CN102916177A - 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 the energy and material preparing technical field, especially nickel cobalt manganese hydroxide presoma and preparation method thereof.
Background technology
Lithium ion battery has the advantages such as high-energy, long-life, memory-less effect and low pollution, 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 positive electrode of occupation rate of market maximum is cobalt acid lithium, but cobalt as the strategic resources reserves seldom, expensive and the security performance sour lithium of cobalt is relatively poor, limited further developing of this material.And nickle cobalt lithium manganate has specific capacity height, Heat stability is good and the advantage such as cheap, is a kind of of tool potentiality in the anode material for lithium-ion batteries, has good application prospect in power fields such as electric motor car, electric tools.
At present, preparation nickle cobalt lithium manganate (LiNi
xCo
yMn
1-x-yO
2) common method high temperature solid-state method and co-precipitation-high temperature solid-state method are arranged.High temperature solid-state method is that nickel source, cobalt source, manganese source, lithium source ball milling is even, carries out high-temperature calcination again.The shortcoming of the method is to be difficult to three kinds of elements of nickel cobalt manganese are mixed, therefore just can not give full play to three's synergy, and the pattern of the material of preparation is difficult to control, usually synthetic powder body material is comprised 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 prepares nickel cobalt manganese hydroxide presoma by coprecipitation first, adds lithium source sintering again, obtains nickle cobalt lithium manganate.In the sintering process of the method after adding the lithium source, substantially do not change pattern and the granularity of presoma, and that the pattern of nickel-cobalt lithium manganate material, granularity play a part in many performances of lithium ion battery is crucial, then the method is the synthetic comparatively desirable preparation method of nickle cobalt lithium manganate, synthesizing the nickel cobalt manganese hydroxide presoma with suitable pattern and granularity becomes the key that affects the nickle cobalt lithium manganate performance, so the researcher has begun deep research to the preparation method of nickel magnesium cobalt hydroxide presoma.For example, 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, the preparation method of this invention nickel cobalt manganese hydroxide presoma is for being injected into continuously respectively nickel salt, cobalt salt, manganese source mixed aqueous solution and NaOH, ammonia spirit in the reactor of band stirring first with pump, regulate the flow of nickel cobalt-manganese salt mixed aqueous solution and ammonia spirit, the control reaction condition obtains sphere 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: take the soluble-salt of nickel, cobalt and manganese as raw material; take ammoniacal liquor or ammonium salt as complexing agent; NaOH is precipitation reagent; the adding water soluble dispersant; adding water soluble antioxidant or use the inert gas control and protection; with solution with and the stream mode be added to reaction kettle for reaction; basic treatment; ageing; Separation of Solid and Liquid, the washing drying obtains nickel cobalt manganese hydroxide presoma.Although above-mentioned disclosed patent can make spherical nickel-cobalt manganese hydroxide presoma, all the surface topography of spherical presoma is not controlled, thereby be unfavorable for the diffusion of lithium ion in the sintering process.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of nickel cobalt manganese hydroxide presoma and preparation method thereof, prepared the nickel cobalt manganese hydroxide presoma of special appearance by method provided by the invention, thereby made the nickel cobalt manganese hydroxide presoma of preparation be conducive to the diffusion of lithium ion in the follow-up sintering process.
In view of this, the invention provides a kind of nickel cobalt manganese hydroxide presoma that has with general formula (I) expression,
Ni
xCo
yMn
1-x-y（OH）
2 （Ⅰ）；
Wherein, 0＜x＜1,0＜y＜1, x+y＜1;
Described nickel cobalt manganese hydroxide presoma is the orderly sphere of piling up of reference book page structure that composite wafer consists of.
Preferably, the thickness of described thin slice is 30 ~ 100nm.
The present invention also provides a kind of preparation method who has with the nickel cobalt manganese hydroxide presoma of general formula (I) expression, may further comprise the steps:
Nickel salt, manganese salt and cobalt salt are mixed, obtain mixed solution, the total concentration of nickel salt, manganese salt and cobalt salt is 1 ~ 2mol/L in the described mixed solution, in the described nickel salt in nickel ion, the cobalt salt in cobalt ions and the manganese salt mol ratio of manganese ion be x:y:1-x-y, 0＜x＜1,0＜y＜1 wherein, 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;
Sodium hydroxide solution and the concentration that with described the first mixed solution, concentration is 2 ~ 10mol/L is that the ammonia spirit of 5 ~ 10mol/L mixes, obtain the second mixed solution, the ratio of the total mole of the molal quantity of described ammoniacal liquor and described nickel ion, cobalt ions and manganese ion is 1 ~ 10:1, it is 9 ~ 13 that the flow of regulating described sodium hydroxide solution makes the pH of described the second mixed solution, ageing after described the second mixed solution reaction obtains having the nickel cobalt manganese hydroxide presoma with general formula (I) expression;
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 the nickel chloride.
Preferably, described manganese salt is one or more in manganese sulfate, manganese nitrate and the manganese chloride.
Preferably, described cobalt salt is one or more in cobaltous sulfate, cobalt nitrate and the 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 presoma and preparation method thereof.In the process of preparation nickel cobalt manganese hydroxide presoma, the present invention reacts the mixed solution of sodium hydroxide solution, ammonia spirit and nickel salt, cobalt salt and manganese salt, by pH and the ammonia spirit amount in the control course of reaction, in course of reaction, add simultaneously the additive with adjusting granule-morphology, obtained the nickel cobalt manganese hydroxide presoma of the spherical structure of the structurally ordered accumulation of reference book laminated.Experimental result shows that the spherical morphology of the nickel cobalt manganese hydroxide presoma of the present invention's preparation is better, uniform particles, and mobility of particle is good, thereby in the follow-up sintering process diffusion that utilizes lithium ion is arranged.
Description of drawings
Fig. 1 is the Ni of the embodiment of the invention 3 preparations
0.5Co
0.3Mn
0.2(OH)
2The high power stereoscan photograph;
The Ni of Fig. 2 embodiment of the invention 3 preparations
0.5Co
0.3Mn
0.2(OH)
2The low power stereoscan photograph;
The Ni of Fig. 3 Comparative Examples 1 preparation of the present invention
1/3Co
1/3Mn
1/3(OH)
2The high power stereoscan photograph.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, but should be appreciated that these describe just as further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind of nickel cobalt manganese hydroxide presoma that has with general formula (I) expression, described nickel cobalt manganese hydroxide presoma is the orderly sphere of piling up of reference book page structure that composite wafer consists of;
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, more preferably 50 ~ 80nm.Nickel cobalt manganese hydroxide presoma of the present invention has special secondary spherical structure, its sphere for being consisted of by special laminated structure, and the accumulation of reference book page structure forms, thereby more is conducive to the diffusion of lithium ion in the sintering process.
In order to obtain the nickel cobalt manganese hydroxide presoma of above-mentioned pattern, the invention also discloses the preparation method of above-mentioned nickel cobalt manganese hydroxide presoma, may further comprise the steps:
Nickel salt, manganese salt and cobalt salt are mixed, obtain mixed solution, the total concentration of nickel salt, manganese salt and cobalt salt is 1 ~ 2mol/L in the described mixed solution, in the described nickel salt in nickel ion, the cobalt salt in cobalt ions and the manganese salt mol ratio of manganese ion be x:y:1-x-y, 0＜x＜1,0＜y＜1 wherein, x+y＜1;
Additive is mixed with described mixed solution, 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;
Sodium hydroxide solution and the concentration that with described the first mixed solution, concentration is 2 ~ 10mol/L is that the ammonia spirit of 5 ~ 10mol/L mixes, obtain the second mixed solution, total mole ratio of the molal quantity of described ammoniacal liquor and described nickel ion, cobalt ions and manganese ion is 1 ~ 10:1, it is 9 ~ 13 that the flow of regulating described sodium hydroxide solution makes the pH of described the second mixed solution, ageing after described the second mixed solution reaction obtains having the nickel cobalt manganese hydroxide presoma with the atomic ratio composition of general formula (I) expression;
Ni
xCo
yMn
1-x-y（OH）
2 （Ⅰ）；
Wherein, 0＜x＜1,0＜y＜1, x+y＜1.
In the process of above-mentioned preparation nickel cobalt manganese hydroxide presoma, at 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 preparation sodium hydroxide solution and ammonia spirit; At last the first mixed solution, sodium hydroxide solution and ammonia spirit are mixed, the three reacts, in the process that above-mentioned three kinds of solution mix, the addition of control ammoniacal liquor and the flow of regulating sodium hydroxide solution, ageing after reaction finishes, thus obtain having the nickel cobalt manganese hydroxide presoma that represents with general formula (I).In course of reaction, concentration, the addition of ammoniacal liquor and the pH of the stage of reaction by the control mentioned solution, and added the additive of regulating granule-morphology, thereby obtained the nickel cobalt manganese hydroxide presoma that the reference book page structure is piled up the spherical structure of formation in order.
According to the present invention, at first nickel salt, manganese salt and cobalt salt are mixed, obtain mixed solution.The total concentration of nickel salt, manganese salt and cobalt salt is 1 ~ 2mol/L in the described mixed solution, in the described nickel salt in nickel ion, the cobalt salt in cobalt ions and the manganese salt mol ratio of manganese ion be x:y:1-x-y, 0＜x＜1,0＜y＜1 wherein, x+y＜1.Described nickel salt is preferably soluble nickel salt, more preferably one or more in nickelous sulfate, nickel nitrate and the nickel chloride; Described cobalt salt is preferably the solubility cobalt salt, more preferably one or more in cobaltous sulfate, cobalt nitrate and the cobalt chloride; Described manganese salt is preferably soluble manganese salt, more preferably one or more in manganese sulfate, manganese nitrate and the manganese chloride.
After the mixed solution preparation of nickel salt, cobalt salt and manganese salt is finished, additive is added in the described mixed solution.Described additive is as the particular matter of regulating nickel cobalt manganese hydroxide presoma pattern, and its consumption also is to regulate the pattern essential condition.The consumption of described additive be in described the first mixed solution nickel ion, cobalt ions and manganese ion total mole number 0.5 ~ 10%, more preferably 2 ~ 7%.Described additive is triethanolamine, shitosan, HPMA or polyacrylic acid.
As preferred version, it is that sodium hydroxide solution and the concentration of 2 ~ 10mol/L is the ammonia spirit of 5 ~ 10mol/L that the present invention has prepared concentration.
Be that the sodium hydroxide solution of 2 ~ 10mol/L and ammonia spirit that concentration is 5 ~ 10mol/L mix with described the first mixed solution, concentration, obtain 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 to obtain the nickel cobalt manganese hydroxide presoma of special appearance, therefore, the present invention defines the concentration of described precipitation reagent and described complexing agent.In the process of preparation the second mixed solution, the ratio of the molal quantity of control ammoniacal liquor and the total mole number of described nickel ion, cobalt ions and manganese ion is 1 ~ 10:1, more preferably 3 ~ 8:1; Regulate simultaneously the sodium hydroxide solution flow take the pH that controls the second mixed solution as 9 ~ 13.Ageing after described the second mixed solution reaction, as preferred version, in the process of described ageing, the pH of control reactant liquor is identical with the pH in the course of reaction, obtains nickel cobalt manganese hydroxide presoma after the ageing.The time of described reaction is preferably 4 ~ 24h, and more preferably 8 ~ 20h most preferably is 10 ~ 15h, and the time of described ageing is preferably 12 ~ 72h, more preferably 24 ~ 36h.
In preparation the second mixed solution process, the present invention mixes the first mixed solution, sodium hydroxide solution and ammonia spirit, has obtained the second mixed solution.The present invention does not select traditional mode of directly nickel salt, manganese salt, cobalt salt, additive, sodium hydroxide solution and ammonia spirit being mixed, if the direct generating nickel cobalt manganese of meeting precipitation of hydroxide after adopting above-mentioned traditional approach to mix, this precipitation is loose structure, can not obtain special secondary spherical nickel cobalt manganese hydroxide presoma.Therefore, the present invention has at first prepared mixed solution, has prepared the first mixed solution again, at last the first mixed solution, sodium hydroxide solution and ammonia spirit is mixed, thereby has obtained the second mixed solution.
According to the present invention, the process of preparation nickel cobalt manganese hydroxide presoma 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）；
By above-mentioned reaction equation as can be known, nickel ion, manganese ion and cobalt ions first with the ammoniacal liquor effect, the ammonium salt of generating nickel cobalt manganese, nickel cobalt manganese ammonium salt again with the effect of precipitation reagent NaOH, thereby nickel cobalt manganese hydroxide presoma is precipitated out, obtains nickel cobalt manganese hydroxide presoma.In above-mentioned course of reaction, [Ni in the additive of the adding meeting influence process (2)
xCo
yMn
1-x-y(NH
3)
n 2+] form the process of precipitation with alkali reaction, thus the pattern of product affected.
The atomic ratio that the prepared nickel cobalt manganese hydroxide presoma of the present invention has with general formula (I) expression forms; Different with the manganese element molal quantity according to selected nickel element, cobalt element, 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 presoma and preparation method thereof.In the process of preparation nickel cobalt manganese hydroxide presoma, the present invention reacts sodium hydroxide solution, ammonia spirit and nickel cobalt-manganese salt solution, by pH and the ammonia spirit amount in the control course of reaction, in course of reaction, add simultaneously the additive with adjusting granule-morphology, obtained the nickel cobalt manganese hydroxide presoma of the spherical structure of the structurally ordered accumulation of reference book laminated.Experimental result shows that the spherical morphology of the nickel cobalt manganese hydroxide presoma of the present invention's preparation is better, uniform particles, and mobility of particle is good, thereby is conducive to the diffusion of lithium ion in the follow-up sintering process.
In order further to understand the present invention, below in conjunction with embodiment nickel cobalt manganese hydroxide presoma provided by the invention and preparation method thereof is elaborated, protection scope of the present invention is not limited by the following examples.
Embodiment 1
(1) mixed solution of preparation 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, the total concentration of nickelous sulfate, cobaltous sulfate and manganese sulfate is 2mol/L in the mixed solution;
(2) in mixed solution, add 2% triethanolamine of nickelous sulfate, cobaltous sulfate and manganese sulfate total mole number;
(3) compound concentration is the NaOH precipitant solution of 5mol/L;
(4) compound concentration is the ammonia spirit of 5mol/L;
(5) above-mentioned three kinds of solution are joined continuously in the reactor of band stirring, the addition of control ammoniacal liquor is NH
3H
2O:(Ni+Co+Mn)=1:1; Regulate NaOH precipitant solution flow take control pH value as 11, logical argon shield in the course of reaction, ageing 36h behind the reaction 20h, pH is consistent with course of reaction for the control ageing process; Separating also, the washing reaction thing obtains having the nickel cobalt manganese hydroxide that represents with general formula (II): Ni
1/3Co
1/3Mn
1/3(OH)
2(II).
The nickel cobalt manganese hydroxide precursor molecule formula of said process preparation is Ni
1/3Co
1/3Mn
1/3(OH)
2, the sphere that the structurally ordered accumulation of the reference book laminated that composite wafer that its sheet thickness of serving as reasons is 30nm consists of forms, Particle Phase is to evenly, good sphericity, mobility of particle is good.
Embodiment 2
(1) mixed solution of preparation 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, the total concentration of nickel chloride, cobalt chloride and manganese chloride is 2mol/L in the mixed solution;
(2) in mixed solution, add 5% HPMA of nickel chloride, cobalt chloride and manganese chloride total mole number;
(3) compound concentration is the NaOH precipitant solution of 10mol/L;
(4) compound concentration is the ammonia spirit of 8mol/L;
(5) above-mentioned three kinds of solution are joined continuously in the reactor of band stirring, the addition of control ammoniacal liquor is NH
3H
2O:(Ni+Co+Mn)=8:1; Regulate NaOH precipitant solution flow take control pH value as 10, logical nitrogen protection in the course of reaction, ageing 48h behind the reaction 20h, pH is consistent with course of reaction for the control ageing process; Separating also, the washing reaction thing obtains having the nickel cobalt manganese hydroxide that represents with general formula (II): Ni
1/3Co
1/3Mn
1/3(OH)
2(II).
The nickel cobalt manganese hydroxide presoma of said process preparation, the sphere that the structurally ordered accumulation of the reference book laminated that the composite wafer that its sheet thickness of serving as reasons is 55nm consists of forms, Particle Phase is to evenly, good sphericity, mobility of particle is good.
Embodiment 3
(1) mixed solution of preparation 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, the total concentration of nickelous sulfate, cobaltous sulfate and manganese sulfate is 2mol/L in the mixed solution;
(2) in mixed solution, add 3% HPMA of nickelous sulfate, cobaltous sulfate and manganese sulfate total mole number;
(3) compound concentration is the NaOH precipitant solution of 5mol/L;
(4) compound concentration is the ammonia spirit of 5mol/L;
(5) above-mentioned three kinds of solution are joined continuously in the reactor of band stirring, the addition of control ammoniacal liquor is NH
3H
2O:(Ni+Co+Mn)=2:1; Regulate NaOH precipitant solution flow take control pH value as 11, logical argon shield in the course of reaction, ageing 24h behind the reaction 18h, pH is consistent with course of reaction for the control ageing process; Separating also, the washing reaction thing obtains having the nickel cobalt manganese hydroxide that represents with general formula (III): Ni
0.5Co
0.3Mn
0.2(OH)
2(III).
The nickel cobalt manganese hydroxide presoma of said process preparation, the sphere that the structurally ordered accumulation of the reference book laminated that the composite wafer that its sheet thickness of serving as reasons is 30nm consists of forms, Particle Phase is to evenly, good sphericity, mobility of particle is good.Fig. 1 and Fig. 2 are the stereoscan photograph of the nickel cobalt manganese hydroxide presoma of embodiment 3 preparations.
Embodiment 4
(1) mixed solution of preparation 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, the total concentration of nickel nitrate, cobalt nitrate and manganese nitrate is 1.5mol/L in the mixed solution;
(2) in mixed solution, add 2% HPMA of nickel nitrate, cobalt nitrate and manganese nitrate salt total mole number;
(3) compound concentration is the NaOH precipitant solution of 8mol/L;
(4) compound concentration is the ammonia spirit of 5mol/L;
(5) above-mentioned three kinds of solution are joined continuously in the reactor of band stirring, the addition of control ammoniacal liquor is NH
3H
2O:(Ni+Co+Mn)=5:1; Regulate NaOH precipitant solution flow take control pH value as 9, logical nitrogen protection in the course of reaction, ageing 48h behind the reaction 20h, pH is consistent with course of reaction for the control ageing process; Separating also, the washing reaction thing obtains having the nickel cobalt manganese hydroxide that represents with general formula (III): Ni
0.5Co
0.3Mn
0.2(OH)
2(III).
The nickel cobalt manganese hydroxide presoma of said process preparation, the sphere that the structurally ordered accumulation of the reference book laminated that the composite wafer that its sheet thickness of serving as reasons is 50nm consists of forms, Particle Phase is to evenly, good sphericity, mobility of particle is good.
Embodiment 5
(1) mixed solution of preparation 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, the total concentration of nickelous sulfate, cobaltous sulfate and manganese sulfate is 1mol/L in the mixed solution;
(2) in mixed solution, add 8% polyacrylic acid of nickelous sulfate, cobaltous sulfate and manganese sulfate salt total mole number;
(3) compound concentration is the NaOH precipitant solution of 10mol/L;
(4) compound concentration is the ammonia spirit of 6mol/L;
(5) above-mentioned three kinds of solution are joined continuously in the reactor of band stirring, the addition of control ammoniacal liquor is NH
3H
2O:(Ni+Co+Mn)=3:1; Regulate NaOH precipitant solution flow take control pH value as 10.5, logical nitrogen protection in the course of reaction, ageing 12h behind the reaction 20h, pH is consistent with course of reaction for the control ageing process; Separating also, the washing reaction thing obtains having the nickel cobalt manganese hydroxide that represents with general formula (IV): Ni
0.4Co
0.2Mn
0.4(OH)
2(IV).
The nickel cobalt manganese hydroxide presoma of said process preparation, the sphere that the structurally ordered accumulation of the reference book laminated that the composite wafer that its sheet thickness of serving as reasons is 35nm consists of forms, Particle Phase is to evenly, good sphericity, mobility of particle is good.
Embodiment 6
(1) mixed solution of preparation 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, the total concentration of nickel nitrate, cobalt nitrate and manganese nitrate is 1.5mol/L in the mixed solution;
(2) in mixed solution, add 6% shitosan of nickel nitrate, cobalt nitrate and manganese nitrate total mole number;
(3) compound concentration is the NaOH precipitant solution of 8mol/L;
(4) compound concentration is the ammonia spirit of 6mol/L;
(5) above-mentioned three kinds of solution are joined continuously in the reactor of band stirring, the addition of control ammoniacal liquor is NH
3H
2O:(Ni+Co+Mn)=10:1; Regulate NaOH precipitant solution flow take control pH value as 13, logical nitrogen protection in the course of reaction, ageing 72h behind the reaction 4h, pH is consistent with course of reaction for the control ageing process; Separating also, the washing reaction thing obtains having the nickel cobalt manganese hydroxide that represents with general formula (IV): Ni
0.4Co
0.2Mn
0.4(OH)
2(IV).
The nickel cobalt manganese hydroxide presoma of said process preparation, the sphere that the structurally ordered accumulation of the reference book laminated that the composite wafer that its sheet thickness of serving as reasons is 100nm consists of forms, Particle Phase is to evenly, good sphericity, mobility of particle is good.
Embodiment 7
(1) mixed solution of preparation 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, the total concentration of nickel nitrate, cobalt nitrate and manganese nitrate is 1mol/L in the mixed solution;
(2) in mixed solution, add 5% shitosan of nickel nitrate, cobalt nitrate and manganese nitrate total mole number;
(3) compound concentration is the NaOH precipitant solution of 8mol/L;
(4) compound concentration is the ammonia spirit of 10mol/L;
(5) above-mentioned three kinds of solution are joined continuously in the reactor of band stirring, the addition of control ammoniacal liquor is NH
3H
2O:(Ni+Co+Mn)=3:1; Regulate NaOH precipitant solution flow take control pH value as 10, logical argon shield in the course of reaction, ageing 36h behind the reaction 24h, pH is consistent with course of reaction for the control ageing process; Separating also, the washing reaction thing obtains having the nickel cobalt manganese hydroxide that represents with general formula (V): Ni
1/6Co
1/6Mn
4/6(OH)
2(V).
The nickel cobalt manganese hydroxide presoma of said process preparation, the sphere that the structurally ordered accumulation of the reference book laminated that the composite wafer that its sheet thickness of serving as reasons is 60nm consists of forms, Particle Phase is to evenly, good sphericity, mobility of particle is good.
Embodiment 8
(1) mixed solution of preparation 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, the total concentration of nickelous sulfate, cobaltous sulfate and manganese sulfate is 2mol/L in the mixed solution;
(2) in mixed solution, add 3% triethanolamine of nickelous sulfate, cobaltous sulfate and manganese sulfate total mole number;
(3) compound concentration is the NaOH precipitant solution of 8mol/L;
(4) compound concentration is the ammonia spirit of 8mol/L;
(5) above-mentioned three kinds of solution are joined continuously in the reactor of band stirring, the addition of control ammoniacal liquor is NH
3H
2O:(Ni+Co+Mn)=5:1; Regulate NaOH precipitant solution flow take control pH value as 11, logical argon shield in the course of reaction, ageing 24h behind the reaction 16h, pH is consistent with course of reaction for the control ageing process; Separating also, the washing reaction thing obtains having the nickel cobalt manganese hydroxide that represents with general formula (V): Ni
1/6Co
1/6Mn
4/6(OH)
2(V).
The nickel cobalt manganese hydroxide presoma of said process preparation, the sheet thickness of serving as reasons are the sphere that the structurally ordered accumulation of reference book laminated that the composite wafer of 50nm consists of forms, and Particle Phase is to evenly, good sphericity, and mobility of particle is good.
Embodiment 9
(1) mixed solution of preparation 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, the total concentration of nickel chloride, cobalt chloride and manganese chloride is 1.5mol/L in the mixed solution;
(2) in mixed solution, add 8% polyvinyl alcohol of nickel chloride, cobalt chloride and manganese chloride total mole number;
(3) compound concentration is the NaOH precipitant solution of 6mol/L;
(4) compound concentration is the ammonia spirit of 8mol/L;
(5) above-mentioned three kinds of solution are joined continuously in the reactor of band stirring, the addition of control ammoniacal liquor is NH
3H
2O:(Ni+Co+Mn)=8:1; Regulate NaOH precipitant solution flow take control pH value as 13, logical nitrogen protection in the course of reaction, ageing 36h behind the reaction 6h, pH is consistent with course of reaction for the control ageing process; Separating also, the washing reaction thing obtains having the nickel cobalt manganese hydroxide that represents with general formula (V): Ni
1/6Co
1/6Mn
4/6(OH)
2(V).
The nickel cobalt manganese hydroxide presoma of said process preparation, the sphere that the structurally ordered accumulation of the reference book laminated that the composite wafer that its sheet thickness of serving as reasons is 80nm consists of forms, Particle Phase is to evenly, good sphericity, mobility of particle is good.
Comparative Examples 1
(1) mixed solution of preparation 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, the total concentration of nickelous sulfate, cobaltous sulfate and manganese sulfate is 2mol/L in the mixed solution;
(2) compound concentration is the NaOH precipitant solution of 5mol/L;
(3) compound concentration is the ammonia spirit of 5mol/L;
(4) above-mentioned three kinds of solution are joined continuously in the reactor of band stirring, the addition of control ammoniacal liquor is NH
3H
2O:(Ni+Co+Mn)=1:1; Regulate NaOH precipitant solution flow take control pH value as 11, logical argon shield in the course of reaction, ageing 36h behind the reaction 20h, pH is consistent with course of reaction for the control ageing process; Separating also, the washing reaction thing obtains having the nickel cobalt manganese hydroxide that represents with general formula (II): Ni
1/3Co
1/3Mn
1/3(OH)
2(II).
The nickel cobalt manganese hydroxide presoma of said process preparation, it is for being that the sheet of 0.5 ~ 1 μ m is piled up the sphere that forms by thickness.Fig. 3 is the Ni of Comparative Examples 1 preparation
0.5Co
0.3Mn
0.2(OH)
2Stereoscan photograph.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection range of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be apparent concerning those skilled in the art, and General Principle as defined herein can in the situation that does not break away from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. a nickel cobalt manganese hydroxide presoma that has with general formula (I) expression 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 presoma is the orderly sphere of piling up of reference book page structure that composite wafer consists of.
2. nickel cobalt manganese hydroxide presoma according to claim 1 is characterized in that the thickness of described thin slice is 30 ~ 100nm.
3. preparation method who has with the nickel cobalt manganese hydroxide presoma of general formula (I) expression may further comprise the steps:
Nickel salt, manganese salt and cobalt salt are mixed, obtain mixed solution, the total concentration of nickel salt, manganese salt and cobalt salt is 1 ~ 2mol/L in the described mixed solution, in the described nickel salt in nickel ion, the cobalt salt in cobalt ions and the manganese salt mol ratio of manganese ion be x:y:1-x-y, 0＜x＜1,0＜y＜1 wherein, 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;
Sodium hydroxide solution and the concentration that with described the first mixed solution, concentration is 2 ~ 10mol/L is that the ammonia spirit of 5 ~ 10mol/L mixes, obtain the second mixed solution, the ratio of the total mole of the molal quantity of described ammoniacal liquor and described nickel ion, cobalt ions and manganese ion is 1 ~ 10:1, it is 9 ~ 13 that the flow of regulating described sodium hydroxide solution makes the pH of described the second mixed solution, ageing after described the second mixed solution reaction obtains having the nickel cobalt manganese hydroxide presoma with general formula (I) expression;
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 the 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 the 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 the 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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