphericity, and mobility of particle is good.Fig. 1 and Fig. 2 is the stereoscan photograph of nickel cobalt manganese hydroxide precursor prepared by embodiment 3.
Embodiment 4
(1) prepare the mixed solution of nickel nitrate, cobalt nitrate, manganese nitrate, the mol ratio of described nickel nitrate, cobalt nitrate and manganese nitrate is 0.5:0.3:0.2, and in mixed solution, the total concentration of nickel nitrate, cobalt nitrate and manganese nitrate is 1.5mol/L;
(2) in mixed solution, the HPMA of 2% of nickel nitrate, cobalt nitrate and manganese nitrate salt total mole number is added;
(3) compound concentration is the sodium hydroxide pellets agent solution of 8mol/L;
(4) compound concentration is the ammonia spirit of 5mol/L;
(5) joined continuously by above-mentioned three kinds of solution in the reactor of band stirring, the addition controlling ammoniacal liquor is NH
3h
2o:(Ni+Co+Mn)=5:1; Regulate sodium hydroxide pellets agent solution flow with control ph for 9, logical nitrogen protection in course of reaction, ageing 48h after reaction 20h, controls ageing process pH consistent with course of reaction; Be separated also washing reaction thing and obtain that there is the nickel cobalt manganese hydroxide represented with general formula (III): Ni
0.5co
0.3mn
0.2(OH)
2(III).
Nickel cobalt manganese hydroxide precursor prepared by said process, it is spherical that the structurally ordered accumulation of its reference book laminated being the composite wafer being 50nm by sheet thickness is formed is formed, and particle is relatively uniform, good sphericity, and mobility of particle is good.
Embodiment 5
(1) prepare the mixed solution of nickelous sulfate, cobaltous sulfate, manganese sulfate, the mol ratio of described nickelous sulfate, cobaltous sulfate and manganese sulfate is 0.4:0.2:0.4, and in mixed solution, the total concentration of nickelous sulfate, cobaltous sulfate and manganese sulfate is 1mol/L;
(2) in mixed solution, the polyacrylic acid of 8% of nickelous sulfate, cobaltous sulfate and manganese sulfate salt total mole number is added;
(3) compound concentration is the sodium hydroxide pellets agent solution of 10mol/L;
(4) compound concentration is the ammonia spirit of 6mol/L;
(5) joined continuously by above-mentioned three kinds of solution in the reactor of band stirring, the addition controlling ammoniacal liquor is NH
3h
2o:(Ni+Co+Mn)=3:1; Regulate sodium hydroxide pellets agent solution flow with control ph for 10.5, logical nitrogen protection in course of reaction, ageing 12h after reaction 20h, controls ageing process pH consistent with course of reaction; Be separated also washing reaction thing and obtain that there is the nickel cobalt manganese hydroxide represented with general formula (IV): Ni
0.4co
0.2mn
0.4(OH)
2(IV).
Nickel cobalt manganese hydroxide precursor prepared by said process, it is spherical that the structurally ordered accumulation of its reference book laminated being the composite wafer being 35nm by sheet thickness is formed is formed, and particle is relatively uniform, good sphericity, and mobility of particle is good.
Embodiment 6
(1) prepare the mixed solution of nickel nitrate, cobalt nitrate, manganese nitrate, the mol ratio of described nickel nitrate, cobalt nitrate and manganese nitrate is 0.4:0.2:0.4, and in mixed solution, the total concentration of nickel nitrate, cobalt nitrate and manganese nitrate is 1.5mol/L;
(2) in mixed solution, the shitosan of 6% of nickel nitrate, cobalt nitrate and manganese nitrate total mole number is added;
(3) compound concentration is the sodium hydroxide pellets agent solution of 8mol/L;
(4) compound concentration is the ammonia spirit of 6mol/L;
(5) joined continuously by above-mentioned three kinds of solution in the reactor of band stirring, the addition controlling ammoniacal liquor is NH
3h
2o:(Ni+Co+Mn)=10:1; Regulate sodium hydroxide pellets agent solution flow with control ph for 13, logical nitrogen protection in course of reaction, ageing 72h after reaction 4h, controls ageing process pH consistent with course of reaction; Be separated also washing reaction thing and obtain that there is the nickel cobalt manganese hydroxide represented with general formula (IV): Ni
0.4co
0.2mn
0.4(OH)
2(IV).
Nickel cobalt manganese hydroxide precursor prepared by said process, it is spherical that the structurally ordered accumulation of its reference book laminated being the composite wafer being 100nm by sheet thickness is formed is formed, and particle is relatively uniform, good sphericity, and mobility of particle is good.
Embodiment 7
(1) prepare the mixed solution of nickel nitrate, cobalt nitrate, manganese nitrate, the mol ratio of described nickel nitrate, cobalt nitrate and manganese nitrate is 1/6:1/6:4/6, and in mixed solution, the total concentration of nickel nitrate, cobalt nitrate and manganese nitrate is 1mol/L;
(2) in mixed solution, the shitosan of 5% of nickel nitrate, cobalt nitrate and manganese nitrate total mole number is added;
(3) compound concentration is the sodium hydroxide pellets agent solution of 8mol/L;
(4) compound concentration is the ammonia spirit of 10mol/L;
(5) joined continuously by above-mentioned three kinds of solution in the reactor of band stirring, the addition controlling ammoniacal liquor is NH
3h
2o:(Ni+Co+Mn)=3:1; Regulate sodium hydroxide pellets agent solution flow with control ph for 10, logical argon shield in course of reaction, ageing 36h after reaction 24h, controls ageing process pH consistent with course of reaction; Be separated also washing reaction thing and obtain that there is the nickel cobalt manganese hydroxide represented with general formula (V): Ni
1/6co
1/6mn
4/6(OH)
2(V).
Nickel cobalt manganese hydroxide precursor prepared by said process, it is spherical that the structurally ordered accumulation of its reference book laminated being the composite wafer being 60nm by sheet thickness is formed is formed, and particle is relatively uniform, good sphericity, and mobility of particle is good.
Embodiment 8
(1) prepare the mixed solution of nickelous sulfate, cobaltous sulfate, manganese sulfate, the mol ratio of described nickelous sulfate, cobaltous sulfate and manganese sulfate is 1/6:1/6:4/6, and in mixed solution, the total concentration of nickelous sulfate, cobaltous sulfate and manganese sulfate is 2mol/L;
(2) in mixed solution, the triethanolamine of 3% of nickelous sulfate, cobaltous sulfate and manganese sulfate total mole number is added;
(3) compound concentration is the sodium hydroxide pellets agent solution of 8mol/L;
(4) compound concentration is the ammonia spirit of 8mol/L;
(5) joined continuously by above-mentioned three kinds of solution in the reactor of band stirring, the addition controlling ammoniacal liquor is NH
3h
2o:(Ni+Co+Mn)=5:1; Regulate sodium hydroxide pellets agent solution flow with control ph for 11, logical argon shield in course of reaction, ageing 24h after reaction 16h, controls ageing process pH consistent with course of reaction; Be separated also washing reaction thing and obtain that there is the nickel cobalt manganese hydroxide represented with general formula (V): Ni
1/6co
1/6mn
4/6(OH)
2(V).
Nickel cobalt manganese hydroxide precursor prepared by said process, pile up for being that reference book laminated that the composite wafer of 50nm is formed is structurally ordered by sheet thickness formed spherical, particle is relatively uniform, good sphericity, and mobility of particle is good.
Embodiment 9
(1) prepare the mixed solution of nickel chloride, cobalt chloride, manganese chloride, the mol ratio of described nickel chloride, cobalt chloride and manganese chloride is 1/6:1/6:4/6, and in mixed solution, the total concentration of nickel chloride, cobalt chloride and manganese chloride is 1.5mol/L;
(2) in mixed solution, the polyvinyl alcohol of 8% of nickel chloride, cobalt chloride and manganese chloride total mole number is added;
(3) compound concentration is the sodium hydroxide pellets agent solution of 6mol/L;
(4) compound concentration is the ammonia spirit of 8mol/L;
(5) joined continuously by above-mentioned three kinds of solution in the reactor of band stirring, the addition controlling ammoniacal liquor is NH
3h
2o:(Ni+Co+Mn)=8:1; Regulate sodium hydroxide pellets agent solution flow with control ph for 13, logical nitrogen protection in course of reaction, ageing 36h after reaction 6h, controls ageing process pH consistent with course of reaction; Be separated also washing reaction thing and obtain that there is the nickel cobalt manganese hydroxide represented with general formula (V): Ni
1/6co
1/6mn
4/6(OH)
2(V).
Nickel cobalt manganese hydroxide precursor prepared by said process, it is spherical that the structurally ordered accumulation of its reference book laminated being the composite wafer being 80nm by sheet thickness is formed is formed, and particle is relatively uniform, good sphericity, and mobility of particle is good.
Comparative example 1
(1) prepare the mixed solution of nickelous sulfate, cobaltous sulfate, manganese sulfate, the mol ratio of described nickelous sulfate, cobaltous sulfate and manganese sulfate is 1/3:1/3:1/3, and in mixed solution, the total concentration of nickelous sulfate, cobaltous sulfate and manganese sulfate is 2mol/L;
(2) compound concentration is the sodium hydroxide pellets agent solution of 5mol/L;
(3) compound concentration is the ammonia spirit of 5mol/L;
(4) joined continuously by above-mentioned three kinds of solution in the reactor of band stirring, the addition controlling ammoniacal liquor is NH
3h
2o:(Ni+Co+Mn)=1:1; Regulate sodium hydroxide pellets agent solution flow with control ph for 11, logical argon shield in course of reaction, ageing 36h after reaction 20h, controls ageing process pH consistent with course of reaction; Be separated also washing reaction thing and obtain that there is the nickel cobalt manganese hydroxide represented with general formula (II): Ni
1/3co
1/3mn
1/3(OH)
2(II).
Nickel cobalt manganese hydroxide precursor prepared by said process, its be by thickness be 0.5 ~ 1 μm sheet pile up formed spherical.Fig. 3 is Ni prepared by comparative example 1
0.5co
0.3mn
0.2(OH)
2stereoscan photograph.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection range of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. there is the nickel cobalt manganese hydroxide precursor represented with general formula (I), it is characterized in that,
Ni
xCo
yMn
1-x-y(OH)
2 (Ⅰ)；
Wherein, 0 < x < 1,0 < y < 1, x+y < 1;
Described nickel cobalt manganese hydroxide precursor is that composite wafer piles up the spherical of the reference book page structure accumulation of formation in order.
2. nickel cobalt manganese hydroxide precursor according to claim 1, is characterized in that, the thickness of described thin slice is 30 ~ 100nm.
3. the preparation method with the nickel cobalt manganese hydroxide precursor represented with general formula (I) described in claim 1 ~ 2, comprises the following steps:
Nickel salt, manganese salt and cobalt salt are mixed, obtain mixed solution, in described mixed solution, the total concentration of nickel salt, manganese salt and cobalt salt is 1 ~ 2mol/L, in described nickel salt, in nickel ion, cobalt salt, in cobalt ions and manganese salt, the mol ratio of manganese ion is x:y:1-x-y, wherein 0 < x < 1,0 < y < 1, x+y < 1;
Additive is mixed with described mixed solution, obtain the first mixed solution, described additive is triethanolamine, shitosan, HPMA or polyacrylic acid, and the ratio of the molal quantity of described additive and described nickel ion, cobalt ions and manganese ion total mole number is 0.005 ~ 0.1:1;
The ammonia spirit be sodium hydroxide solution and the concentration of 2 ~ 10mol/L by described first mixed solution, concentration being 5 ~ 10mol/L mixes, obtain the second mixed solution, the molal quantity of described ammoniacal liquor and the ratio of described nickel ion, cobalt ions and manganese ion total mole are 1 ~ 10:1, the flow of described sodium hydroxide solution is regulated to make the pH of described second mixed solution be 9 ~ 13, ageing after described second mixed solution reaction, obtains having the nickel cobalt manganese hydroxide precursor represented with general formula (I);
Ni
xCo
yMn
1-x-y(OH)
2 (Ⅰ)；
Wherein, 0 < x < 1,0 < y < 1, x+y < 1.
4. preparation method according to claim 3, is characterized in that, described nickel salt is one or more in nickelous sulfate, nickel nitrate and nickel chloride.
5. preparation method according to claim 3, is characterized in that, described manganese salt is one or more in manganese sulfate, manganese nitrate and manganese chloride.
6. preparation method according to claim 3, is characterized in that, described cobalt salt is one or more in cobaltous sulfate, cobalt nitrate and cobalt chloride.
7. preparation method according to claim 3, described reaction is carried out under protective atmosphere.
8. preparation method according to claim 7, is characterized in that, described protective atmosphere is nitrogen or argon gas.
9. preparation method according to claim 3, is characterized in that, the time of described reaction is 4 ~ 24h.
10. preparation method according to claim 3, is characterized in that, the time of described ageing is 24 ~ 72h.
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| CN103137962B (en) * | 2013-03-11 | 2014-11-26 | 广东邦普循环科技有限公司 | Method for preparing nickel-cobalt-manganese hydroxide |
| CN103325992B (en) * | 2013-06-06 | 2015-05-13 | 南通瑞翔新材料有限公司 | Lithium ion battery positive electrode material precursor nickel-cobalt-manganese hydroxide powder and preparation method thereof |
| CN103482711B (en) * | 2013-09-06 | 2015-09-09 | 大连瑞源动力有限公司 | A kind of ultrasonic wave added prepares the method for ternary cathode material of lithium ion battery presoma |
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| CN104577100A (en) * | 2014-12-13 | 2015-04-29 | 山东精工电子科技有限公司 | Method for preparing lithium ion secondary battery positive electrode material LiNi0.5Co0.2Mn0.3O2 by adding high-polymer saccharides as forming media |
| CN105244495B (en) * | 2015-10-08 | 2018-08-31 | 昆明理工大学 | A kind of preparation method of complex hydroxide nanometer sheet |
| CN106920960B (en) * | 2015-12-28 | 2019-09-06 | 有研工程技术研究院有限公司 | The nickel-cobalt-manganese ternary complex hydroxide and regulation construction method of dynamic microstructure |
| CN105762352B (en) * | 2016-02-24 | 2019-05-03 | 宁波富理电池材料科技有限公司 | Positive electrode material precursor and preparation method thereof and positive electrode and preparation method thereof |
| CN107959023B (en) * | 2017-11-28 | 2021-02-19 | 清远佳致新材料研究院有限公司 | Preparation method of sulfur, nickel, cobalt and manganese three-element mixed hydroxide with low sodium content |
| CN108736009A (en) * | 2018-05-29 | 2018-11-02 | 中伟新材料有限公司 | Cobalt nickel lithium manganate ternary material and preparation method thereof |
| CN109037670A (en) * | 2018-07-10 | 2018-12-18 | 湖南鸿捷新材料有限公司 | A kind of method of continuity preparation little particle ternary precursor material |
| CN109742337B (en) * | 2018-12-07 | 2022-03-29 | 北京理工大学 | Ternary cathode material precursor and method for regulating crystal face growth of ternary cathode material precursor |
| CN110504445A (en) * | 2019-08-29 | 2019-11-26 | 湖南金富力新能源股份有限公司 | A kind of nickel cobalt aluminium ternary precursor and the preparation method and application thereof |
| CN112978813B (en) * | 2021-05-10 | 2021-08-10 | 金驰能源材料有限公司 | Nickel-containing hydroxide precursor, preparation method thereof and positive electrode material |
| CN114447316A (en) * | 2022-01-26 | 2022-05-06 | 华东理工大学 | Nickel-cobalt-manganese hydroxide precursor, preparation and application thereof, and positive electrode material containing nickel-cobalt-manganese hydroxide precursor |
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