CN101777639A - Method for preparing lithium battery anode material precursor - Google Patents
Method for preparing lithium battery anode material precursor Download PDFInfo
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- CN101777639A CN101777639A CN200910105025A CN200910105025A CN101777639A CN 101777639 A CN101777639 A CN 101777639A CN 200910105025 A CN200910105025 A CN 200910105025A CN 200910105025 A CN200910105025 A CN 200910105025A CN 101777639 A CN101777639 A CN 101777639A
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a method for preparing a lithium battery anode material precursor, which comprises the following steps of: adding a surfactant into a reaction cylinder; adding salt solution of nickel, salt solution of manganese or/and cobalt to carry out aging reaction with alkali solution; and dewatering and drying after the reaction is finished to obtain the lithium battery anode material precursor. The invention provides the method for preparing the lithium battery anode material precursor having regular topography, large specific surface area and high tap density.
Description
Technical field
The present invention relates to a kind of preparation method of lithium battery material, relate in particular to a kind of preparation method of lithium battery anode material precursor.
Background technology
The widely used positive electrode of commercial li-ion battery mainly is LiCoO
2LiCoO
2Discharge platform high power capacity height, good cycle, its production technology are easy to control, and properties of product are stable.But to be Co poisonous and the limited cost of material of cobalt resource is higher and fluctuation is bigger for its shortcoming.The LiMn of doping vario-property spinel structure
2O
4Have low price, nontoxic, advantage such as safe in utilization.But its discharge capacity is lower, even its discharge capacity also has only about 110mAh/g under the good situation of circulation, it at high temperature capacity attenuation do not reach instructions for use soon yet.In addition, the LiCoO that has layered crystal structure
2Also might substitute LiCoO
2LiMn with spinel structure
2O
4And become the positive electrode of lithium ion battery.Facts have proved LiCoO
2Production technology is difficult to control homogeneity of product and the battery processing characteristics also has gap from industrial applications.LiCoO in addition
2Compare LiCoO during as the battery overcharge of positive electrode
2Dangerous phenomenons such as easier generation battery explosion catches fire.At present, adopt nickel manganese cobalt acid lithium more and more as anode material of lithium battery.
Nickel manganese cobalt acid lithium is as anode material of lithium battery, its precursor directly carries out the ageing reaction with nickel, manganese, cobalt salt solution and aqueous slkali and gets in cylinder, after the ageing reaction is finished, the precursor that drying obtains, the precursor pattern that aforesaid way is produced is irregular, and specific area is also bigger, and tap density is lower.
Summary of the invention
The technical problem to be solved in the present invention is, at the above-mentioned defective of prior art, provides a kind of pattern rule, specific area big, the preparation method of the lithium battery anode material precursor that tap density is high.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of lithium battery anode material precursor, in reaction cylinder, add earlier surfactant, add the salting liquid, manganese of nickel again or/and the salting liquid of cobalt and aqueous slkali carry out the ageing reaction, reaction finishes, and the dry lithium battery anode material precursor that gets anhydrates.
Preferred manufacturing procedure is: add earlier surfactant in reaction cylinder, the salting liquid that adds nickel again, manganese is or/and cobalt salt solution and aqueous slkali carry out the ageing reaction, surfactant concentration＜1g/L, nickel, manganese is or/and the mol ratio of cobalt salt and alkali is 1: 2, the mixing speed of reaction is 150～250 commentaries on classics/min, nickel, manganese is or/and the salting liquid flow of cobalt is 8～12ml/min, regulate the aqueous slkali flow, the pH value of reactant liquor is remained between the 10-11, carry out the ageing reaction, reaction finishes, and continues to stir 20～40min, centrifugal then anhydrating, the dry lithium battery anode material precursor that gets.
Between the nickel salt of described participation ageing reaction, manganese salt, the cobalt salt mol ratio be arbitrary proportion.
Described surfactant is two kinds of surfactant mixtures or Tween-80.
Described two kinds of mixtures that surfactant mixtures is polyvinyl alcohol and neopelex.
The mass ratio of described polyvinyl alcohol and neopelex is 1: 1.
Surfactant concentrations＜0.3g/L in the ageing reaction.
Aqueous slkali is an alkali hydroxide soln.
The concentration of described aqueous slkali is 0.3-0.6mol/L.
The present invention utilizes surfactant to do dispersant, helps the ageing reaction and generates spheric granules of uniform size, and by changing the addition of surfactant, reach different dispersion effects, reaches the requirement of product to granular size simultaneously.Added surfactant, ageing product pattern rule, specific area is bigger, and product tap density height has finally reached the purpose that improves tap density and capacity.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples, in the accompanying drawing:
Fig. 1 is the SEM figure of embodiment 1 lithium battery anode material precursor;
Fig. 2 is the SEM figure of embodiment 2 lithium battery anode material precursors;
Fig. 3 is the XRD figure of embodiment 1 lithium battery anode material precursor;
Fig. 4 is the XRD figure of embodiment 2 lithium battery anode material precursors;
Fig. 5 is the XRD figure of embodiment 1 anode material of lithium battery;
Fig. 6 is the XRD figure of embodiment 2 anode material of lithium battery;
Fig. 7 is the SEM figure of embodiment 3 lithium battery anode material precursors;
Fig. 8 is the SEM figure of embodiment 4 lithium battery anode material precursors;
Fig. 9 is the SEM figure of embodiment 5 lithium battery anode material precursors;
Figure 10 is the SEM figure of embodiment 6 lithium battery anode material precursors;
Figure 11 is the SEM figure of embodiment 7 lithium battery anode material precursors;
Figure 12 is the SEM figure of embodiment 8 lithium battery anode material precursors.
Wherein, XRD figure adopts Japanese Rigaku D/max of science 2550 full-automatic X-ray diffractometers, and testing conditions is: radiographic source: CuK α; Voltage: 40KV; Electric current: 250mA; Sweep speed: 8 °/min; Filtering mode: graphite monochromator.
It is the KYKY2800 type electron microscope of instrument technical development responsibility Co., Ltd of section of middle section that SEM figure adopts.
Embodiment
Embodiment 1, the neopelex of elder generation's 0.03g/L concentration of adding 100ml in reaction cylinder and the mixture of polyvinyl alcohol, wherein the mol ratio of neopelex and polyvinyl alcohol is 1: 1, add mol ratio again and be 0.4: 0.4: 0.2 nickel, manganese, the sulfate liquor of cobalt (comprises nickelous sulfate 3421g, manganese sulfate 2193g, cobaltous sulfate 1851g, pure water 14.5L) the NaOH 16L reaction of 16L and 4mol/L, regulating mixing speed is 200 commentaries on classics/min, the salting liquid flow is 10ml/min, regulate the aqueous slkali flow, pH value is remained between the 10-11, carry out the ageing reaction, after reaction finishes, continue to stir half an hour, then slurry is put in the centrifuge, after anhydrating, put into oven drying then, obtain as Fig. 1, precursor shown in 3.If with the precursor that obtains and lithium salts mixing and ball milling in certain proportion, sintering obtains anode material of lithium battery as shown in Figure 5.
Embodiment 2: the adding mol ratio is 0.4: 0.4: 0.2 a nickel, manganese, the cobalt sulfate liquor (comprises nickelous sulfate 3421g, manganese sulfate 2193g, cobaltous sulfate 1851g, pure water 14.5L,) 16L and 4mol/L NaOH 16L reaction, regulating mixing speed is 200 commentaries on classics/min, and the salting liquid flow is 10ml/min, regulates the aqueous slkali flow, pH value is remained between the 10-11, carry out the ageing reaction, after reaction finishes, continue to stir half an hour, then slurry is put in the centrifuge, after anhydrating, put into oven drying then, present embodiment does not add surfactant, obtain as Fig. 2, precursor shown in 4, with the precursor that obtains and lithium salts mixing and ball milling in certain proportion, sintering obtains anode material of lithium battery as shown in Figure 6.
Embodiment 3: the neopelex of elder generation's 0.15g/L concentration of adding 100mL in reaction cylinder and the mixture of polyvinyl alcohol, wherein the mol ratio of neopelex and polyvinyl alcohol is 1: 1, adding mol ratio again is the NaOH 16L reaction of 0.475: 0.475: 0.05 nickel, manganese, cobalt sulfate liquor and 4mol/L, mixing speed is 150 commentaries on classics/min, the salting liquid flow is 8ml/min, all the other steps are with embodiment 1, do not repeat them here, reaction obtain the mixing nickel manganese binary precursor of cobalt, its pattern as shown in Figure 7.
Embodiment 4: be the 4mol/L NaOH reaction of 0.475: 0.475: 0.05 nickel, manganese, cobalt sulfate liquor and 16L with mol ratio, mixing speed is 150 commentaries on classics/min, and the salting liquid flow is 8ml/min, and whole process does not add surfactant.All the other steps do not repeat them here with embodiment 2, reaction obtain the mixing nickel manganese binary precursor of cobalt, and its pattern is as shown in Figure 8.
Embodiment 5: the neopelex of elder generation's 0.06g/L concentration of adding 100mL in reaction cylinder and the mixture of polyvinyl alcohol, wherein the mol ratio of neopelex and polyvinyl alcohol is 1: 1, adding mol ratio again is the 4mol/L NaOH reaction of 0.45: 0.45: 0.1 nickel, manganese, cobalt sulfate liquor and 16L, mixing speed is 250 commentaries on classics/min, the salting liquid flow is 12ml/min, all the other steps are with embodiment 1, do not repeat them here, reaction obtains nickel manganese cobalt ternary precursor, and its pattern as shown in Figure 9.
Embodiment 6: the 4mol/L NaOH reaction that with mol ratio is 0.45: 0.45: 0.1 nickel, manganese, cobalt sulfate liquor and 16L, whole process does not add surfactant, mixing speed is 250 commentaries on classics/min, the salting liquid flow is 12ml/min, all the other steps are with embodiment 2, do not repeat them here, reaction obtains nickel manganese cobalt ternary precursor, and its pattern as shown in figure 10.
Embodiment 7: the neopelex of elder generation's 0.06g/L concentration of adding 100mL in reaction cylinder and the mixture of polyvinyl alcohol, wherein the mol ratio of neopelex and polyvinyl alcohol is 1: 1, adding mol ratio again is 0.8: 0.2 nickel, the sulfate liquor of cobalt and the 4mol/L NaOH reaction of 16L, mixing speed is 200 commentaries on classics/min, the salting liquid flow is 10ml/min, all the other steps are with embodiment 1, do not repeat them here, reaction obtains nickel cobalt binary precursor, and its pattern as shown in figure 11.
Embodiment 8: with mol ratio is 0.8: 0.2 nickel, the sulfate liquor of cobalt and the 4mol/L NaOH reaction of 16L, whole process does not add surfactant, mixing speed is 250 commentaries on classics/min, the salting liquid flow is 12ml/min, all the other steps are with embodiment 2, do not repeat them here, reaction obtains nickel cobalt binary precursor, and its pattern as shown in figure 12.
Embodiment 9: add 1g surfactant Tween-80 earlier in reaction cylinder, add mol ratio again and be 0.4: 0.4: 0.2 nickel: the 4mol/L NaOH reaction of manganese: cobalt sulfate liquor 16L (concentration is 2mol/L) and 16L, in the course of reaction, the color of material is dark partially, on the precursor color that precursor that the ageing reaction obtains and normal reaction obtain, the hardness difference is arranged all.
Particle diameter, tap density testing result such as the following table of the precursor of embodiment 1～8 preparation:
| Ratio (Ni: Mn: Co) | Whether add surfactant (Y/N) | ??D50(μm) | Tap density (g/cm 3) | |
| Embodiment 1 precursor | ??0.4∶0.4∶0.2 | ??Y | ??11.32 | ??2.10 |
| Embodiment 2 precursors | ??0.4∶0.4∶0.2 | ??N | ??9.54 | ??1.71 |
| Ratio (Ni: Mn: Co) | Whether add surfactant (Y/N) | ??D50(μm) | Tap density (g/cm 3) | |
| Embodiment 3 precursors | ??0.475∶0.475∶0.05 | ??Y | ??9.20 | ??1.93 |
| Embodiment 4 precursors | ??0.475∶0.475∶0.05 | ??N | ??9.78 | ??1.26 |
| Embodiment 5 precursors | ??0.45∶0.45∶0.1 | ??Y | ??9.60 | ??1.95 |
| Embodiment 6 precursors | ??0.45∶0.45∶0.1 | ??N | ??6.46 | ??1.58 |
| Embodiment 7 precursors | ??0.8∶0∶0.2 | ??Y | ??10.31 | ??2.01 |
| Embodiment 8 precursors | ??0.8∶0∶0.2 | ??N | ??12.14 | ??1.9 |
In the table as can be known, adding embodiment 1, embodiment 3, embodiment 5, the embodiment 7 of surfactant and the embodiment 2,4,6,8 that does not add surfactant compares, the pattern of embodiment 1,3,5,7 precursors all changes to some extent, and particle is tight, and tap density is big.
Claims (9)
1. the preparation method of a lithium battery anode material precursor, it is characterized in that, earlier in reaction cylinder, add surfactant, add the salting liquid, manganese of nickel again or/and the salting liquid of cobalt and aqueous slkali carry out ageing reacts, reaction finishes, and the dry lithium battery anode material precursor that gets anhydrates.
2. the preparation method of lithium battery anode material precursor according to claim 1, it is characterized in that, in reaction cylinder, add earlier surfactant, the salting liquid that adds nickel again, manganese is or/and cobalt salt solution and aqueous slkali carry out the ageing reaction, surfactant concentration＜1g/L, nickel, manganese is or/and the mol ratio of cobalt salt and alkali is 1: 2, the mixing speed of reaction is 150～250 commentaries on classics/min, nickel, manganese is regulated the aqueous slkali flow or/and the salting liquid flow of cobalt is 8～12ml/min, the pH value of reactant liquor is remained between the 10-11, carry out the ageing reaction, reaction finishes, and continues to stir 20～40min, centrifugal then anhydrating, the dry lithium battery anode material precursor that gets.
3. the preparation method of lithium battery anode material precursor according to claim 1 and 2 is characterized in that, between the nickel salt of described participation ageing reaction, manganese salt, the cobalt salt mol ratio be arbitrary proportion.
4. the preparation method of lithium battery anode material precursor according to claim 1 and 2 is characterized in that, described surfactant is two kinds of surfactant mixtures or Tween-80.
5. the preparation method of lithium battery anode material precursor according to claim 4 is characterized in that, described two kinds of mixtures that surfactant mixtures is polyvinyl alcohol and neopelex.
6. the preparation method of lithium battery anode material precursor according to claim 5 is characterized in that, the mass ratio of described polyvinyl alcohol and neopelex is 1: 1.
7. the preparation method of lithium battery anode material precursor according to claim 1 and 2 is characterized in that, surfactant concentrations＜0.3g/L in the ageing reaction.
8. the preparation method of lithium battery anode material precursor according to claim 1 and 2 is characterized in that, aqueous slkali is an alkali hydroxide soln.
9. the preparation method of lithium battery anode material precursor according to claim 8 is characterized in that, the concentration of described aqueous slkali is 0.3-0.6mol/L.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103311525A (en) * | 2013-06-08 | 2013-09-18 | 深圳华粤宝电池有限公司 | Preparation method of positive material of lithium-ion battery |
| CN106892464A (en) * | 2017-03-03 | 2017-06-27 | 北京理工大学 | A kind of preparation method of ternary anode material precursor |
| CN107910547A (en) * | 2017-11-30 | 2018-04-13 | 中能东道集团有限公司 | A kind of anode material for lithium-ion batteries of height ratio capacity and preparation method thereof |
| CN112723426A (en) * | 2020-12-31 | 2021-04-30 | 格林美（无锡）能源材料有限公司 | Porous positive electrode material precursor, preparation method thereof and ternary positive electrode material |
| CN114988479A (en) * | 2022-05-20 | 2022-09-02 | 上海锦源晟新能源材料有限公司 | Manganese-containing material and preparation method thereof, and lithium manganate and preparation method and application thereof |
| CN114988384A (en) * | 2022-05-20 | 2022-09-02 | 上海锦源晟新能源材料有限公司 | Lithium manganate material, preparation method thereof and secondary battery |
-
2009
- 2009-01-13 CN CN200910105025A patent/CN101777639A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103311525A (en) * | 2013-06-08 | 2013-09-18 | 深圳华粤宝电池有限公司 | Preparation method of positive material of lithium-ion battery |
| CN103311525B (en) * | 2013-06-08 | 2015-06-24 | 深圳华粤宝电池有限公司 | Preparation method of positive material of lithium-ion battery |
| CN106892464A (en) * | 2017-03-03 | 2017-06-27 | 北京理工大学 | A kind of preparation method of ternary anode material precursor |
| CN107910547A (en) * | 2017-11-30 | 2018-04-13 | 中能东道集团有限公司 | A kind of anode material for lithium-ion batteries of height ratio capacity and preparation method thereof |
| CN107910547B (en) * | 2017-11-30 | 2020-09-22 | 深圳绿霆动力科技有限公司 | High-specific-capacity lithium ion battery positive electrode material and preparation method thereof |
| CN112723426A (en) * | 2020-12-31 | 2021-04-30 | 格林美（无锡）能源材料有限公司 | Porous positive electrode material precursor, preparation method thereof and ternary positive electrode material |
| CN114988479A (en) * | 2022-05-20 | 2022-09-02 | 上海锦源晟新能源材料有限公司 | Manganese-containing material and preparation method thereof, and lithium manganate and preparation method and application thereof |
| CN114988384A (en) * | 2022-05-20 | 2022-09-02 | 上海锦源晟新能源材料有限公司 | Lithium manganate material, preparation method thereof and secondary battery |
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Open date: 20100714 |