CN101285197A - Preparing method for precursor of lithium ionic cell positive material - Google Patents
Preparing method for precursor of lithium ionic cell positive material Download PDFInfo
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- CN101285197A CN101285197A CNA2008101107547A CN200810110754A CN101285197A CN 101285197 A CN101285197 A CN 101285197A CN A2008101107547 A CNA2008101107547 A CN A2008101107547A CN 200810110754 A CN200810110754 A CN 200810110754A CN 101285197 A CN101285197 A CN 101285197A
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- sodium hydroxide
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Abstract
The invention relates to a method for synthesizing a lithium ion battery anode material precursor, which is characterized in that: the synthetic process of the method is to use corresponding metal salts to prepare metal salt solution with a total concentration for metallic ions of between 0.1 and 3 moles per liter according to the stoichiometric proportion of precursor composite hydroxid, to add the prepared metal salt solution with sodium hydroxide solution with a concentration of between 0.1 and 5 moles per liter, to control the pH value of liquid in a reaction kettle to be between 7 and 14 through the addition amount of the sodium hydroxide solution, and to prepare the composite hydroxid provided with a single beta-Ni(OH) 2 crystal structure under the conditions of a control reaction potential of -0.5 to 0 volts, the reaction time of between 1 and 48 hours and a reaction temperature of between 30 and 80 DEG C. The material prepared by the method is provided with the single beta-Ni(OH) 2 crystal structure with uniform granularity and good shape (spherical shape or sphere-liked shape).
Description
Technical field
A kind of synthetic method of precursor of lithium ionic cell positive material relates to a kind of preparation method by control solution potential synthesis of anode material of lithium-ion battery presoma complex hydroxide.
Background technology
Advantages such as lithium ion battery has operating voltage height, big, the memoryless benefit of specific energy, pollution is little, self-discharge rate is low, have extended cycle life, it is the secondary cell of giving priority to 21 century, it is widely used in the electrical equipment such as mobile telephone, notebook computer, pick up camera, electric bicycle, and new purposes (as electromobile, energy-accumulating power station) is among developing.
Anode material for lithium-ion batteries LiNi
xCo
yMn
zM
1-x-y-zO
2Receive much concern its same LiCoO owing to having the excellent comprehensive performance
2And LiNiO
2α-NaFeO is equally arranged
2Structure and theoretical specific capacity, but this material has LiCoO
2, LiNiO
2Wait other positive electrode material incomparable advantage.Cobalt acid lithium owing to cost an arm and a leg, poor safety performance is not suitable as power cell.2. lithium manganate has advantages such as low cost, environmental protection, security are good, but its energy density is low, cycle performance is poor, the problems of dissolution of manganese was outstanding when carbon was done negative pole.3. lithium nickel cobalt dioxide volume ratio cobalt acid lithium increases, but the preparation cost height, overcharges and have safety issue.4. iron lithium phosphate has advantages such as with low cost, environmental friendliness, security be good, but its volume energy density is lower.Comparatively speaking, LiNi
xCo
yMn
zM
1-x-y-zO
2Theoretical specific capacity higher, about 278mAh/g, good cycle, volume change little (less than 2%) in the charge and discharge process, tap density is big, the energy density height, and actual specific capacity can reach 140-180mAh/g (same nickel, cobalt, manganese ratio are relevant with doped element M content), the synthetic method simple possible has overcome LiMn
2O
4, LiNiO
2, LiCoO
2And LiFePO
4The part shortcoming, therefore become lithium-ion secondary cell, particularly one of preferred material of minitype motivation battery.
At present, preparation anode material for lithium-ion batteries LiNi
xCo
yMn
zM
1-x-y-zO
2Method a lot, as solid reaction process, co-precipitation-high-temperature sintering process, sol-gel method, freeze-drying, microwave method etc.Generally, traditional synthetic method solid reaction process of all sampling is characterized in that reactant obtains active material by repetitious grinding, pulverizing, sintering, and some also needs by auxiliary processes such as granulation or compressing tablets.The agglomerating process also is long, generally needs 12～48 hours, even the longer time.Its objective is by at high temperature heating long period of time in the hope of obtaining not exist the required thing phase of dephasign.The high-temperature heating process that these are long is unfavorable for controlling the size and the structure of powder, therefore at high temperature crystal grain grow up normally inevitable with the particulate polymerization.Utilize co-precipitation-high-temperature sintering process can overcome the shortcoming of solid reaction process, its presoma has had good physics pattern and each element is evenly distributed, and has shortened the generated time and the temperature in high temperature sintering stage so greatly, has avoided growing up and polymerization of crystal grain.
But co-precipitation-high-temperature sintering process is very high to the requirement of the every index of presoma, and it requires presoma not only will have good physical performance index, and requires each element to be evenly distributed, and electrochemical activity is good.Carbonate deposition synthetic presoma electrochemical activity is poor, and is poor with the positive electrode material chemical property that this forerunner's system is equipped with; Do not pass through the presoma that control solution proper voltage becomes, the element skewness, not good with the positive electrode material cycle performance that this forerunner's system is equipped with.
Summary of the invention
Purpose of the present invention is exactly the deficiency that exists at above-mentioned prior art, proposes a kind of control solution potential that passes through, and synthesizes to have β-Ni (OH)
2The complex hydroxide presoma of crystalline structure, preparation has good electrochemical activity and element is evenly distributed, and prepares the synthetic method of the precursor of lithium ionic cell positive material low than temperature, that the time is short.
The objective of the invention is to be achieved through the following technical solutions.
A kind of synthetic method of precursor of lithium ionic cell positive material, it is characterized in that its building-up process is is the metal salt solution of 0.1～3mol/L with corresponding metal salt by the stoichiometric ratio preparing metal total ion concentration of prepared presoma complex hydroxide, with the metal salt solution adding concentration of preparation is the sodium hydroxide solution of 0.1～5mol/L, pH value by liquid in the add-on control reactor of sodium hydroxide solution is 7-14, at the control reaction potential be-0.5-0V, reaction is 1-48h, and temperature of reaction is to make under the 30-80 ℃ of condition to have single β-Ni (OH)
2The complex hydroxide of crystalline structure.
The synthetic method of a kind of precursor of lithium ionic cell positive material of the present invention, the current potential that it is characterized in that solution in the described control reactor is by the control that is incorporated as any or its mixture reductive agent in hydrazine hydrate, formic acid, formate, oxalic acid, the oxalate for-0.5-0V process.
The synthetic method of a kind of precursor of lithium ionic cell positive material of the present invention is characterized in that described corresponding metal salt is any or its mixture in vitriol, nitrate and the muriate.
Method of the present invention is fit to be prepared as follows precursor of lithium ionic cell positive material: monobasic, binary or polynary system compound N i
xCo
yMn
zM
1-x-y-zO
2(OH)
2(0≤x, y＜1,0＜z≤1 and 0＜x+y+z≤1 wherein, M is Ca, Mg, Ti, Cr, Fe, Cu, Zn, a kind of among the Al).By the control solution potential, can prevent the oxidation of Mn and the generation of α type hydroxide hydrate, for preparing pure phase has β-Ni (OH)
2The complex hydroxide presoma of crystalline structure, each element of this presoma is evenly distributed, and electrochemical activity is good, helps preparing high performance positive electrode material.
Description of drawings
Fig. 1 adopts method synthetic Ni of the present invention
0.8Co
0.1Mn
0.1(OH)
2The X-ray diffraction spectrogram.
Fig. 2 adopts method synthetic presoma Ni of the present invention
0.8Co
0.1Mn
0.1(OH)
2Scanning electricity border photo.
Fig. 3 adopts method synthetic presoma Ni of the present invention
0.4Co
0.18Mn
0.4Mg
0.02(OH)
2XRD
Fig. 4 adopts method synthetic presoma Ni of the present invention
0.4Co
0.18Mn
0.4Mg
0.02(OH)
2SEM
Fig. 5 adopts method synthetic presoma Ni of the present invention
0.3Co
0.35Mn
0.3Al
0.05(OH)
2XRD
Fig. 6 adopts method synthetic presoma Ni of the present invention
0.3Co
0.38Mn
0.3Al
0.05(OH)
2SEM
Embodiment
A kind of synthetic method of precursor of lithium ionic cell positive material, this method may further comprise the steps;
1, press stoichiometric ratio with the soluble metallic salt wiring solution-forming, the metal ion total concn is 0.1～3mol/L in the salts solution; The sodium hydroxide of predetermined amount is made into the solution that concentration is 0.1～5mol/L; The deionized water that in reactor, adds predetermined amount.
2, metal salt solution, sodium hydroxide solution and reductive agent are joined in the reactor simultaneously, control solution pH value is 7～14, and solution potential is-0.5V～0V that mixing solutions stopped in reactor 1～48 hour.So just synthesized precursor of lithium ionic cell positive material complex hydroxide Ni
xCo
yMn
zM
1-x-y-z(OH)
2
By the control solution potential, can prevent the oxidation of Mn and the generation of α type hydroxide hydrate, for preparing pure phase has β-Ni (OH)
2The complex hydroxide presoma of crystalline structure, each element of this presoma is evenly distributed, and electrochemical activity is good, helps preparing high performance positive electrode material.
Embodiment 1
The ratio that in stoichiometric ratio nickel, cobalt, manganese is 8: 1: 1 is made into the solution that total concentration of metal ions is 1mol/L to metal-salt, and sodium hydroxide is made into the solution that concentration is 3mol/L, and end liquid adds the deionized water of 4L.With the 2L metal salt solution, sodium hydroxide solution and hydrazine hydrate join in the 30L reactor simultaneously, and CONTROLLED POTENTIAL is at-0.3v, and temperature remains on 45 ± 1 ℃, pH value is controlled at 10.5 ± 0.05, stops the synthetic required precursor of lithium ionic cell positive material complex hydroxide Ni of 24h
0.8Co
0.1Mn
0.1(OH)
2
Fig. 1 is the synthetic Ni of institute
0.8Co
0.1Mn
0.1(OH)
2The X-ray diffraction spectrogram.Fig. 2 is presoma Ni
0.8Co
0.1Mn
0.1(OH)
2Stereoscan photograph.
From the X-ray diffraction spectrogram as can be seen, presoma Ni
0.8Co
0.1Mn
0.1(OH)
2Complete in crystal formation has β-Ni (OH)
2Crystalline structure, without any assorted peak.From the photo of the scanning of Fig. 2 electricity border as can be seen, presoma Ni
0.8Co
0.1Mn
0.1(OH)
2Pattern is a spheroidal particle, particle diameter about 8 μ m, even particle size distribution.
In stoichiometric ratio nickel, cobalt, manganese, magnesium is 4: 1.8: 4: 0.2 ratio is made into the solution that total concentration of metal ions is 1.5mol/L to metal-salt, and sodium hydroxide is made into the solution that concentration is 2.5mol/L, and end liquid adds the deionized water of 3L.With the 2L metal salt solution, sodium hydroxide solution and hydrazine hydrate join in the 30L reactor simultaneously, and CONTROLLED POTENTIAL is at-0.2v, and temperature remains on 65 ± 1 ℃, pH value is controlled at 10.0 ± 0.05, stops the synthetic required precursor of lithium ionic cell positive material complex hydroxide Ni of 40h
0.4Co
0.18Mn
0.4Mg
0.02(OH)
2
Fig. 3 is the synthetic Ni of institute
0.4Co
0.18Mn
0.4Mg
0.02(OH)
2The X-ray diffraction spectrogram.Fig. 4 is presoma Ni
0.4Co
0.18Mn
0.4Mg
0.02(OH)
2Scanning electricity border photo.
From the X-ray diffraction spectrogram as can be seen, presoma Ni
0.4Co
0.18Mn
0.4Mg
0.02(OH)
2Complete in crystal formation has β-Ni (OH)
2Crystalline structure, without any assorted peak.From the photo of the scanning of Fig. 4 electricity border as can be seen, presoma Ni
0.4Co
0.18Mn
0.4Mg
0.02(OH)
2Pattern is a spheroidal particle, and particle diameter is about 10 μ m.
Embodiment 3: in stoichiometric ratio nickel, cobalt, manganese, aluminium is 3: 3.5: 3: 0.5 ratio is made into the solution that total concentration of metal ions is 2.0mol/L to metal-salt, and sodium hydroxide is made into the solution that concentration is 2.0mol/L, and end liquid adds the deionized water of 4L.With the 4L metal salt solution, sodium hydroxide solution and hydrazine hydrate join in the 30L reactor simultaneously, and CONTROLLED POTENTIAL is at-0.25v, and temperature remains on 45 ± 1 ℃, pH value is controlled at 10.2 ± 0.05, stops the synthetic required precursor of lithium ionic cell positive material complex hydroxide Ni of 48h
0.3Co
0.35Mn
0.3Al
0.05(OH)
2
Fig. 5 is the synthetic Ni of institute
0.3Co
0.35Mn
0.3Al
0.05(OH)
2The X-ray diffraction spectrogram.Fig. 6 is presoma Ni
0.3Co
0.35Mn
0.3Al
0.05(OH)
2Scanning electricity border photo.
From the X-ray diffraction spectrogram as can be seen, presoma Ni
0.3Co
0.35Mn
0.3Al
0.05(OH)
2Complete in crystal formation has β-Ni (OH)
2Crystalline structure, without any assorted peak.From the photo of the scanning of Fig. 6 electricity border as can be seen, presoma Ni
0.3Co
0.35Mn
0.3Al
0.05(OH)
2Pattern is a spheroidal particle, and particle diameter is about 10 μ m.
Embodiment 3
Other condition is with example 1, corresponding metal salt is the metal salt solution of 3mol/L by the stoichiometric ratio preparing metal total ion concentration of prepared presoma complex hydroxide, with the metal salt solution adding concentration of preparation is the sodium hydroxide solution of 0.1mol/L, pH value by liquid in the add-on control reactor of sodium hydroxide solution is 12-14, at the control reaction potential be-0.5-0V, reaction is 48h, and temperature of reaction is to make under 30 ℃ of conditions to have single β-Ni (OH)
2The complex hydroxide of crystalline structure.
Other condition is with example 2, corresponding metal salt is the metal salt solution of 0.1mol/L by the stoichiometric ratio preparing metal total ion concentration of prepared presoma complex hydroxide, with the metal salt solution adding concentration of preparation is the sodium hydroxide solution of 5mol/L, pH value by liquid in the add-on control reactor of sodium hydroxide solution is 10-12, at the control reaction potential be-0.5-0V, reaction is 40h, and temperature of reaction is to make under 30 ℃ of conditions to have single β-Ni (OH)
2The complex hydroxide of crystalline structure.
Claims (3)
1. the synthetic method of a precursor of lithium ionic cell positive material, it is characterized in that its building-up process is is the metal salt solution of 0.1～3mol/L with corresponding metal salt by the stoichiometric ratio preparing metal total ion concentration of prepared presoma complex hydroxide, with the metal salt solution adding concentration of preparation is the sodium hydroxide solution of 0.1～5mol/L, pH value by liquid in the add-on control reactor of sodium hydroxide solution is 7-14, at the control reaction potential be-0.5-0V, reaction is 1-48h, and temperature of reaction is to make under the 30-80 ℃ of condition to have single β-Ni (OH)
2The complex hydroxide of crystalline structure.
2. the synthetic method of the described a kind of precursor of lithium ionic cell positive material of a tree name claim 1, the current potential that it is characterized in that solution in the described control reactor is by the control that is incorporated as any or its mixture reductive agent in hydrazine hydrate, formic acid, formate, oxalic acid, the oxalate for-0.5-0V process.
3. the synthetic method of the described a kind of precursor of lithium ionic cell positive material of a tree name claim 1 is characterized in that described corresponding metal salt is any or its mixture in vitriol, nitrate and the muriate.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274480A (en) * | 2013-06-06 | 2013-09-04 | 南通瑞翔新材料有限公司 | Precursor of polynary positive electrode material for lithium ion battery, and preparation method thereof |
| CN109119612A (en) * | 2018-08-27 | 2019-01-01 | 高点(深圳)科技有限公司 | Positive electrode material precursor and preparation method thereof, positive electrode and preparation method thereof, Anode and battery |
| CN110799460A (en) * | 2017-06-23 | 2020-02-14 | 尤米科尔公司 | β -Nickel hydroxide doped with aluminum |
| EP3659974A1 (en) * | 2018-11-27 | 2020-06-03 | Basf Se | Process for making a nickel composite hydroxide |
| CN114684874A (en) * | 2022-03-08 | 2022-07-01 | 宜宾光原锂电材料有限公司 | Doped high-rate 5-series monocrystal precursor and preparation method thereof |
-
2008
- 2008-05-29 CN CNA2008101107547A patent/CN101285197A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274480A (en) * | 2013-06-06 | 2013-09-04 | 南通瑞翔新材料有限公司 | Precursor of polynary positive electrode material for lithium ion battery, and preparation method thereof |
| CN110799460A (en) * | 2017-06-23 | 2020-02-14 | 尤米科尔公司 | β -Nickel hydroxide doped with aluminum |
| CN110799460B (en) * | 2017-06-23 | 2022-11-15 | 尤米科尔公司 | Aluminum-doped beta-nickel hydroxide |
| US11919783B2 (en) | 2017-06-23 | 2024-03-05 | Umicore | Beta-nickel hydroxide doped with aluminum |
| CN109119612A (en) * | 2018-08-27 | 2019-01-01 | 高点(深圳)科技有限公司 | Positive electrode material precursor and preparation method thereof, positive electrode and preparation method thereof, Anode and battery |
| EP3659974A1 (en) * | 2018-11-27 | 2020-06-03 | Basf Se | Process for making a nickel composite hydroxide |
| CN114684874A (en) * | 2022-03-08 | 2022-07-01 | 宜宾光原锂电材料有限公司 | Doped high-rate 5-series monocrystal precursor and preparation method thereof |
| CN114684874B (en) * | 2022-03-08 | 2023-08-08 | 宜宾光原锂电材料有限公司 | Doped high-magnification 5-series single crystal precursor and preparation method thereof |
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Open date: 20081015 |