CN104701530A - Preparation method of in-situ doped and modified nickel cobalt manganese lithium oxide positive material - Google Patents
Preparation method of in-situ doped and modified nickel cobalt manganese lithium oxide positive material Download PDFInfo
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Abstract
The invention discloses a preparation method of an in-situ doped and modified nickel cobalt manganese lithium oxide positive material. The preparation method of the in-situ doped and modified nickel cobalt manganese lithium oxide positive material is characterized by introducing metal elements in the process of preparing a nickel cobalt manganese precursor to stabilize the structure and implementing atom-scale mixing of doped elements and main elements in the process of preparing the precursor. Compared with the solid phase surface doping, the method can be used for stabilizing the material structure as a whole, so that the sintered positive material is relatively high in stability under the high voltage, thereby working under the relatively high voltage; the battery capacity is greatly improved; meanwhile, the cycle performance is greatly improved; by virtue of the preparation method of the positive material, a process of producing the precursor and a process of doping in the later period are integrated, so that the preparation process is simplified; the cost is saved; the raw materials are bulk chemical products; the industrialization is liable to implement.
Description
Technical field
The present invention relates to technical field of lithium ion battery positive pole material preparation, the preparation method of the cobalt nickel oxide manganses lithium anode material of particularly a kind of in-situ doped modification.
Background technology
It is high that lithium ion battery has specific energy, has extended cycle life, the little and advantages of environment protection of memory-less effect, self discharge, has been widely used in the equipment such as small-sized electronic product and electric automobile.And the performance of lithium ion battery depends primarily on the performance of positive electrode.So developing the high and constitutionally stable positive electrode of energy density becomes the focus that people pay close attention to.
Nickel-cobalt-manganternary ternary anode material is one of study hotspot of anode material of lithium battery of new generation.Such material combines LiNiO
2, LiCoO
2, LiMnO
2the advantage of three kinds of materials, and the deficiency that compensate for homogenous material to a certain extent, Co can reduce cation mixing, stable laminated structure; Ni can improve the capacity of material; Mn can reduce the cost of material, improves fail safe.There is obvious trielement synergistic effect, traditional LiCoO will be replaced gradually
2positive electrode.In the positive electrode of ternary system, the ratio of 5:2:3 (Ni:Co:Mn) both well considered stability, highlighted again its electro-chemical activity, was most widely used at present, the tertiary cathode material that market demand is maximum.
Along with electronic equipment is to the lifting of lithium ion battery with high energy density demand, traditional positive electrode can not meet the demands.Research shows, improves charging voltage, can improve the capacity of battery, and then improve its energy density.But positive electrode under high voltages structure becomes unstable, makes the cycle performance of battery decline.At present; most domestic positive electrode manufacturer all with the presoma of upstream firm for positive electrode prepared by raw material; the element doping modification in later stage is also all carried out on the presoma basis prepared; its structure is protected by forming stable superficial layer; but this has modified the surface of material, improve limited extent.
Summary of the invention
The object of the present invention is to provide in a kind of process preparing nickel cobalt manganese presoma and introduce metallic element to stablize its structure, achieve the preparation method of the cobalt nickel oxide manganses lithium anode material of the in-situ doped modification mixed of atom level between doped chemical with main element ion.
For this reason, technical scheme of the present invention is as follows:
A preparation method for the cobalt nickel oxide manganses lithium anode material of in-situ doped modification, comprises the steps:
1) soluble-salt of nickel, cobalt, manganese is configured in proportion nickeliferous, cobalt, manganese metal cation mixing salt solution (I), the mixed solution (II) of configuration NaOH and ammoniacal liquor;
2) salting liquid of configuration containing doped metallic elements A, and add complexing agent wherein and at the uniform velocity stir 0.2 ~ 2h, obtain mixed solution (III);
3) by step 1) and step 2) in the mixing salt solution (I) that configures, the mixed solution (II) of NaOH and ammoniacal liquor and mixed solution (III) pump in reactor simultaneously and carry out coprecipitation reaction, the flow of control NaOH and ammoniacal liquor mixed solution (II) makes the pH of mixed reaction solution in reactor remain between 11 ~ 12, wherein, in reactor, the mixing speed of mixed solution is 200 ~ 400 revs/min, reaction temperature is 40 ~ 70 DEG C, reaction time is 12 ~ 24h, coprecipitation reaction terminates rear continuation ageing reaction solution 1 ~ 2h, then by the sediment that obtains through washing, dry, obtain in-situ doped nickel-cobalt-manganese ternary presoma,
4) by step 3) in the in-situ doped nickel-cobalt-manganese ternary presoma that obtains and lithium carbonate Homogeneous phase mixing in high-speed mixer in proportion, then bell furnace is placed in, in air atmosphere with 4 ~ 10 DEG C/min ramp to 880 ~ 980 DEG C insulation roasting 8 ~ 16h, be down to room temperature after completion of the reaction, after pulverizing, sieving, obtain the cobalt nickel oxide manganses lithium anode material of in-situ doped modification.
Described step 1) in the concentration of mixing salt solution (I) of nickeliferous, cobalt, manganese metal cation of configuration be 2 ~ 2.3mol/L.
Described step 1) in NaOH solution concentration be 2 ~ 6mol/L, the concentration of described ammonia spirit is 10 ~ 15mol/L.
Described step 2) in described doped metallic elements A be at least one in aluminium, magnesium, titanium, zirconium, the doping of described doped metallic elements A accounts for 0.1 ~ 0.5wt% of in-situ doped nickel-cobalt-manganese ternary presoma gross mass.The salt of described doped metallic elements A is aluminium, one or more in sulfate, nitrate and chloride corresponding to magnesium, titanium, zirconium.
Described step 2) in described complexing agent be at least one in disodium ethylene diamine tetraacetate, natrium citricum, sodium lactate, sodium tartrate, sodium salicylate, the addition of described complexing agent and the mol ratio of doped chemical A are 0.5 ~ 1:1.
Described step 3) in the molecular formula of in-situ doped nickel-cobalt-manganese ternary presoma of preparation be Ni
xco
ymn
za
1-x-y-z(OH)
2, wherein, x:y:z is 5:2:3.
Described step 4) in described lithium carbonate and the mol ratio of in-situ doped nickel-cobalt-manganese ternary presoma be 1 ~ 1.05:1.
The preparation method of the cobalt nickel oxide manganses lithium anode material of this in-situ doped modification, metallic element is introduced to stablize its structure in the process preparing nickel cobalt manganese presoma, in precursor power process, achieve mixing of atom level between doped chemical with main element, adulterate relative to solid phase surface, this method of modifying can make Doped ions enter in the lattice of presoma, fundamentally stablizes its structure.
Compared with prior art, cobalt nickel oxide manganses lithium anode material prepared by the preparation method of the cobalt nickel oxide manganses lithium anode material of this in-situ doped modification is used:
(1) adulterate relative to traditional solid phase surface, the method stabilizes material structure on the whole, make to sinter the positive electrode obtained there is higher stability under high voltages to can be implemented in higher operating at voltages, significantly improve battery capacity, its cycle performance have also been obtained larger improvement simultaneously;
(2) production presoma operation and later stage doping operation unite two into one by the present invention, and both simplified preparation flow, cost-saved again, the raw material adopted is large chemical products, easily realizes industrialization.
Accompanying drawing explanation
Fig. 1 is the preparation process schematic diagram of the preparation method of the cobalt nickel oxide manganses lithium anode material of in-situ doped modification of the present invention;
Fig. 2 is the XRD figure of Modified Nickel cobalt manganese hydroxide precursor prepared by embodiment 1;
Fig. 3 is the XRD figure of modified oxidized nickel cobalt manganese lithium anode material prepared by embodiment 1;
Fig. 4 is the SEM figure of modified oxidized nickel cobalt manganese lithium anode material prepared by embodiment 1;
Fig. 5 is the cobalt nickel oxide manganses lithium anode material of embodiment 1 preparation and the button cell cyclic curve (5C, 2.3 ~ 4.5V) of the cobalt nickel oxide manganses lithium anode material of non-doped metallic elements.
Embodiment
Below in conjunction with accompanying drawing, the preparation method to the cobalt nickel oxide manganses lithium anode material of in-situ doped modification of the present invention is described in detail, but the present invention is not only confined to following examples.
Figure 1 shows that the schematic flow sheet of the preparation method of the cobalt nickel oxide manganses lithium anode material of this in-situ doped modification.
In following examples 1 ~ 3 and comparative example 1, adopt the cobalt nickel oxide manganses lithium anode material of in-situ doped modification prepared by technical scheme in embodiment or comparative example as active material, be to electrode with Li sheet, button simulated battery is assembled into, to assess the chemical property of this positive electrode in glove box.
Embodiment 1
1) be the mixing salt solution (I) that 5:2:3 is configured to nickeliferous, cobalt, the manganese metal cation of 10L 2.3mol/L by the soluble-salt of nickel, cobalt, manganese by the mol ratio of nickel, cobalt, manganese element, the NaOH solution of configuration 10L 6mol/L and the ammoniacal liquor of 2.2L 12mol/L by obtained for the two mixing mixed solution (II);
2) titanyl sulfate of 20g is configured to 5L titanyl sulfate solution, and adds 40ml concentrated hydrochloric acid, stir, and add 10g sodium lactate wherein, at the uniform velocity stir 2h, obtain the mixed solution (III) of containing metal titanium;
3) by step 1) and step 2) in configure mixing salt solution (I), NaOH and ammoniacal liquor mixed solution (II) and containing metal titanium mixed solution (III) pump in reactor simultaneously, the flow of control NaOH and ammoniacal liquor mixed solution makes the pH of mixed reaction solution in reactor be 11.9, in reactor, the mixing speed of mixed solution is 350 revs/min, reaction temperature is 50 DEG C, after coprecipitation reaction time 12h, after the sediment washing obtained, drying, obtain in-situ doped nickel-cobalt-manganese ternary presoma;
4) by step 3) in the in-situ doped nickel-cobalt-manganese ternary presoma of the 500g that obtains and 223g lithium carbonate Homogeneous phase mixing in high-speed mixer, rotating speed is 800 revs/min.Then be placed in bell furnace, with 8 DEG C/min ramp to 950 DEG C insulation roasting 14h, be down to room temperature after completion of the reaction, after pulverizing, sieving, obtain the cobalt nickel oxide manganses lithium anode material of in-situ doped modification.
Embodiment 2
1) be the mixing salt solution (I) that 5:2:3 is configured to nickeliferous, cobalt, the manganese metal cation of 10L 2mol/L by the soluble-salt of nickel, cobalt, manganese by the mol ratio of nickel, cobalt, manganese element, the NaOH solution of configuration 12L 4mol/L and the ammoniacal liquor of 2L 12mol/L by obtained for the two mixing mixed solution (II);
2) aluminum nitrate of 43g is configured to 4.5L aluminum nitrate solution, adds 42g disodium ethylene diamine tetraacetate wherein, at the uniform velocity stir 1h, obtain the mixed solution (III) of containing metal aluminium;
3) by step 1) and step 2) in configure mixing salt solution (I), NaOH and ammoniacal liquor mixed solution (II) and containing metal aluminium mixed solution (III) pump in reactor simultaneously, the flow of control NaOH and ammoniacal liquor mixed solution makes the pH of mixed reaction solution in reactor be 11.5, in reactor, the mixing speed of mixed solution is 300 revs/min, reaction temperature is 50 DEG C, after coprecipitation reaction time 10h, after the sediment washing obtained, drying, obtain in-situ doped nickel-cobalt-manganese ternary presoma;
4) by step 3) in the in-situ doped nickel-cobalt-manganese ternary presoma of the 500g that obtains and 219g lithium carbonate Homogeneous phase mixing in high-speed mixer, rotating speed is 800 revs/min.Then be placed in bell furnace, with 6 DEG C/min ramp to 950 DEG C insulation roasting 12h, be down to room temperature after completion of the reaction, after pulverizing, sieving, obtain the cobalt nickel oxide manganses lithium anode material of in-situ doped modification.
Embodiment 3
1) be the mixing salt solution (I) that 5:2:3 is configured to nickeliferous, cobalt, the manganese metal cation of 10L 2mol/L by the soluble-salt of nickel, cobalt, manganese by the mol ratio of nickel, cobalt, manganese element, the NaOH solution of configuration 26L 2mol/L and the ammoniacal liquor of 2.5L 10mol/L by obtained for the two mixing mixed solution (II);
2) 7g magnesium nitrate and 17g aluminum nitrate are configured to the magnesium nitrate of 4L and the mixed solution of aluminum nitrate, add 26g disodium ethylene diamine tetraacetate wherein, at the uniform velocity stir 0.5h, obtain the mixed solution (III) of containing metal magnalium;
3) by step 1) and step 2) in configure mixing salt solution (I), NaOH and ammoniacal liquor mixed solution (II) and containing metal magnalium mixed solution (III) pump in reactor simultaneously, the flow of control NaOH and ammoniacal liquor mixed solution makes the pH of mixed reaction solution in reactor be 11.3, in reactor, the mixing speed of mixed solution is 250 revs/min, reaction temperature is 60 DEG C, after coprecipitation reaction time 12h, by the sediment obtained through washing, drying, obtain in-situ doped nickel-cobalt-manganese ternary presoma;
4) by step 3) in the in-situ doped nickel-cobalt-manganese ternary presoma of the 500g that obtains and 213g lithium carbonate Homogeneous phase mixing in high-speed mixer, rotating speed is 700 revs/min.Then be placed in bell furnace, with 4 DEG C/min ramp to 880 DEG C insulation roasting 8h, be down to room temperature after completion of the reaction, after pulverizing, sieving, obtain the cobalt nickel oxide manganses lithium anode material of in-situ doped modification.
Comparative example 1
1) be the mixing salt solution (I) that 5:2:3 is configured to nickeliferous, cobalt, the manganese metal cation of 10L 2.3mol/L by the soluble-salt of nickel, cobalt, manganese by the mol ratio of nickel, cobalt, manganese element, the NaOH solution of configuration 10L 6mol/L and the ammoniacal liquor of 2.2L 12mol/L by obtained for the two mixing mixed solution (II);
2) by step 1) in the mixing salt solution (I), NaOH and the ammoniacal liquor mixed solution (II) that configure pump in reactor simultaneously, the flow of control NaOH and ammoniacal liquor mixed solution makes the pH of mixed reaction solution in reactor be 11.9, in reactor, the mixing speed of mixed solution is 350 revs/min, reaction temperature is 50 DEG C, after coprecipitation reaction time 12h, by the sediment obtained through washing, drying, obtain unadulterated nickel-cobalt-manganese ternary presoma;
3) by step 2) in the unadulterated nickel-cobalt-manganese ternary presoma of 500g, 223g lithium carbonate and the 1.94g titanium dioxide Homogeneous phase mixing in high-speed mixer that obtain, rotating speed is 800 revs/min.Then be placed in bell furnace, with 8 DEG C/min ramp to 950 DEG C insulation roasting 14h, be down to room temperature after completion of the reaction, after pulverizing, sieving, obtain the cobalt nickel oxide manganses lithium anode material of solid phase doping.
Performance test:
With this material for positive pole, be to electrode with metal lithium sheet, in glove box, be assembled into button cell.
Comparing embodiment 1 and comparative example 1, namely compare the electric cycle performance of the positive electrode obtained by the in-situ doped method of modifying of liquid phase and solid phase surface doping vario-property two kinds of methods.Within the scope of 2.3 ~ 4.5V, carry out charge and discharge cycles test under 5C multiplying power to battery, its cyclic curve of first 100 times as shown in Figure 5.Be 127.2mAh/g by the discharge capacity first of in-situ doped modified positive electrode, the discharge capacity of the 100th time is 119.4mAh/g, and capability retention is up to 93.9%; And the discharge capacity first of the positive electrode of solid phase doping vario-property is 115.5mAh/g, the discharge capacity of the 100th time is 91.9mAh/g, and capability retention is only 79.6%, illustrates that, through in-situ doped modified, material cycle performance under high voltages significantly improves.
In addition, also by carrying out X-ray diffraction (XRD) and scanning electron microscopy (SEM) test to embodiment 1 ~ 3, to adopting the intermediate obtained in the cobalt nickel oxide manganses lithium anode material preparation method of in-situ doped modification and the positive electrode finally obtained to analyze, all lead to the same conclusion.
Analyze for embodiment 1 below.
Figure 2 shows that the XRD figure of the nickel cobalt manganese hydroxide precursor of in-situ doped modification prepared by embodiment 1.As can be seen from the figure, each diffraction maximum of presoma all corresponds to hydroxide characteristic peak; Figure 3 shows that the XRD figure of the cobalt nickel oxide manganses lithium anode material of in-situ doped modification prepared by embodiment 1.As can be seen from the figure, the peak type of material is sharp-pointed and exist without dephasign peak, is typical α-NaFeO
2type structure, (006)/(102) and (110)/(108) two to the division of division peak obviously, have good hexagonal layer structure.Fig. 4 is the SEM figure of positive electrode prepared by embodiment 1, and as can be seen from the figure, product sphericity is better, and particle size is between 10 ~ 15 μm mostly.
Visible, the method achieve mixing of atom level between doped chemical with main element, adulterate relative to the solid phase of comparative example 1, this method of modifying can make Doped ions enter in the lattice of presoma, fundamentally stablize its structure, compared with therefore adulterating with traditional solid phase surface, positive electrode prepared by the method has higher stability under high voltages, can be implemented in higher operating at voltages, while significantly improving battery capacity, its cycle performance have also been obtained larger improvement.
Claims (9)
1. a preparation method for the cobalt nickel oxide manganses lithium anode material of in-situ doped modification, is characterized in that, comprise the steps:
1) soluble-salt of nickel, cobalt, manganese is configured in proportion nickeliferous, cobalt, manganese metal cation mixing salt solution (I); The mixed solution (II) of configuration NaOH and ammoniacal liquor;
2) salting liquid of configuration containing doped metallic elements A, and add complexing agent wherein and at the uniform velocity stir 0.2 ~ 2h, obtain mixed solution (III);
3) by step 1) and step 2) in the mixing salt solution (I) that configures, the mixed solution (II) of NaOH and ammoniacal liquor and mixed solution (III) pump in reactor simultaneously and carry out coprecipitation reaction, the flow of control NaOH and ammoniacal liquor mixed solution (II) makes the pH of mixed reaction solution in reactor remain between 11 ~ 12, wherein, in reactor, the mixing speed of mixed solution is 200 ~ 400 revs/min, reaction temperature is 40 ~ 70 DEG C, reaction time is 12 ~ 24h, coprecipitation reaction terminates rear continuation ageing reaction solution 1 ~ 2h, then by the sediment that obtains through washing, dry, obtain in-situ doped nickel-cobalt-manganese ternary presoma,
4) by step 3) in the in-situ doped nickel-cobalt-manganese ternary presoma that obtains and lithium carbonate Homogeneous phase mixing in high-speed mixer in proportion, then bell furnace is placed in, in air atmosphere with 4 ~ 10 DEG C/min ramp to 880 ~ 980 DEG C insulation roasting 8 ~ 16h, be down to room temperature after completion of the reaction, after pulverizing, sieving, obtain the cobalt nickel oxide manganses lithium anode material of in-situ doped modification.
2. the preparation method of the cobalt nickel oxide manganses lithium anode material of in-situ doped modification according to claim 1, is characterized in that, described step 3) in the molecular formula of in-situ doped nickel-cobalt-manganese ternary presoma of preparation be Ni
xco
ymn
za
1-x-y-z(OH)
2, wherein, x:y:z is 5:2:3.
3. the preparation method of the cobalt nickel oxide manganses lithium anode material of in-situ doped modification according to claim 2, it is characterized in that, described step 2) in described doped metallic elements A be at least one in aluminium, magnesium, titanium, zirconium, the doping of described metal element A accounts for 0.1 ~ 0.5wt% of in-situ doped nickel-cobalt-manganese ternary presoma gross mass.
4. the preparation method of the cobalt nickel oxide manganses lithium anode material of the in-situ doped modification according to any one of claims 1 to 3 claim, it is characterized in that, described step 1) in the concentration of mixing salt solution (I) of nickeliferous, cobalt, manganese metal cation of configuration be 2 ~ 2.3mol/L.
5. the preparation method of the cobalt nickel oxide manganses lithium anode material of the in-situ doped modification according to any one of claims 1 to 3 claim, it is characterized in that, described step 1) described in NaOH and the mixed solution (II) of ammoniacal liquor mixed by the ammonia spirit of concentration to be the NaOH solution of 2 ~ 6mol/L and concentration be 10 ~ 15mol/L.
6. the preparation method of the cobalt nickel oxide manganses lithium anode material of the in-situ doped modification according to any one of claims 1 to 3 claim, it is characterized in that, described step 2) in described complexing agent be at least one in disodium ethylene diamine tetraacetate, natrium citricum, sodium lactate, sodium tartrate, sodium salicylate, the addition of described complexing agent and the mol ratio of doped chemical A are 0.5 ~ 1:1.
7. the preparation method of the cobalt nickel oxide manganses lithium anode material of the in-situ doped modification according to any one of claims 1 to 3 claim, it is characterized in that, described step 4) in described lithium carbonate and the mol ratio of in-situ doped nickel-cobalt-manganese ternary presoma be 1 ~ 1.05:1.
8. the preparation method of the cobalt nickel oxide manganses lithium anode material of the in-situ doped modification according to any one of claims 1 to 3 claim, is characterized in that, described step 1) in the working speed of high-speed mixer be 500 ~ 1000 revs/min.
9. the preparation method of the cobalt nickel oxide manganses lithium anode material of the in-situ doped modification according to any one of claims 1 to 3 claim, is characterized in that, described in sieve after obtain in-situ doped modification cobalt nickel oxide manganses lithium anode material particle diameter be 10 ~ 20 μm.
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2015
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| CN115259239A (en) * | 2022-06-24 | 2022-11-01 | 广东金晟新能源股份有限公司 | Zirconium ion in-situ doped high-nickel ternary precursor, preparation method and application thereof |
| CN115385393A (en) * | 2022-08-23 | 2022-11-25 | 荆门市格林美新材料有限公司 | Zirconium-doped nickel-cobalt-manganese hydroxide and preparation method and application thereof |
| CN115321610A (en) * | 2022-08-31 | 2022-11-11 | 荆门市格林美新材料有限公司 | Zirconium-aluminum double-doped nickel-cobalt-manganese hydroxide and preparation method and application thereof |
| CN116161710A (en) * | 2023-02-24 | 2023-05-26 | 广东邦普循环科技有限公司 | Modified lithium cobalt oxide positive electrode material, preparation method thereof and lithium battery |
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